JP2015209407A - Hairdressing cosmetics - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide hairdressing cosmetics which give the hair a soft texture and a natural finish feeling, have no stickiness, strongly fixe a hairstyle, and can keep it for a long period of time.SOLUTION: The hairdressing cosmetics comprise components (A) and (B): (A) organopolysiloxane graft polymer represented by the following formula (1) and (B) cationic or nonionic thickening polymer.

Description

  The present invention relates to a hairdressing cosmetic.

  Recent hair styling products are required to fix and maintain the hair in the desired shape, and at the same time to keep the hair natural and not stiff or sticky. In hair styling, in order to increase the set holding power of hairstyles, it is necessary to increase the blending amount of adhesive polymer and set polymer that forms a strong film, and fix the hairstyle by the adhesiveness of the polymer and the polymer film. It is common.

  Many hairdressers fix the hairstyle by stickiness and impart durability to the hairstyle, but on the other hand, stickiness is strongly expressed and it is often difficult to keep the hair natural. Was a problem. On the other hand, hair styling that forms a strong film can suppress stickiness, but once the formed film is broken, the hairstyle often cannot be maintained. In addition, the hair styling material with such a film-forming ability can easily make a hairstyle with an emphasis on three-dimensionality and volume, but it is stiff and still insufficient to maintain a natural feel on the hair.

  The same applies to curling hair using a curling iron. The curl is firmly attached, but the appearance and feel are required to have a natural finish. For example, Patent Document 1 has a polymer segment derived from an unsaturated monomer having an N, N-dimethylacrylamide content of 50% by mass or more at a specific ratio in the side chain of an organopolysiloxane segment that is a main chain. Hair cosmetics containing organopolysiloxane graft polymers have been proposed as hair cosmetics that give hair a soft feel and a natural finish, are non-sticky, firmly fix the hairstyle, and can last for a long time. .

International Publication No. 2014/002707

  However, in the hair cosmetic described in Patent Document 1, when applied to wet hair, desired effects such as firm fixation of the hair, no stickiness, and long-lasting duration can be obtained, but the hair is dry. When it is applied to the hair, it is difficult to spread on the hair, resulting in unevenness. As a result, there is a problem that the hair setting property is deteriorated and the touch is deteriorated.

  In order to eliminate the difficulty and unevenness of spreading to dry hair, it is considered effective to thicken the composition to an appropriate viscosity using a thickening polymer. However, depending on the type of thickening polymer used in combination with the organopolysiloxane graft polymer of Patent Document 1, the present inventor may use a mixed composition of an organopolysiloxane graft polymer and a thickening polymer when used for hairstyling with a hair iron. It was found that when the coating film was heated to a high temperature, the soft feel of the hair after the styling that the organopolysiloxane graft polymer had was lost, and the firmness and roughness were generated.

  Therefore, the present invention provides a soft touch and a natural finish for both dry and wet hair, has no stickiness, firmly fixes the hairstyle, and can be sustained for a long time. The present invention relates to a cosmetic and a hair styling method.

  And as a result of repeated research, the present inventors satisfy the above requirements by using a cationic or nonionic thickening polymer together with a specific organopolysiloxane graft polymer, and are suitable for hair styling with a hair iron. It has been found that a hairdressing cosmetic can be obtained.

The present invention provides a hair styling cosmetic containing the following components (A) and (B).
(A) Organopolysiloxane graft polymer represented by the following general formula (1)

[Where,
R ¹ may be the same or different and represents an alkyl group having 1 to 8 carbon atoms,
R ² may be the same or different and represents 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 may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a hydroxyl group, an amino group or a mono- or di-C _1-4 alkylamino group,
p represents a number from 50 to 2,000, q represents a number from 3 to 50, and m represents a number from 10 to 100.
However, in the m repeating units, the ratio of the repeating units in which two R ^{5 s} are both methyl groups is 50% by mass or more and 100% by mass or less. ]
(B) Thickening polymer selected from the group consisting of cationic thickening polymer and nonionic thickening polymer

Furthermore, the present invention provides a hair styling method for temporarily styling a hair shape, including the following steps (i) to (iii).
(i) A step of applying the hair styling cosmetic composition to hair
(ii) A step of shaping the hair while heating to 140-230 ° C. with a hair iron
(iii) The process of loosening the hair bundle and creating a natural hairstyle with volume

  According to the hair styling cosmetic and hair styling method of the present invention, it gives a soft feel and a natural finish to both dry and wet hair, has no stickiness, firmly fixes the hairstyle, It can last for a long time, and is also suitable for styling with a hair iron.

  In the present invention, the “hair iron” is a straight iron, a curling iron, a curling iron, a wave iron, a waffle iron, etc., or other names such as an iron that is subjected to heat treatment in contact with hair, an iron tool, etc. Is included.

[Component (A): Organopolysiloxane Graft Polymer Represented by Formula (1)]
Component (A) is an organopolysiloxane having a specific proportion of polymer segments derived from unsaturated monomers that are derived from N, N-dimethylacrylamide at 50% by mass or more in the side chain of the organopolysiloxane segment that is the main chain. It is a siloxane graft polymer. In the component (A), the polymer segment derived from the unsaturated monomer (hereinafter simply referred to as “polymer segment (b)”) is surrounded by m parentheses in the general formula (1). The organopolysiloxane segment (a) refers to the whole excluding the polymer segment 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 a linear, branched, or cyclic alkyl group. From the viewpoint of water dispersibility of the graft polymer of component (A), a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 4 carbon atoms is more preferable. A linear or branched alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is more preferable.

R ² is a hydroxyl group or a hydrocarbon group having 1 to 22 carbon atoms. The hydrocarbon group having 1 to 22 carbon atoms may be saturated or unsaturated, and may be linear or branched. Or a branched alkyl group is preferred. R ² is more preferably a hydroxyl group or a hydrocarbon group having 1 to 8 carbon atoms. Examples of the hydrocarbon group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, tert- Examples thereof include a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a hydroxyl group or a methyl group is preferable, and a methyl group is more preferable.

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

In the present invention, the alkylene group which may contain a hetero atom is one or more atoms or functional groups selected from an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and —NR ³¹ CO—. It may be divided by a group. That is, the alkylene group which may contain a hetero atom may have a structure of “— (alkylene group moiety 1) — (the above atom or functional group) — (alkylene group moiety 2) —”. The carbon number of the alkylene group means the sum of the carbon number of the alkylene group part 1 and the carbon number of the alkylene group part 2, that is, the sum of the carbon number of the part other than the above atoms or functional groups that divide the alkylene group. Say. Here, R ³¹ is an alkyl group having 1 to 3 carbon atoms. In the case where an alkylene group which may contain a hetero atom is interrupted by the above atom or functional group, it may be interrupted by —NHCO— from the viewpoint of easy production of the graft polymer of component (A). preferable.

