CN1794965B - Hair care emulsions - Google Patents
Hair care emulsions Download PDFInfo
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- CN1794965B CN1794965B CN200480014517.0A CN200480014517A CN1794965B CN 1794965 B CN1794965 B CN 1794965B CN 200480014517 A CN200480014517 A CN 200480014517A CN 1794965 B CN1794965 B CN 1794965B
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Abstract
The invention relates to a hair care emulsion which comprises a nonionic surfactant being solid at ordinary temperatures and having a Krafft point of 40 DEG C or above, an oil, and water with the mean particle diameter of dispersoids being 0.5mum or below and which enables the glossiness of hair to be retained; and a hair care emulsion which consists of an oil-in-water emulsion composition containing as the oil phases the following two kinds of oil phases and which can improve the touch just after application: 1) an oil phase made of a nonionic surfactant which is solid at ordinary temperatures and has a Krafft point of 40 DEG C or above and having a mean particle diameter of 0.5mum or below and 2) an oil phase made of a surfactant and/or an alkyl-modified carboxyvinyl polymer and having a mean particle diameter of 0.5 to 100 mu m.
Description
The application advocates the priority of Japanese patent application 2003-147185 that applied on 05 26th, 2003 and the Japanese patent application 2003-32460 that applied on 09 17th, 2003, and its content is cited entirely here.
Technical field
The present invention relates to the invention as the emulsification composition of hair cosmetic composition.
Background technology
All the time, have much to be mainly used in to make hair be rich in glossy hair style agent, majority is that to utilize oil content that hair is rich in glossy in them.Therefore, such hair style agent, be the emulsification composition that has cooperated oil content mostly, but such substrate has the good hair that makes and is rich in glossy effect after just using, but as time goes by, because oil content is attached to last or oil content diffusions such as finger, thereby can confirm that gloss has the tendency of evanescence.
In order to solve this class problem, the applicant has applied for a kind of oil-in-water oil-in-water type hair compositions, as surfactant, used krafft points such as sucrose fatty acid ester more than or equal to 40 ℃ nonionic surfactant, and, oil phase (emulsified particle) is by miniaturization, and oil-phase component can slowly discharge.This hair care emulsions has excellent typing power after just using, on the other hand, can confirm with the harder tendency of sense of touch.
Existing document related to the present invention is as follows.
Patent documentation 1 (No. 2711541 communique of Japan Patent) has been put down in writing in gelled composition the oil in polyol type emulsification composition that adds oil content and form, and described gelled composition adds sucrose fatty acid ester, polynary alcohol and water and forms.
Patent documentation 2 (No. 2849339 communique of Japan Patent) has been put down in writing in the cosmetics of oiliness material and water, contains the emulsified make-up of alkyl androstanediol and sucrose fatty acid ester.
Patent documentation 3 (spy opens flat 11-171739 communique) has been put down in writing and has been contained the hair cosmetic composition of specific hair caring with macromolecule and sucrose fatty acid ester.
Summary of the invention
The present invention at first as the 1st invention, provides to make to continue to be rich in glossy hair compositions.And then, as the 2nd invention, providing a kind of method that improves the use sense of touch after just the using of hair care emulsions, described hair care emulsions has used above-mentioned sucrose fatty acid ester etc., and contains fine emulsified particle.
As the 1st invention, the present inventor furthers investigate above-mentioned problem, found that by using specific surfactant, be controlled at oil content a certain amount of or below it, and, use emulsified particle by miniaturization emulsification composition as hair cosmetic composition, can make hair continue to be rich in gloss, thereby finish the present invention.
That is, the invention provides a kind of hair care emulsions (below, be also referred to as this emulsification composition), it contains following (a)～(c), and average emulsifying particle diameter is smaller or equal to 0.5 μ m.
(a) be solid and krafft point at normal temperatures more than or equal to 40 ℃ non-ionic surface active agent (below, be also referred to as specific surfactant)
(b) oil content [content with respect to the non-ionic surface active agent of (a), for smaller or equal to 10 times of amounts (mass ratio)]
(c) water
Known in addition, so-called krafft point is meant, in surfactant, to the rapid temperature that increases of the dissolubility of water, when this temperature is following, surfactant only is dissolved into the unimolecule shape, when this temperature or its are above, can be dissolved into unimolecule shape and micellelike (according to upright Co., Ltd. that publishes altogether: chemical voluminous dictionary).
As the 2nd invention, the present inventor furthers investigate for solving above-mentioned problem, found that by above-mentioned fine emulsified particle and other specific emulsified particles are coexisted at aqueous phase, a kind of hair care emulsions of oil-in-water type can be provided, it can remain on the glossiness of giving originally when using fine emulsified particle, and, can improve the sense of touch after just having used, thereby finish the present invention.
That is, the invention provides a kind of hair care emulsions (below, be also referred to as this emulsification composition), it is an O/W emulsion composition, as oil phase, contains following 2 kinds of oil phases.
(d) by room temperature down for solid and krafft point form more than or equal to 40 ℃ non-ionic surface active agent, mean diameter is smaller or equal to the oil phase of 0.5 μ m (below, be also referred to as rigid oil phase).
(e) formed by surfactant and/or alkyl-modified carboxy vinyl polymer, mean diameter is the oil phase (below, be also referred to as soft oil phase) of 0.5～100 μ m.
This emulsification composition is the O/W emulsion composition that is obtained in the aqueous phase coexistence by above-mentioned rigid oil phase and soft oil phase, as long as the final emulsification composition of making satisfies this condition, to its manufacture method without limits.
Typical method is, modulation contains the O/W emulsion composition (below, be also referred to as the 1st emulsification composition) of rigid oil phase and contains the emulsification composition (below, be also referred to as the 2nd emulsification composition) of soft oil phase respectively, both are mixed, make this emulsification composition thus.
About the 1st emulsification composition
The 1st emulsification composition is a kind of O/W emulsion composition, and it contains following (a)～(c), and average emulsifying particle diameter is smaller or equal to 0.5 μ m.
(a) be solid at normal temperatures, and krafft point is more than or equal to 40 ℃ non-ionic surface active agent (below, be also referred to as hard type surfactant)
(b) oil content [content with respect to the non-ionic surface active agent of (a), for smaller or equal to 10 times of amounts (mass ratio)]
(c) water
Is a kind of nonionic surfactant as krafft point more than or equal to the hard type surfactant of 40 ℃ non-ionic surface active agent, it sharply increases more than or equal to 40 ℃ temperature the time the dissolubility of water, but after dissolving, if this aqueous surfactant solution is returned to room temperature, then the solid content of surfactant is separated out.
