JP7211842B2 - hair composition - Google Patents

Description

The present invention relates to hair compositions.

Various film-forming agents are used to style the hair into desired hairstyles. However, when an effective amount of these film-forming agents is blended in order to secure the hair styling function, the hair-styling retention is excellent, but on the other hand, the film-forming agent has the negative characteristics of "stiffness" and "strength" due to excessive film feeling. There is a problem that an undesirable feel such as "squeaky" or "crunchy" is conspicuous.

Therefore, in compositions containing a film-forming agent, attempts have hitherto been made mainly to suppress the occurrence of an unfavorable feel, which is a negative characteristic of the film-forming agent. Specifically, for example, a hair cosmetic containing a water-dispersible polyester resin and a film-forming resin (see, for example, Patent Document 1), and a film-forming polymer and polyglycerin having a specific average degree of polymerization. A hair cosmetic (see, for example, Patent Document 2), a hair cosmetic containing a carboxyl group-containing thickening polymer compound, an alkaline substance, a pasty oil agent at room temperature, and a polymer compound having film-forming ability (for example, See Patent Document 3), a hair setting agent composition containing a specific polyorganosiloxane-polyoxyalkylene block block copolymer and a film-forming polymer (see, for example, Patent Document 4), and film-forming for hair styling. A hair cosmetic composition containing a polymer compound, a specific fatty acid ester, and a polyether-modified silicone has been proposed (see, for example, Patent Document 5).

However, in these attempts, since the feeling of use is interesting, although it is possible to give a certain degree of hair styling retention power, it is not possible to maximize the hair styling retention power that the film-forming agent should originally exhibit. There are drawbacks. Therefore, it is conceivable to attempt to maximize only the hair styling retention power of the film-forming agent, but it is difficult to maximize only the hair styling retention power in the application of the above-described conventional methods. be.

In addition, since the film-forming agent is inferior in moisture resistance, there is a problem that sufficient hair styling retention cannot be maintained under high humidity. Furthermore, when an attempt is made to sufficiently exert the hair styling retention power of the film-forming agent on the hair, not only is the feeling of use worsened, but also the formed film is peeled off by hand combing after hair styling, and the film is left on the hair. There is also a so-called flaking problem, such as generation of white powder.

JP-A-7-187964 JP-A-2001-122738 JP-A-2002-370941 Japanese Patent Application Laid-Open No. 2004-244328 JP 2007-223943 A

The present invention has been made in view of the above-mentioned prior art, and is capable of sufficiently exerting the hair styling retention power, which is the excellent hair styling property inherent to the film-forming agent, even under high humidity conditions. An object of the present invention is to provide a hair composition that does not cause excessive filmy feeling and flaking, which are negative characteristics of a forming agent.

In order to solve the above problems, the hair composition of the present invention comprises vinylpyrrolidone/N,N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate, vinylimidazolium trichloride/vinylpyrrolidone copolymer, polyvinyl pyrrolidone/alkylaminoacrylate/vinylcaprolactam copolymer, methylvinylimidazolium chloride/vinylpyrrolidone copolymer, vinylpyrrolidone/dimethylaminopropyl methacrylamide/lauryldimethylaminopropyl methacrylamide copolymer, polyvinylpyrrolidone, vinyl acetate/ (A) a film-forming agent containing at least one selected from the group consisting of a vinylpyrrolidone copolymer and a vinylpyrrolidone/methacrylamide/vinylimidazole copolymer; and (B) a cyclic compound represented by the following general formula (1): Contains oligosaccharides. However, in formula (1), R represents a hydrogen atom or an unsubstituted alkyl group having 1 to 20 carbon atoms, a plurality of R may be the same or different, and n represents an integer of 0 to 3.

The hair composition of the present invention has the effect of being able to sufficiently exhibit the hair-styling holding power, which is the excellent hair-styling property originally possessed by the film-forming agent, even under high humidity conditions. At that time, there is an effect that flaking and "stiff," "squeaky," and "crunchy" feel caused by excessive film feeling, which are negative characteristics of the film-forming agent, do not occur.

FIG. 2 shows steps for synthesizing cyclic oligosaccharides according to one embodiment. FIG. 2 shows steps for synthesizing cyclic oligosaccharides according to another embodiment. 1 is a photograph of a molecular model showing the molecular structure of a cyclic oligosaccharide according to one embodiment. 1 is a photograph of a molecular model showing the molecular structure of cyclodextrin. 1 is an FT-IR spectrum diagram of fully methylated cellulose and partially methylated cellulose in Synthesis Example 1. FIG. 1 is a 1H-NMR spectrum diagram of fully methylated cellulose in Synthesis Example 1. FIG. 1 is a MALDI-TOF MS spectrum diagram of a crude product before hexamer isolation in Synthesis Example 1. FIG. 1 is a 1H-NMR spectrum diagram of a methylated cyclic cellooligosaccharide (hexamer) of Synthesis Example 1. FIG. 1 is a NOESY spectrum diagram of a methylated cyclic cellooligosaccharide (hexamer) of Synthesis Example 1. FIG. FIG. 10 is a partially enlarged view of FIG. 9; 13 is a 13C-NMR spectrum diagram of the methylated cyclic cellooligosaccharide (hexamer) of Synthesis Example 1. FIG. 1 is a MALDI-TOF MS spectrum diagram of the methylated cyclic cellooligosaccharide (hexamer) of Synthesis Example 1. FIG. 1 is a HPLC chromatogram of methylated cyclic cellooligosaccharide (hexamer) and fully methylated α-cyclodextrin of Synthesis Example 1. FIG. 2 is a MALDI-TOF MS spectrum diagram of partially acetylated cellooligosaccharide in Synthesis Example 2. FIG. 2 is a MALDI-TOF MS spectrum diagram of a crude product containing acetylated cyclic cellooligosaccharides in Synthesis Example 2. FIG. 1 is a MALDI-TOF MS spectrum diagram of a crude product containing cyclic cellooligosaccharides in Synthesis Example 2. FIG.

[Cyclic cellooligosaccharide]
First, the cyclic oligosaccharide (also referred to as cyclic cellooligosaccharide) (B) represented by the general formula (1) according to the present embodiment will be described in detail.

