CN1909883A - Monophase microemulsion composition, o/w ultrafine emulsion external formulation and process for producing the same - Google Patents
Monophase microemulsion composition, o/w ultrafine emulsion external formulation and process for producing the same Download PDFInfo
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Abstract
A one-phase microemulsion composition, which can be easily prepared without the use of special equipment, has high safety, and stays stable for a long period in an ultrafine emulsion state when the composition is added to an aqueous formulation, is provided by appropriately adjusting the ratio of (A) a hydrophilic nonionic surfactant, (B) a lipophilic nonionic surfactant, (C) an oil component, (D) a water-miscible solvent that does not interdissolve with the oil component, and the critical micelle concentration (CMC) of the hydrophilic nonionic surfactant in the water-miscible solvent is higher than that of the hydrophilic nonionic surfactant in water, and (E) water.
Description
Related application
The application advocates Japanese patent application 2004-1451 number priority of the application on January 6th, Japanese patent application 2004-1450 number 1 of application on January 6th, 2004, here cites.
Technical field
The present invention relates to Monophase microemulsion composition, O/W ultrafine emulsion external formulation and preparation method thereof, particularly relate to the Monophase microemulsion composition preparation method easy, compositions safety and it is added into the safety of the O/W ultrafine emulsion external formulation that water prescription obtains, the raising of stability.
Background technology
Known in the past at various fields use such as cosmetics, pharmaceuticals, pesticide, water paint, wax, food ultra micro emulsion formulations, particularly O/W ultra micro emulsion formulations is used as the external agent.As the method for this ultra micro emulsion formulations of preparation, the known Monophase microemulsion that following operation is obtained is matched with the method in the water prescription.
Method one is: add hydrocarbon ils such as cyclohexane extraction, cycloheptane in the nonionic surfactant water-soluble liquid of high HLB, elevated temperature is then before the cloud point of non-ionic surface active agent, the rapid regional (Can Zhao Xiao Tagayasu Den who increases three works of solubilizing amount that hydrocarbon ils occurs, " solution and dissolubility ", ball is kind, 1991,209 to 225 pages).Known, to the single liquid phase zone (Iw) of cloud point, oil sharply increases at the dissolubility of aqueous phase, forms so-called Monophase microemulsion in the solubilising critical temperature shown in the phasor.But, the Monophase microemulsion zone that obtains by non-ionic surface active agent-hydro carbons of former studies, keeping its hydrophilic-oil loving very narrow temperature province (about several ℃ to 10 ℃) is stable on thermodynamics, but exceed a little this temperature province then system become turbid, the result is separated into biphase.Therefore, this Monophase microemulsion is applied to cosmetics, medicine field is very difficult.
Method two is: with the combination of cosurfactants such as anion surfactant and amylalcohol, hexanol, capryl alcohol, make system reach hydrophilic-lipophilic balance (HLB), the zone that utilizes the solubilizing amount of hydrocarbon ils sharply to increase in this very narrow scope.Method three is: add electrolyte in the combination of lipophile nonionic surfactant and specific ionic surfactant or lipophile nonionic surfactant and ionic surfactant, from it is formed in system reaches the scope of very narrow ratio of hydrophilic-lipophilic balance (HLB), the regional (Can Zhao Xiao Tagayasu Den three, Xi Strip that utilize the solubilizing amount of hydrocarbon ils sharply to increase grand it, oiling is learned, 35,308 to 314 pages (1986), the spy opens clear 58-128311 communique, and the spy opens clear 58-131127 communique).In addition, known as method four with silicone oil and siloxane type surfactants, hydrophilic surfactant active's combination, adjust the method (opening flat 10-120524 communique) of hydrophilic-lipophilic balance (HLB) with reference to the spy.
But, use these methods, though high to the stability of temperature, but the composition that the Thermodynamically stable of the Monophase microemulsion that obtains exists is very limited, breaks away from this scope and then muddiness, separation can take place, therefore, there is the prescription of actual product to be very limited, or the problem that is complicated.In addition, there is problem the safety, the zest aspect that are engaged in human body of ionic surfactant, cosurfactant.
In addition, known the fluid mixture that contains water and oil is applied strong shearing force, make the miniaturization of microemulsion particle and obtain the method (open clear 63-12654 communique with reference to the spy, the spy opens flat 1-293131 communique) of ultra micro emulsion.These are to use for example go-devices such as リ Application type high pressure homogenizer, utilize high pressure that sample is extruded between narrow slit, and cavitation when being converted to normal pressure and sinuous flow are with the method for dispersed particle miniaturization.In addition, novel high-pressure emulsification device has also been proposed, but rise as the emulsifying pressure setting being got very high fiducial temperature when then handling with the high-pressure emulsification device, therefore usually influence the stability (with reference to special fair 2-976526 communique, the spy opens flat 11-47580 communique) of emulsion.
In addition, the method handled with ultrasonic irradiation etc. has been proposed also, but the extensive difficulty of making when being to use ultrasound wave.As above, when preparing the ultra micro emulsion,, therefore need the so special device of high-pressure emulsification device owing to need very big energy by physical method.
Summary of the invention
Therefore, the problem of researcher is a kind of Monophase microemulsion composition of exploitation, and it does not use special device in the past easily to prepare, and is safe and can be used as that the ultra micro emulsion is steady in a long-term to be existed when making an addition to water prescription.
In view of the above problems, the inventor furthers investigate, found that: by with (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content, (D) and the immiscible aqueous solvent of above-mentioned oil content, the critical micelle concentration (c.m.c) of wherein above-mentioned hydrophilic nonionic surfactant in this aqueous solvent is than the height in water, and (E) water is adjusted into proper proportion, can not use special device, and only prepare thermodynamically stable Monophase microemulsion phase by at room temperature mixing, stirring.And find that the Monophase microemulsion composition that will obtain like this is added in the water prescription, the particle diameter that can obtain excellent in stability is 10 to 500nm O/W ultra micro emulsion, thereby has finished the present invention.
Promptly, a first aspect of the present invention is a Monophase microemulsion composition, it is characterized in that, contain (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content, (D) and the immiscible aqueous solvent of above-mentioned oil content, the critical micelle concentration (c.m.c) of wherein above-mentioned hydrophilic nonionic surfactant in this aqueous solvent be than height in water, and (E) water.
And, in above-mentioned Monophase microemulsion composition, (A) HLB of hydrophilic nonionic surfactant be 13 or more than, (B) HLB of lipophile nonionic surfactant be 6 or below suit.In addition, in above-mentioned Monophase microemulsion composition, (C) use level of oil content is that 10 to 40 quality % are advisable.And in above-mentioned Monophase microemulsion composition, (C) oil content is that silicone oil is advisable.And in above-mentioned Monophase microemulsion composition, (C) oil content is a kind or above being advisable that is selected from decamethylcyclopentaandoxane, polydimethylsiloxane, the PSI.
In addition, in above-mentioned Monophase microemulsion composition, (D) aqueous solvent is that the aqueous solvent that has 3 or following hydroxyl in the molecule is advisable.In above-mentioned Monophase microemulsion composition, (D) aqueous solvent is for being selected from a kind or above being advisable in polypropylene glycol ethylene glycol copolymer or its dimethyl ether, Polyethylene Glycol or its alkyl ether, polyoxyalkylene dicarboxylic ester, 1,3 butylene glycol, dipropylene glycol, isoamyl glycol (isoprene glycol), the glycerol.
In addition, a second aspect of the present invention is the preparation method of Monophase microemulsion composition, it is characterized in that having following step: and above-mentioned hydrophilic nonionic surfactant therein critical micelle concentration (c.m.c) immiscible with above-mentioned oil content mixed stirring than the high aqueous solvent in water with (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content, (D), prepares the W/O emulsion preparation operation of W/O emulsion; And (E) water is added in this W/O emulsion, make the O/W Monophase microemulsion that changes O/W Monophase microemulsion phase mutually into change operation mutually.
A third aspect of the present invention is the O/W ultrafine emulsion external formulation, it is characterized in that, immiscible and above-mentioned hydrophilic nonionic surfactant critical micelle concentration (c.m.c) therein is than its high aqueous solvent and (E) water in water with above-mentioned oil content to contain (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content, (D), and the emulsifying particle diameter is 10 to 500nm.
In addition, a fourth aspect of the present invention is the preparation method of O/W ultrafine emulsion external formulation, it is characterized in that having following operation: and above-mentioned hydrophilic nonionic surfactant therein critical micelle concentration (c.m.c) immiscible with above-mentioned oil content mixed stirring than the high aqueous solvent in water with (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content, (D), prepares the W/O emulsion preparation operation of W/O (Water-In-Oil solvent-borne type) emulsion; (E) water is added in this W/O emulsion, makes and change O/W Monophase microemulsion phase mutually into, the O/W Monophase microemulsion preparation section of preparation O/W Monophase microemulsion; With this O/W Monophase microemulsion further is added into (F) water prescription, the O/W ultra micro emulsion preparation operation of modulation O/W ultra micro emulsion.
