JP5331422B2 - Aqueous hair cleanser - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair cleansing agent which efficiently leaves silicone on hair damaged by a chemical treatment so as to impart smoothness to the hair at rinsing and after drying, foams well and undergoes little yellowing during storage. <P>SOLUTION: The aqueous hair cleansing agent comprises (A) an anionic surfactant, (B) a branched polyglycerol-modified silicone, (C) cationized galactomannan and water. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an aqueous hair cleansing agent.

  In recent years when hair damage has become steady due to the widespread use of coloring agents and permanent agents, in addition to the basic functions as a cleaning agent such as foaming and detergency, hair cleaning agents have smoothness during rinsing and smoothness after drying. Now, the function of providing conditioning effects such as unity has become important. Generally, a cationized polymer is blended in the hair cleansing agent in order to impart smoothness during rinsing. The cationized polymer incorporated in the hair cleanser remains on the hair surface by forming a water-insoluble complex with the anionic surfactant when diluted with water in the process of using the hair cleanser. And give smoothness during rinsing. However, the smoothness and unity after drying were not sufficient, and there was room for improvement.

As means for solving this, Patent Document 1 discloses a cleaning cosmetic composition containing a cleaning base and at least one of an amino-modified silicone and a cationic polymer. Amino-modified silicone has a hydrophilic amino group that is easily cationically charged, so it has the property of being easily adsorbed to the anionically charged hair surface and is expected to improve the smoothness and cohesion of hair after drying. Is done. However, a large amount of an anionic active agent is incorporated in a general hair cleansing agent as a cleaning base. In such a system, the amino group of the amino-modified silicone interacts electrostatically with the anionic active agent. Therefore, the cationic property of the amino-modified silicone is reduced or lost, and the hydrophobicity is increased. As a result, the adsorptivity to hair decreases due to the decrease in cationicity. For this reason, the smoothness after drying may not be obtained sufficiently. In addition, the strong hydrophobicity gives hair a strong squeaky feeling that touches the rubber in the water stream when rinsing the cleaning agent, and may inhibit foaming. Chemicals such as hair coloring agents and permanent agents The conditioning effect on hair damaged by the treatment was not sufficient.
Furthermore, since the primary amino group in the amino-modified silicone is easily oxidized, the cleaning agent containing the amino-modified silicone has a problem that the appearance color is easily yellowed.

  As means for solving these problems, Patent Document 2 discloses a detergent composition containing an anionic surfactant, a cationic polymer, and a silicone derivative having a group containing both a hydroxyl group and a nitrogen atom as a side chain bonded to a silicon atom. Things are listed. Since this silicone derivative has many hydroxyl groups as well as amino groups, it has a relatively high hydrophilicity even when interacting with an anionic activator, so that squeezing during rinsing is alleviated and smoothness is improved. In addition, yellowing is also improved because it does not have a primary amino group. However, there is still room for improvement in terms of smoothness after drying and yellowing.

As means for solving these problems, Patent Document 3 proposes a hair cleansing agent containing silicone modified with a branched polyglycerol group. Since the branched polyglycerol-modified silicone does not contain an amino group, the branched polyglycerol-modified silicone has no interaction with an anionic active agent, and there is no problem regarding stability such as yellowing. In addition, since the structure has a large amount of hydroxyl groups, it has high hydrophilicity and excellent lubricity in water. For this reason, it has been reported that the smoothness during rinsing is improved and the smoothness and moistness of the hair after drying are improved. However, the residual property to hair having no adsorbing group such as an amino group is low, and there is still room for improvement in terms of the conditioning effect for damaged hair.
JP-T-2001-517606 JP 2004-67638 A JP-A-2005-97150

  The present invention, even for hair damaged by chemical treatment, has good foaming and slippery foam quality at the time of shampooing, has a smooth feel at the time of rinsing, gives smoothness to the finished hair, An object of the present invention is to provide a stable aqueous hair cleanser with little yellowing during storage.

  By combining the use of an anionic active agent, branched polyglycerol-modified silicone and cationized galactomannan, the present inventors have effectively left silicone on the hair surface even on damaged hair, and smoothed the surface during rinsing. It was found that a hair cleanser capable of achieving the above-mentioned properties, giving smoothness to the finished hair, having good foaming and little yellowing during storage was obtained.

That is, according to the present invention, the following components (A), (B), (C):
(A) an anionic surfactant,
(B) The glycerol groups represented by the following structural formulas (1), (2), (3), (4) or (5) are the same or different and are bonded together in an average of 4 or more, and the structural formula (1) Or a branched polyglycerol chain containing at least one group represented by (5) is represented by the following general formula (7), a divalent group represented by the following general formula (6) on the silicon atom of silicone: A branched polyglycerol-modified silicone bonded via at least one linking group selected from the group consisting of a divalent group and a trivalent group represented by the following general formula (8):
(C) cationized galactomannan,
And an aqueous hair cleanser containing water.

_{^{- (R 1) p -O- (}} AO) q - (6)
(In the general formula (6), 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, AO is an alkyleneoxy group having 1 to 4 carbon atoms or an aryleneoxy group having 6 to 10 carbon atoms, p is a number of 0 or 1, q is a number of 0 to 30, and q AOs are the same or different. May be.)

(In the general formula (7), R ² may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms or an alkenylene group, u is a number of 0 or 1, v Is a number from 0 to 30, AO is as defined above, and v AOs may be the same or different.)

(In the general formula (8), R ³ may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms or an alkenylene group, z is a number of 0 or 1, x Is a number from 0 to 30, y is a number from 0 to 30, AO is as defined above, and x and y AOs may be the same or different.)

  The water-based hair cleanser of the present invention can effectively remain on the hair surface even in hair damaged by chemical treatment, has excellent smoothness during rinsing, good foaming, and yellowing during storage. Few.

The aqueous hair cleansing agent of the present invention contains the following components (A) to (C) and water. Hereinafter, each component will be specifically described.
(A) Anionic surfactant (B) Branched polyglycerol-modified silicone (C) Cationized galactomannan

First, the component (A) will be described.
In the aqueous hair cleansing agent of the present invention, as the component (A) anionic surfactant, specifically, sulfuric acid type, sulfonic acid type and carboxylic acid type can be used. Examples of the sulfuric acid type include alkyl sulfates, polyoxyalkylene alkyl ether sulfates, and polyoxyalkylene alkenyl ether sulfates. Examples of the sulfonic acid-based compounds include sulfosuccinic acid alkyl ester salts, polyoxyalkylene sulfosuccinic acid alkyl ester salts, alkane sulfonic acid salts, and the like. Examples of the carboxylic acid-based compounds include higher fatty acid salts and alkyl ether carboxylates. Of these, polyoxyalkylene alkyl ether sulfates and alkyl sulfates are preferred, and those represented by the following general formula (10) or (11) are particularly preferred.

