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    • 专利摘要:
    THICKENING COMPOSITION, AND, COSMETIC PREPARATION A thickening composition is obtained that exhibits excellent sensations in use, namely, it exhibits excellent freshness, non-stickiness, and compatibility with the skin, and leaves no residue on the skin. Furthermore, the thickener composition can stably maintain viscosity in a region of low and medium viscosity, and does not cause any change in viscosity even when a salt-like component is added. Cosmetics are also obtained that contain the same. A thickener composition containing (a) 0.1% to 2% by weight of a specific hydrophobic modified poly (ether-urethane) (associative thickener) and b) 0.1% to 2% by weight of a microgel obtained by grinding a gel consisting of a gelatinizable hydrophilic compound in a mass ratio of (a) / (b) from 0.1: 0.9 to 0.9: 0.1 and having a viscosity of 50 to 50,000 mPa.s (as determined by a BL type viscometer at 12 revolutions and at 25 ° C); and cosmetics that contain the thickener composition.
    公开号:BR112012027445B1
    申请号:R112012027445-7
    申请日:2011-04-27
    公开日:2020-11-03
    发明作者:Ayano Matsuo；Masayuki Shirao
    申请人:Shiseido Company, Ltd；
    IPC主号:
    专利说明:

    DESCRIPTION FIELD OF THE INVENTION
    [1] The present invention relates to a thickener composition having a low to moderate viscosity and to a cosmetic preparation containing the composition. More precisely, the invention relates to a thickening composition that exhibits excellent sensations in use, namely, exhibits excellent freshness, non-stickiness, and combines with the sensitivity of the skin, and leaves no residue on the skin, and it can stably maintain viscosity in a low to moderate viscosity range, and to a cosmetic preparation containing the composition. PREVIOUS TECHNIQUE
    [2] So far, for thickening cosmetics, it is known to use a polysaccharide thickening agent such as xanthan gum, a hydrophilic synthetic polymer such as poly (acrylic acid), and a clay mineral such as bentonite or the like.
    [3] However, when using a polysaccharide such as xanthan gum or the like as a thickening agent in a system containing both an active ingredient and a salt, although it exhibits excellent system stability, it does however have a disadvantage when in use. to provide a sticky feeling. When using a hydrophilic synthetic polymer such as poly (acrylic acid) or the like, it exhibits a good feeling of non-stickiness and freshness in use; however, if a pharmaceutical ingredient and a salt are highly incorporated within a system, a decrease in viscosity occurs and its tolerance to ions is unsatisfactory. In addition, when a clay mineral such as bentonite or the like is used as a thickening agent, it has a disadvantage of providing a harsh feeling in use.
    [4] On the other hand, as a water-soluble thickening agent having an excellent thickening effect, a thickening agent consisting of a denatured hydrophobic poly (ether-urethane) (associative polymer) has been developed (Patent Reference 1), and it is used in cosmetics (Patent References 2 and 3). That is, Patent Reference 2 discloses a cosmetic composition containing a hydrophobic denatured poly (ether-urethane), and a carboxy-vinyl polymer and / or xanthan gum; and Patent Reference 3 discloses an external skin preparation containing a hydrophobic denatured polyurethane and collagen.
    [5] In addition, as a thickening agent having a non-stickiness in use and providing a feeling of freshness in use, a microgel has been developed, which is prepared by grinding or grinding a hydrophilic compound gel having a gelling capacity, and is used in cosmetics (Patent Reference 4). Another type of microgel, different from the aforementioned microgel, has been separately developed by free radical polymerization of a water soluble polymerizable monomer; and a thickener composition as well as a cosmetic preparation containing said radically polymerized microgel and a poly (ether-urethane) are disclosed (Patent Reference 5).
    [6] However, each of the compositions and each of the cosmetics, disclosed in Patent References 2 to 5 cited above is for the purpose of preparing a base having a relatively high viscosity such as a creamy or similar base. The Patent Reference composition 2 has a thickening effect and good sensations in use, such as moisture and non-stickiness, but has not been investigated with respect to its viscosity stability in use in a low to moderate viscosity range and to your feeling of freshness in use. Also, the Patent Reference composition 3 has a thickening effect and a good feeling of elasticity in use, but it has not been investigated in relation to its viscosity stability in a low to moderate viscosity range and its feeling of freshness in use. The Patent Reference thickener 4 has a thickening effect and a feeling of freshness in use, but it has also not been investigated regarding its viscosity stability over a low to moderate viscosity range and its freshness sensation in use and its feeling of incorporation into the skin. The Patent Reference composition 5 has a thickening effect, and a new type sensation (new type elastic sensation), but it has also not been investigated regarding its viscosity stability in a low to moderate viscosity range. REFERENCES OF THE PREVIOUS TECHNIQUE PATENT REFERENCES Patent Reference 1: JP 9-71766A Patent Reference 2: JP 2000-239120A Patent Reference 3: JP 2005-343841A Patent Reference 4: JP 2001-342451A Patent Reference 5: JP 2007-291026A SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION
    [7] The present inventors have found that, by combining conventional water-soluble thickening agents, a synergistic thickening effect can be achieved which could not be achieved by individual aqueous solutions, and by using them, a thickening composition can be prepared, which can stably maintain its viscosity in a low to moderate viscosity range, which excels in sensations during and after its application, and which, even when a saline-type pharmaceutical ingredient or salt is incorporated into it, can still exhibit its thickening effect without any influence of those added ingredients on the thickening effect of the composition, and with these discoveries the present inventors have completed the present invention.
    [8] Therefore, the invention is intended to provide a thickening composition that exhibits excellent sensations in use, namely, exhibits excellent freshness, non-stickiness and incorporates into the skin's sensation, and leaves no residue on the skin, which it can stably maintain its viscosity in a low to moderate viscosity range and which, even when a salt-type ingredient is incorporated into it, does not change viscosity, and to provide a cosmetic preparation containing the composition. MEANS TO SOLVE THE PROBLEMS
    [9] To solve the problems mentioned above, the invention provides a pharmaceutical composition comprising (a) from 0.1% to 2% by weight of a hydrophobic denatured poly (ether-urethane) represented by the following formula (I), and ( b) from 0.1% to 2% by mass of a microgel to be obtained by grinding a gel consisting of a hydrophilic compound having a gelling capacity, in a component (a) / component (b) ratio of 0.1 / 0.9 to 0.9 to 0.1 (by mass), and which has a viscosity of 50 to 50,000 mPa-s (with BL type viscometer, 12 revolutions, 25 ° C).