In addition, in the preparation method of above-mentioned O/W ultrafine emulsion external formulation, (A) HLB of hydrophilic nonionic surfactant be 13 or more than, (B) HLB of lipophile nonionic surfactant be 6 or below suit.In addition, in the preparation method of above-mentioned O/W ultrafine emulsion external formulation, (C) use level of oil content is that 10 to 40 quality % are advisable.And in the preparation method of above-mentioned O/W ultrafine emulsion external formulation, (C) oil content is that silicone oil is advisable.In the preparation method of above-mentioned O/W ultrafine emulsion external formulation, (C) oil content is a kind or above being advisable that is selected from decamethylcyclopentaandoxane, polydimethylsiloxane, the PSI.
In the preparation method of above-mentioned O/W ultrafine emulsion external formulation, (D) aqueous solvent is that the aqueous solvent that has 3 or following hydroxyl in the molecule is advisable.In addition, in the preparation method of above-mentioned O/W ultrafine emulsion external formulation, (D) aqueous solvent is a kind or above being advisable that is selected from polypropylene glycol ethylene glycol copolymer or its dimethyl ether, Polyethylene Glycol or its alkyl ether, polyoxyalkylene dicarboxylic ester, 1,3 butylene glycol, dipropylene glycol, isoamyl glycol, the glycerol.
The invention effect
Monophase microemulsion composition of the present invention does not use the so special device of high-pressure emulsification device easily to prepare, and safe to human body.Further, by Monophase microemulsion composition of the present invention is added in the water prescription, but easily prepare O/W ultrafine emulsion external formulation steady in a long-term, though the particle diameter of the O/W ultrafine emulsion external formulation that obtains like this is very little, be 10 to 500nm, but good stability.
Description of drawings
[Fig. 1] illustrates the figure that Monophase microemulsion composition of the present invention generates.
Among [Fig. 2] embodiments of the invention 1-1, the phase equilibrium diagram when changing water addition and temperature.
The Monophase microemulsion composition that [Fig. 3] obtains embodiments of the invention 1-1 drops in the water, at room temperature preserve 1 month after, by the measurement result of light scattering determining particle diameter.
The specific embodiment
Below describe formation of the present invention in detail.
Monophase microemulsion composition of the present invention is characterised in that, its contain (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content, (D) with above-mentioned oil content immiscible and above-mentioned hydrophilic nonionic surfactant critical micelle concentration (c.m.c) therein than high aqueous solvent in water and (E) water.
O/W ultrafine emulsion external formulation of the present invention is characterised in that, it contains (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content, (D), and immiscible and above-mentioned hydrophilic nonionic surfactant critical micelle concentration (c.m.c) therein is than high aqueous solvent in water and (E) water with above-mentioned oil content, and the emulsifying particle diameter is 10 to 500nm.
In addition, in the present invention, " Monophase microemulsion " be meant in water/surfactant/oil system, and be transparent or semitransparent, be made of and the compositions of thermodynamically stable system single liquid phase (the micelle oil solution phase of micellar aqueous solution phase that the complete solubilising of oil content forms or the complete solubilising of moisture).In addition, in the present invention, " ultra micro emulsion " is meant in water/surfactant/oil system, the emulsification system that constitutes by two kinds of liquid phases (oil phase is emulsified in the system of aqueous phase or water and is emulsified in system in the oil phase), the emulsified particle miniaturization is to transparent or semitransparent degree, the compositions of thermodynamic unstable system.
Above-mentioned " Monophase microemulsion " and " ultra micro emulsion " is transparent or semitransparent compositions, only be difficult to difference with outward appearance, but for example in case temperature is risen to high temperature, when returning to original temperature then, as return to equal state then for " Monophase microemulsion " (Thermodynamically stable), if do not return to equal state then for " ultra micro emulsion " (thermodynamic instability), can clearly distinguish the two like this.
(A) hydrophilic nonionic surfactant that the present invention is used is not particularly limited, and it is dissolved that micelle preferably takes place in aqueous solvent pellucidly, and particularly HLB is 13 or above.As (A) hydrophilic examples of nonionic surfactants that the present invention uses, can enumerate polyoxyethylene fatty acid glyceride, polyoxyethylene methyl polysilicone alkyl copolymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, maltose alcohol hydroxyl group aliphatic alkyl ether, alkylation polysaccharide, alkyl polyglucoside, sucrose fatty acid ester etc.
(B) lipophile nonionic surfactant that the present invention is used is not particularly limited, and it is dissolved that micelle does not preferably take place in aqueous solvent, and particularly HLB is 6 or following.As (B) lipophile examples of nonionic surfactants that the present invention uses, can enumerate polyoxyethylene fatty acid glyceride, polyoxyethylene methyl polysilicone alkyl copolymer, fatty acid sorbitan ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, cithrol, alkanoyl diglycollic amide, fatty acid isopropanol amide etc.
(A) hydrophilic nonionic surfactant that the present invention is used and (B) mass ratio of lipophile nonionic surfactant be not particularly limited, be preferably 3: 7 to 7: 3.As exceeding this ratio, the zone that then generates stable Monophase microemulsion sometimes is very narrow.(A) the hydrophilic nonionic surfactant and (B) concentration of lipophile nonionic surfactant be not particularly limited, but preferably with respect to 1 part of (C) oil content, (A) the hydrophilic nonionic surfactant and (B) the total amount of lipophile nonionic surfactant be 0.5 to 2 part.During less than 0.5 part,, can not get the high Monophase microemulsion of stability sometimes, surpass 2 parts, consider not preferred from safety then because amount of surfactant is too much because surfactant is few.
(C) oil content that the present invention is used is not particularly limited, and can suitably use for example silicone oil, hydrocarbon ils, ester oil etc., in addition, and also can be with these 2 kinds or above mixing use.(C) oil content as the present invention uses can preferably use silicone oil.As the example of silicone oil, can enumerate polydimethylsiloxane, cyclohexyl methyl siloxanes, poly-diphenyl siloxane, poly-alkylsiloxane etc., can be with these 2 kinds or above mixing use.The concentration of (C) oil content that the present invention is used is not particularly limited, and generally is preferably 10 to 40 quality % of total composition.As surpassing 40 quality %, then be difficult to obtain the high Monophase microemulsion of stability.
(D) aqueous solvent that the present invention uses be necessary for (C) oil content immiscible and (A) critical micelle concentration (c.m.c) of hydrophilic nonionic surfactant in this aqueous solvent than the high aqueous solvent in water.When this (D) aqueous solvent and above-mentioned (C) oil content mix, or (A) critical micelle concentration (c.m.c) of hydrophilic nonionic surfactant in this aqueous solvent than in water when low, even other conditions all satisfy, also can not get stable Monophase microemulsion phase.In addition, critical micelle concentration of the present invention (c.m.c) is meant the critical micelle concentration of measuring (c.m.c) under 25 ℃ temperature conditions.
As (D) aqueous solvent that the present invention uses, so long as solvent as described above, then there is no particular limitation, can be according to (C) oil content and (A) kind suitably selection use from known aqueous solvent of hydrophilic nonionic surfactant.At this, aqueous solvent be meant with water molten at room temperature for liquid material, can enumerate for example unary alcohol, polyalcohols, ketone, aldehydes, ethers, amine, lower aliphatic acids, polyethylene glycols or derivatives thereof etc.
In addition, in aqueous solvent arbitrarily, for the critical micelle concentration (c.m.c) of (A) hydrophilic nonionic surfactant in this aqueous solvent whether than the height in water, can be by measuring the critical micelle concentration (c.m.c) of (A) hydrophilic nonionic surfactant under two kinds of conditions in this aqueous solvent and in the water, the two critical micelle concentration (c.m.c) is compared to determine.But for aqueous solvent, the critical micelle concentration (c.m.c) of in most cases measuring the hydrophilic nonionic surfactant in independent aqueous solvent is very difficult.In this case, aqueous solvent-the aqueous solution of an amount of this aqueous solvent is added in preparation in water, measure the critical micelle concentration (c.m.c) of (A) hydrophilic nonionic surfactant under two kinds of conditions in this aqueous solvent-aqueous solution and in the water (separately), the two is compared get final product.(A) critical micelle concentration (c.m.c) value of hydrophilic nonionic surfactant in aqueous solvent-aqueous solution is worth when high than critical micelle concentration (c.m.c) in water, can determine this aqueous solvent for the critical micelle concentration (c.m.c) of (A) hydrophilic nonionic surfactant than the high aqueous solvent in water.
More specifically, for example, aqueous solvent-aqueous solution that the aqueous solvent dissolves arbitrarily of modulation 10% obtains in water, when critical micelle concentration (c.m.c) value of (A) hydrophilic nonionic surfactant in this 10% aqueous solvent-aqueous solution than the high 0.01g/100g of value of the critical micelle concentration (c.m.c) in water or when above, can determine this aqueous solvent for the critical micelle concentration (c.m.c) of (A) hydrophilic nonionic surfactant than the high aqueous solvent in water.
