WO2020137220A1

WO2020137220A1 - High internal oil phase oil-in-water emulsion composition

Info

Publication number: WO2020137220A1
Application number: PCT/JP2019/044591
Authority: WO
Inventors: 知子佐藤; バーナードピービンクス; アナマリアバーゴロドリゲス
Original assignee: 株式会社資生堂
Priority date: 2018-12-28
Filing date: 2019-11-13
Publication date: 2020-07-02
Also published as: JPWO2020137220A1; JP2024026824A

Abstract

The present invention provides a high internal oil phase oil-in-water emulsion composition which exhibits excellent emulsion stability. A high internal oil phase oil-in-water emulsion composition of the present disclosure contains water and oil droplets that are dispersed in the water; each of the oil droplets contains an associated body that contains a cationic polymer and an anionic polymer, and an oil component; the oil component is contained in an amount of 50% or more relative to the total amount of the water and the oil component; and the associated body is present in each oil droplet at the interface with the aqueous phase.

Description

Takauchi oil phase oil-in-water emulsion composition

The present disclosure relates to a Takauchi oil phase oil-in-water emulsion composition.

　In recent years, oil-in-water emulsion compositions that highly contain oil have been used in cleansing cosmetics and the like.

In Patent Document 1, (a) glycerin 5 to 30% by mass, (b) water 1 to 15% by mass, (c) polar oil 50 to 90% by mass, and (d) polymerization degree of 5 to 6 An optimum oil-in-water emulsion composition as a cleansing agent is disclosed, which comprises 0.1 to 5 mass% of polyglycerin fatty acid ester.

Patent Document 2 contains an oily component, an aqueous component, and a surfactant, the oily component is 40% by mass or more of the entire composition, and the oily component is a solid fat having a melting point of 45 to 75° C. An oil-in-water emulsion composition containing 0.2 to 4.0% by mass, wherein the inside of the forearm coated with 0.3 g of the oil-in-water emulsion composition is loaded by the second finger, the third finger, and the fourth finger. An oil-in-water emulsion composition with excellent cleansing power, in which the emulsifier type begins to change to an oily state in 1 to 20 revolutions in a test in which orbital movement is performed at 0.1 to 8.0 N with a major axis of 10 cm and a minor axis of 5 cm. The thing is disclosed.

Patent Document 3 discloses a high internal oil phase oil-in-water emulsion composition suitable for cosmetics, which contains 70 to 90% by weight of fats and oils and does not contain higher alcohols.

Patent Document 4 contains one or more kinds of polyglyceryl fatty acid esters, one or more kinds selected from N-long chain acyl acidic amino acids and salts thereof, and one or more kinds of oily substances. Disclosed is an oil-in-water type emulsion cosmetic for skin in which the content of the oily substance is 30 to 70% by weight of the total amount of the cosmetic.

JP, 2007-153754, A JP, 2018-111667, A Japanese Patent Laid-Open No. 2000-015085 Japanese Patent Laid-Open No. 2002-212029

In a conventional oil-in-water emulsion composition, a surfactant is generally used when oil is highly emulsified. However, the surfactant used in such an emulsification system generally does not stay near the interface with the aqueous phase in the oil droplet (emulsified particle), and for example, in the oil phase or other adjacent oil droplets. It is considered to be in an equilibrium state where it can move to an interface or the like. As a result, a portion where the oil component is exposed at the interface of the oil droplet occurs, and in particular, in the high internal oil phase oil-in-water emulsion composition, it is easy to aggregate and coalesce with the oil component in another adjacent oil droplet. , The emulsion stability tended to decrease.

Therefore, the subject of the present disclosure is to provide a high internal oil phase oil-in-water emulsion composition having excellent emulsion stability.

