JP2005097152A - Hair cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare a skin cosmetic which has excellent compounding stability and high affinity to hair, can give sufficient smooth touch, flexibility, and gloss to highly damaged hair in a small amount without giving stickiness, and can reduce dryness to well protect / modify the hair. <P>SOLUTION: This hair cosmetic comprises a branched polyglycerol-modified silicone to whose one silicon atom at least one branched polyglycerol chain that is bound to three or more glycerol groups or glycidols represented by formulas (1), (2), (3) or (4) on the average and that contains at least one group represented by formula (1)is bound through a binding group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention has excellent blending stability, good touch at the time of application, can effectively protect / repair, modify or stylist hair with a small amount of use, and has a healthy and beautiful gloss and extremely high gloss on the hair after use. The present invention relates to a hair cosmetic that can impart a smooth texture.

  In recent years, the chance of serious chemical damage to hair has increased rapidly due to the establishment of bleaching and hair coloring treatment in addition to thermal damage caused by blow styling. As a result, physical damage to the hair is further promoted, and not only the cuticle on the hair surface layer is peeled / deleted, but also the internal elasticity of the hair is lost due to the loss of lipid inside the hair, Serious problems such as breakage or deterioration / hardening have become apparent. The luster of the hair is extremely lost, the texture becomes rough, the finger passage / comb passage deteriorates, the hair is twisted and the wave phase is not uniform, and the hair is not coherent, making hair styling extremely difficult.

  For concealing minor damage to hair and improving gloss, conventionally, rinses and conditioners based on cationic compounds, hair pack treatments, hair waxes based on high melting point waxes, higher alcohols, etc. Treatments such as application of a cream, hair mousse or gel-type makeup / hairdressing agent containing a wetting agent and a shaping polymer have been widely performed. In addition, a technique for coexisting various silicone bases, that is, unmodified dimethyl silicone, alkyl-modified, polyether-modified silicone and other modified silicones as an effect of improving the effect to some extent is disclosed (for example, Patent Document 1 and Patent Document 2). However, these existing hair treatment methods are extremely ineffective against the severe hair damage as described above. This is because the affinity of these conventionally used bases to hair is extremely fragile, so in commercial products such as rinses and conditioners that are rinsed after use, most of them are washed away with water. In other words, even a leave-on product system such as hair wax or hair mousse is washed away by sweat or sebum, so that a permanent and sufficient effect cannot be obtained. In addition, in anticipation of such loss, attempts have been frequently made to blend a large amount of a hair treatment base in advance or to set an excessive amount of blended composition, but the stickiness or hair quality becomes abnormally heavy. Detrimental in feel / feel.

On the other hand, amino-modified silicone is known as a material that can be efficiently adsorbed on the protein surface even in a small amount and improved in touch. Patent Document 3 discloses its application to hair cosmetics. However, this base is extremely irritating to the skin and ocular mucosa and is difficult to be used in large quantities as a popular product. By reducing the functional group density or making a co-modified with a polyether group, adsorption and residue can be prevented. The fact is that it is used only in a limited combination formulation. On the other hand, as a related invention aiming at significant reduction of skin irritation, Patent Document 4 exemplifies a hair cleansing agent containing triglycerin-modified silicone described in Patent Document 5, but the base of this structure is used for hair. Since sufficient affinity cannot be obtained, the desired hair improving effect cannot be exhibited even if an excessive amount is blended. Furthermore, all of these existing silicone bases are easily separated / precipitated in various hair cosmetic product systems due to their small intermolecular interaction, and it is important that the blending stability is extremely poor. It was a problem.
JP-A-5-65216 Japanese Patent Laid-Open No. 7-285834 JP-A-9-71517 JP-A-9-71504 JP-A-4-20531

  An object of the present invention is to have a structure with excellent blending stability and extremely low irritation to the skin and mucous membranes, and has a high affinity to hair and can be efficiently adsorbed to the hair surface, resulting in serious damage. Even if the hair is not sticky, the hair can be given a smoothness, flexibility, and luster with a small amount of use, and the hair is well protected / modified by reducing the crispness. It is to provide a hair cosmetic capable of realizing targeted and beautiful hair.

  The present inventors have found that all the above problems can be solved by using a hair cosmetic containing a branched polyglycerin-modified silicone modified with a specific polyglycerol group having high affinity for hair.

  That is, in the present invention, three or more glycerol groups or glycidol groups represented by the following structural formula (1), (2), (3) or (4) are bonded on average, and the structural formula (1) A hair cosmetic composition comprising a branched polyglycerol-modified silicone in which at least one branched polyglycerol chain containing at least one branched glycerol group is bonded to the silicon atom of the silicone via a linking group.