R ¹⁰ O (CH ₂ CH ₂ O) _n SO ₃ M (10)
R ¹⁰ OSO ₃ M (11)
(In the general formulas (10) and (11), R ¹⁰ represents an alkyl group or alkenyl group having an average carbon number of 10 to 18, and M represents an alkali metal, alkaline earth metal, ammonium, alkanolamine or basic amino acid. And n represents a number of 1 to 5 in terms of mass average.)

Among these, from the viewpoint of achieving both quick foaming and good foam feel, R ¹⁰ in the general formula (10) is an alkyl group having an average carbon number of 12 to 14, n is about 1 in terms of mass average, M Polyoxyethylene alkyl ether sulfates in which is ammonium or sodium are preferred.

  The component (A) may be used singly or in combination of two or more, and the content thereof is foaming, from the viewpoint of liquidity at the time of use and cleanability, the aqueous hair cleansing agent of the present invention The content is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 8 to 20% by mass.

Next, the component (B) will be described.
In the aqueous hair cleansing agent of the present invention, component (B) is a branched polyglycerol-modified silicone, and a specific branched polyglycerol chain is bonded to the silicone main chain. The branched polyglycerol chain is formed by bonding groups having a glycerol skeleton represented by the following structural formulas (1) to (5) having different bonding modes to each other. That is, a branched glycerol groups represented by the following structural formula (1), b glycerol groups represented by the following structural formula (2), and c linear chains represented by the following structural formula (3) An average of four or more glycerol groups, d terminal glycerol groups represented by the following structural formula (4), and e branched glycerol groups represented by the following structural formula (5) are bonded in any combination; It contains at least one group represented by the structural formula (1) or (5).
The groups represented by the following structural formulas (1) to (5) are also referred to as groups (1) to (5), respectively.

  In the branched polyglycerol chain, the groups (1), (2), (3) and (5) may be bonded to each other in any sequence. As the number of groups (1) and / or groups (5) increases, the branched structure develops, and the group (4) is present at the end of each branched chain.

  The average number of bonds (a + b + c + d + e) of the groups (1), (2), (3), (4) and (5) in the branched polyglycerol chain is determined by NMR analysis or molecular weight comparison with the precursor silicone, The number is preferably 4 or more, more preferably 4 to 201, still more preferably 4 to 101, particularly preferably 4 to 51, and most preferably 4 to 21. The branching ratio [(a + e) / (a + b + c + d + e)] in the branched polyglycerol chain is preferably 1/20 or more, more preferably 1/10 or more, and particularly preferably 1/6 or more, from the viewpoint of smoothness during rinsing. preferable. [(A + e) / (a + b + c + d + e)] is preferably less than 1/2 from the viewpoint of smoothness during rinsing. In the branched polyglycerol chain, the groups (1), (2), (3), (4) and (5) may be arbitrarily bonded.

  The number of groups (1) (that is, a) is preferably 0 to 100, more preferably 1 to 100, and even more preferably 2 to 100 in the branched polyglycerol chain. 2 to 50 are particularly preferable, 2 to 25 are particularly preferable, and 2 to 10 are most preferable.

  The number of groups (2) (ie, b) and the number of groups (3) (ie, c) may be the same or different, and is preferably 0 to 199, and preferably 0 to 198. More preferably, it is more preferably 0 to 196, particularly preferably 0 to 96, particularly preferably 0 to 46, and most preferably 0 to 16.

  The number of groups (4) (that is, d) is preferably 1 to 101, more preferably 2 to 101, still more preferably 3 to 101, and 3 to 51. It is particularly preferable that 3 to 26 are present, particularly preferably 3 to 11 are present.

  The number of groups (5) (ie, e) is preferably 1 when a is 0, and is preferably 0 or 1 when a is 1 or more.

  In addition, as the component (B), one or more branched glycerol groups represented by the structural formula (1) are bonded to a silicon atom of silicone in which a is 1 or more and e is 0 via a linking group. More preferred is a branched polyglycerol-modified silicone having at least one branched polyglycerol chain contained therein. The linking group will be described later.

  At this time, in the structural formula (1), the two oxygen atoms are bonded to the same or different glycerol groups represented by the structural formula (1), (2), (3) or (4). .

  When a is 1 or more and e is 0, the two oxygen atoms in the structural formula (1) may be the same or different, and the structural formula (1), (2), (3) or (4) Is bonded to the oxygen atom of the structural formula (2), and the glycerol group represented by the structural formula (1), (2), (3) or (4) is bonded to the structure. A glycerol group represented by the structural formula (1), (2), (3) or (4) is bonded to the oxygen atom of the formula (3).

  In the present invention, the branched polyglycerol-modified silicone as the component (B) has a branched polyglycerol chain containing at least one group represented by the structural formula (1) or (5) having a silicon atom of the following general formula: One or more selected from the group consisting of a divalent group represented by (6), a divalent group represented by the following general formula (7), and a trivalent group represented by the following general formula (8) At least one is bonded through a linking group.

Among these, the group represented by the following general formula (6) (hereinafter referred to as the linking group (6)) is a divalent group having an ether group, and is preferable from the viewpoint of chemical stability in the detergent. . In the linking group (6), the (R ¹ ) _p side is bonded to the silicon silicon atom, and the (AO) _q side is bonded to the branched polyglycerol chain.

_{^{- (R 1) p -O- (}} AO) q - (6)
(In the general formula (6), 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, AO is 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 is a number of 0 or 1, and q is 0 to 0. 30 represents a number, and q AOs may be the same or different.)

In the general formula (6), R ¹ is preferably a linear or branched alkylene or alkenylene group having 1 to 22 carbon atoms from the viewpoint of smoothness during rinsing.
Also, as substituents in R ^1, hydroxy group, an amino group (having 1 to 22 carbon atoms), an imino group (having 1 to 22 carbon atoms), a carboxyl group, an alkoxy group (having 1 to 22 carbon atoms), an acyl group (carbon Formula 1-22) is mentioned.

  In the general formula (6), AO is preferably an alkyleneoxy group having 1 to 4 carbon atoms from the viewpoint of smoothness during rinsing.

Of the linking groups represented by the general formula (6), the most preferred linking group is represented by the following general formula (12). In the linking group of the general formula (12), the trimethylene side is bonded to the silicon silicon atom, and the oxygen atom side is bonded to the branched polyglycerol chain.
—CH ₂ CH ₂ CH ₂ —O— (12)

In addition, as the other linking group in the component (B), a linking group containing an oxyphenylene group is preferable from the viewpoint of smoothness at the time of rinsing, and specifically, 2 represented by the following general formula (7). And a trivalent group represented by the following general formula (8). In the linking group (7), the (R ² ) _u side is bonded to the silicon atom of the silicone chain, and the (AO) _v side is bonded to the branched polyglycerol chain. In the linking group (8), the (R ³ ) _z side is bonded to the silicon atom of the silicone chain, and the (AO) _x and (AO) _y sides are bonded to the branched polyglycerol chain.