<Aspect 1>
Including water and oil droplets dispersed in water,
The oil droplets include an aggregate containing a cationic polymer and an anionic polymer, and an oil component,
The oil content is 50% or more based on the total amount of the water and the oil content,
The aggregate is present at the interface of the oil droplet with the aqueous phase,
Takauchi oil phase oil-in-water emulsion composition.
<Aspect 2>
The composition according to aspect 1, wherein the oil content is 74% or more based on the total amount of the water and the oil content.
<Aspect 3>
The composition according to aspect 1 or 2, wherein the cationic polymer and the anionic polymer are not surfactants by themselves.
<Aspect 4>
The aspect 1 to 3 wherein the cationic polymer has a cationization degree of 0.5 meq/g or more, and the anionic polymer has an anionization degree of 0.5 meq/g or more. Composition.
<Aspect 5>
The cationic polymer is diallyldimethylammonium chloride, 3-(methacrylamido)propyltrimethylammonium chloride, propyltrimonium chloride acrylamide, dimethylmethylene piperidinium chloride, hydroxyethyl cellulose hydroxypropyl trimethyl ammonium chloride ether, hydroxyethyl cellulose, guar gum hydroxypropyl. Trimethylammonium chloride ether, cationized locust bean gum, dimethylallylammonium chloride acrylamide copolymer, and at least one component selected from the group consisting of chitin and chitosan, and,
The anionic polymer is hyaluronic acid, carboxyvinyl polymer, carboxymethyl cellulose, acrylic acid, methacrylic acid, styrene sulfonic acid, acroyl dimethyl taurine, acroyl dimethyl taurate ammonium, alginic acid, aspartic acid, chondroitin sulfate, polyglutamic acid, and them. At least one component selected from the group consisting of salts of
The composition according to any one of aspects 1 to 4.
<Aspect 6>
The cationic polymer contains at least one component selected from hydroxyethyl cellulose hydroxypropyl trimethyl ammonium chloride ether, and diallyl dimethyl ammonium chloride, and,
The anionic polymer contains hyaluronic acid, carboxyvinyl polymer, carboxymethyl cellulose, and at least one component selected from the group consisting of salts thereof,
The composition according to any one of aspects 1 to 4.
<Aspect 7>
A cosmetic base comprising the composition according to any one of aspects 1 to 6.

According to the present disclosure, it is possible to provide a high internal oil phase oil-in-water emulsion composition having excellent emulsion stability.

Conventional high internal phase emulsions obtained using surfactants generally have a share that is applied to the skin, and the emulsified particles coalesce all at once, resulting in a sudden decrease in spreadability. Is obtained. The high internal oil phase oil-in-water emulsion composition of the present disclosure has a feature that its change is rapid and large as compared with the case of a system using such a surfactant, and thus it is an unprecedented novelty. You can get a good feeling.

It is a graph regarding a time-dependent change of elongation weight in an oil-in-water emulsion composition having an oil content of 75%. It is a graph regarding a time-dependent change of elongation weight in an oil-in-water emulsion composition having an oil content of 40%.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments and can be variously modified and implemented within the scope of the gist of the invention.

An oil-in-water emulsified composition in a high internal oil phase according to an embodiment of the present disclosure includes water, and an oil droplet dispersed in water, and the oil droplet is an aggregate including a cationic polymer and an anionic polymer, And 50% or more of the total amount of water and oil, and the aggregate is present at the interface with the aqueous phase in the oil droplets.

Although not limited by the principle, it is considered that the oil-in-water emulsion composition of the present disclosure has a high oil content and is excellent in emulsion stability as follows.

The aggregate contained in the high internal oil phase oil-in-water emulsion composition of the present disclosure is also called a polyion complex, in which a cationic polymer and an anionic polymer are aggregated and entangled by electrostatic interaction or the like. It is an aggregate of such a structure and is in a state like a solid particle. In addition, in an emulsion composition containing oil, such an aggregate is present at the interface between the continuous aqueous phase and the oil phase as the dispersed phase, and functions like an emulsifier.

In oil-in-water emulsion compositions, a surfactant is generally used as an emulsifier. Such a surfactant is generally not in the vicinity of the interface between the oil droplet and the water phase, and is in an equilibrium state where it can move to another place such as the water phase. As a result, a part where the oil component is exposed at the interface of the oil droplet is generated, and particularly in the high internal oil phase oil-in-water emulsion composition, it is easy to aggregate and coalesce with the oil component in another adjacent oil droplet, Emulsion stability decreases.

On the other hand, in the case of the oil-in-water emulsion composition of the present disclosure, the aggregate formed at the interface with the aqueous phase in the oil droplet is an aggregate having an entangled structure assembled by electrostatic interaction or the like. Yes, presents a solid state containing water. That is, the system of the present disclosure is considered to be a kind of Pickering emulsion stabilized with solid particles. Unlike the surfactant, the aggregate formed on the interface of the oil droplet hardly peels off from the interface. Since the oil phase and the water phase can be physically separated, the emulsion stability in a stationary state is improved as compared with a general surfactant.

