JP6903492B2 - Hair styling composition - Google Patents

Description

The present invention relates to a hair styling composition.

In hair styling products, in general, in order to increase the set holding power of the hairstyle, the amount of the adhesive polymer or the setting polymer forming a strong film is increased.

A hair styling agent containing a large amount of a film-forming polymer adheres the hairs to each other to form a hairstyle and fixes the hairs to each other to give the hairstyle a durability. However, on the other hand, there are problems that the hair becomes stiff due to being fixed, and that the formation of a thick bundle results in an unnatural finish without movement. On the other hand, many women prefer a natural and dynamic finish, both in terms of feel and finish. Therefore, in addition to fixing and maintaining the hair in the desired shape, it is also necessary to keep the hair in a natural finish without making it stiff.

In response to such a requirement, in Patent Document 1, hair having a specific organopolysiloxane graft polymer dispersed in water, which has the ability to set hair, the retention of hair shape after setting, and the soft feel after setting. Cosmetics are disclosed.

Japanese Unexamined Patent Publication No. 2014-77112

On the other hand, hairstyles that make use of wave perms and hairstyles that make use of the original curly hair have not only been firmly curled in recent years, but also have a soft touch and a three-dimensional effect with clear ridges and shadows. There is a growing demand for a certain style, a style with movements with the tips of the hair pointing in random directions, and a style that lasts for a long time.

However, with the hair cosmetics described in Patent Document 1, although curls can be firmly attached to give a natural feel, a three-dimensional effect with clear ridges and shadows and movement of hair tips in random directions I couldn't finish it in a certain style. Furthermore, there is a problem that the set collapses due to physical stimulation in daily life activities, and the sustainability of the created wave style is inferior.

Therefore, according to the present invention, it is possible to create a wave style in which the finish is soft and natural, but the curls are firmly attached, the ridges and shadows are clearly attached, and the hair tips are oriented in random directions. It relates to a hair styling cosmetic that can be used and has excellent durability against physical irritation after hair styling.

The present inventor has found that a hair styling composition satisfying the above requirements can be obtained by using the organopolysiloxane graft polymer described in Patent Document 1 in combination with a film-forming polymer and a surfactant in a specific ratio. ..

The present invention contains the following components (A), (B) and (C), and the mass ratio (A) / (B) of the component (A) to the component (B) is 1 or more and 100 or less, and the component ( Provided is a hair styling composition in which the total mass ratio [(A) + (B)] / (C) of the components (A) and (B) to C) is 1.30 or more and 30 or less.
(A) An organopolysiloxane graft polymer having an organopolysiloxane segment as a main chain and a polymer segment derived from an unsaturated monomer as a side chain, and N, N-dimethylacrylamide in the polymer segment. Organopolysiloxane graft polymer containing 50% by mass or more and 100% by mass or less of the derived repeating unit, and the ratio of organopolysiloxane segments in the whole is 10% by mass or more and 70% by mass or less.
(B) Non-crosslinked film-forming polymer without organosiloxane segment skeleton
(C) Surfactant

The hair styling composition of the present invention has a soft and natural finish, yet has a firm curl, a three-dimensional effect with clear ridges and shadows, and a wave style in which the tips of the hair move in random directions. It can be finished to the hair and has excellent durability against physical stimulation after hair styling.

[Component (A): Specific organopolysiloxane graft polymer]
Component (A) is an organopolysiloxane graft polymer having an organopolysiloxane segment as a main chain and a polymer segment derived from an unsaturated monomer as a side chain, and a weight derived from this unsaturated monomer. The coalesced segment contains 50% by mass or more and 100% by mass or less of repeating units derived from N, N-dimethylacrylamide (hereinafter, also referred to as "DMAAm"), and the ratio of the organopolysiloxane segment in the whole is 10% by mass or more and 70% by mass%. The following polymers. Ingredient (A) is a polymer with the INCI name of "Polysilicone-28".

In the graft polymer of component (A), from the viewpoint of firmly curling, two or more side chains are attached to any silicon atom of the organopolysiloxane segment constituting the main chain 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. It is more preferable to do so.

<Organopolysiloxane segment>
The graft polymer of component (A) has an organopolysiloxane segment as the main chain. The chemical structure of the organopolysiloxane segment is not particularly limited, but a preferred specific example thereof includes a modified organopolysiloxane segment represented by the following general formula (1) or (2).

In the general formulas (1) and (2), R ¹ independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ² contains a heteroatom. Represents a good alkylene group. p represents a number of 2 or more and 4000 or less, and q represents a number of 2 or more and 250 or less. In the formula, the combination mode of p repeating units and q repeating units may be such that the repeating units are connected in a block shape or in a random shape.

In the general formulas (1) and (2), ^{examples of the alkyl group represented by R 1} include a linear, branched chain, or cyclic alkyl group, and the number of carbon atoms of the alkyl group represented by ^{R 1 is} From the viewpoint of water dispersibility of the component (A), it is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. Specific examples of the alkyl group represented by R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group and heptyl. Examples thereof include a group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an octadecyl group, a nonadecil group, an eikosyl group and a docosyl group. The water dispersibility of the component (A) is a property that the component (A) can be stably dispersed in a composition containing water as a main component. If this property is good, the component (A) can be stably blended with the hair cosmetics using water as the main solvent, the curl can be firmly attached to the hair, and the hair washability is also good. preferable.

The ^{number of carbon atoms of the aryl group represented by R 1} is preferably 6 or more and 12 or less, and more preferably 6 or more and 9 or less, from the viewpoint of improving the water dispersibility of the component (A). Specific examples of the aryl group represented by R ¹ include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group and the like.

Among these, ^{as R 1} , a linear or branched alkyl group having 1 to 6 carbon atoms is preferable from the viewpoint of improving the water dispersibility of the component (A), and the linear chain or a branched chain having 1 to 3 carbon atoms is preferable. The alkyl group of the branched chain is more preferable, and the methyl group is further preferable.

In the general formulas (1) and (2), p is preferably used from the viewpoint of firmly applying curls and improving the feel (reducing stickiness) of the hair after setting the hair with the hair styling composition of the present invention. The number is 50 or more, more preferably 80 or more, still more preferably 100 or more, and from the viewpoint of improving the water dispersibility of the component (A), it is preferably 2000 or less, more preferably 1300 or less, still more preferably 700. The numbers are as follows.

