JP6580862B2 - Hairdressing composition - Google Patents

Description

  The present invention relates to a hairdressing composition.

  In recent years, with the widespread use of straight irons, it has become easy to make swelled and peculiar hair straight, but there are many women who perform blow styling that can create a natural straight shape.

  When performing blow styling, it is common to apply a hair styling agent to the hair and then adjust the hair shape with a dryer while applying tension with a brush. For example, in Patent Document 1, heat is applied to hair treated with an imposition hair care composition containing silicone by using a heating device to induce a decrease in the bending elastic modulus due to heat on the hair, thereby providing good hair setting properties. Giving is disclosed.

  On the other hand, 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 products, in order to increase the set-holding power of a hairstyle, it is common to fix the hairstyle with the adhesiveness of the adhesive polymer or the polymer film of the set polymer that forms a strong film. For example, Patent Document 2 discloses that setting power and lack of stickiness can be achieved by using a hair cosmetic containing an acrylic silicone polymer and polyethylene glycol. Moreover, in patent document 3, a specific organopolysiloxane graft polymer has thermoplasticity, and the hair cosmetics using this have high setting power and non-stickiness, and are excellent in maintaining the hair shape. It is disclosed. In Patent Document 4, a hair styling cosmetic containing a polyalkylene glycol that is solid at room temperature, a polyalkylene glycol that is liquid at room temperature, a film-forming polymer, and a sugar alcohol in a certain ratio is excellent in setability and re-styling properties. Is disclosed.

Special Table 2001-518488 JP 2013-227312 A International Publication No. 2014/002707 Pamphlet JP 2010-2752912 A

  However, the finish of blow styling largely depends on the skill of the consumer's blow technology, and even if a styling agent with high hair styling properties is used, it is insufficient to make swelled and peculiar hair natural There is.

  For example, when the hair care composition described in Patent Document 1 is used as a hair styling agent for blowing, there is a problem that if the heating is insufficient, the hair with undulations and peculiarities cannot be made clean and natural straight. Further, even when a hair styling agent having high hair styling properties and no stickiness described in Patent Document 2 and Patent Document 3 is used as a blow styling agent, swelled and peculiar hair is clean and natural when the blowing technique is inferior. There was a problem that could not be straight. In addition, the hairdressing material described in Patent Document 3 has a hair tip after hairdressing due to the characteristics of the polymer used when the hair is brushed many times after applying the hairstyling agent, such as blow styling. In some cases, it was difficult to put together. Further, in Patent Document 4, the film of the film-forming polymer is too softened with polyethylene glycol, so that it becomes sticky when blown or the setability to correct waviness and peculiarity is lowered, resulting in a fine finish. There was no problem.

  Therefore, the present invention relates to a hair styling composition capable of styling hair with undulations and peculiarities into a clean and natural straight hair without depending on the skill of the blowing technique.

  The present inventors do not depend on the skill of the blowing technique, and in order to shape swelled and peculiar hair into a clean and natural straight hair, while applying to the hair well while applying water properly, The hair styling agent that hits the brush moderately at the time of blowing was considered effective and examined. As a result, it has been found that by combining a specific organopolysiloxane graft polymer and a pasty or solid polyhydric alcohol at a certain ratio, a hair styling composition that satisfies the above requirements can be obtained.

The present invention provides a hairdressing composition comprising components (A) and (B), wherein the mass ratio (A) / (B) of the components (A) and (B) is 0.1 or more and 15 or less. Is.
(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) a polyhydric alcohol that is in the form of a paste or solid

  The hair styling composition of the present invention is well-familiar with the hair when applied, and is appropriately caught on the brush when blown, so that it is easy to apply an appropriate tension to the hair. It is easy to put it together into a clean straight, and after blowing it can give a smooth feel without catching on the brush. In addition, you can create a cohesive style up to the hair ends.

[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. The component (A) can be preferably used as a blow styling agent because it can impart a slight resistance to the brush when blown when applied onto the hair. 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. Branched alkyl groups are 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and tert-butyl. Group, pentyl group, hexyl group, heptyl group, octyl group and the like. Among them, a hydroxyl group or a methyl group is more 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 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 graft polymer of component (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 2,000 or less, preferably 1,300 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 from the viewpoint of improving the setting power when the hair is set with the hairdressing composition containing the organopolysiloxane graft polymer of component (A) and the holding power of the hair shape after setting. Preferably it 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. Below, more preferably 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 +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 ¹ -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, y ¹ is a number of positive.