Further, the oil-in-water emulsion composition of the present disclosure can highly contain an oil content of 74% or more based on the total amount of water and the oil content. The oil-in-water emulsion composition of the present disclosure is such that the emulsified particles are soft droplets, unlike the inorganic particles, and the above-mentioned associated body is formed at the interface of the oil droplets to sufficiently stabilize the emulsified particles. Therefore, it is considered that the oil component can be stably contained in the composition more than the state of the close-packed structure.

Further, in general, when the internal oil phase has a volume of more than 74% with respect to the total amount of water and oil, the emulsified particles come close to each other, and the frictional force of the emulsified particles causes the thickening agent to the external water phase. The system is thickened even if it does not contain. The polymer forming the aggregate in the system of the present disclosure includes those having a thickening function by itself, but the thickening function is lost when the aggregate is formed. However, when the system contains 74% or more of the internal oil phase, the system can be thickened even if the thickening function of the aggregate is lost.

<< Takauchi oil phase oil-in-water emulsion composition >>
The high internal oil phase oil-in-water emulsion composition of the present disclosure (which may be simply referred to as “emulsion composition”) includes water and oil droplets dispersed in water, and the oil droplets include a cationic polymer and An anionic polymer-containing aggregate, and an oil component are contained, and the oil component is contained in an amount of 50% or more based on the total amount of water and the oil component, and the aggregate is present at the interface between the oil droplet and the aqueous phase. ..

The emulsion composition of the present disclosure has excellent emulsion stability. Here, the emulsion stability means, for example, a state in which the size of the emulsified particles (oil droplets) does not change for 1 month or more at 50° C. or 3 months or more at room temperature (5 to 35° C.). it can.

The emulsion composition of the present disclosure is also excellent in emulsion stability under low viscosity. The viscosity of the emulsified composition can be evaluated using, for example, a rheometer MCR-302 (manufactured by Anton-Paar). For example, the viscosity at a shear rate of 1,000/s in a linear region of the measurement object when measured at 32° C. and 1 atm is 800 mPa·s or more, 900 mPa·s or more, or 1, 5 seconds after the start of shearing. It can be defined as 000 mPa·s or more, and can be defined as 10,000 mPa·s or less, 9,500 mPa·s or less, or 9,000 mPa·s or less.

The size (average particle diameter) of the oil droplets can be defined as, for example, the average value of the projected area circle equivalent diameters of 10 or more oil droplets observed with an optical microscope, or the particle shape of the oil droplets can be spherical. Assuming that, it can be defined as the average value of the diameter of the oil droplet optically measured by the dynamic light scattering method or the like. Further, if the proportion of the internal oil phase exceeds 74%, it may be impossible to hold the sphere due to the contact of oil droplets. In such a case, dilute the system with water and measure. Good.

As described above, the emulsified composition of the present disclosure has a sharply reduced elongation when applied with a share enough to be applied to the skin, as compared with a conventional high internal phase emulsion obtained using a surfactant. It is possible to obtain an unprecedented new feeling of use that the change in “compatibility” is rapid and large.

Regarding such a feeling of use (change in phase inversion feeling), for example, using a Tribomaster (manufactured by Trinity Lab Co., Ltd.), which will be described later, changes in the weight of elongation (may be simply referred to as “elongation weight”). Can be evaluated at. For example, the emulsion composition of the present disclosure can achieve 20% or more, 25% or more, or 30% or more with respect to the reduction rate of elongation weight calculated by the following formula 1. The upper limit value of the reduction rate is not particularly limited, but can be defined as, for example, 80% or less, 75% or less, or 70% or less.

The reduction rate of the elongation weight of the emulsion composition may be calculated from the following Equation 1 from the elongation weight of the emulsion composition 1 second after the start of measurement and the elongation weight of the emulsion composition 20 seconds after the start of measurement. it can:
Reduction rate of elongation weight (%)={(elongation weight of emulsified composition 1 second after the start of measurement−elongation weight of emulsified composition 20 seconds after the start of measurement)×100}/(1 second after the start of measurement) Elongation Weight of Emulsion Composition in Eq.

<Oil drop>
The oil-in-water emulsion composition of the present disclosure includes oil droplets as an oil phase or a dispersed phase, and the oil droplets include an aggregate containing a cationic polymer and an anionic polymer, and an oil component.

(Aggregate)
When a cationic polymer and an anionic polymer are mixed in an aqueous solution, both polymers are aggregated by at least electrostatic interaction to form an aggregate (solid particle) called entangled polyion complex. At this time, a hydrophobic interaction may be further added depending on the types of both polymers.