    [10] [In formula (I), R1, R2 and R4 each independently represent an alkylene group having 2 to 4 carbon atoms, or a phenylethylene group; R3 represents an alkylene group having 1 to 10 carbon atoms and optionally having a urethane bond; Rs represents a linear, branched or secondary alkyl group having 8 to 36 carbon atoms; m indicates a number of 2 or more; h indicates a number of 1 or more; k indicates a number from 1 to 500; and n indicates a number from 1 to 200].
    [11] The invention also provides the thickener composition mentioned above in which Ri, R2 and R4 in the formula (I) mentioned above each independently represent an alkylene group having 2 to 4 carbon atoms, R3 represents an alkylene group having 1 at 10 carbon atoms and optionally having a urethane bond, Rs represents a linear, branched or secondary alkyl group having 12 to 24 carbon atoms, m is 2, h is 1, k is a number from 100 to 300, and n is a number from 10 to 100.
    [12] The invention also provides the thickener composition mentioned above in which component (b) is a microgel having an average particle size from 0.1 pm to 1,000 pm, as prepared by grinding a gel formed by dissolving a compound hydrophilic having a gelling capacity in water or an aqueous component followed by its cold maintenance.
    [13] The invention also provides the thickener composition mentioned above in which the hydrophilic compound having a gelling capacity is one or more selected from agar, carrageenan, curdlan, gelatin, gellan gum and alginic acid.
    [14] The invention also provides the thickener composition mentioned above which additionally contains one or more selected from pharmaceutical ingredients and salts.
    [15] The invention also provides a pharmaceutical preparation that contains the thickener composition mentioned above. ADVANTAGE EFFECTS OF THE INVENTION
    [16] According to the invention, a thickening composition is provided which exhibits excellent sensations in use, namely, exhibits excellent freshness, non-stickiness and is incorporated into the sensation of the skin, and leaves no residue on the skin, which it can stably maintain its viscosity in a low to moderate viscosity range and which, even when a salt-type ingredient is incorporated in it, does not change viscosity, and also a cosmetic preparation containing the composition. BRIEF DESCRIPTION OF THE DRAWINGS
    [17] [Fig. 1] Shows an explanatory drawing of the denatured hydrophobic poly (ether-urethane) (associative thickener) for use in the invention. MODE FOR CARRYING OUT THE INVENTION
    [18] The invention is now described in detail. <Component (a)>
    [19] Component (a) for use in the invention is a denatured hydrophobic poly (ether-urethane) represented by the following formula (I). The copolymer is an associative thickener. The associative thickener is a copolymer having a hydrophilic portion as its backbone and hydrophobic portions at its terminals, and the hydrophobic portions of the copolymer are associated with each other to exhibit a thickening effect. In the associative thickener of the type, the hydrophobic portions of the copolymer are associated with each other in an aqueous medium and its hydrophilic portion is in the form of a loop or a bridge, as shown in Fig. 1, thereby exhibiting a thickening effect.
    [20] In formula (I), R1, R2 and R4 each independently represent an alkylene group having 2 to 4 carbon atoms, or a phenylethylene group, preferably an alkylene group having 2 to 4 carbon atoms.
    [21] R3 represents an alkylene group having 1 to 10 carbon atoms and optionally having a urethane bond.
    [22] Rs represents a linear, branched or secondary alkyl group having 8 to 36 carbon atoms, preferably 12 to 24 carbon atoms.
    [23] m indicates a number of 2 or more, preferably 2.
    [24] h indicates a number of 1 or more, preferably 1.
    [25] k indicates a number from 1 to 500, preferably a number from 100 to 300.
    [26] n indicates a number from 1 to 200, preferably a number from 10 to 100.
    [27] The hydrophobic denatured poly (ether-urethane) represented by the formula (I) mentioned above is preferably obtained, for example, by the reaction of one or more polyether polyols represented by Ri - [(O-R2) k-OH] m (where Ri, R2, kem are as defined above) with one or more polyisocyanates represented by R3- (NCO) h + i (where R3 and h are as defined above) and one or more polyether mono-alcohols represented by HO- (R4-O) n-R5 (where R4, Rs and n are as defined above).
    [28] In this case, Ri to Rs in formula (I) are each determined by the adopted compounds, ie, Ri - [(O-R2) k-OH] m, R3- (NCO) h + i and HO- (R4 - O) used n-Rs. Although the proportion of these three compounds is not particularly restricted, it is preferable that the ratio of the isocyanate group derived from polyisocyanate to the hydroxyl group derived from polyether polyol and polyether monoalcohol, NCO / OH is 0.8 / 1 to 1.4 / 1.
    [29] The polyether-polyol compound represented by the formula Ri - [(O-R2) k-OH] m mentioned above can be prepared by means of polymerization by the addition of a hydric polyol and an alkylene oxide or an oxide of styrene, such as propylene oxide, butylene oxide, and epichlorohydrin or the like.
    [30] Here the polyol is preferably dihydric to octahydric, and its examples include dihydric alcohols, such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, and neopentyl glycol; trihydric alcohols, such as glycerin, trihydroxy isobutane, 1,2,3-butanotriol, 1,2,3-pentanotriol, 2-methyl-1, 2,3-propanotriol, 2-methyl-2,3 , 4-butanotriol, 2-ethyl-1,2,3-butanotriol, 2,3,4-pentanotriol, 2,3,4-hexanotriol, 4-propyl-3,4,5-heptanotriol, 2,4-dimethyl -2,3,4-pentanotriol, pentamethyl-glycerin, pentaglycerin, 1,2,4-butanotriol, 1,2,4-pentanotriol, trimethylol-ethane, and trimethylol-propane; tetrahydric alcohols, such as pentaerythritol, 1,2,3,4-pentanetretrol, 2,3,4,5-hexanetretrol, 1,2,4,5-pentanetretrol, and 1,3,4,5-hexanetretrol; pentahydric alcohols, such as adonitol, arabitol, and xylitol; hexahydric alcohols, such as dipentaerythritol, sorbitol, mannitol, and iditol; octahydric alcohols such as sucrose.
    [31] R2 is determined due to the alkylene oxide, styrene oxide or the like to be added. Especially as readily available and for display of excellent effect, alkylene oxides having 2 to 4 carbon atoms or styrene oxide are preferred.