  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.

  In addition, 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 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 composition of the present invention and the hair shape holding 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 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 ^{33 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 composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving swell correction power and imparting smoothness after hairdressing. Further, it is preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and further preferably 2% from the viewpoint of giving a more natural feeling of unity. It is below mass%.

[Component (B): Pasty or solid polyhydric alcohol]
The polyhydric alcohol of component (B) is a paste or solid. Here, the paste form in the present invention refers to those classified as a solid at 25 ° C. and a liquid at 50 ° C. according to Standard Test Method D4359-90 of the American Society for Testing and Materials (ASTM). The term “solid” refers to those classified as a solid at 25 ° C. and a solid at 50 ° C. according to Standard Test Method D4359-90 of the American Society for Testing and Materials (ASTM). Those that are classified as solid.

  Specific examples of such pasty or solid polyhydric alcohols include polyethylene glycol, polypropylene glycol, polybutylene glycol sorbitol, mannitol and the like. Preferable examples of the pasty polyhydric alcohol include polyethylene glycol having a number average molecular weight of 1,000 to 3,000 and polyethylene polypropylene glycol having a number average molecular weight of 3,000 to 9,000. Further, preferable examples of the solid polyhydric alcohol include polyethylene glycol having a number average molecular weight of 3,000 to 10,000,000 and polyethylene polypropylene glycol having a number average molecular weight of 9,000 to 10,000,000.

  The above polyhydric alcohol can be used alone or in combination of two or more. From the viewpoint of controlling the magnitude of the resistance given to the brush at the time of blowing to a more appropriate range and improving the cohesiveness, More preferably, a solid polyhydric alcohol and a solid polyhydric alcohol are used in combination. In this case, the combined ratio (paste / solid) is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.2 or more, and preferably 10.0 or less, more preferably 5.0 or less, by mass ratio. More preferably, it is 3.0 or less, More preferably, it is 2.0 or less, More preferably, it is 1.0 or less, More preferably, it is 0.5 or less.

  The content of the component (B) in the hairdressing composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05%, from the viewpoint of enhancing the hooking by the brush due to thermoplasticity during hairdressing and imparting excellent hairstyling properties. More than 0.1% by weight, more preferably more than 0.15% by weight, more preferably more than 0.15% by weight. Further, the hair is not easily sticky after hair styling due to its thermoplasticity during hair styling, and excellent hair styling. From the standpoint of providing both a high quality and a light touch, it is preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and further preferably 2% by mass or less. More preferably, it is 1 mass% or less.

  In addition, the mass ratio (A) / (B) of component (A) to component (B) controls the amount of resistance given to the brush at the time of blowing, strengthens the catching by the brush, and sticks to the hair after hair styling From the viewpoint of providing excellent hair uniting properties, excellent hair-styling properties, and a light touch, it is 0.1 or more, preferably 0.15 or more, more preferably 0.2 or more, more preferably 0.4 or more. And 15 or less, preferably 10 or less, more preferably 7 or less, and still more preferably 5.5 or less.

[Component (C): Cationic surfactant]
The hair styling composition of the present invention may further contain a cationic surfactant as component (C). The cationic surfactant is selected from quaternary ammonium salts such as alkyl quaternary ammonium salts and alkyl ether quaternary ammonium salts, and tertiary amines such as hydroxy ether alkylamine, ether amine and alkylamidoamine and salts thereof. One or more.

  Preferable cationic surfactants include alkyl quaternary ammonium salts represented by the following general formula (2).

[Wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 28 carbon atoms or a benzyl group, and at least one is an alkyl group having 8 or more carbon atoms. R ¹⁰ and R ¹¹ may be the same or different, represents a hydroxyalkyl group having an alkyl group or hydroxyalkyl group, or the total number of moles added 10 following the polyoxyethylene group having 1 to 5 carbon atoms, An ^- is , Showing anion. ]

In the alkyl quaternary ammonium salt represented by the general formula (2), when R ⁸ or R ⁹ is an alkyl group, those having 16 to 24 carbon atoms are preferred, and a linear alkyl group is preferred. Examples of An ⁻ include halide ions such as chloride ions and bromide ions, and organic anions such as ethyl sulfate ions and methyl carbonate ions. Halide ions are preferable, and chloride ions are more preferable.