Specifically, as hard type surfactant, be preferably sucrose fatty acid ester (sucrose monostearate, sucrose palmitic acid ester, sucrose monolaurate, sucrose monooleate acid esters, sucrose distearate, sucrose dipalmitate, sucrose dilaurate, sucrose dioleate, sucrose coco-nut oil fatty acid ester etc.), polyglyceryl fatty acid ester (polyglycereol monostearate, polyglycereol monoleate etc.).
The specific embodiment
The 1st invention
As mentioned above, specific surfactant is a kind of non-ionic surface active agent, it is a krafft point more than or equal to 40 ℃ non-ionic surface active agent, promptly, in temperature during more than or equal to 40 ℃, the dissolubility of water is sharply increased, but after dissolving, if this aqueous surfactant solution is returned to room temperature, then the solid content of surfactant is separated out.
Specifically, as specific surfactant, be preferably sucrose fatty acid ester (sucrose monostearate, sucrose palmitic acid ester, sucrose monolaurate, sucrose monooleate acid esters, sucrose distearate, sucrose dipalmitate, sucrose dilaurate, sucrose dioleate, sucrose coco-nut oil fatty acid ester etc.), polyglyceryl fatty acid ester (polyglycereol monostearate, polyglycereol monoleate etc.).
The content of the specific surfactant in this emulsification composition is preferably 0.5～6 quality % of compositions, is preferably 1～3 quality % of compositions especially.When this content during less than 0.5 quality % of compositions, what have that oil content produces gives luster effect inadequate tendency, and when greater than 6 quality % of compositions, surfactant becomes and separates out easily, and problem is also arranged on the usability of goods.
In this emulsification composition, (for example also can contain specific surfactant other surfactant in addition, non-ionic surface active agent, amphoteric surfactant, anion surfactant, cationic surfactant beyond the specific surfactant), even but do not contain these materials in fact, also can reach the desirable effect of the present invention.In addition, what is called " not containing surfactant in fact " is meant here, does not contain the material that generally uses as surfactant, but can contain all compositions with faint surface activity effect.
Oil content is the general oil content that can use in hair cosmetic composition, cosmetics for skin.For example, for example can list, hydrocarbon ils such as liquid paraffin, squalane, Oleum menthae, Jojoba oil, American Avocado Tree wet goods vegetable and animals oils, ester oils such as isooctyl acid cetyl ester, isopropyl myristate, myristic acid isocetyl ester, higher alcohols such as spermol, isooctadecanol, behenyl alcohol, stearic acid, senior fatty acids such as Palmic acid, behenic acid etc.
In addition, can list dimethyl polysiloxane, methyl phenyl silicone, cyclic dimethyl polysiloxane, polyether-modified polysiloxanes, amino modified polysiloxane, betanin modified polyorganosiloxane, alkyl-modified polysiloxanes, the silicone oil of alkoxy-modified polysiloxanes etc. etc.
Wherein, preferably use silicone oil as all or part of of oil content.
The content of the oil content in this emulsification composition is preferably, and is more than or equal to 3 quality % with respect to compositions, and, be smaller or equal to 10 times of amounts (mass ratio) with respect to specific surfactant.When the content of oil content, exists by what oil content produced and gives luster effect inadequate tendency during less than 3 quality % with respect to compositions,, be difficult to make the emulsified particle particle diameter in 0.5 μ m when be when measuring with respect to specific surfactant greater than 10 times.
The content of the water in this emulsification composition, being preferably with respect to compositions is about 50～70 quality %.
In this emulsification composition, except that above-mentioned neccessary composition, as required, can contain general composition habitual in hair cosmetic composition, cosmetics for skin.That is, can cooperate thickening agent, spice, antiseptic, polyhydric alcohol, UV absorbent, antioxidant, various medicinal ingredients etc.
This emulsification composition is an O/W emulsion composition, and its emulsified particle must be the minuteness particle of mean diameter smaller or equal to 0.5 μ m.When its average emulsifying particle diameter during greater than 0.5 μ m, emulsified particle breaks easily, and can confirm that this emulsification composition is used for hair the time, gives glossy effect and passs in time the tendency of variation is arranged.In addition, there is no particular limitation to the lower limit of this emulsified particle mean diameter, preferably fine as far as possible.But,,, need to use surfactant more than or equal to general allowance in order to make the emulsified particle particle diameter less than 0.01 μ m even use the miniaturization method of the emulsified particle particle diameter of the such physics of high-pressure emulsification facture (aftermentioned).Therefore, the lower limit of the emulsified particle particle diameter of this emulsification composition is preferably about 0.01 μ m.In addition, and then, reduce in hope under the situation of surfactant use level, the following of emulsified particle particle diameter is limited to about 0.1 μ m.
By making emulsified particle become such minuteness particle, even make and place at normal temperatures, also confirm not have particular surface the separating out of agent of living, emulsified particle is also stable, consequently, by using this emulsification composition, can through the time ground give gloss to hair.
In this emulsification composition, by making the emulsified particle miniaturization, make the total surface area of the emulsified particle in the compositions increase, most of sorption of specific surfactant is in oil-water interfaces, can suppress to be accompanied by the merging of the evaporable emulsified particle of continuous phase (water) thus.Consequently, when spreading upon this emulsification composition on the hair, can prevent that whole oil contents are diffused on the hair immediately, by from emulsified particle, slowly emitting oil content, can through the time ground give gloss to hair.In addition,, can destroy emulsified particle simply, from emulsified particle, discharge oil content, can give hair luster easily by touching, carry out combing with hands.
There is no particular limitation to the miniaturization method of emulsified particle, usually, handles by carrying out high-pressure emulsification, can obtain the emulsified particle of the desired size of miniaturization.In addition, in addition, utilize microemulsion method etc. also can obtain desirable fine emulsified particle.In addition, emulsion process is so long as can make the method for O/W emulsion composition, and also there is no particular limitation.
Typical method is, for example preferably make oil-phase component mix, carry out pre-emulsifying with water, carry out the miniaturization of the emulsified particle of high-pressure emulsification processing etc. then and handle, carried out the oil-phase component that miniaturization is handled by in water-phase component, adding, and make it to disperse, can obtain this emulsification composition.
