JP6688664B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to hair cosmetics.

  Hair is damaged by chemical treatment such as hair color treatment, perm treatment, etc., heat treatment by a heat tool such as a hair dryer, iron, etc. As a result, the good feel and the beautiful appearance that healthy hair originally has are impaired. As a means for solving this problem, hair cosmetics such as hair conditioners and hair treatments are used, and various technical proposals have been made.

  Since organopolysiloxane has many excellent features, various forms are incorporated into hair cosmetics. For example, in Patent Document 1, a hair cosmetic used in a rinse-off mode in which an N-propionyl polyethyleneimine / methyl polysiloxane copolymer is used in combination with a tertiary amine compound and a polyoxypropylene alkyl ether type nonionic surfactant is disclosed. It is described that the hair can be provided with smoothness and firmness after rinsing and drying.

  Further, in the field of hair styling products, a side chain of an organopolysiloxane segment, which is a main chain, has a polymer segment derived from an unsaturated monomer in which 50% by mass or more of N, N-dimethylacrylamide is derived from an unsaturated monomer. It is described that a hair cosmetic containing an organopolysiloxane graft polymer is excellent in setting properties and its durability (see Patent Documents 2 to 4).

JP 2012-31168 JP International Publication 2014/002707 Pamphlet JP 2015-209407 JP JP 2015-209406 JP

  By the way, wet damaged hair is easily entangled, and the entanglement that occurs during drying with a dryer or the like after washing hair is a further accumulation of damage and a psychological burden on the consumer.

  However, with the hair cosmetic composition described in Patent Document 1, although the smoothness to the hair after rinsing and after drying and the firmness, elasticity, and luster of the hair after drying can be imparted, the cosmetic composition was applied to the hair. The smoothness of the hair during the post-rinse and the entanglement in the hair drying process have not been suggested at all, and there is still room for improvement.

  Further, the hair cosmetics described in Patent Documents 2 to 4 are intended to firmly fix the hairstyle by styling the hair without rinsing after application and to maintain the styling for a long time. There is no suggestion of entanglement during rinsing or in the drying process in the case of a use form in which it is rinsed off after application.

  Therefore, the present invention relates to a hair cosmetic composition in which hair during rinsing is smooth, entanglement of hair in the drying process after rinsing is suppressed, and cohesion after drying is excellent.

  The present inventor has found that a hair cosmetic in which a specific organopolysiloxane graft polymer, a cationic surfactant and a higher alcohol are used in combination solves all of the above problems, and has completed the present invention. It was

The present invention provides a hair cosmetic composition containing the following components (A), (B) and (C).
(A) an organopolysiloxane graft polymer having an organopolysiloxane segment (a) as a main chain and an unsaturated monomer-derived polymer segment (b) as a side chain, wherein the unsaturated monomer The polymer segment (b) derived from the polymer contains 50% by mass or more and 100% by mass or less of repeating units derived from N, N-dimethylacrylamide, and does not differ from the organopolysiloxane segment (a) in the organopolysiloxane graft polymer. An organopolysiloxane graft polymer in which the mass ratio (a) / (b) of the polymer segment (b) derived from a saturated monomer is 10/90 or more and 70/30 or less.
(B) Cationic surfactant
(C) Higher alcohol

  The hair cosmetic composition of the present invention has smooth hair during rinsing, suppresses entanglement of hair in the drying process, and is excellent in cohesion of hair after drying.

[Component (A): Organopolysiloxane graft polymer having repeating units derived from N, N-dimethylacrylamide]
As the component (A), an organopolysiloxane graft polymer represented by the following general formula (1) is preferable.

[In the formula,
R ¹ may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms,
R ^{2 s} may be the same or different and represent a hydroxyl group or a hydrocarbon group having 1 to 22 carbon atoms,
R ³ represents an alkylene group which may contain a hetero atom,
R ⁴ represents a hydrogen atom or a methyl group,
R ^{5 s} may be the same or different, and represent a hydrogen atom, or a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a hydroxyl group, an amino group or a mono- or di-C _1-4 alkylamino group,
p represents a number of 50 or more and 2,000 or less, q represents a number of 3 or more and 50 or less, and m represents a number of 10 or more and 100 or less.
However, the ratio of the repeating units in which two R ^5's are both methyl groups in the m repeating units is 50% by mass or more and 100% by mass or less. ]

  Component (A) has a polymer segment (b) derived from an unsaturated monomer in which 50% by mass or more of N, N-dimethylacrylamide is derived from the side chain of the organopolysiloxane segment (a) which is the main chain. In the organopolysiloxane graft polymer, the mass ratio (a) / (b) of the organopolysiloxane segment (a) and the polymer segment (b) derived from an unsaturated monomer is 10/90 or more and 70/30 or less. is there. When the organopolysiloxane graft polymer represented by the general formula (1) is used as the component (A), the polymer segment (b) derived from the unsaturated monomer means m units in the general formula (1). The organopolysiloxane segment (a) refers to the entire unit excluding the polymer segment (b) derived from the unsaturated monomer in the general formula (1).

In the general formula (1), R ¹ is an alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group include linear, branched, or cyclic alkyl groups. From the viewpoint of water dispersibility of the organopolysiloxane graft polymer as the component (A), R ¹ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear chain having 1 to 4 carbon atoms. Alternatively, a branched chain alkyl group is more preferable, a linear or branched chain alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable.

R ² is a hydroxyl group or a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group having 1 to 22 carbon atoms may be saturated or unsaturated, and may be linear or branched. From the viewpoint of availability, a linear or branched alkyl group is preferable. R ² is more preferably a hydroxyl group or a hydrocarbon group having 1 to 8 carbon atoms, and as the hydrocarbon group having 1 to 8 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, tert- Examples thereof include a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. Among them, a hydroxyl group or a methyl group is preferable, and a methyl group is more preferable, from the viewpoint of availability of the raw material at the time of producing the organopolysiloxane graft polymer of the component (A).

R ³ is an alkylene group which may contain a hetero atom, and the carbon number thereof is preferably 2 or more, more preferably from the viewpoint of availability of the raw material at the time of producing the organopolysiloxane graft polymer of the component (A). Is 3 or more, and from the viewpoint of water dispersibility of the organopolysiloxane graft polymer of the component (A), it is preferably 20 or less, more preferably 10 or less, still more preferably 8 or less.

In the present invention, the alkylene group which may contain a hetero atom is an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and one or more atoms or functional groups selected from —NR ³¹ CO—. It may be separated by a group. That is, the alkylene group which may contain a hetero atom may have a structure of "-(alkylene group moiety 1)-(atom or functional group of the above)-(alkylene group moiety 2)-". The carbon number of the alkylene group is the sum of the carbon number of the alkylene group portion 1 and the carbon number of the alkylene group portion 2, that is, the sum of the carbon numbers of the above-mentioned atoms or functional groups that divide the alkylene group. Say. Here, R ³¹ is an alkyl group having 1 to 3 carbon atoms. When the alkylene group which may contain a hetero atom is divided by the atom or the functional group, it is divided by -NHCO- from the viewpoint of easy production of the organopolysiloxane graft polymer of the component (A). Is preferred.

  In the present invention, the alkylene group which may contain a hetero atom includes a hydroxyl group, an amino group, an alkyl (having 1 to 3 carbon atoms) amino group, a dialkyl (having 1 to 3 carbon atoms) amino group, an amino group and a carbon number. One or more monovalent groups selected from an amide group, a carboxy group, and an alkyl (having 1 to 3 carbon atoms) ester group obtained by dehydration condensation of 2 to 4 fatty acids may be substituted. In this case, the number of carbon atoms of the alkylene group which may contain a hetero atom does not include the number of carbon atoms of these substituents. From the viewpoint of easy availability of raw materials at the time of producing the organopolysiloxane graft polymer of the component (A), the alkylene group which may contain a hetero atom is an acetamido group, an alkyl (having 1 to 3 carbon atoms) amino group, And one or more monovalent groups selected from amino groups are preferably substituted.