  Note that the glycerol group or glycidol group represented by the structural formula (1), (2), (3) or (4) is bonded to the two oxygen atoms of the structural formula (1), which are the same or different. A glycerol group or a glycidol group represented by the structural formula (1), (2), (3) or (4) is bonded to the oxygen atom of the structural formula (2), and the oxygen of the structural formula (3) A glycerol group or glycidol group represented by the structural formula (1), (2), (3) or (4) is bonded to the atom.

When ring-opening polymerization of glycidol (2,3-epoxy-1-propanol) using an alkali metal catalyst, a transfer reaction of active species occurs, and a polyglycerol mainly having a glycerol group as shown in the structural formula (3) is obtained. (Vandenberg, EJ et al, J. Polym. Sci., Polym. Chem. 1985, 23 , 915). In this case, the branched structure represented by the structural formula (1) and the group represented by the structural formula (2) which is an original glycidol-type ring-opening structure are also contained in a slight amount. Further, here, when the amount of the catalyst for the starting species is adjusted and glycidol is dripped very slowly, the branched structure represented by the structural formula (1) is extremely developed, and a dendrimer-like multibranched polyglycerol is obtained. (Frey, H. et al, Macromolecules. 1999, 32 , 4240). Further, the present inventors have found a method for obtaining a multi-branched polyglycerol-modified silicone having a branched structure in a polyglycerol group by using a silicone derivative having a special functional group as a precursor. Furthermore, the present inventors have found that polyglycerol groups in which units are bonded to each other via an ether bond have a very flexible skeletal structure. +1) becomes a highly active primary hydroxy group and a large number of terminal hydroxy groups are confined in a narrow space area with free movement restricted, allowing chelate multi-element adsorption, single or molecular The present inventors have found that in a state where glycerol groups are arranged in a linear form having a very large degree of freedom of movement of the chain, only a very small adsorptivity is exhibited, whereas a remarkable adsorption promoting effect is exhibited. In particular, when this highly-branched polybranched polyglycerol group is linked to a hydrophobic unit such as silicone, the number of solvent molecules to be hydrated or solvated increases dramatically. It has been found that not only can it be solubilized, it can also dramatically enhance its adsorption effect on the hair. Moreover, this branched polyglycerol-modified silicone has extremely low irritation to the skin and mucous membranes, has excellent blending stability in various hair cosmetic products, and does not stick even to severely damaged hair. It has been found that the use of can provide sufficient smoothness, flexibility, and gloss to the hair, and can protect and improve the hair well by reducing the crispness, thereby realizing healthy and beautiful hair with good cohesion.

  The hair cosmetic composition of the present invention has excellent blending stability, good touch when applied, and can effectively protect / repair, improve, or style hair even with extremely severe damage even with a small amount of hair. Furthermore, the hair after use can be given a healthy and beautiful gloss and a very smooth texture.

[Branched polyglycerol chain]
In the present invention, the branched polyglycerol chain contains one or more branched glycerol groups represented by the structural formula (1) (hereinafter referred to as group (1)) as branching groups. The branched polyglycerol chain is represented by a group (1), b glycidol groups represented by structural formula (2) (hereinafter referred to as group (2)), and c structural formulas (3). A glycerol group (hereinafter referred to as group (3)) and d glycerol groups represented by structural formula (4) (hereinafter referred to as group (4)) as terminal groups are combined to form.

  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) is present at the end of each branched chain.

The branched polyglycerol-modified silicone of the present invention contains one or more branched structures of the group (1), as will be described later, in ¹³ C-NMR analysis, δ78.0-81.0 ppm is characteristic of the group (1). It can be proved easily from the fact that the peak of is seen. Preferably, the content of the average group (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 can be easily determined by NMR analysis or molecular weight comparison with the precursor silicone. However, it is preferably 3 or more, more preferably 3 to 201, still more preferably 3 to 101, in order for the branched polyglycerol-modified silicone of the present invention to maintain appropriate silicone properties. 3 to 51 is particularly preferable, and 3 to 21 is most preferable.

  In the present invention, the average branching ratio in all branched polyglycerol chains is preferably a / (a + b + c + d) of 1/20 to 1/2, and preferably 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 2 to 10 are present, and most preferably 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 and most preferred that 3 to 11 are present. The groups (2) and (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, more preferably 0 to 46, and most preferably 0 to 16.

[Linking group]
In the branched polyglycerol-modified silicone of the present invention, the linking group that connects 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)
(Wherein R ¹ may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 28 carbon atoms, and A ¹ O is carbon. C1-4 alkyleneoxy group (also referred to as an oxyalkylene group) or arylene group having 6 to 10 carbon atoms (also referred to as oxy arylene group), p is a number of 0 to 30, p pieces of a ¹ O is They 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 And an alkylenephenylene group having 1 to 22 carbon atoms, and a trimethylenephenylene group is 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 a substituent 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 atom) ~ 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 preferably, particularly 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 preferred 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 the present invention, the linking group that bonds 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.