The size (average particle size) of the aggregate is preferably 10 nm or more, or 50 nm or more, and is preferably 50 μm or less, 10 μm or less, or 1 μm or less. When the size of the aggregate is within such a range, the fixing property of the aggregate at the oil-water interface can be improved, and relatively small emulsified particles can be prepared.

The size of the aggregate can be measured, for example, by a dynamic light scattering method (DLS) using an aqueous dispersion containing the aggregate.

The mixing ratio of the cationic polymer and the anionic polymer can be defined by, for example, the molar ratio of the ionic charge of the anionic polymer to the ionic charge of the cationic polymer. The molar ratio can be in the range of 20:1 to 1:20, and preferably in the range of 15:1 to 1:15. An aggregate obtained by mixing both polymers in such a range, particularly in a range capable of being ionically neutralized, is likely to be formed at the interface between the oil droplet and the aqueous phase without precipitation.

The total amount of the cationic polymer and the anionic polymer to be blended is 0.05 mass% or more, 0.07 mass% or more, or the total amount of the emulsified composition, from the viewpoint of the emulsion stability of the emulsified composition, or It can be 0.1 mass% or more, and can be 20 mass% or less, 15 mass% or less, 10 mass% or less, 5 mass% or less, 3 mass% or less, or 2 mass% or less.

a. Cationic Polymer The cationic polymer of the present disclosure is not limited to the following, but for example, a cationic polymer that does not exhibit surface activity by itself can be used. As such a cationic polymer, for example, a cationic polymer having a cationization degree of 0.5 meq/g or more, 0.7 meq/g or more, or 0.9 meq/g or more can be used. The upper limit of the degree of cationization is not particularly limited, but may be, for example, 20 meq/g or less, 18 meq/g or less, or 15 meq/g or less. Here, the unit “meq/g” of the degree of cationization and the degree of anion described below means a cationic dissociative group (cationic ion) or anionic dissociative group per 1 g of a monomer constituting the cationic polymer or the anionic polymer. It shows how many millimoles of (anionic ion) are contained.

Specific cationic polymers include, for example, diallyldimethylammonium chloride (DADMAC), 3-(methacrylamido)propyltrimethylammonium chloride (MAPTAC), propyltrimonium chloride acrylamide, dimethylmethylene piperidinium chloride, and hydroxyethyl cellulose hydroxypropyl. Trimethylammonium chloride ether (cationized cellulose), hydroxyethyl cellulose (cationized HEC), guar gum hydroxypropyl trimethylammonium chloride ether (cationized guar gum), cationized locust bean gum, dimethylallylammonium chloride acrylamide copolymer, and chitin. Mention may be made of homopolymers or copolymers containing at least one component selected from the group consisting of chitosan.

Among them, a homopolymer or a copolymer containing at least one component selected from hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride ether and diallyldimethylammonium chloride is preferable from the viewpoint of emulsion stability, thickening and the like.

The amount of the cationic polymer in the emulsion composition of the present disclosure is, from the viewpoint of the emulsion stability of the emulsion composition, etc., relative to the total amount of the emulsion composition, 0.05% by mass or more, 0.07% by mass or more, Alternatively, it can be 0.1% by mass or more, and can be 20% by mass or less, 15% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, or 2% by mass or less. ..

b. Anionic Polymer The anionic polymer of the present disclosure is not limited to the following, but for example, an anionic polymer that does not exhibit surface activity by itself can be used. As such an anionic polymer, for example, an anionic polymer having an anionization degree of 0.5 meq/g or more, 0.7 meq/g or more, or 0.9 meq/g or more can be used. The upper limit of the anionization degree is not particularly limited, but can be, for example, 20 meq/g or less, 18 meq/g or less, or 15 meq/g or less.

Specific anionic polymers include, for example, hyaluronic acid, carboxyvinyl polymer, carboxymethyl cellulose, acrylic acid, methacrylic acid, styrene sulfonic acid, acroyl dimethyl taurine, ammonium acroyl dimethyl taurine, alginic acid, aspartic acid, chondroitin sulfate, Mention may be made of homopolymers or copolymers containing at least one component selected from the group consisting of polyglutamic acid and salts thereof.

Among them, a homopolymer or a copolymer containing at least one component selected from the group consisting of hyaluronic acid, carboxyvinyl polymer, carboxymethylcellulose, and salts thereof is preferable from the viewpoint of emulsion stability, thickening property, and the like.