In the present invention, the alkylene group which may contain a hetero atom is a divalent hetero atom selected from —O—, —S—, —NH—, —NR ³² —, and —COO—, or a hetero atom. A divalent group containing may be substituted. Here, R ³² is an alkyl group (having 1 to 3 carbon atoms) which may be substituted with a dimethylamino group. The hetero atom, or a divalent group containing a hetero atom, is an unsaturated monomer when an alkylene group which may contain a hetero atom acts as a linking group with a polymer segment derived from an unsaturated monomer. It is linked to a polymer segment derived from the body. In other cases, it is bonded to a hydrogen atom. From the viewpoint of easy production of the organopolysiloxane graft polymer of the component (A), the alkylene group which may contain a hetero atom is preferably substituted by -S-.

The alkylene group (R ³ ) which may contain a hetero atom is a polymer segment derived from an unsaturated monomer through the hetero atom, preferably a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably a sulfur atom. It is preferably bound to
Therefore, the "alkylene group which may contain a hetero atom" represented by R ³ is:
(A) an unsubstituted alkylene group,
(A) an alkylene group separated by one or more atoms or functional groups selected from an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and —NR ³¹ CO—,
(C) Hydroxyl group, amino group, alkyl (C1 to C3) amino group, dialkyl (C1 to C3) amino group, amino group and fatty acid having C2 to C4 obtained by dehydration condensation An alkylene group substituted with one or more monovalent groups selected from an amide group, a carboxy group, and an alkyl (having 1 to 3 carbon atoms) ester group,
(D) In addition to a divalent heteroatom selected from —O—, —S—, —NH—, —NR ³² — and —COO—, or an alkylene group substituted with a divalent group containing a heteroatom, the above An alkylene group consisting of a combination of two or more of (a), (c) and (d) is applicable.

Specific examples of the alkylene group which may contain a hetero atom of R ³ include the following formulas (i) to (xii). Among them, the following formulas (xi) and (xii) are preferable from the viewpoint of ease of production of the organopolysiloxane graft polymer of the component (A).

In formulas (i) to (xii), * represents a site bonded to the silicon atom in the general formula (1), and ** represents a site bonded to the polymer segment derived from the unsaturated monomer.
In the formula (xii), X ³¹ is at least one selected from —O—, —OCO—, —COO—, —CONH—, and —NHCO—, and is used in the production of the organopolysiloxane graft polymer of the component (A). From the viewpoint of easiness, -CONH- or -NHCO- is preferable, and -NHCO- is more preferable.

In the formula (xii), R ³³ is a hydroxyl group, an amino group, an alkyl (having 1 to 3 carbon atoms) amino group, a dialkyl (having 1 to 3 carbon atoms) amino group, an amino group and 2 to 4 carbon atoms. Is an alkylene group which may be substituted with one or more monovalent groups selected from an amide group, a carboxy group and an alkyl (having 1 to 3 carbon atoms) ester group obtained by dehydration condensation of the fatty acid of. As the substituent, an acetamide group, an alkyl (having 1 to 3 carbon atoms) amino group, and an amino group are preferable from the viewpoint of availability of raw materials during production. The number of carbon atoms of the alkylene group represented by R ³³ is preferably 2 or more, more preferably 3 or more, from the viewpoint of ease of production of the organopolysiloxane graft polymer of the component (A). From the viewpoint of the water dispersibility of the organopolysiloxane graft polymer (A), it is preferably 10 or less, more preferably 6 or less.
Specific examples of R ³³ include the following formulas (xiii) to (xv).

In formula (xiv), X ⁻ represents anion such as chloride ion, halide ion such as bromide ion, acetate ion, alkyl (having 1 to 3 carbon atoms) sulfate ion.

R ⁴ represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.

R ^{5 s} may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a hydroxyl group, an amino group or a mono- or di-C _1-4 alkylamino group. The hydrocarbon group having 1 to 8 carbon atoms in R ⁵ may be saturated or unsaturated, may be linear or branched, and is preferably a linear or branched alkyl group. R ⁵ is preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a hydroxymethyl group, a hydroxyethyl group, or a dimethylaminopropyl group from the viewpoint of availability of raw materials during production. Of these, a hydrogen atom, a methyl group and a tert-butyl group are more preferable.

In R ^{1 to} R ⁵ , R ¹ and R ² are methyl groups, R ³ is the formula (xii), R ⁴ is a hydrogen atom, R ⁵ is a hydrogen atom which may be the same or different, methyl More preferred are polymers that are selected from groups and tert-butyl groups. Further preferred is a polymer having the INCI name of Polysilicone-28.

However, in the m repeating units in the general formula (1), the ratio of the repeating units in which two R ^5's are both methyl groups is 50% by mass or more from the viewpoint of good water dispersibility of the component (A). , Preferably 70% by mass or more, more preferably 75% by mass or more, from the viewpoint of smoothing hair during rinsing, suppressing entanglement of hair in the drying process after rinsing, and improving cohesion after drying. , 100 mass% or less, preferably 95 mass% or less, more preferably 90 mass% or less.

  p is 50 or more, preferably 80 or more, more preferably 100 or more, from the viewpoint of smoothing hair during rinsing, suppressing entanglement of hair in the drying process after rinsing, and improving cohesion after drying, Further, it is 2,000 or less, preferably 1,300 or less, more preferably 700 or less. From the viewpoint of water dispersibility of the organopolysiloxane graft polymer of the component (A), q is 3 or more, preferably 5 or more, and 50 or less, preferably 30 or less. m is 10 or more, preferably 15 or more, more preferably 20 or more, and 100 or less, preferably 70 or less, from the viewpoint of good water dispersibility of the organopolysiloxane graft polymer of the component (A). It is preferably 50 or less.

  Further, from the viewpoint of water dispersibility of the component (A), and from the viewpoint of smoothing hair during rinsing, suppressing entanglement of hair in the drying process after rinsing, and improving cohesion after drying, the organopolysiloxane segment ( The mass ratio (a) / (b) of the polymer segment (b) derived from a) to the unsaturated monomer is 10/90 or more, preferably 20/80 or more, more preferably 30/70 or more. , More preferably 35/65 or more, and 70/30 or less, preferably 60/40 or less.

  In the present specification, the above mass ratio (a) / (b) is defined as “added at the time of production” when the organopolysiloxane graft polymer of component (A) is produced from the radical-reactive organopolysiloxane described below. The total mass (c) of the radical-reactive organopolysiloxane that is produced and the total mass (d) of the unsaturated monomer that is added at the time of production indicate that the It is considered to be the same as the ratio (c) / [(d)-(e)] with "value obtained by subtracting" total mass (e) of polymer derived from saturated monomer "(the following formula (I)).

    (a) / (b) = (c) / [(d) − (e)] (I)

  In addition, in the organopolysiloxane graft polymer molecule of the component (A), the number average molecular weight (MNg) of the organopolysiloxane segment between polymer segments derived from adjacent unsaturated monomers (hereinafter, referred to as “molecular weight between grafting points”). From the viewpoint of smoothing hair during rinsing, suppressing entanglement of hair in the drying process after rinsing, and improving cohesion after drying, preferably 500 or more, more preferably 700 or more, and further preferably Is 1,000 or more, more preferably 1,500 or more, and from the viewpoint of water dispersibility of the organopolysiloxane graft polymer of component (A), preferably 10,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less, still more preferably Is less than 2,500.

Here, the "organopolysiloxane segment between the polymer segments derived from adjacent unsaturated monomers" is, as shown in the following formula, a bond to the organopolysiloxane segment of the polymer segment derived from an unsaturated monomer. A portion surrounded by a broken line between two points from the point (bonding point A) to the bonding point (bonding point B) of the polymer segment derived from the unsaturated monomer adjacent thereto, which is one R ¹ and SiO units, and one R ^3, a segment composed of a y + 1 pieces of R ¹ ₂ SiO units say.

In the formula, R ¹ and R ³ have the same meanings as in the general formula (1), —W—R ⁶ represents a polymer segment derived from an unsaturated monomer, and W represents a weight derived from an unsaturated monomer. show coalescence, R ⁶ represents a residue or a hydrogen atom of the polymerization initiator, y represents a positive number.

