|HAO WANATA MARIAUS009782336B2 DEL DIA AT MAN KAN MO MALT (12 ) United States Patent (10 ) Patent No. : US 9 ,782 ,336 B2 Haraya et al. ( 45 ) Date of Patent : Oct . 10 , 2017 (54 ) MOISTURIZER AND COSMETIC 2015 /0010489 AL 1/ 2015 Sugimoto 2015 /0038563 A12 /2015 Fournier CONTAINING SAME 2015/ 0111859 Al 4 /2015 Sugimoto et al. (71 ) Applicant: AJINOMOTO CO . , INC ., Tokyo (JP ) FOREIGN PATENT DOCUMENTS ( 72 ) Inventors : Nana Haraya , Kawasaki ( JP ) ; Eiko FR 2 900 047 Al 10 / 2007 Oshimura , Kawasaki ( JP ) 9 - 87126 A 3 / 1997 JP 10 - 500707 A 1 / 1998 ( 73 ) Assignee : AJINOMOTO CO . , INC ., Tokyo (JP ) 2004 - 075585 A 3 / 2004 JP 2005 - 289873 A 10 / 2005 5423002 B2 2 / 2014 ( * ) Notice : Subject to any disclaimer , the term of this WO WO 87 /01935 Al 4 / 1987 patent is extended or adjusted under 35 WO WO 2007/ 148831 A112 / 2007 U . S . C . 154 (b ) by 0 days . WO WO 2013 / 147328 A 10 / 2013 WO WO 2013 / 153330 A2 10 / 2013 ( 21 ) Appl. No. : 15 / 455, 528 WO WO 2014 /007290 Al 1 / 2014 ( 22 ) Filed : Mar. 10 , 2017 OTHER PUBLICATIONS ((65 ) Prior Publication Data International Search Report dated Dec. 1 , 2015 in PCT/ JP2015 / US 2017 /0181947 A1 Jun . 29, 2017 075691 . Related U .S . Application Data Primary Examiner — Raymond Henley, III (63 ) Continuation of application No . (74 ) Attorney , Agent, or Firm — Oblon , McClelland , PCT / JP2015/ 075691 , filed on Sep . 10 , 2015. Maier & Neustadt, L . L . P . (30 ) Foreign Application Priority Data (57 ) ABSTRACT The present invention provides a composition containing Sep . 10 , 2014 ( JP ) ...... 2014 -184373 ( A ) and ( B ) , which shows a decreased peculiar odor of (51 ) Int. Ci. acylproline and a salt thereof, has a moist feeling and is A61K 31 /40 ( 2006 .01 ) superior in the stability : A61K 31/ 19 ( 2006 .01 ) (A ) acylproline represented by the formula (1 ) or a salt A61K 8 /49 ( 2006 . 01 ) thereof A610 19 / 00 ( 2006 .01 ) A61K 8 / 365 ( 2006 .01 ) (52 ) U . S . CI. CPC ...... A61K 8 /4913 (2013 .01 ) ; A61K 8 /365 ( 2013. 01 ); A61Q 19 / 00 ( 2013 .01 ) COOH (58 ) Field of Classification Search ??? ...... A61K 31/ 40 ; A61K 31/ 19 USPC ...... 514 /423 , 557 0 R1 See application file for complete search history . (wherein an acyl group represented by R1C0 — is an acyl (56 ) References Cited group induced from saturated or unsaturated fatty acid having 3 -23 carbon atoms) U . S . PATENT DOCUMENTS ( B ) a zinc salt of pyrrolidone carboxylate . 4 ,837 ,026 A 6 / 1989 Rajakhyaksha 2002 /0127193 AL 9 / 2002 Ascione et al. 20 Claims, No Drawings US 9 ,782 ,336 B2 MOISTURIZER AND COSMETIC DOCUMENT LIST CONTAINING SAME Patent Documents CROSS REFERENCES TO RELATED 5 patent document 1 : WO 2013147328 APPLICATIONS patent document 2 : WO 2014007290 patent document 3 : JP - A - 2004 - 075585 This application is a continuation of International Patent Application No. PCT/ JP2015 /075691 , filed on Sep . 10 , 10 SUMMARY OF THE INVENTION 2015 , and claims priority to Japanese Patent Application No. Problems to be Solved by the Invention 2014 -184373 , filed on Sep . 10 , 2014, both of which are incorporated herein by reference in their entireties . An object of the present invention is to provide a com position having less odor peculiar to acylproline or a salt thereof, having a moist feeling and superior in the stability . BACKGROUND OF THE INVENTION Means of Solving the Problems Field of the Invention The present inventors have conducted intensive studies in The present invention relates to a composition comprising 20 an attempt to solve the above -mentioned problems and particular acylproline or a salt thereof and a zinc salt of found for the first time that the peculiar odor of acylproline pyrrolidone carboxylate and having a suppressed peculiar or a salt thereof can be reduced by combining acylproline or odor . The present invention relates to the composition fur - a salt thereof with Zinc PCA . Even though Zinc PCA is preferable 25 water- soluble , an insoluble precipitate is formed when com ther comprising hydroxycarboxylic acid , which is preferable 25 binedwat with acyl proline or a salt thereof and its use is for addition to cosmetics and the like having superior restricted . Therefore , they have further studied and found appearance. that a transparent solution (composition ) having superior Discussion of the Background stability can be obtained by adding hydroxycarboxylic acid , Acylamino acid salts are known as low irritative surfac - 30 which resulted in the completion of the present invention . Accordingly , the present invention provides the follow tants having high safety , and are particularly used for ing. cleansing agents for sensitive skin . Among them , acyl pro - [ 1 ] A composition comprising the following ( A ) and ( B ) : line salt is known to be a material useful as a moisturizer (A ) acylproline represented by the formula (1 ) or a salt having hygroscopicity and moisture retention property (pat bot. - 35 thereof ent documents 1 and 2 ). On the other hand , acylamino acid salts such as acylpro line salt and the like have defects in that a peculiar odor is produced when the blending amount