WO2008035563A1

WO2008035563A1 - Hair cosmetic

Info

Publication number: WO2008035563A1
Application number: PCT/JP2007/067169
Authority: WO
Inventors: Katsunori Ohnuma; Motohiro Kageyama
Original assignee: Lion Corporation
Priority date: 2006-09-21
Filing date: 2007-09-04
Publication date: 2008-03-27
Also published as: JPWO2008035563A1; CN101500536B; CN101500536A

Abstract

By using a combination of (A) a chitosan compound with (B) a polyurethane resin, it is possible to provide a hair cosmetic which can impart tension and elasticity to thin and soft hair having been damaged and weakened by a chemical treatment such as coloring or perming, ensures flexible finishing with smooth finger-pass and no coarse feeling, regulate stickiness and roughness and thus achieve a favorable hair texture.

Description

Specification

Hair cosmetics

Technical field

[0001] The present invention relates to a hair cosmetic, and more particularly, to a hair cosmetic that gives firmness and firmness to damaged, thin, soft hair, suppresses stickiness, prevents wrinkling, and finishes it smoothly and smoothly according to the finger. is there.

Background art

[0002] Usually, hair is damaged by daily hair care and hair makeup behavior. It is known that in daily hair washing behavior, the sebum and hair constituent proteins of the hair are eluted by the surfactant as the main ingredient, and the cuticle is peeled off by repeated daily blows. ing. In addition, the frequency of cold perms, hair coloring, hair bleaching, etc. has increased due to the increased awareness of fashion, and chemical treatment with chemicals has promoted the dissolution of structural proteins in hair and structural changes, which has spurred damage.

[0003] In addition, hair that has been born with a narrow diameter or that has become thin and soft as it ages has a problem that it is difficult to style! As shown above, if the hair is damaged as described above, the styling property is further deteriorated, and the squeaky feeling tends to deteriorate remarkably. I got it.

[0004] For such a problem, hair cosmetics containing a film-forming resin such as polyacrylic acid or polybule polymer have been proposed for the purpose of giving firmness to thin hair and facilitating styling. . However, while these hair cosmetics give a firmness and firmness, they appear stiff and squeezed and the feel is reduced, and the film formed on the hair also has physical strength and strength. There was a problem that the firmness of the skin decreased with time because it was easily disintegrated by moisture.

[0005] Therefore, conventionally, there has been a strong demand for imparting a sense of volume to hair that does not impair the natural feel of hair that is inherent to the hair. Against this background, several methods have been proposed. For example, collagen derivatives and keratin induction There have been proposed methods for penetrating and replenishing hair with components similar to body hair (Patent Document 1: Japanese Patent Laid-Open No. 60-243010, Patent Document 2: Japanese Patent Laid-Open No. 2-53712). In addition, a method of coating the hair surface with a natural polymer compound has also been proposed (Patent Document 3: Japanese Patent Laid-Open No. 59-65008, Patent Document 4: Japanese Patent Laid-Open No. 62-36308, Patent Document 5: Special). JP-A-62-29404, Patent Document 6: JP-A-62-221615, Patent Document 7: JP-A-1 009911 1, Patent Document 8: JP-A-4308525, Patent Document 9: JP-A-1 24971 No. 1).

[0006] However, in these methods, there is a case where the touch surface is improved. The thin and soft hair weakened by the force damage gives a firmness and a squeaky styling, and is caused by damage. In terms of the effect of improving the feel deterioration, it was a force that was not really satisfactory. That is, hair that is damaged by thin and soft hair quality gives a firmness that is sufficiently satisfactory in styling properties, suppresses stickiness and stiffness, and has an effect of improving the feel of damaged hair Cosmetics were desired.

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 60-243010

Patent Document 2: JP-A-2-53712

Patent Document 3: Japanese Patent Laid-Open No. 59-65008

Patent Document 4: JP-A 62-36308

Patent Document 5: Japanese Patent Publication No. 62 29404

Patent Document 6: Japanese Patent Laid-Open No. 62-221615

Patent Document 7: Japanese Patent Laid-Open No. 1009911

Patent Document 8: Japanese Patent Laid-Open No. 4 308525

Patent Document 9: Japanese Patent Laid-Open No. 1 24971 1

Patent Document 10: Japanese Unexamined Patent Publication No. 2000-290143

Disclosure of the invention

Problems to be solved by the invention

[0008] The present invention is damaged and weakened by chemical treatments such as coloring and perm, and gives firmness and firmness to thin and soft hair. The purpose of the present invention is to provide a hair cosmetic that can suppress hair and give a good hair feel And

Means for solving the problem

[0009] The inventors of the present invention used chitosans and polyurethane resin in combination to form a strong and uniform film of chitosans, and the polyurethane resin gives flexibility and elasticity. It has been found that it can give firmness and firmness without squeezing through the fingers, suppress stickiness, and provide a good styling feel.

[0010] Therefore, the present invention

[1]. A hair cosmetic containing (A) chitosans and (B) a polyurethane resin,

[2]. The hair cosmetic composition according to [1], wherein the component (A) is chitosan, partially deacetylated chitin, or a water-soluble chitosan derivative having a hydrophilic group introduced into a salt thereof.

[3]. The hair cosmetic composition according to [1] or [2], wherein the component (B) is a polyurethane resin having a cationic group,

[4] Further, (C) the hair cosmetic composition according to [1], [2] or [3], which contains one or more selected from polyphenols, polyphenol salts, and polyphenol derivatives,

[5]. The hair cosmetic composition according to [4], wherein the component (C) is a gallic acid derivative.

The invention's effect

[0011] According to the present invention, there is provided a hair cosmetic composition that gives firmness and firmness to damaged thin and soft hair, and is free of squeaking and squeezing, and has a strong hair and imparts a good hair feel. can do.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] The hair cosmetic composition of the present invention is a hair cosmetic composition containing (A) chitosans and (B) a polyurethane resin.

