JP5349908B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic that does not wash away.

  In recent years, due to the effects of chemical treatment with hair color, etc., and physical treatment with blow, etc., the hair surface cuts off and the inside of the hair is hollowed out due to the outflow of lipid inside the hair, resulting in loss of gloss. The surface of the hair becomes hydrophilic and the hair tends to get tangled. As a result, there is a problem in that the finger passage becomes worse and the tips of the hair are not collected.

  Various treatments for applying hair cosmetics have been widely performed to conceal hair damage and improve gloss. When applying hair cosmetics to damaged hair, the touch and appearance of finishing, such as passing through, drying and finishing fingers, and gloss, are important factors in providing hair cosmetics. It becomes. In addition, damaged hair is difficult to bundle and has poor holding. Therefore, in addition to improving the feel and gloss, it is also important to be able to make a beautiful hair style, such as the unity of the hair ends and the durability of the unity, and to maintain it.

  Hair cosmetics containing branched polyglycerol-modified silicones are known as having good fingering when applied to hair, and have been able to protect / repair, modify, or style hair, and have tried to give gloss and a smooth texture. (Patent Document 1). However, although this technology is superior in fingering improvement, hair protection / repair, and a modification effect that improves gloss and smoothness, it does not take into account the cohesiveness and sustainability of the hair tips. Is insufficient.

  On the other hand, in order to improve the cohesiveness of damaged hair, the persistence of the cohesion, and to improve the stickiness during drying, a hair cosmetic containing a specific organopolysiloxane is combined with an organic acid and an organic solvent. Known (Patent Document 2). However, this technique can improve the cohesiveness and the sustainability of the cohesiveness, but is insufficient in terms of stickiness at the time of application and fingering.

JP 2005-97152 A Japanese Unexamined Patent Publication No. 2006-069899

  Therefore, the present invention can impart sufficient effects to the hair at the time of application, drying, dryness after drying, and the cohesiveness of the hair ends and the persistence of the hair ends after finishing. An object of the present invention is to provide a hair cosmetic that can be used.

  The present inventors have found that the above-mentioned problems can be solved by using a hair cosmetic that does not wash away using a combination of a branched polyglycerol-modified silicone and a poly (N-acylalkylenimine) -modified silicone.

  The present invention provides a non-washing-out type hair cosmetic that contains the following components (A) and (B) and has a mass ratio (A) / (B) of both components of 0.05 to 20. It is.

  (A) Branched glycerol represented by the following structural formula (1) having an average of 3 or more glycerol groups represented by the following structural formula (1), (2), (3) or (4). Branched polyglycerol-modified silicone in which at least one branched polyglycerol chain containing at least one group is bonded to the silicon atom of the silicone via a linking group: 0.05 to 5% by mass

  (B) At least one silicon atom of the organopolysiloxane segment is bonded to the following general formula (10) via an alkylene group containing a hetero atom.

[Wherein, R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and m represents a number of 2 or 3. ]
A poly (N-acylalkyleneimine) comprising repeating units represented by the formula is bonded, and the mass ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40/60. An organopolysiloxane having a weight average molecular weight of 12,000 to 500,000: 0.05 to 4% by mass

  The present invention also provides a hair treatment method in which the above-described hair cosmetic is applied to the hair and then left for at least 3 hours without being washed away.

  The hair cosmetic composition of the present invention can impart sufficient effects to the hair both in the smooth feel at the time of application and in the unity and the unity of the finished product.

[(A): Branched polyglycerol-modified silicone]
In the branched polyglycerol-modified silicone of component (A), the branched polyglycerol chain contains one or more branched glycerol groups (hereinafter referred to as group (1)) represented by the structural formula (1) as branching groups. The branched polyglycerol chain is represented by a group (1), b glycerol group represented by structural formula (2) (hereinafter referred to as group (2)), and c structural formula (3). A glycerol group (hereinafter referred to as group (3)) and d glycerol groups represented by structural formula (4) as terminal groups (hereinafter referred to as group (4)) are group (1), (2) or It is formed by bonding via an oxygen atom of (3).

  In the branched polyglycerol chain, the groups (1), (2) and (3) may be bonded to each other in any sequence. As the number of groups (1) increases, the branched structure develops, and the group (4) exists at the end of each branched chain.

As described later, the branched polyglycerol-modified silicone of component (A) contains at least one branched structure of group (1) based on δ 78.0-81.0 ppm in ¹³ C-NMR analysis. This can be proved by the fact that a unique peak is seen. Preferably, the average number of groups (1) per branched polyglycerol chain is 1 or more.

  In the present invention, the average total number of bonds (a + b + c + d) of the groups (1), (2), (3) and (4) in the branched polyglycerol chain is 3 or more, and NMR analysis or molecular weight comparison with the precursor silicone Is required. The average total number of bonds is more preferably 3 to 201, still more preferably 3 to 101, in order for the branched polyglycerol-modified silicone of component (A) to maintain appropriate silicone properties. -51 is particularly preferable, and 3-21 is most preferable.

  In the present invention, the ratio of the average branching in all the branched polyglycerol chains is preferably a / (a + b + c + d) of 1/20 to 1/2, and 1/10 to 1 / 2 is more preferable, and 1/5 to 1/2 is particularly preferable.

  In one branched polyglycerol chain, 1 to 100 groups (1) are preferably present, more preferably 2 to 100 groups, still more preferably 2 to 50 groups, and more preferably 2 to 25 groups. It is particularly preferred that there are 2 to 10 and most preferred that 2 to 10 are present. 2 to 101 groups (4) are preferably present in one branched polyglycerol chain, more preferably 3 to 101 groups, still more preferably 3 to 51 groups, and more preferably 3 to 26 groups. It is particularly preferred that there are 3 to 11, most preferably 3 to 11. The group (2) and the group (3) are the same or different, and are preferably 0 to 198, more preferably 0 to 196, and more preferably 0 to 96 in one branched polyglycerol chain. More preferably, it is present, particularly preferably 0 to 46, and most preferably 0 to 16.