thereof is increased or 40* when a long time has passed after blending . COOH For example , as a method for solving the problem of the unpleasant unique odor of base that the acylamino acid salt 07R has, a method of masking odor by using a synthetic flavor 43 (wherein an acyl group represented by Rd _ CO — is an acyl has been found . However, some of the people having group induced from saturated or unsaturated fatty acid sensitive skin are allergic to synthetic flavors and such having 3 - 23 carbon atoms) flavors are suggested to pose problems in terms of safety ( B ) a zinc salt of pyrrolidone carboxylate . acid salt is 50 [ 2 ] The composition of [ 1 ] , wherein , in ( A ) , the acyl group (patent document 3) . That is, when an acylamino acid salt is 50 represented by R - CO — is an acyl group induced from blended in a cosmetic and the like, masking of the peculiar saturated or unsaturated fatty acid having 6 - 14 carbon odor is performed . In this case , masking means “ adding an atoms. aroma ” , by which deodorizing is not achieved . In addition , [3 ] The composition of [ 1 ] or [ 2 ], wherein the acylproline since the odor is fixed to cosmetics and so on , application of 55 represented by the formula ( 1) is decanoylproline . [ 4 ] The composition of any one of [ 1 ] - [ 3 ] , wherein the salt masking to the manufacture of cosmetics having own scent of acylproline represented by the formula ( 1 ) is a sodium is avoided . salt . In addition , a zinc salt of pyrrolidone carboxylate ( PCA ) [5 ] The composition of any one of [ 1 ]- [ 4 ], wherein a content 60 of ( A ) is 0 . 001 wt % - 40 wt % relative to the whole weight (hereinafter sometimes to be abbreviated as Zinc PCA ) of the composition . known to have a sebum suppressive effect , an antibacterial [6 ] The composition of any one of [ 1 ] -[ 5 ], wherein a content action , a skin astringent effect, an antiaging effect and the of ( B ) is 0 .01 wt % - 10 wt % relative to the whole weight of the composition . like is a useful cosmetic material conventionally used widely 65 [ 7 ] The composition of any one of [ 1 ]- [6 ] , further compris for skin external preparations and hair cosmetics for various ing ( C ) hydroxycarboxylic acid . applications . [ 8 ] The composition of [ 7 ] , wherein ( C ) is citric acid . US 9 ,782 , 336 B2 [ 9 ] The composition of [7 ] or [ 8 ], wherein a weight ratio of According to the present invention , moreover , since a ( B ) to ( C ) [ ( B )/ ( C ) ] is less than 1. transparent state can be maintained even when acylproline [ 10 ] The composition of any one of [ 1 ] - [ 9 ] , which is a or a salt thereof and Zinc PCA are blended , cosmetics and moisturizer . the like having superior appearance can be produced . [ 11 ] A cosmetic comprising the composition of any one of 5 In addition , since appearance can be freely changed by [ 1 ] - [ 9 ] [ 12 ] A method of decreasing an odor of the following ( A ) in coloration and the like , the composition is useful for the a composition comprising ( A ) , comprising a step of placing production of cosmetics and the like . ( B ) in coexistence : ( A ) acylproline represented by the formula ( 1 ) or a salto DETAILED DESCRIPTION OF THE thereof 10 PREFERRED EMBODIMENTS The present invention relates to a composition comprising ( 1) the following ( A ) and ( B ) , or ( A ), ( B ) and ( C ) : ( A ) acylproline represented by the formula ( 1) or a salt thereof COOH

0 R1 20 (wherein an acyl group represented by R ? — C0 — is an acyl COOH group induced from saturated or unsaturated fatty acid having 3 - 23 carbon atoms) , ( B ) a zinc salt of pyrrolidone carboxylate . 07R [ 13 ] A method of suppressing production of an insoluble 25 solid in a composition comprising the following ( A ) and ( B ) , (wherein an acyl group represented by RI _ CO is an acvl which comprises a step of placing ( C ) in coexistence : group induced from saturated or unsaturated fatty acid ( A ) acylproline represented by the formula (1 ) or a salt having 3 - 23 carbon atoms) (hereinafter sometimes to be thereof abbreviated as acylproline of the present invention , 30 ( B ) a zinc salt of pyrrolidone carboxylate , (C ) hydroxycarboxylic acid (hereinafter sometimes to be (1 ) abbreviated as the composition of the present invention ) . ( A ) Acylproline N ' COOH Acylproline to be used in the present invention is repre 35 sented by the formula ( 1) : 0R1 (wherein an acyl group represented by is an acyl group induced from saturated or unsaturated fatty acid having 3 - 23 40 carbon atoms) , COOH ( B ) a zinc salt of pyrrolidone carboxylate , (C ) hydroxycarboxylic acid . [ 14 ] A method of moisturizing skin , comprising applying , to 0 R1 the skin , a composition comprising the following ( A ) and 45 ( B ) in an amount effective for moisturizing the skin : In the formula ( 1) ( A ) acylproline represented by the formula ( 1) or a salt thereof