(A) Chitosans

The chitosans of the present invention include (1) chitosan, partially deacetylated chitin and salts thereof, (2) a water-soluble oligomer obtained by decomposing (1) above, (3) hydrophilic to (1) above And water-soluble chitosan derivatives into which a group has been introduced. These may be used alone or in appropriate combination of two or more. [0013] (1) Chitosan and partially deacetylated chitin are chitin (/ 3 1, 4 poly N acetyl darcosamine), the main structural polysaccharide of arthropods, mollusks, anal animals, and fungi. Obtained by deacetylation. Chitosan is a completely deacetylated product of chitin (/ 3 1, 4 polydarcosamine), and a partially deacetylated chitin having a degree of deacetylation of about 45 to 55% is preferably used.

[0014] Chitosan or partially deacetylated chitin salts include inorganic salts such as hydrochlorides and nitrates, acetates, lactates, glycolates, pyrrolidone carboxylates, kenates, succinates, malic acids. Organic acid salts such as salts can be mentioned.

[0015] (2) Water-soluble oligomer obtained by decomposing the above (1)

(3) The water-soluble chitosan derivatives having a hydrophilic group introduced in (1) above are hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxyethyl 'hydroxypropyl chitosan, (poly) oxyalkylene chitosan, carboxymethyl chitosan. , Carboxyethyl chitosan, succinylated carboxymethyl chitosan, phosphorylated chitosan, sulfated chitosan, quaternized chitosan, N-glycidyltrimethylammonium chitosan, dihydropropyl chitosan, N-2-hydroxypropylsulfonic acid chitosan, etc. It is done. Furthermore, a copolymer of chitosan and a water-soluble monomer, such as a chitosan-methacrylic acid copolymer or a chitosan bur copolymer, may be mentioned.

[0016] The (2) water-soluble oligomer and (3) the water-soluble chitosan derivative introduced with a hydrophilic group can be obtained by the methods described in, for example, DE3541305 and JP-A-62-2221615. In other words, chitosan hydrolyzes the N-acetyl group of chitin and is itself water-insoluble. Therefore, it can be converted into a water-soluble chitosan derivative by controlling the molecular weight or by inducing chitosan into a water-soluble compound. .

[0017] The chitosans are preferably water-soluble oligomers, hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxyethyl hydroxypropyl chitosan, quaternized chitosan, and salts thereof. Of these, hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxychechil. Hydroxypropyl chitosan, or salts thereof, and a thin, uniform film with high flexibility on the hair surface can be formed even on thin hair. This is particularly preferable because the whole can be given a sense of volume without becoming heavy. [0018] The amount of component (A) is not particularly limited, but is usually 0.00;! To 5 mass%, preferably 0.0;! To 3 mass% with respect to the total amount of the hair cosmetic. By setting this range, it is possible to obtain the desired effect.

[0019] (B) Polyurethane resin

The polyurethane resin is (1) a resin obtained by polyaddition reaction of a polyisocyanate and an active hydrogen-containing compound. These can be used alone or in combination of two or more.

[0020] (1) Polyisocyanate

Diisocyanates and trifunctional or higher polyfunctional isocyanates, such as aromatic polyisocyanates having 6 to 20 carbon atoms (except for carbon in the NCO group) 6 to 20 carbon atoms; Aliphatic polyisocyanate, C6-C15 alicyclic polyisocyanate, C8-C15 araliphatic polyisocyanate and modified products of these polyisocyanates (urethane groups, carpositimides) Group, alophanate group, burette group, uretdione group, uretoimine group, isocyanurate group, modified product containing oxazolidone group) and a mixture of two or more of these.

Specific examples of the aromatic polyisocyanate include, for example, 1,3 phenylene diisocyanate, 1,4 phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2 , 6 Tolylene diisocyanate (TDI), Crude TDI, 2, 4, 1-diphenylmethane diisocyanate (MDI), 4, 4'-diphenylmethane diisocyanate (MDI), 4, 4'-diisocyanate Anatobiphenyl, 3, 3, 1-dimethyl-4,4'-diisocyanatobiphenyl, 3,3, -dimethyl-4,4, -diisocyanatodiphenylmethane, crude MDI [crude diaminodiphenylmethane [formaldehyde and fragrance condensation products of family Amin (Anirin) or mixtures thereof; phosgene product of diamino diphenyl mixture of trifunctional or higher polyamine enyl methane and a small amount of (e.g. 5 to 20 weight ^_0/0)]; polyaryl Soshianeto], 1, 5-naphthylene diisocyanate iso shea Aneto, 4, 4 ', 4 "triphenylmethane triisostearate Xia sulfonates, m-isocyanatophenyl sulfonyl Ruisoshianeto include p- isocyanatophenyl sulfonyl iso Xia sulfonates.

[0022] Specific examples of the aliphatic polyisocyanate include, for example, ethylene diisocyanate. , Tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethine diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethinore force proate) Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2 isocyanatoethyl-2, 6 diisocyanatohexanoate.

[0023] Specific examples of the alicyclic polyisocyanate include, for example, isophorone diisocyanate.

(IPDI), dicyclohexylmethane 4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methinolecyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohex Examples include xenene 1,2-dicarboxylate, 2,5-norbornane diisocyanate, and 2,6-norbornane diisocyanate.

[0024] Specific examples of the aromatic aliphatic polyisocyanate include m-xylylene diisocyanate, p-xylylene diisocyanate, α, a, α ', α, monotetramethylxylylene diisocyanate. Can be mentioned.

[0025] Examples of the modified polyisocyanate include modified MDI (urethane modified MDI, carpositimide modified MDI, trihydrocarbyl phosphate modified MDI), urethane modified TDI, burette modified HDI, isocyanurate modified HDI, isocyanurate modified IPDI, etc. And polyisocyanate modifications and mixtures of two or more thereof.

Among these, preferred are aliphatic and alicyclic polyisocyanates, particularly HDI, IPDI, and hydrogenated MDI because they are less likely to discolor due to aging.

[0027] Active hydrogen-containing compound

The active hydrogen-containing compound includes (2) a low molecular polyfunctional active hydrogen-containing compound and (3) a high molecular polyol.

[0028] (2) The low molecular weight polyfunctional active hydrogen-containing compound includes a low molecular weight polyol.