The amount of the anionic polymer in the emulsion composition of the present disclosure, from the viewpoint of the emulsion stability of the emulsion composition, relative to the total amount of the emulsion composition, 0.05 mass% or more, 0.07 mass% or more, Alternatively, it can be 0.1% by mass or more, and can be 20% by mass or less, 15% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, or 2% by mass or less. ..

c. Other Cationic Polymers and Anionic Polymers In addition to the above cationic polymers and anionic polymers, other cationic polymers and anionic polymers are added to the emulsion composition of the present disclosure within a range that does not impair the effects of the present disclosure. You may. However, in consideration of emulsion stability and the like, it is preferable not to include other cationic polymers and anionic polymers.

(Oil content)
The oil content is not limited to the following, but for example, at least one of liquid oil, solid oil, wax, hydrocarbon oil, synthetic ester oil, silicone oil, etc. can be used.

Examples of liquid oils and fats include 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, linseed oil. , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.

Examples of the solid fats and oils include cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, beef tallow, mutton fat, hardened beef tallow, palm kernel oil, pork fat, beef bone fat, sorghum kernel oil, hardened oil, and beef. Leg oil, syrup, hydrogenated castor oil and the like can be mentioned.

Examples of the waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivota wax, whale wax, montan wax, nuka wax, lanolin, capock wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, Examples thereof include reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol acetate, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether.

Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, olefin oligomer, isododecane, and isohexadecane.

Examples of synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, Myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate , Diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, tri-2-ethylhexane Acid glycerin, glyceryl trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoate glyceride, castor oil Fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate , Di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate and the like.

Examples of the silicone oil include chain silicones such as dimethyl polysiloxane (dimethicone), methylphenyl polysiloxane, and methyl hydrogen polysiloxane; cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Silicone etc. are mentioned.

The emulsified composition of the present disclosure can contain an oil component in an amount of 50% or more, 60% or more, 70% or more, or 74% or more with respect to the total amount of water and the oil component. The upper limit of the content is not particularly limited, but can be specified to be 85% or less, or 80% or less, for example.

<water>
Water that can be used in the emulsified composition of the present disclosure is not particularly limited, but water used for cosmetics, quasi drugs, and the like can be used. For example, purified water, ion-exchanged water, tap water, etc. can be used.

<Arbitrary ingredients>
The emulsion composition of the present disclosure may optionally contain various components depending on the intended use of the emulsion composition, etc., within a range that does not impair the effects of the present disclosure. Examples of the various components include additive components that can be usually added to cosmetics, such as higher alcohols, lower alcohols, polyhydric alcohols, various extracts, anionic surfactants, cationic surfactants and amphoteric interfaces. Activator, nonionic surfactant, humectant, antioxidant, buffer, preservative, antioxidant aid, organic powder, pigment, dye, pigment, fragrance, chelating agent, pH adjuster, ultraviolet absorber , Gelling agents (thickeners) and the like.

The emulsion composition of the present disclosure preferably does not include a surfactant separately from the viewpoint of emulsion stability, low irritation to the skin, etc., and a gelling agent (thickener) separately from the viewpoint of usability and the like. It is preferable not to include it.

The various components can be added to the aqueous phase as a continuous phase and/or can be added to the oil content as a dispersed phase depending on their properties.

<<Use of Emulsion Composition>>
The emulsion composition of the present disclosure can exhibit a moist feel when applied to the skin, and further, the emulsion composition of the present disclosure has a higher internal phase emulsion using a surfactant, When applied to the skin and spread, it can give a feeling of use (phase inversion) such that the emulsified particles disintegrate more significantly. Further, the emulsified composition of the present disclosure, despite having a high degree of oil content, because it exhibits an oil-in-water type form, unlike the water-in-oil type emulsified composition, in water It can be dispersed and washed off with water. Therefore, the emulsion composition of the present disclosure exhibiting such performance can be used, for example, as a base for cosmetics, particularly as a base for cosmetics applied to the skin.

Specifically, the emulsified composition of the present disclosure can be used, for example, for cleansing cosmetics such as make-up remover, body shampoo or skin cleansing agents, sunscreen cosmetics (sunscreen agents), massage cosmetics, skin care cosmetics such as emulsions. , Can be used as makeup cosmetics and the like. In particular, it is preferably used as a cleansing cosmetic or a skin cleanser.