  In the branched polyglycerol-modified silicone of component (A), the linking group that bonds the silicon atom of the silicone and the aforementioned branched polyglycerol chain is preferably a divalent or trivalent group having an ether group.

The divalent group having an ether group is preferably a group represented by the general formula (5) (hereinafter referred to as a linking group (5)). In the linking group (5), the R ¹ side is bonded to the silicon atom of the silicone chain, and the (A ¹ O) _p side is bonded to the branched polyglycerol chain.

-R ¹ -O- (A ¹ O) _p- (5)
[In the formula, R ¹ may have a substituent, a linear or branched alkylene group, an alkenylene group or an arylene group having a carbon number of 6 to 28 from 1 to 22 carbon atoms, A ¹ O Represents an alkyleneoxy group having 1 to 4 carbon atoms (also referred to as an oxyalkylene group) or an aryleneoxy group having 6 to 10 carbon atoms (also referred to as an oxyarylene group), p represents a number from 0 to 30; A ¹ O may be the same or different. ]

In the linking group (5), the arylene group in R ¹ includes an alkylene arylene group, an arylene alkylene group, and an alkylene arylene alkylene group. The alkylene group or alkenylene group preferable as R ¹ is an alkylene group or alkenylene group having 1 to 16 carbon atoms, particularly preferably 1 to 12 methylene, ethylene, propylene, trimethylene, butylene, tetramethylene, pentamethylene, hexamethylene. , Heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene group, and the like. Preferred arylene groups as R ¹ include an alkylene group Are alkylene phenylene groups having 1 to 22 carbon atoms, and trimethylene phenylene groups are preferred. Among these R ¹ , an ethylene group, a propylene group, a trimethylene group, or a trimethylenephenylene group is more preferable, and an ethylene group, a trimethylene group, or a trimethylenephenylene group is particularly preferable from the viewpoint of easy synthesis of raw materials.

As substituents in R ¹ , a hydroxy group, an amino group (1 to 22 carbon atoms), an imino group (1 to 22 carbon atoms), a carboxy group, an alkoxy group (1 to 22 carbon atoms), an acyl group (1 carbon number) ~ 22) and the like.

In the linking group (5), A ¹ O is preferably an ethyleneoxy group, a propyleneoxy group or a phenyleneoxy group, and more preferably an ethyleneoxy group or a phenyleneoxy group.

In the linking group (5), p is preferably 0 to 20, more preferably 0 to 15, further preferably 0 to 10, particularly preferably 0 to 5, and 0 or 1 from the viewpoint of easy availability of raw materials. Most preferred. In particular, when R ¹ is an ethylene group or trimethylene group, 1 is most preferable, and when R ¹ is an alkylene arylene group, 0 is most preferable.

The p A ¹ Os may be the same or different and may be alternating, random or block, or a periodic arrangement other than these, or may be of a random type.

  In the present invention, the most preferable linking group is a divalent linking group represented by the following general formula (7) (hereinafter referred to as linking group (7)). In the linking group (7), the trimethylene side is bonded to the silicon atom of the silicone chain, and the oxygen atom side is bonded to the branched polyglycerol chain.

  In the linking group (7), the bonding mode of the oxygen atom and trimethylene group bonded to the phenylene group of the oxyphenylene group may be any of the ortho, meta, and para positions, and a mixture thereof. However, the ortho position is desirable from the viewpoint of raw material availability.

In the branched polyglycerol-modified silicone of component (A), the linking group that binds the silicon atom of the silicone chain and the aforementioned branched polyglycerol chain may be a trivalent group. Among such linking groups, a group represented by the following general formula (6) (hereinafter referred to as linking group (6)) or a group represented by the following general formula (8) (hereinafter referred to as linking group (8)). Is preferred). In the linking group (6), the R ¹ side is bonded to the silicon atom of the silicone chain, the (A ² O) _q and (A ³ O) _r sides are bonded to the branched polyglycerol chain, and the linking group (8) , The trimethylene side is bonded to the silicon atom of the silicone chain, and the two oxygen atom sides are each bonded to the branched polyglycerol chain.

[Wherein, R ¹ represents the above meaning, A ² O and A ³ O each independently represents an alkyleneoxy group having 1 to 4 carbon atoms or an aryleneoxy group having 6 to 10 carbon atoms, and q represents 1 to The number of 30 and r represents a number of 1 to 30, and q A ² O and r A ³ O may be the same or different. ]

In the linking group (6), A ² O and A ³ O are the same or different and are preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group or a phenyleneoxy group, more preferably a methyleneoxy group or ethyleneoxy group. It is a group.

  In the linking group (6), q and r are each a number of 1 to 30, preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1.

q A ² Os and r A ³ Os may be the same or different, and when they are different, the mutual bonding mode of A ² O and A ³ O is an alternating type, a block type, or other than these It may be a periodic array or may be a random type.

  In the linking group (8), any two of the two oxygen atoms and trimethylene groups bonded to the phenylene group of the oxyphenylene group can be in any of ortho, meta, and para positions. Or a mixture thereof.

  The silicone that forms the branched polyglycerol-modified silicone of component (A) is derived from a polysiloxane having two or more silicon atoms, and the shape of the polysiloxane can be linear, branched, or cyclic. There may be. Moreover, the number average molecular weight of polysiloxane becomes like this. Preferably it is 300-700,000, More preferably, it is 300-200,000, More preferably, it is 1000-20,000. The number average molecular weight can be determined by gel permeation chromatography (hereinafter referred to as GPC) method, light scattering method or the like.

  The branched polyglycerol-modified silicone of component (A) is preferably a linear silicone represented by general formula (9) (hereinafter referred to as silicone (9)).