For example, when (A) the hydrophilic nonionic surfactant is polyoxyethylene (20 moles) glyceryl isostearate, critical micelle concentration (c.m.c) in polyoxyethylene (14 moles) polyoxypropylene (7 moles) dimethyl ether 10% aqueous solution is 0.51g/100g, critical micelle concentration in water (c.m.c) is 0.26g/100g, because therefore high 0.25g/100g we can say critical micelle concentration (c.m.c) ratio the high aqueous solvent in water of polyoxyethylene (14 moles) polyoxypropylene (7 moles) dimethyl ether for (A) hydrophilic nonionic surfactant.
In addition, as (D) aqueous solvent that the present invention uses, preferably (A) hydrophilic nonionic surfactant critical micelle concentration (c.m.c) in this aqueous solvent is high more good more.Particularly, (A) hydrophilic nonionic surfactant critical micelle concentration (c.m.c) in preferred 10% aqueous solvent-aqueous solution value than the high 0.01g/100g of value of the critical micelle concentration (c.m.c) in water or more than, more preferably 0.04g/100g or more than, further preferred 0.10g/100g or more than.If the difference of (A) hydrophilic nonionic surfactant critical micelle concentration (c.m.c) in this (D) aqueous solvent and the critical micelle concentration (c.m.c) in the water is too small, then the stability region of Monophase microemulsion phase is narrow, and system can become unstable sometimes.
In addition, (C) oil content and (D) combination of aqueous solvent used as the present invention, (D) not mix with (C) oil content be essential to aqueous solvent.As this combination, for example can enumerate, when (C) oil content is polydimethylsiloxane, as (D) aqueous solvent, be polypropylene glycol ethylene glycol copolymer or its dimethyl ether, Polyethylene Glycol or its ethylether, 1,3 butylene glycol, dipropylene glycol, isoamyl glycol etc.; During (C) for ring dimethyl siloxane (5 aggressiveness),, be polypropylene glycol ethylene glycol copolymer or its dimethyl ether, Polyethylene Glycol or its ethylether etc. as (D) aqueous solvent; When (C) being PSI,, be polypropylene glycol ethylene glycol copolymer or its dimethyl ether, 1,3 butylene glycol, glycerol etc. as (D) aqueous solvent.
(D) aqueous solvent as the present invention's use, can enumerate the aqueous solvent that intramolecularly has 3 or following hydroxyl particularly, more specifically, can enumerate polypropylene glycol ethylene glycol copolymer or its alkyl ether, Polyethylene Glycol or its alkyl ether, polyoxyalkylene dicarboxylic ester, 1,3-butanediol, dipropylene glycol, isoamyl glycol, 1,2-pentanediol, 1,2-hexanediol, 2-methyl isophthalic acid, 3-propanol, ethyl carbitol, 1,2-butanediol, glycerol etc., can according to (C) oil content and (A) kind of hydrophilic nonionic surfactant suitably select in the middle of these to use.In addition, as (D) of the present invention aqueous solvent, can be with these 2 kinds or above being used in combination.On the other hand, the water-soluble substances that intramolecularly has 4 or above hydroxyl at room temperature is solid usually, can not be used as (D) of the present invention aqueous solvent mostly.In addition, the use level of (D) aqueous solvent that the present invention is used is not particularly limited, with respect to total composition, preferably cooperate 5 quality % or more than.If less than 5 quality %, then stable Monophase microemulsion alpha region is very narrow.
The use level of (E) water that the present invention is used is not particularly limited, but must suitably regulate use level according to the kind or the use level of (A) to (D) that use, makes in the zone that Monophase microemulsion forms.In addition, (A) critical micelle concentration (c.m.c) of hydrophilic nonionic surfactant in (D) aqueous solvent is high more, and the many more tendencies of amount that form Monophase microemulsion mutually necessary (E) water are then arranged.
In addition, will contain above-mentioned (A) to (E) and further be added in (F) water prescription, can obtain O/W ultrafine emulsion external formulation of the present invention as O/W Monophase microemulsion that must composition.(F) water prescription that the present invention uses is so long as water or be the prescription of main medium with aqueous solvent, then be not particularly limited, except water or aqueous solvent, also can cooperate the composition that is generally used for cosmetics, pharmaceuticals etc. with the use level of the scope that stability do not exerted an influence.
In addition, the final water use level of O/W ultrafine emulsion external formulation of the present invention by Monophase microemulsion generate the use level of used (E) water and (F) in the water prescription aqueous use level with.Total use level to institute of the present invention water is not particularly limited, and with respect to O/W ultrafine emulsion external formulation total amount, generally is preferably 30 to 99 quality %.
Below, be example with the general preparation method of Monophase microemulsion composition of the present invention and O/W ultrafine emulsion external formulation, principle of the present invention is carried out simple declaration.
The method for making example
1) and above-mentioned hydrophilic nonionic surfactant therein critical micelle concentration (c.m.c) immiscible with above-mentioned oil content mixed stirring than the high aqueous solvent in water with (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content, (D), and obtaining (C) oil content is that foreign minister, (D) aqueous solvent are W/O (Water-In-Oil solvent-borne type) emulsion of inner phase.
2) above-mentioned W/O emulsion is stirred on the limit, and the limit slowly adds (E) water, then takes place to being the transformation mutually of the O/W Monophase microemulsion phase of inner phase with (C) oil content.And, near this changes that amount of generation mutually, as stop the interpolation of (E) water, then generate thermodynamically stable O/W Monophase microemulsion composition.
3) above-mentioned O/W Monophase microemulsion is added in (F) water prescription, obtains particle diameter and be 10 to 500nm O/W ultrafine emulsion external formulation.
Principle
1) and if above-mentioned hydrophilic nonionic surfactant therein critical micelle concentration (c.m.c) immiscible with above-mentioned oil content mixed stirring than the high aqueous solvent in water with (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content, (D), then generation (C) oil content is that foreign minister, (D) aqueous solvent are W/O (Water-In-Oil solvent-borne type) emulsion (Fig. 1 (a)) of inner phase.
At this, usually (A) hydrophilic nonionic surfactant is adsorbed in water-oil phase interface, but be somebody's turn to do critical micelle concentration (c.m.c) height of (A) hydrophilic nonionic surfactant in (D) aqueous solvent, can be dissolved in (D) aqueous solvent by unimolecule, thus overslaugh to the absorption at water-oil phase interface.On the other hand, though (B) the lipophile nonionic surfactant (D) aqueous solvent exist and also can be adsorbed in water-oil phase interface.Therefore, when water only is made of (D) aqueous solvent, can think that almost the state that is adsorbed in water-oil phase interface with (B) lipophile nonionic surfactant only forms the W/O emulsion.
2) then, as in above-mentioned W/O emulsion, slowly adding (E) water, then (E) water and (D) aqueous solvent mix, (E) water content of aqueous phase increases gradually.Thus, because the content of (E) water that (A) critical micelle concentration of hydrophilic nonionic surfactant (c.m.c) is lower than (D) aqueous solvent increases, the critical micelle concentration (c.m.c) of (A) hydrophilic nonionic surfactant of water integral body reduces gradually.So, originally only be dissolved in (A) hydrophilic nonionic surfactant of the aqueous phase that constitutes by (D) aqueous solvent with the unimolecule form, because the reduction of critical micelle concentration (c.m.c) becomes and can not be dissolved in aqueous phase with the unimolecule form, and is adsorbed in water-oil phase interface gradually.So, increase along with (A) hydrophilic nonionic surfactant amount that is adsorbed in water-oil phase interface, finally when (A) hydrophilic nonionic surfactant that is adsorbed in water-oil phase interface and (B) lipophile nonionic surfactant arrive certain specific amount and compare, system reaches hydrophilic-lipophile balance, becomes 3 phases (Fig. 1 (b)) of oil phase-surfactant phase-water.At this moment, think when the hydrophilic-lipophilic balance (HLB) of system becomes impartial (C) the solubilizing amount maximum of oil content.
As adding (E) water again, then final single liquid phase that the micellar aqueous solution of aqueous phase takes place to be solubilized into fully to (C) oil content, promptly the transformation mutually of O/W (oil-in-water type) Monophase microemulsion phase generates O/W Monophase microemulsion composition of the present invention.(Fig. 1 (c)).
3) then, the O/W Monophase microemulsion composition that obtains as mentioned above is added in (F) water prescription, so the emulsified particle of this O/W Monophase microemulsion is keeping small particle diameter and is being scattered in the water prescription, obtain particle diameter and be 10 to 500nm O/W ultrafine emulsion external formulation.Though the O/W ultrafine emulsion external formulation particle diameter that obtains is very little, can be in the existence steady in a long-term of wide temperature range.
Monophase microemulsion composition of the present invention and O/W ultrafine emulsion external formulation roughly generate by the above mechanism of action.In addition, preparation is during Monophase microemulsion composition, in the time of can thinking the hydrophilic-lipophilic balance (HLB) of the system of reaching, and the solubilizing amount maximization of oil content, the solubilizing amount of moisture in oil phase is also maximum simultaneously.Therefore, by mixing above-mentioned (A) each composition in the proper ratio, also can generate thermodynamically stable W/O Monophase microemulsion composition to (E).Therefore, Monophase microemulsion composition of the present invention be not limited to O/W type, w/o type either party, can select preferred any one party preparation according to purpose.