<<Method for producing emulsified composition>>
The oil-in-water emulsion composition of the present disclosure can be produced using a known method. For example, both a cationic polymer and an anionic polymer can be added to water and stirred to prepare a mixed liquid, and an oil component can be added to the mixed liquid and stirred to obtain an oil-in-water emulsion composition. You may mix|blend the said arbitrary component with water or oil suitably as needed.

Alternatively, to some of the water, any one of the cationic polymer and the anionic polymer is added to prepare a mixed liquid, and an oil component is added to the mixed liquid and stirred to emulsify the emulsified solution. Prepare A. Next, the other polymer is added to some other water to prepare the mixed solution B, and the mixed solution B is added to the emulsified solution A and stirred to obtain an oil-in-water type emulsion composition. .. You may mix|blend the said arbitrary component with water or oil suitably as needed.

The present disclosure will be described in more detail with reference to examples below, but the present disclosure is not limited thereto. In addition, hereinafter, unless otherwise specified, the compounding amount is shown by mass part.

<<Examples 1 to 4 and Comparative Examples 1 to 5>>
The following evaluations were performed on the emulsion composition obtained by the production method shown below, and the results are shown in Table 1.

<Evaluation of viscosity>
Using a rheometer MCR302 manufactured by Anton Paar, the viscosity at a shear rate of 1000/s was measured under the conditions of 32° C. and 1 atm. The viscosity in Table 1 shows the viscosity 5 seconds after the start of shearing. Here, the viscosity of the composition whose emulsion stability was evaluated as “C” below was not measured.

<Evaluation of emulsion stability>
The size of the oil droplets within 1 hour after the preparation of the emulsified composition and the size of the oil droplets after storage for 1 month at 50° C. were visually observed, and the emulsion stability was evaluated according to the following criteria:
A: Almost no change in oil droplet size.
B: The oil droplet size was slightly increased.
C: The oil droplet size was clearly increased.

<Method for producing emulsified composition>
(Example 1)
Carboxyvinyl polymer having an anionization degree of 14.1 meq/g which is an anionic polymer (Carbopol (trademark) 981 polymer manufactured by Lubrizol Advanced Materials) and cation having a cationization degree of 1.0 meq/g which is a cationic polymer. Cellulose (UCARE (trademark) polymer JR-400 (hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride ether) manufactured by Dow Chemical Co., Ltd.) was prepared in advance so as to be a 5% by mass aqueous solution. Then, the solution containing the cationized cellulose and the solution containing the carboxyvinyl polymer are stirred and mixed at room temperature so as to have a mass ratio of 14:1 (ionically neutral) to prepare an aggregate, Ion-exchanged water was added to this to prepare Dispersion A having a total polymer concentration of 3.33% by mass or 1.00% by mass. Next, liquid paraffin, which is an oil component, was gradually added to this dispersion A so that the amount of oil and the polymer concentration in the emulsion composition shown in Table 1 were gradually added to the dispersion liquid A while stirring and mixing at room temperature. A drop type emulsion composition was prepared.

(Example 2)
As the anionic polymer, hyaluronic acid having an anionization degree of 2.6 meq/g (Biohyaro (trademark) 12 manufactured by Shiseido Co., Ltd.), and as the cationic polymer, cationized cellulose having a cationization degree of 1.0 meq/g (Dow) An oil-in-water emulsion composition of Example 2 in the same manner as in Example 1 except that UCARE (trademark) polymer JR-400 (hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride ether) manufactured by Chemicals was used. I made things.

(Example 3)
Carboxymethyl cellulose having an anionization degree of 1.5 meq/g (Serogen (trademark) FSH manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as the anionic polymer, and PDADMAC( having a cationization degree of 6.2 meq/g as the cationic polymer. An oil-in-water type emulsion composition of Example 3 was produced in the same manner as in Example 1 except that Marcote (trademark) 100 (polydiallyldimethylammonium chloride) manufactured by Nalco was used.

(Example 4)
Carboxymethyl cellulose having an anionization degree of 1.5 meq/g (Serogen (trademark) F manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as the anionic polymer, and cationization having a cationization degree of 1.0 meq/g as the cationic polymer. Oil-in-water type of Example 4 in the same manner as in Example 1 except that cellulose (UCARE (trademark) polymer JR-400 (hydroxyethyl cellulose hydroxypropyl trimethyl ammonium chloride ether) manufactured by Dow Chemical Co., Ltd.) was used. To prepare an emulsified composition.