[Wherein R ² , R ³ , R ⁴ , t R ⁵ , t R ⁶ , R ⁷ , R ⁸ , R ⁹ are the same or different and represent a linking group to which a branched polyglycerol chain is bonded. A linear or branched alkyl group having 1 to 22 carbon atoms, an alkenyl group or an alkoxy group, or an aryl group having 6 to 22 carbon atoms, which may have a substituent, R ² , At least one of R ³ , R ⁴ , t R ⁵ , t R ⁶ , R ⁷ , R ⁸ and R ⁹ is a linking group to which a branched polyglycerol chain is bonded. t represents a number from 0 to 10,000. ]

In silicone (9), R ² , R ³ , R ⁴ , t R ⁵ , t R ⁶ , R ⁷ , R ⁸ , R ⁹ other than the linking group to which the branched polyglycerol chain is bonded Are the same or different and may have a linear or branched alkyl group, alkenyl group, or alkoxy group having 1 to 22 carbon atoms, or may have a substituent. Is an aryl group having ˜22, but examples of the alkyl group having 1 to 22 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, trifluoropropyl group, etc. Examples of the alkenyl group having 1 to 22 carbon atoms include vinyl group and allyl group. Examples of the alkoxy group having 1 to 22 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyl. Yloxy, heptyloxy, and octyloxy group. Examples of the aryl group having 6 to 22 carbon atoms include a phenyl group. Among these, a linear or branched alkyl group having 1 to 12 carbon atoms, a vinyl group, an allyl group, or a phenyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a phenyl group is particularly preferable. Among these, a methyl group is more preferable from the viewpoint of versatility and price, but a phenyl group is more preferable from the viewpoint of heat resistance.

In the silicone (9), R ^{2 to} R ⁹ may have a phenyl group, phenoxy group, hydroxy group, carboxy group, amino group (0 to 14 carbon atoms), imino group, (aminoethyl) ) Amino group, (dimethylaminoethyl) amino group, polyoxyalkylene group, mercapto group, epoxy group, and polysiloxysilyl group. Of these, hydroxy, amino, (aminoethyl) amino, (dimethylaminoethyl) amino, polyoxyalkylene, and polysiloxysilyl groups are particularly preferred. Moreover, when it has these substituents, as R < ² > -R < ⁹ >, an ethyl group or a propyl group is especially preferable.

In the silicone (9), at least one, preferably 1 to 10, more preferably R ² , R ³ , R ⁴ , t R ⁵ , t R ⁶ , R ⁷ , R ⁸ , R ⁹ 1 to 5, particularly preferably 1 to 2, are a linking group to which a branched polyglycerol chain is bonded. This linking group may be located at any of the side chain, one end and / or both ends of the silicone (9), or may be a mixture thereof.

One selected from the group consisting of R ^{2 to} R ⁴ and one selected from the group consisting of R ^{7 to} R ⁹ represent a linking group to which a branched polyglycerol chain is bonded, and the remaining R ^{2 to} R ⁴ and When R ^{7 to} R ⁹ , t R ⁵ , and t R ⁶ represent other groups, the branched polyglycerol-modified silicone of component (A) becomes a branched polyglycerol-modified silicone of both end substitution type, In addition, it is easy to adopt a higher order structure by being interconnected in a solvent, and is very preferable as a branched polyglycerol-modified silicone to be blended in the hair cosmetic composition of the present invention. In that case, it is particularly preferable that the remaining R ^{2 to} R ⁴ and R ^{7 to} R ⁹ , t R ⁵ , and t R ⁶ are methyl groups.

In addition, when the linking group to which the branched polyglycerol chain is bonded is present in 3 or more selected from t R ⁵ and t R ⁶ , the polyglycerol-modified silicone is a side-chain polysubstituted branched polyglycerol. It becomes a modified silicone, and it is preferable as the branched polyglycerol-modified silicone as the component (A) to be blended in the hair cosmetic composition of the present invention because of its hydrophilicity and adsorption ability.

  T in the silicone (9) represents a number of 0 to 10,000, preferably a number of 1 to 3,000, more preferably a number of 5 to 500, and particularly preferably a number of 10 to 150.

  The number average molecular weight of the branched polyglycerol-modified silicone of component (A) is preferably 500 to 500,000, more preferably 750 to 200,000, particularly preferably 1,000 to 100,000. The measuring method of this number average molecular weight is based on GPC (in terms of polystyrene or polyethylene glycol).

  The branched polyglycerol-modified silicone of component (A) is composed of the total number of silicon atoms (Si) in the silicone and the groups (1), (2), (3) and (4) in the branched polyglycerol chain (hereinafter referred to as glycerol). (G) (G) ratio (G / Si) is preferably 0.001 to 50, more preferably 0.05 to 10, still more preferably 0.07 to 3, and particularly preferably 0.1 to 1. Within this range, the rate of adsorption to hair is particularly high when various hair cosmetics are blended.

  The branched polyglycerol-modified silicone of component (A) contains a small amount of the branched polyglycerol chain in the branched polyglycerol chain as long as it does not significantly impair the characteristics of the blending stability, hair affinity, and hair protection / modification ability. An ethyleneoxy group and / or a propyleneoxy group may be present. Ethyleneoxy groups and / or propyleneoxy groups may be present randomly in the branched polyglycerol chain, or a plurality of ethyleneoxy groups and / or propyleneoxy groups form a chain and block in the branched polyglycerol chain. May be present. In this case, the block composed of a plurality of ethyleneoxy groups and / or propyleneoxy groups may be present in the vicinity of the linking group of the branched polyglycerol chain, may be present at the terminal, or may be present in the middle. You may do it. When an ethyleneoxy group and / or a propyleneoxy group are present, the ethyleneoxy group and / or propyleneoxy group is preferably present at 0.001 to 0.5 molar equivalents relative to 1 molar equivalent of a glycerol group, and 0.02 to 0.2 molar equivalents. More preferably, it is present.