(1) 50 07R is also shown by R1 _ C0 — in the present specification . COOH An acyl group represented by R - C0 — is an acyl group 55 induced from fatty acid having 3 - 23 carbon atoms, prefer 0 R1 ably an acyl group induced from fatty acid having 4 - 18 carbon atoms, more preferably an acyl group induced from (wherein an acyl group represented by R - CO is an acyl fatty acid having 6 - 14 carbon atoms, further preferably an group induced from saturated or unsaturated fatty acid acyl group induced from fatty acid having 10 - 12 carbon having 3 -23 carbon atoms) , 60 atoms, and a decanoyl group is more preferable . The fatty ( B ) a zinc salt of pyrrolidone carboxylate . acid may be saturated or unsaturated , and an acyl group induced from a saturated fatty acid is preferable . Effect of the Invention Examples of the acyl group represented by R } _ CO include propanoyl group , isopropanoyl group , butanoyl According to the present invention , a composition useful 65 group , isobutanoyl group , sec- butanoyl group , tert- butanoyl as a moisturizer and the like ,which has a less peculiar odor group , pentanoyl group , isopentanoyl group , sec -pentanoyl derived from acylproline or a salt thereof can be provided . group, tert -pentanoyl group, hexanoyl group , heptanoyl US 9 , 782 ,336 B2 group , octanoyl group , tert -octanoyl group , 2 - ethylhexanoyl (B ) Zinc Salt of Pyrrolidone Carboxylate group , nonanoyl group , isononanoyl group , decanoyl group , As the zinc salt of pyrrolidone carboxylate ( Zinc PCA ) to isodecanoyl group , undecanoyl group , lauroyl group , myris - be used in the present invention , Zinc L - PCA salt or Zinc toyl group , palmitoyl group, stearoyl group , eicosanoyl DL - PCA salt can be used , and Zinc L -PCA salt is preferably group , behenoyl group , undecylenoyl group and oleoyl 5 used . It is possible to use each of these alone or in a mixture . group and the like . Of these, decanoyl group , lauroyl group , When a DL form is used , the ratio of the D form and the L butanoyl group , pentanoyl group , hexanoyl group , octanoyl fault is not particularly limited . As Zinc PCA , any of one group , undecanoyl group , myristoyl group , palmitoyl group , obtained by the above -mentioned chemical synthesis method , natural one derived from an animal or plant , one stearoyl group , eicosanoyl group , behenoyl group is prefer 10 obtained by a fermentation method or gene recombination able , decanoyl group , lauroyl group , octanoyl group , method , and a commercially available product may be used . hexanoyl group are more preferable , and decanoyl group is In the composition of the present invention , the content of further preferable . ( B ) Zinc PCA is generally 0 .01 wt % - 10 wt % . While the To be specific , acylproline represented by the formula ( 1 ) lower limit is not particularly limited , 0 . 1 wt % is preferable , is preferably decanoylproline, lauroylproline , butanoylprotamoy pro - 15 and the upper limit is preferably 5 wt % , more preferably 4 line , pentanoylproline , hexanoylproline, octanoylproline , wt % . When the amount added is less than 0 .01 wt % , the undecanoylproline, myristoylproline, palmitoylproline , effect of suppressing the odor of ( A ), and an anti- inflam stearoylproline , eicosanoylproline or behenoylproline is matory effect are not sufficiently exhibited , and when an preferablepreferable , decanoylprolinedecanoylproline , lauroylproline , octanoylproline amount exceeding 10 wt % is used , the feeling of use is or hexanoylproline is more preferable , and decanoylproline 20 impaired since a frictional feeling of the skin is produced , is further preferable. both of which are not preferable . The long chain acyl group represented by R - C0 — may Reduction of odor means that a peculiar odor becomes be an acyl group induced from an acid having a single weak and does not bother, or is not sensed . composition , or an acyl group induced from naturally Acylproline or a salt thereof of the present invention has obtained mixed fatty acids such as coconut oil fatty acid , 25 both hygroscopicity and moisture retention property . castor oil fatty acid , olive oil fatty acid , palm oil fatty acid On the other hand , PCA is one of the components con and the like or fatty acid ( including branched fatty acid ) stituting the natural moisturizing factor which is an impor obtained by synthesis . One kind of these may be used , or two tant component having a role of keeping a moisture com or more kinds selected from the above -mentioned groups ponent in the stratum corneum . Zinc PCA , which has been may be used in a mixture . 