[0029] As the low molecular weight polyfunctional active hydrogen-containing compound, OH equivalent [number average molecular weight per hydroxyl group (according to GPC measurement; the same applies hereinafter)] is less than 300 (preferably 30 to 250) 2 to 10 Or more polyols (preferably divalent to trivalent) can be used. Specific examples of (2-1) include dihydric alcohols such as aliphatic diols [linear diols (ethylene glycol, Diethylene glycol, 1,3-propanediol, 1,4 butanediol, 1,5-pentanediol, 1,6-hexanediol, etc., and branched diols (propylene glycol, neopentyl glycol, 3 methyl-1, 5 pentanediol, 2 methylol 2,4 pentanediol, 2,2 jetyl 1,3 propanediol, 1,2-butanediol, 1,3 butanediol, 2,3 butanediol, etc.), a diol having a carboxyl group A certain dimethylolpropionic acid] and a diol having a cyclic group [for example, those described in JP-B-45-1474; 1,4 bis (hydroxymethyl) cyclohexane, m-xylylene glycol, p-xylylene glycol , Divalent phenols (bisphenol A (poly) oxyalkylene ethers (alkylene group Prime number 2-4), etc.], trivalent to 10-valent or higher polyhydric alcohols such as alkane polyols (glycerin, trimethylolpropane, pentaerythritol, sonolebithonole, etc., and their intermolecular or intramolecular dehydrates [di Pentaerythritol, polyglycerin (degree of polymerization 2-8), sorbitan, etc.], saccharides and derivatives thereof (glycosides) (sucrose, methyldarcoside, etc.); and their alkylene oxides (hereinafter abbreviated as AO. Carbon number 2 10 or more] low molar adducts; and mixtures of two or more of these, preferred! / Are aliphatic diols, more preferably 1,3-butanediol. 3-methyl-1,5-pentanediol and dimethylolpropionic acid.

[0030] (3) As the polymer polyol, an OH equivalent [number average molecular weight per hydroxyl group] of 300 or more (preferably 300 to 10,000) is 2 to 4 or more (preferably 2 to 3). Can be used. (3) includes (3-1) polyester polyol, (3-2) polyether polyol, and mixtures of two or more thereof.

[0031] Examples of (3-1) polyester polyols include condensed polyester polyols (by polycondensation of polyols and polycarboxylic acids).

[0032] The polyol in (3-1) is a low molecular weight polyol [for example, one or more selected from the above-mentioned (2-1)] and a polyether polyol [for example, (3-2) described later] Can be used.

[0033] The polycarboxylic acids in (3-1) include polycarboxylic acids and ester-forming derivatives thereof. Specific examples include aliphatic polycarboxylic acids [functional group number 2-6, carbon number 3 To 30 polycarboxylic acids such as succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, hexahydrophthalic acid, etc.], aromatic polycarboxylic acids [functional group number 2-6, C8-C30 polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, trimellitic acid, pyromellitic acid, etc.]; these ester-forming derivatives [acid anhydride , Lower alkyl (1 to 4 carbon atoms) ester (dimethyl ester, jetyl ester, etc.), acid halide (acid chloride, etc.): maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.]; The mixture of 2 or more types is mentioned. Of these, aliphatic polycarboxylic acids are preferred.

[0034] (3-2) includes a compound in which AO is added to a compound having two or more active hydrogen atoms.

[0035] Examples of the compound having an active hydrogen atom include a low molecular polyol [for example, (2-1) above];

Divalent phenols [eg bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), monocyclic phenols (catechol, hydroquinone, etc.)]; amines [primary monoamines such as alkyl or alkenylamine (carbon number 1 To 20), aniline, alkanolamine (2 to 4 carbon atoms of hydroxylalkyl group)] and the like.

[0036] AO includes ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide, 1,3-butylene oxide, 1,4-butylene oxide, 2,3-butylene. Examples thereof include oxides, styrene oxides, α-olefin oxides having 5 or more carbon atoms; 10 or more carbon atoms, epichlorohydrin, and combinations of two or more thereof (block and / or random-added caro).

[0037] Of these, preferred are fatty acid diols and divalent phenols with addition of soot and soot. Specifically, the ビス · ΡΟ adduct of the above bisphenol Α (4,4'-isopropylidenediphenol) can be mentioned. In this case, the equivalent weight of (3) is from the viewpoint of hair feel, force, etc., preferably 300 to 10,000, more preferably 500 to 5,000, particularly preferably <1,000, 000.

[0038] The polyurethane resin used in the present invention may be cationic, nonionic, anionic or amphoteric, and commercially available polyurethane resins include Rubyset PUR (manufactured by BASF): DynamX (Japan NSC) ), Heralol UC-4 (manufactured by Sanyo Chemical Co., Ltd.) The power to raise S. As a particularly preferable form of the polyurethane resin, a polyurethane resin having a cationic group is preferable from the viewpoint of improving the feel to damaged hair. As the cationic group, it is preferable to neutralize a polyurethane resin having a tertiary amine group with an acid or to contain a quaternary ammonium base. Furthermore, from the viewpoint of formulation, the cationic polyurethane resin is preferably blended in the form of an emulsion dispersed in water. Examples of the polyurethane resin (B) of the present invention include HEAROL UC-4 (trade name: manufactured by Sanyo Kasei Co., Ltd.), which is a cationic polyurethane resin emulsion. The components of the polyurethane resin are shown below.

Noreviset P. U. R.: IPDI, dimethylolpropionic acid, isophthalic acid, adipic acid, 2-methylolene 2, 4-pentanediol (hexylene glycol), neopentino glycol

DynamX: IPDI, dimethylolpropionic acid, 4,4 'isopropylidenediphenol ΕΟ · ΡΟ adduct

Hairol UC—4: IPDI, Butylene glycol, Alkylmethyljetanol ammonium methylsulfate (cationic group)

[0039] The number average molecular weight of the polyurethane resin is usually 10,000 or more, preferably 15,000-1, 000,000. GPC analysis was used as a method for measuring the number average molecular weight.

[0040] (B) The amount of the component is not particularly limited, 0.1 to ordinary hair cosmetic total amount from 01 to 5 weight ^_0/0, preferably from 0.05 to 3 mass ^_0/0. Within this range, a firmer feeling can be obtained, and when it exceeds 5% by mass, it may cause a stiff feeling.