In the general formulas (1) and (2), q is preferably 3 or more, more preferably 5 or more, from the viewpoint of improving the water dispersibility of the component (A), and is the hair styling composition of the present invention. From the viewpoint of improving the setting force (force to firmly attach the curl) and the durability of the hair shape after setting, the number is preferably 50 or less, more preferably 30 or less.

In the general formulas (1) and (2), ^{a part or all of the alkylene group (R 2} ) which may contain a hetero atom is an organopolysiloxane segment which is a main chain and an unsaturated monomer which is a side chain. It binds to the derived polymer segment and functions as a linking group for both segments. When some of the alkylene groups, which may contain heteroatoms, are not attached to the polymer segment derived from the unsaturated monomer, such groups are attached to the main chain and hydrogen atoms.

The carbon number of the alkylene group which may contain a hetero atom is preferably 2 or more, more preferably 3 or more, and the number of carbon atoms of the component (A) is preferably 2 or more, more preferably 3 or more, from the viewpoint of availability of the raw material for producing the component (A). From the viewpoint of improving water dispersibility, it is preferably 20 or less, more preferably 10 or less, still more preferably 8 or less.

The alkylene group, which may contain a heteroatom, is separated by one or more atoms or functional groups selected from oxygen atom, sulfur atom, -NH-, -COO-, -NHCO-, and -NR ^{3 CO-.} You may be. Here, R ³ is an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms. That is, the alkylene group which may contain a hetero atom may have a structure of "-(alkylene group portion 1)-(the above atom or functional group)-(alkylene group portion 2)-", in this case. , The carbon number of the alkylene group means the sum of the carbon number of the alkylene group portion 1 and the carbon number of the alkylene group portion 2. When the alkylene group which may contain a hetero atom is partitioned by the above-mentioned atom or functional group, it is preferably partitioned by −NHCO− from the viewpoint of ease of production of the component (A).

The alkylene group which may contain a hetero atom is a hydroxyl group, an amino group, an alkyl (1 or more and 3 or less carbon atoms) amino group, a dialkyl (1 or more and 3 or less carbon atoms) amino group, an amino group and 2 or more and 4 or less carbon atoms. One or more monovalent groups selected from an amide group, a carboxy group, and an alkyl (carbon number 1 or more and 3 or less) ester group obtained by dehydration condensation of the above 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 the substituent. From the viewpoint of availability of the raw material for producing the component (A), the alkylene group which may contain a heteroatom is one selected from an acetamido group, an alkyl (carbon number 1 to 3) amino group, and an amino group. It is preferable that the above monovalent groups are substituted.

The alkylene group which may contain a heteroatom is a divalent heteroatom selected from -O-, -S-, -NH-, -NR ^30- , and -COO-, or a divalent heteroatom containing a heteroatom. The groups may be substituted. Here, R ³⁰ is an alkyl group (having 1 or more carbon atoms and 3 or less carbon atoms) in which the dimethylamino group may be substituted. The heteroatom or a divalent group containing a heteroatom is an unsaturated monomer when an alkylene group that may contain a heteroatom acts as a linking group with a polymer segment derived from an unsaturated monomer. It is bound to the polymer segment of origin. In other cases, it is bonded to a hydrogen atom. From the viewpoint of ease of production of the component (A), it is preferable that the alkylene group containing a hetero atom is substituted with —S−.

The alkylene group (R ² ), which may contain a hetero atom, is unsaturated mono-saturated via the hetero atom, preferably a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably a sulfur atom, from the viewpoint of firmly curling. It is preferably bonded to a polymer segment derived from a metric.

Therefore, the ^{"alkylene group which may contain a hetero atom" represented by R 2} is (i) an unsubstituted alkylene group, (ii) an oxygen atom, a sulfur atom, -NH-, -COO-, and -NHCO. An alkylene group partitioned by one or more atoms or functional groups selected from − and −NR ³ CO−, (iii) hydroxyl group, amino group, alkyl (1 to 3 carbon atoms) amino group, dialkyl (carbon number) 1 or more and 3 or less) One or more selected from an amide group, a carboxy group and an alkyl (1 or more and 3 or less) ester group obtained by dehydration condensation of an amino group and an amino group and a fatty acid having 2 or more and 4 or less carbon atoms. A divalent or divalent heteroatom selected from an alkylene group in which the monovalent group is substituted, (iv) -O-, -S-, ^{-NH-, -NR 30- and -COO-.} In addition to the alkylene group substituted with the above group, the alkylene group composed of the combination of (ii), (iii) and (iv) described above corresponds to this.

Specific examples of the alkylene group which may contain a hetero atom include the following formulas (i) to (xii). Among them, the following formulas (xi) and (xii) are preferable from the viewpoint of easiness in manufacturing the component (A).

In formulas (i) to (xii), * represents a site that binds to a silicon atom in the general formula (1) or (2), and ** binds to a polymer segment derived from an unsaturated monomer. Represents a part.

In formula (xii), X ¹ is one or more selected from -O-, -OCO-, -COO-, -CONH-, and -NHCO-, and from the viewpoint of ease of manufacture of component (A). , -CONH-, -NHCO- are preferable, and -NHCO- is more preferable.

Further, in the formula (xii), R ⁴ is a hydroxyl group, an amino group, an alkyl (carbon number 1 or more and 3 or less) amino group, a dialkyl (carbon number 1 or more and 3 or less) amino group, an amino group and a carbon number 2 or more and 4 or less. It is an alkylene group in which one or more monovalent groups selected from an amide group, a carboxy group and an alkyl (carbon number 1 or more and 3 or less) ester group obtained by dehydration condensation of the above fatty acids may be substituted. As the substituent, an acetamide group, an alkyl (carbon number 1 or more and 3 or less) amino group, and an amino group are preferable from the viewpoint of availability of a production raw material. The carbon number of the alkylene group represented by R ⁴ is preferably 2 or more, more preferably 3 or more, and the water dispersibility of the component (A) from the viewpoint of ease of production of the component (A). From the viewpoint of improving the above, it is preferably 10 or less, more preferably 6 or less.
Specific examples of R ⁴ include the following equations (xiii) to (xv).