Cyclodextrin is conventionally known as a cyclic oligosaccharide. Cyclodextrin has a cyclic structure in which glucose is linked by α-1,4 glucosidic bonds, as represented by the following general formula (x) (where m is an integer of 1 to 3), Generally, there are α-cyclodextrins with 6 glucose linkages, β-cyclodextrins with 7 glucose linkages, and γ-cyclodextrins with 8 glucose linkages.

On the other hand, the cyclic cellooligosaccharide according to the present embodiment is a compound represented by the general formula (1), and is a cyclic cello-oligosaccharide in which structural units that are glucose or a derivative thereof are linked by a β-1,4 glucosidic bond. have structure. n in formula (1) represents an integer of 0 to 3, and therefore the cyclic oligosaccharide represented by formula (1) is composed of pentamers, hexamers, heptamers and octamers of the above structural units. , or a mixture of two or more thereof.

The cyclic cellooligosaccharide according to the embodiment of the present invention can be obtained, for example, by bonding terminal hydroxyl groups of an oligosaccharide represented by the following general formula (2) to cyclize it, as described later. However, in formula (2), R represents a hydrogen atom or a substituent thereof, a plurality of R may be the same or different, and k represents an integer of 3-6.

When all R in formula (1) are hydrogen atoms, it is a chemically unmodified (i.e., unsubstituted) cyclic oligosaccharide represented by the following formula (3) (here, in formula (3) n represents an integer of 0 to 3.).

The cyclic oligosaccharide of the formula (3) differs from the cyclodextrin of the above formula (x) only in that the linking structure between glucose is β-1,4 bond and α-1,4 bond. Generally, substituents can be introduced using known chemical modification methods applied to cyclodextrins. Therefore, the cyclic oligosaccharide of formula (1) can have substituents similar to those of known cyclodextrins.

As described above, R in formula (1) may be all hydrogen atoms, all may be substituents, or hydrogen atoms and substituents may coexist. When coexisting, the ratio of both is not particularly limited. For example, OR is divided into a group corresponding to a primary hydroxy group (OR ¹ ) and a group corresponding to a secondary hydroxy group (OR ² ) of a glucose constitutional unit, and formula (1) is replaced by the following general formula (1-1 ), all of R ¹ may be substituents and all of R ² may be hydrogen atoms, some of R ¹ may be substituents and the remainder of R ¹ and all of R ² may be hydrogen atoms, All of R ¹ and part of R ² may be substituents and the rest of R ² may be hydrogen atoms. Further, all of R ² may be substituents and all of R ¹ may be hydrogen atoms, some of R ² may be substituents and the remainder of R ² and all of R ¹ may be hydrogen atoms, all of R ² and R A part of ¹ may be a substituent and the remainder of R ¹ may be a hydrogen atom. Furthermore, both R ¹ and R ² may be partly substituted and the remainder may be hydrogen atoms.

The substituent represented by R in formula (1) is a group that substitutes the hydroxy hydrogen of glucose, and includes various groups that can be derived from the hydroxy hydrogen of glucose through one or more reactions.

Specifically, the substituent represented by R (hereinafter referred to as substituent R) includes a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted unsubstituted cycloalkenyl group, substituted or unsubstituted aryl group (e.g., phenyl group, tolyl group, etc.), substituted or unsubstituted aralkyl group (e.g., benzyl group, phenethyl group, trityl group, etc.), acyl group, silyl groups, sulfonyl groups, sugar residues, substituted or unsubstituted polyoxyalkylene groups, and the like. The number of carbon atoms in the substituent R is not particularly limited, and may be, for example, 1-40, 1-30, or 1-20.

The substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted cycloalkenyl group, substituted aryl group, and substituted aralkyl group, which are examples of the substituent R, include, for example, a hydroxy group as a substituent such as a hydroxyalkyl group. Those having a sulfo group or a derivative group thereof as a substituent such as a sulfoalkyl group or a salt or ester group thereof, a carboxy group or a derivative group thereof as a substituent such as a carboxymethyl group or a salt or ester group thereof and the like. The hydrocarbon group constituting the ester group here includes, for example, an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms.

Examples of the acyl group, which is an example of the substituent R, include monocarboxylic acid residues that form an ester bond with the oxygen atom in -OR such as an acetyl group and a benzoyl group (for example, R: -CO-Q ¹ ), or a residue of a dicarboxylic acid such as succinic acid. In the case of a dicarboxylic acid residue, the carboxy group that is not ester-bonded to glucose forms an ester group in either an acid form or a metal salt. (eg, R: -CO-Q ² -COO-Q ³ ). Here, Q ¹ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms (preferably 1 to 6), and the organic group includes an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, An aralkyl group is mentioned. ^Q2 represents a hydrocarbon group having 1 to 6 carbon atoms (such as an alkanediyl group). Q ³ represents a hydrogen atom, an alkali metal, or an organic group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and examples of the organic group include alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, An aralkyl group is mentioned.

Examples of the silyl group, which is an example of the substituent R, include trialkylsilyl groups such as a tert-butyldimethylsilyl group. Examples of the sulfonyl group include arylsulfonyl groups such as p-toluenesulfonyl group. Furthermore, examples of sugar residues include glucosyl groups, mantosyl groups, and the like.

Examples of the substituted or unsubstituted polyoxyalkylene group, which is an example of the substituent R, include groups having repeating units of oxyalkylene having 1 to 4 carbon atoms such as a polyoxyethylene group, and the terminal OH is amino may be substituted with a substituent such as a group, an azide group, or a trityl group. The number of repetitions of the oxyalkylene group is not particularly limited, and may be, for example, 2-20.

As for the substituents R listed above, only one of the plurality of Rs in the formula (1) may be introduced, or two or more of them may be introduced in combination.

The cyclic oligosaccharide having a β-1,4 glucosidic bond according to the present embodiment is produced through a step of cyclizing by bonding the terminal hydroxyl groups of the oligosaccharide represented by the general formula (2). can be done. R in Formula (2) represents a hydrogen atom or a substituent thereof. Examples of the substituent represented by R in formula (2) include the same substituents as in formula (1) described above, preferably R is an alkyl group or an acyl group, for example, the formula OR in (2) is an acylated (more preferably acetylated) hydroxy group of glucose (that is, an acyloxy group, preferably an acetyloxy group), an alkylated (more preferably methylated) hydroxy group of glucose ) (ie, an alkoxy group, preferably a methoxy group).