Examples of the alkyl quaternary ammonium salt represented by the general formula (2) include a mono long chain alkyl quaternary ammonium salt (R ⁸ is an alkyl group having ⁸ to 28 carbon atoms, and R ⁹ is an alkyl group having 1 to 6 carbon atoms. Specific examples thereof include alkyltrimethylammonium chlorides such as behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride. Among them, behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride are preferable. Is preferred.

  A component (C) can be used individually or in combination of 2 or more types. The content of the component (C) in the hair styling composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass, from the viewpoint of imparting excellent fingering after hair styling and a soft feel to the hair. % Or more, and more preferably 0.2% by mass or more. In addition, from the viewpoint of providing excellent fingering after hair styling and soft touch to the hair and achieving no stickiness, it is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass. It is as follows.

[Component (D): Organopolysiloxane represented by the general formula (3)]
The hair styling composition of the present invention further contains, as component (D), at least two silicon atoms of the organopolysiloxane segment constituting the main chain via an alkylene group containing a hetero atom, the following general formula (3 );

[Wherein, R ¹² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aralkyl group or an aryl group, and n represents 2 or 3. ]
An organopolysiloxane formed by bonding poly (N-acylalkyleneimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 1,600, and the mass ratio of the organopolysiloxane segment (a) constituting the main chain to the poly (N-acylalkylenimine) segment (b) (A / b) is 65/35 to 82/18,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 10,000 to 100,000,
Organopolysiloxane can be included.

  The poly (N-acylalkylenimine) segment in component (D) can be bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a hetero atom, It is preferably bonded to one or more silicon atoms excluding both ends via the alkylene group, and more preferably bonded to two or more silicon atoms excluding both ends via the alkylene group.

The alkylene group containing a hetero atom functions as a linking group for the poly (N-acylalkylenimine) segment. Examples of the alkylene group include C2-C20 alkylene groups containing 1 to 3 nitrogen atoms, oxygen atoms or sulfur atoms, and are represented by any of the following formulas (i) to (vii). And a group represented by the following formula (i) or (ii) is more preferable. In the formula, An ⁻ represents a counter ion of a quaternary ammonium salt, for example, ethyl sulfate ion, methyl sulfate ion, chloride ion, iodide ion, sulfate ion, p-toluenesulfonate ion, perchlorate ion. Is exemplified.

Examples of the alkyl group having 1 to 22 carbon atoms represented by R ¹² in the general formula (3) include linear, branched or cyclic alkyl groups having 1 to 22 carbon atoms, specifically, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Octadecyl group, nonadecyl group, eicosyl group, docosyl group and the like. Among these, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms, and specific examples include a benzyl group, a phenethyl group, a trityl group, a naphthylmethyl group, and an anthracenylmethyl group. Among them, an aralkyl group having 7 to 14 carbon atoms is preferable, and an aralkyl group having 7 to 10 carbon atoms is more preferable.
Examples of the aryl group include an aryl group having 6 to 14 carbon atoms, and specific examples include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group. An aryl group having 6 to 12 carbon atoms is preferred, and an aryl group having 6 to 9 carbon atoms is more preferred.
Among these, as R < ¹² >, a C1-C6 alkyl group is especially preferable.

  The mass ratio (a / b) of the organopolysiloxane segment (a) to the poly (N-acylalkylenimine) segment (b) is 65/35 to 82/18, but it breaks even at an elongation of 300% or more. Preferably from 68/32 to 80 / from the viewpoint of both plasticity deformation and ensuring sufficient film strength, and improvement of both styling properties of setability and sustainability when used as a hair cosmetic described below. 20, more preferably 70/30 to 79/21.

In the present specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of the present invention in deuterated chloroform and analyzing it by nuclear magnetic resonance ( ¹ H-NMR) analysis. The value calculated | required from the integral ratio of the alkyl group of this, or a phenyl group, and the methylene group in a poly (N-acyl alkylene imine) segment.

  Moreover, the weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is preferably 1,500 to 3,500, which gives the hair cohesiveness after hair styling and the flexibility to the hair. From the viewpoint, it is preferably 1,600 to 3,200, more preferably 1,700 to 3,000.