This emulsification composition is the emulsification composition that hair is used, and for example, can form liquid state, gel, paste, milkiness is aqueous, aerosol is vaporific, aerosol foam shape etc., usually any dosage form of commercially available hair cosmetic composition.
According to the present invention, provide a kind of through the time give the hair care emulsions of hair luster.
The 2nd invention
The content of the hard type surfactant in the 1st emulsification composition is preferably 0.5～6 quality % in the goods prescription, be preferably 1～3 quality % especially.
In the 1st emulsification composition, (for example also can contain hard type surfactant other surfactant in addition, non-ionic surface active agent, amphoteric surfactant, anion surfactant, cationic surfactant beyond the hard type surfactant), even but do not contain these surfactants in fact, also can produce the 1st emulsification composition of target.
The oil content that uses among the present invention is the general oil content that can be used in hair cosmetic composition, the cosmetics for skin.For example can list, hydrocarbon ils such as liquid paraffin, squalane, Oleum menthae, Jojoba oil, American Avocado Tree wet goods vegetable and animals oils, ester oils such as isooctyl acid cetyl ester, isopropyl myristate, myristic acid isocetyl ester, higher alcohols such as spermol, isooctadecanol, behenyl alcohol, stearic acid, the higher fatty acids class of Palmic acid, behenic acid etc. etc.
As the silicone oil that uses in the present invention, as oil content, can list dimethyl polysiloxane, methyl phenyl silicone, cyclic dimethyl polysiloxane, polyether-modified polysiloxanes, amino modified polysiloxane, betanin modified polyorganosiloxane, alkyl-modified polysiloxanes, the silicone oil of alkoxy-modified polysiloxanes etc. etc.
Wherein, preferably use silicone oil as all or part of of oil content.
The content of the oil content in the 1st emulsification composition is preferably more than in the goods prescription and equals 3 quality %, and, be preferably smaller or equal to 10 times of amounts (mass ratio) with respect to hard type surfactant.When the content of oil content in the goods prescription during less than 3 quality %, what have that oil content produces gives luster effect inadequate tendency, when be when measuring greater than 10 times with respect to hard type surfactant, is difficult to make the emulsified particle particle diameter in 0.5 μ m.
As mentioned above, the 1st emulsification composition is an O/W emulsion composition, and its emulsified particle (rigid oil phase) must be the minuteness particle of mean diameter smaller or equal to 0.5 μ m.When this average emulsifying particle diameter during greater than 0.5 μ m, emulsified particle becomes and breaks easily, when this emulsification composition is used for hair, can confirm to give the tendency that glossy effect changes in time variation.In addition, there is no particular limitation to the lower limit of the mean diameter of rigid oil phase, preferably fine as far as possible.But,,, also need to use surfactant more than or equal to general allowance in order to make the emulsified particle particle diameter less than 0.01 μ m even use the miniaturization method of the emulsified particle particle diameter of the such physics of high-pressure emulsification facture.Therefore, the lower limit of the particle diameter of the rigid oil phase of the 1st emulsification composition is preferably about 0.01 μ m.In addition, and then, reduce in hope under the situation of use level of surfactant, the following of particle diameter of rigid oil phase is limited to about 0.1 μ m.
There is no particular limitation to the miniaturization method of rigid oil phase, but usually, handle by carrying out high-pressure emulsification, can obtain the particle of rigid oil phase of the desired size of miniaturization.In addition, in addition, utilize microemulsion method etc., also can obtain fine rigid oil phase.
Emulsion process is so long as can make the method for O/W emulsion composition, and just there is no particular limitation.For example, after the oil-phase component that contains hard type surfactant is mixed with water, carrying out pre-emulsifying, carry out the miniaturization of the emulsified particle of high-pressure emulsification processing etc. and handle, by adding above-mentioned miniaturization handled thing in hydrotropism's composition, and make it to disperse, can produce the 1st emulsification composition.
About the 2nd emulsification composition
The 2nd emulsification composition is a kind of O/W emulsion composition, and it contains following (d)～(f), and average emulsifying particle diameter is 0.5～100 μ m.
(d) surfactant and/or alkyl-modified carboxy vinyl polymer
(b) oil content
(c) water
Surfactant can use any in non-ionic surface active agent, amphoteric surfactant, cationic surfactant, the anion surfactant, but is preferably non-ionic surface active agent.
As non-ionic surface active agent, can list, the POE dehydrating sorbitol monooleate, POE anhydrosorbitol monostearate, the POE sorbitan fatty ester class of POE anhydrosorbitol four oleates etc., POE is sorbityl monododecanoate, the POE sorbitol monooleate, POE Sorbitol five oleates, the POE Sorbitol fatty acid ester of POE Sorbitol monostearate etc., the POE glyceryl monostearate, the single glyceryl isostearate of POE, the POE fatty acid glycerine esters of POE three glyceryl isostearates etc., the POE monoleate, the POE distearate, the POE dioleate, the POE fatty acid ester of diglycol stearate etc., the POE lauryl ether, the POE oleyl ether, the POE stearyl ether, POE docosyl ether, POE-2-octyl group lauryl ether, the POE alkyl ether of POE cholestane alcohol ether etc., the POE octyl phenyl ether, the POE nonylplenyl ether, the POE alkyl phenyl ethers of POE dinonyl phenyl ether etc., the POEPOP cetyl ether, POEPOP-2-decyl four decyl ethers, the POEPOP single-butyl ether, the POEPOP hydrogenated lanolin, the POEPOP alkyl ether of POEPOP glycerin ether etc., four POE, four POP 1 of ethylenediamine condensation substance class etc., 2-ethylenediamine condensation substance class, the POE Oleum Ricini, the POE hardened castor oil, POE hardened castor oil list isostearate, POE hardened castor oil three isostearates, POE hardened castor oil list pyroglutamic acid list isostearic acid diester, the POE Oleum Ricini or the hardened castor oil derivant of POE hardened castor oil maleic acid etc., the POE Cera Flava lanolin derivative of POE Sorbitol Cera Flava etc., cocoanut fatty acid diethanolamide, lauric monoethanolamide, the alkanolamide of fatty acid isopropanol amide etc., the POE methyl glycol fatty acid ester, the POE alkylamine, the POE fatty acid amide, POE nonyl phenyl formaldehyde condensation products, alkyl ethoxy dimethyl amine oxide, the hydrophilic non-ionic surfactant of three oil base phosphoric acid etc. etc.