[0041] For the purpose of repairing damage, the hair cosmetic composition of the present invention preferably contains one or more selected from (C) polyphenols, polyphenol salts, and polyphenol derivatives. Polyphenols include, for example, gallotannic acid, kebulinic acid, hamamelitannin, azeltannin, gallic acid, baronic acid, kebulic acid, hexahydroxydiphenic acid, ellagic acid, caffeic acid, p-tamaric acid, ferulic acid, sinapinic acid And chlorogenic acid.

[0042] Examples of the polyphenol salt include the sodium salt, potassium salt, ammonium salt, and triethanolamine salt of the above polyphenol. Polyphenol derivatives include erosion Preference is given to, for example, m-digallic acid, dehydrodigallic acid, gallic acid methyl ester 3-dalcoside, gallic acid methyl ester 4 dalcoside, gallic acid propyl ester 3-dalcoside, gallic acid methyl ester 3-maltoside, Gallic acid 3-Dalcoside, Gallic acid 3-Maltoside, Octyl gallate 3-Maltoside, Gallic acid 3-Daluronide, Galate thulonide gallate, Methyl gallate 3,5-Didarcoside, Gallic acid 3, 4-Zydarcoside, Gallic acid Acid 3,5--Didalcoside, 4-galactosamino gallic acid, 4 darcosamino gallic acid, 3-galactosamino gallic acid, 3--darcosamino gallic acid, 3-- (N-acetylethyl latatosamino) gallic acid, 3-- (N Cetyldarcosamino) gallate, 3- (N-acetylcylcosamino) gallate Trium, 3- (N-acetyltilcosamino) gallic acid methyl ester, 3,5-digalactosamino gallic acid, 3,5-didarcosamino gallic acid, 3,5-di (N-acetylgallatatosamino) gallic acid Acid, 3,5-Di (N-acetylethylcolcamino) gallic acid, 4-glyceryl gallic acid, 4 (diglyceryl) gallic acid, 4 (decaglyceryl) gallic acid, sodium 4-glyceryl gallate, methyl 4-glyceryl gallate Examples thereof include gallic acid glycosides such as esters, 3,4-diglyceryl gallic acid, 3,5-diglyceryl gallic acid, and 3,4,5-triglyceryl gallic acid. Among these, gallic acid disaccharides such as gallic acid methyl ester 3,5-didarcoside, gallic acid 3,4-didarcoside, gallic acid 3,5-didarcoside, etc. due to the supply of raw gallic acid and ease of production, And 3— (N-acetylethylgalcosamino) gallic acid, 3 -— (N-acetylyldarcosamino) gallic acid, 3 -— (N-acetylyldarcosamino) sodium gallate, 3 -— (N-acetildarco Samino) gallic acid having N-acetyl dalcosamino group such as methyl gallate, 4-glyceryl gallic acid, 4-glyceryl sodium gallate, 3, 4-diglyceryl gallic acid, 3, 5-diglyceryl gallic acid 3, 4, 5-triglyceryl gallic acid having a glyceryl group such as gallic acid is preferable, and gallic acid 3, 5-didarcoside, 3- (N SE Rudarukosamino) gallic acid, 4 Guriseriru gallate, 3, 4-diglyceryl gallate, 3, 4, 5 triglyceryl gallic acid is more preferred.

4 A gallic acid derivative containing a sugar residue having an amino group or an amide group such as dalcosamino gallic acid has, for example, a gallic acid ester having a corresponding amino group or amide group. It can be obtained with the force S obtained by hydrolyzing the alkyl group after reacting with the o-alkylated sugar.

[0044] A gallic acid derivative containing a glyceryl group, such as 4-glyceryl gallic acid, can be obtained by dihydroxylation of a corresponding olefin compound. Examples of the dihydroxylation method include a method in which olefin is directly dihydroxylated with osmium oxide, a method in which an epoxy compound is used as an intermediate using a peroxide of an organic acid, and the ring is opened. For example, when methyl gallate-4O aryl ether is reacted with an organic acid such as formic acid or peracetic acid, olefins are oxidized and then reacted with the organic acid to form a mixture of esteno-dihydroxyl compounds. When these compounds are subjected to hydrolysis without isolation or purification, the target compound can be obtained. An olefin compound as an intermediate can be obtained by reacting a gallic acid ester with allyl bromide in the presence of a base. In addition, as a method of hydrolysis of gallic acid ester, there are a method of treating with basic water and a method of treating with acidic water.

[0045] The amount of component (C) is not particularly limited, but is usually 0.00;! To 5% by mass, more preferably 0.0;! To 3% by mass, based on the total amount of hair cosmetics. . Within this range, more damage repair effect can be obtained, and in the range exceeding 5% by mass, it may be difficult to control the coloring specific to polyphenols.

[0046] In addition to the above-described components, the hair cosmetic of the present invention includes one or more kinds of various components generally used in cosmetics, quasi-drugs, pharmaceuticals, etc., as long as the effects of the present invention are not impaired. Or two or more kinds can be combined in an appropriate combination. Examples of such components include ayuionic surfactants, cationic surfactants, amphoteric surfactants, noionic surfactants, fats and oils, polymer compounds, amino acids, polyhydric alcohols and the like.

[0047] Examples of the anionic surfactant include sodium α-olefin sulfonate, potassium a-olefin sulfonate, sodium stearate, sodium palmitate, sodium laurate, sodium coconut oil fatty acid, stearin. Arginine acid, Arginine normitate, Argiyun laurate, Argyyun coconut oil fatty acid, Sodium lauryl sulfate, Polyoxyethylene alkyl ether sodium sulfate, Polyoxyethylene alkyl ether Ammonium sulfate, polyoxyethylene alkyl ether sodium phosphate, polyoxyethylene polyoxypropylene alkyl ether sodium phosphate, sodium lauroyl sarcosine, coconut oil fatty acid methyl-β-alanine sodium, dioctyl sulfosuccinate sodium, Examples thereof include disodium polyoxyethylene alkyl sulfosuccinate, sodium polystyrene sulfonate, disodium sulfosuccinate, Ν-lauroinole Ν methylolene β-arayun sodium, monolauryl amide sodium malate, and the like.