Wherein (xiv), X ^- represents chloride, halide ions such as bromide ion, an acetate ion, an alkyl (having 1 to 3 carbon atoms) anion such as sulfate ion.

<Polymer segment derived from unsaturated monomer>
The graft polymer of the component (A) has a polymer segment derived from an unsaturated monomer as a side chain, and from the viewpoint of improving the water dispersibility of the component (A), the polymer segment derived from the unsaturated monomer The repeating unit derived from DMAAm is contained in an amount of 50% by mass or more, preferably 70% by mass or more, and more preferably 75% by mass or more. Further, from the viewpoint of improving the reduction of stickiness of the hair after setting the hair with the hair styling composition agent of the present invention, the ratio of the repeating unit derived from DMAAm in the polymer segment derived from the unsaturated monomer is 100% by mass or less. , Preferably 95% by mass or less, more preferably 90% by mass or less.

Here, the repeating unit derived from the unsaturated monomer means a repeating unit formed during the polymerization of the unsaturated monomer. Further, in the graft polymer of the component (A), the content of the repeating unit derived from DMAAm in the polymer segment derived from the unsaturated monomer can be measured by the NMR method.

In the polymer segment derived from the unsaturated monomer, the portion other than the repeating unit derived from DMAAm is composed of the repeating unit derived from the unsaturated monomer (excluding DMAAm) copolymerizable with DMAAm. Repeating units derived from unsaturated monomers copolymerizable with DMAAm include olefins, halogenated olefins, vinyl esters, (meth) acrylic acid esters, (meth) acrylamides (excluding DMAAm), etc. Repetitive units derived from saturated monomers can be mentioned. In the polymer segment derived from the unsaturated monomer, the portion other than the repeating unit derived from DMAAm may consist of a repeating unit derived from a single type of unsaturated monomer copolymerizable with DMAAm, or two types. It may consist of the repeating unit derived from the above unsaturated monomer.

Specific examples of olefins include ethylene, propylene, and isobutylene. Specific examples of the halogenated olefin include vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride. Specific examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl versatic acid and the like.

Specific examples of (meth) acrylic acid esters include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, isobutyl (meth) acrylic acid, n-butyl (meth) acrylic acid, and the like. Tert-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic (Meta) acrylic acid ester having an alkyl group having 1 to 16 carbon atoms such as cyclohexyl acid; (meth) having an alkyl group having 1 to 16 carbon atoms substituted with a hydroxyl group such as 2-hydroxyethyl (meth) acrylate. ) Acrylic acid ester; and (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polyethylene glycol monomethyl ether and the like.

Specific examples of (meth) acrylamides other than DMAAm include (meth) acrylamides such as acrylamide and methacrylamide; and N, N-dialkyl (meth) acrylamides such as N, N-diethyl (meth) acrylamide (however, DMAAm). (Excluding); N-alkyl (meth) acrylamides such as N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, and N-tert-octyl (meth) acrylamide; N-mono-substituted (meth) acrylamides having a carbonyl group on a substituent on a nitrogen atom such as diacetone (meth) acrylamide; an amino group on a substituent on a nitrogen atom such as N, N-dimethylaminopropyl (meth) acrylamide. N-mono-substituted (meth) acrylamides having a hydroxyl group; N-mono-substituted (meth) acrylamides having a hydroxyl group at a substituent on the nitrogen atom such as N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide Can be mentioned.

Among these, (meth) acrylamides and (meth) acrylic acid esters excluding DMAAm are preferable from the viewpoint of improving the setting ability of hair and the retention of hair shape after setting, and acrylamide, methacrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-hydroxyethyl (meth) ) Acrylamide, N-methylol (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, (meth) ) Tert-Butyl acrylate, 2-hydroxyethyl (meth) acrylate are more preferred, N-tert-butyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, diacetone (meth) acrylamide, (meth) acrylate. Methyl, ethyl (meth) acrylate, tert-butyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide are more preferred, N-tert-butyl (meth) acrylamide, N-hydroxyethyl (meth). Acrylamide, diacetone (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, and tert-butyl (meth) acrylate are more preferred, and N-tert-butyl (meth) acrylamide is even more preferred.

<Structure of organopolysiloxane graft polymer>
The ratio of the organopolysiloxane segment in the graft polymer of the component (A) is 10% by mass from the viewpoint of firmly curling and reducing the stickiness of the hair after setting the hair with the hair styling composition of the present invention. The above is preferably 20% by mass or more, more preferably 30% by mass or more, and from the viewpoint of improving the water dispersibility of the graft polymer of the present invention, it is 70% by mass or less, preferably 60% by mass. Hereinafter, it is more preferably 50% by mass or less. The content of the organopolysiloxane segment in component (A) can be measured by NMR.

Further, from the viewpoint of improving the water dispersibility of the component (A), firmly adhering the curl, and reducing the stickiness of the hair after setting the hair with the hair styling composition of the present invention, the organopolysiloxane segment ( The mass ratio (a / b) of a) to the polymer segment (b) derived from the unsaturated monomer is preferably 10/90 or more, more preferably 20/80 or more, still more preferably 30/70 or more. It is more preferably 35/65 or more, preferably 70/30 or less, more preferably 65/35 or less, still more preferably 60/40 or less.

In the present specification, the mass ratio (a / b) means that when the graft polymer of the component (A) is produced from the radical-reactive organopolysiloxane described later, "radical reactivity compounded at the time of production" is used. From "total mass of organopolysiloxane (c)" and "total mass of unsaturated monomer blended during production (d)", "unsaturated monomer not bonded to organopolysiloxane produced during production" It is considered to be the same as the ratio (c / (de)) to the value obtained by subtracting the "total mass (e)" of the derived polymer (formula (I) below).
a / b = c / (d-e) (I)

Further, the number average molecular weight (MNg) of the organopolysiloxane segment between the polymer segments derived from the adjacent unsaturated monomers (hereinafter, may be referred to as “intergraft point molecular weight”) is determined by the hair styling composition of the present invention. From the viewpoint of improving the setting force when the hair is set and the holding force of the hair shape after setting, the component is preferably 500 or more, more preferably 700 or more, further preferably 1000 or more, still more preferably 1500 or more. From the viewpoint of improving the water dispersibility of (A), it is preferably 10,000 or less, more preferably 5000 or less, still more preferably 3000 or less, still more preferably 2500 or less.