(In the formula, 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 It is an ethyleneoxy group.

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

The q A ² Os and the r A ³ Os may be the same or different. In the case where they are different, the mutual bonding mode of the A ² O and A ³ O may be 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), for any two of the two oxygen atoms and trimethylene groups bonded to the phenylene group of the oxyphenylene group, the bonding modes are the ortho, meta, and para positions relative to each other. Any of these may be used, or a mixture thereof may be used.

[Branched polyglycerol-modified silicone]
The silicone forming the branched polyglycerol-modified silicone of the present invention is derived from a polysiloxane having two or more silicon atoms, and the shape of the polysiloxane is any of linear, branched, and cyclic. Also good. 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 a gel permeation chromatograph (hereinafter referred to as GPC) method, a light scattering method, or the like.

  The branched polyglycerol-modified silicone of the present invention is preferably a linear silicone represented by the 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 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 , R ³ , R ⁴ , at least one of R ⁵ , t R ⁶ , R ⁷ , R ⁸ , R ⁹ is a linking group to which a branched polyglycerol chain is bonded, where t is a number from 0 to 10,000. Show.)
In the 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 , Which may be the same or different and each may have a substituent, 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, Examples of the alkyl group having 1 to 22 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and trifluoropropyl groups. Examples of the alkenyl group include a vinyl group and an allyl group. Examples of the alkoxy group having 1 to 22 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyl. Oxy, heptyloxy, octyloxy, and a phenoxy group. Examples of the aryl group having 6 to 22 carbon atoms include a phenyl group. In these, a C1-C12 linear or branched alkyl group, 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 the present invention becomes a branched polyglycerol-modified silicone of both end substitution type, and is used in water and other It is highly preferable as a branched polyglycerol-modified silicone to be blended in the hair cosmetic composition of the present invention because it can be interconnected in a solvent and easily adopt a higher order structure. 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.

When the linking group to which the branched polyglycerol chain is bonded is present in three or more selected from t R ⁵ and t R ⁶ , the branched polyglycerol-modified silicone of the present invention is a side chain multi-substituted type. The branched polyglycerol-modified silicone is improved, and hydrophilicity and adsorptivity are enhanced, and it is preferable as the branched polyglycerol-modified silicone to be blended in the hair cosmetic composition of the present invention.

  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 the present invention 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 the present invention has a total number of silicon atoms (Si) in the silicone and groups (1), (2), (3) and (4) in the branched polyglycerol chain (hereinafter referred to as glycerol group number). ) (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.

  In the branched polyglycerol-modified silicone of the present invention, as long as it does not significantly inhibit the blending stability, affinity for hair, and hair protection / modification ability, which are the characteristics of the branched polyglycerol-modified silicone of the present invention. A small amount of ethyleneoxy group and / or propyleneoxy group may be present in the branched polyglycerol chain. 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 the ethyleneoxy group and / or propyleneoxy group is present, the ethyleneoxy group and / or propyleneoxy group is preferably present in an amount of 0.001 to 0.5 molar equivalents relative to 1 molar equivalent of the glycerol group. More preferably, it is present at 0.02 to 0.2 molar equivalent.

  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 in the presence of an alkali metal catalyst such as potassium to a polysiloxane having an epoxy group or a hydroxyl group as a reactive group.

[Hair cosmetic]
In the hair cosmetic composition of the present invention, the content of the branched polyglycerol-modified silicone of the present invention can be appropriately selected according to the purpose of the hair cosmetic composition, and is not particularly limited. 50 mass% is preferable, 0.001-30 mass% is more preferable, 0.05-15 mass% is still more preferable, 0.1-12 mass% is especially preferable, 0.5-10 mass% is the most preferable.

  The form of the hair cosmetic of the present invention is not particularly limited, and is a water-in-oil or oil-in-water emulsified hair cosmetic, oil-based hair cosmetic, spray-type hair cosmetic, pasty hair cosmetic, solid hair cosmetic. Any of water-based hair cosmetics, gel-like hair cosmetics, and the like may be used. Further, the type of the hair cosmetic composition of the present invention is not particularly limited. For example, hair protecting / repairing, modifying or improving texture of hair such as rinse, conditioner, hair treatment, pre-shampoo, hair pack, hair lotion, etc .; hair spray, Hair conditioners such as hair waxes, hair gels, hair mousses, hair mists; and hair cosmetics such as hair nourishing agents.

  The hair cosmetic composition of the present invention may contain a nitrogen-containing compound for improving its effect. The nitrogen-containing compound is not particularly limited as long as it is used in ordinary hair cosmetics, and is a primary, secondary or tertiary amine compound and a salt thereof, various quaternary ammonium salts, primary or secondary. Alternatively, a polymer compound having a tertiary amino group or a salt thereof or a quaternary ammonium group can be used. Two or more of these nitrogen-containing compounds may be blended. The compounding amount of the nitrogen-containing compound is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to 15% by mass in the hair cosmetic composition of the present invention.