A method for producing a cellulose-derived cyclic cellooligosaccharide as a cyclic oligosaccharide according to one embodiment will be described with reference to FIG.

In the production method shown in FIG. 1, first, cellulose represented by formula (4) is acetylated (here, p in the formula is a number corresponding to the number of repetitions of two molecules of glucose in cellulose). Cellulose has a structure in which glucose units are linked by β-1,4 glucosidic bonds, and adjacent glucose units are turned inside out and arranged in a line to form a linear structure. Therefore, cellulose has strong intramolecular and intermolecular hydrogen bonds and is insoluble in water. By acetylating the hydroxy groups of cellulose to eliminate hydrogen bonds, flexibility is imparted to the molecular chain. Note that partially acetylated cellulose may be used as a starting material.

Acetylation can be performed, for example, by reacting cellulose with acetic anhydride in the presence of perchloric acid (see, for example, P. Arndt et al., Cellulose, 2005, 12, 317). Acetylation yields cellulose triacetate (completely acetylated cellulose) represented by formula (5) in which all three hydroxy groups of each structural unit of cellulose are acetylated.

Then, the glucosidic bond is cleaved from the cellulose triacetate to synthesize the partially acetylated cellooligosaccharide represented by the formula (6). Cleavage of glucosidic bonds can be performed by adding concentrated sulfuric acid to cellulose triacetate (for example, H. Namazi et al., J. Appl. Polym. Sci., 2008, 110, 4034. and T. Kondo, D. G. Gray, J. Appl. Polym. Sci. 1992, 45, 417). Then, by separating and purifying after cleavage, it has 5 to 8 glucose units as shown in formula (6), and has hydroxy groups at positions 1 and 4 of the glucose units at both ends, A chain-shaped partially acetylated cellooligosaccharide having a structure in which all other hydroxy groups are acetylated is obtained. The cellooligosaccharide of formula (6) is an oligosaccharide represented by formula (2) above in which -OR is -O-Ac (where Ac is an acetyl group).

Next, the hydroxy groups at both ends of the partially acetylated cellooligosaccharide represented by formula (6) are bonded together to cyclize it. The cyclization method is not particularly limited, and for example, the terminal 1-hydroxy group of the partially acetylated cellooligosaccharide represented by formula (6) may be trichloroacetimidated and then cyclized. Trichloroacetimidation can be performed by reacting the partially acetylated cellooligosaccharide with trichloroacetonitrile, and then adding a boron trifluoride diethyl ether complex to the partially acetylated cellooligosaccharide that has been trichloroacetimidated. By reacting, the glucose units at both ends are linked by β-1,4 glucosidic bonds to form a ring.

By adding a boron trifluoride diethyl ether complex to the partially acetylated cellooligosaccharide without converting it to trichloroacetimidate, the glucose units at both ends are linked by β-1,4 glucosidic bonds to form a cyclic structure. can be

As a result, an acetylated cyclic cellooligosaccharide represented by formula (7) is obtained. The acetylated cyclic cellooligosaccharide of formula (7) is a cyclic oligosaccharide represented by formula (1) above in which all —ORs are —O—Ac.

Then, the acetyloxy group of the acetylated cyclic cellooligosaccharide represented by the formula (7) is hydrolyzed using, for example, a base catalyst (sodium hydroxide, triethylamine, etc.) to obtain the compound represented by the above formula (3). cyclic oligosaccharides are obtained.

FIG. 2 is a diagram showing steps of synthesizing a cyclic oligosaccharide according to another embodiment. In the example of FIG. 2, a partially methylated cellulose represented by the formula (10), in which the hydroxy groups of the cellulose are partially methylated, was used as a starting material to obtain a methylated cyclic cellooligot represented by the formula (13). Synthesize sugar.

In the production method shown in FIG. 2, first, partially methylated cellulose is methylated to synthesize fully methylated cellulose. Methylation can be carried out, for example, by reacting partially methylated cellulose with sodium hydride and iodomethane (see, for example, J. N. Bemiller, Earle E. Allen, JR., J. Polym. Sci. 1967, 5, 2133.). As a result, a fully methylated cellulose represented by formula (11) in which all three hydroxy groups of each structural unit of cellulose are methylated is obtained.

Then, the partially methylated cellooligosaccharide represented by the formula (12) is synthesized by cleaving the glucosidic bond of the fully methylated cellulose. Glucosidic bond cleavage is the same as in FIG. Then, by separating and purifying after cleavage, it has 5 to 8 glucose units as shown in formula (12), and has hydroxyl groups at positions 1 and 4 of the glucose units at both ends, A chain-shaped partially methylated cellooligosaccharide having a structure in which all other hydroxy groups are methylated is obtained. The cellooligosaccharide of formula (12) is an oligosaccharide represented by formula (2) above in which —OR is —O—Me (where Me represents a methyl group).

Next, the hydroxy groups at both ends of the partially acetylated cellooligosaccharide represented by formula (12) are combined to cyclize. The cyclization method is not particularly limited, and for example, the partially methylated cellooligosaccharide may be reacted with trifluoromethanesulfonic anhydride (Tf ₂ O) and 2,6-di-tert-butylpyridine (DBP). can be done. As a result, the glucose units at both ends are linked by β-1,4 glucosidic bonds to form a cyclic structure, and the methylated cyclic cellooligosaccharide represented by the formula (13) is obtained. This methylated cyclic cellooligosaccharide is a cyclic oligosaccharide represented by the above formula (1) in which all —ORs are —O—Me.

In the cyclic oligosaccharide represented by the formula (1), the substituent for R in the formula can be introduced using a known chemical modification method basically applied to cyclodextrins, as described above. . For example, to introduce an alkoxy group such as a methoxy group as —OR, a method of alkylating a hydroxy group described in JP-A-61-200101 may be used. In addition, in the case where R is a substituted alkyl group, a sulfoalkyl group or a carboxymethyl ester group can be introduced via an ether oxygen by the methods described in JP-A-11-60610 and JP-A-2013-28744. may be used. When R is an acyl group, the method described in JP-A-4-81403 may be used to introduce a dicarboxylic acid residue such as succinic acid. In addition, when R is a sulfonyl group, the method described in JP-A-2016-69652 may be used to introduce a tosyl group via an ether oxygen.

As a method for introducing a substituent, it is not always necessary to first synthesize an acetylated cyclic cellooligosaccharide as described above, and then hydrolyze it into a cyclic oligosaccharide of formula (3) before introducing a substituent. Instead, after cyclization, it may be directly converted to other substituents.