(In the general formula (7), R ² may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms or an alkenylene group, u is a number of 0 or 1, v Is a number from 0 to 30, AO is as defined above, and v AOs may be the same or different.)

(In the general formula (8), R ³ may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms or an alkenylene group, z is a number of 0 or 1, x Is a number from 0 to 30, y is a number from 0 to 30, AO is as defined above, and x and y AOs may be the same or different.)

In the linking group (7) and the linking group (8), (R ² ) _u and (R ³ ) _z are groups that connect the silicon atom of the silicone chain and the phenylene group of the oxyphenylene group contained in the linking group. . R ² and R ³ are preferably an alkylene group or alkenylene group having 1 to 16 carbon atoms, particularly preferably 1 to 12, and ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene Nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene group and the like. Among these, an ethylene, propylene or trimethylene group is more preferable, and an ethylene or trimethylene group is particularly preferable.

As substituents which may be present in R ² and R ³ , a hydroxyl group, an amino group (C1-22), an imino group (C1-22), a carboxyl group, an alkoxy group (C1 22), an acyl group (C1-C22), etc. are mentioned. u and z are 0 or 1, but 1 is more preferable.

  In the linking group (7) and the linking group (8), AO is an oxyalkylene group or an oxyarylene group that connects the branched polyglycerol chain and the oxygen atom of the oxyphenylene group contained in the linking group, Bonded to the branched polyglycerol chain on the oxygen side of the oxyarylene group, and bonded to the oxygen atom of the oxyphenylene group on the alkylene or arylene side of the oxyalkylene group or oxyarylene group. As AO, an oxyethylene group, an oxypropylene group or an oxyphenylene group is preferable, and among these, an oxyethylene group is particularly preferable.

  v, x and y are each a number of 0 to 30, preferably 0 to 15, more preferably 0 to 5, and most preferably 0. When v, x, and y are non-zero numbers, v AOs, x AOs, and y AOs may be the same or different. It may be an alternating type, a block type, a periodic arrangement other than these, or a random type.

In the linking group (7), the bonding mode of the oxygen atom and the (R ² ) _u group (the silicon atom on the silicone chain when u is 0) bonded to the phenylene group of the oxyphenylene group is the ortho position, the meta Either the position or the para position may be used, or a mixture thereof may be used.

  Among the oxyphenylene group-containing linking groups, the most preferable one is a linking group represented by the following general formula (13) (hereinafter referred to as linking group (13)). In the linking group (13), 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 (13), the bonding mode of the oxygen atom and trimethylene group bonded to the phenylene group of the oxyphenylene group may be any of ortho, meta, and para positions, and a mixture thereof. However, the ortho position, the para position or a mixture thereof is more preferable.

  The branched polyglycerol-modified silicone of component (B) is derived from a polysiloxane having two or more silicon atoms, and the polysiloxane skeleton may be linear, branched or cyclic. Among these, from the viewpoint of smoothness after drying, linear silicone represented by the general formula (14) (hereinafter referred to as silicone (14)) is preferable.

(In the general formula (14), R ²¹ , R ²² , R ²³ , t R ²⁴ , t R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ may be the same or different, and the branched polyglycerol chain is A linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, which may represent a bonded linking group, may have a substituent, and may be substituted with a fluorine atom; or An aryl group having 6 to 22 carbon atoms, wherein at least one of R ²¹ , R ²² , R ²³ , t R ²⁴ , t R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ is a branched polyglycerol chain; Is a linking group to which t represents a number of 0 to 10,000.)

In the silicone (14), R ²¹ , R ²² , R ²³ , t R ²⁴ , t R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ other than the linking group to which the branched polyglycerol chain is bonded are A linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, which may be the same or different and may have a substituent and may be substituted with a fluorine atom, or the number of carbon atoms 6 to 22 aryl groups. Examples of the alkyl group having 1 to 22 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and trifluoropropyl. Group and the like. Examples of the alkenyl group having 1 to 22 carbon atoms include vinyl groups and allyl groups. Examples of the alkoxy group having 1 to 22 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, and hexyloxy. Group, heptyloxy group, octyloxy group, phenoxy group and the like. Moreover, as a C6-C22 aryl group, a phenyl group, methylphenyl, ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, t-butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, laurylphenyl , Myristylphenyl, cetylphenyl group and the like. Among these, from the viewpoint of smoothness after drying, a linear or branched alkyl group having 1 to 12 carbon atoms, a vinyl group, an allyl group, or an aryl group having 6 to 12 carbon atoms is preferable. -3 alkyl groups or phenyl groups are more preferred, methyl groups, propyl groups or phenyl groups are particularly preferred, and methyl groups and phenyl groups are most preferred.

In the silicone (14), R ^{21 to} R ²⁸ may have a phenyl group, phenol group, hydroxy group, carboxy group, amino group (0 to 14 carbon atoms), imino group, (aminoethyl) ) Amino group, (dimethylaminoethyl) amino group, polyoxyalkylene group, mercapto group, and epoxy group. When it has these substituents, a propyl group is particularly preferable as R ^{21 to} R ²⁸ .

In the silicone (14), at least one of R ²¹ , R ²² , R ²³ , t R ²⁴ , t R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , preferably 1 to 10, more preferably 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 on the side chain, one end and / or both ends of the silicone (14), or may be a mixture thereof.

One selected from the group consisting of R ^{21 to} R ²³ and one selected from the group consisting of R ^{26 to} R ²⁸ represent a linking group to which a branched polyglycerol chain is bonded, and the remaining R ^{21 to} R ²³ and R ^{26 to} R ²⁸ , t R ²⁴ , and t R ²⁵ are particularly preferably a methyl group. That is, it is a branched polyglycerol-modified silicone of both ends type.

In addition, when the linking group to which the branched polyglycerol chain is bonded is present in three or more selected from t R ²⁴ and t R ²⁵ , it is preferable to be a side-chain multi-substituted branched polyglycerol-modified silicone. .

  T in silicone (14) shows the number of 0-10000, Preferably it is the number of 1-3000, More preferably, it is the number of 5-500, Most preferably, it shows the number of 10-150.

  The number average molecular weight of the branched polyglycerol-modified silicone of component (B) is preferably 500 to 700000, more preferably 750 to 200000, and particularly preferably 1000 to 100,000. The number average molecular weight is measured by GPC method (standard polystyrene or polyethylene glycol conversion).