  The molecular weight between grafting points is the average value of the molecular weight of the portion surrounded by the broken line in the above formula, and is the mass (g / mol) of the organopolysiloxane segment per mol of the polymer segment derived from the unsaturated monomer. Can be understood. The molecular weight between grafting points is the case where the organopolysiloxane graft polymer of the component (A) is produced from the radical-reactive organopolysiloxane described below, and all radical-reactive functional groups and unsaturated monomer-derived When bound to a polymer, it is considered to be the same as the reciprocal value of the number of moles (mol / g) of the radical-reactive functional group present per unit mass of the radical-reactive organopolysiloxane.

  Further, the weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is from the viewpoint of smoothing hair during rinsing, suppressing entanglement of hair in the drying process after rinsing, and improving cohesion after drying. It is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, still more preferably 15,000 or more. MWsi is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 60,000 or less, still more preferably 50,000 or less, from the viewpoint of water dispersibility of the organopolysiloxane graft polymer as the component (A).

  When the organopolysiloxane graft polymer of the component (A) is produced from the radical-reactive organopolysiloxane described below, the organopolysiloxane segment has a skeleton in common with the radical-reactive organopolysiloxane, and therefore MWsi is a radical It is almost the same as the weight average molecular weight (MWra) of the reactive organopolysiloxane and is regarded as the same in the present invention. The MWra is measured by gel permeation chromatography (GPC) under the measurement conditions described in Examples and converted into polystyrene.

The weight average molecular weight (MWt) of the organopolysiloxane graft polymer of component (A) makes the hair smooth during rinsing, suppresses the entanglement of hair in the drying process after rinsing, and improves the cohesion after drying. Preferably 10,000 or more, more preferably 14,000 or more, more preferably 17,000 or more, more preferably 30,000 or more, from the viewpoint of water dispersibility of the organopolysiloxane graft polymer of the component (A), preferably 200,000 or less, more preferably Is 160,000 or less, more preferably 130,000 or less, and further preferably 95,000 or less.
In the present specification, MWt is measured by GPC under the measurement conditions described in Examples and converted into polystyrene.

  Further, when the organopolysiloxane graft polymer of the component (A) is produced from the radical-reactive organopolysiloxane, it is obtained from the following formula (II) from MWra and the reciprocal of the above mass ratio (a) / (b). The calculated weight average molecular weight (MWtcalc) of the component (A) organopolysiloxane graft polymer smoothes the hair during rinsing, suppresses entanglement of hair in the drying process after rinsing, and improves cohesion after drying. From the viewpoint of preferably 10,000 or more, more preferably 14,000 or more, more preferably 17,000 or more, more preferably 30,000 or more, from the viewpoint of water dispersibility of the organopolysiloxane graft polymer of the component (A), preferably 200,000. Or less, more preferably 160,000 or less, further preferably 130,000 or less, further preferably 95,000 or less.

  MWtcalc = MWra × {1 + mass ratio (b / a)} (II)

(Production of organopolysiloxane graft polymer)
Examples of the method for producing the organosiloxane graft polymer of the component (A) include the method described in Patent Document 2. Specifically, there is a graft-from method in which a radical-reactive organopolysiloxane represented by the following general formula (1a) is radical-polymerized with a (meth) acrylamide-based monomer.

[In the formula, R ¹ , R ² , p and q have the same meaning as in the general formula (1), and R ⁷ is an alkyl group having a radical-reactive functional group (hereinafter also referred to as “radical-reactive group-containing alkyl group”). Say). ]

  Here, the radical-reactive functional group refers to a functional group capable of generating a radical, and examples thereof include an ethylenically unsaturated group, a halogeno group such as a chloro group and a bromo group, and a sulfanyl group (mercapto group). To be Among these, the sulfanyl group is preferable from the viewpoint of reactivity with unsaturated monomers and control of molecular weight.

In the general formula (1a), the carbon number of the radical-reactive group-containing alkyl group represented by R ⁷ is preferably 2 or more, more preferably 3 or more from the viewpoint of easy availability of the radical-reactive organopolysiloxane. Also, from the viewpoint of water dispersibility of the organopolysiloxane graft polymer of the component (A), it is preferably 20 or less, more preferably 10 or less, still more preferably 8 or less.
In the present invention, the carbon number of the radical-reactive group-containing alkyl group does not include the carbon number of the radical-reactive functional group even when the radical-reactive functional group has carbon. Even when the contained alkyl group is one in which the above-mentioned monovalent group is substituted, the carbon number of the monovalent group is not included.

In the general formula (1a), the radical reactive group-containing alkyl group represented by R ⁷ includes a hydroxyl group, an amino group, an alkyl (having 1 to 3 carbon atoms) amino group, a dialkyl (having 1 to 3 carbon atoms) amino group. , One or more monovalent groups selected from an amide group obtained by dehydration condensation of an amino group and a fatty acid having 2 to 4 carbon atoms, a carboxy group, and an alkyl (1 to 3 carbon atom) ester group, May be. Among these substituents, an acetamide group, an alkyl (having 1 to 3 carbon atoms) amino group, and an amino group are preferable from the viewpoint of easy availability of raw materials during the production of the radical-reactive organopolysiloxane.

In the general formula (1a), the radical-reactive group-containing alkyl group represented by R ⁷ is one selected from an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and —NR ⁷¹ CO—. It may be divided by the above atoms or functional groups. Here, R ⁷¹ is an alkyl group having 1 to 3 carbon atoms. When the radical-reactive group-containing alkyl group is divided by the atom or functional group, it is preferable that the radical-reactive organopolysiloxane is separated by —NHCO— from the viewpoint of availability or ease of production. .

Specific examples of the radical-reactive group-containing alkyl group in the present invention include groups represented by the following formulas (xvi) to (xix). Above all, on the production of the radical-reactive organopolysiloxane, or the ease of availability. From the viewpoint of, the following formulas (xviii) and (xix) are preferable. X ⁷¹ and R ^{72 in} formula (xix), and their preferred embodiments are the same as X ³¹ and R ^{32 in} formula (xii), and their preferred embodiments, respectively.

  The radical-reactive organopolysiloxane in which the radical-reactive group is a sulfanyl group is also available as a commercial product, for example, "KF-2001" (manufactured by Shin-Etsu Chemical Co., Ltd.). The radical-reactive organopolysiloxane is obtained by reacting an organopolysiloxane having at least one reactive functional group selected from a hydroxyl group, an amino group, a carboxy group, and an epoxy group with a radical reactivity-imparting agent. You can also As the reactive functional group, a hydroxyl group, an amino group, and an epoxy group are preferable from the viewpoint of availability, and an amino group is preferable from the viewpoint of reactivity and handleability.

  The weight average molecular weight (MWra) of the radical-reactive organopolysiloxane represented by the general formula (1a) makes the hair smooth during rinsing, suppresses the entanglement of hair in the drying process after rinsing, and improves the cohesion after drying. From the viewpoint of improving, preferably 3,000 or more, more preferably 5,000 or more, further preferably 10,000 or more, more preferably 15,000 or more, from the viewpoint of good water dispersibility of the component (A), preferably 200,000 or less. , More preferably 100,000 or less, still more preferably 60,000 or less, still more preferably 50,000 or less.

  The number of moles of radical-reactive groups present per unit mass of the radical-reactive organopolysiloxane represented by the general formula (1a) makes the hair smooth during rinsing and suppresses the entanglement of hair in the drying process after rinsing. From the viewpoint of improving the cohesion after drying, preferably 1/500 mol / g or less, more preferably 1/700 mol / g or less, still more preferably 1 / 1,000 mol / g or less, and the component (A). From the viewpoint of good water dispersibility, the amount is preferably 1 / 10,000 mol / g or more, more preferably 1 / 5,000 mol / g or more, still more preferably 1 / 3,000 mol / g or more.