    [32] The alkylene oxide, styrene oxide or the like to be added may be in the form of homopolymerization or random polymerization or block polymerization of two or more of their different types. The mode of addition can be any common. The degree of polymerization k is from 1 to 500. The proportion of the ethylene group that occupies R2's is preferably 50 to 100% by mass of all R2's.
    [33] The molecular weight of Ri - [(O-R2) k-OH] m is preferably 500 to 100,000, more preferably 1,000 to 50,000.
    [34] The polyisocyanate represented by the formula R3- (NCO) h + i mentioned above can be one as long as it has at least two isocyanate groups in the molecule. Examples include aliphatic diisocyanates, aromatic diisocyanates, alicyclic diisocyanates, biphenyl diisocyanates, and phenylmethane di-, tri- and tetraisocyanates.
    [35] Exemplary aliphatic diisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl diether -isocyanate, 2,2-dimethyl-pentane-diisocyanate, 3-methoxy-hexane-diisocyanate, octamethylene-diisocyanate, 2,2,4-trimethyl-pentane-diisocyanate, nonamethylene-diisocyanate , decamethylene-diisocyanate, 3-butoxyhexane-diisocyanate, 1,4-butylene-glycol-dipropyl-ether-diisocyanate, thio-dihexyl-diisocyanate, meta-xylylene-diisocyanate , para-xylylene-diisocyanate, and tetramethyl-xylylene-diisocyanate.
    [36] Exemplary aromatic diisocyanates include methaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethyl benzene diisocyanate, ethyl -benzene-diisocyanate, isopropyl-benzene-diisocyanate, tolidine-diisocyanate, 1,4-naphthalene-diisocyanate, 1,5-naphthalene-diisocyanate, 2,6-naphthalene-diisocyanate , and 2,7-naphthalene-diisocyanate.
    [37] Exemplary alicyclic diisocyanates include hydrogenated xylylene diisocyanate, and isophorone diisocyanate.
    [38] Exemplary biphenyl diisocyanates include biphenyl diisocyanate, 3,3'-dimethyl-biphenyl-diisocyanate, and 3,3'-dimethoxy-biphenyl diisocyanate.
    [39] Exemplary phenyl-methane-diisocyanates include diphenyl-methane-4,4'-diisocyanate, 2,2'-dimethyl-diphenyl-methane-4,4'-diisocyanate, diphenyl-methane-4 , 4'-diisocyanate, 2,5,2 ', 5'-tetramethyl-phenyl-methane-4,4'-diisocyanate, cyclohexyl-bis (4-isocyanate-phenyl) -methane, 3, 3'-dimethoxy-diphenyl-methane-4,4'-diisocyanate, 4,4'-dimethoxy-diphenyl-methane-3,3'-diisocyanate, 4,4'-dietoxy-diphenyl-methane-3 , 3'-diisocyanate, 2,2'-dimethyl-5,5'-dimethoxy-diphenyl-methane-4,4'-diisocyanate, 3,3'-dichloro-diphenyl-dimethyl-methane 4.4 '-disisocyanate, and benzophenone-3,3'-diisocyanate.
    [40] Exemplary phenyl-methane-triisocyanates include 1-methyl-benzene-2,4,6-triisocyanate, 1,3,5-trimethyl-benzene-2,4,6-triisocyanate, 1, 3,7-naphthalene-triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenyl-methane-2,4,4'-triisocyanate, 3-methyl-diphenyl-methane-4,6, 4'-triisocyanate, triphenylmethane-4,4 ', 4' '- triisocyanate, 1,6,11-undecane-triisocyanate, 1,8-diisocyanate-4-isocyanate-methyl- octane, 1,3,6-hexamethylene-triisocyanate, bicycloheptane-triisocyanate, and tris (isocyanate-phenyl) -thio-phosphate.
    [41] The dimers and trimers (with cyanurate bond) of those polyisocyanate compounds are also usable here; and its biuret compounds as reacted with amines are also usable.
    [42] Polyisocyanates having a urethane bond are also usable, which are prepared by reacting these polyisocyanate compounds with polyols. Like polyols, dihydric to octahydric ones are preferred. The polyols mentioned above are preferred. In the case where a polyhydric polyisocyanate such as R.3- (NCO) h + i is used, those polyisocyanates having urethane bond are preferred.
    [43] The polyether monoalcohol represented by the formula HO- (R4-O) n-Rs mentioned above is not particularly restricted as long as the polyether monoalcohol is a linear, branched or secondary monohydric alcohol polyether. The type compound is obtainable by polymerization in addition of a linear, branched or secondary monoalcohol with an alkylene oxide or the like such as ethylene oxide, propylene oxide, butylene oxide, and epichlorohydrin, etc.
    [44] The linear alcohol as it is called here is one represented by the following formula (II). R6-OH (n)
    [45] Branched alcohol is represented by the following formula (III).
    [46] Secondary alcohol is represented by the following formula (IV).
    [47] Consequently, Rs is a residue of the formulas (II) to (IV) mentioned above as derived by the removal of the hydroxyl group from it. In formulas (II) to (IV), RÓ, R7, Rs, Rio and Rn each represent a hydrocarbon group or a fluorocarbon group, and include, an alkyl group, an alkenyl group, an alkyl-aryl group, an cycloalkyl group, and a cycloalkenyl group.
    [48] Exemplary alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyla, octyl, 2-ethylhexyl, nonila, decila, undecila, dodecyl , tridecyl, isotridecyl, myristyl, palmitile, stearyl, isostearyl, eicosyl, docosyl, tetracosyl, triacontyl, 2-octyl-dodecyl, 2-dodecyl-hexadecyl, 2-tetradecyl-octadecyl, and monomethyl-branched isostearyl.
    [49] Exemplary alkenyl group includes vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, and oleyl.
    [50] Exemplary alkyl-aryl group includes phenyl, toluyl, xylyl, cumenyl, mesity, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethyl-phenyl, propyl-phenyl, butyl-phenyl, pentyl-phenyl, hexyl-phenyl , heptyl-phenyl, octyl-phenyl, nonyl-phenyl, oc-naphthyl, and β-naphthyl.
    [51] Exemplary cycloalkyl group and cycloalkenyl group include cyclo-pentyl, cyclohexyl-, cycloheptyl, methyl-cyclo-pentyl, methyl-cyclohexyl-, methyl-cycloheptyl, cyclo-pentenyl, cyclohexenyl, cycloheptenyl, methyl-cyclo-pentenyl, methyl-cyclohexenyl, and methyl-cycloheptenyl.