  Such a branched polyglycerol-modified silicone includes, for example, a platinum-based catalyst comprising a hydropolysiloxane having a hydrogen atom bonded to a part of a silicon atom in a silicone chain and a branched polyglycerol compound having an aliphatic unsaturated group. It can be obtained by hydrosilylation reaction in the presence, or by ring-opening graft polymerization of glycidol to polysiloxane having an epoxy group or a hydroxyl group as a reactive group in the presence of an alkali metal catalyst such as potassium.

  Ingredient (A) may be used in combination of two or more thereof, and the content thereof is 0.05 to 5% by mass in the hair cosmetic composition of the present invention from the viewpoint of being non-sticky and easy to touch. However, Preferably it is 0.07-3 mass%, More preferably, it is 0.1-2 mass%. As a commercial item of component (A), Sofcare GS-G (Kao Corporation) can be mentioned.

[(B): Organopolysiloxane]
The alkylene group containing a hetero atom intervening in the bond between an organopolysiloxane segment and poly (N-acylalkyleneimine) has 2 to 20 carbon atoms containing 1 to 3 nitrogen atoms, oxygen atoms and / or sulfur atoms. An alkylene group is mentioned. As a specific example,

Etc. In particular, a C2-C5 alkylene group containing a nitrogen atom is preferable. Examples of the alkyl group represented by R ¹⁰ in the general formula (10) include a methyl group and an ethyl group, and examples of the cycloalkyl group represented by R ¹ include those having 3 to 6 carbon atoms. Examples of the aralkyl group include phenylalkyl and naphthylalkyl, and examples of the aryl group include phenyl, naphthyl, and alkyl-substituted phenyl.

  The organopolysiloxane of component (B) can be produced by a known method, for example, according to the method described in JP-A-7-133352, the following general formula (11)

[Wherein, R ¹¹ is the same or different and represents a saturated alkyl group having 1 to 22 carbon atoms or a phenyl group, and R ¹² and R ¹³ each represent the same group as R ¹¹ , or

R ¹⁴ represents a group represented by the above formula, a represents an integer of 100 to 4000, and b represents an integer of 1 to 300. ]
And an organopolysiloxane represented by the following general formula (12)

[Wherein, R ¹⁰ and m are as defined above. ]
It is produced by reacting a terminal reactive poly (N-acylalkyleneimine) obtained by ring-opening polymerization of a cyclic imino ether represented by the formula:

  Here, the ring-opening polymerization of the cyclic iminoether (12) can be performed according to the method described in, for example, Liebigs Ann. Chem., P996 to p1009 (1974). The polymerization initiator is a compound having strong electrophilic reactivity, such as methyl, ethyl, 3-propenyl, benzyl ester, etc. of strong acid such as benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, sulfuric acid and the like. Can be used. In particular, toluenesulfonic acid alkyl ester, sulfuric acid dialkyl ester, trifluoromethanesulfonic acid alkyl ester, and the like can be preferably used. When, for example, 2-substituted-2-oxazoline is used as the cyclic imino ether (12), poly (N-acylethyleneimine) (corresponding to m = 2 in the formula (10)) is obtained, and 2-substituted-dihydro- If 2-oxazine is used, poly (N-acylpropylenimine) (corresponding to m = 3 in the formula (10)) can be obtained.

  The poly (N-acylalkyleneimine) chain and the silicone chain are linked by ester formation reaction by condensation of carboxyl group and hydroxyl group; amide formation reaction by condensation of carboxyl group and amino group; alkyl halide Reaction of primary, secondary or tertiary amino group with secondary, tertiary or quaternary ammonium; addition reaction of Si-H group to vinyl group; β-hydroxyamine with epoxy group and amino group Many techniques such as formation reactions can be used. Of these, as disclosed in JP-A-2-276824, JP-A-4-85334, JP-A-4-85335, JP-A-4-96933, etc. The method of reacting the end-reactive poly (N-acylalkylenimine) obtained by polymerization with the organopolysiloxane represented by the formula (11), that is, the modified organopolysiloxane having the above substituent in the side chain, is simple and effective. It is.

  The reaction between the organopolysiloxane containing an amino group and the reactive terminal of poly (N-acylalkylenimine) obtained by cationic polymerization of a cyclic imino ether can be performed, for example, as follows. Initiator is a polar solvent, preferably acetonitrile, valeronitrile, dimethylformamide, dimethylacetamide, chloroform, methylene chloride, ethylene chloride, ethyl acetate, methyl acetate, etc., or a mixed solvent with other solvents as required And heated to 40 to 150 ° C, preferably 60 to 100 ° C. The cyclic imino ether represented by the above general formula (12) is charged all at once, or dropped when the reaction is intense, and polymerization is carried out. The progress of the polymerization can be traced by quantifying the residual amount of the cyclic imino ether as a monomer with an analytical instrument such as gas chromatography. Even when the cyclic imino ether is consumed and the polymerization is completed, the active species at the growing end maintain the reactivity. Without isolating the polymer, this polymer solution and the organopolysiloxane containing an amino group in the molecule are mixed and reacted at 5 to 100 ° C., preferably 20 to 60 ° C. The mixing ratio can be appropriately selected as desired, but it is preferable to react at a ratio of 0.1 to 1.3 molar equivalents of poly (N-acylalkylenimine) with respect to 1 mol of amino group in the organopolysiloxane. A block copolymer or graft polymer having poly (N-acylalkylenimine) segments on polydimethylsiloxane can be obtained.

In the organopolysiloxane of component (B), the mass ratio of the organopolysiloxane segment to the poly (N-acylalkylenimine) segment is 98/2 to 40/60. In particular, from the viewpoint of improving the unit of the hair ends and the sustainability thereof, 82/18 to 65/35, more preferably 80/20 to 68/32, and more preferably 79/21 to 70/30. This mass ratio was determined by dissolving 5% by mass of the organopolysiloxane of component (B) in deuterated chloroform, and analyzing the nuclear group and the alkyl group or phenyl group in the organopolysiloxane segment by nuclear magnetic resonance ( ¹ H-NMR) analysis. The value obtained from the integral ratio of methylene groups in the poly (N-acylalkylenimine) segment.