As described above, the cyclic oligosaccharide according to the present embodiment can be synthesized from cellulose, which is the most abundant organic compound on earth and is a renewable non-edible plant resource. can be achieved.

Further, when the molecular structures of the cyclic oligosaccharide according to the present embodiment and cyclodextrin are compared, the cyclic oligosaccharide according to the present embodiment has higher hydrophobicity in the pores than cyclodextrin. Specifically, the molecular structure of the cyclodextrin represented by the formula (x) is as shown in FIG. 4, whereas the molecular structure of the cyclic oligosaccharide represented by the formula (3) is as shown in FIG. be. 3 and 4, white atoms are hydrogen atoms, black atoms are carbon atoms, and gray atoms therebetween are oxygen atoms.

As shown in FIG. 4, in cyclodextrin, the glucoside oxygen linking the glucose units faces the inside of the pore, so the interior of the pore is in a hydrophobic environment similar to ether. In contrast, as shown in FIG. 3, in the cyclic oligosaccharide according to the present embodiment, the glucoside oxygen faces outward, and the oxygen atoms do not face the inside of the vacancy. Therefore, in the cyclic oligosaccharide according to the present embodiment, the inside of the pore is in a more hydrophobic environment than cyclodextrin, and it is possible to take in highly hydrophobic substances. As a result, it can be expected to have higher guest inclusion ability and higher guest selectivity, for example, in water.

Since the cyclic oligosaccharide according to the present embodiment has the property of enclosing a hydrophobic guest molecule or a part thereof in the pore, similarly to cyclodextrin, volatile substances are nonvolatile and sustained release, nonvolatile. For the purpose of stabilizing stable substances and solubilizing poorly soluble substances, it can be used for applications such as foods, cosmetics, toiletry products, and pharmaceuticals.

[Hair composition]
The hair composition of the present invention contains (A) a film-forming agent and (B) a cyclic cellooligosaccharide.

The film-forming agent of component (A) is not particularly limited as long as it can impart excellent hair styling properties, but examples include anionic film-forming agents, cationic film-forming agents, amphoteric film-forming agents, and nonionic film-forming agents. etc. These (A) components may be used individually by 1 type, and can also be used in combination of 2 or more types as appropriate.

Specific anionic film-forming agents include, for example, alkyl (meth)acrylate copolymers, (meth)acrylic acid/alkyl (meth)acrylate copolymers, acrylic resin alkanolamines, methyl vinyl ether/maleate esters Copolymer, vinyl acetate/crotonic acid copolymer, crotonic acid/vinyl acetate/vinyl neodecanoate copolymer, vinyl acetate/crotonic acid/vinyl propionate copolymer, vinyl acetate/monobutyl maleate/isoboro Ryl acrylate copolymer, acrylic acid/alkyl acrylate/alkyl acrylamide copolymer, vinylpyrrolidone/acrylates/alkyl (meth)acrylate copolymer, styrene/alkyl (meth)acrylate copolymer, styrene/acrylic Examples include acid amide copolymers, urethane-acrylic copolymers, sodium polystyrene sulfonate, and the like. In this specification, "(meth)acryl" means both "acryl" and "methacryl".

Specific cationic film-forming agents include, for example, vinylpyrrolidone/N,N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate, O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxy chloride, Ethylcellulose, vinylimidazolium trichloride/vinylpyrrolidone copolymer, hydroxyethylcellulose/dimethyldiallylammonium chloride, polyvinylpyrrolidone/alkylaminoacrylate/vinylcaprolactam copolymer, methylvinylimidazolium chloride/vinylpyrrolidone copolymer, vinylpyrrolidone/ A dimethylaminopropyl methacrylamide/lauryldimethylaminopropyl methacrylamide copolymer can be exemplified.

Specific amphoteric film-forming agents include, for example, N-methacryloyloxyethyl N,N-dimethylammonium-α-N-methylcarboxybetaine/methacrylic acid alkyl ester copolymer, N,N dimethyl-N-(2- methacryloyloxyethyl)amine=N-oxide・methacrylic acid alkyl ester copolymer, hydroxypropyl acrylate/butylaminoethyl methacrylate/octylamide acrylate copolymer, dialkylaminoethyl methacrylate/methacrylic acid alkyl ester copolymer Monochloroacetic acid amphoterate, isobutylene/diethylaminopropylmaleimide/maleic acid copolymer and the like can be exemplified.

Examples of specific nonionic film-forming agents include polyvinylpyrrolidone, vinyl acetate/vinylpyrrolidone copolymer, vinylpyrrolidone/methacrylamide/vinylimidazole copolymer, polyvinyl alcohol, and polyvinylcaprolactam.

Cationic film-forming agents and nonionic film-forming agents are preferably used as suitable component (A) from the viewpoint of ease of hair bundle formation. Therefore, it is more preferable to use a vinylpyrrolidone-based film-forming agent in which vinylpyrrolidone is one component. Specifically, vinylpyrrolidone/N,N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate, vinylimidazolium trichloride/vinylpyrrolidone copolymer, polyvinylpyrrolidone/alkylamino acrylate/vinylcaprolactam copolymer, chloride Methylvinylimidazolium/vinylpyrrolidone copolymer, vinylpyrrolidone/dimethylaminopropyl methacrylamide/lauryldimethylaminopropyl methacrylamide copolymer, polyvinylpyrrolidone, vinyl acetate/vinylpyrrolidone copolymer, vinylpyrrolidone/methacrylamide/vinylimidazole At least one selected from the group of copolymers can be preferably used. Coalescing can most preferably be used.

The content of component (A) is not particularly limited as long as the desired effect is sufficiently imparted, but in general, from the viewpoint of exhibiting sufficient hair styling retention power, 0.5% by mass or more in the composition is used. It is preferably 1% by mass or more, more preferably 1% by mass or more. In addition, from the viewpoint of suppressing undesirable coating feeling and flaking, the content is preferably 8% by mass or less, more preferably 5% by mass or less. From these points of view, the content of component (A) is preferably 0.5 to 8% by mass, more preferably 1 to 5% by mass.