(Comparative Example 1)
As the anionic polymer, a microgel having an anionization degree of 3.4 meq/g (manufactured by Toho Chemical Industry ((N,N'-dimethylacrylamide-2-acrylamido-2-methylpropanesulfonic acid sodium-N,N'-methylenebis Acrylamide copolymer)), and as a cationic polymer, a MAPTAC/PAA copolymer having a cationization degree of 3.2 meq/g (Mercoat (trademark) 2001 (3-(methacrylamido)propyltrimethylammonium chloride manufactured by Nalco), An oil-in-water emulsion composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that a copolymer with polyallylamine)) was used. In this emulsified composition, when oil was added to some extent, the oil was no longer emulsified, and a considerable amount of oil floated on the top.

(Comparative example 2)
As the anionic polymer, sodium alginate (Duck Algin NSPH manufactured by Kikkoman Biochemifa Corporation) having an anionization degree of 5.7 meq/g, and as the cationic polymer, cationic locust bean having a cationization degree of 1.0 meq/g. An oil-in-water emulsion composition of Comparative Example 2 was produced in the same manner as in Example 1 except that gum (Catinal CLB-100 manufactured by Toho Chemical Industry Co., Ltd.) was used.

(Comparative example 3)
An anionization degree of 14.1 meq/g anionic polymer carboxyvinyl polymer (Carbopol (trademark) manufactured by Lubrizol Advanced Materials Co., Ltd. 981 polymer) containing only an aggregate-free dispersion A was used. A composition of Comparative Example 3 was prepared in the same manner as in Example 1. The composition turned white for a moment when mixed, but separated immediately like a separate type dressing.

(Comparative Example 4)
An anionization degree was the same as in Example 1 except that an aggregate-free dispersion A containing only hyaluronic acid (Biohyaro (trademark) 12 manufactured by Shiseido Co., Ltd.) having a degree of 2.6 meq/g was used. The composition of Comparative Example 4 was prepared.

(Comparative example 5)
Except that a dispersion A containing no aggregates, containing only PDADMAC having a cationization degree of 6.2 meq/g (Mercote (trademark) 100 (polydiallyldimethylammonium chloride) manufactured by Nalco) was used. A composition of Comparative Example 5 was prepared in the same manner as in 1.

<result>
As can be seen from the results in Table 1, in the case of the emulsified compositions containing the aggregates of Examples 1 to 4, as compared with the compositions of Comparative Examples 3 to 5 which do not contain the aggregates. It was confirmed that 50% or more of oil could be included. The compositions in Comparative Examples 1 and 2 contained an anionic polymer and a cationic polymer, but could not contain 50% or more of oil. This is because, in the combination of the anionic polymer and the cationic polymer in Comparative Examples 1 and 2, the aggregate was not sufficiently formed, or even if something like the aggregate was formed, It is considered that this is because the oil droplets do not exist at the interface with the aqueous phase.

<<Example 5 and Comparative Example 6>>
With respect to the emulsion composition obtained by the production method shown below, the following elongation weight (phase inversion feeling) was evaluated, and the results are shown in FIGS. 1 and 2.

<Evaluation of elongation weight (phase inversion feeling)>
The elongation weight of the emulsified composition was measured using Tribomaster manufactured by Trinity Lab. In this measurement, 10 μl of a sample of the emulsified composition was placed on the artificial leather, and the force applied when the 1 cm square tip reciprocates 5 cm while applying a load of 50 g on the sample at a speed of 5 cm/sec. It was measured.

(Example 5)
A carboxyvinyl polymer having an anionization degree of 14.1 meq/g (Carbopol (trademark) 981 polymer manufactured by Lubrizol Advanced Materials), which is an anionic polymer, and a cation having a cationization degree of 1.0 meq/g, which is a cationic polymer. Cellulose (UCARE (trademark) polymer JR-400 (hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride ether) manufactured by Dow Chemical Co., Ltd.) was prepared in advance so as to be a 5% by mass aqueous solution. Then, the solution containing the cationized cellulose and the solution containing the carboxyvinyl polymer are stirred and mixed at room temperature so as to have a mass ratio of 14:1 (ionically neutral) to prepare an aggregate, Ion-exchanged water was added to this to prepare a dispersion B having a total polymer concentration of 3.33% by mass. Next, liquid paraffin which is an oil component was gradually added to this dispersion B while stirring and mixing at room temperature while gradually adding so that the oil amount was 74% and the polymer concentration in the emulsion composition was 0.96% by mass. To produce an oil-in-water type emulsion composition.