  Examples of the (meth) acrylamide-based monomer that is radically reacted with the radical-reactive organopolysiloxane represented by the general formula (1a) include acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N. -Isopropylacrylamide, Nt-butylacrylamide, N, N-dimethylaminopropylacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide and the like can be mentioned. In the present invention, of the (meth) acrylamide-based monomers, N, N-dimethyl (meth) acrylamide is 50% by mass or more from the viewpoint of good water dispersibility of the component (A), It is preferably 70% by mass or more, more preferably 75% by mass or more, and from the viewpoint of smoothing hair during rinsing, suppressing entanglement of hair in the drying process after rinsing, and improving cohesion after drying. It is 100% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less.

  The method for polymerizing the unsaturated monomer in the presence of the radical-reactive organopolysiloxane is not particularly limited, and a bulk polymerization method, a solution polymerization method, a suspension polymerization method or the like can be adopted, but a solution polymerization method is particularly preferable. .

  Examples of the polymerization initiator include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), and lauroyl peroxide and benzoyl peroxide. Examples thereof include oxide-based initiators and persulfate-based initiators such as ammonium persulfate. The polymerization may be initiated by generating radicals by irradiation with light or the like. As the polymerization initiator, 2,2′-azobis (2,4-dimethylvaleronitrile) is preferable from the viewpoint of reactivity.

  The content of the organopolysiloxane graft polymer of the component (A) in the hair cosmetic composition of the present invention makes the hair smooth during rinsing, suppresses the entanglement of hair in the drying process after rinsing, and improves the cohesion after drying. From the standpoint of the above, the content is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, further preferably 0.008% by mass or more, further preferably 0.010% by mass or more, and the hair during rinsing is smooth and after rinsing. From the viewpoint of suppressing entanglement of hair in the drying process and excellent in cohesion after drying, and not causing stickiness of hair after drying, it is preferably 2% by mass or less, more preferably 1.5% by mass or less, still more preferably 1.0% by mass or less, More preferably 0.8 mass% or less, more preferably 0.5 mass% or less, more preferably 0.20 mass% or less, further preferably 0.15 mass% or less, and further preferably The content is 0.10% by mass or less, more preferably 0.08% by mass or less, further preferably 0.05% by mass or less, further preferably 0.04% by mass or less.

[Component (B): Cationic surfactant]
Examples of the cationic surfactant as the component (B) include (i) alkyltrimethylammonium salt, (ii) alkoxyalkyltrimethylammonium salt, (iii) dialkyldimethylammonium salt, (iv) alkyldimethylamine and salts thereof, (V) Alkoxyalkyl dimethylamine and its salt, (vi) Alkylamido amine and its salt, etc. are mentioned.

(I) Alkyltrimethylammonium Salt Examples of the alkyltrimethylammonium salt include those represented by the following general formula (2).
_{^{R 8 -N + (CH 3)}} 3 X - (2)
[In the formula, R ⁸ represents an alkyl group having 12 to 22 carbon atoms, X ⁻ represents a halide ion such as chloride ion, bromide ion or the like; methosulfate ion, ethosulfate ion, metphosphate ion, etophosphate ion , Methcarbonate ion and the like. ]

  Specific examples include cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, behenyl trimethyl ammonium methosulfate and the like.

(Ii) Alkoxyalkyltrimethylammonium Salt Examples of the alkoxyalkyltrimethylammonium salt include those represented by the following general formula (3).
^{R 9 -O-R 10 -N +} (CH 3) 3 X - (3)
[In the formula, R ⁹ represents an alkyl group having 12 to 22 carbon atoms, R ¹⁰ represents an ethylene group or a propylene group which may be substituted by a hydroxy group, and X ⁻ represents a halogen such as chloride ion or bromide ion. Compound ion; methosulfate ion, ethosulfate ion, metophosphate ion, ethosulfate ion, methocarbonate ion and the like. ]

  Specific examples include stearoxypropyltrimethylammonium chloride, stearoxyethyltrimethylammonium chloride, stearoxyhydroxypropyltrimethylammonium chloride and the like.

(Iii) Dialkyldimethylammonium Salt Examples of the dialkyldimethylammonium salt include those represented by the following general formula (4).
_{^{(R 11) 2 N + (}} CH 3) 2 X - (4)
[In the formula, each R ¹¹ independently represents an alkyl group having 12 to 22 carbon atoms or a benzyl group, and X ⁻ is a halide ion such as a chloride ion or a bromide ion; methosulfate ion, ethosulfate ion or metphos Examples thereof include a phosphate ion, an etophosphate ion, a metcarbonate ion and the like. ]

  Specific examples include distearyldimethylammonium chloride, dicetyldimethylammonium chloride, dilauryldimethylammonium chloride, and dialkyl (C12-18) dimonium chloride.

(Iv) Alkyldimethylamine and its salt Alkyldimethylamine reacts with an acid to form a quaternary ammonium salt, which serves as a surfactant. Therefore, alkyl dimethylamine and its salts are defined herein as cationic surfactants. Moreover, the content is converted into the mass of alkyldimethylamine. Examples of the alkyldimethylamine and salts thereof include those represented by the following general formula (5) and salts thereof.
R ¹² -N (CH ₃ ) ₂ (5)
[In the formula, R ¹² represents an alkyl group having 12 to 22 carbon atoms. ]

  Examples of the salt include salts with an organic acid or an inorganic acid. Examples of the organic acid include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and phthalic acid; polycarboxylic acids such as polyglutamic acid; Examples thereof include hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid and citric acid; acidic amino acids such as glutamic acid and aspartic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid and the like. Among these, organic acids are preferable, dicarboxylic acids, hydroxycarboxylic acids and acidic amino acids are preferable, and maleic acid and succinic acid are more preferable as dicarboxylic acids. As the hydroxycarboxylic acid, glycolic acid, lactic acid and malic acid are more preferable. Glutamic acid is more preferable as the acidic amino acid.

  Specific examples of the alkyldimethylamine and salts thereof include N, N-dimethylbehenylamine, N, N-dimethylstearylamine and organic acid salts thereof, and N, N from the viewpoint of smoothness of hair during rinsing. -Lactic acid salts of dimethylbehenylamine, glycolic acid salts of N, N-dimethylstearylamine and the like are preferable.

(V) Alkoxyalkyl dimethylamine and its salt Alkoxyalkyl dimethylamine reacts with an acid, becomes a quaternary ammonium salt, and becomes a surfactant. Therefore, alkoxyalkyl dimethylamine and its salts are defined herein as cationic surfactants. Moreover, the content is converted into the mass of the alkoxyalkyl dimethylamine. Examples of the alkoxyalkyldimethylamine and salts thereof include those represented by the following general formula (6) and salts thereof.
^{R 13 -O-R 14 -N (} CH 3) 2 (6)
[In the formula, R ¹³ represents an alkyl group having 12 to 22 carbon atoms, and R ¹⁴ represents an ethylene group or a propylene group. ]

  Examples of the salt include salts with an organic acid or an inorganic acid. Examples of the organic acid include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and phthalic acid; polycarboxylic acids such as polyglutamic acid; Examples thereof include hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid and citric acid; acidic amino acids such as glutamic acid and aspartic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid and the like. Among these, organic acids are preferable, dicarboxylic acids, hydroxycarboxylic acids and acidic amino acids are preferable, and maleic acid and succinic acid are more preferable as dicarboxylic acids. As the hydroxycarboxylic acid, glycolic acid, lactic acid and malic acid are more preferable. Glutamic acid is more preferable as the acidic amino acid.

  Specific examples of the alkoxydimethylamine and its salt include N, N-dimethyl-3-hexadecyloxypropylamine, N, N-dimethyl-3-octadecyloxypropylamine and their organic acid salts. From the viewpoint of the smoothness of the hair, lactate of N, N-dimethyl-3-hexadecyloxypropylamine and glycolate of N, N-dimethyl-3-octadecyloxypropylamine are preferable.