  In addition, the weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments of the organopolysiloxane of component (B) is 1500 from the standpoint of improving setability and its sustainability. To 3500, more preferably 1600 to 3200, and more preferably 1700 to 3000.

Here, the “organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments” means the bonding point of the poly (N-acylalkyleneimine) segment to the organopolysiloxane segment as shown in the following formula ( A portion surrounded by a broken line between two points from a bonding point α) to a bonding point (bonding point β) of a poly (N-acylalkylenimine) segment adjacent thereto, and one R ¹¹ SiO unit A segment composed of one A ⁴ and y + 1 R ¹¹ ₂ SiO units.

[Wherein R ¹¹ represents the same meaning as described above, A ⁴ represents an alkylene group containing a hetero atom, W represents a poly (N-acylalkyleneimine) segment, and J represents a residue of a polymerization initiator. , Y represents a positive number. ]

  MWg can be understood as the mass (g / mol) of the organopolysiloxane segment per mole of the poly (N-acylalkylenimine) segment, and the functional group of the modified organopolysiloxane as the raw material compound is poly (N- 100% substitution with acylalkylenimine) corresponds to the functional group equivalent (g / mol) of the modified organopolysiloxane.

  The MWg can be obtained by the following formula using the content (Csi) of the organopolysiloxane segment constituting the main chain and the molecular weight (MWox) of the poly (N-acylalkylenimine) segment.

  The molecular weight (MWox) of the poly (N-acylalkylenimine) segment refers to a number average molecular weight measured by a gel permeation chromatography (GPC) measurement method described later, preferably 500 to 10,000, more preferably 800 to 1600, More preferably, it is 850-1500, More preferably, it is 900-1400. Thereby, a set property and its sustainability can be improved further.

  In the organopolysiloxane of component (B), the weight average molecular weight of the organopolysiloxane (11), which is the raw material compound, is soluble in polar solvents such as water, ease of handling after dissolution, and setability and sustainability. From the viewpoint of improvement, 10,000 to 100,000, further 20,000 to 80,000, and more preferably 30,000 to 60,000 are preferable. In addition, the average molecular weight of organopolysiloxane (11) which is a raw material compound is a weight average molecular weight in terms of polystyrene measured by GPC under the following measurement conditions.

Column: Super HZ4000 + Super HZ2000 (manufactured by Tosoh Corporation)
Eluent: 1 mM triethylamine / THF
Flow rate: 0.35mL / min
Column temperature: 40 ° C
Detector: UV
Sample: 50μL

  The weight average molecular weight of the organopolysiloxane of component (B) is 12,000 to 500,000, but 12,000 to 150,000, more preferably 24,000 to 120,000, and even more than 37,000 to 92,000 from the viewpoint of further improving the setability and its sustainability. Is preferred. In addition, the weight average molecular weight of the organopolysiloxane of the component (B) is the weight average molecular weight of the organopolysiloxane (11) as the raw material compound, the aforementioned organopolysiloxane segment and the poly (N-acylalkyleneimine) segment), and It can obtain | require from mass ratio of.

  Examples of the component (B) organopolysiloxane include poly (N-formylethyleneimine) organosiloxane, poly (N-acetylethyleneimine) organosiloxane, and poly (N-propionylethyleneimine) organosiloxane. The INCI name includes Polysilicone-9.

  Two or more kinds of component (B) may be used in combination, and the content thereof is 0.05 to 4 in the hair cosmetic composition of the present invention from the viewpoint that it is non-sticky and has improved cohesiveness of the hair tips. Although it is mass%, Preferably it is 0.07-3 mass%, More preferably, it is 0.1-2 mass%.

  In the hair cosmetic composition of the present invention, the content ratio (A) / (B) of the component (A) and the component (B) is 0.05 to 20 from the viewpoint of not stickiness and improving the unity of the hair tips. However, it is preferably 0.1 to 15, more preferably 0.4 to 7.

[(C): iso fatty acid or anteiso fatty acid or salt thereof]
The hair cosmetic composition of the present invention further comprises, as a component (C), an isofatty acid having 12 to 30 carbon atoms, an anteisofatty acid having 12 to 30 carbon atoms, or a salt thereof, from the viewpoint of further improving the texture of the fingertips and hair ends. It is preferable to contain.

  As the component (C), an isofatty acid having 12 to 30 carbon atoms, an anteiso fatty acid having 12 to 30 carbon atoms or a salt thereof, 14-methylpentadecanoic acid, 15-methylhexadecanoic acid, 16-methylheptadecanoic acid as isofatty acid , 17-methyloctadecanoic acid, 18-methylnonadecanoic acid, 19-methyleicosanoic acid, 20-methylheneicosanoic acid, and 13-methylpentadecanoic acid, 14-methylhexadecanoic acid, 15-methylheptadecane as antiiso fatty acids Examples include acids, 16-methyloctadecanoic acid, 17-methylnonadecanoic acid, 18-methyleicosanoic acid, and 19-methylheneicosanoic acid. These salts include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, organic amines such as ammonium salt, triethanolamine salt, diethanolamine salt and monoethanolamine salt. Examples include basic amino acid salts such as salts, lysine salts, and arginine salts. These fatty acids are preferably saturated fatty acids, more preferably 14 to 24, and particularly preferably 16 to 22. Examples of commercially available products include 18MEA (manufactured by Croda Japan).

Two or more types of the fatty acid of component (C) or a salt thereof may be used in combination. Moreover, although content in the hair cosmetics of this invention is 0.001-5 mass%, 0.01-3 mass% is preferable, and also 0.1-2 mass% is more preferable.