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

In the formula, R ¹ independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ² represents an alkylene group which may contain a heteroatom. -R ⁵ indicates a polymer segment derived from an unsaturated monomer, R ⁵ indicates a residue or a hydrogen atom of a polymerization initiator, and y indicates a positive number.

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

Further, the weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is determined from the viewpoint of improving the setting force when the hair is set by the hair styling composition of the present invention and the holding force of the hair shape after setting. It is preferably 3000 or more, more preferably 5000 or more, still more preferably 10,000 or more, still more preferably 15,000 or more. The MWsi is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 60,000 or less, still more preferably 50,000 or less, from the viewpoint of improving the water dispersibility of the component (A).

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

The weight average molecular weight (MWt) of the graft polymer of the component (A) is preferably 10,000 from the viewpoint of improving the setting force when the hair is set by the hair styling composition of the present invention and the holding force of the hair shape after setting. The above is more preferably 14,000 or more, further preferably 17,000 or more, still more preferably 30,000 or more, and from the viewpoint of improving the water dispersibility of the component (A), it is preferably 200,000 or less, more preferably 160,000 or less, still more preferably. It is 130,000 or less, more preferably 95,000 or less. Within the range, sufficient film strength can be secured, water dispersibility is improved, and the setting force and the holding force of the hair shape after setting are further improved without stickiness. can do. In the present specification, MWt is measured by GPC under the measurement conditions described in Examples and converted to polystyrene.

Further, when the graft polymer of the component (A) is produced from a radically reactive organopolysiloxane, the component (A) obtained by using the following formula (II) from the reciprocal of the MWra and the above-mentioned mass ratio (a / b). The calculated weight average molecular weight (MWtcalc) of is preferably 10,000 or more from the viewpoint of improving the setting force when the hair is set with the hair cosmetic containing the component (A) and the holding power of the hair shape after setting. , More preferably 14,000 or more, still more preferably 17,000 or more, still more preferably 30,000 or more, and from the viewpoint of improving the water dispersibility of the component (A), preferably 200,000 or less, more preferably 160,000 or less, still more preferably 130,000. Below, it is more preferably 95,000 or less.
MWtcalc = MWra × {1 + mass ratio (b / a)} (II)

<Manufacturing method of organopolysiloxane graft polymer>
The method for producing the graft polymer of the component (A) is not particularly limited. For example, (i) an organopolysiloxane having a reactive functional group and an unsaturated group having a functional group capable of reacting with the reactive functional group at the end. A graft-onto method (polymer reaction method) in which a polymer segment derived from a monomer is reacted, and (ii) a graft-from method in which an unsaturated monomer is radically polymerized in the presence of a radically reactive organopolysiloxane described later. And so on. Among these, from the viewpoint of reducing the load during production, (ii) the graft-from method in which an unsaturated monomer is radically polymerized in the presence of a radically reactive organopolysiloxane is preferable.
Hereinafter, a method for producing the graft polymer of the component (A) by the graft-from method will be described.

(Radical reactive organopolysiloxane)
The graft polymer of the component (A) can be produced by radical polymerization of an unsaturated monomer in the presence of a radically reactive organopolysiloxane represented by the following general formula (4) or (5).

In the formula, R ¹¹ independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ¹² is an alkyl group having a radically reactive functional group (hereinafter, “radical reaction”). Also referred to as "sexual group-containing alkyl group").

In the general formulas (4) and (5), ^{the preferred mode of R 11 is the same as the preferred mode of R 1 in} the general formulas (1) and (2). Further, p and q in the general formulas (4) and (5) are synonymous with p and q in the general formulas (1) and (2), respectively, and preferable modes are the general formulas (1) and (5), respectively. It is the same as the preferable mode of p and q in 2).

In the present invention, the radical-reactive functional group refers to a functional group capable of generating radicals, 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). Be done. Among these, a sulfanil group is preferable from the viewpoint of reactivity with unsaturated monomers and control of molecular weight.

In the general formulas (4) and (5), the ^{number of carbon atoms of the radical-reactive group-containing alkyl group represented by R 12} is preferably 2 or more, more preferably from the viewpoint of easy availability of the radical-reactive organopolysiloxane. Is 3 or more, and from the viewpoint of improving the water dispersibility of the component (A), it is preferably 20 or less, more preferably 10 or less, and further preferably 8 or less.

The carbon number of the radical-reactive group-containing alkyl group does not include the carbon number of the radical-reactive functional group even when the radical-reactive functional group has carbon, and the radical-reactive group-containing alkyl group contains carbon. Even when the above-mentioned monovalent group is substituted, the carbon number of the monovalent group is not included.

In the general formulas (4) and (5), the ^{radically reactive group-containing alkyl group represented by R 12} is a hydroxyl group, an amino group, an alkyl (1 or more and 3 or less carbon atoms) amino group, and a dialkyl (1 or more and 3 or less carbon atoms). ) 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 an amino group, an amino group and a fatty acid having 2 or more and 4 or less carbon atoms. May be replaced. Among these substituents, an acetamido group, an alkyl (carbon number 1 to 3) amino group, and an amino group are preferable from the viewpoint of availability of a raw material for producing a radically reactive organopolysiloxane.

In the general formulas (4) and (5), the ^{radical-reactive group-containing alkyl group represented by R 12} is derived from an oxygen atom, a sulfur atom, -NH-, -COO-, -NHCO-, and -NR ¹³ CO-. It may be partitioned by one or more atoms or functional groups of choice. Here, R ¹³ is an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms. When the radical-reactive group-containing alkyl group is partitioned by the above-mentioned atom or functional group, it is preferably partitioned by -NHCO- from the viewpoint of availability or ease of production of the radical-reactive organopolysiloxane. ..

Specific examples of the radical-reactive group-containing alkyl group in the present invention include the following formulas (xvi) to (xix), and among them, from the viewpoint of producing or easily obtaining a radical-reactive organopolysiloxane. The following formulas (xviii) and (xix) are preferable. ^{X 11} and R ^{14 in} formula (xix), ^{and their preferred modes, are similar to X 1} and R ^{4 in} formula (xii), respectively, and their preferred modes.