  In the present invention, the alkylene group which may contain a hetero atom includes a hydroxyl group, an amino group, an alkyl (C1 or more and 3 or less) amino group, a dialkyl (C1 or more and 3 or less) amino group, an amino group and a carbon number. One or more monovalent groups selected from amide groups, carboxy groups, and alkyl (1 to 3 carbon atoms) ester groups obtained by dehydration condensation of 2 or more and 4 or less fatty acids may be substituted. In this case, the carbon number of the alkylene group which may contain a hetero atom does not include the carbon number of these substituents. From the viewpoint of easy availability of raw materials when producing the graft polymer of component (A), the alkylene group which may contain a hetero atom includes an acetamido group, an alkyl (C1 or more and 3 or less) amino group, and an amino group. It is preferable that at least one monovalent group selected from is substituted.

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

The alkylene group (R ³ ) which may contain a hetero atom is a polymer segment derived from an unsaturated monomer via the hetero atom, preferably a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably a sulfur atom. It is preferable that it is couple | bonded with.
Therefore, the “alkylene group optionally containing a heteroatom” represented by R ³ includes
(A) an unsubstituted alkylene group,
(B) an oxygen atom, a sulfur atom, -NH -, - COO -, - NHCO-, and one or more atoms or functional shed alkylene group by a group selected from -NR ³¹ CO-,
(C) A hydroxyl group, an amino group, an alkyl (C1 or more and 3 or less) amino group, a dialkyl (C1 or more and 3 or less) amino group, an amino group and a fatty acid having 2 or more and 4 or less carbon atoms are 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 (C 1 or more and 3 or less) ester group;
(D) In addition to an alkylene group substituted with a divalent heteroatom selected from —O—, —S—, —NH—, —NR ³² — and —COO—, or a divalent group containing a heteroatom, An alkylene group consisting of a combination of two or more of (i), (c) and (d) is applicable.

Specific examples of the alkylene group that may contain a hetero atom of R ³ include the following formulas (i) to (xii). Of these, the following formulas (xi) and (xii) are preferred from the viewpoint of ease of production of the graft polymer of component (A).

In formulas (i) to (xii), * represents a site bonded to a silicon atom in the general formula (1), and ** represents a site bonded to a polymer segment derived from an unsaturated monomer.
In the formula (xii), X ³¹ is at least one selected from —O—, —OCO—, —COO—, —CONH—, and —NHCO—, which facilitates the production of the graft polymer of component (A). From the viewpoint, -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 (C 1 or more and 3 or less) amino group, a dialkyl (C 1 or more and 3 or less) amino group, an amino group and 2 or more and 4 or less 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. The substituent is preferably an acetamido group, an alkyl (having 1 to 3 carbon atoms) amino group, and an amino group from the viewpoint of availability of raw materials during production. The alkylene group represented by R ³³ from the viewpoint of ease of production of the graft polymers of component (A), preferably 2 or more, more preferably 3 or more, components (A) From the viewpoint of water dispersibility of the graft polymer, it is preferably 10 or less, more preferably 6 or less.
Specific examples of R ³³ include the following formulas (xiii) to (xv).

In the formula (xiv), X ⁻ represents anions such as halide ions such as chloride ions and bromide ions, acetate ions, and alkyl (C 1 or more and 3 or less) sulfate ions.

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

R ⁵ may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms which may be substituted by 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, and may be linear or branched, but 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. Of these, a hydrogen atom, a methyl group, and a tert-butyl group are preferable.

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

However, from the viewpoint of good water dispersibility of the component (A), in the m repeating units in the general formula (1), the ratio of the repeating units in which two R ⁵ are both methyl groups is 50% by mass or more. , Preferably 70% by mass or more, more preferably 75% by mass or more, and 100% by mass or less, preferably 95% by mass or less, more preferably 90% or less, from the viewpoint of reducing the stickiness of the hair after setting the hair. It is below mass%.

  p is 50 or more, preferably 80 or more, more preferably 100 or more, and 2000 or less, preferably 1300 or less, more preferably 700 or less, from the viewpoint of reducing the stickiness of the hair after setting the hair. . q is 3 or more, preferably 5 or more, and 50 or less, preferably 30 or less, from the viewpoint of the water dispersibility of the graft polymer of component (A). m is 10 or more, preferably 15 or more, more preferably 20 or more, and 100 or less, preferably 70 or more, from the viewpoint of good setting properties and good water dispersibility of the graft polymer of component (A). Below, more preferably 50 or less.

  Further, from the viewpoint of water dispersibility of the component (A) and the reduction of stickiness of the hair after setting the hair, the mass ratio (a / b) of the organopolysiloxane segment (a) to the polymer segment (b) Is preferably 10/90 or more, more preferably 20/80 or more, further preferably 30/70 or more, still more preferably 35/65 or more, and preferably 70/30 or less, more preferably 60/40 or less. More preferably, it is 50/50 or less.

  In the present specification, the mass ratio (a / b) is defined as “radical reactivity introduced during production” when the graft polymer of component (A) is produced from the radical reactive organopolysiloxane described later. From "total mass of organopolysiloxane (c)" and "total mass of unsaturated monomer added during production (d)" derived from unsaturated monomers not bonded to organopolysiloxane produced during production It is considered that the ratio (c / (d−e)) to the value obtained by subtracting the “total mass (e) of the polymer of (e)” is the same (the following formula (I)).

    a / b = c / (d−e) (I)

  In addition, in the graft polymer molecule of 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 graft points”). ) Is preferably 500 or more, more preferably from the viewpoint of improving the setting power when hair is set with a hair cosmetic containing the organopolysiloxane graft polymer of component (A) and the holding power of the hair shape after setting. Is 700 or more, more preferably 1,000 or more, more preferably 1,500 or more. From the viewpoint of the water dispersibility of the graft polymer of component (A), it is preferably 10,000 or less, more preferably 5,000 or less, and still more preferably 3,000 or less. More preferably, it is 2,500 or less.

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

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

  The molecular weight between graft points is an average value of the molecular weight of the portion surrounded by a broken line in the above formula, and is the mass (g / mol) of the organopolysiloxane segment per mole of the polymer segment derived from the unsaturated monomer. Can be solved. The molecular weight between graft points is the case where the graft polymer of component (A) is produced from the radical reactive organopolysiloxane described later, and all radical reactive functional groups and polymers derived from unsaturated monomers Is bound to the value of the reciprocal of the number of moles of radical reactive functional groups (mol / g) 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 preferably from the viewpoint of the setting power when the hair is set with the hairdressing cosmetic composition of the present invention and the holding power of the hair shape after setting. Is 3,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and 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, and even more preferably 50,000 or less, from the viewpoint of the water dispersibility of the graft polymer of component (A).