[(D): Organic carboxylic acid or salt thereof]
The hair cosmetic composition of the present invention preferably further contains an organic carboxylic acid having 2 to 8 carbon atoms or a salt thereof as component (D). Examples of the organic carboxylic acid having 2 to 8 carbon atoms include glycolic acid, lactic acid, citric acid, tartaric acid, malic acid, levulinic acid, acetic acid, maleic acid, and fumaric acid. Of these, α-hydroxy acids are preferable, and glycolic acid, citric acid, malic acid, and lactic acid, particularly malic acid, lactic acid, and citric acid are preferable. Examples of these salts include salts with alkali metals, alkaline earth metals, ammonia, organic amine compounds and the like. Two or more organic acids or salts thereof can be used in combination.

  Two or more of these components (D) may be used in combination, and at least malic acid or a salt thereof is preferably used. The content of component (D) is the amount of free acid converted from the viewpoint of the effect of internal modification (such as cavity repair) of hair, improvement of mass, improvement of set retention, and moisture resistance of the mass. The content is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 10% by mass.

[(E): Organic solvent]
The hair cosmetic composition of the present invention preferably further contains an organic solvent selected from the group consisting of aromatic alcohol, N-alkylpyrrolidone, alkylene carbonate, polypropylene glycol, lactone and cyclic ketone as component (E).

  Examples of the organic solvent of component (E) include those selected from the following (e1) to (e5).

  (e1) Aromatic alcohol represented by general formula (13)

[Wherein R ¹⁵ represents a group R ¹⁶ —Ph—R ¹⁷ — (R ¹⁶ ; a hydrogen atom, a methyl group or a methoxy group, R ¹⁷ ; a bond or a saturated or unsaturated divalent carbon atom having 1 to 3 carbon atoms. Hydrogen group, Ph; paraphenylene group), Y and Z each represent a hydrogen atom or a hydroxyl group, and c, d and e each represent an integer of 0 to 5. However, when c = d = 0, Z is a hydroxyl group and R ¹⁵ is not a group R ¹⁶ -Ph-. ]

  (e2) N-alkylpyrrolidone or N-alkylpyrrolidone having a C1-C18 alkyl group or alkenyl group bonded to a nitrogen atom

  (e3) C2-C4 alkylene carbonate

  (e4) Polypropylene glycol having a number average molecular weight of 100 to 1000

  (e5) Lactone or cyclic ketone represented by general formula (14), (15) or (16)

[Wherein, X represents a methylene group or an oxygen atom, R ¹⁸ and R ¹⁹ represent different substituents, and f and g represent 0 or 1. ]

Among the organic solvents as component (E), examples of (e1) include benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol and the like. . Examples of (e2) include N-methylpyrrolidone, N-octylpyrrolidone, N-laurylpyrrolidone and the like. Examples of (e3) include ethylene carbonate and propylene carbonate. As the (e4) polypropylene glycol having a number average molecular weight of 100 to 1000, those having a number average molecular weight of 100 to 500, particularly those having a polymerization degree of 2 to 5 are preferred. In (e5), R ¹⁸ and R ¹⁹ in the general formulas (14) to (16) are linear, branched or cyclic alkyl groups, hydroxyl groups, sulfonic acid groups, phosphoric acid groups, carboxy groups, phenyl groups. , A sulfoalkyl group, an alkyl phosphate group, a carboxyalkyl group, etc. are preferable. In particular, in the case of γ-lactone, the γ-position is substituted, and in the case of δ-lactone, the δ-position (that is, the methylene adjacent to the hetero oxygen atom) is substituted. C1-C6 linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups are preferred. When it is desired to increase the water solubility of the compounds (14) to (16), R ¹⁸ or R ¹⁹ has an acidic group such as a sulfonic acid group, a phosphoric acid group or a carboxy group, or an alkyl group substituted with these. Is preferred. Among (e5), examples of the lactone include γ-butyrolactone, γ-caprolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, δ-heptanolactone, and the like, from the viewpoint of lactone stability. Γ-lactone, particularly γ-butyrolactone and γ-caprolactone are preferred. Among (e5), examples of the cyclic ketone include cyclopentanone, cyclohexanone, cycloheptanone, 4-methylcycloheptanone and the like.

  Particularly preferred components (E) include benzyl alcohol, benzyloxyethanol, propylene carbonate and polypropylene glycol (number average molecular weight 300 to 500, particularly 400).

  In addition, the component (E) used in the present invention is preferably liquid at 25 ° C., and ClogP needs to be −2 to 3, and from the viewpoint of promoting penetration, it should be −1 to 2. Is preferred. Here, ClogP is a calculated value of the octanol-water-partition coefficient (logP) defined by the following formula, which is a measure representing the distribution of substances between the octanol phase and the water phase. An example is described in Vol. 71, No. 6 (1971).

logP = log ([Substance] _Octanol / [Substance] _Water )

[In the formula, [Substance] _Octanol represents the molar concentration of the substance in the 1-octanol phase, and [Substance] _Water represents the molar concentration of the substance in the aqueous phase. ]

  Specifically, ClogP of the main component (E) is benzyl alcohol (1.1), 2-benzyloxyethanol (1.2), 2-phenylethanol (1.2), 1-phenoxy-2-propanol (1.1), polypropylene Glycol 400 (0.9), propylene carbonate (-0.41), and γ-butyrolactone (-0.64).

  Ingredient (E) may be used in combination of two or more, and the content thereof is from the point of use feeling, hair gloss and promotion of modification effect (improvement of elasticity, improvement of moisture resistance, etc.). 0.1-40 mass% in the hair cosmetics of invention is preferable, Furthermore, 0.5-10 mass%, Especially 1-5 mass% is preferable.

  The mass ratio of the organic carboxylic acid of component (D) or salt thereof and the organic solvent of component (E) effectively exhibits effects such as internal hair improvement (such as cavity repair), improved set-up, and improvement of mass. Therefore, it is preferable that (D) :( E) = 10: 1 to 1: 7, particularly 4: 1 to 1: 3.