The weight average molecular weight (MWra) of the radically reactive organopolysiloxane is considered to be the same as the MWsi in the present invention, and thus its preferred mode is similar to that of the MWsi. In the present invention, MWra is measured by GPC under the measurement conditions described in Examples and converted to polystyrene.

The number of moles of radical-reactive functional groups present per unit mass of radical-reactive organopolysiloxane improves the setting force when the hair is set with the hair conditioning composition of the present invention and the holding power of the hair shape after setting. It is preferably 1/500 mol / g or less, more preferably 1/700 mol / g or less, still more preferably 1/1000 mol / g or less, and preferably 1 from the viewpoint of water dispersibility of the component (A). / 10,000 mol / g or more, more preferably 1/5000 mol / g or more, still more preferably 1/3000 mol / g or more.

The radical-reactive organopolysiloxane in which the radical-reactive group is a sulfanil group can also be obtained as a commercially available product, and examples thereof include "KF-2001" (manufactured by Shin-Etsu Chemical Co., Ltd.).

(Organopolysiloxane having a reactive functional group)
The radically reactive organopolysiloxane can also be obtained by reacting an organopolysiloxane having a reactive functional group represented by the following general formula (6) or (7) with a radical reactivity imparting agent. As the organopolysiloxane having the reactive functional groups represented by the general formulas (6) and (7), those having various structures are commercially available and are easily available.

In the formula, R ²¹ independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ²² is an alkyl group having a reactive functional group (hereinafter, “containing a reactive group”). Also referred to as an "alkyl group"). p and q are synonymous with p and q in the general formulas (4) and (5), respectively, and the preferred modes are the same as the preferred modes of p and q in the general formulas (4) and (5), respectively. is there. ^{Further, the preferred mode of R 21 in} the general formulas (6) and (7) is the same as the preferred mode ^{of R 11 in} the general formulas (4) and (5).

In the present invention, the reactive functional group refers to a hydroxyl group, an amino group, a carboxy group, or an epoxy group. The organopolysiloxane having a reactive functional group has one or more substituents selected from a hydroxyl group, an amino group, a carboxy group, and an epoxy group. 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.

In the general formulas (6) and (7), the ^{number of carbon atoms of the reactive group-containing alkyl group represented by R 22} is preferably 2 or more from the viewpoint of easy availability of an organopolysiloxane having a reactive functional group. It is more preferably 3 or more, and from the viewpoint of improving the water dispersibility of the component (A), it is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less.

Specific examples of the reactive group-containing alkyl group in the present invention include the following formulas (xx) to (xxvii), and from the viewpoint of availability, one or more selected from (xx) to (xxiii) is preferable, and the reaction From the viewpoint of sex, (xxiii) is more preferable.

The weight average molecular weight (MWsim) of the organopolysiloxane having a reactive functional group is preferable from the viewpoint of improving the setting force when the hair is set with the hair styling composition of the present invention and the holding force of the hair shape after setting. Is 3000 or more, more preferably 5000 or more, further preferably 10,000 or more, further preferably 15,000 or more, and from the viewpoint of water dispersibility of the component (A), preferably 200,000 or less, more preferably 100,000 or more. Below, it is more preferably 60,000 or less, still more preferably 50,000 or less. In the present invention, MWsim is measured by GPC under the measurement conditions described in Examples and converted to polystyrene.

The number of moles of the reactive functional group present per unit mass of the organopolysiloxane having the reactive functional group is the setting force when the hair is set by the hair conditioner composition of the present invention and the holding force of the hair shape after the setting. It is preferably 1/500 mol / g or less, more preferably 1/700 mol / g or less, still more preferably 1/1000 mol / g or less from the viewpoint of improving the water dispersibility of the component (A). Is 1/10000 mol / g or more, more preferably 1/5000 mol / g or more, still more preferably 1/3000 mol / g or more.

(Radical reactivity imparting agent)
In the present invention, the radical reactivity-imparting agent is an agent that reacts with a reactive functional group of an organopolysiloxane having a reactive functional group to add a radical reactive functional group to the organopolysiloxane having a reactive functional group. Say.

Examples of the radical reactivity-imparting agent include a radical reactive functional group in the molecule and a carboxy group, an ester group, an epoxy group, a hydroxyl group, and a hydroxyl group capable of reacting with the reactive functional group of the organopolysiloxane having the reactive functional group. A compound having one or more functional groups selected from lactones can be used, and when the reactive functional group of the organopolysiloxane having the reactive functional group is a hydroxyl group, an amino group, or an epoxy group, , Thiolactones which may have a substituent can be used.

The radical-reactive functional group of the radical-reactivity imparting agent and its preferred mode are the same as the radical-reactive functional group of the radical-reactive organopolysiloxane and its preferred mode. Among them, from the viewpoint of reactivity during polymerization, the radical reactivity-imparting agent preferably has a sulfanyl group (mercapto group) as a radical-reactive functional group, and for example, sulfanyl such as 3-mercaptopropionic acid. Examples thereof include compounds having a radical and a carboxy group in the molecule, lactones having a sulfanyl group such as γ-butyrolactone thiol, and the like. Examples of the thiolactone that may have a substituent include γ-thiobutyrolactone, N-acetyl-DL-homocysteine thiolactone, DL-homocysteine thiolactone hydrochloride and the like. Of these, as the radical reactivity-imparting agent, N-acetyl-DL-homocysteine thiolactone is preferable from the viewpoint of improving the reactivity with the reactive organopolysiloxane and the reactivity at the time of polymerization.

The amount of the radical reactivity-imparting agent used is preferably 0.8 equivalents or more, more preferably 0.9 equivalents or more, and more preferably 0.9 equivalents or more, with respect to the total amount of the reactive functional groups of the organopolysiloxane having the reactive functional groups. From the viewpoint of reducing the amount of unreacted radical reactivity-imparting agent after the reaction, 1.2 equivalents or less is preferable, and 1.1 equivalents or less is more preferable.

(Manufacture of radically reactive organopolysiloxane)
A solvent may be used in the reaction between the radical reactivity-imparting agent and the organopolysiloxane having a reactive functional group. Solvents include water, alcohols such as methanol, ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate; hydrocarbons such as hexane and cyclohexane; ethers such as diethyl ether and tetrahydrofuran. Kind: Aromatic compounds such as benzene and toluene; Halogenized hydrocarbons such as dichloromethane and chloroform. From the viewpoint of reducing the environmental load, it is preferable not to use a solvent.