In these non-ionic surface active agents, especially preferably use POE hardened castor oil derivant.
The content of the surfactant in the 2nd emulsification composition is preferably 0.01～5 quality % in the goods prescription, be preferably 0.1～3 quality % especially.
The emulsifying agent that alkyl-modified carboxy vinyl polymer also can be used as the 2nd emulsification composition uses.Alkyl-modified carboxy vinyl polymer can synthesize, and also can use commercially available product.As commercially available product, can list for example CARBOPOL 1342, PEMULEN TR-1, PEMULEN TR-2 (being B.F.Goodrich Chemical society system) etc.
The content of the alkyl-modified carboxy vinyl polymer in the 2nd emulsification composition is preferably 0.01～2 quality % in the goods prescription, be preferably 0.05～1 quality % especially.In addition, in the 2nd emulsification composition, surfactant and alkyl-modified carboxy vinyl polymer can use respectively, also can be used in combination mutually.
As the oil content of the 2nd compositions, the same with the oil content that uses in above-mentioned the 1st emulsification composition, can use the general oil content that can in hair cosmetic composition, cosmetics for skin, use.Promptly, for example can list, hydrocarbon ils such as liquid paraffin, squalane, Oleum menthae, Jojoba oil, American Avocado Tree wet goods vegetable and animals oils, ester oils such as isooctyl acid cetyl ester, isopropyl myristate, myristic acid isocetyl ester, higher alcohols such as spermol, isooctadecanol, behenyl alcohol, stearic acid, senior fatty acids such as Palmic acid, behenic acid etc.
In addition, oil content as the 2nd emulsification composition, also can list dimethyl polysiloxane, methyl phenyl silicone, ring dimethyl polysiloxane, polyether-modified polysiloxanes, amino modified polysiloxane, betanin modified polyorganosiloxane, alkyl-modified polysiloxanes, the silicone oil of alkoxy-modified polysiloxanes etc. etc.
Wherein, preferably use silicone oil as all or part of of oil content.
Used general method was modulated when the 2nd emulsification composition can use the preparation O/W emulsion composition.That is, emulsifying agent method, alternate addition method are waited and modulate the 2nd emulsification composition.
As mentioned above, the 2nd emulsification composition is an O/W emulsion composition, and its emulsified particle (soft oil phase) must be that mean diameter is the particle of 0.5～100 μ m.When this average emulsifying particle diameter during, can confirm that goods have and after just using, be difficult to give glossy tendency when greater than 100 μ m, the tendency of the stability of destroying emulsified particle is arranged less than 0.5 μ m.
This emulsification composition
As mentioned above, this emulsification composition is the hair care emulsions that the soft oil phase of the rigid oil phase of the 1st emulsification composition and the 2nd emulsification composition obtains in the aqueous phase coexistence.
Therefore, can make this emulsification composition by merely the 1st emulsification composition being mixed with the 2nd emulsification composition.If increase the ratio of the rigid oil phase in this emulsification composition, then form the hair goods of paying attention to typing power, if increase the ratio of soft oil phase, then can confirm to have the hair that becomes the use sense of touch after paying attention to especially just the having used tendency of goods.Consider such tendency, select the rigid oil phase in this emulsification composition and the coexistence ratio of soft oil phase, still, in the mass ratio of each oil content amount in mutually, (the rigid oil phase: soft oil phase), be preferably 1: 4～4: 1 that is about 1: 10～10: 1.In addition, the water in this emulsification composition and the ratio of oil phase also can be selected according to concrete goods form, (the water: oil phase) that by quality ratio, is about 20: 1～3: 1.
In addition, from making the viewpoint of efficient, this emulsification composition preferably makes by following method: fill the water-phase component of a side emulsification composition, to wherein adding water-phase component by simplification and the opposing party's of having been changed on a small quantity oil-phase component, mix then.When the manufacture method that makes in this way, it is the 2nd emulsification composition that modulation contains soft oil phase, the 1st emulsification composition that in the 2nd emulsification composition, mixes water coverlet purification then and changed on a small quantity, because the rigid oil phase when operating like this in the 1st emulsification composition is more strong than soft oil phase, survivable, it is convenient to handle, so be preferred.Be preferably specifically, after pre-emulsifying, the emulsification composition based on rigid oil phase of implementing microemulsion method such as high-pressure emulsification and modulating be mixed in other synthetic the 2nd emulsification composition.
In this emulsification composition, except above-mentioned neccessary composition, as required, can contain general composition habitual in hair-dressing cosmetics, skin cosmetic.That is, can cooperate thickening agent, spice, antiseptic, polyhydric alcohol, screening uv-ray agent, antioxidant, various medicinal ingredients etc.In these general compositions, the oiliness composition can be included in rigid oil phase and/or the soft oil phase as required.In addition, for water composition, also can be included in the 1st emulsification composition and the 2nd emulsification composition two sides' aqueous phase, or be included in any aqueous phase of these two emulsification compositions, make this emulsification composition, but most cases is: the aqueous phase that mainly is included in the 2nd emulsification composition is more efficient.
This emulsification composition, using it under the situation of hair, after just using, oil-phase component in the soft oil phase discharges, and makes the hair after just using moisten, be rich in gloss, and then, as time goes by, by the oil-phase component in the rigid oil phase is slowly discharged, can through the time ground give moistening after just using, gloss to hair, and hair is finalized the design.
This emulsification composition is the emulsification composition that hair is used, and can make for example liquid state, gel, paste, milkiness is aqueous, aerosol is vaporific, any dosage form of commercially available hair cosmetic composition usually such as aerosol foam shape.
Below, put down in writing embodiments of the invention, but the present invention is not subjected to the qualification of these embodiment.Under the situation that does not have special explanation, use level content is represented with quality %.
The 1st invention
[test example 1] is about the research of method for making (emulsified particle particle diameter)
According to following prescription, modulate same prescription and the different 2 kinds of emulsification compositions (embodiment 1, comparative example 1) of compound method.