  Furthermore, the hair cosmetic composition of the present invention can contain ethanol. The content of ethanol is preferably 0.01 to 30% by mass, and particularly preferably 0.1 to 10% by mass in the hair cosmetic composition of the present invention.

  Oils are used to improve the feeling of hair unity after drying. Oils include hydrocarbons such as squalene, squalane, liquid isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, liquid baraffin, cycloparaffin; castor oil, cacao oil, mink oil, avocado oil, olive oil, etc. Glycerides; waxes such as beeswax, whale wax, lanolin, microcrystalline wax, ceresin wax, carnauba wax; higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol; myristic acid Octyldodecyl, hexyl laurate, cetyl octanoate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, isono Esters such as tridecyl nanate; higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearyl acid, isopalmitic acid; other isostearyl glyceryl Examples include ether and polyoxypropylene butyl ether. Among these, branched hydrocarbons such as squalene, squalane, liquid isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, and α-olefin oligomer are particularly preferable.

  The content of the oil agent is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, particularly 0.5 to 5% by mass in the hair cosmetic composition of the present invention from the viewpoint of good unity and no stickiness. Is preferred.

  The hair cosmetic composition of the present invention may contain a surfactant from the viewpoints of system stability including solubilization and dispersibility of the solvent, and improvement in touch. As the surfactant, any of a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and an anionic surfactant can be used.

  Examples of the cationic surfactant include quaternary ammonium salts represented by the following general formula (17).

[In the formula, R ²⁰ and R ²¹ each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms or a benzyl group, and when simultaneously forming a hydrogen atom or a benzyl group, Except when it becomes an alkyl group. An ⁻ represents an anion. ]

Here, one of R ²⁰ and R ²¹ is preferably an alkyl group having 16 to 24 carbon atoms, more preferably 22 alkyl groups, particularly a linear alkyl group, and the other is a lower alkyl group having 1 to 3 carbon atoms, particularly A methyl group is preferred. Examples of the anion Z ⁻ include halide ions such as chloride ions and bromide ions; organic anions such as ethyl sulfate ions and methyl carbonate ions, and halide ions, particularly chloride ions are preferable.

  As the cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Stearyl trimethyl ammonium and behenyl trimethyl ammonium chloride are preferable.

  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharide surfactants, alkyl amine oxides, and alkyl amido amine oxides. Of these, polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether is particularly preferable.

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series.

  Anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, Examples include α-sulfo fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, and sulfosuccinate esters. Counter ions of the anionic residue of the surfactant include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms Alkanolamine having 1 to 3 (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). Examples of the counter ion of the cationic residue include halide ions such as chloride ion, bromide ion and iodide ion, methosulphate ion and saccharinate ion.

  Of these, cationic surfactants are preferred from the viewpoint of feel. The surfactant can be used alone or in combination of two or more, and from the viewpoint of the stability of the system including solubilization of the solvent and emulsification of the oil agent, the content thereof is in the hair cosmetic composition of the present invention. 0.01 to 10% by mass, particularly 0.05 to 3% by mass is preferable.

  In addition to the above-described components, the hair cosmetic of the present invention can be appropriately mixed with components used in normal hair cosmetics depending on the purpose. Examples of such components include anti-dandruff agents; vitamin agents; bactericides; anti-inflammatory agents; chelating agents; humectants such as sorbitol and panthenol; colorants such as dyes and pigments; hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, Viscosity adjusters such as clay minerals; pH adjusters such as sodium hydroxide and potassium hydroxide; plant extracts; pearlizing agents; fragrances; dyes; ultraviolet absorbers; antioxidants; other encyclopedias of shampoos Ingredients described in ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS) are listed.

  The hair cosmetic composition of the present invention preferably has a pH at 25 ° C. of 2.5 to 4.5 when diluted 20 times with water, more preferably 2.5 to 4, particularly 3 to 4.

  The form of the hair cosmetic composition of the present invention can be appropriately selected from liquid form, gel form, paste form, cream form, wax form, etc., but a liquid form using water or a lower alcohol, particularly water, as the solvent is preferred.

  The hair cosmetic composition of the present invention is preferably used as a hair styling agent, hair conditioning agent or the like. Examples of the dosage form include pump spray, aerosol spray, pump foam, aerosol foam, gel, lotion and the like.

[Hair treatment method]
The hair cosmetic composition of the present invention can obtain a hair-modifying effect by being applied to the hair and then left without being washed away. Here, “leaving without washing” means that the time from application to hair until the next washing is at least 3 hours, preferably 6 hours or more.

  Furthermore, the effect of this invention can be heightened more by heating hair cosmetics after apply | coating to hair. For heating, a dryer, a heater, a trowel, an iron, or the like can be used. When using a drier, a heater, etc., as temperature, 60 to 150 degreeC, especially 70 to 120 degreeC is preferable. The heating time is preferably 10 seconds to 30 minutes, more preferably 20 seconds to 20 minutes, and particularly preferably 30 seconds to 10 minutes. When using a trowel, iron or the like, the temperature is preferably 80 ° C to 250 ° C, particularly 100 ° C to 200 ° C. The heating time is preferably 0.5 seconds to 3 minutes, more preferably 1 second to 2 minutes, and particularly preferably 2 seconds to 30 seconds. Also, the time from application of the hair cosmetic to heating and heating is preferably within 1 hour, more preferably within 45 minutes, and particularly preferably within 30 minutes.

  Further, in daily life, by repeating the treatment with the hair cosmetic of the present invention, preferably by repeating 3 times or more, more preferably by repeating 7 times or more, the cohesiveness of the hair itself and the fingering property are further improved. Can be made.