The reaction temperature is preferably 70 ° C. or higher, more preferably 90 ° C. or higher from the viewpoint of improving reactivity, and preferably 200 ° C. or lower from the viewpoint of improving the chemical stability of the obtained radical-reactive polysiloxane, 150 ° C. or higher. More preferably, it is below ° C.

The reaction time is preferably 1 hour or more, more preferably 2 hours or more, and more preferably 10 hours or less, more preferably 5 hours or less, from the viewpoint of sufficiently advancing the reaction.

In the reaction, from the viewpoint of the reactivity of the obtained radical-reactive organopolysiloxane, the conversion rate of at least one of the reactive functional group of the organopolysiloxane having the reactive functional group and the radical reactivity-imparting agent is 80% or more. It is preferable to carry out until it becomes 90% or more, and it is more preferable to carry out until it becomes 90% or more.

The method for measuring the conversion rate differs depending on the reactive functional group of the organopolysiloxane having the reactive functional group used in the reaction and the radical reactivity imparting agent, but both can be measured by a known method. For example, when the reactive functional group of an organopolysiloxane having a reactive functional group is an amino group and the radical reactivity-imparting agent is a thiolactone, the conversion rate of the amino group is "Petite product total base value test method (Petroleum product total base value test method). Perchloric acid method) ”(JIS K2501), and the conversion rate of thiolactones can be determined using the liquid chromatograph method.

(Manufacture of organopolysiloxane graft polymer)
The method for polymerizing the unsaturated monomer in the presence of the radically reactive organopolysiloxane is not particularly limited, and a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or the like can be adopted. Among them, the solution polymerization method is used. preferable.

The amount of the unsaturated monomer used as a raw material is preferable with respect to the total amount of the radically reactive organopolysiloxane as a raw material and the unsaturated monomer as a raw material from the viewpoint of water dispersibility of the component (A). Is 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and from the viewpoint of reducing stickiness of the hair after setting the hair with the hair conditioner composition of the present invention, it is preferable. It is 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.

The content of DMAAm in the unsaturated monomer as a raw material is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 75% by mass or more, from the viewpoint of water dispersibility of the component (A). Further, from the viewpoint of firmly attaching curls and reducing the stickiness of the hair after setting the hair with the hair styling composition of the present invention, it is preferably 100% by mass or less, more preferably 95% by mass or less, and further. It is preferably 90% by mass or less.

When the content of DMAAm in the unsaturated monomer is not 100% by mass, the unsaturated monomer contains an unsaturated monomer copolymerizable with DMAAm (excluding DMAAm). Specific examples and preferred modes of the unsaturated monomer are the same as those of the unsaturated monomer copolymerizable with DMAAm described above and preferred modes thereof.

When the unsaturated monomer is polymerized by the solution polymerization method, the raw material radical-reactive organopolysiloxane, the unsaturated monomer, and the obtained component (A) are all dissolved or uniformly used as the solvent. There is no particular limitation as long as it is dispersed in.
Specific examples of the solvent include water, alcohols such as methanol, ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate; hydrocarbons such as hexane and cyclohexane; diethyl ether and tetrahydrofuran. Ethers such as; aromatic compounds such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform and the like. These can be used alone or in combination of two or more.

Among these, from the viewpoint of obtaining the component (A) having a more uniform side chain molecular weight distribution, alcohols having 1 to 8 carbon atoms such as water, ethanol and isopropanol, and alcohols having 2 or more carbon atoms such as ethyl acetate and butyl acetate have 2 or more carbon atoms. It is preferable to use one or more solvents selected from ethers having 8 or less carbon atoms, diethyl ethers, and ethers having 2 to 8 carbon atoms such as tetrahydrofuran, and the viewpoint of bringing the solvent into the hairdressing composition during the production of the graft polymer. Therefore, it is more preferable to use one or more selected from alcohols having 1 or more and 3 or less carbon atoms such as water and ethanol.

The amount of the solvent used is not particularly limited as long as all of the radical-reactive organopolysiloxane, the unsaturated monomer and the obtained organopolysiloxane graft polymer, which are the raw materials, are dissolved or uniformly dispersed, but the operation during production is not particularly limited. From the viewpoint of ease of use and productivity, the amount is preferably 20% by mass or more, more preferably 40% by mass or more, and more preferably 40% by mass or more, based on the total mass of the radical-reactive organopolysiloxane and the unsaturated monomer added at the time of production. It is preferably 60% by mass or more, more preferably 100% by mass or more, and from the viewpoint of reactivity, preferably 1000% by mass or less, more preferably 900% by mass or less, still more preferably 400% by mass or less, still more preferably. Is less than 300% by mass.

As the polymerization initiator, azo-based initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile); Oxide-based initiators; examples thereof include persulfate-based initiators such as ammonium persulfate. Further, the polymerization may be started 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 amount of the polymerization initiator used is not particularly limited, but is preferably 10% by mass or less with respect to the total mass of the unsaturated monomer to be added, from the viewpoint of the weight average molecular weight of the graft polymer of the obtained component (A). , More preferably 1% by mass or less, and from the viewpoint of reactivity, preferably 0.001% by mass or more, more preferably 0.01% by mass or more.

The temperature at the time of the polymerization reaction can be appropriately selected depending on the type of polymerization initiator and solvent used, but is preferably 50 ° C. or higher, more preferably 60 ° C. or higher from the viewpoint of the polymerization reaction rate. Further, the reaction is preferably carried out at normal pressure in order to reduce the equipment load used in the polymerization reaction, and the temperature during the polymerization reaction is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, from the viewpoint of reacting below the boiling point of the solvent. is there.

The polymerization reaction is preferably carried out until the conversion rate of the unsaturated monomer is 80% or more, and more preferably 90% or more. The upper limit of the conversion rate is 100%. The conversion rate of unsaturated monomers ^{can be determined by nuclear magnetic resonance (1} H-NMR) analysis. Specific operations will be described in Examples.