    [52] In the formula (III) above, FG represents a hydrocarbon group or a fluorocarbon group, and includes, for example, an alkylene group, an alkenylene group, an alkyl-arylene group, a cycloalkylene group, and a cyclo group -alkenylene.
    [53] Rs represents a hydrocarbon group or a fluorocarbon group, and is preferably an alkyl group; and most preferably, the total number of carbon atoms making up the group is 8 to 36, much more preferably 12 to 24.
    [54] The alkylene oxide, styrene oxide or the like to be added can be in the form of homopolymerization or a random polymerization or block polymerization of two or more different types thereof. The mode of addition can be any common. The degree of polymerization n is from 0 to 1000, preferably from 1 to 200, more preferably from 10 to 200. The proportion of the ethylene group that occupies R4S is preferably from 50 to 100% by weight of all R4S, more preferably from 65 % to 100% by weight. The preferred modality gives a good associative thickener for the purpose of the invention.
    [55] To produce the copolymer represented by the formula (I), the compounds can be reacted in the same way as the common polyether and isocyanate reaction, for example, by heating at 80 ° C to 90 ° C for 1 to 3 hours.
    [56] In the reaction of the polyether polyol (A) represented by Ri - [(O-R2) k-OH] m, the polyisocyanate (B) represented by R3- (NCO) h + i and the polyether monoalcohol ( C) represented by HO- (R4-O) n-Rs, any others can be generated as by-products unlike the copolymer having the structure of formula (I). For example, in the case in which a diisocyanate is used, the main product is the copolymer of the type CBABC represented by the formula (I), and in addition to it, other copolymers such as one of the type CBC, one of the type CB- (AB) XABC and the like can be generated as by-products. In this case, without specific separation of the formula-type copolymer (I), a mixture containing the formula-type copolymer (I) can be used in the invention.
    [57] In the invention, a commercial product can be used as component (a). As the commercial product, "Adekanol GT-700" (from ADEKA CORPORATION), etc., is exemplified.
    [58] The amount of component (a) to be incorporated into the thickener composition of the invention is 0.1% to 2% by weight, preferably from 0.2% to 1.5% by weight. When the amount is less than 0.1% by mass, then the effect of component (a) cannot be obtained; but on the other hand, when more than 2% by mass is incorporated, then the viscosity may increase excessively and the efficiency in producing the composition may be less, and occasionally the stickiness effect in use will occur. Component (b)
    [59] As a microgel of component (b) obtained by grinding or crushing a gel of a hydrophilic compound having a gelling capacity, a microgel having an average particle size of 0.1 pm to 1000 is preferably used in the present invention. pm, as prepared by grinding or crushing a gel formed by dissolving a hydrophilic compound having a gelation capacity in water or an aqueous component followed by its cold maintenance.
    [60] The hydrophilic compound having a gelling capacity is not restricted as long as it is a water-soluble compound having a gelling capacity and is capable of being used in the field of cosmetics and drugs. Specifically, those exemplified include hydrophilic proteins having a gelling capacity, such as gelatin and collagen; hydrophilic polysaccharides, such as agar, curdlan, scleroglycan, sizofiran, gellan gum, alginic acid, carrageenan, mannan, pectin, and hyaluronic acid. Among all of the above, especially for use here are gelatin, agar, curdlan, gellan gum, alginic acid and carrageenan, because they are hardly influenced by salts and ions and are capable of forming a stable gel. One or more hydrophilic compounds having a gelling capacity can be used here.
    [61] The hydrophilic compound having a gelling capacity is dissolved in water or an aqueous component, then allowed to cool and solidify to form a gel. The compound can be dissolved in water or an aqueous component by mixing, heating or the like.
    [62] For gelation (solidification), heating of the system can be stopped after its dissolution, and then the system is left as such (statically maintained as such) until it can be cooled to a temperature lower than the temperature of gelation (solidification temperature).
    [63] The aqueous component can be any usable in the field of cosmetics and drugs. The component may contain a glycol, such as 1,3-butylene glycol, propylene glycol or the like, or a lower alcohol, such as ethanol, propanol or the like, and in addition to it, any other ingredient capable of being generally incorporated as an aqueous phase ingredient in cosmetics. For such an ingredient, a chelating agent such as metaphosphate salts, edetate salts and the like, and a pH controlling agent, and a preservative, etc., are exemplified, but not limited to them. In the case where gellan gum is used as the hydrophilic compound having a gelling capacity, a cation is preferably added to the aqueous component to further increase the strength of the gel. The cation is preferably a monovalent or divalent cation, but is not limited to this. In concrete terms, an acid capable of releasing a monovalent cation (H +) (eg, acetic acid, citric acid, etc.) or a salt capable of releasing a monovalent or divalent cation, for example, Mg ++, Ca ++, Na + or K + ( eg, magnesium chloride, calcium chloride, sodium chloride, potassium chloride, etc.) can be added to the component.
    [64] The strength of the gel is not specifically defined, as long as it can be at such a level that the gel itself can maintain its shape and can form a microgel in the next step. In the invention, a gel having a considerably high gel resistance can be used, and for example, a gel having a gel resistance of about 1,000 g / cnr (as measured according to the method of “Agar and Marine Products Guild of Japan ”) or smaller can be used, but on the other hand, a gel having a considerably low gel resistance than a gel resistance of approximately 30 g / cm2 can give a micro gel for use here. From the point of view of improving a sensation in use, a gel having a gel resistance of approximately 100 g / cm2 is preferred.
    [65] Combined with the hydrophilic compound mentioned above having a gelling capacity, a thickener compound without a gelling capacity for the purpose of modifying the sensation in use is also usable here. Exemplary thickening compound not having a gelling capacity includes hydrophilic synthetic polymers, such as typically poly (acrylic acid), poly (ethylene glycol), polyacrylamide, poly (alkyl-acrylamide) / polyacrylamide, carboxymethyl-cellulose, cellulose copolymer cationized, and pluronic, as well as natural hydrophilic polymers, such as xanthan gum, succinoglycan, guar gum, locust bean gum, and also clay minerals, such as laponite, bentonite, and smectite. Salts of these compounds are also usable here. Additionally, the use of a hydrophilic thickener compound without a gelling capacity makes it possible to control the gel resistance of the gel to be obtained in any desired manner. When the proportion of the thickening compound not having a gelling capacity is increased, then the strength of the gel decreases. One or more such thickening compounds having no gelling ability can be used herein.