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

The weight average molecular weight (MWt) of the graft polymer of component (A) is preferably 10,000 or more from the viewpoint of the setting power when the hair is set with the hairdressing cosmetic composition of the present invention and the hair shape retention power after setting. More preferably 14,000 or more, further preferably 17,000 or more, more preferably 30,000 or more, and from the viewpoint of water dispersibility of the graft polymer of component (A), preferably 200,000 or less, more preferably 160,000 or less, and still more preferably 130,000. Hereinafter, it is more preferably 95,000 or less. If it is within the range, sufficient film strength can be secured, water dispersibility becomes excellent, non-stickiness, and setting power and holding power of hair shape after setting are further improved. can do.
In this specification, MWt is measured by GPC under the measurement conditions described in the Examples and converted to polystyrene.

  Further, when the graft polymer of component (A) is produced from a radical-reactive organopolysiloxane, the component (A) obtained by using the following formula (II) from the reciprocal of MWra and the aforementioned mass ratio (a / b) The calculated weight average molecular weight (MWtcalc) of the graft polymer is preferably 10,000 or more from the viewpoint of the setting power when the hair is set with the hairdressing cosmetic composition of the present invention and the holding power of the hair shape after setting. 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 graft polymer of component (A), preferably 200,000 or less, more preferably 160,000 or less, more preferably 130,000 or less. More preferably, it is 95,000 or less.

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

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

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

  Here, the radical reactive functional group means 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). It is done. Among these, a sulfanyl group is preferable from the viewpoint of reactivity with an unsaturated monomer and molecular weight control.

In general formula (1a), the number of carbon atoms 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. In addition, from the viewpoint of the water dispersibility of the graft polymer of component (A), it is preferably 20 or less, more preferably 10 or less, and still more preferably 8 or less.
In the present invention, the number of carbon atoms of the radical reactive functional group-containing alkyl group does not include the number of carbon atoms of the radical reactive functional group even when the radical reactive functional group has carbon. Also when the containing alkyl group is the above-described monovalent group 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 (1 to 3 carbon atoms) amino group, a dialkyl (1 to 3 carbon atoms) amino group. One or more monovalent groups selected from an amide group, a carboxy group, and an alkyl (carbon number of 1 to 3) ester group obtained by dehydration condensation of an amino group and a fatty acid of 2 to 4 carbon atoms are substituted. It may be. Of these substituents, an acetamido group, an alkyl (C1 or more and 3 or less) 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 interrupted by the above atoms or functional groups, it is preferable that the radical-reactive group-containing alkyl group is interrupted by —NHCO— from the viewpoint of availability of radical-reactive organopolysiloxane or 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). Among them, production of a radical-reactive organopolysiloxane or easiness of acquisition is preferred. From the viewpoint, the following formulas (xviii) and (xix) are preferable. X ⁷¹ and R ^{72 in} formula (xix) and preferred embodiments thereof are the same as X ³¹ and R ^{32 in} formula (xii) and preferred embodiments thereof, respectively.

The radical reactive organopolysiloxane whose radical reactive group is a sulfanyl group can also be obtained as a commercial product, such as “KF-2001” (manufactured by Shin-Etsu Chemical Co., Ltd.). The radical reactive organopolysiloxane is obtained by reacting an organopolysiloxane having one or more reactive functional groups 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 of the organopolysiloxane represented by the general formula (1a) is preferably 3,000 or more, more preferably 5,000 or more, and still more preferably 10,000 or more, from the viewpoint of the setting power and the holding power of the hair shape after setting. More preferably, it is 15,000 or more, and from the viewpoint of good water dispersibility of component (A), it is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 60,000 or less, and even more preferably 50,000 or less.

  The number of moles of the radical reactive group present per unit mass of the organopolysiloxane represented by the general formula (1a) is preferably 1/500 mol from the viewpoint of improving the setting power and the hair shape holding power after setting. / g or less, more preferably 1/700 mol / g or less, still more preferably 1 / 1,000 mol / g or less, and preferably 1 / 10,000 mol / g from the viewpoint of good water dispersibility of the component (A). g or more, more preferably 1 / 5,000 mol / g or more, still more preferably 1/3000 mol / g or more.

  Examples of (meth) acrylamide monomers that undergo radical reaction with the 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. In the present invention, among these (meth) acrylamide monomers, N, N-dimethyl (meth) acrylamide is 50% by mass or more, preferably 70% by mass or more, more preferably 75% by mass or more, Moreover, it is 100 mass% or less, Preferably it is 95 mass% or less, More preferably, it is 90 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, etc. 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 peroxides such as lauroyl peroxide and benzoyl peroxide. Examples thereof include oxide initiators and persulfate initiators such as ammonium persulfate. Further, polymerization may be initiated by generating radicals by light irradiation or the like. As the polymerization initiator, 2,2′-azobis (2,4-dimethylvaleronitrile) is preferable from the viewpoint of reactivity.

  The content of the component (A) in the hairdressing cosmetic composition of the present invention is preferably 2% by mass or more, more preferably 2.3% by mass or more, and still more preferably 2.6% by mass or more, from the viewpoint of imparting good setability. In addition, from the viewpoint of achieving both good setting properties and a natural feel, it is preferably 6% by mass or less, more preferably 5.5% by mass or less, and even more preferably 5% by mass or less.

[Component (B): cationic or nonionic thickening polymer]
Examples of cationic thickening polymers include natural or semi-synthetic cationic polysaccharides, synthetic polymers containing amino groups or ammonium groups in the side chains of polymer chains, or diallyl quaternary ammonium salts as constituent units. Can be mentioned.

  Specific examples of the cationic polysaccharide include cationized cellulose derivatives (for example, Lion: Leogard G, GP, Dow Chemical: YUCA Polymer JR-125, JR-400, JR-30M, LR-400, LR-30M, Akzo Nobel: Cellcoat H-100, L-200), cationized guar gum derivatives (for example, Solvay: Jaguar C-13S, C-17, DSP Gokyo Food & Chemical: Labor Gum CG -M, CG-M7, CG-M8M), hydroxypropyl chitosan (for example, Ichimaru Falcos: Chitofilmer HV-10), chitosan dl-pyrrolidone carboxylate (for example, Union Carbide: Kitomer PC) , Etc.

  As a synthetic cationic polymer containing an amino group or an ammonium group in the side chain of the polymer chain, trialkylaminoalkyl (meth) acrylate, trialkylaminoalkyl (meth) acrylamide, (meth) acrylamide, vinylamine or the like as a structural unit Examples include synthetic cationic polymers including methacryloyloxyethylenetrimonium chloride polymer (INCI name: Polyquaternium-37, for example, BASF: Cosmedia Ultragel 300, SALCARE SC95, Sigma 3V: synthalen CR), (acrylic acid / methyl acrylate / 3-methacryloylaminopropyltrimethylammonium chloride) copolymer (INCI name: Polyquaternium-47, eg Lubrizol: Marquat 2201), (acrylic acid / acrylamide / methyl methacrylic) Amidopropyltrimethylammonium chloride) copolymer (INCI name: Polyquaternium-53, eg Lubrizol: Marquat 2003), (Dimethylacrylamide / ethyltrimonium methacrylate methacrylate) copolymer (eg BASF: Tinobis CD), (Vinylamine / Vinyl) Alcohol) copolymers (for example, Sekisui Specialty Chemical Company: SEVOL ULTALUX AD, Mitsubishi Chemical Company: Diafix C-601) and the like.