  In the branched polyglycerol-modified silicone of component (B), the number of silicon atoms (Si) in the silicone and the groups (1), (2), (3), (4) and (5) in the branched polyglycerol chain The ratio (G / Si) of the total number G (hereinafter referred to as the number of glycerol groups) is preferably 0.001 to 50, more preferably 0.05 to 10 from the viewpoint of coexistence of smoothness after rinsing and drying. 0.1-3 are more preferable and 0.15-1 are especially preferable.

  In the branched polyglycerol-modified silicone of component (B), a small amount of ethyleneoxy group and / or propyleneoxy group may be present in the branched polyglycerol chain as long as the effect of the present invention is not significantly inhibited. 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 are blocked 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. The ethyleneoxy group and / or propyleneoxy group is preferably present in an amount of 0.001 to 0.5 molar equivalent, more preferably 0.02 to 0.2 molar equivalent.

  Such a branched polyglycerol-modified silicone includes, for example, a branched polyglycerol compound having a reactive unsaturated group and a so-called organohydrogen silicone in which a hydrogen atom is bonded to a part of a silicon atom in a silicone chain. It can be obtained by a hydrosilylation reaction in the presence of a catalyst. The branched polyglycerol compound having a reactive unsaturated group is obtained by adding glycidol (2,3-3-) to a compound having a reactive unsaturated group and a functional group (preferably a hydroxy group or a carboxy group) in the presence of an acidic catalyst or a basic catalyst. Epoxy-1-propanol) can be obtained by adding and reacting while controlling the addition rate. A branched polyglycerol compound having a high degree of branching can be produced by slowing the addition rate.

  In addition, as a reactive group, an acidic catalyst or a basic catalyst such as potassium is added to silicone having one or more functional groups selected from the group consisting of hydroxy group, carboxy group, amino group, imino group, mercapto group and epoxy group. Component (B) can also be produced by a method of adding glycidol in the presence and ring-opening graft polymerization.

  Two or more kinds of the branched polyglycerol-modified silicone of component (B) may be used simultaneously in the aqueous hair cleansing agent of the present invention. In addition, the content of the aqueous hair cleansing composition in the composition is 0.01 to in terms of blending stability of the composition, foaming, liquid properties at the time of use, smoothness at the time of rinsing, and unity after drying. 10 mass% is preferable, Furthermore, 0.05-5 mass%, Especially 0.1-3 mass% is preferable.

Next, the component (C) will be described.
The cationized galactomannan of the component (C) is a water-soluble cationized polymer in which a quaternary nitrogen-containing group is introduced into a galactomannan having mannose as a main unit and a galactose unit as a side chain. Galactomannans are obtained, for example, from the endosperm of legume seeds. A galactose to mannose ratio of 1: 1 is fenugreek gum, 1: 2 is guar gum, 1: 3 is tara gum, and 1: 4 is locust bean gum. As commercial products of cationized galactomannan, as cationized fenugreek gum, Kachinal CF-100 (Toho Chemical Industry Co., Ltd.) and as cationized guar gum, Jaguar C-13S and Jaguar C-17 (Rhodia Co., Ltd.) For example, Katchinal CT-100 (Toho Chemical Industry Co., Ltd.), and cationized locust bean gum includes Katchinal CLB-100 (Toho Chemical Industry Co., Ltd.).

  The component (C) is preferably one or a combination of two or more of cationized fenugreek gum, cationized tara gum, and cationized locust bean gum from the viewpoint of smoothness of rinsing.

  These (C) components can be used alone or in combination of two or more. The cationized galactomannan of component (C) is 0.01 to 3 mass in the aqueous hair cleansing agent of the present invention from the viewpoints of foaming, liquidity at the time of use, smoothness at the time of rinsing, and smoothness at the time of drying. % Is preferable, and further 0.05 to 1% by mass, particularly 0.1 to 0.6% by mass is preferable.

  Since the aqueous hair cleansing agent of the present invention contains the above components (A) to (C), it has rich foaming and is excellent in smooth fingering and smooth finish when foaming. is there. In addition, yellowing during storage is suppressed and storage stability is excellent. Although this reason is not necessarily clear, it is guessed that (B) component remains efficiently on the hair surface by including component (A)-(C).

  In addition, from the viewpoint of silicone persistence to the hair, smoothness during rinsing, and smoothness after drying, the mass ratio of component (B) / component (C) in the aqueous hair cleanser is 1/10 to 10 / 1, more preferably 1/7 to 7/1, and particularly preferably 1/5 to 5/1.

In order to further improve the cleaning performance, the aqueous hair cleansing agent of the present invention may contain a nonionic surfactant or an amphoteric surfactant.
Nonionic surfactants include polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene sorbit fatty acid ester, polyoxyalkylene glycerin fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene ether Examples include alkylene (hardened) castor oil, sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, fatty acid alkanolamide, alkyl glycoside, monoalkyl or monoalkenyl glyceryl ether, and the like.

Among these, polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters such as polyoxyethylene (C ₈ -C ₂₀ ) fatty acid esters, and polyoxyalkylenes such as polyoxyethylene hydrogenated castor oil (Hardened) castor oil and alkyl glycoside are preferred.

  Fatty acid alkanolamides are also suitable, which may be either monoalkanolamides or dialkanolamides, and those having an acyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms are preferred. Further, those having a hydroxyalkyl group having 2 to 3 carbon atoms are preferred, for example, oleic acid diethanolamide, palm kernel oil fatty acid diethanolamide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide. Coconut oil fatty acid monoethanolamide, lauric acid isopropanolamide, lauric acid monoethanolamide, and the like.

  Monoalkyl glyceryl ether or monoalkenyl glyceryl ether is also suitable, and the alkyl group or alkenyl group is preferably a linear or branched alkyl group having 4 to 10 carbon atoms, particularly 8 to 10 carbon atoms. Specifically, n-butyl group, isobutyl group, n-pentyl group, 2-methylbutyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n -A decyl group, an isodecyl group, etc. are mentioned, 2-ethylhexyl group and an isodecyl group are especially preferable.

  Examples of amphoteric surfactants include betaine surfactants. Of these, betaine surfactants such as alkyldimethylaminoacetic acid betaine, fatty acid amidopropyl betaine, and alkylhydroxysulfobetaine are more preferred, and fatty acid amidopropyl betaine is particularly preferred. The fatty acid amidopropyl betaine preferably has an acyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and in particular, lauric acid amidopropyl betaine, palm kernel oil fatty acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine and the like. preferable.