The content of component (B) is not particularly limited as long as the desired effect is sufficiently imparted, but usually from the viewpoint of exhibiting sufficient hair styling retention power, the content of component (B) is 0.15% by mass or more in the composition. It is preferably 0.2% by mass or more, more preferably 0.2% by mass or more. From the viewpoint of flaking, it is preferably 4% by mass or less, more preferably 3% by mass or less. From these points of view, the content of component (B) is preferably 0.15 to 4% by mass, more preferably 0.2 to 3% by mass.

In the present invention, it is preferable that the mass content ratio of the above components (A) and (B) is adjusted in the range of (A):(B)=1:0.06 to 1:2. The reason for this is that when the amount of component (B) is less than 0.06 parts by weight per 1 part by weight of component (A), the excellent hair styling function peculiar to component (B) can be sufficiently exhibited. It is not preferable because it cannot be used and the hair styling holding power is inferior. Further, when the amount of component (B) is more than 2 parts by weight with respect to 1 part by weight of component (A), the coating feeling peculiar to component (A) is inhibited by component (B), and flaking is prevented. This is not desirable because it will occur.

Moreover, the composition for hair of the present invention can contain ethanol from the viewpoint of quick-drying. Ethanol to be used is not particularly limited as long as it can be used as a raw material for cosmetics. The content of ethanol in the composition is preferably 2 to 50% by mass, more preferably 5 to 30% by mass.

Water is used as the remainder of the hair composition of the present invention. The water to be used is not particularly limited as long as it can be used as a raw material for cosmetics, but purified water is usually used. The content of water in the present invention is preferably 30 to 97% by mass, more preferably 50 to 90% by mass in the composition.

The composition for hair according to the present invention may contain, in addition to the above-described components, components commonly used in cosmetics, such as polyhydric alcohols, sugar alcohols, surfactants, and so on, as long as they do not impair the effects of the present invention. Thickeners, pH adjusters, preservatives, UV absorbers, humectants, coloring agents, perfumes, etc. can be appropriately blended depending on the purpose.

The hair composition of the present invention can be suitably used as a hair styling agent because it can sufficiently exhibit the hair styling retention property, which is the excellent hair styling property inherent in the film-forming agent.

The dosage form is not particularly limited as long as the desired effects are sufficiently imparted. can be applied.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In the following examples, "%" means "% by mass" unless otherwise specified.

[Cyclic cellooligosaccharide]
Synthesis of cyclic cellooligosaccharides used in this example and the like are described below. Analysis and measurement methods are as follows.

(Infrared absorption spectrum (FT-IR))
Measured with a Fourier transform infrared spectrophotometer (“FT/IR4700ST model” manufactured by JASCO Corporation) (ATR method).

(NMR)
Measured with "JNM-ECS400" manufactured by JEOL Ltd.

(mass spectrometry)
Measured with a matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (MALDI-TOF MS) ("Voyager ^TM RP" manufactured by Nippon Perceptive Limited).

(HPLC)
Column: ODS ("Wakosil 5C18 AR" manufactured by Wako Pure Chemical Industries, Ltd., inner diameter 4.6 mm, length 150 mm)
Mobile phase: acetonitrile/water = 8/2 (volume ratio)
Flow rate: 1.0 mL/min Temperature: 30°C
Detection: ELSD (“Model400 ELSD” manufactured by SoftTA, USA).

(TLC)
Developing solvent: methanol/chloroform=1/40 (volume ratio).

<Synthesis Example 1. Synthesis of methylated cyclic cellooligosaccharide>
First, synthesis of a methylated cyclic cellooligosaccharide, which is one aspect of the cyclic cellooligosaccharide according to the present embodiment, will be described.

(1-1 Synthesis of fully methylated cellulose from partially methylated cellulose)
JN Bemiller, Earle E. Allen, JR., J. Polym. Sci. 1967, 5, 2133. The details of the reaction formula and synthesis method are as follows.

Partially methylated cellulose (2.01 g, 5.03×10 ⁻⁵ mol, Sigma-Aldrich “cellulose acetate (Mn~30,000)”) vacuum-dried at 80° C. overnight was dried in DMSO under a nitrogen atmosphere. (110 mL). This solution was added to sodium hydride (content: 60%, 1.81 g, 4.53×10 ⁻² mol) and stirred at 50° C. for 16 hours. Iodomethane (2.95 mL, 4.74×10 ⁻² mol) was added dropwise thereto over 30 minutes and stirred at 50° C. for 24 hours. Methanol (3.85 mL) was added to the system to deactivate unreacted sodium hydride, and the resulting solution was added to water (350 mL) for reprecipitation. The resulting solid was separated by centrifugation and vacuum dried at 60° C. to obtain the product (white powdery solid) (1.90 g, 95% yield).

The FT-IR spectrum of the product is shown in FIG. 5 together with the FT-IR spectrum of the starting partially methylated cellulose. In partially methylated cellulose as a raw material, an absorption peak based on OH stretching vibration was observed near 3400 cm ⁻¹ as shown in FIG. 5(a). In contrast, in the FT ^- IR spectrum of the product, absorption peaks were observed at 2915, 1455, and 1050 cm ⁻¹ as shown in FIG. Absorption peaks disappeared, confirming that all hydroxy groups were methylated.

The results of ¹ H-NMR analysis of the product are shown below, and the NMR spectrum is shown in FIG.
¹ H-NMR (400MHz, chloroform-d): δ 2.92 (t, 1H), 3.19 (t, 1H), 3.27(m,1H), 3.37 (s, 3H), 3.52 (s,3H), 3.56 ( s, 3H), 3.69-3.61 (m, 2H), 3.75 (m, 1H), 4.31 (d, 1H).

From the above, it was confirmed that the product was fully methylated cellulose.

(1-2 Synthesis of partially methylated cellooligosaccharides from fully methylated cellulose)
With reference to the method described in T. Kondo, DG Gray, J. Appl. Polym. Sci. 1992, 45, 417, partially methylated cellooligosaccharides (5-8 glucose units) were synthesized from fully methylated cellulose. rice field. The details of the reaction formula and synthesis method are as follows.

Permethylated cellulose (0.55 g, 1.2×10 ⁻² mmol) vacuum-dried at 80° C. was dissolved in dehydrated dichloromethane (30 mL) under a nitrogen atmosphere. Boron trifluoride diethyl etherate (7.2 mL, 56 mmol, manufactured by Wako Pure Chemical Industries, Ltd., content: 46.0 to 49.0% (BF ₃ )) was added thereto and stirred at room temperature for 6 hours. . A saturated aqueous sodium bicarbonate solution (15 mL) was added to the resulting solution to terminate the reaction. After extraction with dichloromethane (30 mL) twice, the collected dichloromethane solutions were dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a brown viscous liquid (crude yield: 0.52 g, crude yield: 93%).