  Synthetic cationic polymers containing diallyl quaternary ammonium salts as structural units include diallyldimethylammonium chloride polymers (INCI name: polyquaternium-6, for example, Lubrizol: Marquat 100), (dimethyldiallylammonium chloride / acrylamide) Copolymer (INCI polyquaternium-7, such as Lubrizol: Marquat 550, 740), (acrylic acid / diallyldimethylammonium chloride) copolymer (INCI name: Polyquaternium-22, such as Lubrizol: Marquat 280, 295), ( Acrylamide / acrylic acid / diallyldimethylammonium chloride) copolymer (INCI name: Polyquaternium-39, for example, Lubrizol Corporation: Marquat Plus 3330, 3331).

  Among these cationic thickening polymers, a crosslinkable cationic thickening polymer is particularly preferable, and among these, a crosslinkable polyquaternium-37 is more preferable.

  Examples of nonionic thickening polymers include synthetic nonionic polymers containing natural or semi-synthetic nonionic polysaccharides, vinyl alcohol, and oxyalkylene as constituent units.

  Specific examples of natural or semi-synthetic nonionic polysaccharides include reacting alkylene oxide with water-soluble natural polysaccharides such as starch, guar gum, locust bean gum, glucomannan, and cellulose, starch, guar gum, locust bean gum, etc. And water-soluble hydroxyalkylated polysaccharides. Specific examples include guar gum (for example, DSP Gokyo Food & Chemical: Fiberlon S) and pullulan (for example, Hayashibara: Pullulan PI-20). Hydroxyethyl cellulose (for example, Daicel Finechem: SE-850, Dow Chemical: Cellosize HEC QP-52000-H), methyl hydroxyethyl cellulose (Akzo Nobel: STRUCTURE CELL 12000M), hydroxypropyl cellulose (for example, Nippon Soda Co., Ltd .: HPC) -H, HPC-M, HPC-L), hydroxypropylmethylcellulose (for example, Shin-Etsu Chemical Co., Ltd .: Metroles 60SH-10000), and the like.

  Specific examples of synthetic nonionic thickening polymers containing vinyl alcohol and polyoxyalkylene as structural units include polyvinyl alcohol (for example, Nippon Synthetic Chemical Co., Ltd .: Gohsenol EG-40, GH-05, KH-20, NH-26), high polymerization degree polyethylene glycol (for example, Dow Chemical Co .: Polyox WSR N-60K, WSR301, WSR303), (PEG-240 / decyltetradeceth-20 / HDI) copolymer (for example, ADEKA: Adecanol GT-700) and the like.

  Among these, cationic thickening polymers are more preferable from the viewpoint of imparting good elongation and conformability to the hair during application of the composition, and smoothness and flexibility of the hair after styling, and trialkylaminoalkyl (meth). Synthetic cationic polymers containing acrylate, trialkylaminoalkyl (meth) acrylamide, and (meth) acrylamide as structural units are more preferable. Polymers of methacryloyloxyethylenetrimonium chloride (INCI name: polyquaternium-37, (dimethylacrylamide / More preferred is ethyltrimonium methacrylate chloride) copolymer.

  Among the above components (B), nonionic thickening polymers are preferred from the viewpoint of providing good elongation and conformability to the hair at the time of application of the composition and imparting firmness and firmness to the hair after styling, and natural, or semi Synthetic nonionic polysaccharides and synthetic nonionic thickening polymers containing polyoxyalkylene as a structural unit are more preferred, and hydroxyethylcellulose, hydroxypropylcellulose, (PEG-240 / decyltetradeceth-20 / HDI) copolymers are more preferred preferable.

  These thickening polymers can be used alone or in combination of two or more. The content of the component (B) in the hairdressing cosmetic composition of the present invention is preferably 0.05% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of imparting good elongation and conformability to the hair at the time of application. More preferably, it is 0.1% by mass or more, and preferably 3% by mass or less, more preferably 2.5% by mass from the viewpoint of achieving both good setability and feel after hair styling and reducing hand stickiness during application. Hereinafter, it is more preferably 2% by mass or less.

  The mass ratio (A) / (B) of the component (A) to the component (B) in the hairdressing cosmetic composition of the present invention gives an appropriate viscosity to the hairdressing cosmetic composition, and prevents stickiness on the hand during application. From the viewpoint of reducing and further achieving good elongation and conformability at the time of application and good setting after hair styling, it is preferably 0.1 or more, more preferably 1 or more, more preferably 2 or more, more preferably 5 or more. is there. Further, it is preferably 100 or less, more preferably 50 or less, further preferably 30 or less, and further preferably 25 or less.

[Other set polymers]
In the hairdressing cosmetic composition of the present invention, the set holding power can be further improved by adding another set polymer as an optional component in addition to the component (A). Examples of the polymer for the set include (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymers such as Yucaformer R205, Yukaformer 301 (Mitsubishi Chemical Co., Ltd.), RAM Resin (Osaka Organic Chemical Co., Ltd.); Diaformer Z-651 ( (Acrylates / Lauryl Acrylate / Stearyl Acrylate / Ethyl Amine Oxide Oxide) Copolymers such as Mitsubishi Chemical); Acrylic Acid / Acrylic Amide / Ethyl Acrylate such as Ultrahold 8 and Ultrahold Strong (BASF) Polymer; Alkyl acrylate / methacrylic acid / silicone copolymer such as Rubyflex Silk (BASF); Polyurethane such as Rubyset PUR (BASF); Polyvinylcaprolactam such as Rubiscol Plus (BASF); Anformer 28 -4910, unformer (Octylacrylamide / hydroxypropyl acrylate / butylaminoethyl methacrylate) copolymers such as LV-71 (above Akzo Nobel); (alkyl acrylate / octyl acrylamide) copolymers such as Annformer HC (Akzo Nobel); (Vinyl acetate / crotonic acid / vinyl neodecanoate) copolymers such as resin 28-2930 (Akzo Nobel); polyurethane-14 / AMP-acrylates copolymers such as Dynam X (Akzo Nobel); Aquaflex SF-40 (Ash (PVP / Vinylcaprolactam / DMAPA acrylic acid) copolymer, etc .; (Isobutylene / ethylmaleimide / hydroxyethylmaleimide) copolymer, such as Aquaflex FX-64 (Ashland); Stylee CC-10 (Ashland) Etc. (vinyl pyrrolide / DMAPA acrylic copolymer); (Vinylpyrrolidone / vinyl acetate) copolymers such as PVP / VA E-735 (Ashland) and Rubiscol VA64P (BASF); Guffcut 440, 734, 755 (Ashland) And polyvinyl pyrrolidone such as Polyquaternium-11, Rubiscol K-12 and K-30 (BASF); and (VP / methacrylamide / vinylimidazole) copolymers such as Rubyset Clear (BASF).