  Examples of nitrogen-containing compounds that can be used in the hair cosmetic composition of the present invention include primary, secondary, or tertiary amine compounds represented by the following general formula (10).

(In the formula, R ¹⁰ is an organic group having 8 to 36 carbon atoms in total, which is a hydroxy group, an alkoxy group, an alkenyloxy group, an acyl group, an acyloxy group, an alkanoylamino group, an alkenoylamino group, an alkylaminocarbonyl group. or alkenyloxy aminocarbonyl group which may be substituted, an alkyl group, an alkenyl group or a polyoxyethylene ethyl group, an aliphatic chain moiety which may be also branched be straight .R ¹¹ Is an alkyl group or an alkenyl group (total carbon number 8 to 21) which may be substituted with a hydroxy group, an alkoxy group, an alkenyloxy group or an acyl group, or a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. group, hydroxyethyl group or a benzyl group, R ¹² is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyethyl group or a base It is Jill group.)
Examples of such amine compounds include N-alkoxypropyl-N, N-dimethylamine and N-alkenyloxypropyl-N, N-dimethyl having a linear or branched alkyl group or alkenyl group having 16 to 24 carbon atoms. Amine, N-alkanoylaminopropyl-N, N-dimethylamine, N-alkylaminocarbonylmethyl-N, N-dimethylamine, N-alkenylaminocarbonylmethyl-N, N-dimethylamine, N-alkylaminocarbonylmethyl- Examples thereof include N, N-diethylamine and N-alkenylaminocarbonylmethyl-N, N-diethylamine.

  When these amine compounds are blended and used in the hair cosmetic composition of the present invention, a mineral acid or various organic acids may be blended simultaneously to form a salt.

  The nitrogen-containing compound that can be used in the hair cosmetic composition of the present invention may also be a primary, secondary or tertiary amine salt or quaternary ammonium salt represented by the following general formula (11).

(Wherein R ¹⁰ , R ¹¹ and R ¹² represent the above meanings, R ¹³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyethyl group or a benzyl group, and X ⁻ represents a halogen ion or an organic group. Indicates an anion.)
Examples of such amine salts or ammonium salts include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride and lauryltrimethylammonium chloride, dialkyldimethylammonium salts such as distearyldimethylammonium chloride, and poly (N, N-dimethyl-3, chloride). 5-methylenepiperidinium), alkylpyridinium salts such as cetylpyridinium chloride, alkyldimethylbenzylammonium salts, alkylisoquinolinium salts, dialkylmoriphonium salts, polyoxyethylene (hereinafter referred to as POE) alkylamine salts, alkylamines Salt, polyamine fatty acid derivative, amyl alcohol fatty acid derivative, benzalkonium chloride, benzethonium chloride, and the above-mentioned linear or branched alkyl group having 16 to 24 carbon atoms N-alkoxypropyl-N, N-dimethylamine, N-alkanoylaminopropyl-N, N-dimethylamine, N-alkylaminocarbonylmethyl-N, N-dimethylamine, N-alkylaminocarbonylmethyl-N, N- Examples thereof include hydrochlorides such as diethylamine, lactates, oxalates, succinates and malates.

  The nitrogen-containing compound that can be used in the hair cosmetic composition of the present invention may also be a cationic group-containing polymer compound. Examples of cationic group-containing polymer compounds include cationized cellulose derivatives, cationized starches, cationized guar gum derivatives, diallyl quaternary ammonium salt homopolymers, diallyl quaternary ammonium salts / acrylamide copolymers, and diallyl quaternary ammonium salts. / Sulfur dioxide copolymer, quaternized polyvinylpyrrolidone derivative, polyglycol polyamine condensate, vinylimidazolium trichloride / vinylpyrrolidone copolymer, hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer, quaternized dimethylaminoethyl ( (Meth) acrylate homopolymer, quaternized dimethylaminoethyl (meth) acrylamide homopolymer, vinylpyrrolidone / quaternized dimethylaminoethyl (meth) acrylate copolymer, poly Nylpyrrolidone / alkylamino (meth) acrylate copolymer, polyvinylpyrrolidone / alkylamino (meth) acrylate / vinylcaprolactam copolymer, vinylpyrrolidone / (meth) acrylamidepropyltrimethylammonium chloride copolymer, alkylacrylamide / acrylate / alkyl Aminoalkyl (meth) aacrylamide / polyethylene glycol (meth) acrylate copolymer, adipic acid / dimethylaminohydroxypropylethylenetriamine copolymer (Cartaretin manufactured by Sandos, USA), JP-A 53-139734, JP-A Examples thereof include cationic polymers described in JP-A-60-36407, and cationized cellulose derivatives are particularly preferable. Two or more of these cationic group-containing polymer compounds may be blended. As described above, the amount of the cationic group-containing polymer compound is preferably 0.1 to 40% by mass in the hair cosmetic composition of the present invention, more preferably 0.1 to 10% by mass, 5% by mass is particularly preferred.