    [66] The proportion of the thickening compound not having a gelling capacity to be incorporated herein can be, but is not limited to, from approximately 1% to 100% by weight of the hydrophilic compound having a gelling capacity.
    [67] Next, the gel formed is ground or ground with a homogenizer, disperser, mechanical stirrer or the like to give a desired microgel. In the invention, the average particle size of the microgel is from 0.1 ym to 1000 ym, preferably from approximately 1 ym to 300 ym, more preferably from approximately 10 ym to 200 ym. When the average particle size of the microgel is greater than 1,000 ym, then the utilization of the composition would be problematic in such a way that there would be a tendency to be difficult to catch the composition with your fingers. On the other hand, when the average particle size is less than 0.1 pm, then the composition could not maintain its viscosity as a gel preparation. The degree of grinding or crushing can be suitably controlled according to the intended purpose of the composition, for example, to such a level that the average particle size of the microgel to be obtained does not exceed the above mentioned range of the invention. In the case where easier usability of the composition is required, the gel is more sufficiently ground by means of high speed agitation to give a microgel having a smaller particle size, but on the other hand, in the case in which a good feeling of the microgel itself is desired, the degree of grinding or crushing can be lowered by gentle agitation to give a microgel having a relatively large particle size.
    [68] The required viscosity of the microgel thus obtained varies depending on its intended use and, therefore, could not be defined indiscriminately. For example, when agar is used at a concentration of approximately 0.5% to 2%, the viscosity of the microgel is preferably approximately 2,000 to 1,000,000 mPa-s as measured by a BL type viscometer (12 revolutions, 25 ° C ).
    [69] The amount of component (b) to be incorporated into the thickener composition of the invention is 0.1% to 2% by weight, preferably from 0.2% to 2% by weight. When the amount is less than 0.1 mass%, then the effect of component (b) cannot be obtained; but on the other hand, when it is greater than 2% by mass, then the sticky sensation in use occasionally occurs.
    [70] In the invention, the combination ratio (by mass) of component (a) to component (b), (a) / (b) is 0.1 / 0.9 to 0.9 / 0.1, preferably from 0.2 / 0.8 to 0.8 / 0.2. When the combination ratio is greater than the above range, then it would impair the feeling of freshness in use, but on the other hand, when it is less than the above range, it could not stably maintain the composition's viscosity and therefore it would be unfavorable.
    [71] In the invention, by combining the components (a) and component (b) mentioned above, a thickening composition can be obtained having an excellent sensation in use, namely excellent freshness and incorporation into the sensation of the skin, leaving no residue on the skin. ; and in comparison with the case of the individual use of component (a) or component (b) separately from each other, the thickening effect of the composition of the present use case of the two simultaneously has been greatly increased. For this purpose, the thickening effect of the composition can be greatly increased, and therefore, both component (a) and component (b) can be incorporated into the composition in a low content, thereby causing the composition viscosity to fall in. low to moderate viscosity range. In common compositions, the change in the amount of the thickening ingredient (thickening agent) to be incorporated in them produces a logarithmic change in the viscosity of the composition. Consequently, even when the amount of thickening agent to be incorporated in the composition is modified only slightly, the viscosity of the composition can change a lot. Specifically, in the case where the thickening agent having a high thickening capacity is used alone, the viscosity of the composition system can be extremely low (for example, like the viscosity of an aqueous solution), or it can often tend to increase (for example, example, like the viscosity of a creamy to viscous liquid), and it is extremely difficult to steadily maintain the viscosity of the composition system so that it falls within a low to moderate viscosity range (for example, the composition exhibits fluidity in a thick gel state when caught by fingers or hands). Due to the situation, the present inventors tried to combine the thickening agents having a high thickening capacity in an extremely low combination ratio (in a concentration not sufficient for the thickening effect), thereby maintaining the viscosity of the composition in a viscosity range. low to moderate level. In the present invention, component (a) and component (b) are combined to exhibit a synergistic thickening effect of the two; and consequently, by combining the two components, it has been possible to easily maintain the viscosity of the system in order to fall within a low to moderate viscosity range in a simplified manner.
    [72] Concretely, it is desirable that the viscosity of the composition of the invention falls within a low to moderate viscosity range of 50 to 50,000 mPa-s (with a BL type viscometer at 25 ° C), more preferably from 100 to 30,000 mPa-s.
    [73] Another advantage of the thickener composition of the invention is that when a pharmaceutical ingredient and a salt are incorporated into it, the composition does not exhibit a decrease in viscosity. The pharmaceutical ingredient and the salt can be any of the oil-soluble and water-soluble.
    [74] Exemplary pharmaceutical ingredient includes vitamins, anti-inflammatory agents, and antimicrobial agents. Specific examples of the pharmaceutical ingredient include vitamins and their derivatives such as water-soluble vitamins B, P, vitamins A, D etc .; pantothenyl-ethyl-ether, calcium pantothenate, glycyrrhizinic acid, glycyrrhizinate salts, glycyrrhetinic acid, glycyrrhetinate salts, royal jelly, polyphenol, nicotinic acid and its derivatives (eg, nicotinamide), resorcinol and its derivatives, salicylic acid and its derivatives , L-ascorbic acid and its derivatives, tranexamic acid and its derivatives, glycoside, urea, xylitol, trehalose, and caffeine.
    [75] Exemplary salt includes salts of organic acid, and salts of inorganic acid. Examples of organic acid salts include hydrochlorides, metal salts (sodium salts, potassium salts), amine salts of citric acid, lactic acid, oxalic acid, and sulfonic acid. Examples of amino acid salts include chlorides, metal salts (sodium salts, potassium salts), amine salts of glycine, alanine, proline, lysine, aspartic acid, and glutamic acid. Examples of inorganic salts include carbonates, phosphates, nitrates, borates, sulfates, sodium, potassium, magnesium, calcium and the like, and halides (sodium chloride, potassium chloride).
    [76] Both the thickening agent of the invention and the cosmetic preparation containing the thickening agent have excellent salt tolerance, and even when a salt or the pharmaceutical ingredient mentioned above in the form of a salt thereof is incorporated into it ), the system stability of the resulting composition is not influenced by any other ingredients simultaneously incorporated into it, and the composition maintains excellent feeling in use.