  Among the above set polymers, acrylic acid / acrylic acid amide / ethyl acrylate copolymer, alkyl acrylate / methacrylic acid / silicone copolymer, polyurethane, (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer, (octyl) Acrylamide / hydroxypropyl acrylate / butylaminoethyl methacrylate) copolymer, acrylic acid / acrylic amide / ethyl alkyl copolymer, polyvinyl caprolactam, (alkyl acrylate / octyl acrylamide) copolymer are preferred, and acrylic acid / Acrylic amide / ethyl acrylate copolymer and polyurethane are preferred. Two or more kinds of the setting polymers other than these components (A) and (B) can be used in combination.

[Cosmetic oil]
The hairdressing cosmetic composition of the present invention may further contain an ester oil for the purpose of imparting a moist feeling to the hair. Examples of the ester oil include isopropyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, octyldodecyl acid myristate, and the like.

  The content of the ester oil in the hairdressing cosmetic composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 2.0% or more, from the viewpoint of imparting a moist feeling to the hair. It is at most mass%, more preferably at most 1.0 mass%.

  Moreover, in the hairdressing cosmetic composition of the present invention, cosmetic oils other than ester oils can be added within a limit (0.1 to 10% by mass) that does not hinder the effects of the present invention. Such cosmetic oils include glycerides such as castor oil, cacao oil, mink oil, avocado oil, olive oil; waxes such as beeswax, whale wax, lanolin, carnauba wax; cetyl alcohol, oleyl alcohol, hexadecyl alcohol, lauryl Higher alcohols such as alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol; hydrocarbon oils such as liquid paraffin, petrolatum, squalane, hydrogenated polyisobutene; silicones other than components (A) and (B) .

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

  Examples of the cationic surfactant include quaternary ammonium salts represented by the following general formula (3).

[Wherein, R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms, or a benzyl group, and at the same time, a hydrogen atom, a benzyl group, a lower alkyl group having 1 to 3 carbon atoms, or these Except when combined. An ⁻ represents an anion. ]

Here, one of R ⁸ and R ⁹ is preferably an alkyl group having 16 to 24 carbon atoms, more preferably 22 alkyl groups, and more preferably a linear alkyl group, and the other is a lower alkyl group having 1 to 3 carbon atoms, Furthermore, a methyl group is preferable.

  Examples of the anion include chloride ion, bromide ion, iodide ion, methyl sulfate ion, ethyl sulfate ion, acetate ion, phosphate ion, sulfate ion, lactate ion, and saccharin ion.

  As the cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specifically, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkylbenzalkonium chloride and the like. Among them, stearyltrimethylammonium chloride and behenyltrimethylammonium chloride are preferable.

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

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series. Among these, betaine surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amidopropyl betaine are preferable, and fatty acid amidopropyl betaine is particularly preferable. The fatty acid amidopropyl betaine preferably has an acyl group having 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms. Among them, amide propyl betaine laurate, palm kernel fatty acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine Etc. are preferred.

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

  Of these, cationic surfactants and nonionic surfactants are preferred from the viewpoint of feel. Surfactant can be used alone or in combination of two or more, the content in the hairdressing cosmetic composition of the present invention is from the point of stability of the system including solubilization of the solvent, emulsification of the oil agent, etc. Preferably it is 0.01 mass% or more, More preferably, it is 0.05 mass% or more, Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less.

[Other optional ingredients]
Furthermore, in the hairdressing cosmetic composition of the present invention, a fragrance, a pigment, and a preservative and an antioxidant can be added to prevent daily deterioration of the hairdressing cosmetic composition in order to increase commercial value. Further, if necessary, a humidity control agent, a curing agent, an antistatic agent, an antifoaming agent, a dispersant, a thickener, an ultraviolet absorber, a colored dye, a dye fixing agent, a propellant and the like can be added.

[Medium]
As the solvent (supporting medium), water, lower alcohols (ethanol, isopropanol, etc.), lactones, etc. can be used, and these can be used alone or in combination. Among these, water, ethanol, or a mixed system of water and ethanol is preferable from the viewpoints of versatility and solubility of the hairdressing cosmetic and ensuring dispersibility. When water is contained in the solvent, the water content is preferably 60% by mass or more, more preferably 65% by mass or more, and further preferably 70% by mass or more in the hairdressing cosmetic composition.

〔viscosity〕
The viscosity of the hairdressing cosmetic composition of the present invention is preferably 10 mPa · s or more, more preferably 20 mPa · s or more, and still more preferably 30 mPa · s or more, from the viewpoint of easily spreading the hair without unevenness. From the viewpoint of ease of spreading on hair and ease of shaping, it is preferably 20,000 mPa · s or less, more preferably 15,000 mPa · s or less, and even more preferably 10,000 mPa · s or less. Here, the viscosity in the present invention refers to a viscosity measured with a B-type viscometer at 30 ° C. In addition, the rotor used at the time of measurement and the number of rotations should be selected according to the viscosity of the hairdressing cosmetic material according to the manual of the measuring machine.

[Drug type]
There is no restriction | limiting in particular as a dosage form of the cosmetics for hairdressing of this invention, A transparent liquid, lotion shape, emulsion, gel shape, foam shape (aerosol, nonaerosol) etc. are possible.

[Hair shaping method]
The hairdressing cosmetic composition of the present invention can be suitably used in a hairdressing method using a hair iron. Especially, it can apply suitably for the hair-styling method which includes the following process (i)-(iii), and hair-forms hair shape temporarily.
(i) A step of applying the hairdressing cosmetic composition of the present invention to hair
(ii) A step of shaping the hair while heating to 140-230 ° C. with a hair iron
(iii) The process of loosening the hair bundle and creating a natural hairstyle with volume

・ Process (i)
In step (i), the hair styling composition of the present invention is applied to the hair at any timing, such as a wet state after shampooing, towel drying, etc., a semi-dry state during drying, a dry state after drying, etc. However, from the viewpoint of imparting high hair styling properties even for a short time, it is preferable to apply to dry hair. The method of application to hair is not uniform depending on the type of dosage form, but it is usually sprayed directly on the hair with a dosage form such as spray, mist, etc. It is a hand or comb with a dosage form such as lotion, foam, gel, cream etc. Application to hair using a brush or the like, and a combination of the two may be used.

  The hair styling composition may be applied to the whole hair or may be applied to a part of the hair.

  The amount of hairdressing composition applied (applied) to the hair is not uniform depending on the content of component (A), the dosage form, and the properties of the agent, but it is usually preferred as a ratio (bath ratio) to the mass of the hair. It is 0.001 or more, more preferably 0.005 or more, more preferably 0.007 or more, still more preferably 0.01 or more, preferably 1 or less, more preferably 0.7 or less, still more preferably 0.5 or less.