The polymerization reaction time is usually 0.1 hour or more and 60 hours or less, preferably 0.5 hours or more, more preferably 1 hour or more, still more preferably 2 hours or more, still more preferably 4 hours or more, from the viewpoint of operability. From the viewpoint of productivity, it is preferably 30 hours or less, more preferably 20 hours or less, still more preferably 10 hours or less. When the polymerization reaction is added over time such as dropping or dividing the raw material, the polymerization reaction time includes the time required for adding the raw material. The polymerization reaction time can be shortened by, for example, raising the polymerization reaction temperature, and can be changed according to the polymerization temperature.

The radical-reactive organopolysiloxane, unsaturated monomer, solvent, polymerization initiator, etc., which are the raw materials, may be added all at once to carry out the polymerization reaction, but in order to control the composition, the polymerization is carried out by dividing or dropping. The reaction may be carried out. For example, (1) a method in which a radically reactive organopolysiloxane, an unsaturated monomer, and a solvent are mixed and heated, and a solution in which an initiator is dissolved is added all at once or in a dropping form; (2) the solvent is heated. A method of dropping a solution in which a radical-reactive organopolysiloxane, an unsaturated monomer, and an initiator are separately or mixed and dissolved in a solvent; (3) Radical-reactive organopolysiloxane, unsaturated There is a method in which a part of the monomer and a solvent are mixed and heated, and a solution in which the initiator and the rest of the unsaturated monomer are dissolved is added all at once or in a dropping form.

Further, after the completion of the polymerization reaction, purification or reduction of unreacted unsaturated monomers may be carried out by a known method, if necessary. For example, unreacted unsaturated monomers and other impurities may be reduced by adding a polymerization initiator and heating, membrane purification, adsorbent treatment, or the like.

The graft polymer of the component (A) can be used alone or in combination of two or more. Among them, the above-mentioned organo for the polymer segment (b) derived from the unsaturated monomer is used from the viewpoint of creating a three-dimensional effect with clear ridges and shadows and a wave style in which the tips of the hair move in random directions. The mass ratio (a / b) of the polysiloxane segment (a) is 10/90 or more and 50/50 or less (hereinafter referred to as "component (A1)"), and 50/50 or more and 70/30 or less. It is preferable to contain both certain substances (hereinafter referred to as "component (A2)"). From the above viewpoint, the a / b of the component (A1) is preferably 20/80 or more, more preferably 30/70 or more, and preferably 48/52 or less, more preferably 46/54 or less. .. From the above viewpoint, the a / b of the component (A2) is preferably 52/48 or more, more preferably 54/46 or more, and preferably 60/40 or less, more preferably 58/42 or less. is there.

Further, from the same viewpoint, the mass ratio of the component (A2) to the component (A1) [(A2) / (A1)] is preferably 1/99 or more, more preferably 3/97 or more, still more preferably 4 /. It is 96 or more, more preferably 5/95 or more, preferably 98/2 or less, more preferably 70/30 or less, still more preferably 30/70 or less, still more preferably 15/85 or less.

The content of the graft polymer of the component (A) in the hair styling composition of the present invention is preferably 0.1% by mass or more, from the viewpoint of imparting excellent settability during hair styling and hair shape sustainability after hair styling. It is preferably 0.15% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and also provides excellent settability at the time of hair styling, imparting hair shape sustainability after hair styling, and a flexible finish. From the viewpoint of compatibility, it is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3.5% by mass or less, still more preferably 3.0% by mass or less.

When the hair styling composition is an aerosol-type hair styling composition, the content of the above component (A) is 100% by mass of the component (also referred to as undiluted solution) obtained by removing the propellant from the aerosol-type hair styling composition. The percentage of time. The same applies to the other components below.

[Component (B): Non-crosslinked film-forming polymer having no organosiloxane segment skeleton]
The non-crosslinked film-forming polymer of the component (B) used in the present invention does not have an organosiloxane segment skeleton, and is, for example, one or more selected from the following (b-1) and (b-2). Examples thereof include film-forming polymers containing structural units derived from monomers.
(b-1) Vinylpyrrolidone
(b-2) (Meta) acrylic acid or an ester or amide thereof The non-crosslinked film-forming polymer of the component (B) includes the structural unit derived from the above (b-1) and the above (b-2). Although those containing both of the structural units derived from them are also included, such film-forming polymers will be classified and described below as film-forming polymers containing the structural units derived from (b-1) for convenience.

(b-1) As a specific example of the film-forming polymer containing a structural unit derived from vinylpyrrolidone,
-As a cationic polymer, vinylpyrrolidone-N, N-dimethylaminoethyl methacrylate copolymer diethyl sulfate (INCI name Polyquaternium-11; Gaffcut 734, Gaffcut 755N, Gaffcut 755N-O (above, manufactured by ISP), etc.) , Vinylpyrrolidone, dimethylaminopropylmethacrylate, lauryldimethylaminopropylmethacrylate copolymer (INCI name: Polyquaternium-55; Stylase W-20 (ISP), etc.), N, N-dimethylaminoethyl methacrylate, diethylsulfate, etc. N, N-dimethylacrylamide / dimethacrylate polyethylene glycol copolymer (INCI name Polyquaternium-52; Sofcare KG-101W-E (manufactured by Kao)), (PVP / vinyl caprolactam / DMAPA acrylate) copolymer (Aquaflex SF) -40 (Ashland), etc.), (Vinylpyrrolidone / DMAPA acrylic acid) copolymer (Stylize CC-10 (Ashland), etc.), Vinyl imidazolium metachloride / vinylpyrrolidone copolymer (INCI name POLYQUATERNIUM- 16; Rubicut HM552 (BASF), etc.), Polypolypyrrolidone / dimethylaminoethyl methacrylate copolymer (Rubiflex (BASF), Copolymer 845, Copolymer 937, Copolymer 958 (Ashland), etc.) , Polyvinylpyrrolidone / dimethylaminoethyl methacrylate / vinyl caprolactam copolymer copolymer (VC-713 (manufactured by Ashland), etc.), etc.
-As nonionic polymers, polyvinylpyrrolidone (Rubiscol K17, Rubiscol K30, Rubiscol K90 (above, manufactured by BASF), etc.), vinylpyrrolidone-vinyl acetate copolymer (Rubiscol VA73E, Rubiscol VA73W, Rubiscol) 37E (above, manufactured by BASF), vinylpyrrolidone, methacrylicamide, vinylimidazole copolymer (rubisset clear (manufactured by BASF), etc.), polyvinylpyrrolidone / vinyl acetate / vinyl propionate ternary copolymer (rubis) Call VAP343 (manufactured by BASF), etc.).