In this specification, “an organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments” means an organopolysiloxane of a poly (N-acylalkyleneimine) segment as shown in the following formula (4): A portion surrounded by a broken line between two points from a bonding point (bonding point α) to a segment to a bonding point (bonding point β) of a poly (N-acylalkyleneimine) segment adjacent thereto. A segment composed of an R ¹³ SiO unit, one R ¹⁷ and y ² +1 R ¹³ ₂ SiO units. The “poly (N-acylalkylenimine) segment” refers to W ² bonded to R ¹⁷ .

In the general formula (4), each R ¹³ independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group, R ¹⁷ represents an alkylene group containing a hetero atom, and W ² represents a poly (N-acylalkyleneimine). ) Segment, R ¹⁸ represents the residue of the polymerization initiator, and y ² represents a positive number.

  MWg is the molecular weight of the part surrounded by the broken line in the above general formula (4), but is understood as the mass (g / mol) of the organopolysiloxane segment per mole of the poly (N-acylalkylenimine) segment. When the functional group of the modified organopolysiloxane, which is a raw material compound, is 100% substituted with poly (N-acylalkyleneimine), it matches the functional group equivalent (g / mol) of the modified organopolysiloxane.

  The molecular weight (MWox) of the poly (N-acylalkylenimine) segment can be measured by a method of calculating from the molecular weight of N-acylalkyleneimine units and the degree of polymerization, or by a gel permeation chromatography (GPC) measurement method described later. Although it is possible, in the present invention, it means the number average molecular weight measured by the GPC measurement method, preferably 500 to 1,600, more preferably 6,000 to 1,500, and still more preferably 700 to 1,400. Thereby, the cohesiveness of the hair after hair shaping and the softness | flexibility to hair can be provided.

  MWg can be obtained by the following formula (I) using the content (Csi) of the organopolysiloxane segment constituting the main chain.

  The weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is 10,000 to 100,000, but preferably from 20,000 to 80,000 from the viewpoint of imparting hair coherence after hair styling and flexibility to the hair. More preferably, it is 30,000-60,000. Since MWsi has a common skeleton with the modified organopolysiloxane that is the raw material compound, MWsi is substantially the same as the weight average molecular weight of the modified organopolysiloxane that is the raw material compound. The average molecular weight of the modified organopolysiloxane that is a raw material compound is measured by GPC under the following measurement conditions and is converted to polystyrene.

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

  The weight average molecular weight (MWt) of the component (D) organopolysiloxane is preferably 12,000 to 150,000, more preferably 24,000 to 120,000, and even more preferably 37,000 to 92,000. Thereby, the cohesiveness of the hair after hair shaping and the softness | flexibility to hair can be provided. In the present specification, MWt can be determined from the weight average molecular weight of the modified organopolysiloxane that is a raw material compound and the above-mentioned mass ratio (a / b).

  The organopolysiloxane of component (D) can be produced by a known method, and can be obtained, for example, according to the method described in JP-A-2009-24114. For example, the following general formula (5):

(In the formula, R ¹³ is as defined above, and R ¹⁴ and R ¹⁵ each represent the same group as R ¹³ , or the following formulas (viii) to (xiii);

R ¹⁶ represents a monovalent group represented by the above formulas (viii) to (xiii), f represents an integer of 135 to 1350, and g represents 3 Represents an integer of ~ 57. Modified organopolysiloxane represented by the following general formula (6);

(In the formula, R ¹² and n are as defined above.)
It is produced by reacting a terminal reactive poly (N-acylalkyleneimine) obtained by ring-opening polymerization of a cyclic imino ether represented by the formula:

The modified organopolysiloxane represented by the general formula (5) preferably has a functional group equivalent of 1,700 to 3,500, more preferably 1,800 to 3,200, still more preferably 2,000 to 3,000, and a weight average molecular weight of preferably 10,000. It is desirable to use those that are ˜100,000, more preferably 20,000 to 80,000, still more preferably 30,000 to 60,000.
The terminal reactive poly (N-acylalkylenimine) is preferably adjusted to have a molecular weight of 800 to 1,600, more preferably 850 to 1,500, and still more preferably 900 to 1,400.