  To apply the hair treatment composition to the entire hair after applying the hair styling composition to the hair, use a method such as brushing the hair and the agent, or passing hands, etc., tools such as brushes, combs, and brushes. The method and a combination of both may be used.

Between step (i) and step (ii) After step (i) and before step (ii), the hair may or may not be dried, but subsequent step (ii) From the viewpoint of preventing damage to the hair due to bumping of moisture and imparting higher hair styling properties, drying is more preferable. Drying can be performed by natural drying, heat drying with a dryer or the like.

・ Process (ii)
Step (ii) may be performed on the entire hair or a part of the hair.
In the step (ii), the step of shaping the hair while heating to 140 to 230 ° C. with a hair iron is performed by any method, such as sliding the hair with a hair iron, sliding the hair with a hair iron, and holding the hair. These may be used singly or in combination, but from the viewpoint of imparting a natural volume with a volume, a method of sliding hair with a hair iron and hair with a hair iron It is preferable to combine the method of winding and holding.

  When the hair is slid between hair irons, any method may be used, such as slid straight, or slid to give curl to the hair while turning the wrist. However, from the viewpoint of imparting a natural style, a method of sliding the hair so as to impart curl to the hair while turning the wrist is preferable.

  When the hair is wound and held with a hair iron, the time for holding the hair with the hair iron is 1 second or more, preferably 3 seconds or more, more preferably 4 seconds or more, from the viewpoint of imparting a good style. The upper limit is more preferably 5 seconds or more, and the upper limit is 60 seconds or less, more preferably 30 seconds or less, and still more preferably 20 seconds or less, from the viewpoint of achieving both a good style and preventing damage to the hair.

  Regardless of the type of hair iron used, the material of the heating section, the set temperature, and the iron operating method, the temperature reached when heating the hair (the temperature of the hair) is determined from the viewpoint of imparting good shapeability. 140 ° C. or higher, preferably 150 ° C. or higher, more preferably 160 ° C. or higher, and 230 ° C. or lower, preferably 220 ° C. or lower, more preferably 210 ° C. More preferably, it is 200 degrees C or less. The heating temperature of the hair can be measured using, for example, a radiation thermometer (model number ST653) manufactured by SENTRY.

-Between step (ii) and step (iii) After step (ii) is performed and the iron is removed from the hair, before performing step (iii), it may or may not be left until the hair temperature returns to room temperature. Although it is good, it is preferable to leave it until it returns to normal temperature from the viewpoint of imparting a good style.

・ Process (iii)
Step (iii) may be performed on the entire hair or a part of the hair.
Step (iii) The step of loosening the hair bundle to create a desired style is to pass the hand comb through the hair bundle, pull out a part of the hair from the hair bundle, break the hair bundle using both hands, and massage the hair bundle by hand The method of using a hand such as putting a finger in a hair bundle and moving it up and down or left and right, a method of using a tool such as a comb or a brush, and a combination of both, etc. From the viewpoint, it is preferable to use a method using a hand alone or in combination, more preferably, a method of putting a finger in a hair bundle and moving it up and down or left and right, and a method of passing a comb through a hair bundle are preferred.

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

<1>
A hairdressing cosmetic comprising the following components (A) and (B):
(A) Organopolysiloxane graft polymer represented by the following general formula (1)

[Where,
R ¹ may be the same or different and represents an alkyl group having 1 to 8 carbon atoms;
R ² may be the same or different and represents 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 may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a hydroxyl group, an amino group or a mono- or di-C _1-4 alkylamino group,
p represents a number from 50 to 2,000, q represents a number from 3 to 50, and m represents a number from 10 to 100.
However, in the m repeating units, the ratio of the repeating units in which two R ^{5 s} are both methyl groups is 50% by mass or more and 100% by mass or less. ]
(B) Thickening polymer selected from the group consisting of cationic thickening polymers and nonionic thickening polymers

<2>
The viscosity is preferably 10 mPa · s or more, more preferably 20 mPa · s or more, further preferably 30 mPa · s or more, preferably 20,000 mPa · s or less, more preferably 15,000 mPa · s or less, and still more preferably. The hairdressing cosmetic composition according to <1>, which is 10,000 mPa · s or less.

<3>
The mass ratio (A) / (B) of the component (A) to the component (B) is preferably 0.1 or more, more preferably 1 or more, still more preferably 2 or more, still more preferably 5 or more. The hairdressing cosmetic composition according to <1> or <2>, which is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, and still more preferably 25 or less.

<4>
The content of the component (A) is preferably 2% by mass or more, more preferably 2.3% by mass or more, further preferably 2.6% by mass or more, and preferably 6% by mass or less, more preferably 5.5% by mass or less, The hair styling cosmetic according to any one of <1> to <3>, more preferably 5% by mass or less.
<5>
The content of component (B) is preferably 0.05% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 3% by mass or less, more preferably 2.5% by mass or less. The hair styling cosmetic composition according to any one of <1> to <4>, more preferably 2% by mass or less.

<6>
The mass ratio (a / b) between the organopolysiloxane segment (a) and the polymer segment (b) of component (A) is preferably 10/90 or more, more preferably 20/80 or more, still more preferably 30/70. More preferably, it is 35/65 or more, preferably 70/30 or less, more preferably 60/40 or less, and still more preferably 50/50 or less, any one of <1> to <5> Hairdressing cosmetics as described in 1.

<7>
R ^{1 of} component (A) is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, still more preferably carbon. The hairdressing cosmetic composition according to any one of <1> to <6>, which is a linear or branched alkyl group having a number of 1 or more and 3 or less, more preferably a methyl group.

<8>
<1> to <7>, wherein R ^{2 of} component (A) is preferably a hydroxyl group or a hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydroxyl group or a methyl group, and still more preferably a methyl group. Hairdressing cosmetics as described in any one of Claims.

<9>
The carbon number of R ^{3 in} the component (A) is preferably 2 or more, more preferably 3 or more, and preferably 20 or less, more preferably 10 or less, and even more preferably 8 or less <1> to < The hair styling cosmetic composition according to any one of 8>.

<10>
R ^{3 of} component (A) is preferably selected from (a) an unsubstituted alkylene group, (b) an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and —NR ³¹ CO—. An alkylene group separated by one or more atoms or functional groups, (u) a hydroxyl group, an amino group, an alkyl (C1 or more and 3 or less) amino group, a dialkyl (C1 or more and 3 or less) amino group, an amino group, An alkylene group substituted with one or more monovalent groups selected from an amide group, a carboxy group, and an alkyl (1 to 3 carbon atoms) ester group obtained by dehydration condensation of a fatty acid having 2 to 4 carbon atoms , (D) a divalent heteroatom selected from —O—, —S—, —NH—, —NR ³² — and —COO—, or an alkylene group substituted with a divalent group containing a heteroatom. Any one or above ( ), (C), (d) The cosmetic for hairdressing according to any one of <1> to <9>, which is an alkylene group consisting of a combination of two or more.