[0048] Examples of cationic surfactants include stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dioleyl dimethyl ammonium chloride. , Didecyldimethyl ammonium chloride, amide butyl dandanine acetate laurate, amido butyl dandanidine acetate myristate amide butyl dandanidine acetate, distearyl dimethyl ammonium sulfate, Ν coconut oil fatty acid L arginine cetyl DL pyrrolidone carboxylic acid Examples include salts.

[0049] Amphoteric surfactants include: 2 alkyl カルボキシ carboxyethyl Ν hydroxy ethyl imidazolium betaine, coconut oil fatty acid amide propyl betaine, lauric acid amide propyl betaine, lauryl dimethylamino acetate betaine, hydrogenated Examples include soybean phospholipid, alkyldiaminoethylglycine hydrochloride, Ν- [3 alkyloxy-2-hydroxypropyl] -L-arginine hydrochloride, sodium laurylaminopropionate, and the like.

[0050] Nonionic surfactants include sucrose fatty acid ester, sorbitan fatty acid ester, sorbitol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene phytosterol ether, polyoxy Ethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene phytosterol ether, hydrogenated castor oil, hydrogenated castor oil fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene polyoxypropylene hydrogenated castor oil, polyoxyethylene hydrogenated castor Examples include oil fatty acid esters and polyoxyethylene polyoxypropylene hardened castor oil fatty acid esters.

[0051] Oils and fats include isopropyl myristate, isopropyl palmitate, ethyl oleate, octyldodecyl neopentanoate, butyloctyl salicylate, and styrene stearate. Lesteryl, polyoxyethylene, liquid paraffin, liquid isoparaffin, squalene, squall, castor oil, jojoba oil, hazelnut oil, sweet almond oil, grape seed oil, southern power oil, safflower oil, olive oil, meadow home oil, Examples include rosehip oil and avogado oil.

[0052] Examples of the polymer compound include hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cationized cellulose, polybutylpyrrolidone, polyvinyl alcohol, acrylic acid / methacrylic acid copolymer, carboxybule polymer, and the like. .

[0053] Examples of amino acids include glycine, ornithine, methionine, alanine, arginine, glutamine, cysteine, cysteic acid, cystine, leucine, isoleucine, aspartic acid, lysine, and fualarayun.

[0054] Examples of the polyhydric alcohol include propylene glycol, dipropylene glycol, glycerin, butylene glycol and the like.

[0055] In addition, preservatives such as paraoxybenzoate and noroxybenzoate, sequestering agents such as edetate, pyrophosphate, kenate, glycolic acid and tartaric acid, liquefied petroleum gas, dimethyl ether, nitrogen, Gases such as carbon dioxide, antioxidants such as dibutylhydroxytoluene, butylhydroxyanisole, erythorbic acid, dilauryl thiodipropionate, sodium sulfate, sodium sulfite, tocopherol, and ascorbyl dipalmitate, p-aminobenzoate Ultraviolet absorbers such as acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, oxybenzone, dioxybenzone, dihydroxydimethoxybenzophenone, pH adjusters, vitamins, dyes, 1 menthol and its derivatives, etc. Add a sticky agent, water, solvent (ethanol etc.) That power S.

[0056] Further, the fragrance composition used in the hair cosmetic composition of the present invention is a hair cosmetic composition when blended with a fragrance composition according to the fragrance compositions A to E described in JP-A-2003-095895. It is preferable that the fragrance composition is blended so that the amount of the fragrance composition is 0.00001 to 10% by mass, and more preferably 0.000;! To 5% by mass. Moreover, dibutylhydroxytoluene (BHT), which is an antioxidant, can be blended with these fragrance compositions A to E to enhance the stability of the fragrance. [0057] The hair cosmetic composition of the present invention is obtained by mixing the above-described components with water and / or ethanol (the remainder is blended so that the total amount of the hair cosmetic composition is 100% by mass) and obtained based on a conventional method. Is possible. The dosage form is not particularly limited, and can be used as various dosage forms such as a solubilizing system, an emulsifying system, a dispersing system, and an oil-water two-layer system. For example, a liquid, an aerosol, a tick, a genere, a cream It can be used in dosage forms such as lotions.

[0058] The hair cosmetic of the present invention is used as a hair cosmetic for hair milk, hair care jewel, hair foam, hair cream, hair tonic, hair liquid, hair lotion, hair spray, shampoo, rinse, conditioner, treatment, etc. it can. Hair cosmetics, such as shampoos, rinses, conditioners, treatments, etc., are used after washing, and hair amino lects, hair care jewels, hair foams, hair creams, hair tonics, hair liquids, hair lotions, hair Examples include sprays and leave-on type hair treatments that are used without being washed away after application (leave-on type). In the present invention, it is suitable for those used without being washed away after application (leave-on type). In the case of using a container, there are no particular restrictions on the material and shape of the container. Polypropylene, polyethylene terephthalate, polyethylene, Eval, laminated containers of these, laminated containers with aluminum foil layers, tinplate, etc. Commonly used containers such as a type container, a pump type container, an aerosol container, a tube type container, a swing-out type container, a roll-on container, a jar container, a pillow pack, a portion container and a capsule can be used.

[0059] The hair cosmetic composition of the present invention is suitable for thin and soft hair damaged and weakened by coloring or permanent chemical treatment from the viewpoint of its effect. It is suitable as.

Example

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In the following examples, unless otherwise specified, “%” of the composition indicates mass%, and when the raw material in the table is a diluted product, it indicates the blending amount (%) as the diluted product.

[0061] [Examples;! To 5, Comparative examples;! To 4] Hair cosmetics having the compositions shown in Table 1 were prepared according to a conventional method. Each hair cosmetic was evaluated as follows. The results are also shown in the table.

[0062] Evaluation method

After applying perm treatment and coloring treatment to fine hair (average hair diameter eS lC ^ mUOg Ocm) with a reduced feel to the touch, apply shampoo and rinse treatment, then apply sample 8 · 8g and dry the hair. Based on the following scores, 10 panelists evaluated the “feel of stiffness”, “goodness of fingering”, “smoothness”, “no creaking”, “no stickiness” and “no stickiness”. The results were shown based on the following evaluation criteria from the total score obtained.