30 functionalized by combining PCA and zinc, is known to As a salt of the compound of the formula ( 1 ) , alkalimetal have an action to suppress sebum , prevent growth of bac salts such as lithium salt , sodium salt , potassium salt and the teria , or suppress skin inflammation , by the moisturizing like ; alkaline earth metal salts such as calcium salt, magne property of PCA and the antibacterial activity of zinc, and is sium salt and the like ; alkanolamine salts such as trietha expected to condition the skin to prevent collagen degrada nolamine salt and the like ; ammonium salt ; and basic Therefore , acylproline or a salt thereof and Zinc PCA can organic salt and the like can be mentioned . Of these , alkali be combined with the above -mentioned ( C ) , and further, metal salt and ammonium salt are preferable , sodium salt , other components and used as a moisturizer ( composition potassium salt , ammonium salt are more preferable , sodium for moisturization ) or an anti - inflammatory agent (compo salt and potassium salt are further preferable , and sodium 40 sition for anti - inflammation ) . The composition of the present salt is particularly preferable, from the aspect of solubility. invention can be blended with cosmetics ( including quasi The production method of the compound represented by drugs ) and the like . the formula ( I ) of the present invention is not particularly in the present invention , moisturizer means one that gives limited , and the compound can be produced easily by moist texture and moist feeling to the skin and hair. combining known methods . To be specific , it can be pre - 45 In the present invention , an anti - inflammatory agent pared by the Schotten - Baumann method using proline and means a useful preparation that suppresses skin inflamma acid chloride . In this case , for example , acid chloride and a tion . base such as sodium hydroxide and the like are simultane- For example , in the composition of the present invention , ously added dropwise . Proline may be an L form or D form , ( A ) is 1 part by weight and ( B ) is generally 0 . 1 - 20 parts by or a mixture thereof. Preferred is an L form . 50 weight, preferably 0 . 2 - 10 parts by weight, more preferably As the compound represented by the formula ( I) or a salt 0 . 2 - 4 . 0 parts by weight. When they are within the afore thereof, any of one obtained by the above -mentioned chemi- mentioned ranges, a composition superior in the effect of cal synthesis method , natural one derived from an animal or reducing the peculiar odor of ( A ) and in a moisturizing effect plant, one obtained by a fermentation method or gene can be provided . recombination method , and a commercially available prod - 55 ( C ) Hydroxycarboxylic Acid uct may be used . The hydroxycarboxylic acid to be used in the present The content of acylproline or a salt thereof in the com - invention is a carboxylic acid having a hydroxy group as position of the present invention is preferably 0 .001 wt % -40 well , and is widely distributed in the body in , for example , wt % relative to the whole weight of the composition . The TCA circuit and the like. As hydroxycarboxylic acid , any of lower limit is more preferably 0 .01 wt % , more preferably 60 one obtained by a chemical synthesis method , natural one 0 .05 wt % , particularly preferably 0 . 1 wt % . From the aspect derived from an animal or plant, one obtained by a fermen of the texture of the composition , the upper limit is prefer - tation method or gene recombination method, and a com ably 35 wt % , more preferably 30 wt % , further preferably mercially available product may be used . 20 wt % , still more preferably 15 wt % , particularly pref- As the hydroxycarboxylic acid , aliphatic hydroxy acid : erably 10 wt % , most preferably 5 wt % . The content of the 65 glycolic acid , lactic acid , tartronic acid , glycolic acid , salt of acylproline can be converted from a free form of the hydroxybutyric acid ( 2 -hydroxybutyric acid , 3 -hydroxybu above- mentioned acylproline . tyric acid , y - hydroxybutyric acid ), malic acid , tartaric acid , US 9 , 782 ,336 B2 citramalic acid , citric acid , isocitric acid , leucine acid , anti- inflammatory agent , antimicrobial agent, preservative , mevalonic acid , pantoic acid , pantothenic acid , ricinoleic antioxidant ,moisturizer , thickener , viscosity modifier, ultra acid , ricinelaidic acid , cerebronic acid , quinic acid , shikimic violet absorber, adiaphoretic , pigment , dye , oxidation dye , acid and the like ; aromatic hydroxy acid : monohydroxyben pH adjuster, pearly sheen agent, wetting agent and the like zoic acid derivative ( salicylic acid , creosotic acid (homo - 5 can be mentioned . These are mere examples , and compo salicyl acid , hydroxy (methyl ) benzoic acid ) , vanillin acid , nents other than these may be contained . syringic acid etc . ) and the like; dihydroxybenzoic acid Examples of the oil solution include fatty acids such as derivative (pyrocatechuic acid , resorcylic acid , protocat- isostearic acid , undecylenoic acid , oleic acid and the like; echuic acid , gentisic acid , orsellinic acid etc . ); trihydroxy - esters such as myristyl myristate , hexyl laurate , decyl oleate , benzoic acid derivative ( gallic acid etc . ) ; phenylacetic acid 10 isopropyl myristate , hexyldecyl dimethyl octanoate , glycer derivative (mandelic acid , benzyl acid , atrolactic acid etc . ) ; ine monostearate , diethyl phthalate , ethylene glycol monos cinnamic acid , hydroxycinnamic acid derivative (melilotic tearate , cetyl octanoate , octyl oxystearate , benzoic acid alkyl acid , phloretic acid , coumaric acid , umbellic acid , caffeic e ster and the like; hydrocarbons such as liquid paraffin , acid , ferulic acid , sinapic acid ) and the like can be men - polyisobutene , petrolatum , squalane and the like ; wax such tioned . Of these, from the aspect of