  The hair cosmetic composition of the present invention may contain various aliphatic alcohols. Examples of the aliphatic alcohol include linear or branched higher alcohols having an alkyl group or alkenyl group having 8 to 36 carbon atoms. Here, carbon number of an alkyl group or an alkenyl group becomes like this. Preferably it is 12-22, More preferably, it is 16-22. Examples of such aliphatic alcohols include cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, C16 gel bealcohol and the like. These aliphatic alcohols may be used in a single composition, or may be used in combination of two or more, or may be used as various composition mixtures. For example, cetostearyl alcohol (C16 / C18 mass ratio of 0.3 to 3.0) used by mixing cetyl alcohol and stearyl alcohol is a suitable example. The blending amount of the aliphatic alcohol may be appropriately selected in consideration of the form and type of the product and the other blending, but is generally preferably 0.1 to 40% by weight in the hair cosmetic composition of the present invention. 0.5-30 mass% is further more preferable, and 1-15 mass% is especially preferable.

  In the hair cosmetic composition of the present invention, when these aliphatic alcohols are used together with the nitrogen-containing compound, their blending mass ratio ([aliphatic alcohol blending amount] / [nitrogen-containing compound blending amount]) is the hair modifying effect. Or from a viewpoint of compounding stability, 1-15 are preferable, More preferably, it is 2-10, More preferably, it is 2.5-5.

  The hair cosmetic composition of the present invention may contain an ingredient having a melting point at room temperature of 40 ° C. or higher. Such formations include hydrocarbons such as paraffin, microcrystalline wax, petroleum jelly, ozokerite, montan wax, vegetable or animal oils such as ground wax, carnauba wax, lanolin, spermaceti, stearic acid, palmitic acid. Examples include fatty acids such as acids and the aforementioned aliphatic alcohols. Two or more of these forming components may be blended. When blending and using these ingredients for the hair cosmetic composition of the present invention, the blending amount is preferably 1 to 80% by weight, more preferably 5 to 50% by weight, and particularly preferably 8 to 30% by weight.

  The hair cosmetic composition of the present invention may contain other silicone compounds. Other silicone compounds include dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, alkyl modified silicone, amino modified silicone, alkyl / amino modified silicone, amide modified silicone, alkyl / amide modified silicone, polyether modified silicone, alkyl / Polyether-modified silicone, amino / polyether-modified silicone, amide / polyether-modified silicone, epoxy-modified silicone, fluorine-modified silicone, oxazoline-modified silicone, and their cross-linked products and cyclic silicone, among others, dimethylpolysiloxane , Methylphenyl polysiloxane, amino-modified silicone, polyether-modified silicone, oxazoline-modified silicone, and cyclic silicone are preferred. There. Two or more of these other silicone compounds may be blended. 0.1-40 mass% is preferable in the hair cosmetics of this invention, as for the compounding quantity of another silicone compound, 0.5-30 mass% is more preferable, 1-15 mass% is especially preferable.

  The hair cosmetic composition of the present invention may contain a nonionic surfactant. Nonionic surfactants include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexyl diglycerol Sorbitan fatty acid esters such as sorbitan, tetra-2-ethylhexyl diglycerol sorbitan, mono-cotton oil fatty acid glycerin, glyceryl monoerucate, glyceryl sesquioleate, glyceryl monostearate, glyceryl oleate, glyceryl monostearate, malic acid, etc. Glycerin fatty acid esters, propylene glycol fatty acid esters such as propylene glycol monostearate, hardened castor oil derived , Lipophilic nonionic surfactants such as glycerin alkyl ether, POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan fatty acid esters such as POE sorbitan tetraoleate, POE sorbite monolaurate, POE sorbite monooleate, POE sorbite fatty acid esters such as POE sorbite pentaoleate, POE sorbite monostearate, POE glycerin fatty acid esters such as POE glycerin monostearate, POE glycerin monoisostearate, POE glycerin triisostearate, POE monooleate, POE POE fatty acid esters such as distearate, POE monodiolate, ethylene glycol distearate, POE lauryl ether, PO POE alkyl ethers such as oleyl ether, POE stearyl ether, POE behenyl ether, POE2-octyldodecyl ether, POE cholestanol ether, POE alkyl phenyl ethers such as POE octyl phenyl ether, POE nonyl phenyl ether, POE dinonyl phenyl ether Pluronic types such as Pluronic, POE / POP cetyl ether, POE / POP2-decyltetradecyl ether, POE / POP monobutyl ether, POE / POP hydrogenated lanolin, POE / POP alkyl ethers such as POE / POP glycerin ether, Tetronic PEO / TetraPOP ethylenediamine condensates, POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisos POE castor oil or hardened castor oil derivatives such as tear, POE cured castor oil towaisostearate, POE cured castor oil monopyroglutamic acid monoisostearic acid diester, POE cured castor oil maleic acid, POE beeswax and lanolin derivatives such as POE sorbite beeswax Alkanolamides such as coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, POE propylene glycol fatty acid ester, POE alkylamine, POE fatty acid amide, sucrose fatty acid ester, POE nonylphenyl formaldehyde condensate, alkylethoxydimethyl Amine oxide, trioleyl phosphate and the like are used. Two or more of these nonionic surfactants may be blended. In the hair cosmetic composition of the present invention, the blend amount of the nonionic surfactant is preferably 0.2 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 2 to 15% by mass.