M

Harness of hair

Compared with untreated hair (shampooed and rinsed with the above evaluation method, sample uncoated hair)

+ 2 points: I felt firmness.

+ 1 point: I felt a little firm.

0 points: Neither.

1 point: Hari · The feeling of stiffness is not so good.

2 points: Hari · I don't feel the stiffness!

Good fingering, suppleness, no squeakiness, no stickiness, no stiffness>

+ 2 points: Very good, + 1 point: Somewhat good, 0 points: Neither, 1 point: Somewhat bad, 2 points: Very bad

Thunder

Total score of 10 people

: 15 points or more

○: 14 to 6 points

△: 5 ~ 0 points

:-1 point or less

[0063] [Table 1]

[0064] Examples of hair cosmetics are shown below, all of which are "harshness", "goodness of fingers", "softness", "no squeakiness", "no stickiness", The evaluation of “no stickiness” was good.

[Example 6]

[Table 2]

Hair mill

Composition%

1.0 Polyurethane resin emulsion 1 2.0 gallic acid 1,3-didarcoside 0.3 rosemary 'one extract 0.1 cholesteryl isostearate 1. 0 fluid isobalafin 3. 0 amino-modified silicone emulsion 2 0.5 Hydrochushchinorelle 'mouth' source 0.3 Polyoxyethylene poly-ter 5.0

(24 E. O.) (24 P. O.)

Stearyltrimethylamine chloride 0.5 Stearinoreanolechol 2.5 Ethanol 0.5 —Hydroxypropionic acid 0.1 Methyl parabenzoate 0.1 Dibutyl dihydroxylate / Rene 0. 01 Fragrance A 0 2 Remaining purified water

1 00. 0 [Example 7]

[Table 3]

Hair care

Composition% Hydroxypropynole Sanchitosan solution 1.0 Polyurethane resin solution 1 1.0

ΡΟΕ (30) Phytostero-nore 0 9 Tetraoleic acid ΡΟΕ (40) Sorbit 0 9 Mouth sali 'one extract 0.1 One gallic acid 3, 5-diglucoside 0.5 Hydroxichetti / Lese / Relose 0.5 Silicone Emanolation 1 2.0 Dihydrated oxybenzophenone 0.1 Sodium pyrophosphate 0.01 Daricholic acid 0.05 Methyl parabenzoate 0.1 Fragrance ■ 0 ■ 7 Tanoinole 20.0 Purified water balance a at 1 00. 0 [0067] [Example 8]

[Table 4

Hair foam

Composition% Hydroxypropynole Sanchitosan solution 1.0 Polyurethane resin emulsion 1 0.8 8 Gallic acid 3, 5-didarcoside 0.5 Amino-modified silicone emulsion 1 0.5

3-Methyl-1,3-butanediol 2.0 Plant squalane 0.1 Stearyltrimethylmonmonyl chloride 0.5 Methyl parabenzoate 0.3 Conocuccinic acid 0.1 Fragrance D 0. 1 Ethanol 3 0. 0 Liquefied petroleum gas 7.0 Balance of purified water

[Example 9]

[Table 5]

hair spray

Composition% Chitosan 2 0. 3 Polyurethane resin solution 2 1. 0 Deglycerated monostearate 1. 0 Polyoxyethylene hardened castor oil (4 0) 0. 5 Perfume C 0. 1 Ethanol Remainder

Α a π 4 · 1 0 0. 0 Above stock solution 5 0 Liquefied petroleum gas 1 0 Dimethinoleatenore 4 0 an 1 1 0 0

[0069] [Example 10]

[Table 6] Hair care

Composition% Chitosan solution 1 1.0 Polyurethane resin emulsion 1 1.0 0 Gallic acid 3, 5-diglucoside 0.5 Stearyl trimethyl ammonium chloride ◦ 5

POE (3 0) Cholesterol nore 0.3 Melis extract 0.1 Monoglycosyl monoisostearate 2.0 Creatun 0.2 Seaweed extract powder 0.2 Tocotrieno / l 0.1 Mes extract 0.1 Rose water 0.1 Trimethylglycine 0.1 Concentrated glycerin 1.5

1, 2 Pentanediol 5.0 Methyl paraoxybenzoate 0.1 Propyl parabenzoate 0. Hydroxychetinorescenellose 0. Quenic acid 0. Purified water Residue

A PI port T 0 0. 0 [Example 11]

[Table 7] Part o 5 1

1

Hair cream

Composition

Hydroxypropinolesan chitosan solution 1.5 Polyurethane resin emulsion 1 2. 0 Gallic acid 3, 5-didarcoside 0.5 Liquid isoparaffin 5. 0 Fuuninotrimethicone 0. 1 Behenyl alcohol 2. 0 Myristyl lactate 2. 0 Ethanol 1. 0 Horse oil 1. 0 Phytosteryl isostearate 0.5 Melissa extract 0. 1 Yuri extract 0. January peach extract 0. 1 Rice extract 0. 1 Ginseng extract 0. 1 Natri hyanorelonate Um 0.1 Polykotatanumu 3 7 0. 1 Di (Power Pre / Nukaf. Phosphoric Acid) PG 0. 5 Setano 1 / Le 0. 5 Behentrimonium methosulfate 0. 5 . 2

P PG— 1-Trideceth 6 0. 2 Arginine 0.05 Alkeneic acid 0.1 Hydroxochet / Lese / Relose 0.1 Polyoctaneum 1 0 0. 1

1,3-Butylene glycol 0.3 Phenoxyethanolate 0.1 Methyl parabenzoate 0.1 Fragrance E 0.2 Purified water remainder a at 1 0 0. 0 [Example 12]

[Table 8] Hair serum

Composition

Hydroxypropynole Sanchitosan Number 1.0 Polyurethane resin emulsion 1 2.0

4-glyceryl gallic acid 0.5 liquid isoparaffin 1.0 propylene glycolenole 5.0 dimethinole silicone 1.0 amodimethicone 0.5 tridecethone 2 2 0.5 dimethicone copolyol / res 0.2