  These nonionic or amphoteric surfactants can be used alone or in combination of two or more in the aqueous hair cleanser. However, when the aqueous hair cleanser of the present invention is in the form of an aqueous liquid cleanser. It is particularly preferable to use fatty acid amidopropyl betaine, fatty acid alkanolamide, and monoalkyl glyceryl ether together with the component (A) because not only foaming power is improved but also an appropriate liquid property is obtained.

  The content of the nonionic or amphoteric surfactant is preferably from 0.1 to 15% by mass in the hair cleansing agent of the present invention because a good foam increasing effect is obtained. From the above points, the range of 0.5 to 8% by mass, particularly 1 to 6% by mass is more preferable.

In order to improve the finish after drying, the aqueous hair cleansing agent of the present invention may further contain a cationic surfactant, silicones other than component (B), and a cationic polymer other than component (C). .
Examples of the cationic surfactant include alkyltrimethylammonium salts, alkoxyalkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylamine salts, alkoxyalkyldimethylamine salts, alkylamidoalkyldimethylamine salts, and the like.

(I) Alkyltrimethylammonium salt For example, what is represented by the following general formula is mentioned.
R ¹¹ —N ⁺ (CH ₃ ) ₃ X ⁻
(In the above formula, R ¹¹ represents an alkyl group having an average carbon number of 12 to 22, and X ⁻ represents a halogen (chlorine or bromine) ion.)
Specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, and behenyltrimethylammonium chloride.

(Ii) Alkoxyalkyltrimethylammonium salt For example, what is represented by the following general formula is mentioned.
R ¹² —O—R ¹³ —N (CH ₃ ) ₃ X ⁻
(In the above formula, R ¹² represents an alkyl group having an average carbon number of 12 to 22, R ¹³ represents an ethylene group or a propylene group, and X ⁻ is the same as above.)
Specific examples include stearoxypropyltrimethylammonium chloride, stearoxyethyltrimethylammonium chloride, stearoxyhydroxypropyltrimethylammonium chloride, and the like.

(Iii) Dialkyldimethylammonium salt For example, what is represented by the following general formula is mentioned.
R ¹⁴ ₂ -N ⁺ (CH ₃ ) ₂ X ⁻
(In the above formula, R ¹⁴ represents an alkyl group having 12 to 22 carbon atoms or a benzyl group, and X ⁻ is the same as above.)
Specifically, distearyl dimethyl ammonium chloride etc. are mentioned.

(Iv) Alkyldimethylamine salt Examples include tertiary amine salts represented by the following general formula.
R ¹⁵ -N (CH _{3) 2}
(In the above formula, R ¹⁵ represents an alkyl group having an average carbon number of 12 to 22.)
Specific examples include organic acid salts of behenyl dimethylamine and stearyl dimethylamine.

(V) Salt of alkoxyalkyldimethylamine For example, a salt of a tertiary amine represented by the following general formula may be mentioned.
R ¹⁶ —O—R ¹⁷ —N (CH ₃ ) ₂
(In the above formula, R ¹⁶ represents an alkyl group having an average carbon number of 12 to 22, and R ¹⁷ represents an ethylene group or a propylene group.)

(Vi) Salts of alkylamidoalkyldimethylamines Examples of salts of tertiary amines represented by the following general formulas.
^{R 18 -CONH-R 19 -N (} CH 3) 2
(In the above formula, R ¹⁸ represents an alkyl group having an average carbon number of 11 to 21, and R ¹⁹ represents an ethylene group or a propylene group.)

As cationic surfactants other than the above (i) to (vi), ethyl lanolin sulfate fatty acid amide propylethyl dimethyl ammonium, ethyl sulfate lanolin fatty acid amide ethyl triethyl ammonium, ethyl sulfate lanolin fatty acid amide propyl triethyl ammonium, methyl sulfate lanolin fatty acid amide ethyl trimethylammonium, lanolin fatty acid amidopropyl dimethylammonium methyl sulfate, ethyl sulfate isoalkanes acid (C ₁₄ ~C ₂₀₎ amidopropyl dimethylammonium ethyl sulfate isoalkanes acid (C ₁₈ ~C ₂₂₎ amidopropyl dimethylammonium, ethyl isostearate sulfate Amidopropylethyldimethylammonium acid, amidopropylethyldimethylammonium ethylsulfonate Examples include kill trimethyl ammonium saccharin.

  Two or more kinds of cationic surfactants may be used in combination, and from the viewpoint of smoothness from the time of shampooing to the time of rinsing, the content thereof is 0.01 to 10% by mass in the aqueous hair cleaning agent of the present invention. Further, 0.05 to 6% by mass, particularly 0.3 to 3% by mass, and particularly 0.5 to 2% by mass are preferable.

Examples of silicones other than the component (B) include the following.
(1) Dimethylpolysiloxane Examples include those represented by the following general formula.
_{(CH 3) 3 SiO - [} (CH 3) 2 SiO] d -Si (CH 3) 3
(In the above formula, d represents a number of 3 to 20000.)

(2) Amino-modified silicone Various amino-modified silicones can be used, but in particular, the average molecular weight of about 3000 to 100000, the name of Amodimethicone, CTFA Dictionary (US, Cosmetic Ingredient Dictionary) 9th edition, 2002, volume 1 , P107 are preferred. Commercially available products include SM 8704C (Toray Dow Corning), DC 929 (Dow Corning), KT 1989 (Momentive Performance Materials), 8500 Conditioning Agent, DOW CORNING TORAY SS-3588, DOW CORNING TORAY. SILSTLE 104 (Toray Dow Corning) etc. are mentioned.

(3) Other silicones Other than the above, polyether-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, alkoxy-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone, alkyl-modified silicone and the like It is done.

  Two or more kinds of these silicones may be used in combination, and from the viewpoint of smoothness from the time of shampooing to the time of rinsing, the content is preferably 0.01 to 10% by mass in the aqueous hair cleanser of the present invention. Furthermore, 0.05 to 5% by mass, particularly 0.1 to 2% by mass is preferable.

  Examples of the cationized polymer other than the component (C) include cationized cellulose, cationized starch, cationized xanthan gum, diallyl quaternary ammonium salt / acrylamide copolymer, vinyl imidazolium trichloride / vinyl pyrrolidone copolymer, hydroxyethyl cellulose / Dimethyldiallylammonium chloride copolymer, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer, polyvinylpyrrolidone / alkylaminoacrylate copolymer, polyvinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymer, vinylpyrrolidone / methacrylamide Propyltrimethylammonium chloride copolymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene Glycol copolymers, adipic acid / dimethylaminohydroxypropylethylenetriamine copolymer (Sandos, Cartaletin), cations described in JP-A-53-139734, JP-A-60-36407 Polymer and the like, and cationized cellulose and diallyl quaternary ammonium salt / acrylamide copolymer are particularly preferable.