(vi) Alkylamidoamine and its salt Alkylamidoamine reacts with an acid to form a quaternary ammonium salt, which serves as a surfactant. Therefore, alkylamidoamines and salts thereof are defined herein as cationic surfactants. Moreover, the content is converted into the mass of alkylamidoamine. Examples of the alkylamidoamine and salts thereof include those represented by the following general formula (7) and salts thereof.
^{_{R 15 -CONH- (CH 2) m}} -N (CH 3) 2 (7)
[In the formula, R ¹⁵ represents an alkyl group having 12 to 22 carbon atoms, and m represents a number of 2 to 4. ]

Among these, those in which R ¹⁵ is an alkyl group having 14 to 22 carbon atoms are preferable.
Examples of the salt include salts with an organic acid or an inorganic acid. Examples of the organic acid include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and phthalic acid; polycarboxylic acids such as polyglutamic acid; Examples thereof include hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid and citric acid; acidic amino acids such as glutamic acid and aspartic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid and the like. Among these, organic acids are preferable, dicarboxylic acids, hydroxycarboxylic acids and acidic amino acids are preferable, and maleic acid and succinic acid are more preferable as dicarboxylic acids. As the hydroxycarboxylic acid, glycolic acid, lactic acid and malic acid are more preferable. Glutamic acid is more preferable as the acidic amino acid.

  Specific alkylamidoamines and salts thereof include N- (3- (dimethylamino) propyl) docosanamid and salts thereof, and N- (3- (dimethylamino) propyl) stearamide and salts thereof.

  Among these, (i) alkyltrimethylammonium salt, (ii) alkoxyalkyltrimethylammonium salt, (iii) dialkyldimethylammonium salt, (v) alkoxyalkyldimethylamine and its salt, (vi) alkylamidoamine and its salt are From the viewpoint of smoothing hair during rinsing and suppressing entanglement of hair in the drying process after rinsing, (iii) dialkyldimethylammonium salt, (v) alkoxyalkyldimethylamine and its salt, (vi) alkylamidoamine and The salt is preferred. Furthermore, N, N-dimethyl-3-hexadecyloxypropylamine and salts thereof, N, N-dimethyl-3-octadecyloxypropylamine and salts thereof, N- (3- (dimethylamino) propyl) docosanamide and its Salts, N- (3- (dimethylamino) propyl) stearamide and salts thereof, dialkyl (C12-18) dimonium chloride, stearoxypropyldimethylamine are preferred.

  As the cationic surfactant as the component (B), any one kind may be used alone or two or more kinds may be used in combination. The content of the component (B) in the hair cosmetic composition of the present invention is preferably 0.01% by mass or more, and more preferably from the viewpoint of smoothing hair during rinsing and suppressing entanglement of hair in the drying process after rinsing. 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, and smoothes the hair during rinsing and suppresses the entanglement of hair in the drying process after rinsing, and at the time of application. From the viewpoint of imparting good smoothness to hair, it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 4% by mass or less, further preferably 3% by mass or less, further preferably 2% by mass or less. Is.

[Component (C): Higher alcohol]
The higher alcohol as the component (C) may be a linear or branched chain, or saturated or unsaturated aliphatic alcohol, and its carbon number is preferably 12 or more, more preferably 14 or more, and further preferably 16 It is above, and is preferably 22 or less, more preferably 20 or less, still more preferably 18 or less. Specific examples include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, cetearyl alcohol, aralkyl alcohol, hexyldecanol, isostearyl alcohol, oleyl alcohol, 2-octyldodecanol and the like. Of these, stearyl alcohol, cetyl alcohol, myristyl alcohol, and cetearyl alcohol are preferable from the viewpoint of ease of spreading during application. Any of these higher alcohols may be used alone or in combination of two or more.

  The content of the component (C) in the hair cosmetic composition of the present invention is preferably from the viewpoint of smoothing hair during rinsing, suppressing entanglement of hair in the drying process after rinsing, and improving cohesion after drying. 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 3% by mass or more, further preferably 4.0% by mass or more, further preferably 4.5% by mass or more, further preferably 5.0% by mass. % Or more, smooth the hair during rinsing, suppress the entanglement of hair in the drying process after rinsing, improve the cohesion after drying, and allow the hair cosmetic composition to be easily spread and dried during application. From the viewpoint of suppressing stickiness of the hair after that, it is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and further preferably 6.5% by mass or less. .

  Further, the mass ratio [(B) + (C)] / (A) of the total amount of the component (B) and the component (C) to the component (A) in the hair cosmetic of the present invention makes the hair smooth during rinsing. From the viewpoint of suppressing entanglement of hair in the drying process after rinsing, improving cohesion after drying, and suppressing stickiness of hair after drying, preferably 1 or more, more preferably 7 or more, and further preferably 15 or more, more preferably 50 or more, more preferably 80 or more, more preferably 100 or more, more preferably 150 or more, more preferably 200 or more, more preferably 230 or more, further preferably 280 or more, more preferably 300 or more. Further, from the viewpoint of smoothing hair during rinsing, suppressing entanglement of hair in the drying process after rinsing, and improving cohesion after drying, preferably 2000 or less, more preferably 1500 or less, further preferably Is 1000 Lower, more preferably 800 or less, more preferably 750 or less, more preferably 600 or less.

[Component (D): Organopolysiloxane other than component (A)]
The hair cosmetic composition of the present invention preferably further contains, as component (D), an organopolysiloxane other than component (A).

  As the organopolysiloxane other than the component (A), dimethylpolysiloxane, methylphenylpolysiloxane, amino-modified silicone, fatty acid-modified polysiloxane, alcohol-modified silicone, aliphatic alcohol-modified polysiloxane, polyether-modified silicone, epoxy-modified silicone, Examples thereof include fluorine-modified silicone, cyclic silicone, alkyl-modified silicone and oxazoline-modified silicone. Among these, dimethylpolysiloxane, amino-modified silicone, polyether-modified silicone, and oxazoline-modified silicone are preferable from the viewpoint of smoothness after drying. These components (D) can be used alone or in combination of two or more.

  The content of the component (D) in the hair cosmetic composition of the present invention is preferably 0.1 from the viewpoint of smoothing hair during rinsing, suppressing entanglement of hair in the drying process after rinsing, and improving cohesion after drying. It is at least mass%, more preferably at least 0.5 mass%, still more preferably at least 1.0 mass%, and it also smooths hair during rinsing, suppresses entanglement of hair in the drying process after rinsing, and provides cohesion after drying. From the viewpoint of improving and simultaneously suppressing stickiness of hair after drying, it is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, further preferably It is 3 mass% or less.

  Further, the mass ratio (D) / (A) of the component (A) to the component (D) in the hair cosmetic composition of the present invention makes the hair smooth during rinsing and suppresses the entanglement of hair in the drying process after rinsing. However, from the viewpoint of improving cohesion after drying, it is preferably 0.5 or more, more preferably 5 or more, still more preferably 15 or more, still more preferably 50 or more, still more preferably 100 or more. From the viewpoints of smoothing, suppressing entanglement of hair in the drying process after rinsing, improving cohesion after drying, and suppressing stickiness of hair after drying, preferably 1000 or less, more preferably 500 or less, and further It is preferably 300 or less, more preferably 200 or less, further preferably 150 or less.

〔water〕
The hair cosmetic composition of the present invention preferably contains water as a medium. Water is the balance of the components (A) to (C) and other components. The content of water is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 75% by mass or more, and preferably 99.4% by mass or less, based on the entire hair cosmetic composition. And more preferably 98% by mass or less, further preferably 97% by mass or less, and further preferably 96% by mass or less.