broad utility , specifically , 15 as lanolin , reduced lanolin , carnauba wax and the like ; glycolic acid , lactic acid , hydroxybutyric acid , malic acid , silicone oil ; fats and oils such as mink oil , cacao oil , coconut tartaric acid , citramalic acid , citric acid , isocitric acid , leu oil, palm kernel oil , camellia oil, sesame oil, castor oil, olive cine acid , mevalonic acid , pantoic acid , pantothenic acid , oil, jojoba oil and the like ; cooligomers of ethylene and ricinoleic acid , cerebronic acid , shikimic acid , salicylic acid , a - olefin , and the like . hydroxy (methyl ) benzoic acid , protocatechuic acid , orsell- 20 A particular example of the silicone oil is silicone oil inic acid , gallic acid , mandelic acid , benzyl acid , cinnamic selected from ether -modified silicone such as methylpoly acid , ferulic acid are preferable , glycolic acid , lactic acid , siloxane, polymeric methylpolysiloxane , polyoxyethylene / hydroxybutyric acid , malic acid , tartaric acid , citric acid , methylpolysiloxane copolymer , polyoxypropylene /methyl pantoic acid , pantothenic acid , shikimic acid , salicylic acid polysiloxane copolymer and poly ( oxyethylene , hydroxy (methyl ) benzoic acid , protocatechuic acid , gallic 25 oxypropylene )/ methylpolysiloxane copolymer and the like ; acid , mandelic acid , cinnamic acid , ferulic acid are more cyclic silicone such as stearoxymethylpolysiloxane , stear preferable, and citric acid is particularly preferable . oxytrimethylsilane , methylhydrogen polysiloxane, decam In the composition of the present invention , the content of ethylcyclopentasiloxane, octamethylcyclotetrasiloxane, tet the hydroxycarboxylic acid is generally 0 .01 wt % - 10 wt % , rahydrotetramethylcyclotetrasiloxane , preferably 0 .05 wt % - 5 wt % . When they are within the 30 methylcyclopolysiloxane, dodecamethylcyclohexasiloxane aforementioned ranges , a composition containing ( A ) and and the like ; amino -modified silicone such as methylphe ( B ) which is a transparent solution free of precipitation can nylpolysiloxane, trimethylsiloxysilicate , aminoethylamino be provided . When the amount exceeds 10 wt % , stimulation propylsiloxane /dimethylsiloxane copolymer and the like , may be felt . silanol -modified polysiloxane , alkoxy -modified polysilox Particularly , from the aspect of solubility of the precipi- 35 ane , fatty acid -modified polysiloxane , fluorine -modified tates produced in the composition containing (A ) and ( B ), a polysiloxane , epoxy -modified polysiloxane , alkoxy -modi weight ratio of ( B ) to (C ) [( B ) (C ) ] is generally less than 1, fied polysiloxane perfluoropolyether, polyvinyl acetate dim preferably not more than 0 . 98 , more preferably not more ethyl polysiloxane , and mixtures thereof. than 0 . 90 . When they are within these ranges of the numeri - While the chelating agent is not particularly limited , cal values, a transparent solution can be provided without 40 preferable examples thereof include a chelating agent producing precipitates . While the lower limit is not particu - selected from triethylenetetramine , 2 - thenoyltrifluoroac larly set, it is not less than 0 .01 , preferably not less than 0 .05 . etone , thioglycolic acid , tartaric acid , succinic acid , 8 - qui The production method of the composition of the present nolinol, pyridine - 2 , 6 -dicarboxylic acid , pyridine, 1, 10 invention is not particularly limited except that the ( B ) / ( C ) phenanthroline , lactic acid , 8 -hydroxyquinoline - 5 - sulfonic ratio is adjusted when ( C ) is added , and the below -men - 45 acid , glycine , 2 , 2 '- pyridylethylenediamine, aurintricarbox tioned additives are added as appropriate , wherein known ylic acid , xylenol orange , 5 - sulfosalicylic acid , salicylic steps may be combined appropriately . acid , pyrocatechol- 3 , 5 - disulfonate , 4 , 5 - dihydroxybenzene Cosmetics containing the composition of the present 1 , 3 - disulfonic acid , 1 , 2 - diaminocyclohexane - N , N , N ', NP - tet invention are also encompassed in the present invention . raacetic acid , citric acid , oxalate , nitrilotriacetic acid , ethyl Examples of the cosmetics ( cosmetic ) include skin cosmet- 50 enediamine - N , N , N ', N '- tetraacetic acid (EDTA ) , ics such as facial cleanser , skin lotion , milky lotion , cream , diethylenetriamine pentaacetic acid , acetylacetone and a salt gel, serum , mask, soap , body shampoo , face powder , foun - thereof , and mixtures thereof and the like. dation , lip rouge , blush , eyeliner , mascara , eye shadow , Examples of the surfactant include anionic surfactants eyebrow pencil and the like, and hair cosmetics such as such as N - long chain acylamino acid salt ( N - long chain acyl shampoo , rinse, conditioner, hair styling agent, hair treat - 55 acidic amino acid salt , N - long chain acyl neutral amino acid ment and the like . While any cosmetics can be provided , salt and the like ) , N - long chain fatty acid acyl- N -methyl skin cosmetics requiring moisturizing and hair cosmetics are taurate , alkyl sulfate and an alkylene oxide adduct thereof, preferable , and specifically , facial cleanser , skin lotion , fatty acid amide ether sulfate , metal salt and weak base salt milky lotion , cream , gel , serum , body shampoo and sham - of fatty acid , sulfosuccinate surfactant, alkylphosphate and poo are more preferable . 