Gradation composition
Use level (quality %)
(A)
The Purified Water surplus
Ethanol 10
* carboxy vinyl polymer 0.35
Potassium hydroxide 0.2
Spice is an amount of
Antiseptic (p-Hydroxybenzoate) 0.1
(B)
Dynamite glycerol 1.6
Dipropylene glycol 3.2
* sucrose monostearate 2.0
Dimethyl polysiloxane (6m.pas) 10
Purified Water is a small amount of
*) シ Application タ レ Application L (with the pure medicine of light Co., Ltd. system)
*) DK ester S-160 (first industrial pharmacy society system)
Operation 1: (B) component that will be except that dimethyl polysiloxane makes it mix with dimethyl polysiloxane 70 ℃ of dissolvings then, carries out pre-emulsifying, and then, carry out high-pressure emulsification with APV ガ ウ リ Application (APV society system) and handle.Then, in blended (A) component, add (B) component that above-mentioned high-pressure emulsification is handled, mix, be modulated into gelatinous emulsification composition (suppurative mastitis) (
Real Execute example 1).In addition, the emulsified particle particle diameter of this suppurative mastitis is 0.3 μ m.
Operation 2: (B) component that will be except that dimethyl polysiloxane makes it mix with dimethyl polysiloxane 70 ℃ of dissolvings then, carries out pre-emulsifying, carries out common emulsifying in homomixer.Then, in (A) component of having mixed, add intact (B) component of above-mentioned emulsifying, mix, be modulated into gelatinous emulsification composition (suppurative mastitis) (
Comparative example 1).
The result: above-mentioned emulsification composition is carried out visual observations, the emulsification composition of the acetonideexample 1 muddy gel that is white in color, relative therewith, the emulsification composition of comparative example 1 has the crystallization of surfactant to separate out and solidify.
The research of the kind of [test example 2] surfactant
According to following prescription, modulated modulator approach all based on the operation 1 of above-mentioned test example 1, but the surfactant different 2 kinds of gelatinous emulsification compositions (suppurative mastitis: embodiment 1,2, comparative example 2) that cooperate.In addition, the emulsified particle particle diameter of the suppurative mastitis of embodiment 2,3 is 0.3 μ m.
Gradation composition
Use level (quality %)
(A)
The Purified Water surplus
Ethanol 10
* carboxy vinyl polymer 0.35
Potassium hydroxide 0.2
Spice is an amount of
Antiseptic (p-Hydroxybenzoate) 0.1
(B)
Dynamite glycerol 1.6
Dipropylene glycol 3.2
* surfactant 2.0
Dimethyl polysiloxane (6m.pas) 10
Purified Water is a small amount of
*) シ Application タ レ Application L (with the pure medicine of light Co., Ltd. system)
*) surfactant:
Embodiment 2: sucrose monostearate (DK ester S-160)
Embodiment 3: polyglyceryl fatty acid ester (tristerin-10)
Comparative example 2: POE (60) hardened castor oil
The result
Form test group by 10 men and women, the suppurative mastitis of the foregoing description 2,3 and comparative example 2 is applied on everyone hair, and makes hair gloss occur, and then the gloss after 4 hours is placed in range estimation, investigates by following standard by combing.
Criterion
Can confirm through the time give gloss: confirming has the gloss that equates when gloss occurring more than or equal to 9 people.
Confirm not through the time give gloss: confirming has gloss equal when gloss occurring less than 1.
Consequently, in the suppurative mastitis of embodiment 2,3, confirm to have through the time gloss, but in the suppurative mastitis of comparative example 2, confirm not have through the time gloss.
The result of test example 1 and test example 2 shows, by using sucrose fatty acid ester or polyglyceryl fatty acid ester as surfactant, and utilize high-pressure emulsification to handle, making average emulsifying particle diameter is 0.1～0.5 μ m, can provide thus through the time give glossy hair care emulsions.
And then, modulate this emulsification composition of following prescription, carry out above-mentioned test 2, results verification, following arbitrary embodiment all can make hair through the time ground be rich in gloss.
[embodiment 4] mousse (hair foam)
Gradation composition
Use level (quality %)
(stock solution)
(A)
The Purified Water surplus
Ethanol 10
Spice is an amount of
P-Hydroxybenzoate 0.1
(B)
Dynamite glycerol 1.6
Dipropylene glycol 3.2
* the sucrose monostearate 2.0
Dimethyl polysiloxane (6m.pas) 10
(filling liquid)
Stock solution 90
Liquefied petroleum gas 10
*) DK ester S-160 (first industrial pharmacy society system)
＜manufacture method 〉
Mix (B) component, carry out pre-emulsifying, use microjet homogenizer (Microfluidizer) to carry out high-pressure emulsification then, to wherein mixing (A) component, modulate stock solution then.In addition, the emulsified particle particle diameter of this stock solution is 0.3 μ m.
Liquefied petroleum gas is mixed in this stock solution, fills, make mousse.
[embodiment 5] hair jelly (hair spray)
Gradation composition
Use level (quality %)
(stock solution)
(A)
The Purified Water surplus
Ethanol 10
Spice is an amount of
P-Hydroxybenzoate 0.1
(B)
Dynamite glycerol 1.6
Dipropylene glycol 3.2
* the sucrose monostearate 2.0
Dimethyl polysiloxane (6m.pas) 10
(filling liquid)
Stock solution 90
Dimethyl ether 10
*) DK ester S-160 (first industrial pharmacy society system)
＜manufacture method 〉
Mix (B) component, carry out pre-emulsifying, carry out high-pressure emulsification with the microjet homogenizer then, to wherein mixing (A) component, modulate stock solution then.In addition, the emulsified particle particle diameter of this stock solution is 0.3 μ m.
Dimethyl ether is mixed in this stock solution, fills, make hair jelly.
[embodiment 6] suppurative mastitis
Gradation composition
Use level (quality %)
(A)
The Purified Water surplus
Ethanol 10
Carboxy vinyl polymer 0.35
Sodium hydroxide 0.2
Phenyl phenol is an amount of
Edetic acid 3 sodium are an amount of
Polyoxyethylene polyoxypropylene
Atactic polymer methyl ether 1
(B)
Glycerol 2
Dipropylene glycol 2
Diglycerol 1
Sucrose monostearate 2
Dimethyl polysiloxane 6mpa.s 10
High molecular dimethyl polysiloxane 1
(polymerization degree n=5000～8000)
Poly-(oxygen ethylene/oxypropylene)
The methyl polysiloxane copolymer 1
Purified Water is a small amount of
＜manufacture method 〉
Will except that (B) component dimethyl polysiloxane, high molecular dimethyl polysiloxane, poly-(oxygen ethylene polyoxypropylene) methyl polysiloxane copolymer 70 ℃ of dissolvings, it is mixed with dimethyl polysiloxane, high molecular dimethyl polysiloxane, poly-(oxygen ethylene polyoxypropylene) methyl polysiloxane copolymer, carry out pre-emulsifying, and then carry out high-pressure emulsification with APV ガ ウ リ Application (APV society system) and handle.Then, in blended (A) component, add (B) component that above-mentioned high-pressure emulsification is handled, mix, be modulated into gel emulsification composition (suppurative mastitis).In addition, the emulsified particle particle diameter of this suppurative mastitis is 0.3 μ m.