In addition, the addition that the emulsifying particle diameter of Monophase microemulsion composition of the present invention can be by (E) water etc. is suitably adjusted, and usually, can generate particle diameter and be 10 to 500nm Monophase microemulsion composition.In addition, in Monophase microemulsion composition of the present invention, in case by operating the preparation Monophase microemulsion composition equally with above-mentioned preparation example, learn the suitable amount ratio of (A) to (E) that can form the Monophase microemulsion phase, later on can be only by cooperating (A) to (E) each composition simultaneously according to this amount ratio, mix, stir, and easily prepare Monophase microemulsion composition.
Do not need with the such special device of high-pressure emulsification device during the Monophase microemulsion composition emulsifying that as above obtains, only by in mixed at room temperature, stir and can easily prepare.In addition, because only by the nonionic surfactant emulsifying smaller to the human body zest, so safety is good.
The O/W Monophase microemulsion composition that obtains as mentioned above is added in (F) water prescription,, can obtains stable O/W ultrafine emulsion external formulation so the emulsified particle of this O/W Monophase microemulsion composition is keeping small particle diameter and is being scattered in the water prescription.Though the O/W ultrafine emulsion external formulation particle diameter that as above obtains is very little, can be in the existence steady in a long-term of wide temperature range.
Therefore, Monophase microemulsion composition of the present invention can be directly as for example bath shampoo, purificant, cleaning wet goods.In addition, also the O/W Monophase microemulsion composition can be matched with in the water prescription, as the O/W ultrafine emulsion external formulation.In addition, because Monophase microemulsion composition of the present invention is the reversible phase of thermodynamics, can preserve for a long time as sealing, during O/W ultrafine emulsion external formulations such as manufacturing beautifying liquid, can be only by O/W Monophase microemulsion of the present invention be added in the water prescription liquid in room temperature, mix, stir and make preparation, so can simplify the manufacturing process of the O/W ultrafine emulsion external formulation that in the past adopted greatly.
In addition, the O/W ultrafine emulsion external formulation that as above obtains also is a category of the present invention.O/W ultrafine emulsion external formulation of the present invention can use in for example applicable to the cosmetics for skin at positions such as skin, hair, hair shampoo article, skin washing product, treatment etc.
In Monophase microemulsion composition of the present invention and O/W ultrafine emulsion external formulation, except above-mentioned essential composition, can cooperate the composition that in medicine, cosmetics, uses usually of the use level that does not influence stability boundary.As the composition that can cooperate, can enumerate for example following substances:
Oil contents such as American Avocado Tree oil, macadimia nut oil, Semen Maydis oil, olive oil, rapeseed oil, Radix Oenotherae erythrosepalae oil, Oleum Ricini, Oleum helianthi, tea-seed oil, Testa oryzae oil, Jojoba oil, cocoa butter, Oleum Cocois, Squalene, Adeps Bovis seu Bubali, haze tallow, Cera Flava, candelilla wax, Brazil wax, spermaceti, lanoline, liquid paraffin, polyoxyethylene (8 moles) oleyl alcohol ether, glyceryl monooleate.Higher alcohols such as capryl alcohol, lauryl alcohol, myristyl alcohol, hexadecanol, cholesterol, plant sterol.Senior fatty acids such as capric acid, lauric acid, myristic acid, Palmic acid, stearic acid, behenic acid, lanolin fatty acid, linoleic acid, linolenic acid.
Wetting agents such as Polyethylene Glycol and alkyl ether thereof, glycerol, Sorbitol, xylitol, maltose alcohol, mucopolysaccharide, hyaluronic acid, chondroitin sulfate, chitosan.Viscosifier such as methylcellulose, ethyl cellulose, arabic gum, polyvinyl alcohol.Organic solvent such as ethanol, 1,3 butylene glycol.Antioxidants such as butylated hydroxytoluene, tocopherol, phytic acid.Antibiotic antiseptics such as benzoic acid, salicylic acid, sorbic acid, p-Hydroxybenzoate (ethylparaben, butyl p-hydroxybenzoate etc.), hexachlorophene.Aminoacid and hydrochlorates such as glycine, alanine, valine, leucine, serine, threonine, phenylalanine, tyrosine, aspartic acid, asparagine, glutamine, taurine, arginine, histidine.Organic acid such as acyl group sarcosine (for example sodium lauroyl sarcosine), glutathion, citric acid, malic acid, tartaric acid, lactic acid.
Vitamin A and derivant thereof, pyridoxine hydrochloride, vitamin B6 tri palmitate, vitamin B6 diocatanoate, vitamin B2 and vitamin(e) B groups such as derivant, vitamin B12, VITAMIN B15 and derivant thereof thereof; Vitamin c class such as ascorbic acid, ascorbic acid phosphoric acid esters (salt), Vitamin C dipalmitate; Vitamin E classes such as alpha-tocopherol, betatocopherol, Gamma-Tocopherol, vitamin E acetate, vitamin E nicotinate; The vitamin D class; Biotin; Pantothenic acid; Vitaminss such as two thioethylamines.Various medicines such as nicotiamide, benzyl nicotinate, gamma oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and derivant thereof, Hinokitiol, sticking rhzomorph, bisabolol, eucalyptol, thymol, inositol, ZAOCAO glycoside (saikoside, ginsenoside, Fructus Luffae saponin, sapindoside etc.), pantoyl ethylether, ethinylestradiol, tranamic acid, cephalanthin, intacellin.
The natural extract that obtains with extraction Radix Rumicis Japonicis such as organic solvent, alcohol, polyhydric alcohol, water, aqueous alcoholic, Radix Sophorae Flavescentis, spatterdock, orange, Salvia japonica Thunb., Herba thymi vulgaris, achillea millefolium, Radix Malvae sylvestris, Rhizoma Chuanxiong, when medicine, Radix Angelicae Sinensis, ト ウ ヒ, birch, Herba Equiseti Hiemalis, Fructus Luffae, Aesculus chinensis Bunge, Herba Saxifragae, Arnica montana, Bulbus Lilii, Radix Artemisia ordosicae, Radix Paeoniae, Aloe, Fructus Gardeniae, Cupressus funebris etc.Cationic surfactants such as stearyl trimethyl ammonium chloride, benzyl chloride alkanamine, Laurel amine oxide.Metals such as disodium edetate, edetate trisodium, sodium citrate, polyphosphate sodium, Polymeric sodium metaphosphate., gluconic acid block agent.
In addition, can also in the scope of not damaging stability, suitably cooperate spice, abrasive cleaner etc.
Below, the embodiment of illustration Monophase microemulsion of the present invention and O/W ultrafine emulsion external formulation, the present invention will be described in more detail, but the present invention is not limited to this.In addition, in the following embodiments, critical micelle concentration is the value of measuring under 25 ℃ temperature conditions.
1. the preparation of Monophase microemulsion composition
Embodiment 1-1
1) will cooperate 4 parts of polyoxyethylene (20 moles) glyceryl isostearate (Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス GWIS-120 (HLB14)) as (A) hydrophilic nonionic surfactant, 6 parts of polyoxyethylene methyl polysilicone alkyl copolymer (KCC of SHIN-ETSU HANTOTAI systems, シ リ コ-Application SC9450:HLB5) as (B) lipophile nonionic surfactant, 10 parts of polydimethylsiloxane (KCC of SHIN-ETSU HANTOTAI systems, シ リ コ-Application KF96-A6T) as (C) oil content, the compositions that polyoxyethylene (14 moles) polyoxypropylene (7 moles) 10 parts of conducts of dimethyl ether (D) aqueous solvent obtains is mixed stirring.
In addition, above-mentioned (D) POE (14) POP (7) dimethyl ether is with (C) polydimethylsiloxane is immiscible, and, the critical micelle concentration (c.m.c) of above-mentioned (A) POE (20) glyceryl isostearate in 10% (D) POE (14) POP (7) dimethyl ether aqueous solution is 0.51g/100g, than the high 0.25g/100g of the critical micelle concentration 0.26g/100g in water.
As a result, obtaining POE (14) POP (7) dimethyl ether is that inner phase, polydimethylsiloxane are foreign minister's W/O (Water-In-Oil solvent-borne type) emulsion.
2) then, the limit stirs above-mentioned 1) the W/O emulsion that obtains, (E) water is slowly added on the limit.
As a result, when adding 12 parts to 15 parts water, compositions becomes transparent or nattier blue O/W Monophase microemulsion phase.