<11>
The hairdressing cosmetic composition according to any one of <1> to <10>, wherein R ^{4 of} component (A) is preferably a hydrogen atom.

<12>
R ^{5 of} component (A) is preferably a linear or branched alkyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a hydroxymethyl group, a hydroxyethyl group and dimethylamino. Any one selected from propyl groups, more preferably any one selected from a hydrogen atom, a methyl group and a tert-butyl group, for hair styling according to any one of <1> to <11> Cosmetics.

<13>
In the m repeating units in the general formula (1), the ratio of the repeating units in which two R ⁵ are both methyl groups is preferably 70% by mass or more, more preferably 75% by mass or more. The hairdressing cosmetic composition according to any one of <1> to <12>, which is not more than mass%, preferably not more than 95 mass%, more preferably not more than 90 mass%.

<14>
Preferably, any of <1> to <13>, wherein the component (B) is selected from a synthetic cationic thickening polymer containing trialkylaminoalkyl methacrylate, trialkylaminoalkyl (meth) acrylamide or acrylamide as a structural unit. The hair styling cosmetic composition according to claim 1.

<15>
Preferably, the component (B) is any one of <1> to <13> selected from natural or semi-synthetic nonionic polysaccharides and synthetic nonionic thickening polymers containing polyoxyalkylene as a structural unit. The cosmetic for hairdressing as described.

<16>
A hair styling method for temporarily styling a hair shape, comprising the following steps (i) to (iii):
(i) The process of applying the hairdressing cosmetics described in any one of <1> to <15> to the hair
(ii) A step of shaping the hair while heating to 140-230 ° C. with a hair iron
(iii) The process of loosening the hair bundle and creating a natural hairstyle with volume

  The synthesis method of the polymer used in the following examples is shown.

Synthesis Example 1 Synthesis of Polysilicone-28 (component (A) polymer)
(1) Synthesis of radical-reactive organopolysiloxane Side-chain primary aminopropyl-modified organopolysiloxane as an organopolysiloxane having a reactive functional group in a separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirrer 100 g of siloxane (weight average molecular weight 30,000, mole number of amino groups per unit mass; 1 / 2,030 mol / g, manufactured by Toray Dow Corning) and 8 g of N-acetyl-DL-homocysteine thiolactone were charged. Under a nitrogen atmosphere, the temperature was raised to 100 ° C. and the mixture was stirred for 3 hours to synthesize a radical-reactive organopolysiloxane A 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 reacted with N-acetyl-DL-homocysteine thiolactone (amino (Conversion rate 99%). Therefore, the number of moles of sulfanyl group per unit mass of the radical reactive organopolysiloxane is 1 / 2,210 mol / g. The weight average molecular weight of the radical-reactive organopolysiloxane determined by GPC measurement was 30,000.

(2) Synthesis of organopolysiloxane graft polymer 101.0 g of ethanol was charged into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring device. While stirring ethanol under reflux at 80 ° C. in a nitrogen atmosphere, the following solution (a) and solution (b) were respectively added to separate dropping funnels and dropped simultaneously over 1 hour.
Solution (a): A solution prepared 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 A synthesized in Synthesis Example 1, 2,2′-azobis (2,4-dimethylvaleronitrile) “V-65B” (Wako Pure Chemical Industries, Ltd.) ), Manufactured by azo polymerization initiator) A solution in which 0.03 g and 43.0 g of ethanol are mixed.

After completion of the dropwise addition, 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 the organopolysiloxane graft polymer B as a white solid. When the residual ratio of the sulfanyl group was measured by the above method, it was 3%.
According to the above method, the content of the polymer derived from the unsaturated monomer not bonded to the organopolysiloxane graft polymer in the mixture containing the organopolysiloxane graft polymer B after the reaction was measured for the obtained mixture. However, it was 29 mass%. It was 56/44 when mass ratio (a / b) of the organopolysiloxane segment (a) and the polymer segment (b) derived from an unsaturated monomer was calculated by the said numerical formula (I).
In this polymer, p in the general formula (1) was 380, q was 15, and m was 27.

The weight average molecular weight of the polymer obtained in Synthesis Example 1 was determined by performing GPC measurement under the following conditions.
<GPC measurement conditions>
Column: Two “K-804L” (manufactured by Tosoh Corporation) connected in series.
Eluent: 1 mM dimethyldodecylamine / chloroform flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI
Sample concentration and sample volume: 5 mg / mL, 500 μL

Moreover, the residual rate of the sulfanyl group was calculated | required with the following method.
In a 10 mL screw tube, 0.6 g of a 50 mass% ethanol solution of an organopolysiloxane graft polymer, 0.15 g of a 10 mass% ethanol solution of N-ethylmaleimide (Sigma Aldrich), and 0.55 g of ethanol are placed for 2 hours at room temperature. Stir. After stirring, 1 g of ethanol was added, the solution was analyzed by gas chromatography, and the amount of N-methylmaleimide was quantified. The residual amount of sulfanyl groups was calculated from the consumption rate of N-methylmaleimide, and the residual rate of sulfanyl groups was calculated from this value and the number of moles of sulfanyl groups per unit mass of the sulfanyl group-modified organopolysiloxane.

Moreover, the measurement of the content of the polymer derived from the unsaturated monomer which is not couple | bonded with the organopolysiloxane graft polymer after completion | finish of reaction was performed as follows.
After 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 Chemicals Research Institute, Size: 4.6 × 150mm, 5μm)
Column temperature: 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
Dissolve 19.0 g (0.12 mol) of diethyl sulfate and 81.0 g (0.82 mol) of 2-ethyl-2-oxazoline in 203.0 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionyl) Ethyleneimine) was synthesized. The number average molecular weight measured by GPC was 1100. A 33% ethyl acetate solution of 300 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32000, amine equivalent 2000) was added all at once and heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (390 g, yield 97%). The content of the silicone segment in the final product was 75% by mass, and the weight average molecular weight was 40000. According to the result of neutralization titration with hydrochloric acid using methanol as a solvent, about 20 mol% of amino groups remained.

The weight average molecular weight of the polymer 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: 0.35mL / min
Column temperature: 40 ° C
Detector: UV
Sample: 50μL

Examples 1-6, Comparative Examples 1-4
Hairdressing cosmetics shown in Table 1 were prepared, and their performance was evaluated according to the following methods and standards. In addition, since Comparative Example 4 lacks setability, no evaluation other than viscosity was performed.