  The hair cosmetic composition of the present invention may contain an anionic surfactant. The anionic surfactant is not particularly limited as long as it is blended in normal hair cosmetics. For example, alkyl (or alkenyl) sulfate, polyoxyalkylene alkyl (or alkenyl) ether sulfate, alkane sulfonic acid Salt, olefin sulfonate, alkylbenzene sulfonate, alkyl (or alkenyl) sulfosuccinate, dialkyl (or dialkenyl) sulfosuccinate, polyoxyalkylene alkyl (or alkenyl) sulfosuccinate, alkyl (or alkenyl) ether carboxylic acid Salt, polyoxyalkylene alkyl (or alkenyl) ether carboxylate, polyoxyalkylene alkyl (or alkenyl) ether phosphate, fatty acid or salt thereof, N-acyl glutamic acid or salt thereof, N-acyl tauric acid or salt thereof, N- And acylmethyl taurine. Of these, POE alkyl ether sulfate, POE alkenyl ether sulfate, and alkyl sulfate are preferable. Two or more of these anionic surfactants may be blended. The blending amount of the anionic surfactant is preferably 0.2 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 2 to 15% by mass in the hair cosmetic composition of the present invention.

  The hair cosmetic composition of the present invention may contain an amphoteric surfactant. The amphoteric surfactant is not particularly limited as long as it is blended with normal hair cosmetics. For example, amide amino acid, carbobetaine, amide betaine, sulfobetaine, hydroxysulfobetaine, amide sulfo Examples include betaine-based, imidazolinium betaine-based, amino acid-based, phosphobetaine-based, and phosphate ester-based amphoteric surfactants. Two or more of these amphoteric surfactants may be blended. The blending amount of the amphoteric surfactant is preferably 0.2 to 40% by mass, more preferably 1 to 30% by mass, and particularly preferably 2 to 15% by mass in the hair cosmetic composition of the present invention.

  The hair cosmetic composition of the present invention can be produced by a usual method using a solvent such as water and / or alcohol depending on the form and type. Examples of the alcohol include monovalent or polyhydric alcohols having 1 to 6 carbon atoms such as ethanol, glycerin, 1,3-butylene glycol, propylene glycol, sorbitol, etc. Among them, monohydric alcohols, particularly ethanol is preferable. The blending amount of the alcohol is preferably 0.2 to 98% by mass, more preferably 0.5 to 85% by mass, and particularly preferably 2 to 75% by mass in the hair cosmetic composition of the present invention. Moreover, it is preferable to set it as 2-500 mass times of the branched polyglycerol modified silicone concerning this invention, and it is more preferable to set it as 5-200 mass times.

  In the hair cosmetic composition of the present invention, other ingredients generally used as hair cosmetic ingredients are appropriately blended according to the form, type, etc. of the hair cosmetic composition as long as the effects of the present invention are not impaired. Can do.

  Examples of such hair cosmetic ingredients include extender pigments such as mica, talc, sericite, kaolin, nylon powder, polymethylsilsesquioxane, and barium sulfate; inorganic pigments such as titanium oxide, zinc white, and iron oxide; Powder whose surface has been hydrophobized by treatment with silicone, metal soap, N-acyl glutamic acid, etc .; glycerol monostearate, glycerol distearate, glycerol monooleate, isopropyl myristate, isopropyl stearate Fatty acids such as esters and butyl stearates or esters thereof; Adsorption or thickeners such as cationized cellulose, carboxybetaine type polymers, and cationized silicones; Polyhydric alcohols having a moisturizing action such as glycol and sorbitol Anti-dandruff agents, vitamins, vasodilators, anti-inflammatory agents, antipruritic agents, bactericides / disinfectants, hormonal agents, etc .; lipids / phospholipids and their derivatives; collagen, keratin, egg white lysozyme and other proteins Various amino acids; water; W / O or O / W type emulsifiers; thickeners such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyacrylic acid, tragacanth, agar, gelatin; other, emulsion stabilizers, chelating agents, UV protection agents, organic acids such as citric acid, lactic acid and malic acid; inorganic salts such as sodium chloride, potassium chloride and potassium carbonate; colorants and pigments such as preservatives, dyes and pigments; fragrances, sorbitol, panthenol, Moisturizers such as glycerin and polyethylene glycol; hydroxyethylcellulose, methylcellulose, polyethyleneglycol Viscosity modifiers such as oil and clay minerals; Plant extracts; Ceramides; Antioxidants; Pearling agents; Others listed in ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS) And the like.