  Further, for example, Marquat 550 (NALCO, copolymer of acrylamide and diallyldimethylammonium salt; CTFA name polyquaternium-7), rubiquat FC370 (BASF, 1-vinyl-2-pyrrolidone and 1-vinyl-3- Copolymer of methylimidazolium salt; CTFA name polyquaternium-16), Gafquat 755N (ISP, copolymer of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate; CTFA name polyquaternium-11), Ucare polymer JR and the same LR series (Amercol, a salt of a reaction product of trimethylammonium substituted epoxide and hydroxyethyl cellulose; CTFA name polyquaternium-10), Poise C-60H, Poise C-80M, Poise C-150L Kao Corporation, salts of reaction product between trimethylammonium substituted epoxide and hydroxyethyl cellulose; CTFA name Polyquaternium-10) may be commercially available, such as.

  These cationized polymers may be used in combination of two or more, and from the point of smoothness from the time of shampooing to the time of rinsing, the content thereof is 0.01 to 3% by mass in the aqueous hair cleaning agent of the present invention. Is more preferable, 0.05 to 2% by mass, particularly 0.1 to 0.5% by mass is preferable.

The aqueous hair cleansing agent of the present invention may further contain a pearling agent containing ethylene glycol monofatty acid ester, ethylene glycol difatty acid ester, ethylene glycol monoalkyl ether or ethylene glycol dialkyl ether.
Examples of the ethylene glycol monofatty acid ester include ethylene glycol monostearate and ethylene glycol monobehenate, and examples of the ethylene glycol difatty acid ester include ethylene glycol distearate and ethylene glycol dibehenate. Examples of the ethylene glycol monoalkyl ether include ethylene glycol monostearyl ether, and examples of the ethylene glycol dialkyl ether include ethylene glycol distearyl ether.
Two or more of these may be used in combination, and the content thereof is from the viewpoint of improving the storage stability of the hair cleaning agent and improving the smoothness during rinsing and rinsing, and improving the stability of the hair cleaning agent. 0.1-10 mass% is preferable in the aqueous hair cleansing agent of this invention, Furthermore, 0.5-5 mass%, Especially 1-4 mass% is preferable.

Moreover, the hair washing agent of this invention can contain an oil agent as another conditioning agent. Oils include hydrocarbons such as squalene, squalane, liquid paraffin, liquid isoparaffin, cycloparaffin;
Fats and oils such as castor oil, cacao oil, mink oil, avocado oil, olive oil, sunflower oil, coconut oil;
Waxes such as beeswax, whale wax, lanolin, carnauba wax;
Higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, glycerin, myristyl alcohol, behenyl alcohol, cetostearyl alcohol;
Ester oils such as isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridecyl isononanoate;
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 examples include isostearyl glyceryl ether and polyoxypropylene butyl ether. Of these, higher alcohols and fats and oils are preferable, and myristyl alcohol, cetyl alcohol, stearyl alcohol, sunflower oil, and camellia oil are particularly preferable. These oil agents can be used alone or in combination of two or more, and the content thereof is preferably 0.1 to 2% by mass, more preferably 0.2 to 1 in the aqueous hair cleansing agent of the present invention. 0.5% by mass, particularly 0.3 to 1.0% by mass is preferable.

  The aqueous hair cleansing agent of the present invention may contain a viscosity modifier, and as the viscosity modifier, hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, polypropylene glycol, ethylene glycol, propylene glycol, isoprene glycol, ethanol, benzyl alcohol Benzyloxyethanol, phenoxyethanol, clay minerals, salts (sodium chloride, ammonium chloride, sodium citrate, etc.), among which benzyl alcohol, ethanol, polypropylene glycol, sodium chloride, and sodium citrate are preferred. Two or more types of viscosity modifiers may be used in combination, and the amount used thereof is preferably 0.01 to 5% by mass in the aqueous hair cleanser of the present invention from the viewpoint of the amount of foam and foam quality, and more preferably 0. 0.05 to 4% by mass, particularly 0.1 to 3% by mass is preferable.

  In addition to the above-described components, the aqueous hair cleansing agent of the present invention can be appropriately blended with components used in ordinary hair cleansing agents depending on the purpose. Such components include, for example, anti-dandruff agents; vitamins; bactericides; anti-inflammatory agents; antiseptics; chelating agents; humectants such as glycerin, sorbitol, and panthenol; colorants such as dyes and pigments; Solvent extract, protein obtained from shell or pearl with pearl layer or hydrolyzate thereof, honey, royal jelly, protein obtained from silk or hydrolyzate thereof, protein-containing extract obtained from legume seed, ginseng Extracts, rice germ extract, hibamata extract, aloe extract, moon peach leaf extract, chlorella extract and other extracts; pearling agents such as titanium oxide; fragrances; pigments; ultraviolet absorbers; antioxidants; ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (by Hunting, Anthony LL, published in 1983, MICELLE PRESS)) And the like.

  The aqueous hair cleansing agent of the present invention preferably has a pH (diluted by 20 mass times with water, 25 ° C.) of 2 to 6 when applied to hair from the viewpoint of improving the gloss and unity of the hair. Is preferably pH 3-5, particularly pH 3.5-4.5. As the pH adjuster, it is preferable to use an organic acid, particularly α-hydroxy acid, and specifically, malic acid, citric acid, lactic acid, and glycolic acid are preferable. Two or more of these organic acids may be used in combination, and the amount used is 0.01 to 5% by mass in the aqueous hair cleansing agent of the present invention in terms of foam quality and improvement in hair flexibility during hair washing. Further, 0.1 to 3% by mass, particularly 0.3 to 2% by mass is preferable. Further, as other pH adjusting agents, bases such as sodium hydroxide, potassium hydroxide, ammonium chloride may be used in combination with these organic acids.

  The form of the aqueous hair cleansing agent of the present invention can be appropriately selected from liquid form and gel form, but a liquid form using water or a lower alcohol, particularly water, as a solvent is preferable.

(Examples 1-7 and Comparative Examples 1-5)
Hair cleaning agents shown in Table 1 were prepared and evaluated by the following evaluation methods. The results are shown in Table 1. The pH is a value obtained by diluting each composition 20 times by mass with water and measuring at 25 ° C.

Evaluation Method (1) Speed of Foaming Using the apparatus described in JP-A-10-73584, evaluation was performed by the method described in Examples of the same publication.
That is, FIG. 1 shows a container 10 that houses an object (hair 1) to which a cleaning agent is applied, protrusions 21 and 22 that come into contact with the hair 1, a measuring instrument 50 that measures foam generated in the container 10, and a container 10 is a motor 30 that moves the container 10 so that the lid 20 that guides the foam generated in the container 10 to the measuring instrument 50 and the hair 1 accommodated in the container 10 and the projections 21 and 22 slide. Is a foaming performance evaluation apparatus equipped with Wet hair 1 with an equal amount of water, inject 1.5 mL of an evaluation sample and 0.3 mL of model sebum made of lanolin from the injection hole 25, measure the amount of foaming, and the time until the amount of foam reaches 250mL It was evaluated by.