60 an alkylene oxide adduct thereof, alkyl ether carboxylic acid Cosmetics may contain components thatmay be generally and the like ; non - ionic surfactants such as ether - type sur added to cosmetics as long as the effects of the present factant ( glycerine ether and an alkylene oxide adduct thereof invention are not inhibited . Specifically , oil solution , chelat and the like ) , ether ester - type surfactant (an alkylene oxide ing agent, surfactant, powder ( organic and inorganic pow - adduct of glycerine ester, an alkylene oxide adduct of ders) , amino acids, polyamino acid and a salt thereof, sugar 65 sorbitan ester and the like ), ester -type surfactant ( polyoxy alcohol and alkylene oxide adduct thereof, lower alcohol, alkylene fatty acid ester, glycerine ester, fatty acid polyglyc animal and plant extracts , nucleic acid , vitamin , enzyme, erine ester, sorbitan ester , sucrose fatty acid ester and the US 9 , 782 ,336 B2 10 like ), alkylglucosides, hydrogenated castor oil pyroglutamic in the aforementioned form of a composition or cosmetic , to acid diester and an ethylene oxide adduct thereof, nitrogen - the skin etc . of a subject in need thereof. For example , it containing surfactants ( fatty acid alkanolamide and the like) ; includes application of a form of cream onto the skin , gel cationic surfactants such as quaternary ammonium salt and the like or spraying a liquid preparation to the skin and (alkylammonium chloride , dialkylammonium chloride and 5 the like . Generally , the “ effective amount” varies depending the like ) , aromatic quaternary ammonium salt (benzalko on the age , sex , symptom , application site of the subject , nium salt and the like ), fatty acid acyl arginine ester and the like; amphoteric surfactant such as betaine - type surfactant dosage form of composition and the like , and an amount of ( carboxybetaine and the like ) , aminocarboxylic acid - type the aforementioned composition and the like to be applied surfactant , imidazoline - type surfactant and the like , and the 10 according" to the symptoms can be mentioned . like . A method of decreasing the odor of ( A ) , which includes Examples of the powder include resin powder such as a step of placing (B ) in coexistence , is also encompassed in nylon beads , silicone beads and the like , nylon powder , the present invention . metal fatty acid soap , yellow iron oxide , red iron oxide, A method of suppressing production of an insoluble solid black iron oxide. chromium oxide . cobalt oxide carbon 15 in the composition containing ( A ) and ( B ) , which includes black , ultramarine , iron blue , zinc oxide, titanium oxide , a step of placing ( C ) in coexistence , is also encompassed in zirconium oxide , silicon oxide , aluminum oxide . cerium the present invention . According to the method of the oxide, titanated mica , boron nitride , barium sulfate , calcium present invention , a simple coexistence of ( C ) can suppress carbonate , magnesium carbonate , aluminum silicate , mag - production of an insoluble solid , make the composition nesium silicate , silicon carbide, dye , lake , sericite , mica , 20 transparent, and prepare a composition optimal for cosmet talc, kaolin , plate -shaped barium sulfate , butterfly -shaped ics and the like . The definition , amount etc . of each are as barium sulfate , fine particles of titanium oxide , fine particles described above . of zinc oxide, fine particles of iron oxide, acyl amino acid A method of moisturizing skin , comprising applying, to such as acyl lysine , acylglutamic acid , acylarginine , acyl- the skin , an effective amount of the above -mentioned com glycine and the like and the like . Furthermore , surface 25 position containing ( A ) and ( B ) for moisturizing the skin is treatment such as silicone treatment, fluorine compound also encompassed in the present invention . treatment, silane coupling agent treatment, silane treatment- In addition , a beauty treatment method for non - therapeu organic titanate treatment, acylated lysine treatment, fatty tic skin care or skin makeup , which includes applying the acid treatment, metallic soap treatment, oil solution treat above -mentioned composition containing ( A ) and (B ) to the ment, amino acid treatment and the like may be applied . 30 Examples of the amino acid include glycine, alanine , skin is also encompassed in the present invention . The serine, threonine, arginine, glutamic acid , aspartic acid , definition etc . of the composition follow those described isoleucine , leucine , valine and the like . above . Examples of the polyamino acid and a salt thereof include polyglutamic acid , polyaspartic acid and the like. 35 EXAMPLES Examples of the sugar alcohol and alkylene oxide adduct thereof include mannitol, sorbitol and the like. The present invention is explained in more detail in the Examples of the lower alcohol include ethanol, propanolo following by referring to Examples. However , the present and the like . Examples of other additive include animal and invention is not limited by the following Examples . plant extracts such as lecithin , gelatin and the like ; nucleic 40 acids such as disodium 5 '- inosinate , disodium 5 '- uridylate < Synthetic Example 1> Synthesis of and the like; vitamins such as vitamin A , C etc . , a derivative Decanoylproline thereof and the like ; enzymes such as papain , protease and the like ; anti - inflammatory agents such as potassium gly Proline (manufactured by Ajinomoto Co ., Inc .) (34 . 