MALDI-TOF-MS measurements revealed that the resulting product was a mixture of partially methylated cellooligosaccharides consisting of 2-11 glucose units. This was subjected to size exclusion chromatography to separate partially methylated cellooligosaccharides consisting of 5-8 glucose units (88 mg, 16% yield).

Size exclusion chromatography used the following as a separation device.
Apparatus: Recycle preparative HPLC LC-9210 NE×T manufactured by Nippon Analytical Industry Co., Ltd. Column: JAIGEL-2HR (exclusion limit molecular weight 5,000) x 2 manufactured by Nippon Analytical Industry Co., Ltd. Flow rate: 9 .5 mL/min Eluent: chloroform Injection volume per injection: 67 mg (1 mL of chloroform)
・Detector: RI-700 II NE×T manufactured by Nippon Analytical Industry Co., Ltd.

(1-3 Synthesis of methylated cyclic cellooligosaccharide from partially methylated cellooligosaccharide)

Under a nitrogen atmosphere, the partially methylated cellooligosaccharide (75 mg, 5.2×10 ⁻⁵ mol) obtained in 1-2 above was dissolved in toluene (18 mL). Trifluoromethanesulfonic anhydride (Tf ₂ O) (15 μL, 9.0×10 ⁻⁵ mol) dissolved in toluene (3 mL) was added dropwise thereto and stirred at room temperature for 1 hour. After that, 2,6-di-tert-butylpyridine (DBP) (185 μL, 8.4×10 ⁻⁴ mol) dissolved in toluene (3 mL) was added dropwise and stirred at room temperature for 17 hours. After that, a saturated aqueous sodium hydrogencarbonate solution (50 mL) was added, and the mixture was extracted with toluene (100 mL). The toluene layer was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting crude product (white solid) was subjected to size exclusion chromatography and medium-pressure column chromatography to purify the methylated cyclic cellooligosaccharide (hexamer ) was obtained (1 mg, 1.5% yield, white solid). The reaction formula is as described above.

Size exclusion chromatography was performed in the same manner as in 1-2 above. The separation conditions by medium pressure column chromatography are as follows.
・Column: ODS (“Universal Column ODS” manufactured by Yamazen Co., Ltd., inner diameter 20 mm, length 84 mm)
- Mobile phase: acetonitrile/water = 8/2 (volume ratio).

Mass spectrometry (MALDI-TOF MS) results for the crude product prior to hexamer purification are shown in FIG. As shown in FIG. 7, peaks corresponding to 5- to 8-mer methylated cyclic cellooligosaccharides were observed.

The results of ¹ H-NMR analysis of the purified product (hexamer) are shown below, and the NMR spectrum is shown in FIG.
¹ H NMR (400 MHz, chloroform-d): 5.08 (d, J = 2.3 Hz, 6H), 4.33 (dd, J = 2.3, 7.7 Hz, 6H), 4.20 (ddd, J = 2.3, 4.5, 7.3 Hz , 6H), 4.03 (dd,J = 2.3, 6.8 Hz, 6H), 3.96 (dd, J = 6.8, 7.7 Hz, 6H), 3.67 (dd, J = 8.2, 9.9Hz, 6H), 3.50 (dd, J = 4.5, 9.5 Hz, 6H), 3.42 (s, 18H), 3.40 (s, 18H), 3.32 (s, 18H) ppm.

FIG. 9 shows the NOESY spectrum of the product, and FIG. 10 shows an enlarged view near the hydrogen (H ₁ ) bonded to the 1-position carbon of the glucose unit.

The results of ¹³ C-NMR analysis of the product are shown below, and the NMR spectrum is shown in FIG.
^13C NMR (400 MHz, chloroform-d): 105.38, 90.72, 87.34, 79.27, 74.20, 72.59, 59.11, 58.86, 57.69 ppm.

The results of mass spectrometry (MALDI-TOF MS) of the product are shown below, and the spectrum is shown in FIG.
MALDI-TOF MS (m/z): 1246 [M+Na] ⁺ .

TLC of the product gave an Rf value of 0.48.

The HPLC results of the product (FIG. 13(a)) are shown in FIG. shown in

From the results of MS spectrum and HPLC, this product has the same molecular weight as permethylated α-cyclodextrin, but it is found to be a different compound. Moreover, from the ¹ H-NMR spectrum and ¹³ C-NMR spectrum, this product is a highly symmetrical compound composed of glucose units in which the hydroxyl groups at the 2-, 3-, and 6-positions are methylated. Conceivable. Furthermore, from the NOESY spectrum (FIGS. 9 and 10), the 1-position proton of the glucose unit shows correlation with the 2-, 3-, 5-, and 6-position protons, while the 4-position proton shows correlation. Therefore, it is considered that the 1-position proton and the 4-position proton are separated from each other, and the glucose units are connected by a β-1,4 bond. From these facts, it can be identified that the chemical structure of the methylated cyclic cellooligosaccharide is represented by the formula (1) (R=methyl group, n=1).

Hereinafter, the methylated cyclic cellooligosaccharide thus obtained is also referred to as "cyclic cellooligosaccharide 1".

<Synthesis Example 2. Synthesis of cyclic cellooligosaccharide>
Next, synthesis of cyclic cellooligosaccharide (R=hydrogen atom in formula (1)), which is another aspect of the cyclic cellooligosaccharide according to the present embodiment, will be described.

(2-1 Synthesis of fully acetylated cellulose from partially acetylated cellulose)
Fully acetylated cellulose was synthesized according to the method described by P. Arndt et al., Cellulose, 2005, 12, 317. The details of the reaction formula and synthesis method are as follows.

Partially acetylated cellulose (manufactured by Sigma-Aldrich, Mn=30000, degree of acetylation=1.48) (4.0 g, 9.3×10 ⁻⁵ mol) was dissolved in acetic acid (80 mL), and acetic anhydride (26 mL, 2.7×10 ⁻¹ mol) and perchloric acid (1.6 mL, 2.8×10 ⁻² mol) were added and stirred at room temperature for 2 hours. The reaction mixture was poured into water (100 mL) and the resulting solid was collected by suction filtration. This was washed with a saturated aqueous sodium bicarbonate solution (500 mL) and then with water (500 mL), and after this washing operation was carried out once more, the solid was vacuum dried at 70° C. to give a white powdery solid (yield: 3.9 g, 80% yield).