[Other optional ingredients]
The hair cosmetic composition of the present invention may further contain other components generally used in hair cosmetic compositions depending on the purpose. For example, high molecular compounds such as cationized cellulose, hydroxyalkyl cellulose, and highly polymerized polyethylene oxide; polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, glycerin monofatty acid ester, polyglycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, Nonionic surfactants such as sucrose fatty acid ester, polyglycerin alkyl ether, fatty acid alkanolamide, and alkyl glycoside; hydrocarbons such as squalene, squalane, liquid paraffin, liquid isoparaffin, and cycloparaffin; castor oil, cocoa oil, mink oil , Avocado oil, olive oil, and other glycerides; beeswax, whale wax, lanolin, carnauba wax, and other waxes; isopropyl palmitate, isopropyl myristate Esters of octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridecyl isononanoate; capric acid, lauric acid, myristic acid, palmitin Higher fatty acids such as acids, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, lanolin fatty acid, isostearyl acid, and isopalmitic acid; oil agents such as isostearyl glyceryl ether and polyoxypropylene butyl ether; ethanol, 1-propanol, 2 -Propanol, butanol, ethylene glycol, propylene glycol, dipropylene glycol, benzyl alcohol, phenoxyethanol, 2-benzyloxyethanol, methyl carbitol Alcohols such as alcohol, ethyl carbitol, propyl carbitol, butyl carbitol, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, glycerin; antidandruff agents such as zinc pyrithione and benzalkonium chloride; pH adjusters; Vitamin agent; Bactericide; Anti-inflammatory agent; Preservative; Chelating agent; Moisturizing agent such as panthenol; Coloring agent such as dye, pigment; Polar solvent extract of eucalyptus; Protein obtained from shell or pearl having nacre Its hydrolyzate, protein or its hydrolyzate obtained from silk, protein-containing extract obtained from seeds of legumes, Panax ginseng extract, rice germ extract, Hibamata extract, camellia extract, aloe extract, Extracts such as moon peach leaf extract and chlorella extract; pearl powder such as mica titanium; Cooling agents such as tall: fragrances; pigments; ultraviolet absorbers; antioxidants; other ingredients such as those listed in ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS) .

(PH)
The pH of the hair cosmetic composition of the present invention is preferably 2.0 or more, more preferably 2.5 or more, still more preferably 3.0 or more, and preferably 6.0 or less, more preferably 5.5 or less, further preferably 5.0 or less, further It is preferably 4.5 or less. In the present invention, the pH of the hair cosmetics refers to the value at 25 ° C. when diluted 20 times by mass with water.

[Form of hair cosmetics]
Examples of the form of the hair cosmetic composition of the present invention include hair conditioning compositions such as hair rinses, hair conditioners, hair treatments, and hair packs. Among them, those used after being rinsed off after application to hair are preferable.

  With regard to the above-described embodiments, preferred aspects of the present invention will be further disclosed below.

<1> A hair cosmetic containing the following components (A), (B) and (C).
(A) an organopolysiloxane graft polymer having an organopolysiloxane segment (a) as a main chain and an unsaturated monomer-derived polymer segment (b) as a side chain, wherein the unsaturated monomer The polymer segment (b) derived from the polymer contains 50% by mass or more and 100% by mass or less of repeating units derived from N, N-dimethylacrylamide, and does not differ from the organopolysiloxane segment (a) in the organopolysiloxane graft polymer. An organopolysiloxane graft polymer in which the mass ratio (a) / (b) of the polymer segment (b) derived from a saturated monomer is 10/90 or more and 70/30 or less.
(B) Cationic surfactant
(C) Higher alcohol

<2> The mass ratio (a) / (b) of the organopolysiloxane segment (a) and the polymer segment (b) derived from an unsaturated monomer is preferably 20/80 or more, more preferably 30/70 or more. , And more preferably 35/65 or more, and preferably 60/40 or less, <1>.

<3> The weight average molecular weight (MWt) of the component (A) is preferably 10,000 or more, more preferably 14,000 or more, further preferably 17,000 or more, further preferably 30,000 or more, preferably 200,000 or less, more preferably 160,000. The hair cosmetic according to <1> or <2>, which is more preferably 130,000 or less, further preferably 95,000 or less.

<4> The hair cosmetic composition according to any one of <1> to <3>, wherein the component (A) is preferably an organopolysiloxane graft polymer represented by the following general formula (1).

[In the formula,
R ¹ may be the same or different and represents an alkyl group having 1 to 8 carbon atoms,
R ^{2 s} may be the same or different, and represent a hydroxyl group or a hydrocarbon group having 1 to 22 carbon atoms,
R ³ represents an alkylene group which may contain a hetero atom,
R ⁴ represents a hydrogen atom or a methyl group,
R ^{5 s} may be the same or different and represent a hydrogen atom, or a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a hydroxyl group, an amino group or a mono- or di-C 1-4 alkylamino group,
p represents a number from 50 to 2000, q represents a number from 3 to 50, and m represents a number from 10 to 100.
However, the ratio of the repeating units in which two R ^5's are both methyl groups in the m repeating units is 50% by mass or more and 100% by mass or less. ]

<5> The ratio of repeating units in which two R ^5's are both methyl groups in the m repeating units in the general formula (1) is preferably 70% by mass or more, more preferably 75% by mass or more, The hair cosmetic composition according to <4>, which is preferably 95% by mass or less, more preferably 90% by mass or less.

<6> The content of the component (A) in the hair cosmetic is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, further preferably 0.008% by mass or more, further preferably 0.010% by mass or more, Further, preferably 2% by mass or less, more preferably 1.5% by mass or less, further preferably 1.0% by mass or less, further preferably 0.8% by mass or less, further preferably 0.5% by mass or less, further preferably 0.20% by mass or less, further Any one of <1> to <5>, which is preferably 0.15 mass% or less, more preferably 0.10 mass% or less, further preferably 0.08 mass% or less, further preferably 0.05 mass% or less, further preferably 0.04 mass% or less. The hair cosmetic composition according to item 1.

<7> Component (B) is preferably (i) alkyltrimethylammonium salt, (ii) alkoxyalkyltrimethylammonium salt, (iii) dialkyldimethylammonium salt, (iv) alkyldimethylamine and salt thereof, (v) alkoxy. One or more selected from alkyldimethylamine and salts thereof, and (vi) alkylamidoamine and salts thereof, more preferably (i) alkyltrimethylammonium salt, (ii) alkoxyalkyltrimethylammonium salt, and (iii) dialkyl. Dimethylammonium salt, (v) alkoxyalkyldimethylamine and its salt, and (vi) one or more kinds selected from alkylamidoamine and its salt, more preferably (iii) dialkyldimethylammonium salt and (v) alkoxyalkyl. Zimechi Amine and its salts, and (vi) alkylamido is an amine and one or more selected from a salt thereof <1> to the hair cosmetic according to any one of <6>.

<8> The content of the component (B) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, further preferably 1.0% by mass or more, and preferably 10% by mass or more. % Or less, more preferably 5% or less, still more preferably 4% or less, still more preferably 3% or less, still more preferably 2% or less, according to any one of <1> to <7> Hair cosmetics as described.

<9> The component (C) is a linear or branched, saturated or unsaturated aliphatic alcohol having a carbon number of preferably 12 or more, more preferably 14 or more, still more preferably 16 or more. Also, the hair cosmetic composition according to any one of <1> to <8>, which is preferably 22 or less, more preferably 20 or less, still more preferably 18 or less.

<10> The content of the component (C) is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 3% by mass or more, further preferably 4.0% by mass or more. , More preferably 4.5 mass% or more, further preferably 5.0 mass% or more, preferably 15 mass% or less, more preferably 10 mass% or less, further preferably 8 mass% or less, more preferably 6.5 mass% The hair cosmetic composition according to any one of <1> to <9> below.

<11> The mass ratio [(B) + (C)] / (A) of the total amount of the component (B) and the component (C) to the component (A) is preferably 1 or more, more preferably 7 or more, and further preferably Is 15 or more, more preferably 50 or more, more preferably 80 or more, more preferably 100 or more, more preferably 150 or more, more preferably 200 or more, further preferably 230 or more, further preferably 280 or more, further preferably 300. Or more, preferably 2000 or less, more preferably 1500 or less, further preferably 1000 or less, more preferably 800 or less, further preferably 750 or less, still more preferably 600 or less <1> to <10> Hair cosmetics given in any 1 paragraph.

<12> Preferably, the hair cosmetic composition according to any one of <1> to <11>, which further contains an organopolysiloxane other than the component (A) as the component (D).

<13> The hair cosmetic composition according to <12>, wherein the component (D) is preferably one or more selected from dimethylpolysiloxane, amino-modified silicone, polyether-modified silicone and oxazoline-modified silicone.

<14> The content of the component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less. The hair cosmetic composition according to <12> or <13>, which is not more than 10% by mass, more preferably not more than 10% by mass, further preferably not more than 5% by mass, further preferably not more than 3% by mass.