54 g ) cyrrhizate and the like ; antimicrobial agents such as tri- 45 was dissolved in 100 g of water , and decanoyl chloride closan , trichloro calban , octopirox , zinc pyrithione and the manufactured by Tokyo Chemical Industry Co. , Ltd .) like ; preservatives such as methylparaben , butylparaben and (52 .01 g ) and 25 % aqueous sodium hydroxide solution were the like ; antioxidants such as dibutylhydroxytoluene and the added while adjusting the mixture to pH 12 . The mixture like ; moisturizers such as isopentyldiol, luvitol and the like ; was neutralized with 75 % sulfuric acid , and the aqueous thickeners such as hydroxypropyl starch phosphoric acid 50 layer was removed . Furthermore , water and ethyl acetate and the like ; viscosity modifiers such as polyoxyalkylene were added and the aqueous layer was removed . Ethyl sorbitan ester , polyoxyethylene glycol distearate , ethanol acetate was evaporated under reduced pressure to give and the like ; ultraviolet absorbers such as octyl- methoxy - decanoylproline (68 . 12 g ) . cinnamate and the like ; adiaphoretics such as aluminum oxide and the like ; pigments such as titanium dioxide and the 55 < Synthetic Example 2 > Synthesis of Decanoyl like; dyes such as tar dye , inorganic dye , dye derived from Prolinate Sodium Salt natural- base and the like; fragrances , pH adjusters such as citric acid , trisodium citrate , sodium carbonate , phosphoric Decanoylproline obtained in Synthetic Example 1 was acid and the like ; pearly sheen agents such as ethylene glycol suspended in a suitable amount of water and neutralized distearate and the like ; humectants such as propylene glycol 60 with sodium hydroxide up to pH 7 , and concentration - dried and the like ; and the like . to give decanoyl prolinate sodium salt . A moisturizing method or inflammation suppressive method including applying a composition containing ( A ) , < Synthetic Example 3 > Synthesis of Lauroylproline ( B ) and ( C ) to a subject is also encompassed in the present invention . The definition of each is as described above . 65 Using proline and lauroyl chloride (manufactured by The application here means topically applying acylproline Tokyo Chemical Industry Co ., Ltd . ) and in the same manner or a salt thereof singly or effective amounts of ( A ) and ( B ) as in Synthetic Example 1 , lauroylproline was obtained . US 9 , 782 ,336 B2 11 12 < Synthetic Example 4 > Synthesis of Lauroylproline O Not less than 6 test subjects admitted the moist feeling . Sodium Salt A 4 or 5 test subjects admitted the moist feeling . x Not more than 3 subjects admitted the moist feeling . Each amount in Examples is shown in wt % . In the Table , Using lauroylproline obtained in Synthetic Example 3 and indication of % is omitted , and used only the numerical in the same manner as in Synthetic Example 2 , lauroylpro value showing the amount. In the Table , “ _ ” shows that line sodium salt was obtained . evaluation was not performed . TABLE 1 Preparation Example 1 2 3 4 5 6 7 8 9 10 Component decanoylproline 0 .20 0 .50 0 .20 0 .50 0 . 20 0 .50 0 .40 0 . 20 0 0 .50 A Na Component Zinc PCA 0. 20 0. 20 0. 50 0. 50 1. 00 1. 00 0 .50 1. 00 1. 00 0 Component citric acid 0. 60 0. 60 0. 60 0 .60 0 .60 0. 60 0. 50 0 0 0. 60 ? water balance balance balance balance balance balance balance balance balance balance total 100 100 100 100 100 100 100 100 100 100 evaluationevaluation 1 : 0 0 0 0 X X X X 0 – clarity and color of solution evaluation 2 : peculiar odor reduction evaluation 3 : moist feeling B / C ratiostio 0. 33 0. 33 0 .83 0. 83 1. 67 1. 67 1. 00

Decanoylproline Na , Zinc PCA , and citric acid were 30 As is clear from Table 1, the combined use of Zinc PCA added to water at a concentration described in Table 1 , and and decanoylproline Na decreased the peculiar odor and a pH was adjusted to 5. 7 with hydrochloric acid or aqueous composition superior in the moist feeling was obtained . It sodium hydroxide solution . The composition for test was was found that an insoluble solid in the composition is completely tightly sealed in a 30 mL glass bottle , stored at 35 dissolved when the B / C ratio is less than 1 . 