Synthesis example 1
Diethyl sulfate (6.5 g, 0.042 mol) and 2-ethyl-2-oxazoline (34.4 g, 0.36 mol) were dissolved in dehydrated ethyl acetate (87 g), heated under reflux for 8 hours under a nitrogen atmosphere, and poly (N-N- Propionylethyleneimine) was synthesized. Here, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32000, amine equivalent 2000) was used, and N-propionylethyleneimine-dimethylsiloxane copolymer was converted into a pale yellow rubber-like semisolid (138 g, yield). 98%). The final product had an organopolysiloxane segment content of 71 mass% and a weight average molecular weight of 46000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that about 22 mol% of amino groups remained.

Synthesis example 2
In the same manner as in Synthesis Example 1, 0.8 g (0.005 mol) of diethyl sulfate, 12.8 g (0.14 mol) of 2-ethyl-2-oxazoline and 29 g of dehydrated ethyl acetate were added to poly (N-propionylethylene having a number average molecular weight of 2700. Imin). Further, using 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 100000, amine equivalent 20000), N-propionylethyleneimine-dimethylsiloxane copolymer was converted into a pale yellow rubbery solid (111 g, yield 98%). ). The content of the organopolysiloxane segment in the final product was 88% by mass, and the weight average molecular weight was 114,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Examples 1-14 and Comparative Examples 1-9
The hair cosmetics shown in Tables 1 and 2 were prepared according to a conventional method, and according to the following methods, “as per finger (after application, during and after drying)”, “set of hair ends (set property)” and “hair We evaluated the sustainability of the previous unit.

〔Evaluation method〕
Make a hair bundle of 20cm, 10g with Japanese hair, soak it in a mixed stock solution of the first and second agents of “Pretia Soft Bubble Bleach Hybrid” manufactured by Kao Corporation at a bath ratio of 1: 1, and 30 at 40 ° C. After standing for a minute, rinse with water. The hair bundle is then treated with a plain plain shampoo and rinsed with water, then treated with a plain plain rinse and rinsed with water. After towel drying, dry with a dryer at 70 ° C for 5 minutes. A hair bundle obtained by repeating the above-described series of treatments for 3 cycles was used as a hair bundle for evaluation.
When applying 0.2g of hair cosmetics to the evaluation hair bundle, "as per finger" (when applied, when dried, and after drying), after drying "hair tip unit" and "hair tip unit persistence" About "sex", sensory evaluation was performed according to the following standard by 10 expert panelists. In addition, drying processing shall be 5 minutes by a 70 degreeC warm air with a dryer (the product made by Panasonic, EH5311). “Fundamental endurance of hair ends” was evaluated by evaluating the “end of hair ends” after drying and then allowed to stand at 25 ° C. and 60% RH for 5 hours. All the evaluations were performed by a five-level evaluation in which “equivalent” was set to 3 with Comparative Example 1 as a comparison target. Tables 1 and 2 show the average score of the evaluation of 10 people.

[As per finger]
With Comparative Example 1 as a comparison target,
5: Good fingering 4: Good fingering 3: Not good 2: Slightly fingering 1: Bad fingering

[Group of hair tips]
With Comparative Example 1 as a comparison target,
5: The unit of the hair tip is good 4: The unit of the hair tip is a little good 3: It cannot be said 2: The unit of the hair tip is a little bad 1: The unit of the hair tip is bad

[Unity endurance of hair ends]
With Comparative Example 1 as a comparison target,
5: The unit of hair ends lasts 4: The unit of hair ends slightly persists 3: It cannot be said 2: The unit of hair tips is slightly difficult to maintain 1: The unit of hair tips hardly persist

Example 15 Emulsified hair cosmetic
(mass%)
Branched polyglycerol-modified silicone (Sofcare GS-G, Kao Corporation) 0.2
Organopolysiloxane (Synthesis Example 1) 0.1
Organopolysiloxane (Synthesis Example 2) 0.3
Alkyltrimethylammonium chloride solution (58% by mass) 0.4
N, N-dimethyloctadecyloxypropylamine 0.25
Cetostearyl alcohol 2.8
18-methyleicosanoic acid 0.2
Malic acid 0.6
Lactic acid 0.6
Benzyl alcohol 0.2
Glycerin 5
Isopropyl palmitate 1.5
Dimethicone (SH-200C (viscosity 100000mm ² / s) Toray Dow Corning) 2
Ethanol 0.7
Sodium hydroxide solution (pH adjuster)

Claims (5)

A hair cosmetic of the type that does not wash away, and contains the following components (A) and (B), and the value of the mass ratio (A) / (B) of both components is 0.05-20.
(A) Branched glycerol represented by the following structural formula (1) having an average of 3 or more glycerol groups represented by the following structural formula (1), (2), (3) or (4). Branched polyglycerol-modified silicone in which at least one branched polyglycerol chain containing at least one group is bonded to the silicon atom of the silicone via a linking group: 0.05 to 5% by mass

(B) At least one silicon atom of the organopolysiloxane segment is bonded to the following general formula (10) via an alkylene group containing a hetero atom.

[Wherein, R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and m represents a number of 2 or 3. ]
A poly (N-acylalkyleneimine) comprising repeating units represented by the formula is bonded, and the mass ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40/60. An organopolysiloxane having a weight average molecular weight of 12,000 to 500,000: 0.05 to 4% by mass Furthermore, the hair cosmetics of Claim 1 containing the following component (C).
(C) C12-30 isofatty acid or anteisofatty acid or salts thereof The hair cosmetic according to claim 1 or 2, further comprising the following components (D) and (E) and having a pH of 2.5 to 4.5 at 25 ° C when diluted 20 times by mass with water.
(D) C2-C8 organic carboxylic acid or salt thereof
(E) an organic solvent selected from the group consisting of aromatic alcohol, N-alkylpyrrolidone, alkylene carbonate, polypropylene glycol, lactone and cyclic ketone The hair cosmetic according to claim 2 or 3, wherein the content of component (C) is 0.001 to 5 mass%. A hair treatment method in which the hair cosmetic according to any one of claims 1 to 4 is applied to the hair and then left for at least 3 hours without being washed away.