POE (1 0) phytosterol 1.0 benyltrimethyl ammonium chloride 0.2 benzyloxyethanol 0.2 rosemary mono extract 0.2 methyl benzoate 0.1. 0 5 Power thione hydrolyzed soy protein 0.1 Hydroxypropyl guar gum 0.2 Cetyltrimethylmonum chloride 0.2 oxybenzone 0.5 Perfume D 0.2 Dibutyl hydroxytoluene 0 0 0 1 Purified water Remainder a πΤ 1 0 0 .0 [Example 13]

[Table 9]

Lins

Composition% Hydroxyl mouth pill 'chitosan solution 0.5 Polyurethane resin emulsion 1 2 .0 Gallic acid 3,5-didarcoside 0.05 Cholesteryl isostearate 2.0 Hydroxybenzophenone 0.1 Isisostearyl myristate 1.0 Amino-modified silicone emulsion 20.5 Stearyl trimethylammonium chloride 1.0 Steari / Rare / Reco / Re 3.0 Polyoxyethylene (20E. O.) hydrogenated castor oil 1.0 Propylene glycol "5.0 Glycerin 'Furactic acid lactic acid 0.1 Benzenorea / reco-monore 0.1 fragrance D 0.1 Balance of purified water a at 1 00 .0 [Example 14]

Ten]

Hair conditioner

Composition% Hydroxypropyl chitosan solution 0.5 Polyurethane resin emulsion 1 2. 0 One gallic acid 3, 5-didarcoside 0. 05 Carboxymethyl chitin 0.2 Stearyl guanoleco 3.0 One glycerin 5.0 Dimethicone / Le 2.0 Benenyltrimethylammonium chloride 1.0 Paraffin 0.5 Acetic acid 0.02 Lactic acid 0.1

ΡΟΕ (20) POP (30) Glycol 2. 0

C (1 2-14) Palace 1 7 0. 01

C (1 2 14) Palace 5 0. 02 Methyl balaxoxybenzoate 0.1 Fragrance A 0.5 Purified water balance Total 1 00. 0 [Example 15]

[Table 11]

Scalp hair care agent

Composition

Hydroxypropinorechitosan Maki 1.0 Polyurethane resin emulsion 10.4 Gallic acid 3,5-didarcoside 0.1 Diolecholesterinoleate oleate 0.2 Licorice extract 0.2 Coleus extract 0.5 Monopentadecanoic acid Glyceride 3.0 Acetic acid DL-α-Tocopheronole 0.1 Coconut oil fatty acid sorbitan 1.0 Sucrose myristate estenole 0.5 Biotin 0.5 0 2 Conocic acid 0.3 Semp'li extract 1.0 Hinokichio / Le 0.1

1 Menthol 0.3 Fragrance C 0.1

9 9 5% ethanol balance a at 1 0 0 .0

[0075] Regarding the main raw materials used in the above examples, the trade names and manufacturers are shown in the following list.

[0076] [Table 12]

Ingredient name Ingredient name Manufacturer Hydoxy, rolchitosan solution (4%) Quito 7 Ilmer Ichimaru 7 Al: Su

Chitosan Solution 1 (3%) HYDAGEN LCMS-LA Rich, Nisshi "Cha. () Chitosan 2 Kimitsuki San San Ina Trading Company

Caruho 'xymethyl chitin Kitin Liquid Iwase Cosf 7

Ho. Resurethane resin Emma 'Resi Yon 1 (24%) Hair Roll UC-4 Sanyo Chemical Industries Co., Ltd. Urethane resin solution 1 (30%) Ruset P.U.R.BASF Shaha. () E. Polyurethane resin solution 2 (28%) DynamX Japan NSC

P0E 7 Itosterol N I KKOL BPS Shi!) Su "Kyoko Chemika! Les" Co., Ltd.

POE Cholesterol EMALEX CS Cytos “曰; φ: Emma / Resi” Yeon () Isostea i) Cholesteryl hexeha. I S CE— A Kao Corporation

Loin mary extract Reomi- 鳳 Toyoda Flavor Co., Ltd.

Moon Peach Extract Moon Peach Extract 1 20KT RE Systems "(¾)

Messa extract Messa extract Maruzen Pharmaceutical Co., Ltd.

Hamamelis extract 7 Alcolex Hamamelis Ichimaru 7 Al: Su

Coleus Extract Coleus Extract Toyotama Fragrance Co., Ltd.

Yu Power!) Extract Yu Extract Koei Kogyo Co., Ltd.

Seaweed I kiss end laminating end ''. Uta 'Kimitsu Chemical Industry

Rice extract Rice germ oil Ichimaru Falcos Co., Ltd.

Ginseng Extract Ginseng Dried Extract Ask Chemical

Licorice Extract Kang-wow Nippon Powder Pharmaceutical Co., Ltd. Sen 7 'Extract Sen 7 "Re-extraction Ϊ Kid Maruzen Pharmaceutical Co., Ltd.

Acetic acid 99% acetate This synthetic chemical industry

? Acid 90% Lactic acid Matsumoto Kosho

"Cholic acid (70%)" ) Your 70 T

Kohata acid Kohata acid Kawasaki Kasei Kogyo Co., Ltd. Quenic acid Quenic acid Iwata Chemical Industry Co., Ltd. Alki ', Nin Shiichi Alki "Nin Co., Ltd. Ajinomoto Takaraco-Ho' Lesion Chloride Stear Chloride;) Luo ¹ U Chiluan ΐ Nyum (50%) Ark "T-800 Lion Atari" Co., Ltd.

Chloride to “Henylylmethyl Ammonium (80%) Card 22-80 Lionata Co., Ltd.

Ami-Hentai 生 Corn Emulsion 1 (40%) FZ-4672 Toita Taucukunin Γ 'Shikon Co., Ltd. Ami-Hentai シ Corn Emulsion Yeon 2 (40%) SM8704C East Ta-Uko-Ta-'Shi!) Corn Co., Ltd. Vinyl Trimethicone FZ 209 ) Cone Co., Ltd. Gallic acid-3, 5-Shi "Ta-Lukosi DGA Mitsui Chemicals, Inc. Table 13] Ingredient name Raw material name Maker Ethanol 95 degree synthetic specific alcohol Shinwa alcohol industry c. Methyl laoxybenzoate NIPAGIN M Kura!) Antshacha. Nha. La 7 Inn Ayakol BC-120 Seiwa Kasei Co., Ltd.