The infrared absorption spectrum of the obtained solid confirmed the presence of a carbonyl group absorption peak (1735 cm ⁻¹ ) and the disappearance of a hydroxy group absorption peak (around 3400 cm ⁻¹ ) observed in the raw material.

(2-2 Synthesis of partially acetylated cellooligosaccharides from fully acetylated cellulose)
Partially acetylated cellooligosaccharides were synthesized from fully acetylated cellulose with reference to the method described in T. Kondo, DG Gray, J. Appl. Polym. The details of the reaction formula and synthesis method are as follows.

The fully acetylated cellulose (0.45 g, 8.3×10 ⁻⁶ mol) synthesized in 2-1 above was dissolved in acetic acid (9.0 mL) at 80° C., and acetic anhydride (150 μL, 1.6×10 ⁻³ mol), concentrated sulfuric acid (35 μL, 6.5×10 ⁻⁴ mol) and water (54 μL, 3.0×10 ⁻³ mol) were sequentially added and stirred at 80° C. for 16 hours. The reaction solution was allowed to cool to room temperature, 20% aqueous magnesium acetate solution (70 μL) was added, the reaction mixture was poured into diethyl ether (100 mL), the resulting solid was collected by suction filtration, and washed with water (100 mL). Vacuum dried (yield 0.16 g).

MALDI-TOF-MS measurements revealed that the resulting product was a mixture of partially acetylated cellooligosaccharides consisting of 2-13 glucose units (see Figure 14).

(2-3 Synthesis of acetylated cyclic cellooligosaccharide from partially acetylated cellooligosaccharide)

The partially acetylated cellooligosaccharide (500 mg, 2.0×10 ⁻⁴ mol) obtained in 2-2 above was dissolved in a mixed solution of dehydrated dichloromethane (27 mL) and dehydrated toluene (3.0 mL). Boron trifluoride diethyl ether complex (800 μL, 7.0×10 ⁻³ mol, manufactured by Wako Pure Chemical Industries, Ltd., content: 46.0 to 49.0% (BF ₃ )) was added thereto and heated to 40° C. and stirred for 15 hours. After that, a saturated aqueous sodium hydrogencarbonate solution (50 mL) was added, and after extraction with 100 mL of chloroform, the solvent was distilled off to obtain a brownish yellowish white solid (200 mg). This was dissolved in dehydrated pyridine (3.0 mL), acetic anhydride (1.5 mL, 1.5×10 ⁻² mol) was added, and the mixture was stirred at room temperature for 24 hours to acetylate the liberated hydroxyl groups. Extraction was performed with saturated saline (100 mL) and chloroform (100 mL), and the solvent was distilled off from the chloroform layer to obtain a brownish yellowish white solid (250 mg). Silica gel column chromatography was performed twice (first mobile phase: methanol/chloroform (1/99), second mobile phase: methanol/chloroform (1/150)) to obtain a crude product (6 mg). The reaction formula is as described above.

The obtained crude product was subjected to MALDI-TOF-MS measurement. The results are shown in FIG. As shown in FIG. 15, similarly to the case of the methylated product of Synthesis Example 1, peaks corresponding to 5- to 8-mer cyclic products were observed. Specifically, in Synthesis Example 2, peaks corresponding to 5- to 8-mer acetylated cyclic cellooligosaccharides were observed together with peaks corresponding to non-cyclized linear 6- to 8-mers.

(2-4 Synthesis of cyclic cellooligosaccharide from acetylated cyclic cellooligosaccharide)

Acetylated cyclic cellooligosaccharide (4.0 mg) was dissolved in methanol (1.2 mL), and water (0.8 mL) was added thereto. Further triethylamine (0.8 mL, 5.5×10 ⁻³ mol) was added and stirred at 40° C. for 24 hours. Evaporation of the solvent gave the crude product (4 mg). The reaction formula is as described above.

The obtained crude product was subjected to MALDI-TOF-MS measurement. The results are shown in FIG. As shown in FIG. 16, a peak corresponding to a 6- to 8-mer cyclic cellooligosaccharide was observed together with a peak corresponding to a 6- to 8-mer linear cellooligosaccharide.

Hereinafter, the cyclic cellooligosaccharide thus obtained is also referred to as "cyclic cellooligosaccharide 2".

[Hair composition]
(Evaluation method)
Using cyclic cellooligosaccharide 1 and cyclic cellooligosaccharide 2, the composition for hair was evaluated by the following method.

In the examples of the present invention, although the film-forming agent can exhibit excellent hair styling retention power, it is prepared as a water dosage form in which problems peculiar to the film-forming agent such as film feeling and flaking remarkably appear, and it is a simple system. was evaluated. In addition, content of (A) component was converted into the pure content.

(Sample preparation 1)
Hair compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were prepared according to the compositions shown in Tables 1 and 2 (the amount is parts by mass) and subjected to the following evaluations.

(Test Example 1: Evaluation of setting force (hardness) by measuring breaking strength)
400 μL of each sample obtained in Examples 1, 2, 6 and Comparative Examples 1, 2 was evenly applied to a 10 cm, 1 g hair tress, and left under constant conditions of constant temperature and humidity of 40° C. and humidity of 30%. It was dried overnight, allowed to stand in a desiccator for 3 hours or more, allowed to cool to 25° C., and then measured for breaking strength (N) with a rheometer NMR-2002J (manufactured by Rheotech). Table 3 shows the results.

For the breakage strength (N), the maximum value was measured by pushing the prepared hair bundle under the conditions of stroke: 20 mm and speed: 60 mm/min.

(Test Example 2: Evaluation of setting force (hardness) under high humidity by measuring breaking strength)
A hair tress prepared in the same manner as in Test Example 1 was further left for 1.5 hours under constant conditions of constant temperature and humidity of 35° C. and 80% humidity, and then measured with a rheometer NMR-2002J (manufactured by Rheotech). The breaking strength (N) was measured under the same measurement conditions as in Test Example 1. Table 3 shows the results.