  In the organopolysiloxane of component (D), at least two silicon atoms of the organopolysiloxane segment having a predetermined molecular weight have poly (N-acylalkylenimine) segments at predetermined intervals via an alkylene group containing a hetero atom, In addition, it has a unique structure combined at a predetermined ratio. Thereby, the cohesiveness of the hair after hair shaping and the softness | flexibility to hair can be provided.

  Examples of the component (D) organopolysiloxane include poly (N-formylethyleneimine) organosiloxane, poly (N-acetylethyleneimine) organosiloxane, and poly (N-propionylethyleneimine) organosiloxane.

  The organopolysiloxane of component (D) can be used alone or in combination of two or more. The content of the component (D) in the hair styling composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass, from the viewpoint of imparting hair cohesiveness after hair styling and flexibility to the hair. % Or more, more preferably 0.2% by mass or more, preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.6% by mass or less.

[Component (E): Nonionic surfactant]
The hairdressing composition of the present invention can further contain a nonionic surfactant as component (E). As the nonionic surfactant of component (E), 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, Examples include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, alkyl saccharide, alkylamine oxide, and alkylamidoamine oxide. Of these, polyoxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil, and alkyl saccharide are preferred, and polyoxyethylene alkyl (12-14) ether and alkyl polyglucoside are more preferred.

  The nonionic surfactant of a component (E) can be used individually or in combination of 2 or more types. The content of the component (E) in the hairdressing composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass, from the viewpoint of imparting hair cohesiveness after hairdressing and flexibility to the hair. % Or more, more preferably 0.2% by mass or more, preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.6% by mass or less.

〔solvent〕
The hairdressing composition of the present invention preferably further contains ethanol and / or water as a solvent. The content of the solvent in the hairdressing composition of the present invention is preferably 4% by mass or more, more preferably 30% by mass or more, from the viewpoint of improving the solubility of the polymer or plasticizer contained in the composition. It is preferably 50% by mass or more, preferably 99% by mass or less, more preferably 98% by mass or less, and still more preferably 95% by mass or less.

[Other optional ingredients]
In addition to the above-described components, the hair styling composition of the present invention may contain components used in normal hair cosmetics depending on the purpose. Examples of such components include polyhydric alcohols (dipropylene glycol, glycerin, polypropylene glycol, sorbitol, etc.) that are liquid at room temperature, organic solvents other than ethanol (aromatic alcohols, etc.), antidandruff agents, vitamin agents, bactericides Agents, anti-inflammatory agents, chelating agents, humectants (such as panthenol), pH adjusters, colorants such as dyes and pigments, plant extracts, pearling agents, fragrances, ultraviolet absorbers, antioxidants and the like.

[Viscosity, dosage form]
The form of the hairdressing composition of the present invention can be appropriately selected from foam, liquid, mist, gel, paste, cream, etc. From the viewpoint of achieving uniform application to the hair, the mist is preferred. . Moreover, hard set agents such as set sprays and set foams, and soft set agents such as set lotions, set gels and blow agents are preferred. The hairdressing composition of the present invention can be used in a jar, a pump dispenser, an aerosol can, a pump mist, a trigger mist, or a non-aerosol foamer container (for example, a pump former or a squeeze foamer). Among these, it is preferable to use in a pump mist container or a trigger mist container.

  Since the hairdressing composition of the present invention can be filled in various containers, it can be suitably used in a wide viscosity range of 1 to 50,000 mPa · s. When used in a pump-type container (pump dispenser), the viscosity is preferably relatively low. The viscosity is preferably 1 mPa · s or more, and preferably 20,000 mPa · s or less. It is preferably 10,000 mPa · s or less, more preferably 10,000 mPa · s or less, more preferably 100 mPa · s or less, and still more preferably 50 mPa · s or less.

  The viscosity here is the B-type viscometer TVB-10M (Toki Sangyo Co., Ltd.) up to 20,000 mPa · s, and the B-type viscometer when the composition exceeds 20,000 mPa · s. TVB-10R (Toki Sangyo Co., Ltd.) and T-BAR STAGE TS-10 (Toki Sangyo Co., Ltd.) are used together, and measured using the following rotors and rotational speeds under the conditions after 60 seconds of rotation at 30 ° C. And The number of revolutions is 30 rpm for viscosities up to 10 mPa · s, 60 rpm for over 10 mPa · s to 20 mPa · s, 30 rpm for over 20 mPa · s to 20,000 mPa · s, and 5 rpm for over 20,000 mPa · s. The rotor is L / Adp when the viscosity of the composition is up to 10 mPa ・ s, M1 up to over 200 mPa ・ s, up to 200 mPa ・ s, M2 up to over 1,000 mPa ・ s, and 1,000 mPa ・ s.・ M3 for s over 4,000 mPa ・ s, M4 for over 4,000 mPa ・ s over 20,000 mPa ・ s, TB for over 20,000 mPa ・ s up to 160,000 mPa ・ s, TC for over 160,000 mPa ・ s Is used.