The foregoing description 1-1 compositions accompany water addition and variation of temperature as shown in Figure 2.By the phase equilibrium diagram of Fig. 2 as can be known, the compositions that the foregoing description 1-1 obtains is the reversible Monophase microemulsion phase of thermodynamics (Wm).In addition, by Fig. 2 also as can be known, in the foregoing description 1-1, the O/W Monophase microemulsion composition that obtains when adding about 13.5 parts water 0 to 30 ℃ this comprise that the wide temperature province of room temperature is stable Monophase microemulsion phase.
Further, when the O/W Monophase microemulsion composition that obtains when 1g is added 13.5 parts of water in the foregoing description 1-1 is added drop-wise in the 49g water, obtain translucent ultra micro emulsion.The ultra micro emulsion that obtains after 1 month, is used the light scattering determining particle diameter in room temperature preservation, and the result as shown in Figure 3.As shown in Figure 3, when the O/W Monophase microemulsion composition that the foregoing description 1-1 is obtained is distributed in the water, be to keep the nominal particle size of the about 80nm of mean diameter to be dispersed in the water, and this ultra micro emulsion can at room temperature steady in a long-termly exist.
Embodiment 1-2
Except that using 10 parts of 1,3 butylene glycols as (D) aqueous solvent, other and embodiment 1-1 operate equally.
In addition, above-mentioned (D) 1, the 3-butanediol is with (C) polydimethylsiloxane is immiscible, and, above-mentioned (A) POE (20) glyceryl isostearate is at 10% (D) 1, critical micelle concentration (c.m.c) in the 3-butanediol aqueous solution is 0.29g/100g, than the high 0.03g/100g of the critical micelle concentration 0.26g/100g in water.
As a result, when adding 1.82 parts of (E) water, obtain the compositions of stable O/W Monophase microemulsion phase.In addition, when being added drop-wise to the O/W Monophase microemulsion composition 1g that obtains in the 49g water, obtain translucent ultra micro emulsion.
Embodiment 1-3
Except that using 10 parts of isoamyl glycol as (D) aqueous solvent, other and embodiment 1-1 operate equally.
In addition, above-mentioned (D) isoamyl glycol is with (C) polydimethylsiloxane is immiscible, and, the critical micelle concentration (c.m.c) of above-mentioned (A) POE (20) glyceryl isostearate in 10% (D) isoamyl, two alcohol-water solution is 0.30g/100g, than the high 0.04g/100g of the critical micelle concentration 0.26g/100g in water.
As a result, when adding 1.89 parts of (E) water, obtain the compositions of stable O/W Monophase microemulsion phase.In addition, when being added drop-wise to the O/W Monophase microemulsion composition 1g that obtains in the 49g water, obtain translucent ultra micro emulsion.
Embodiment 1-4
Except that using 10 parts of dipropylene glycols as (D) aqueous solvent, other and embodiment 1-1 operate equally.
In addition, above-mentioned (D) dipropylene glycol is with (C) polydimethylsiloxane is immiscible, and, the critical micelle concentration (c.m.c) of above-mentioned (A) POE (20) glyceryl isostearate in 10% (D) dipropylene glycol aqueous solution is 0.36g/100g, than the high 0.10g/100g of the critical micelle concentration 0.26g/100g in water.
As a result, when adding 3.00 parts of (E) water, obtain the compositions of stable O/W Monophase microemulsion phase.In addition, when being added drop-wise to the O/W Monophase microemulsion composition 1g that obtains in the 49g water, obtain translucent ultra micro emulsion.
Embodiment 1-5
Except that using 10 parts of Polyethylene Glycol (400 moles) as (D) aqueous solvent, other and embodiment 1-1 operate equally.
In addition, above-mentioned (D) Polyethylene Glycol (400 moles) is with (C) polydimethylsiloxane is immiscible, and, (critical micelle concentration (c.m.c) in D Polyethylene Glycol (400 moles) aqueous solution is 0.45g/100g to above-mentioned (A) POE (20) glyceryl isostearate, than the high 0.19g/100g of the critical micelle concentration 0.26g/100g in water 10%.
As a result, when adding 7.83 parts of (E) water, obtain the compositions of stable O/W Monophase microemulsion phase.In addition, when being added drop-wise to the O/W Monophase microemulsion composition 1g that obtains in the 49g water, obtain translucent ultra micro emulsion.
Comparative example 1-1
Except that not using (A) hydrophilic nonionic surfactant, other and embodiment 1-1 operate equally.
As a result, become the compositions of W/O emulsion phase, and do not obtain the compositions of Monophase microemulsion phase.In addition, the W/O emulsion 1g that obtains is added drop-wise in the 49g water, does not also obtain transparent or semitransparent ultra micro emulsion.
Comparative example 1-2
Except that not using (B) lipophile nonionic surfactant, other and embodiment 1-1 operate equally.
As a result, become the compositions of W/O emulsion phase, and do not obtain the compositions of Monophase microemulsion phase.In addition, the W/O emulsion 1g that obtains is added drop-wise in the 49g water, does not also obtain transparent or semitransparent ultra micro emulsion.
Comparative example 1-3
Except that not using (D) aqueous solvent, other and embodiment 1-1 operate equally.
As a result, when adding 0.91 part of (E) water, though generation becomes the combined thing of layered liquid crystal, and do not obtain the compositions of Monophase microemulsion phase to the transformation mutually of O/W phase.In addition, combined thing 1g is added drop-wise in the 49g water with the layered liquid crystal that obtains, and also fails to obtain transparent or semitransparent ultra micro emulsion.
Comparative example 1-4
Except that using 10 parts of glycerol as (D) aqueous solvent, other and embodiment 1-1 operate equally.
In addition, above-mentioned (D) glycerol is with (C) polydimethylsiloxane is immiscible, and, the critical micelle concentration (c.m.c) of above-mentioned (A) POE (20) glyceryl isostearate in 10% (D) glycerol (400 moles) aqueous solution is 0.25g/100g, than the low 0.01g/100g of the critical micelle concentration 0.26g/100g in water.
As a result, when adding 7.83 parts of (E) water,, do not obtain the compositions of Monophase microemulsion phase though generation becomes the combined thing of layered liquid crystal to the transformation mutually of O/W phase.In addition, even the combined thing 1g of the layered liquid crystal that obtains is added drop-wise in the 49g water, also fail to obtain transparent or semitransparent ultra micro emulsion.
The result of the test of the foregoing description 1-1 to 1-5 and comparative example 1-1 to 1-4 formed with the cooperation of various compositionss be summarized in the following table 1.In addition, evaluation content is as follows.
The generation of Monophase microemulsion composition
Confirm whether the emulsion compositions that embodiment 1-1 to 1-5 and comparative example 1-1 to 1-4 generate forms the Monophase microemulsion phase.
Zero forms the Monophase microemulsion phase.
* do not form the Monophase microemulsion phase.
The generation of ultra micro emulsion (when adding in the water)
The emulsion compositions 1g of embodiment 1-1 to 1-5 and comparative example 1-1 to 1-4 generation is added in the 49g ion exchange water, stir, confirm whether to generate the ultra micro emulsion.
Zero generates transparent or semitransparent ultra micro emulsion.
* do not generate transparent or semitransparent ultra micro emulsion.
[table 1]
| Embodiment | Comparative example | ||||||||
| 1-1 | 1-2 | 1-3 | 1-4 | 1-5 | 1-1 | 1-2 | 1-3 | 1-4 | |
| (A) POE (20) glyceryl isostearate: HLB14 (B) POE methyl polysilicone alkyl copolymer: HLB5 (C) polydimethylsiloxane | 4.0 6.0 10.0 | 4.0 6.0 10.0 | 4.0 6.0 10.0 | 4.0 6.0 10.0 | 4.0 6.0 10.0 | - 6.0 10.0 | 4.0 10.0 | 4.0 6.0 10.0 | 4.0 6.0 10.0 |
| (D) POE (14) POP (7) | 6.0 - - - | - 6.0 - - - | - 6.0 - - | - - 6 0 - | - - - 6.0 - | 6.0 - - - | 6.0 - - - | - - - - | - - - 6.0 |
| (E) water | 12.5 | 1.82 | 1.89 | 3.00 | 7.83 | 0.91 | 9.63 | ||
| Generate Monophase microemulsion composition and generate ultra micro emulsion (when being added in the water) | ○ ○ | ○ ○ | ○ ○ | ○ ○ | ○ ○ | × × | × × | × × | × × |
Shown in above-mentioned table 1, use (A) of the present invention all to obtain the compositions of good Monophase microemulsion phase to the embodiment 1-1 to 1-5 of (E).And, when the Monophase microemulsion composition that embodiment 1-1 to 1-5 is obtained is added in the water, can obtain the good ultra micro emulsion of the transparency.
Relative therewith, do not have to cooperate (A) hydrophilic nonionic surfactant comparative example 1-1, not have to cooperate the comparative example 1-2 of (B) lipophile nonionic surfactant and do not have cooperation (D) though the comparative example 1-3 of aqueous solvent has carried out same operation, do not form the Monophase microemulsion phase.
In addition, use glycerol also not form the Monophase microemulsion phase as the comparative example 1-4 of (D) aqueous solvent.