  The hair cosmetic composition of the present invention may be composed only of the above-mentioned composition. Depending on the type and form of the hair cosmetic composition, chlorofluoroalkane, liquefied petroleum gas, dimethyl ether, carbon dioxide gas, carbon dioxide gas + It can also be used as an aerosol agent using compressed gas or liquefied gas such as isopentane, nitrogen gas, nitrogen gas + isopentane, air.

The assignment of each peak in the ¹ H-NMR spectrum of the branched polyglycerol-modified silicone obtained in the following examples is somewhat shifted depending on the solvent, but is generally as follows.

0.0-0.2 ppm: Si—C H ₃
0.6-0.7 ppm: Si—C H ₂ —CH ₂ — (4H)
_{1.5-1.7ppm: Si-CH 2 -C H} 2 - (4H)
_{2.4-2.7ppm: Si-CH 2 -CH 2} -C H 2 - (4H)
3.3-4.0 ppm: H of branched polyglycerol chain (excluding terminal hydroxy groups, 5H × number of glycerol groups)
6.7-7.2 ppm: phenol (8H)
In addition, in the ¹³ C-NMR spectrum, the assignment of the peak derived from each carbon of the groups (1) to (4) forming the branched polyglycerol chain was referred to the values described in Macromolecules, 1999, 32, 4240.

The average number of glycerol chains can be determined by ¹ H-NMR spectrum as follows: H number of branched polyglycerol chains / (5 × number of linking groups).

Synthesis Example 1: Synthesis Example of Branched Polyglycerol-modified Silicone A (Linking Group: —CH ₂ CH ₂ CH ₂ —C ₆ H ₄ —O—) Phenol-modified silicone (trade name; BY16 manufactured by Toray Dow Corning Co., Ltd.) -752 [both ends modified, specific gravity = 0.99 g / mL, viscosity = 110 cSt, hydroxy group equivalent = 1500 (average molecular weight = 3000 equivalent), GPC (column: G4000HXL + G2000HXL (manufactured by Tosoh Corporation)), THF solution (50 mmol / L acetic acid addition), 40 ° C., polystyrene conversion) Measured value; number average molecular weight (Mn) = 2340, weight average molecular weight (Mw) = 4780]) was taken in a flask, and 15 mL of 1M potassium hydroxide ethanol solution was added and stirred. While heating to 95 ° C under reduced pressure, the potassium-modified phenol-modified silane was treated as a pale orange oil. To obtain a cone. Under vigorous stirring, 77.8 g (3.5 equivalents) of glycidol was added over 5 hours using a quantitative feed pump. After further heating and stirring for 20 minutes and cooling to room temperature, a pale yellow viscous oily product was obtained. Ethanol (500 mL) was added to the obtained branched polyglycerol-modified silicone, and potassium was removed and concentrated using a cation exchange resin to obtain a branched polyglycerol-modified silicone A as a slightly yellow oil (yield 99.5%). By analysis of ¹³ C-NMR spectrum, it was confirmed from the presence of a signal (78.0 to 81.0 ppm) derived from the methine carbon of the group (1) that it was a branched polyglycerol-modified silicone having the group (1). Further, by analysis of the ¹ H-NMR spectrum, the average number of glycerol groups (G) = 7.0 (3.5 on one side), the average number of silicon atoms (Si) = 33.5, and the G / Si ratio is 0.21. According to GPC analysis, the number average molecular weight (Mn) was 2850.

Synthesis Example 2: Synthesis Example of Branched Polyglycerol-modified Silicone B (Linking Group: —CH ₂ CH ₂ CH ₂ —C ₆ H ₄ —O—) Phenol-modified silicone (X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd.) 200 g of both ends modified, specific gravity = 0.99 g / mL, viscosity = 110 cSt, hydroxy group equivalent = 32 mg KOH / g (average molecular weight = 3500 equivalent)]) was added to the flask, and 8.01 g of 30% potassium methoxide methanol solution was added. While stirring, the mixture was heated to 60 ° C. under reduced pressure, and all methanol was distilled off to obtain a potassium-modified phenol-modified silicone as a yellow oil. The temperature was raised to 95 ° C., and 21.2 g (2.5 equivalents) of glycidol was added over 4 hours under a stream of argon with vigorous stirring using a metered liquid feed pump. After further heating and stirring for 15 minutes, the mixture was allowed to cool to room temperature to obtain a transparent slightly yellow pasty product. The obtained branched polyglycerol-modified silicone was concentrated after desalting by cation exchange treatment to obtain branched polyglycerol-modified silicone B (213 g) as a high-viscosity slightly yellow oily substance. Yield 96.2%. By analysis of ¹³ C-NMR spectrum, it was confirmed from the presence of a signal (78.0 to 81.0 ppm) derived from the methine carbon of the group (1) that it was a branched polyglycerol-modified silicone having the group (1). Moreover, by analysis of ¹ H-NMR spectrum, the average number of glycerol groups (G) = 5.2 (one side 2.6), the average number of silicon atoms (Si) = 38.5, and the G / Si ratio was 0.14. .