The 2nd invention
According to the present invention, a kind of hair care emulsions can be provided, its not only after just using, but also can through the time hair moistened or be rich in gloss, a kind of hair care emulsions that can finalize the design also is provided.Below, come best mode of the present invention is described with embodiment, but scope of the present invention is not only limited to this.
[test example]
By following table 1-1,2 prescription the present invention is estimated.
Table 1-1
| Embodiment 7 | Embodiment 8 | |
| 1. ion exchange water 2. ethanol 3. carboxy vinyl polymers 4. potassium hydroxide 5. spice 6. methyl parahydroxybenzoate 7. dynamite glycerols 8. dipropylene glycol 9. sucrose monostearates, 10. dimethyl polysiloxanes (6mPa.s) 11. dimethyl polysiloxanes (20mPa.s) 12. polyoxyethylene hardened castor oils (6OEO) 13. alkyl-modified carboxy vinyl polymers (*) | Surplus 10 0.5 0.25 0.2 0.1 1.6 3.2 2 10 5 2- | Surplus 10 0.5 0.35 0.2 0.1 1.6 3.2 2 10 5-0.2 |
* B.F.Goodrich Chemical society system
Table 1-2
| Comparative example 3 (only high-pressure emulsification) | Comparative example 4 (no high-pressure emulsification) | Comparative example 5 (no high-pressure emulsification) | |
| 1. ion exchange water 2. ethanol 3. carboxy vinyl polymers 4. potassium hydroxide 5. spice 6. methyl parahydroxybenzoate 7. dynamite glycerols 8. dimethylene glycerol 9. sucrose monostearates, 10. dimethyl polysiloxanes (6mPa.s) 11. dimethyl polysiloxanes (20mPa.s) 12. polyoxyethylene hardened castor oils (6OEO) 13. alkyl-modified carboxy vinyl polymers (*) | Surplus 10 0.5 0.25 0.2 0.1 1.6 3.2 2 10 5-- | Surplus 10 0.5 0.25 0.2 0.1 1.6 3.2-10 5 2- | Surplus 10 0.5 0.35 0.2 0.1 1.6 3.2-10 5-0.2 |
* B.F.Goodrich Chemical society system
＜manufacture method 〉
Embodiment 7: (A component) part with 7,8,9 and 1 is 70 ℃ of dissolvings.It is mixed with 10, carry out high-pressure emulsification and handle.(B component) make 3 to be dissolved in 1, join dissolved 5,62 in, mix.To wherein add lysed 12 and a part 1, a part 8 and 11 emulsified behind the material, add 4, carry out thickening.To wherein adding the A component and mixing.
Embodiment 8: (A component) part with 7,8,9 and 1 is 70 ℃ of dissolvings.It is mixed with 10, carry out high-pressure emulsification and handle.(B component) make 3,13 to be dissolved in 1, join dissolved 5,62 in, mix.Carry out emulsifying to wherein adding 11, add 4 and carry out thickening.To wherein adding the A component and mixing.
Comparative example 3: (A component) part with 7,8,9 and 1 is 70 ℃ of dissolvings.It is mixed with 10, carry out high-pressure emulsification and handle.(B component) make 3 to be dissolved in 1, join dissolved 5,62 in, mix, and then, add 4 and carry out thickening.To wherein adding the A component and mixing.
Comparative example 4: make 3 be dissolved in 1, with its join dissolved 5,62 in, mix.And then, add 7,8.To wherein adding lysed 12 and 8 and 10,11 emulsified materials of a part, add 4 then and carry out thickening.To wherein adding the A component and mixing.
Comparative example 5: make 3,13 be dissolved in 1, with its join dissolved 5,62 in, mix.And then, add 7,8.Carry out emulsifying to wherein adding 10,11, add 4 and carry out thickening.
Test method
Form experimental group (male 8 people by 16 people, women 8 people), on everyone hair, smear the above-mentioned 3 kinds of trial targets of each 5g respectively, to 1) gloss after just having smeared, slim and graceful, no greasy feeling, 2) just smeared gloss after the combing, slim and graceful, 3) smear the gloss of combing after 4 hours, merrily and lightheartedly carry out actual in-service evaluation.
(evaluation methodology)
Gloss
◎: be evaluated as glossy more than or equal to 13 people
Zero: 11～12 people are evaluated as glossy
Zero △: 7～10 people are evaluated as glossy
△: 5～6 people are evaluated as glossy
*: be evaluated as glossy smaller or equal to 4 people
Merrily and lightheartedly
◎: be evaluated as merrily and lightheartedly more than or equal to 13 people
Zero: 11～12 people are evaluated as merrily and lightheartedly
Zero △: 7～10 people are evaluated as merrily and lightheartedly
△: 5～6 people are evaluated as merrily and lightheartedly
*: be evaluated as merrily and lightheartedly smaller or equal to 4 people
No greasy feeling
◎: be evaluated as no greasy feeling more than or equal to 13 people
Zero: 11～12 people are evaluated as no greasy feeling
Zero △: 7～10 people are evaluated as no greasy feeling
△: 5～6 people are evaluated as no greasy feeling
*: be evaluated as no greasy feeling smaller or equal to 4 people
The result
This result of the test is as shown in table 2.
Table 2
Can distinguish according to table 2, the present invention's product (embodiment 7,8) with only compare as the comparative example 3 of oil phase with rigid oil phase, no greasy feeling and slim and graceful aspect also keep the evaluation equal with it, and then, gloss excellence after just having smeared, carry out combing after, also can keep the gloss of equal extent.In addition, even through after 4 hours, also can keep excellent state.
Can distinguish in addition, and be that the comparative example 4 of oil phase is compared with 5 with soft oil phase only, and the gloss after the combing is also very excellent, and then even through after 4 hours, gloss is compared with 5 with comparative example 4, and is also more excellent.