[Hair shaping method]
The hairdressing composition of the present invention can be suitably used for both wet hair and dry hair, and is particularly suitable for blow styling. The hair styling method using the hair styling composition of the present invention may be operated in the same manner as normal blow styling. After applying the hair styling composition to the hair, an appropriate amount of hair bundle is taken from the hair, and a hair dryer There is a method in which the operation of stretching the hair in the length direction of the hair bundle is performed over a predetermined time using a hairstyling tool such as a comb or a brush while applying hot air.

  More specifically, the width of the hair bundle taken from the hair is preferably 1 to 10 cm, more preferably 2 to 8 cm, and further preferably 2 to 5 cm, which allows appropriate tension to be applied to the hair. The temperature of the warm air of the dryer is preferably 50 to 130 ° C, more preferably 60 to 120 ° C. As a hair styling tool used to stretch the hair bundle in the direction from the root to the tip of the hair, in addition to combs and brushes, it is also possible to use a drier that can attach a brush attachment to the air vent. This operation takes 2 to 20 seconds from the viewpoint of obtaining sufficient hair-styling effect by applying sufficient heat to the hair and drying it, and preventing excessive damage to the hair due to fatigue of the arm and heat. It is necessary to carry out, and it is preferable to take a time of 3 to 18 seconds, more preferably 5 to 15 seconds.

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

Synthesis Example 1 Synthesis of organopolysiloxane graft polymer (polysilicone-28; polymer of component (A))
(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 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 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 synthesized in (1) above, 2,2′-azobis (2,4-dimethylvaleronitrile) “V-65B” (Wako Pure Chemical Industries, Ltd.) Manufactured, azo polymerization initiator) 0.03 g and ethanol 43.0 g mixed solution.

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 an organopolysiloxane graft polymer as a white solid. When the residual ratio of the sulfanyl group was measured by the above method, it was 3%.
When 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 after completion of the reaction was measured according to the above method for the obtained mixture. 29% by 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).
The weight average molecular weight of the organopolysiloxane graft polymer was 63,000. 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

Synthesis Example 2: Synthesis of N-propionylpolyethyleneimine / methylpolysiloxane copolymer A (polymer of component (D)) Polysilicone-9 was synthesized according to Synthesis Example 1 of JP 2013-023465 A. In the obtained organopolysiloxane, the molecular weight (MWox) of the poly (N-propionylethyleneimine) segment was 800, and the weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain was 50,000. Further, the content of the silicone segment in the final product was 75% by mass, and the weight average molecular weight was 67,000. The organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments was calculated to be 2,500.

Synthesis Example 3 Synthesis of N-propionylpolyethyleneimine / methylpolysiloxane copolymer B (polymer of component (D)) Polysilicone-9 was synthesized according to Synthesis Example 4 of JP-A-2013-023465. The obtained organopolysiloxane had a molecular weight (MWox) of 1,300 with the poly (N-propionylethyleneimine) segment and a weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain of 32,000. Further, the content of the organopolysiloxane segment of the final product was 71% by mass, and the weight average molecular weight was 46000. The organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments was calculated to be 2,500.

Examples 1-10, Comparative Examples 1-5
A hair styling composition shown in Tables 1 to 3 was prepared, and a performance evaluation was performed according to the following method and standard using a mist container (Yoshino Kogyo Co., Ltd., pump dispenser: YSR chip: 0.3J) filled with the hair styling composition. went.
For performance evaluation, a hair bundle of 30cm and weight of 3.0g was made using Wavy hair with Chinese color processing history, washed with Kao's success medicated shampoo h, and towel dried. Then, what was naturally dried at room temperature under normal humidity for 6 hours was used as a hair bundle for evaluation.
In Tables 1 to 3, Examples 1, 4, and 6 to 10 are reference examples and are not included in the scope of claims.