    [77] Until now, a compound maintaining a gelling capacity, such as agar, carrageenan, curdlan, gelatin or the like has been used as a thickening agent, but in such a case, the compound is heated, dissolved and gradually cooled with stirring. to give a viscous liquid without solidification (gelling) (for example, JP-11-209262A). However, in the case in which a compound having a gelling capacity is gradually cooled with stirring to give a thickening agent according to the method mentioned above, the degree of thickening of the system is limited. Especially, when a pharmaceutical ingredient or a salt is incorporated, the viscosity of the resulting system is lowered.
    [78] Contrary to this, in the invention, a microgel prepared once by complete gelation (solidification) of the compound and then by grinding or grinding, it is used as a thickening agent. The thickening agent in the invention thus prepared in the manner as above is not one that exhibits the thickening effect due to entanglement at the molecular level, unlike the thickened polysaccharides or synthetic polymeric thickening agents hitherto used in common cosmetics, but it is one that exhibits the thickening effect due to friction of the microgel particles formed by grinding a gel. Consequently, the thickening agent in the invention is quite free from a tackiness problem that is characteristic of polymer solutions, and can provide in use a very fresh feeling. Polymer solutions may exhibit reduced viscosity when influenced by the pharmaceutical ingredient or by the salt incorporated in them, and therefore, the incorporation of such a pharmaceutical ingredient or such salt is often limited in the art. However, the invention is free of the problem and can therefore expand the forms in formulation of cosmetics, etc.
    [79] In the case in which a pharmaceutical ingredient or water-soluble salt is used in the invention, the ingredient or salt can be dissolved in water or an aqueous component together with the hydrophilic component having a gelling capacity to be therein, then it is kept cooled and solidified to form a gel, and then the gel can be ground to give a microgel; or the hydrophilic component having a gelling capacity can first be dissolved in water or an aqueous component, then kept cooled and solidified to give a gel, then the gel is ground into a microgel, and then the resulting microgel can be mixed with the pharmaceutical ingredient or salt.
    [80] On the other hand, in the case in which the pharmaceutical ingredient or salt to be used is an oil-soluble, a preferred embodiment of using the oil-soluble ingredient or salt is as follows: the hydrophilic component having a gelling capacity it is first dissolved in water or an aqueous component, then it is allowed to cool and solidify to form a gel, and the gel is ground into a microgel, although on the other hand unlike this, the pharmaceutical ingredient or oil-soluble salt is pre-emulsified in an aqueous phase together with any other oily components to be in it, and then the pre-emulsified mixture is further mixed with the aforementioned microgel and emulsified to give the intended composition.
    [81] In the case where the thickener composition obtained according to the invention is used as a cosmetic, or is incorporated into a cosmetic, in general, additive ingredients capable of being incorporated into cosmetics, for example, moisturizer, preservative, powder, dye, fragrance, pH controlling agent and the like can be suitably incorporated into it within a range that does not detract from the purpose and advantage of the invention. Specific examples of the shape of the cosmetic include slightly thick gels, emulsions, etc. Specific examples of the cosmetics in which the invention is preferably applied include moisturizing gel, massage gel, beauty essence, skin lotion, milky lotion, makeup cosmetics, sunscreen articles, hair care cosmetics such as fixing agent hair, hair gel, etc., as well as hair dye, and body care items.
    [82] The use of the thickening composition obtained according to the invention as a cosmetic preparation makes it possible to greatly increase the thickening capacity of the cosmetic and improves the sensations of the cosmetic in use. In addition, even when a pharmaceutical ingredient and a salt are incorporated into the cosmetic preparation in a high proportion, or for example, when the ingredient or salt is incorporated into it in a proportion of about 20% by weight of the entire amount of the cosmetic preparation , there is no problem of reducing the viscosity of the system, and the cosmetic preparation can still maintain its viscosity of the system. In addition, the cosmetic preparation is stable for a long period of time, causing no water release from it. Preferably, the pharmaceutical ingredient or salt to be incorporated into the composition is at least approximately 0.1% by weight of the entire amount of the cosmetic preparation for the purpose of ensuring the intended effect of the additive incorporation. EXAMPLES
    [83] The invention is described below concretely with reference to the following Examples, by which, however, whatever the invention is is not limited. Unless specifically stated otherwise, the amount incorporated is in terms of% by mass.
    [84] In the following Examples, the compounds mentioned below were used as the constituent components.
    [85] • Hydrophobic denatured poly (ether-urethane) [component (a)]: A copolymer represented by the formula (I) mentioned above was used, where Ri, R2 and R4 are each an ethylene group, R3 = hexamethylene group, R5 = 2-dodecyl-dodecyl group, h = 1, m = 2, k = 120, n = 20, ("Adekanol GT-700" from ADEKA CORPORATION).
    [86] • Agar microgel [component (b)]: A 2% aqueous dispersion of agar was heated to 90 ° C, and after confirmation of its complete dissolution, it was statically left as such to give a gel composition not fluid. The gel was ground with a homogenizer to give an agar microgel (having an average particle size of about 50 pm) for use here.
    [87] • Gellan gum microgel [component (b)]: An aqueous dispersion of 1% gellan gum was heated to 80 ° C, and after confirmation of its complete dissolution, an aqueous solution of 2.8% chlorine gum sodium was added therein and uniformly stirred, and statically left as such to give a non-fluid gel composition. The gel was ground with a homogenizer to give a gelan gum microgel (having an average particle size of about 50 pm) for use here. (Example 1: Thickened synergistic effect and salt tolerance effect by the combination of component (a) and component (b))
    [88] First, the following test was performed to confirm the thickened synergistic effect and the salt tolerance effect by combining component (a) and component (b) for use in the invention.
    [89] Component (a) and component (b) were added in pure water each in the amount listed in Tables 1 and 2 shown below to prepare an aqueous solution, and then after this it was left at room temperature (25 ° C) for 1 minute, its viscosity (mPa-s) was measured with a BL type viscometer (rotor number 3, 12 rotations).
    Tabela 2][90] A salt was added to the sample prepared above, and mixed by stirring. This was left at room temperature (25 ° C) for 1 minute, and its viscosity (mPa-s) after adding salt was measured with a BL type viscometer (number 3 rotor, 12 rotations). The tolerance to salt in relation to the change in viscosity was thus assessed. The results are shown in Tables 1 and 2. [Table 1] Table 2]
    [91] As is obvious from the results shown in Tables 1 and 2, for example, comparing compositions 1 and 4 with composition 5, comparing compositions 2 and 4 with composition 6, and comparing compositions 13 and 14 with composition 15, it has been confirmed that the combination of component (a) and component (b) significantly increased the thickening effect compared to the effect of compositions containing either of component (a) or component (b) alone.