<15> The mass ratio (D) / (A) of the component (D) to the component (A) is preferably 0.5 or more, more preferably 5 or more, further preferably 15 or more, further preferably 50 or more, further preferably 100 or more, preferably 1000 or less, more preferably 500 or less, further preferably 300 or less, further preferably 200 or less, further preferably 150 or less <12> ~ <14> in any one of Hair cosmetics as described.

<16> pH when diluted 20 times by mass with ion-exchanged water is preferably 2.0 or more, more preferably 2.5 or more, further preferably 3.0 or more, and preferably 6.0 or less, more preferably 5.5 or less. The hair cosmetic composition according to any one of <1> to <15>, which is more preferably 5.0 or less, and further preferably 4.5 or less.

<17> The hair cosmetic composition according to any one of <1> to <16>, which is preferably a hair conditioning composition.

<18> The hair cosmetic composition according to <17>, which is preferably applied to hair and then washed off.

Synthesis Example 1 Synthesis of Polysilicone-28 (organopolysiloxane graft polymer represented by general formula (1) of component (A))
(1) Synthesis of radical-reactive organopolysiloxane A side chain primary aminopropyl-modified organopolysiloxane as an organopolysiloxane having a reactive functional group in a separable flask equipped with a reflux cooling tube, a thermometer, a nitrogen introduction tube, and a stirrer. 100 g of siloxane (weight average molecular weight: 30,000, number of amino groups per unit mass: 1 / 2,030 mol / g, manufactured by Toray Dow Corning Co., Ltd.) and 8 g of N-acetyl-DL-homocysteine thiolactone were charged. In a nitrogen atmosphere, the temperature was raised to 100 ° C. and the mixture was stirred for 3 hours to synthesize a radical-reactive organopolysiloxane having a sulfanyl group. When the residual amount of amino groups was measured by potentiometric titration, 99% of the amino groups of the side chain primary aminoisopropyl-modified organopolysiloxane used as a raw material had reacted with N-acetyl-DL-homocysteine thiolactone (amino Base conversion rate 99%). Therefore, the number of moles of the sulfanyl group per unit mass of the radical-reactive organopolysiloxane is 1 / 2,210 mol / g. The weight average molecular weight (MWra) of the radical-reactive organopolysiloxane determined by GPC measurement was 30,000.

(2) Synthesis of organopolysiloxane graft polymer 101.0 g of ethanol was placed in a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube, and a stirrer. While stirring ethanol under a nitrogen atmosphere at 80 ° C. under reflux, the following solution (a) and solution (b) were placed in separate dropping funnels, respectively, and simultaneously added dropwise over 1 hour.
Solution (a): A solution obtained by mixing 76.8 g of N, N-dimethylacrylamide (DMAAm), 19.2 g of N-tert-butylacrylamide (tBuAAm) and 96.0 g of ethanol.
Solution (b): 64.0 g of radical-reactive organopolysiloxane synthesized in (1) above, 2,2'-azobis (2,4-dimethylvaleronitrile) "V-65B" (Wako Pure Chemical Industries, Ltd.) Azo polymerization initiator), 0.03 g, and ethanol 43.0 g.

After the dropping was completed, the reaction mixture was stirred at 80 ° C. for 3 hours and then cooled. The reaction time is 4 hours in total. Ethanol was removed from the reaction mixture at room temperature (25 ° C.) under reduced pressure (20 kPa) over 4 hours to obtain a mixture containing an organopolysiloxane graft polymer as a white solid. When the residual ratio of the sulfanyl group was measured by the method described below, it was 3%.
According to the method described below for the obtained mixture, the content of the polymer derived from the unsaturated monomer that is not bonded to the organopolysiloxane graft polymer in the mixture containing the organopolysiloxane graft polymer after the reaction was measured. However, it was 29% by mass (note that the ratio of the polymer derived from the unsaturated monomer that is not bonded to the organopolysiloxane graft polymer to the total mass of the charged unsaturated monomers was 48% by mass). is there). The mass ratio (a) / (b) between the organopolysiloxane segment (a) and the polymer segment (b) derived from the unsaturated monomer was calculated by the above formula (I) to be 56/44. The weight average molecular weight (MWt) measured under the conditions described below was 63,000, and the molecular weight between graft points (MNg) was 2210. In the polymer segment (b) derived from an unsaturated monomer, the ratio of repeating units derived from N, N-dimethylacrylamide was 80% by mass.
In addition, this organopolysiloxane graft polymer has the formula (1) in which R ¹ and R ² are both methyl groups, R ³ is the formula (xii) (X ³¹ is —NHCO—, and R ³³ is the formula (xv). Is an alkylene group which may contain a heteroatom represented by, R ⁴ is a hydrogen atom, two R ⁵ are both methyl groups or one is a tert-butyl group and the other is a hydrogen atom. Yes, p is 380, q is 15, and m is 27.

The weight average molecular weight (MWra) of the radical-reactive organopolysiloxane used in Synthesis Example 1 and the weight average molecular weight (MWt) of the polymer obtained in Synthesis Example 1 are measured by GPC under the following conditions. I asked for it.
<GPC measurement conditions>
Column: Two "K-804L" (manufactured by Tosoh Corporation) are used in series.
Eluent: 1 mM dimethyldodecylamine / chloroform solution Flow rate: 1.0 mL / min
Column temperature: 40 ℃
Detector: RI
Sample concentration and sample volume: 5 mg / mL, 500 μL

Further, the residual ratio of the sulfanyl group was obtained by the following method.
In a 10 mL screw tube, 0.6 g of a 50% by mass ethanol solution of an organopolysiloxane graft polymer, 0.15 g of a 10% by mass ethanol solution of N-ethylmaleimide (manufactured by Sigma-Aldrich), and 0.55 g of ethanol were placed at room temperature for 2 hours. It was stirred. After the completion of stirring, 1 g of ethanol was added, and the solution was analyzed by gas chromatography to quantify the amount of N-methylmaleimide. The residual amount of the sulfanyl group was calculated from the consumption rate of N-methylmaleimide, and the residual ratio of the sulfanyl group was calculated from this value and the number of moles of the sulfanyl group per unit mass of the sulfanyl group-modified organopolysiloxane.

In addition, the content of the polymer derived from the unsaturated monomer that is not bonded to the organopolysiloxane graft polymer after the reaction was measured as follows.
After the completion of the polymerization reaction, the content (% by mass) of the polymer derived from the unsaturated monomer in the mixed solution containing the organopolysiloxane graft polymer after removing the solvent was measured by liquid chromatography. The measurement conditions are shown below.

[Measurement conditions for liquid chromatography]
Detector: UV absorptiometer (measurement wavelength: 230nm)
Column: ODS column “L-column ODS” (manufactured by Japan Chemical Substance Evaluation and Research Institute, size: 4.6 × 150 mm, 5 μm)
Column temperature: A constant temperature around 30 ° C. Mobile phase A: 2% phosphoric acid aqueous solution, mobile phase B: 2% phosphoric acid ethanol solution Flow rate: 0.5 mL / min
Sample concentration and sample volume: 1-2 mg / mL, 10.0 μL

Synthesis Example 2 Synthesis of Polysilicone-9 0.77 g (0.005 mol) of diethyl sulfate and 12.9 g (0.13 mol) of 2-ethyl-2-oxazoline were dissolved in 28 g of dehydrated ethyl acetate and heated under reflux for 8 hours under a nitrogen atmosphere, A terminally reactive poly (N-propionylethyleneimine) was synthesized. When the number average molecular weight was measured by GPC, it was 2700. A 33% ethyl acetate solution containing 100 g of a side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 100,000, amine equivalent 20,000) was added all at once, and the mixture was heated under reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a colorless solid (108 g, yield 95%). The content of the organopolysiloxane segment in the final product was 88% by mass, and the weight average molecular weight was 114,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.
The weight average molecular weight of the Polysilicone-9 obtained in Synthesis Example 2 was determined by performing GPC measurement under the following conditions.
<GPC measurement conditions>
Column: Super HZ4000 + Super HZ2000 (manufactured by Tosoh Corporation)
Eluent: 1 mM triethylamine / THF
Flow rate: 0.35 mL / min
Column temperature: 40 ℃
Detector: UV
Sample: 50 μL

Examples 1-9, Comparative Examples 1-2
A hair conditioner having the composition shown in Table 1 was prepared, and various evaluations were performed according to the methods described below. Note that Examples 5 to 9 in Table 1 are reference examples, and are not included in the scope of the claims.