(Measurement method of viscosity)
About the composition of each Example and the comparative example, it measured by 30 degreeC and the conditions after 60-second rotation by B type viscometer TVB-10M (Toki Sangyo Co., Ltd.) until the viscosity was 20,000 mPa * s. When the viscosity of the composition is 20,000 mPa · s or more, use a B-type viscometer TVB-10R (Toki Sangyo) and T-BAR STAGE TS-10 (Toki Sangyo) at 30 ° C for 60 seconds. Measured according to the conditions after rotation.
The number of revolutions was 30 rpm until the viscosity was 10 mPa · s, 60 rpm for 10 to 20 mPa · s, 30 rpm for 20 to 20,000 mPa · s, and 5 rpm for 20,000 mPa · s or more. In addition, the rotor is L / Adp up to a viscosity of 10 mPa · s, M1 for 10 to 200 mPa · s, M2 for a viscosity of 200 to 1,000 mPa · s, M3 for a viscosity of 1,000 to 4,000 mPa · s, and 4,000 to 4,000 20,000 mPa · s was measured using M4, and when the viscosity was 20,000 to 160,000 mPa · s, a TB rotor was used, and when it exceeded 160,000 mPa · s, a TC rotor was used.

(Evaluation hair bundle)
Make a hair bundle of 30cm, 10g, 4cm width with Japanese straight hair with no chemical treatment history, and bath ratio to the mixed solution of the first agent and the second agent of "Pretia Soft Bubble Bleach Hybrid" manufactured by Kao Soak 1: 1 and leave at 40 ° C for 30 minutes, then rinse with water. Next, this hair bundle is treated with the shampoo shown in Table 1, rinsed with water, then treated with plain rinse shown in Table 2, and rinsed with water. After towel drying, dry with a dryer at 70 ° C for 5 minutes. A hair bundle obtained by repeating the above-described series of treatments twice was used as an evaluation hair bundle.

(hair iron)
A hair iron made by Koizumi Seiki (model number: VSI-1904, pipe diameter 19 mm) was used.

(Evaluation method)
"Ease of spreading evenly when applied to wet hair"
After shampooing with the shampoo shown in Table 1, the rinse shown in Table 2 was applied, rinsed, and towel-dried, and 0.3 g of each hairdressing cosmetic composition was taken and spread over the entire evaluation hair bundle. The hair styling cosmetic was evaluated for ease of extension to the hair.
The evaluation is alternative to whether the panelists of 7 people are “easy to stretch uniformly” / “cannot say either” / “difficult to stretch uniformly” when each composition is processed by the above operation. Table 1 shows the number of people selected for these options in order.

"Ease of spreading evenly when applied to dry hair"
Each hairdressing cosmetic composition (0.3 g) was picked up, and the ease of extension of the hairdressing cosmetic composition onto the hair when spread over the entire evaluation hair bundle was evaluated.
The evaluation is alternative to whether the panelists of 7 people are “easy to stretch uniformly” / “cannot say either” / “difficult to stretch uniformly” when each composition is processed by the above operation. Table 1 shows the number of people selected for these options in order.

"No squeaky feeling when applied to dry hair"
The evaluation hair treated by the same method as “Ease of spreading uniformly when applied to dry hair” was evaluated for the absence of squeaky feeling when spread.
The evaluation is to allow 7 panelists to select either “no squeak”, “neither”, or “squeak” when each composition is processed by the above operation. Table 1 shows the number of selected options in order.

"Curlability"
The evaluation hair bundle after evaluating “ease of spreading when applied to dry hair” was held for 10 seconds after being wound around a hair iron, and then the hair bundle was removed from the iron. The condition after the hair bundle was left for 15 minutes in an environment of 25 ° C. and 50% RH was evaluated from the viewpoint of curling property.
Evaluation was made by selecting whether the panelists of 7 people were “curled firmly” / “cannot say either” / “curled not firmly” when each composition was processed by the above operation. Table 1 shows the number of these options selected in order.

"Curl's persistence"
About the state of curl of the hair bundle after shaking the hair bundle after evaluating "curling ability" up and down for 30 minutes at 25 ° C, 50% RH, with a swinging width of 10cm, shaking speed of 60 times / min. Evaluation was performed.
The evaluation was performed by letting seven panelists choose one of “Curl is firmly attached”, “Neither can be said” or “Curl is not firmly attached”. The number of people who selected these options was shown in order.

"No stuffiness when fingering through hair bundles"
An evaluation was made on the firmness of the hair bundle when the hair bundle was touched after evaluating the “curl persistence”.
The evaluation was performed by having the seven panelists select one of “no worries”, “neither”, or “wow”, and the selection of these options is shown in Table 3. The number of people was shown in order.

"No hair stickiness after finishing"
The evaluation was made on the non-stickiness of the hair when the hair bundle was touched after evaluating the “curl persistence”.
The evaluation was performed by having the seven panelists select one of “Non-sticky”, “Neither”, or “Non-sticky”. Table 3 shows the number of people selected for these options in order. Indicated.

Example 7
5% by mass of polyorganosiloxane graft polymer obtained in Synthesis Example 1
Polyquaternium-37 (* 1) 0.5% by mass
Ethanol 15% by mass
Residual amount of water When the viscosity of this hair treatment agent was measured in the same manner as in Examples 1 to 6, it was 1,800 mPa · s. Moreover, the applicability to wet hair and the applicability to dry hair were good, and the squeaky feeling at the time of application was small.

Claims (8)

A hairdressing cosmetic comprising the following components (A) and (B):
(A) Organopolysiloxane graft polymer represented by the following general formula (1)

[Where,
R ¹ may be the same or different and represents an alkyl group having 1 to 8 carbon atoms;
R ² may be the same or different and represents 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 may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a hydroxyl group, an amino group or a mono- or di-C _1-4 alkylamino group,
p represents a number from 50 to 2,000, q represents a number from 3 to 50, and m represents a number from 10 to 100.
However, in the m repeating units, the ratio of the repeating units in which two R ^{5 s} are both methyl groups is 50% by mass or more and 100% by mass or less. ]
(B) Thickening polymer selected from the group consisting of cationic thickening polymers and nonionic thickening polymers   The hairdressing cosmetic composition according to claim 1, having a viscosity of 10 mPa · s or more and 20000 mPa · s or less.   The hairdressing cosmetic composition according to claim 1 or 2, wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 0.1 or more and 100 or less.   The hairdressing cosmetic composition according to any one of claims 1 to 3, wherein the content of the component (A) is 2 mass% or more and 6 mass% or less.   The hairdressing cosmetic composition according to any one of claims 1 to 4, wherein the content of the component (B) is 0.05 mass% or more and 3 mass% or less.   The component (B) is selected from synthetic cationic thickening polymers containing trialkylaminoalkyl methacrylate, trialkylaminoalkyl (meth) acrylamide or acrylamide as a constituent unit. Hairdressing cosmetics.   The hairdressing makeup according to any one of claims 1 to 5, wherein the component (B) is selected from a synthetic nonionic thickening polymer containing a natural or semi-synthetic nonionic polysaccharide or polyoxyalkylene as a structural unit. Fee. A hair styling method for temporarily styling a hair shape, comprising the following steps (i) to (iii):
(i) A step of applying the hair styling cosmetic composition according to any one of claims 1 to 7 to hair.
(ii) A step of shaping the hair while heating to 140-230 ° C. with a hair iron
(iii) The process of loosening the hair bundle and creating a natural hairstyle with volume