    [92] As is obvious from the comparison between compositions 8 and 11, from the comparison between compositions 5 and 12, from the comparison between compositions 18 and 20 and from the comparison between compositions 21 and 22, it has also been confirmed that the combination provides an excellent salt tolerance effect. (Examples 2 to 3, Comparative Examples 1 to 5: Sensations in use)
    [93] Samples were prepared having the composition shown in Tables 3 and 4 below. The samples were tested for their sensations in use according to the evaluation standards mentioned below. The results are shown in Table 5. [Sensations in use during application to the skin (freshness, non-stickiness, incorporation into the skin sensation, absence of residue on the skin without twisting)]
    [94] Expert panelists (10 women) tested the samples (compositions) of Examples and Comparative Examples, and evaluated them in relation to the sensations in use during their application on the skin, namely in relation to freshness, non-stickiness, incorporation in the sensation of the skin and the absence of residue on the skin (without twisting), according to the evaluation standards mentioned below. (Evaluation)
    [95] ®: 8 or more panelists responded that the sensations in use were excellent.
    [96] O: 6 to 7 panelists responded that the sensations in use were excellent.
    [97] Δ: 3 to 5 panelists responded that the sensations in use were excellent.
    [Tabela 4] [Tabela 5][98] x: 2 or less panelists responded that the sensations in use were excellent. [Table 3] [Table 4] [Table 5]
    [99] As is obvious from the results shown in Table 5, it has been confirmed that the combination of component (a) and component (b) incorporated in cosmetics provides excellent sensations in use, compared to cosmetics comprising any of the component ( a) or component (b) alone as the thickening agent in it (comparison between Example 2 and Comparative Example 2, comparison between Example 3 and Comparative Example 3). Comparative Examples 4 and 5 are compositions shown in "Patent Reference 2" (reference to the prior art). The samples of these Comparative Examples 4 and 5 were good in relation to the sensations in use, namely, in relation to hydration and non-stickiness; however, the samples from Examples 2 and 3 were better than these in terms of comprehensive evaluation of sensations in use.
    Exemplo de Formulação 2: Protetor Exemplo de Formulação 3: Loção leitosa para pele Exemplo de Formulação 4: Gel transparent Exemplo de Formulação 5: gel de essência Exemplo de Formulação 6: Loção leitosa branqueadora Exemplo de Formulação 7: Loção de limpeza facial Exemplo de Formulação 8: Base[100] Examples of formulation of the invention are shown below. Formulation Example 1: Milky Skin Lotion Formulation Example 2: Protector Formulation Example 3: Milky Skin Lotion Formulation Example 4: Transparent gel Formulation Example 5: Essence Gel Formulation Example 6: Milky Whitening Lotion Formulation Example 7: Facial Cleansing Lotion Formulation Example 8: Base INDUSTRIAL APPLICABILITY
    [101] The thickening composition and the cosmetic containing the composition of the invention are excellent in sensations in use, namely, excellent in freshness, non-stickiness and incorporation in the sensation of the skin, leaving no residue on the skin, and can stably maintain its viscosity in a low to moderate level range.
    权利要求:
    Claims (4)
    [0001]
    em que Ri, R2 e R4 representam cada um independentemente um grupo alquileno tendo de 2 a 4 átomos de carbono, ou um grupo fenil- etileno; R3 representa um grupo alquileno tendo de 1 a 10 átomos de carbono e opcionalmente tendo uma ligação uretano; Rs representa um grupo alquila linear, ramificado ou secundário tendo de 8 a 36 átomos de carbono; m indica um número de 2 ou mais; h indica um número de 1 ou mais; k indica um número de 1 a 500; e n indica um número de 1 a 200; e (b) de 0,1% a 2% em massa de um microgel a ser obtido por moagem de um gel de um composto hidrofílico tendo uma capacidade de gelificação, caracterizadapelo fato de que o composto hidrofílico é ágar e/ou goma gelana, em uma proporção em massa de componente (a) / componente (b) é de 0,1/0,9 a 0,9 a 0,1, e a composição espessante tem uma viscosidade de 50 a 50.000 mPa-s, como medido com um viscosímetro do tipo BL em 12 rotações por minuto e 25°C.1. Cosmetic preparation containing a thickener composition comprising: (a) from 0.1% to 2% by weight of a hydrophobic denatured poly (ether-urethane) represented by the following formula (I), wherein R1, R2 and R4 each independently represent an alkylene group having 2 to 4 carbon atoms, or a phenylethylene group; R3 represents an alkylene group having 1 to 10 carbon atoms and optionally having a urethane bond; Rs represents a linear, branched or secondary alkyl group having 8 to 36 carbon atoms; m indicates a number of 2 or more; h indicates a number of 1 or more; k indicates a number from 1 to 500; en indicates a number from 1 to 200; and (b) from 0.1% to 2% by weight of a microgel to be obtained by grinding a gel of a hydrophilic compound having a gelling capacity, characterized by the fact that the hydrophilic compound is agar and / or gellan gum, in a mass ratio of component (a) / component (b) is 0.1 / 0.9 to 0.9 to 0.1, and the thickener composition has a viscosity of 50 to 50,000 mPa-s, as measured with a BL type viscometer at 12 revolutions per minute and 25 ° C.
    [0002]
    2. Cosmetic preparation according to claim 1, characterized by the fact that Ri, R2 and R4 in formula (I) each independently represent an alkylene group having from 2 to 4 carbon atoms, R3 represents an alkylene group having from 1 to 10 carbon atoms and optionally having a urethane bond, Rs represents a linear, branched or secondary alkyl group having 12 to 24 carbon atoms, m is 2, h is 1, k is a number from 100 to 300, and n is a number from 10 to 100.
    [0003]
    Cosmetic preparation according to claim 1 or 2, characterized by the fact that component (b) is a microgel having an average particle size of 0.1 pm to 1,000 pm, as prepared by grinding a gel formed by dissolving of a hydrophilic compound having a gelation capacity in water or an aqueous component followed by its cold maintenance.