In this test, can judge, the present invention's product goods just used the back and through the time the usability excellence.
Below, enumerate prescription of the present invention example as embodiment, hair-dressing cosmetics of these prescription examples all shown with above-mentioned test in the present invention's product on an equal basis or more excellent firm use the back and through the time usability.
[embodiment 9] cystose compositions
Gradation composition
Use level (quality %)
1. dimethyl polysiloxane (20mPa.s) 5.0
2. high polymerization dimethyl polysiloxane
(degree of polymerization 8000, volatility iso-alkane solution 20%) 10.0
3. ethanol 5.0
4. concentrated glycerin 2.0
5. propylene glycol 3.0
6. dipropylene glycol 1.5
7.POE (60) hardened castor oil 1.0
8. sucrose monostearate 1.0
9.POE (20) cetyl ether 0.2
10. methyl parahydroxybenzoate 0.2
11. hydrolysis avenin liquid 0.1
12. octyl methoxycinnamate 0.1
13. spice is an amount of
14. ion exchange water surplus
＜manufacture method 〉
(A component) carried out high-pressure emulsification and handled 1,4,6,8 and a part of 14 heating for dissolving, the emulsion that to obtain average emulsifying particle diameter be 0.1 μ m.
(B component) with 2,5,7 (after the heating for dissolving), 9,12 and an amount of 14 usefulness homomixers mix the emulsion that to obtain average emulsifying particle diameter be 5 μ m.
In 11, add 14, then to wherein add dissolved 10,13 3.After wherein adding the B component, and then add A component and mixing.
Ratio in respect to 90 parts of synthetic like this stock solutions being 10 parts is filled into LPG (20 ℃ of 0.43MPa) in the container, obtains the cystose hair care emulsions.
[embodiment 10] emulsifiable paste shape compositions
Gradation composition
Use level (quality %)
1. dimethyl polysiloxane (20mPa.s) 5.0
2. high polymerization dimethyl polysiloxane
(degree of polymerization 10000, volatility iso-alkane solution 20%) 8.0
3. ethanol 15.0
4. concentrated glycerin 1.0
5.1,3-butanediol 3.0
6. dipropylene glycol 1.0
7.POE (100) hardened castor oil 1.0
8. sucrose monostearate 0.5
9. carboxy vinyl polymer 0.5
10. methyl butex 0.2
11. pigment is an amount of
12. the amino methyl propanol is an amount of
13. spice is an amount of
14. ion exchange water surplus
＜manufacture method 〉
(A component) part, 4,6 with 1,8 and a part of 14 heating for dissolving is carried out high-pressure emulsification and is handled, the emulsion that to obtain average emulsifying particle diameter be 0.05 μ m.
(B component) with 1,2,5,7 (after the heating for dissolving), 9,12 and an amount of 14 usefulness homomixers mix the emulsion that to obtain average emulsifying particle diameter be 2.5 μ m.
With 9 dissolvings, join in 14 11, to wherein add dissolved 10,13 3.Then, after wherein adding the B component, add A component and mixing.Then, add 12 and carry out thickening, obtain the hair care emulsions of emulsifiable paste shape.
[embodiment 11] emulsifiable paste shape compositions
Gradation composition
Use level (quality %)
1. dimethyl polysiloxane (20mPa.s) 8.0
2. high molecular aminopropyl polydimethylsiloxane
(molecular weight is about 1,000,000, dimethyl polysiloxane solution 20%) 1.0
3. ethanol 10.0
4. concentrated glycerin 1.0
5.1,3-butanediol 1.5
6. dipropylene glycol 1.5
7. sucrose monostearate 0.8
8. alkyl-modified carboxy vinyl polymer 0.2
9. carboxy vinyl polymer 0.5
10. phenyl phenol 0.2
11. royal jelly extract 0.2
12. the amino methyl propanol is an amount of
13. spice is an amount of
14. ion exchange water surplus
＜manufacture method 〉
(A component) part, 4,6 with 1,7 and a part of 14 heating for dissolving is carried out high-pressure emulsification and is handled, the emulsion that to obtain average emulsifying particle diameter be 0.08 μ m.
(B component) with 11 join dissolved 8,9 14 in, add 1,2,5, mix the emulsion that to obtain average emulsifying particle diameter be 30 μ m then with homomixer.To wherein adding 3 dissolved 10,13 and A component and mixing, add 12 and carry out thickening, obtain the hair care emulsions of emulsifiable paste shape.
[embodiment 12] cystose compositions
Gradation composition
Use level (quality %)
1. liquid paraffin 3.0
2. the volatility isoparaffin 2.0
3. high polymerization dimethyl polysiloxane (degree of polymerization 10000) 2.0
4. oleic acid 2.0
5.2-undecyl-N, N, N-(hydroxyethyl carboxymethyl)
-2-imidazoline sodium 3.0
6. ethanol 10.0
7. concentrated glycerin 1.0
8. propylene glycol 1.5
9. dipropylene glycol 1.5
10. sucrose monostearate 0.8
11. phenyl phenol 0.2
12. spice is an amount of
13. ion exchange water surplus
＜manufacture method 〉
(A component) handled by high-pressure emulsification 1,7,9,10 and a part of 13 heating for dissolving, the emulsion that to obtain average emulsifying particle diameter be 0.05 μ m.
(B component) mixes 2,3,4, with its join 5,8 and a part 13 in, emulsifying, the emulsion that to obtain average emulsifying particle diameter be 5 μ m.
In 13, add the B component and be dissolved in 11 in 6,12, mix, add the A component then.
In the ratio that with respect to 92 parts of synthetic like this stock solutions is 8 parts, in container, fill LPG (20 ℃ of 0.39MPa), obtain the cystose hair care emulsions.
Claims (20)
1. a hair care emulsions contains following (a)～(c), and average emulsifying particle diameter is smaller or equal to 0.5 μ m,
(a) hard type surfactant promptly is solid and krafft point at normal temperatures more than or equal to 40 ℃ non-ionic surface active agent,
(b) oil content, its content is smaller or equal to 10 times of amounts with respect to the non-ionic surface active agent of (a) by quality ratio, is more than or equal to 3 quality % with respect to compositions,
(c) water.
2. hair care emulsions as claimed in claim 1, average emulsifying particle diameter is more than or equal to 0.01 μ m.