Can think following reason: (A) critical micelle concentration (c.m.c) of POE (20) glyceryl isostearate in glycerol low than in water, the critical micelle concentration (c.m.c) of (A) hydrophilic nonionic surfactant of aqueous phase does not reduce because of the interpolation of (E) water, therefore be adsorbed in (A) hydrophilic nonionic surfactant at water-oil phase interface and (B) balance of lipophile nonionic surfactant can't be impartial, thereby the transformation mutually to the O/W phase takes place.
And, even the emulsion that comparative example 1-1 to 1-4 is obtained is added in the water, do not obtain the good ultra micro emulsion of the transparency yet.
In addition, the Monophase microemulsion composition with the foregoing description 1-1 to 1-5 is added to the ultra micro emulsion that obtains in the water under all temps condition, carried out the evaluation of ageing stability, the results are summarized in following table 2.In addition, evaluation content is as follows.
Ageing stability in the water
The Monophase microemulsion composition 1g that obtains is added in the 49g ion exchange water, stir, under all temps condition, placed one month, estimate ageing stability by following metewand.
◎: outward appearance is not seen variation fully
Zero: outward appearance changes (muddiness) slightly
△: observe oil float
*: separate fully
[table 2]
| Ageing stability in the water | Embodiment | ||||
| 1-1 | 1-2 | 1-3 | 1-4 | 1-5 | |
| 0 ℃ of .1 month room temperature, 1 month 37 ℃, 1 month 50 ℃, 1 month Micycle, 1 month | ◎ ◎ ◎ ○ ◎ | ◎ ◎ ◎ ◎ ◎ | ◎ ◎ ◎ ◎ ◎ | ◎ ◎ ◎ ◎ ◎ | ◎ ◎ ◎ ◎ ◎ |
Shown in above-mentioned table 2, be added into the ultra micro emulsion that obtains in the water all in wide temperature province long-term stability by adopting (A) of the present invention to the Monophase microemulsion composition of the embodiment 1-1 to 1-5 of (E), ageing stability is good.
As from the foregoing, regulate (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content, (D) with above-mentioned oil content immiscible and above-mentioned hydrophilic nonionic surfactant therein critical micelle concentration (c.m.c) than the high aqueous solvent in water and (E) water be proper proportion, can prepare thermodynamically stable Monophase microemulsion phase thus, and, when adding to the Monophase microemulsion that obtains in the water, can obtain the ultra micro emulsion of excellent in stability.
2.O/W the preparation of ultrafine emulsion external formulation
Then, the inventor uses the Monophase microemulsion 2g of the foregoing description 1-1, adds among the water prescription 48g of common beautifying liquid, prepares the beautifying liquid of O/W ultra micro emulsion thus, and transmitance, ageing stability are estimated.Final cooperation composition and evaluation result one are listed in table 2.Evaluation content is as follows.
Transmitance
Use Color-Eye7000A (manufacturing of マ Network ベ ス company), measure the transmitance (Δ E%) of the beautifying liquid that obtains.
Ageing stability
The beautifying liquid 50g that obtains is filled in the container, at room temperature placed 1 month, utilize following metewand, estimate ageing stability.
◎: outward appearance is not seen variation fully
Zero: outward appearance changes (muddiness) slightly
△: observe oil float
*: separate fully
[table 3]
| Beautifying liquid | Use level (quality %) |
| 1,3-BDO glycerine ion exchange water carboxyl vinyl polymer potassium hydroxide dimethyl silicone polymer polyoxyethylene polymethyl siloxane copolymer p OE (20) glyceryl isostearate POE (14) POP (7) dimethyl ether | 2.88 1.92 93.44 0.0288 0.0096 0.92 0.552 0.368 0.92 |
| Transmitance (Δ E%) ageing stability (room temperature, 1 month) | 85.0 ◎ |
By above-mentioned table 3 as can be known, the O/W Monophase microemulsion composition with embodiment 1-1 is added into the beautifying liquid transparency height that obtains in the water prescription, ageing stability.
As from the foregoing, by O/W Monophase microemulsion of the present invention is added in (F) water prescription, can be made into the O/W ultrafine emulsion external formulation of the transparency, excellent in stability.
Embodiment 2
Below, enumerate other embodiment of Monophase microemulsion composition of the present invention, further specify the present invention, but the present invention is not limited to this.
Embodiment 2-1
Use level (quality %)
(1) polydimethylsiloxane 31.4
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application KF96-A6T)
(2) polyoxyethylene polymethyl siloxane copolymer 1 8.9
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 12.6
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) 1,3 butylene glycol 31.4
(5) ion exchange water 5.7
Only with above-mentioned (1) to (5) in mixed at room temperature, placement, promptly obtaining with the polydimethylsiloxane is foreign minister's Monophase microemulsion.
Embodiment 2-2
Use level (quality %)
(1) polydimethylsiloxane 31.4
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application KF96-A6T)
(2) polyoxyethylene polymethyl siloxane copolymer 1 8.8
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 12.5
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) the isoamyl glycol 31.4
(5) ion exchange water 5.9
Only with above-mentioned (1) to (5) in mixed at room temperature, placement, promptly obtaining with the polydimethylsiloxane is foreign minister's Monophase microemulsion.
Embodiment 2-3
Use level (quality %)
(1) polydimethylsiloxane 30.3
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application KF96-A6T)
(2) polyoxyethylene polymethyl siloxane copolymer 1 8.2
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 12.1
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) dipropylene glycol 30.3
(5) ion exchange water 9.1
Only with above-mentioned (1) to (5) in mixed at room temperature, placement, promptly obtaining with the polydimethylsiloxane is foreign minister's Monophase microemulsion.
Embodiment 2-4
Use level (quality %)
(1) polydimethylsiloxane 26.4
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application KF96-A6T)
(2) polyoxyethylene polymethyl siloxane copolymer 1 5.9
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 10.6
(Japanese エ マ Le ジ ヨ Application Co., Ltd., エ マ レ Star Network ス
GWIS-120)
(4) PEG400 26.4
(5) ion exchange water 20.7
Only with above-mentioned (1) to (5) in mixed at room temperature, placement, obtain polydimethylsiloxane and be foreign minister's Monophase microemulsion.
Embodiment 2-5
Use level (quality %)
(1) polydimethylsiloxane 23.5
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application KF96-A6T)
(2) polyoxyethylene polymethyl siloxane copolymer 1 4.1
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 9.4
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) polyoxyethylene (14 moles) polyoxypropylene (7 moles) dimethyl 23.5
Ether
(5) ion exchange water 29.4
Only with above-mentioned (1) to (5) in mixed at room temperature, placement, promptly obtaining with the polydimethylsiloxane is foreign minister's Monophase microemulsion.
Embodiment 2-6
Use level (quality %)
(1) decamethyl five siloxanes 25.3
(KCC of SHIN-ETSU HANTOTAI system, KF995)
(2) polyoxyethylene polymethyl siloxane copolymer 1 2.6
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 12.6
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) PEG400 25.3
(5) ion exchange water 24.1
Only with above-mentioned (1) to (5) in mixed at room temperature, placement, promptly obtaining with decamethyl five siloxanes is foreign minister's Monophase microemulsion.
Embodiment 2-7
Use level (quality %)
(1) decamethyl five siloxanes 23.3
(KCC of SHIN-ETSU HANTOTAI system, KF995)
(2) polyoxyethylene polymethyl siloxane copolymer 1 1.7
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 11.7
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) polyoxyethylene (14 moles) polyoxypropylene (7 moles) dimethyl 23.3
Ether
(5) ion exchange water 30.1
Only with above-mentioned (1) to (5) in mixed at room temperature, placement, promptly obtaining with decamethyl five siloxanes is foreign minister's Monophase microemulsion.
Embodiment 2-8
Use level (quality %)
(1) PSI 32.0
(KCC of SHIN-ETSU HANTOTAI system, KF-56)
(2) polyoxyethylene polymethyl siloxane copolymer 1 9.2
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 12.8
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) 1,3 butylene glycol 32.0
(5) ion exchange water 3.9
Only with above-mentioned (1) to (5) in mixed at room temperature, placement, promptly obtaining with the PSI is foreign minister's Monophase microemulsion.
Embodiment 2-9
Use level (quality %)
(1) PSI 30.9
(KCC of SHIN-ETSU HANTOTAI system, KF-56)
(2) polyoxyethylene polymethyl siloxane copolymer 1 8.5
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 12.3
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) 1,3 butylene glycol 30.9
(5) ion exchange water 7.4
Only with above-mentioned (1) to (5) in mixed at room temperature, placement, promptly obtaining with the PSI is foreign minister's Monophase microemulsion.
Embodiment 3
Below, the Formulation Example of enumerating Monophase microemulsion composition of the present invention further specifies, but the present invention is not limited thereto.