45° C . for 4 months, cooled to room temperature and the Where a numerical limit or range is stated herein , the following evaluation was performed . endpoints are included . Also , all values and subranges < Formulation Evaluation 1> Clarity and Color of Solution withinwit a numerical limit or range are specifically included as As mentioned above, clarity and color of the prepared if explicitly written out. composition were confirmed , and evaluated according to the 40 As used herein the words “ a ” and “ an ” and the like carry following criteria . the meaning of “ one or more .” O transparent aqueous solution was obtained . Obviously , numerous modifications and variations of the x precipitation was confirmed . present invention are possible in light of the above teach < Formulation Evaluation 2 > Peculiar Odor 45 ings . It is therefore to be understood that, within the scope The peculiar odor of the composition of the present of the appended claims, the invention may be practiced invention was tested by 8 healthy men and women . Whether otherwise than as specifically described herein . the peculiar odor of the composition prepared as mentioned All patents and other references mentioned above are above caught his /her attention was searched , and evaluated incorporated in full herein by this reference , the same as if according to the following criteria . ' set forth at length . O Not less than 6 test subjects denied concern about the peculiar odor. The invention claimed is : A4 or 5 test subjects denied concern about the peculiar odor. 1. A composition , comprising : x Not more than 3 test subjects denied concern about the 55 (A ) at least one acylproline represented by formula ( 1) or peculiar odor. a salt thereof The test subjects were made to recognize the odor of decanoylproline Na in advance as the peculiar odor of component A . < Formulation Evaluation 3 > Moist Feeling 60 (1 ) The moist feeling of the composition of the present invention was tested by 8 healthy men and women . The COOH composition prepared as mentioned above was applied to the inside of a 8x2 cm skin area of the inner surface of the 65 0 R1 forearm , and whether a moist feeling was sensed was searched , and evaluated according to the following criteria . US 9 , 782 ,336 B2 13 14 wherein R ? _ CO — is an acyl group derived from a satu wherein R ' - CO — is an acyl group derived from a satu rated or unsaturated fatty acid having 3 to 23 carbon atoms; rated or unsaturated fatty acid having 3 to 23 carbon atoms , and said method comprising combining in said composition : (B ) a zinc salt of pyrrolidone carboxylate . ( B ) a zinc salt of pyrrolidone carboxylate . 2 . The composition according to claim 1 , wherein 5 13 . The method according to claim 12 . wherein R ? CO — is an acyl group derived from a saturated or unsaturated fatty acid having 6 to 14 carbon atoms. R ! _ C0 — is an acyl group derived from a saturated or 3 . The composition according to claim 1 . wherein ( A ) said unsaturated fatty acid having 6 to 14 carbon atoms. acylproline represented by formula ( 1 ) is decanoylproline . 14 . The method according to claim 12 , wherein ( A ) said 4 . The composition according to claim 1 , wherein said salt acylproline represented by formula ( 1 ) is decanoylproline . of said acylproline representedi by formulaformula (( 1 ) is a sodium 10 15 . The method according to claim 12 , wherein said salt salt . of said acylproline represented by formula ( 1 ) is a sodium 5 . The composition according to claim 1 , wherein ( A ) said salt. at least one acylproline represented by formula ( 1 ) or a salt 16 . A method of suppressing production of an insoluble thereof is present in an amount of 0 .001 wt % to 40 wt % solid in a composition comprising : relative to the total weight of said composition . ( A ) at least one acylproline represented by formula ( 1 ) or 6 . The composition according to claim 1 , wherein ( B ) said a salt thereof zinc salt of pyrrolidone carboxylate is present in an amount of 0 .01 wt % to 10 wt % relative to the total weight of said composition . 7 . The composition according to claim 1 , further com - 20 prising: ( C ) at least one hydroxycarboxylic acid . COOH 8 . The composition according to claim 7 , wherein ( C ) said at least one hydroxycarboxylic acid is citric acid . 9 . The composition according to claim 7 , wherein a 75 0 R1 weight ratio of ( B ) to ( C ) [ ( B ) / ( C ) ] is less than 1 . 10 . The composition according to claim 1 , which is a wherein R1 _ CO is an acyl group derived from a satu moisturizer. rated or unsaturated fatty acid having 3 to 23 carbon atoms; 11 . A cosmetic , comprising a composition according to and claim 1 . 30 ( B ) a zinc salt of pyrrolidone carboxylate , said method 12 . A method of decreasing an odor of a compositions comprising combining in said composition : comprising : ( C ) at least one hydroxycarboxylic acid . ( A ) an acylproline represented by formula ( 1) or a salt 17 . The method according to claim 16 , wherein thereof R - CO — is an acyl group derived from a saturated or 35 unsaturated fatty acid having 6 to 14 carbon atoms. 18 . The method according to claim 16 , wherein ( A ) said acylproline represented by formula ( 1 ) is decanoylproline . 19 . The method according to claim 16 , wherein said salt COOH of said acylproline represented by formula ( 1 ) is a sodium 40 salt . 20 . The method according to claim 16 , wherein (C ) said 0 R1P / at least one hydroxycarboxylic acid is citric acid . * * * *