(Comparative example 6)
Comparative Example 6 was carried out in the same manner as in Example 5 except that liquid paraffin was added to Dispersion B so that the oil content was 40% and the polymer concentration in the emulsion composition was 1.4% by mass. To prepare an emulsified composition.

<result>
As is clear from the results of FIG. 1, the emulsified composition having a high oil content in Example 5 had a peculiar phase inversion sensation that the elongation was drastically reduced in the range of about 20 seconds from the initial measurement stage. Was present. On the other hand, as is clear from the results of FIG. 2, the emulsion composition of Comparative Example 6 having a low oil content showed almost no change in elongation weight from the initial stage of measurement to about 40 seconds and showed a phase inversion sensation at all. There wasn't.

<<Example of formulation of composition>>
Hereinafter, formulation examples of the emulsion composition of the present disclosure will be given, but the formulation examples are not limited thereto. In addition, when the cleansing agent described in the following prescription examples is simply applied to the skin, it can be fixed to the skin without dripping, while the applied cleansing agent is spread on the skin surface. Had a use feeling (phase inversion feeling) such that the emulsified particles rapidly collapse.

Further, the obtained cleansing agent, despite having a high degree of oil content, exhibits an oil-in-water form, which is different from a cleansing agent comprising an emulsion composition in a water-in-oil form. I was able to wash it off with water.

<Prescription example 1 cleansing agent>
(Component) (mass%)
Purified water Carboxyvinyl polymer with proper anionization degree of 14.1 meq/g 0.07
Cationized cellulose with a degree of cationization of 1.0 meq/g 0.93
Isododecane 10
Dimethyl silicone 30
Triethylhexanoin 10
Liquid paraffin 24
1,3-butylene glycol 10
Ion-exchanged water Remaining antiseptic Suitable amount Perfume Suitable amount

(Method for producing cleansing agent)
A carboxyvinyl polymer having an anionization degree of 14.1 meq/g and a cationized cellulose having a cationization degree of 1.0 meq/g were each dissolved in ion-exchanged water to prepare 2% by mass and 5% by mass aqueous solutions, respectively. This aqueous solution, a moisturizing agent and a preservative were mixed by stirring at room temperature to prepare a dispersion liquid a containing an aggregate. The oil and the fragrance mixed in the dispersion liquid a were gradually added, and the mixture was stirred and mixed at room temperature to prepare a cleansing agent.

Claims

Including water and oil droplets dispersed in water,
The oil droplets include an aggregate containing a cationic polymer and an anionic polymer, and an oil component,
The oil content is 50% or more based on the total amount of the water and the oil content,
The aggregate is present at the interface of the oil droplet with the aqueous phase,
Takauchi oil phase oil-in-water emulsion composition.
The composition according to claim 1, wherein the oil content is 74% or more based on the total amount of the water and the oil content.
The composition according to claim 1 or 2, wherein the cationic polymer and the anionic polymer are not surfactants by themselves.
4. The method according to claim 1, wherein the cationic polymer has a cationization degree of 0.5 meq/g or more, and the anionic polymer has an anionization degree of 0.5 meq/g or more. The composition according to the item.
The cationic polymer is diallyldimethylammonium chloride, 3-(methacrylamido)propyltrimethylammonium chloride, propyltrimonium chloride acrylamide, dimethylmethylene piperidinium chloride, hydroxyethyl cellulose hydroxypropyl trimethyl ammonium chloride ether, hydroxyethyl cellulose, guar gum hydroxypropyl. Trimethylammonium chloride ether, cationized locust bean gum, dimethylallylammonium chloride acrylamide copolymer, and at least one component selected from the group consisting of chitin and chitosan, and,
The anionic polymer is hyaluronic acid, carboxyvinyl polymer, carboxymethyl cellulose, acrylic acid, methacrylic acid, styrene sulfonic acid, acroyl dimethyl taurine, acroyl dimethyl taurate ammonium, alginic acid, aspartic acid, chondroitin sulfate, polyglutamic acid, and them. At least one component selected from the group consisting of salts of
The composition according to any one of claims 1 to 4.
The cationic polymer contains at least one component selected from hydroxyethyl cellulose hydroxypropyl trimethyl ammonium chloride ether, and diallyl dimethyl ammonium chloride, and,
The anionic polymer contains hyaluronic acid, carboxyvinyl polymer, carboxymethyl cellulose, and at least one component selected from the group consisting of salts thereof,
The composition according to any one of claims 1 to 4.
A cosmetic base comprising the composition according to any one of claims 1 to 6.