Embodiment 3-1
Bath shampoo use level (quality %)
(1) polydimethylsiloxane 18.5
(KCC of SHIN-ETSU HANTOTAI system, KF-96-A6T)
(2) squalane 5.0
(3) polyoxyethylene polymethyl siloxane copolymer 1 4.0
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(4) polyoxyethylene (20 moles) glyceryl isostearate 9.4
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(5) polyoxyethylene (14 moles) polyoxypropylene (7 moles) dimethyl 23.5
Ether
(6) spice 0.1
(7) ion exchange water 29.4
Above-mentioned (1) to (7) are at room temperature mixed, obtain the transparent bath shampoo that constitutes by Monophase microemulsion.As this bath shampoo is added in the bath, then oil content is diffused as nattier blue ultra micro emulsion rapidly, and do not have oil float in the bath next day yet.
Embodiment 3-2
Transparent purificant use level (quality %)
(1) polydimethylsiloxane 20.6
(KCC of SHIN-ETSU HANTOTAI system, KF-96-A6T)
(2) high polymerization polydimethylsiloxane (KCC of SHIN-ETSU HANTOTAI system, 2.3
G-20)
(3) polyoxyethylene polymethyl siloxane copolymer 1 3.7
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(4) polyoxyethylene (20 moles) glyceryl isostearate 9.1
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(5) 1,3 butylene glycol 22.9
(6) ion exchange water 31.4
Above-mentioned (1) to (6) are at room temperature mixed, obtain the transparent purificant that constitutes by Monophase microemulsion.This purificant sense of touch is smooth.
Embodiment 3-3
Cleansing oil use level (quality %)
(1) decamethyl five siloxanes 23.3
(KCC of SHIN-ETSU HANTOTAI system, KF995)
(2) polyoxyethylene polymethyl siloxane copolymer 1 4.0
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 9.4
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) PEG400 23.5
(5) spice 0.1
(6) ion exchange water 29.4
Above-mentioned (1) to (6) are at room temperature mixed, obtain the cleansing oil that constitutes by Monophase microemulsion.This cleansing oil cosmetic clean result excellence, particularly flushing is fast.
Embodiment 4
Below, the Formulation Example of enumerating O/W ultrafine emulsion external formulation of the present invention further specifies, but the present invention is not limited thereto.
Embodiment 4-1
Beautifying liquid use level (quality %)
(1) polydimethylsiloxane 1.2
(KCC of SHIN-ETSU HANTOTAI system, KF96-A6T)
(2) polyoxyethylene methyl polysilicone alkyl copolymer 0.76
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 0.5
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) 1,3 butylene glycol 3.0
(5) glycerol 4.0
(6) CVP Carbopol ETD2050 0.03
(7) potassium hydroxide 0.01
(8) tranamic acid 0.1
(9) spice 0.1
(10) ion exchange water 90.31
Stir composition (1) to (4), slowly add ion exchange water, obtain transparent microemulsion after, in the beautifying liquid base with its adding (5) to (10), obtain beautifying liquid.The gained beautifying liquid is stable, and usability is moistening.
Embodiment 4-2
Cream use level (quality %)
(1) polydimethylsiloxane 3.14
(KCC of SHIN-ETSU HANTOTAI system, KF96-A6T)
(2) polyoxyethylene polymethyl siloxane copolymer 1 .88
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 1.25
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) the isoamyl glycol 3.14
(5) glycerol 5.0
(6) CVP Carbopol ETD2050 1.0
(7) potassium hydroxide 0.3
(8) the Chamomile extracting solution 0.1
(9) spice 0.1
(10) ion exchange water 84.09
Stir composition (1) to (4), slowly add ion exchange water, obtain transparent microemulsion after, in the cream base with its adding (5) to (10), obtain cream.Gained cream is stable, and usability is moistening.
Embodiment 4-3
Washing liquid use level (quality %)
(1) decamethylcyclopentaandoxane 12.1
(KCC of SHIN-ETSU HANTOTAI system, KF-995)
(2) polyoxyethylene polymethyl siloxane copolymer 1 .88
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 1.25
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) PEG400 6.0
(5) lauroyl N methyl taurine sodium 0.5
(6) spice 0.1
(7) ion exchange water 68.7
Stir composition (1) to (4), slowly add ion exchange water, obtain transparent microemulsion after, in the washing liquid base with its adding (5) to (7), obtain washing liquid.The gained washing liquid is stable, and usability is moistening.
Embodiment 4-4
Purificant use level (quality %)
(1) polydimethylsiloxane 2.06
(KCC of SHIN-ETSU HANTOTAI system, KF96-A6T)
(2) high polymerization polydimethylsiloxane (KCC of SHIN-ETSU HANTOTAI system, 0.23
G20)
(3) polyoxyethylene polymethyl siloxane copolymer 1 .37
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(4) polyoxyethylene (20 moles) glyceryl isostearate 0.91
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(5) 1,3 butylene glycol 2.29
(6) high polymerization degree dimethyl siloxane methyl (aminopropyl) silica 0.2
Alkyl copolymer
(7) sclerosis colza oleyl alcohol 3.0
(8) glycerol 3.5
(9) 3-methyl isophthalic acid, 3-butanediol 5.0
(10) hydroxy stearic acid 0.5
(11) the 2 ethyl hexanoic acid cetyl ester 1.0
(12) isononyl isononanoate 0.5
(13) セ Application サ マ-(Na Le コ corporate system, CI-50) 0.2
(14) stearic acid dimethylaminopropyl amide 1.0
(15) マ-コ-ト 550 (manufacturing of カ Le go Application company) 1.0
(16) L-glutamic acid 0.5
(17) phenyl phenol 0.5
(18) lecithin 0.1
(19) spice 0.1
(20) pigment 0.1
(21) ion exchange water 79.6
Stir composition (1) to (5), slowly add ion exchange water, obtain transparent microemulsion after, in the purificant base with its adding (6) to (21), obtain purificant.The gained purificant is stable, and sense of touch is along sliding.
Embodiment 4-5
The agent use level of washing one's face (quality %)
(1) decamethylcyclopentaandoxane 0.25
(KCC of SHIN-ETSU HANTOTAI system, KF-995)
(2) polyoxyethylene methyl polysilicone alkyl copolymer 0.13
(KCC of SHIN-ETSU HANTOTAI system, シ リ コ-Application SC9450)
(3) polyoxyethylene (20 moles) glyceryl isostearate 0.13
(Japanese エ マ Le ジ ヨ Application Co., Ltd. system, エ マ レ Star Network ス
GWIS-120)
(4) PEG400 0.25
(5) glycerol 6.0
(6) dipropylene glycol 4.0
(7) isostearic acid 2.0
(8) lauric acid 8.0
(9) myristic acid 9.0
(10) two isostearic acid macrogol esters 4.0
(11) cocoanut fatty acid diethanolamide 2.5
(12) coco-nut oil fatty acid sarcosine triethanolamine 10.0
(13) 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole quinoline betaine 13.0
(14) polychlorostyrene dimethylated methylene phenylpiperidines liquid 0.5
(15) triethanolamine 12.4
(16) sodium chloride 0.5
(17) edetate trisodium 0.01
(18) spice 0.1
(19) ion exchange water 27.61
Stir composition (1) to (4), slowly add ion exchange water, obtain transparent microemulsion after, in the agent base of washing one's face with its adding (5) to (19), obtain the agent of washing one's face.The gained agent of washing one's face is stable, and usability is moistening.
Claims (18)
1. Monophase microemulsion composition is characterized in that, contains:
(A) the hydrophilic nonionic surfactant,
(B) the lipophile nonionic surfactant,
(C) oil content,
(D) aqueous solvent, this aqueous solvent and above-mentioned oil content are immiscible, and critical micelle concentration (c.m.c) ratio the height in water of above-mentioned hydrophilic nonionic surfactant in this aqueous solvent, and
(E) water.
2. the described Monophase microemulsion composition of claim 1 is characterized in that, (A) HLB of hydrophilic nonionic surfactant be 13 or more than, (B) HLB of lipophile nonionic surfactant be 6 or below.
3. claim 1 or 2 described Monophase microemulsion compositions is characterized in that, (C) use level of oil content is 10 to 40 quality %.
4. any described Monophase microemulsion composition in the claim 1 to 3 is characterized in that (C) oil content is a silicone oil.
5. the described Monophase microemulsion composition of claim 4 is characterized in that, (C) oil content be selected from decamethylcyclopentaandoxane, polydimethylsiloxane, the PSI a kind or more than.
6. any described Monophase microemulsion composition in the claim 1 to 5 is characterized in that, (D) use level of aqueous solvent be 5 quality % or more than.
7. any described Monophase microemulsion composition in the claim 1 to 6 is characterized in that, (D) aqueous solvent is the aqueous solvent that intramolecularly has 3 or following hydroxyl.
8. the described Monophase microemulsion composition of claim 7, it is characterized in that, (D) aqueous solvent be selected from polypropylene glycol ethylene glycol copolymer or its dimethyl ether, Polyethylene Glycol or its alkyl ether, polyalkylene oxide dicarboxylic ester, 1,3 butylene glycol, dipropylene glycol, isoamyl glycol, the glycerol a kind or more than.