    [0004]
    4. Cosmetic preparation according to claim 1, characterized by the fact that it additionally contains one or more selected from pharmaceutical ingredients and salts.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5281654A|1993-01-14|1994-01-25|Rohm And Haas Company|Polyurethane mixture|
    JP3581452B2|1995-09-06|2004-10-27|旭電化工業株式会社|Viscosity modifier|
    JP2985083B2|1997-10-28|1999-11-29|花王株式会社|External preparation for skin|
    US6440431B1|1998-12-17|2002-08-27|Shiseido Co., Ltd.|Cosmetic composition|
    FR2802094B1|1999-12-13|2002-01-18|Oreal|DECOLORING COMPOSITION FOR KERATINIC FIBERS COMPRISING A COMBINATION OF TWO POLYURETHANE POLYETHERS|
    JP3531735B2|2000-01-11|2004-05-31|株式会社資生堂|Method for producing thickener and cosmetic|
    EP1158021B1|2000-01-11|2011-10-05|Shiseido Company Limited|Microgels and external preparations containing the same|
    JP4584400B2|2000-03-30|2010-11-17|株式会社Ａｄｅｋａ|Gel fragrance composition|
    TWI296932B|2000-06-26|2008-05-21|Shiseido Co Ltd|
    JP2005343841A|2004-06-04|2005-12-15|Shiseido Co Ltd|Skin care preparation for external use|
    JP5035948B2|2006-04-26|2012-09-26|株式会社資生堂|Thickening composition and cosmetic|
    US7741401B2|2007-03-21|2010-06-22|Rohm And Haas Company|Thickener blend composition and method for thickening aqueous systems|JP5373046B2|2011-12-19|2013-12-18|株式会社資生堂|Oil-in-water emulsion composition|
    JP6242037B2|2012-03-16|2017-12-06|株式会社 資生堂|Oil-in-water emulsified skin cosmetic|
    JP6362243B2|2013-06-07|2018-07-25|株式会社Adeka|Gel composition for cosmetics|
    JP6480134B2|2013-10-04|2019-03-06|御木本製薬株式会社|Cosmetics|
    JP2015091783A|2013-10-04|2015-05-14|御木本製薬株式会社|External preparation for skin|
    US9520180B1|2014-03-11|2016-12-13|Hypres, Inc.|System and method for cryogenic hybrid technology computing and memory|
    CN106102709A|2014-03-28|2016-11-09|株式会社高丝|Cosmetics|
    US20170216189A1|2014-08-05|2017-08-03|Covestro Deutschland Ag|Polyurethane urea solutions for cosmetic compositions|
    JP6254058B2|2014-09-05|2017-12-27|富士フイルム株式会社|Topical skin preparation|
    JP6208644B2|2014-09-29|2017-10-04|富士フイルム株式会社|Topical skin preparation|
    JP2016069336A|2014-09-30|2016-05-09|富士フイルム株式会社|Gel aqueous cosmetics|
    JP6113695B2|2014-10-31|2017-04-12|株式会社 資生堂|Elastic gel composition|
    FR3029423B1|2014-12-03|2017-01-06|Oreal|COMPOSITIONS COMPRISING AN ASSOCIATIVE POLYURETHANE, ALCOHOL OR FATTY ACID, NON-IONIC SURFACTANT AND PIGMENT|
    KR101525403B1|2014-12-31|2015-06-03|한불화장품주식회사|Shape-restoring hydrogel composition for mask pack and producing method thereof|
    JP6284894B2|2015-03-20|2018-02-28|富士フイルム株式会社|Aqueous gel cosmetics|
    US10980714B2|2015-05-07|2021-04-20|L'oreal|Cleansing scrub composition|
    US20190380923A1|2015-12-17|2019-12-19|L'oreal|Composition of gel/gel type based on hydrophobic coated pigments and a liquid fatty acid and/or a glycol compound|
    FR3045334B1|2015-12-17|2020-01-03|L'oreal|GEL / GEL COMPOSITION BASED ON HYDROPHOBIC COATED PIGMENTS AND A FATTY LIQUID ACID|
    EP3449896B1|2016-04-28|2021-03-17|Shiseido Company, Ltd.|Oil-in-water solid cosmetic|
    CA3029824A1|2016-07-05|2018-01-11|Rohm And Haas Company|Compositions comprising polyether-urethane-urea additives for block resistance and open time|
    US11166885B2|2016-09-22|2021-11-09|Colgate-Palmolive Company|Personal care gel and method|
    FR3060356B1|2016-12-21|2020-01-17|L'oreal|COMPOSITION COMPRISING BAICALIN AND / OR A DERIVATIVE THEREOF AND A NON-IONIC ASSOCIATIVE POLYURETHANE|
    KR20200051678A|2017-09-07|2020-05-13|가부시키가이샤 아데카|A cosmetic composition comprising an aqueous gelling agent, and a method for producing the aqueous gelling agent and its cosmetic composition|
    US20210000720A1|2017-09-07|2021-01-07|Adeka Corporation|Skin- or hair-cleansing composition containing aqueous gelling agent, and methods for producing aqueous gelling agent and cleansing composition|
    WO2019051341A2|2017-09-08|2019-03-14|Maple Ridge, Llc|Tissue bonding copolymers of oil|
    JP6966284B2|2017-09-29|2021-11-10|株式会社 資生堂|Underwater oil type emulsified cosmetic|
    CN111526867A|2017-12-28|2020-08-11|株式会社资生堂|Cosmetic preparation|
    JP6408184B1|2018-04-16|2018-10-17|株式会社 資生堂|Thick water based cosmetic|
    KR101970638B1|2018-07-20|2019-04-19|엠엘에스|Cosmetic composition for mask pack|
    JP2020023478A|2018-07-31|2020-02-13|株式会社Adeka|Cosmetic emulsion composition|
    KR102107420B1|2019-05-17|2020-05-07|한국콜마주식회사|Cosmetic composition for improving wrinkle comprising anionic polymers and urethane|
    WO2021123857A1|2019-12-19|2021-06-24|L V M H Recherche|Oil-in-water emulsified cosmetic|
    CN111944113B|2020-07-08|2021-07-20|华南理工大学|Photoreaction type polyurethane associative thickener with benzophenone side group at end, preparation method and application thereof|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-04-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    2022-02-22| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2010-104081|2010-04-28|
    JP2010104081A|JP4979095B2|2010-04-28|2010-04-28|Thickening composition and cosmetics containing the same|
    PCT/JP2011/060262|WO2011136270A1|2010-04-28|2011-04-27|Thickening composition and cosmetics containing same|
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