<Swelling correction after hair styling>
A hair styling composition 0.3 g was uniformly applied to the evaluation hair bundle using a pump mist, and then brush blow was performed once from the root to the hair tip using a commercially available round brush. The time for passing the brush from the root to the hair tip was 7 seconds (assuming a rough brush blow) or 15 seconds (assuming a careful brush blow). The correction power of the hair swell after the treatment was visually confirmed. The evaluation was made by selecting whether “swelling is stretching” / “not being able to say” / “swelling is not stretching” when 7 panelists treated each composition by the above operation. I was selected.

<A collection of hair tips after hair styling>
Evaluation was performed by visually observing the state of the unity of the hair ends after the same treatment as in the evaluation of <swelling correction force after hair styling>. In the evaluation, seven panelists were allowed to select one of “the hair ends were gathered” / “neither” or “the hair tips were not gathered”.

<Shape persistence under high humidity after finishing>
In the evaluation of <swelling correction power after hair styling>, the hair bundle treated under the same conditions as when brush blowing was set for 15 seconds to pass the brush from the root to the tip of the hair in a thermostatic bath at 25 ° C and 90% RH After standing for 15 minutes, the hair bundle shape was observed. In the evaluation, seven panelists were allowed to select either “hair shape persists” / “neither” or “hair shape did not persist”.

<Ease of applying tension when styling hair>
When assessing <swelling correction power after hair styling>, seven panelists were given the ease of applying tension to the hair bundle during brush blowing with a brush passing time from the root to the hair tip of 15 seconds. The selection was made as to whether “the tension is not applied”, “the tension is applied moderately”, or “the tension is too strong”.

<Smoothness of hair bundle after hair styling>
For the smoothness of the hair bundle after the treatment of swell correction after hair styling, 7 panelists choose whether it is “smooth” / “neither” or “not smooth” I was selected.

Formulation Example 1
(mass%)
Ethanol 19.8
Polysilicone of Synthesis Example 1-28 1.2
Malic acid 0.05
N-propionylpolyethyleneimine / methylpolysiloxane copolymer A of Synthesis Example 2 0.76
Steartrimonium chloride 0.28
PEG-400 0.2
PEG-60 hydrogenated castor oil 0.2
(C12-14) S-Palace-2 0.2
Lactic acid 0.1708
Amodimethicone 0.1612
Dipropylene glycol 0.1
Benzyl alcohol 0.1
PEG-32 0.05
CETEARETH-7 0.0324
CETEARETH-25 0.0064
Perfume 0.07
Water remaining

Claims (6)

A hairdresser composition comprising components (A) and (B), wherein the mass ratio (A) / (B) of component (A) to component (B) is from 0.1 to 15.
(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) a polyhydric alcohol component comprising a paste-like polyhydric alcohol and a solid polyhydric alcohol   The hair styling composition according to claim 1, wherein the content of component (A) is 0.01% by mass or more and 10% by mass or less.   The hairdressing composition according to claim 1 or 2, wherein the content of the component (B) is 0.01% by mass or more and 7% by mass or less. The pasty polyhydric alcohol is one or more selected from polyethylene glycol having a number average molecular weight of 1,000 to 3,000 and polyethylene polypropylene glycol having a number average molecular weight of 3,000 to 9,000, and the solid polyhydric alcohol is The hairdressing composition according to any one of claims 1 to 3, which is one or more selected from polyethylene glycol having a number average molecular weight of 3,000 to 10,000,000 and polyethylene polypropylene glycol having a number average molecular weight of 9,000 to 10,000,000. Furthermore, the hairdressing composition in any one of Claims 1-4 containing the following components (C).
(C) Cationic surfactant Furthermore, the hairdressing composition in any one of Claims 1-5 containing the following components (D).
(D) At least two silicon atoms of the organopolysiloxane segment constituting the main chain, via an alkylene group containing a hetero atom, the following general formula (3);

[Wherein, R ¹² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aralkyl group or an aryl group, and n represents 2 or 3. ]
An organopolysiloxane formed by bonding poly (N-acylalkyleneimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 1600, and the mass ratio of the organopolysiloxane segment (a) constituting the main chain to the poly (N-acylalkylenimine) segment (b) (A / b) is 65/35 to 82/18,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 10,000 to 100,000,
Organopolysiloxane