<PH measuring method>
The pH was measured at 25 ° C using a pH meter (HM-30R type manufactured by Toa DKK Co., Ltd.) after the sample was diluted 20 times by mass with purified water and dissolved by stirring.

<Sensory evaluation method>
(Hair bundle for evaluation)
A straight hair having a length of 20 cm, a width of 6 cm and a weight of 20 g was prepared from Japanese straight hair having no history of chemical treatment. After moistening this hair bundle for 30 seconds in running water at 40 ° C, apply 2.0 g of model shampoo whose formulation is shown below and lather it, then rinse with warm water at 40 ° C for 30 seconds while passing your finger through the hair bundle. Shed Then, excess water was wiped off with a towel, and the hair bundle was dried for 3 minutes with a dryer (Solis TYPE315, manufactured by Can Co., setting is high / very hot) and used for evaluation.

(Composition of model shampoo)
(Ingredient) (mass%)
Polyoxyethylene (2.5) sodium lauryl ether sulfate 15.5
Lauric acid diethanolamide 2.28
Disodium edetate 0.1
Sodium benzoate 0.5
Oxybenzone 0.03
Phosphoric acid 0.075
Dibutyl hydroxytoluene 0.01
Sodium chloride 0.8
Red No. 106 0.00012
Fragrance 0.26
Purified water Remaining amount (total) 100

(Processing method)
After moistening the hair bundle for evaluation for 30 seconds in running water at 40 ° C, 2.0 g of the above model shampoo was applied and foamed, and then rinsed with warm water at 40 ° C for 30 seconds while passing a finger through the hair bundle. . After applying 2.0 g of the hair conditioners of the Examples and Comparative Examples, the hair was rinsed with warm water at 40 ° C. for 30 seconds while passing a finger through the hair bundle. The excess water was wiped off with a towel, and the product was dried with a drier (Can, Solids TYPE 315, setting high / very hot) for 30 seconds with a finger. Then, excess water was wiped off with a towel, and the hair was dried for 3 minutes while passing a finger from the root of the bundle to the tips of the hair once every 5 seconds.

(Smoothness of hair during rinsing)
Regarding the smoothness of the hair when rinsing the hair cosmetics in the above treatment, the seven panelists can select "smooth" / "cannot say" / "not smooth" Let me choose. The number of panelists who answered “smooth” / “not sure” / “not smooth” is shown in order.

(Cohesion of hair after drying)
Regarding the cohesion of the hair after drying, seven panelists were allowed to select one of "cohesive" / "cannot say" / "uncoordinated". The numbers of the panelists who answered "unified" / "cannot say" / "ungrouped" are shown in order.

<Combing of dry hair (combing force measurement)>
(Hair bundle for evaluation)
A bunching process was carried out once by preparing a hair bundle of 200 cm / cm ² density, a growing angle of 60 °, and a length of 25 cm of Japanese straight hair with no history of chemical treatment that was planted in a 6 cm × 6 cm area. Hair tresses were used for evaluation.
For bleaching, apply Kao's lyepretia foam bleach at a mixing ratio of 1 and 2 to a hair bundle at a bath ratio of 1: 1 and then seal the whole hair bundle with wrap. Then, after allowing to stand at room temperature for 20 minutes, it was performed by rinsing with tap water at 40 ° C. for 30 seconds.

(Evaluation methods)
The above evaluated hair bundle was wetted in running water at 40 ° C. for 30 seconds, washed with 2.0 g of the above model shampoo, and then rinsed with warm water at 40 ° C. for 30 seconds while passing a finger through the hair bundle. After that, 2.0 g of the hair cosmetics of Examples and Comparative Examples were applied and blended in, and then rinsed with warm water at 40 ° C. for 30 seconds while passing a finger through the hair bundle. Wipe off excess water with a towel, dry it with a dryer (Can, Solids TYPE315, setting is high / very hot) once every 5 seconds while passing your finger through the root of the bundle to the tip of the hair, and combing once every 30 seconds. The force was measured, and the average value of the results obtained by measuring three times in total was calculated and shown in Table 1.
The value of one combing force is measured with a brush made of resin having a total of 75 teeth at 5 mm intervals in the range of 3 cm × 10 cm square with a tooth length of 2 cm and a speed of 25 cm / sec. The load when passing 10 times from the root to the tip of the hair was measured with a load cell (CB17-2K-11 manufactured by NMB), and an average value of 10 times was calculated.

* 1: Farmin DM-E80 manufactured by Kao
* 2: Kotamin D-2345P manufactured by Kao Corporation
* 3: Calcol 8098 manufactured by Kao Corporation
* 4: Dimethicone mixture: Weight average molecular weight 4,000,000: Weight average molecular weight 5000 = 30:70 (weight ratio) * 5: Momentive Performance Materials Japan KK, Silicone XS65-C0032
* 6: Toray Dow Corning, SS-3588
* 7: HEC Daicel SE850K manufactured by Daicel Corporation

Claims (9)

Contains the following components (A), (B) and (C), and the mass ratio [(B) + (C)] / (A) of the total amount of component (B) and component (C) to component (A) is Hair cosmetics that are 80 or more and 2000 or less .
(A) an organopolysiloxane graft polymer having an organopolysiloxane segment (a) as a main chain and an unsaturated monomer-derived polymer segment (b) as a side chain, wherein the unsaturated monomer The polymer segment (b) derived from the polymer contains 50% by mass or more and 100% by mass or less of repeating units derived from N, N-dimethylacrylamide, and does not differ from the organopolysiloxane segment (a) in the organopolysiloxane graft polymer. An organopolysiloxane graft polymer in which the mass ratio (a) / (b) of the polymer segment (b) derived from a saturated monomer is 10/90 or more and 70/30 or less.
(B) Cationic surfactant
(C) Higher alcohol The hair cosmetic composition according to claim 1, wherein the mass ratio [(B) + (C)] / (A) of the total amount of the component (B) and the component (C) to the component (A) is 80 or more and 1000 or less.   The hair cosmetic composition according to claim 1 or 2, wherein the content of the component (A) in the hair cosmetic composition is 0.001% by mass or more and 2% by mass or less.   The hair cosmetic composition according to claim 1, further comprising an organopolysiloxane other than the component (A) as the component (D).   The hair cosmetic composition according to any one of claims 1 to 4, wherein a mass ratio (D) / (A) of the component (D) to the component (A) is 0.5 or more and 1000 or less. The hair cosmetic composition according to any one of claims 1 to 5, wherein the component (A) is an organopolysiloxane graft polymer represented by the following general formula (1).

[In the formula,
R ¹ may be the same or different and represents an alkyl group having 1 to 8 carbon atoms,
R ^{2 s} may be the same or different, and represent a hydroxyl group or a hydrocarbon group having 1 to 22 carbon atoms,
R ³ represents an alkylene group which may contain a hetero atom,
R ⁴ represents a hydrogen atom or a methyl group,
R ^{5 s} may be the same or different, and represent a hydrogen atom, or a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a hydroxyl group, an amino group or a mono- or di-C _1-4 alkylamino group,
p represents a number from 50 to 2000, q represents a number from 3 to 50, and m represents a number from 10 to 100.
However, the ratio of the repeating units in which two R ^5's are both methyl groups in the m repeating units is 50% by mass or more and 100% by mass or less. ]   The hair cosmetic according to any one of claims 1 to 6, which has a pH of 2.0 or more and 6.0 or less when diluted 20 times by mass with ion-exchanged water.   The hair cosmetic composition according to any one of claims 1 to 7, which is a hair conditioning composition.   The hair cosmetic composition according to claim 8, which is applied to hair and then washed off.