3. hair care emulsions as claimed in claim 1, average emulsifying particle diameter is more than or equal to 0.1 μ m.
4. as each described hair care emulsions of claim 1～3, room temperature is sucrose fatty acid ester and/or polyglyceryl fatty acid ester for solid and krafft point more than or equal to 40 ℃ non-ionic surface active agent down.
5. as each described hair care emulsions of claim 1～3, contain silicone oil in the oil content.
6. hair care emulsions as claimed in claim 4 contains silicone oil in the oil content.
7. as each described hair care emulsions of claim 1～3, do not contain hard type surfactant surfactant in addition in fact.
8. hair care emulsions as claimed in claim 4 does not contain hard type surfactant surfactant in addition in fact.
9. hair care emulsions as claimed in claim 5 does not contain hard type surfactant surfactant in addition in fact.
10. hair care emulsions as claimed in claim 6 does not contain hard type surfactant surfactant in addition in fact.
11., form by high-pressure emulsification processing carrying out emulsifying as each described hair care emulsions of claim 1～3.
12. hair care emulsions as claimed in claim 4 forms by high-pressure emulsification processing carrying out emulsifying.
13. hair care emulsions as claimed in claim 5 forms by high-pressure emulsification processing carrying out emulsifying.
14. hair care emulsions as claimed in claim 6 forms by high-pressure emulsification processing carrying out emulsifying.
15. hair care emulsions as claimed in claim 7 forms by high-pressure emulsification processing carrying out emulsifying.
16., form by high-pressure emulsification processing carrying out emulsifying as each described hair care emulsions of claim 8～10.
17. a hair care emulsions is an O/W emulsion composition, in the described hair care emulsions of claim 1 and then contain following oil phase,
(d) formed by surfactant and/or alkyl-modified carboxy vinyl polymer, mean diameter is the oil phase of 0.5～100 μ m, and described surfactant is other surfactant beyond the above-mentioned hard type surfactant.
18. hair care emulsions as claimed in claim 17, room temperature are sucrose fatty acid ester and/or polyglyceryl fatty acid ester for solid and krafft point more than or equal to 40 ℃ non-ionic surface active agent down.
19. manufacture method as claim 17 or 18 described hair care emulsions, obtain by mixing following 2 kinds of O/W emulsion compositions, described 2 kinds of O/W emulsion compositions are: containing by hard type surfactant is to be that solid and krafft point are formed more than or equal to 40 ℃ non-ionic surface active agent under the room temperature, and mean diameter is smaller or equal to the O/W emulsion composition of the oil phase of 0.5 μ m; Formed with above-mentioned hard type surfactant other surfactant and/or the alkyl-modified carboxy vinyl polymer in addition that contains by under the room temperature being liquid, the O/W emulsion composition of the oil phase of mean diameter 0.5 μ m～100 μ m.
20. the manufacture method of hair care emulsions as claimed in claim 19, the O/W emulsion composition that contains following oil phase is to utilize the emulsifying of high-pressure emulsification method to obtain emulsification composition, and described oil phase is: by room temperature down for solid and krafft point is formed more than or equal to 40 ℃ non-ionic surface active agent, mean diameter is smaller or equal to the oil phase of 0.5 μ m.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP147185/2003 | 2003-05-26 | ||
| JP2003147185A JP4010980B2 (en) | 2003-05-26 | 2003-05-26 | Emulsifying composition for hair |
| JP324603/2003 | 2003-09-17 | ||
| JP2003324603A JP4812241B2 (en) | 2003-09-17 | 2003-09-17 | Emulsifying composition for hair |
| PCT/JP2004/007532 WO2004103324A1 (en) | 2003-05-26 | 2004-05-26 | Hair care emulsions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1794965A CN1794965A (en) | 2006-06-28 |
| CN1794965B true CN1794965B (en) | 2010-05-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200480014517.0A Expired - Fee Related CN1794965B (en) | 2003-05-26 | 2004-05-26 | Hair care emulsions |
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| JP (1) | JP4010980B2 (en) |
| CN (1) | CN1794965B (en) |
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|---|---|---|---|---|
| JP5491054B2 (en) * | 2009-03-31 | 2014-05-14 | 株式会社コーセー | Oil-in-water emulsified hair cosmetic |
| JP5697150B2 (en) * | 2010-09-09 | 2015-04-08 | 旭化成ワッカーシリコーン株式会社 | Silicone emulsion |
| ES2803202T3 (en) * | 2015-05-26 | 2021-01-25 | Elc Man Llc | Method for the formation of a styling hair care composition |
| JP6357449B2 (en) * | 2015-07-13 | 2018-07-11 | 株式会社ミロット | Method for producing emulsified composition for hair |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1118992A (en) * | 1993-02-09 | 1996-03-20 | 普罗克特和甘保尔公司 | Cosmetic compositions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0693996B2 (en) * | 1984-12-03 | 1994-11-24 | 武田薬品工業株式会社 | Emulsified composition |
| FR2725369B1 (en) * | 1994-10-07 | 1997-01-03 | Oreal | COSMETIC OR DERMATOLOGICAL COMPOSITION CONSISTING OF AN OIL IN WATER EMULSION BASED ON OIL CELLS PROVIDED WITH A LAMELLAR LIQUID CRYSTAL COATING |
| JPH10259114A (en) * | 1997-03-14 | 1998-09-29 | Shiseido Co Ltd | Oil-in-water type emulsified composition |
| JP3778237B2 (en) * | 1997-09-19 | 2006-05-24 | ライオン株式会社 | Method for producing O / W emulsion |
-
2003
- 2003-05-26 JP JP2003147185A patent/JP4010980B2/en not_active Expired - Fee Related
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2004
- 2004-05-26 CN CN200480014517.0A patent/CN1794965B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1118992A (en) * | 1993-02-09 | 1996-03-20 | 普罗克特和甘保尔公司 | Cosmetic compositions |
Non-Patent Citations (2)
| Title |
|---|
| 张立军等.安全高效冷烫剂的研制.日用化学工业32 6.2002,32(6),76-77. |
| 张立军等.安全高效冷烫剂的研制.日用化学工业32 6.2002,32(6),76-77. * |
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| Publication number | Publication date |
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| JP4010980B2 (en) | 2007-11-21 |
| JP2004346047A (en) | 2004-12-09 |
| CN1794965A (en) | 2006-06-28 |
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