  In the apparatus of FIG. 1, as the hair 1, hair obtained by implanting 30 g of hair having a length of 90 mm on a disk 11 having a diameter of about 160 mm was used. The container 10 has a cylindrical shape having a diameter of 160 mm and a height of 220 mm, and the lid 20 includes three columnar projections having a diameter of 15 mm and a height of 12 mm as the first projection 21. As the projection 22, a projection having 9 projections 10 mm long, 2 mm wide and 12 mm high was used. Moreover, the rotation speed of the container 10 by the motor was set to 70 rotations per minute.

The evaluation criteria are as follows.
◎: Less than 100 seconds ○: More than 100 seconds and less than 200 seconds △: More than 200 seconds and less than 300 seconds ×: More than 300 seconds

(2) Slippery feeling when foaming After rinsing a human hair bundle of 25 cm in length, 5.5 cm in width and 10 g in weight with warm water at 40 ° C, excess water is removed, and 0.5 g of hair cleanser is added. Used and foamed well by hand for about 30 seconds. At that time, the sense of slip was subjected to sensory evaluation. The evaluation was performed by five people, and the total value of the evaluation was shown. The evaluation criteria are as follows.
4: Slip well 3: Slightly slide 2: Not slippery 1: Not slippery

(3) Slippery feeling when rinsing After rinsing a human hair bundle of 25 cm in length, 5.5 cm in width and 10 g in weight with warm water of 40 ° C, excess water is removed and 0.5 g of hair washing agent is added. Used and foamed well by hand for about 30 seconds. Thereafter, the hair feeling with bubbles was rinsed with hot water of 40 ° C. at a flow rate of 2 L / min, and the slip feeling was subjected to sensory evaluation. The evaluation was performed by five people, and the total value of the evaluation was shown. The evaluation criteria are as follows.
4: Slip well 3: Slightly slide 2: Not slippery 1: Not slippery

(4) Smoothness after drying The hair bundle treated in the same way as the evaluation of slipping at the time of foaming was rinsed with running water (2 L / min) at 40 ° C., and then the moisture was sufficiently wiped off with a towel and dried naturally. After drying, smoothness was evaluated. The evaluation was performed by five people, and the total value of the evaluation was shown. The evaluation criteria are as follows.
4: Good 3: Somewhat good 2: Not very good 1: Not good

(5) Yellowing of hair cleaning agent after storage at 50 ° C. for 1 month After the hair cleaning agent was filled in a 110 mL glass bottle and stored at 50 ° C. for 1 month, the yellowing of the appearance color was visually determined. When determining yellowing, a sample stored at 5 ° C. for 1 month was used as a reference.
○: No yellowing △: Slightly yellowed ×: Clearly yellowed

  Moreover, in each example, the branched polyglycerol modified silicone shown in the following synthesis examples was used.

(Synthesis example of branched polyglycerol-modified silicone)
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 (manufactured by Toray Dow Corning, trade name: BY16- 752; hydroxyl group equivalent: 1500) 150 g was added to a flask, and 5.61 g of potassium methoxide (30% methanol solution) was added. The mixture was heated to 60 ° C. under reduced pressure with stirring, and all the methanol was distilled off to give a yellow oil. As a product, potassium-modified phenol-modified silicone was obtained. The temperature was raised to 95 ° C., and 39.9 g (5.4 equivalents) of glycidol was added over 3.5 hours under a stream of argon with vigorous stirring over a period of 3.5 hours. After further heating and stirring for 20 minutes and cooling to room temperature, a pale yellowish white solid 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 as a slightly yellow oily substance. (Yield 98%)

The obtained branched polyglycerol-modified silicone A has a group (1) branched from the presence of a signal (78.0 to 81.0 ppm) derived from the methine carbon of the group (1) by analysis of ¹³ C-NMR spectrum. It was confirmed that it was a polyglycerol-modified silicone. Further, by analysis of the ¹ H-NMR spectrum, the average number of glycerol groups (G) = 10.9 (one side 5.5), the average number of silicon atoms (Si) = 31.9, and the G / Si ratio is 0.34, According to GPC analysis (column: KF-804L (× 2), aliphatic amine / chloroform solution, 40 ° C., polystyrene conversion), the number average molecular weight (Mn) was 4100.

(Synthesis Example 2) Synthesis Example of Branched Polyglycerol-Modified Silicone B (Linking Group: —CH ₂ CH ₂ CH ₂ —O—) According to the method described in JP-A-4-20531, it is represented by the following structural formula. Allylated diisopropylidenetriglycerin was obtained.

  30.0 g of a commercially available organohydrogenpolysiloxane (manufactured by Chisso Corporation, trade name: IC-8461-1F20-BL), 14.4 g of the allylated diisopropylidene triglycerin, 150 g of isopropyl alcohol, chloroplatinic acid (2%) 0.4 g of isopropyl alcohol solution) and 0.4 g of potassium acetate (10% ethanol solution) were placed in a flask and reacted at the solvent reflux temperature for 5 hours. Further, 20.5 g of 1-hexene was added and reacted for 2 hours. 100 g of 0.01M hydrochloric acid was added, and the mixture was reacted at isopropyl alcohol reflux temperature for 5 hours. The solvent was distilled off under reduced pressure as it was to obtain triglycerin-modified silicone.

  40.0 g of the obtained triglycerin-modified silicone was placed in a flask, 1.4 g of potassium methoxide (30% methanol solution) was added, and the mixture was heated to 60 ° C. under reduced pressure while stirring to distill off all the methanol. The potassium triglycerin-modified silicone was obtained as a yellow oil. The temperature was raised to 95 ° C., and 5.0 g of glycidol was added under a stream of argon with vigorous stirring over a period of 3.5 hours using a quantitative feed pump. After further heating and stirring for 20 minutes and cooling to room temperature, a pale yellowish white solid product was obtained. 150 mL of ethanol 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 as a slightly yellow oily substance. From the IR and NMR measurements, it was confirmed that the obtained compound was a branched polyglycerol-modified silicone containing groups (1) to (5). The average number of glycerol groups (G) = 16 (8 on one side), the average number of silicon atoms (Si) = 90.5, the G / Si ratio was 0.18, and the number average molecular weight (Mn) was 8000.