Example 1 and Comparative Example 1
The present invention and the comparative rinse composition of the composition shown in Table 1 were prepared, and sensory evaluation regarding blending stability and feel was performed by the following methods. The results are shown in Table 1.

<Compounding stability evaluation method>
The rinse composition was stored at 50 ° C. for 3 months, and changes in appearance (separation / separation of components, turbidity, etc.) were visually observed and evaluated according to the following criteria.
○: Separation / layering of components and turbidity are not observed ×: Separation / layering of components or turbidity is observed <Sensory evaluation method for touch>
Hair treatment was performed according to the following method, and a specialized panelist performed sensory evaluation on touch. Sensory evaluation was performed according to the following criteria.
・ Hair washing method After thoroughly wetting a hair bundle for testing (damaged hair obtained by cumulative bleaching treatment of Japanese female hair 5 times, length: approx. 15 cm, mass: 20 g) with 40 ° C. warm water, 3 g of rinse composition is applied. did. After fully adapting to the whole, it was rinsed with warm water for 30 seconds. The towel was dried and dried with a dryer while lightly brushed, and then touch evaluation was performed.
-Touch Evaluation Criteria Hair slipperiness ○: Gives the hair a slipperiness and is very dry △: Gives the hair a slight slippage and slightly freezing ×: The hair has no slippage feeling and is squeezed Hair flexibility ○: Hair is smooth and very soft Δ: Hair is slightly smooth and slightly soft ×: Hair is stiff / Glossy ○: Hair is glossy and rich in gloss Slightly glossy X: Hair is not glossy and has a rough appearance Ease of hair uniting ○: Hair unit is very good and the phase is aligned Δ: Hair unit is slightly good, but phase is not good Not aligned x: Hair is not organized at all

  As shown in the results of Table 1, the rinse composition of the present invention was able to recognize a very high conditioning effect (improvement of slipping, flexibility, gloss / gloss and ease of grouping) without impairing the blending stability.

  Hereinafter, formulation examples suitable for obtaining the effects of the present invention will be given.

Formulation Example 1
Hair cosmetics having the composition shown in Table 2

Formulation Example 2
Hair cosmetics having the composition shown in Table 3

Formulation Example 3
Hair cosmetics having the composition shown in Table 4

Claims (8)

Branched glycerol represented by the following structural formula (1), wherein three or more glycerol groups or glycidol groups represented by the following structural formula (1), (2), (3) or (4) are bonded on average. A hair cosmetic comprising a branched polyglycerol-modified silicone in which at least one branched polyglycerol chain containing at least one group is bonded to a silicon atom of the silicone via a linking group.

The hair cosmetic composition according to claim 1, wherein the linking group is a group having an ether group represented by the general formula (5) or (6).
—R ¹ —O— (A ¹ O) _p − (5)
(Wherein R ¹ may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 28 carbon atoms, and A ¹ O is carbon. C1-4 alkyleneoxy group (also referred to as an oxyalkylene group) or arylene group having 6 to 10 carbon atoms (also referred to as oxy arylene group), p is a number of 0 to 30, p pieces of a ¹ O is They may be the same or different.)

(In the formula, 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.) The hair cosmetic according to claim 1, wherein the linking group is a group represented by the general formula (7) or (8).

  Furthermore, the hair cosmetics in any one of Claims 1-3 containing a nitrogen-containing compound.   Furthermore, the hair cosmetics in any one of Claims 1-4 containing an aliphatic alcohol.   Furthermore, the hair cosmetics in any one of Claims 1-5 containing at least 1 sort (s) of surfactant chosen from a nonionic surfactant, an anionic surfactant, and an amphoteric surfactant.   Furthermore, hair cosmetics in any one of Claims 1-6 containing melting | fusing part whose melting | fusing point in normal temperature is 40 degreeC or more. The hair cosmetic composition according to any one of claims 1 to 7, wherein the branched polyglycerol-modified silicone is a silicone represented by the following structural formula (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 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 , R ³ , R ⁴ , at least one of R ⁵ , t R ⁶ , R ⁷ , R ⁸ , R ⁹ is a linking group to which a branched polyglycerol chain is bonded, where t is a number from 0 to 10,000. Show.)