From the results shown in Table 3, the hair compositions of Examples 1, 2, and 6, compared with the hair compositions of Comparative Examples 1 and 2, contained the film-forming agent (A) in an amount of It can be seen that the combination with the cyclic cellooligosaccharide of the component (B) provides the same degree of breaking strength despite the small amount. From this, it can be seen that the hair composition of the present invention exhibits excellent setting power (hardness).

Furthermore, in the measurement of breaking strength under high humidity, the hair compositions of Examples 1, 2 and 6 show higher values than the hair compositions of Comparative Examples 1 and 2. That is, in the hair compositions of Comparative Examples 1 and 2, in which the component (A) was used alone, the breakage strength was remarkably lowered under high humidity, and the setting power (hardness) could not be maintained. The hair compositions of Examples 1, 2, and 6, which were combined with the cyclic cellooligosaccharide of component B, exhibited a small decrease in breaking strength and a high breakage strength despite the small amount of the film-forming agent of component (A). It can be seen that the setting force (hardness) is maintained even under humidity.

In general, film-forming agents are inferior in moisture resistance, and thus it is difficult to exhibit sufficient setting power (hardness) under high humidity. However, it can be said that it shows the behavior of retaining the setting force (hardness). This also suggests that in the composition for hair of the present invention, the moisture resistance of the component (A) is enhanced by some influence, and the above-described breaking strength measurement result is similar to the cyclic strength of the component (B). This result is presumed to support that part or all of the film-forming agent (A) is included in the cellooligosaccharide.

(Test Example 3: Evaluation of hair styling retention power by curl retention)
1000 μL of each sample obtained in Examples 1 to 7 and Comparative Examples 1 to 5 was uniformly applied to a 30 cm, 2 g hair bundle, wound around a rod with a diameter of 1 cm, and held at a constant temperature of 40 ° C. and a humidity of 30%. It was dried overnight under constant humidity conditions, left in a desiccator for 3 hours or more, and allowed to cool to 25°C. After that, the hair bundle was removed from the rod, and the length (L1) of the curled hair bundle was measured. Next, it was hung under constant conditions of constant temperature and humidity of 35° C. and humidity of 80%, and the length (L2) was measured again after 3 hours. A curl retention value (%) was calculated based on the following formula and evaluated according to the following evaluation criteria. Table 4 shows the results.

The curl retention value was calculated by substituting the hair bundle length (L1) and the hair bundle length (L2) into the following equation. It should be noted that the closer the curl retention value is to "100", the less the degree of change in the curled hair bundle, and the better the hair styling retention under high humidity.
Curl retention value (%) = ((30-L2)/(30-L1)) x 100

<Evaluation criteria for hair styling retention power by curl retention>
◎: Curl retention value of 85% or more ○: Curl retention value of 65% or more and less than 85% △: Curl retention value of 45% or more and less than 65% ×: Curl retention value of 25% or more and less than 45% × ×: Curl retention value is less than 25%

(Test Example 4: Evaluation of coating feeling)
A sensory evaluation panel of 20 people used a wig (Lesson mannequin: manufactured by Eucalyptus Japan) to raise the hair of the wig with the hair compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 10. I had my hair done. Next, the hair was touched with fingertips, and sensory evaluation was performed according to the following evaluation criteria for the "feeling of film" on the surface of the hair. The evaluation was carried out under constant conditions of constant temperature and humidity of 23° C. and humidity of 60%. Table 4 shows the results.

In addition, the evaluation of the "feeling of film" was based on the fact that the hair surface was "stiff" and "squeaky" despite having the feeling of film required to maintain the hairstyle, compared with wig hair that had not been styled. ” and those in which the “crunchy” feeling (excessive coating feeling) was not conspicuous were evaluated as “appropriate coating feeling”.

<Evaluation Criteria for Film Feeling>
◎: 16 or more out of 20 people answered that they felt a suitable coating feeling ○: 11 to 15 out of 20 people answered that they felt a suitable coating feeling Responded to feeling a feeling of covering ×: 5 or less out of 20 answered that they felt a suitable feeling of covering

(Test Example 5: Evaluation of flaking)
After the evaluation in Test Example 4, the hair was continuously combed 10 times with fingertips from the hairline to the tip, and visually evaluated according to the following evaluation criteria. Table 4 shows the results.

<Evaluation Criteria for Flaking>
◎: 16 or more out of 20 people answered that significant flaking did not occur ○: 11 to 15 out of 20 people answered that significant flaking did not occur Answered that no significant flaking occurred ×: 5 or less out of 20 answered that no significant flaking occurred

From the results shown in Table 4, the hair compositions of Examples 1 to 7 had higher curl retention values even under high humidity compared to the hair compositions of Comparative Examples 1 to 5. Since the degree of change in curled hair tufts is small, it can be seen that the film-forming agent can sufficiently exhibit its hair styling retention power, which is an excellent hair styling property originally possessed by the film forming agent. In addition, it can be seen that excessive film feeling and conspicuous flaking, which are negative characteristics of the film-forming agent, did not occur at that time.

Although several embodiments of the invention have been described above, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and modifications can be made without departing from the scope of the invention. These embodiments, their omissions, replacements, modifications, etc., are included in the invention described in the scope of claims and equivalents thereof, as well as being included in the scope and gist of the invention.

Claims (2)

Vinylpyrrolidone/N,N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate, vinylimidazolium trichloride/vinylpyrrolidone copolymer, polyvinylpyrrolidone/alkylaminoacrylate/vinylcaprolactam copolymer, methyl vinylimidazolium chloride/ Group of vinylpyrrolidone copolymer, vinylpyrrolidone/dimethylaminopropyl methacrylamide/lauryldimethylaminopropyl methacrylamide copolymer, polyvinylpyrrolidone, vinyl acetate/vinylpyrrolidone copolymer, vinylpyrrolidone/methacrylamide/vinylimidazole copolymer A composition for hair containing (A) a film-forming agent containing at least one selected from and (B) a cyclic oligosaccharide represented by the following general formula (1). However, in formula (1), R represents a hydrogen atom or an unsubstituted alkyl group having 1 to 20 carbon atoms, multiple Rs may be the same or different, and n represents an integer of 0 to 3.

The (A) film-forming agent is one or more selected from vinylpyrrolidone/N,N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate and polyvinylpyrrolidone , and R in formula (1) is a hydrogen atom or a methyl group .

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