* 1 Lauryl ether (1) Ammonium sulfate: Ethylene oxide mass average addition mole number 1
* 2 Amino-modified silicone: "Silicone KT1989", Momentive Performance Materials * 3 Aminoglycol-modified silicone: "JP-8500 Conditioning Agent", Toray Dow Corning * 4 Cationized fenugreek gum: "Catinal CF-100 (Toho Chemical Industry Co., Ltd.)
* 5 Cationized guar gum: “Jaguar C-17” (Rhodia)
* 6 Cationized tara gum: “Kachinar CTR-100” (Toho Chemical Industries)
* 7 Cationized locust bean gum: “Catinal CLB-100” (Toho Chemical Industries)
* 8 Cationized hydroxyethyl cellulose: “Poise C-80M” (Kaosha)
* 9 Dimethylpolysiloxane emulsion: Silicone CF2460, Toray Dow Corning, average particle size 20 μm, effective content 75% by mass

  From Table 1, in Examples 1-7, in comparison with the effects (Comparative Examples 1 to 3) of the component (B) or (C) alone for Comparative Examples 4 and 5 containing only the component (A), the component (A) Due to the inclusion of ~ (C), these synergistic effects resulted in faster foaming than in the comparative example, and improved slipping feeling from the time of foaming to rinsing and after drying. Furthermore, yellowing due to storage could be suppressed and storage stability could be improved.

(Prescription example)
(Example 8) Conditioning shampoo
(mass%)
Oxyethylene (1) ammonium lauryl ether sulfate 13.0
(Ethylene oxide average addition mole number 1)
Branched polyglycerol-modified silicone A 0.1
Dimethylpolysiloxane emulsion 2.0
(“Silicone CF2450”, effective 60 mass%, Toray Dow Corning)
Isodecyl glyceryl ether 0.4
Amino-modified silicone 0.1
("8500 Conditioning Agent", Toray Dow Corning)
Cationized tara gum 0.3
("Kachinar CTR-100", Toho Chemical Industry Co., Ltd.)
Cationized hydroxyethyl cellulose 0.3
("Poise C-80M", Kao Corporation)
Diallyldimethylammonium chloride / acrylamide copolymer 1.2
("Marcote 550", Ondeonalco, effective content 8.5% by mass)
Ethylene glycol distearate 2.0
Lauroylamidopropylbetaine 1.0
Lauryl hydroxysulfobetaine 0.1
Myristyl alcohol 0.6
Cetyl alcohol 0.1
Cocoyl monoethanolamide 1.8
Polyoxyethylene (16) lauryl ether 0.7
Polypropylene glycol (mass average molecular weight 400) 0.5
Benzyl alcohol 0.3
Ethanol 3.0
Camellia oil 0.01
Panthenol 0.05
Royal Jelly 0.01
Refined honey 0.01
Silk extract 0.05
Hydrolyzed conchiolin protein 0.01
Rosehip extract 0.01
Sodium chloride 0.2
Perfume Appropriate amount Malic acid 0.5
pH adjuster (lactic acid) Amount to reach pH 3.9 Ion-exchanged water Balance

(Example 9) Conditioning shampoo
(mass%)
Polyoxyethylene (2) sodium lauryl ether sulfate 13.0
(Ethylene oxide average addition mole number 2)
Branched polyglycerol-modified silicone B 2.0
Dimethylpolysiloxane emulsion 1.5
(“Silicone CF2450”, effective 60 mass%, Toray Dow Corning)
Isodecyl glyceryl ether 0.7
Amino-modified silicone 0.1
("SS-3588", Toray Dow Corning)
Cationized tara gum 0.2
("Kachinar CTR-100", Toho Chemical Industry Co., Ltd.)
Diallyl quaternary ammonium salt homopolymer 0.8
("Marcote 100", Ondeonalco, effective 40% by mass)
Ethylene glycol distearate 3.0
Lauroylamidopropylbetaine 2.0
Sodium cocoamphoacetate 1.0
Cocoyl monoethanolamide 0.5
Myristyl alcohol 0.5
Cetyl alcohol 0.5
Polyoxyethylene (16) lauryl ether 1.0
Benzyl alcohol 1.0
Polypropylene glycol (mass average molecular weight 400) 0.2
Sodium chloride 1.0
Lanolin fatty acid 0.10
Stearoxypropyl dimesylamine 0.10
Hydrolyzed conchiolin solution (dry matter 3% by mass) 0.05
Panax ginseng extract (dry matter 3% by weight) 0.05
Soybean extract (dry matter 0.4% by mass) 0.05
Eucalyptus extract (dry matter 0.2% by mass) 0.05
Rice germ oil 0.05
Glycolic acid 1.0
Perfume Appropriate amount pH adjuster (sodium hydroxide) Amount of pH 3.9 Ion-exchanged water Balance

(Example 10) Conditioning shampoo
(mass%)
Ammonium lauryl sulfate 6.0
Polyoxyethylene (1) ammonium lauryl ether sulfate 10.0
(Ethylene oxide average addition mole number 1)
Branched polyglycerol-modified silicone A 0.8
Dimethylpolysiloxane emulsion 0.9
(“Silicone CF2450”, effective 60 mass%, Toray Dow Corning)
Amino-modified silicone 0.5
("JP-8500 Conditioning Agent", Toray Dow Corning)
Cationized guar gum 0.3
("Jaguar C-13", Rhodia)
Ethylene glycol distearate 3.0
Cocoyl monoethanolamide 0.8
Stearyl alcohol 0.9
Glycerin 1.0
Sodium chloride 0.2
Metaxylene sulfonic acid 0.2
Benzyloxyethanol 0.5
Malic acid 0.7
Perfume Appropriate amount of lactic acid 0.1
pH adjuster (citric acid) Amount to reach pH 5.5 Ion-exchanged water Balance

  The hair cleansing agents of Examples 8 to 10 had quick foaming and good sliding during rinsing, had smoothness after drying, and were excellent in storage stability.

It is a schematic block diagram of the apparatus used for evaluation regarding the speed of foaming.

Claims (2)

The following components (A), (B), (C):
(A) an anionic surfactant,
(B) The glycerol groups represented by the following structural formulas (1), (2), (3), (4) or (5) are the same or different and are bonded together in an average of 4 or more, and the structural formula (1) or (5) at least one comprises branched polyglycerol chain a group represented by is bound at least one via a divalent connecting Yuimoto represented to the silicon atoms of the silicone by the following general formula (13) Branched polyglycerol modified silicone,
(C) cationized galactomannan,
And it contains water, component (B) / weight ratio of component (C) is 1 / 10-10 / 1 der Ru aqueous hair cleansing agent.

The aqueous hair cleansing agent according to claim 1, wherein the cationized galactomannan of the component (C) is one or a combination of two or more of cationized fenugreek gum, cationized tara gum, and cationized locust bean gum. .

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