Fluid isoha. Raffin IP Sol ', Todo 1620 Idemitsu Petrochemical Co., Ltd. 匕 Trochechtilcellulose HEC SZ-25 Sumitomo Seika Co., Ltd. Oxyethylene pho. ! ) Oxiph ° Lohi. Renk "?

Ata "Power Car Hole. GH-200 Asahi Denka Co., Ltd.

Seryl ether (24E. 0.) (24P. 0.)

Stearyl Alcohol Conol 30SS Shin Nippon Rika Co., Ltd. Setanol Loro l C 16 Henkel

"7 'Chirecht" Xitoluene Ionol CP Motooka Tsusho

E'Hydroxyethylene hydrogenated castor oil EMALEX HC series "Day; φ: Emulsy Yon ():" Human Roxy ", Gamma, 7 Emsaw 100 ° 7 ° Kasei Co., Ltd. p sodium phosphate Mouth Sodium Phosphate Taihei Chemical Industry Co., Ltd.

3_Methyl _ 1, 3—Fu “Tanshi” All Iso, Renk ', Ϊ Cole S Co., Ltd. Tarare

Noh! ) Serine Pharmacopoeia "Taki Serine Sakamoto Pharmaceutical Co., Ltd.

1, 2 Enchanted 'All 2/016020 HYDROLI TE- 5 Iwase Kos Co., Ltd. Plant Staran PHYTOSQUALAN Iwase Cosf 7 Co., Ltd. Nsyl alcohol L 7 Atchem

メチル Methylta "lysine" Amikoto Asahi Kasei Corporation

Taleatinin Taleatinin Inabata fragrance

Tetraoleic acid POE power "NIKKOL GO shi!" -Su "Nikko Chemicals" Myristyl lactate Sege 'soft C 17 koku' nisshaha.

'(Force, ril / force, phosphoric acid) PG milliliter PC Kota Nisshacha. N

POE (20) POP (30) "Recall letter" cuff. Luronoshi; J Asahi Denka Kogyo Co., Ltd. Horse oil Refined horse oil Iwase Cosf 7

1 Menthol 1 Menthol Shiono Perfume Co., Ltd. Acetic acid D α-Toco 7 Erol Oxalic acid DL—α-Tocopherol DSM 2 Ut Palm oil fatty acid sol tanne 5 S-20 Sanyo Chemical Industries Co., Ltd. Karenhi Laurate “Tan SL-10 Nikko Chemicals” Co., Ltd.

4-ta ' ¹ ) gallic acid synthetic product * 1

Fragrance A, B, C, D, E Fragrance composition described in JP-A-2003-095895

4-glyceryl eroded premature oxidation> 成 1

Add 33.2 g of potassium carbonate to a mixture of 36.8 g of methyl gallate, 300 mL of acetone, and 60 mL of DMF (dimethylformamide), stir, heat and reflux for 20 minutes, then add 24.2 g of allyl bromide dropwise. And refluxed for another 5 hours. After distilling off the solvent under reduced pressure, 200 mL of ethyl acetate and 200 mL of water were added for liquid separation, and the resulting organic layer was washed with 10 mL of saturated saline and concentrated. Hexane 300m to the residue obtained L was added and stirred to obtain crude crystals as a precipitate. After the hexane solution was decanted, the crude crystals were crystallized using ethyl acetate and hexane, which was collected by filtration and dried to obtain 9.4 g of methyl 4 O aryl gallate.

In a mixed solution of 6 mL of formic acid and 6 mL of 30% hydrogen peroxide solution, adjust the temperature so that the internal temperature becomes 30 to 35 ° C, and count 2 g of methyl 4 O allyl gallate obtained by the above method. The reaction was divided over 1 hour and added over 1 hour, followed by reaction for 2 hours while adjusting the temperature so that the internal temperature was 35-40 ° C. 20 mL of water and 30 mL of toluene were added to the reaction system for liquid separation, the toluene layer was removed, and then 30 mL of ethyl acetate was added to the aqueous layer for separation and extraction. Furthermore, 30 mL of ethyl acetate was added to the aqueous layer for re-extraction and combined with the previous ethyl acetate layer. This organic layer was washed sequentially with 20 mL of water, 20 mL of aqueous sodium bicarbonate, and 20 mL of aqueous sodium bisulfite solution, and then this organic layer was washed until the aqueous layer became neutral while adjusting the pH with an aqueous sodium hydroxide solution. . After confirming that the peroxide remained on the potassium iodide starch paper, it was concentrated, and the resulting residue was purified by silica gel column chromatography (silica gel 60 g, developing solvent: Hexane / ethyl acetate = 1/4 (volume ratio)). The obtained 4-glyceryl gallic acid methyl ester and its formate were combined to obtain 0.35 g. This was added to an aqueous solution of 1 mL of water and 0.2 g of sodium hydroxide and reacted at room temperature for 3 hours. 14 mol / L hydrochloric acid was added to adjust the reaction solution to pH 1 and the precipitated crystals were collected by filtration, then washed with 2 mL of water and dried to obtain 0.20 g of 4 glyceryl gallic acid powder.

Claims

The scope of the claims

[1] A hair cosmetic containing (A) chitosans and (B) a polyurethane resin.

[2] The hair cosmetic according to claim 1, wherein the component (A) is a water-soluble chitosan derivative having a hydrophilic group introduced into chitosan, partially deacetylated chitin, or a salt thereof.

[3] The hair cosmetic according to claim 1 or 2, wherein the component (B) is a polyurethane resin having a cationic group.

[4] The hair cosmetic according to claim 1, 2 or 3, further comprising (C) one or more selected from polyphenols, polyphenol salts, and polyphenol derivatives.

5. The hair cosmetic according to claim 4, wherein the component (C) is a gallic acid derivative.