9. the preparation method of Monophase microemulsion composition is characterized in that, possesses following operation:
With (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content and (D) and above-mentioned hydrophilic nonionic surfactant therein critical micelle concentration (c.m.c) immiscible with above-mentioned oil content mixes stirring than the high aqueous solvent in water, prepare the W/O emulsion preparation operation of W/O (Water-In-Oil solvent-borne type) emulsion; With
Add (E) water in this W/O emulsion, the O/W Monophase microemulsion that changes O/W Monophase microemulsion phase mutually into changes operation mutually.
10.O/W ultrafine emulsion external formulation is characterized in that, contains:
(A) the hydrophilic nonionic surfactant,
(B) the lipophile nonionic surfactant,
(C) oil content,
(D) aqueous solvent, this aqueous solvent and above-mentioned oil content are immiscible, and critical micelle concentration (c.m.c) ratio the height in water of above-mentioned hydrophilic nonionic surfactant in this aqueous solvent, and
(E) water,
And its emulsifying particle diameter is 10 to 500nm.
11.O/W the preparation method of ultrafine emulsion external formulation is characterized in that, has following operation:
With (A) hydrophilic nonionic surfactant, (B) lipophile nonionic surfactant, (C) oil content and (D) and above-mentioned hydrophilic nonionic surfactant therein critical micelle concentration (c.m.c) immiscible with above-mentioned oil content mixes stirring than the high aqueous solvent in water, prepare the W/O emulsion preparation operation of W/O (Water-In-Oil solvent-borne type) emulsion;
In this W/O emulsion, add (E) water, change O/W Monophase microemulsion phase mutually into, thus the O/W Monophase microemulsion preparation section of preparation O/W Monophase microemulsion; With
This O/W Monophase microemulsion further is added in (F) water prescription the O/W ultra micro emulsion preparation operation of preparation O/W ultra micro emulsion.
12. the preparation method of the described O/W ultrafine emulsion external formulation of claim 11 is characterized in that, (A) HLB of hydrophilic nonionic surfactant be 13 or more than, (B) HLB of lipophile nonionic surfactant be 6 or below.
13. the preparation method of claim 11 or 12 described O/W ultrafine emulsion external formulations is characterized in that, (C) use level of oil content is 10 to 40 quality %.
14. the preparation method of any described O/W ultrafine emulsion external formulation is characterized in that in the claim 11 to 13, (C) oil content is a silicone oil.
15. the preparation method of the described O/W ultrafine emulsion external formulation of claim 14 is characterized in that, (C) oil content be selected from decamethylcyclopentaandoxane, polydimethylsiloxane, the PSI a kind or more than.
16. the preparation method of any described O/W ultrafine emulsion external formulation is characterized in that in the claim 11 to 15, (D) use level of aqueous solvent be 5 quality % or more than.
17. the preparation method of any described O/W ultrafine emulsion external formulation is characterized in that in the claim 11 to 16, (D) aqueous solvent is the aqueous solvent that intramolecularly has 3 or following hydroxyl.
18. the preparation method of the described O/W ultrafine emulsion external formulation of claim 17, it is characterized in that, (D) aqueous solvent be selected from polypropylene glycol ethylene glycol copolymer or its dimethyl ether, Polyethylene Glycol or its alkyl ether, polyalkylene oxide dicarboxylic ester, 1,3 butylene glycol, dipropylene glycol, isoamyl glycol, the glycerol a kind or more than.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004001450A JP4681234B2 (en) | 2004-01-06 | 2004-01-06 | One-phase microemulsion composition and method for producing the same |
| JP001450/2004 | 2004-01-06 | ||
| JP001451/2004 | 2004-01-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1909883A true CN1909883A (en) | 2007-02-07 |
| CN100536818C CN100536818C (en) | 2009-09-09 |
Family
ID=34816963
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800019948A Active CN100536818C (en) | 2004-01-06 | 2005-01-06 | Monophase microemulsion composition, O/W ultrafine emulsion external formulation and process for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4681234B2 (en) |
| CN (1) | CN100536818C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1942167B (en) * | 2004-04-15 | 2010-05-26 | 陶氏康宁公司 | Low molecular weight silicone oil-in-water emulsion |
| CN102281858A (en) * | 2009-01-14 | 2011-12-14 | 株式会社资生堂 | Process for producing O/W microemulsion preparation for external application |
| CN110760328A (en) * | 2019-10-30 | 2020-02-07 | 中国石油化工股份有限公司 | Method for cleaning oil sludge sand and recovering crude oil |
| TWI806589B (en) * | 2022-05-05 | 2023-06-21 | 國立中山大學 | Micro-emulsion substrate, method of forming the same and application of using the same |
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| JP4643377B2 (en) * | 2005-07-07 | 2011-03-02 | 株式会社資生堂 | One-phase microemulsion composition and method for producing O / W ultrafine emulsion external preparation |
| DE102005059835A1 (en) * | 2005-12-13 | 2007-06-14 | Beiersdorf Ag | Cosmetic preparation, useful for hairstyle formation and for temporary deformation and stabilization of the hairstyle, in the form of a solid oil-in-water micro-emulsion, comprises an emulsifier and a polyvalent alcohol |
| JP4602999B2 (en) | 2007-01-29 | 2010-12-22 | 花王株式会社 | Cleansing composition |
| JP2009102236A (en) * | 2007-10-22 | 2009-05-14 | Shiseido Co Ltd | Oil-in-water type emulsified composition and its manufacturing method |
| JP5117208B2 (en) * | 2008-01-30 | 2013-01-16 | 株式会社 資生堂 | Highly polar oil-containing oil-in-water ultrafine emulsion external preparation and method for producing the oil-in-water ultrafine emulsion external preparation |
| JP5311842B2 (en) * | 2008-02-20 | 2013-10-09 | 株式会社マンダム | Cleansing cosmetic and method for producing the same |
| JP5243078B2 (en) * | 2008-03-31 | 2013-07-24 | 株式会社 資生堂 | Highly polar oil-containing oil-in-water ultrafine emulsion external preparation and method for producing the oil-in-water ultrafine emulsion external preparation |
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| JP2016050191A (en) * | 2014-09-01 | 2016-04-11 | ポーラ化成工業株式会社 | Liquid composition |
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| JP6501151B2 (en) * | 2015-03-31 | 2019-04-17 | 日油株式会社 | Milky cleansing agent |
| US20230049975A1 (en) * | 2019-12-27 | 2023-02-16 | Suntory Holdings Limited | Beverage containing dispersed plant oil |
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| JPS5689832A (en) * | 1979-12-24 | 1981-07-21 | Pola Chem Ind Inc | Production of oil-in-water type emulsion |
| JPS577234A (en) * | 1980-06-17 | 1982-01-14 | Nippon Saafuakutanto Kogyo Kk | Preparation of oil in water type emulsion |
| JPS58131127A (en) * | 1982-01-29 | 1983-08-04 | Pola Chem Ind Inc | Solubilizing agent good in temperature resistance and method therefor |
| JPS63107740A (en) * | 1986-10-23 | 1988-05-12 | Pola Chem Ind Inc | Preparation of oil-in-water-type emulsion |
| JPH03128321A (en) * | 1989-06-12 | 1991-05-31 | Res Inst For Prod Dev | Artificial oxygen-carrier |
| JP3484300B2 (en) * | 1996-10-21 | 2004-01-06 | 花王株式会社 | Transparent or translucent emulsified cosmetic |
| JP3367863B2 (en) * | 1997-05-07 | 2003-01-20 | ジーイー東芝シリコーン株式会社 | Silicone emulsion, method for producing the same, and hair cosmetic |
| JP2003003013A (en) * | 2001-06-19 | 2003-01-08 | Nikko Chemical Co Ltd | Oil-in-water emulsifier composition composed of alkylated polysaccharide and cosmetic using the same |
| JP2003002822A (en) * | 2001-06-21 | 2003-01-08 | Sekisui Chem Co Ltd | Bath agent |
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| CN1942167B (en) * | 2004-04-15 | 2010-05-26 | 陶氏康宁公司 | Low molecular weight silicone oil-in-water emulsion |
| CN102281858A (en) * | 2009-01-14 | 2011-12-14 | 株式会社资生堂 | Process for producing O/W microemulsion preparation for external application |
| CN102281858B (en) * | 2009-01-14 | 2013-05-01 | 株式会社资生堂 | Process for producing o/w microemulsion preparation for external application |
| CN110760328A (en) * | 2019-10-30 | 2020-02-07 | 中国石油化工股份有限公司 | Method for cleaning oil sludge sand and recovering crude oil |
| CN110760328B (en) * | 2019-10-30 | 2022-01-25 | 中国石油化工股份有限公司 | Method for cleaning oil sludge sand and recovering crude oil |
| TWI806589B (en) * | 2022-05-05 | 2023-06-21 | 國立中山大學 | Micro-emulsion substrate, method of forming the same and application of using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005193134A (en) | 2005-07-21 |
| JP4681234B2 (en) | 2011-05-11 |
| CN100536818C (en) | 2009-09-09 |
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