Of these, vinylpyrrolidone / N, N-dimethylaminoethylmethacrylic acid copolymer diethylsulfate, vinylpyrrolidone / dimethylaminopropylmethacrylic acid / lauryldimethylaminopropylmethacrylic acid copolymer, N, N-dimethylaminoethylmethacrylic acid At least one selected from acid diethyl sulfate / N, N-dimethylacrylamide / dimethacrylic acid polyethylene glycol copolymer, polyvinylpyrrolidone, vinylpyrrolidone / vinylacetate copolymer) is preferable, and vinylpyrrolidone / N, N-dimethyl is preferable. Aminoethyl Methacrylic Acid Copolymer Diethyl Sulfate, Vinyl Pyrrolidone / Dimethylaminopropyl Methacrylic Acid / Lauryl Dimethylaminopropyl Methacrylic Acid Copolymer, N, N-Dimethylaminoethyl Methacrylic Acid Diethyl Sulfate / N, N-Dimethylacrylamide / At least one selected from the dimethacrylic acid polyethylene glycol copolymer and polyvinylpyrrolidone is more preferable.

(b-2) Specific examples of the film-forming polymer containing a structural unit derived from (meth) acrylic acid or an ester or amide thereof include
-As anionic polymers, acrylic resin alkanolamine solution (plus size L-53P, plus size L-9540B (above, manufactured by Mutual Chemical Industry Co., Ltd.), etc.), acrylic acid / acrylic acid ester copolymer (Diahold (Mitsubishi Chemical) , Etc.), Acrylic acid / Acrylic acid amide / Ethyl acrylate copolymer (Unformer V-42, Dermacryl 79 (above, made by Axonobel), Ultrahold 8, Ultrahold strong (above, BASF) (Manufactured by), etc.), Alkyl acrylate copolymer (Aniset NF-1000, Aniset HS-3000 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc.) Nobel Co., Ltd.), Acrylate Copolymer (Thiramar Fix A1000 (DSM), Rubimer 100P (BASF), etc.), (Acrylate / Hydroxyalkyl Acrylate) Copolymer (Accudyne 180 (Dow Chemical), etc.) ), (Acrylates / alkyl succinate (C1,2) / hydroxyalkyl acrylate) copolymers (Accudyne LT-120 (manufactured by Dow Chemical Co., Ltd.), etc.), etc.
-As nonionic polymers, (Acrylate / methoxymethacrylate PEG-23) copolymer (described in JP-A-2015-13842), (dimethylacrylamide / hydroxyethyl acrylate / methoxyethyl acrylate) copolymer (plus size L- 2700, plus size L-2714 (above, manufactured by GOO CHEMICAL CO., LTD.), Etc.
-As cationic polymers, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymer (INCI name Polyquaternium-99; plus size L-515 (manufactured by Reciprocal Chemical Industry Co., Ltd.), etc.), alkylacrylamide / alkylaminoalkyl Acrylamide / polyethylene glycol methacrylate copolymer (described in JP-A-8-291206) can be mentioned.
-As an amphoteric polymer, acrylates, lauryl acrylate, stearyl acrylate, ethylamine methacrylate copolymer (diaformer Z651 (manufactured by Mitsubishi Chemical Corporation), etc.), methacryloyloxyethylcarboxybetaine, alkyl methacrylate copolymer (Yukaformer) M75, Yukaformer R205 (above, manufactured by Mitsubishi Chemical Co., Ltd.), octylacrylamide, hydroxypropyl acrylate, butylaminoethyl methacrylate copolymer (unformer 28-4910, unformer SH30 (above, manufactured by Axonobel)) ) Etc.).

Of these, acrylates, lauryl acrylate, stearyl acrylate, ethylamine methacrylate copolymer, acrylic resin alkanolamine solution, (Acrylate / methoxyPEG-23 methacrylate) copolymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / At least one selected from the polyethylene glycol methacrylate copolymer is preferable.

The above component (B) can be used alone or in combination of two or more. Among them, it is more preferable to use two or more of the polymers listed as preferable in combination.

The content of the non-silicone non-crosslinked film-forming polymer of the component (B) in the hair conditioner composition of the present invention is preferably 0.01% by mass or more from the viewpoint of improving the setting force and the holding force of the hair shape after setting. , More preferably 0.02% by mass or more, further preferably 0.05% by mass or more, still more preferably 0.15% by mass or more, and from the viewpoint of reducing stickiness at the time of setting and improving flexibility after setting, it is preferable. It is 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less.

The hair styling composition of the present invention comprises a particular organopolysiloxane graft polymer and a particular film-forming polymer. By containing two kinds of such specific polymers and further containing a surfactant, the detailed reason is unknown, but the finish is soft and natural, but the curls are firmly attached, and the ridges and shadows are clear. It was found that a hair styling composition can be obtained with a three-dimensional wave style in which the tips of the hair are oriented in random directions, and the hair styling composition has excellent durability against physical stimulation after hair styling. ..

As a result of the examination, the mass ratio (A) / (B) of the component (A) to the component (B) is that the component (A) has a soft feel after setting and a three-dimensional effect with ridges and shadows clearly attached. From the viewpoint of achieving a certain finish, it is 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, and improving the holding power of the hair shape after setting. From the above viewpoint, it is 100 or less, preferably 90 or less, more preferably 70 or less, still more preferably 30 or less, still more preferably 15 or less.

[Component (C): Surfactant]
The hair styling composition of the present invention may contain a surfactant from the viewpoint of system stability including solvent solubilization, dispersibility, etc., and improvement of 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 a quaternary ammonium salt represented by the following general formula (8).

[In the formula, R and R'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 or a lower alkyl group having 1 to 3 carbon atoms or a combination thereof. Except when An ^- indicates an anion. ]

Here, it is preferable that one of R and R'is an alkyl group having 16 to 24 carbon atoms, further 22 carbon atoms, and further a linear alkyl group, and the other is a lower alkyl group having 1 to 3 carbon atoms, and further. Is preferably a methyl group.

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, saccharin ion and the like.

As the cationic surfactant, a monolong-chain alkyl quaternary ammonium salt is preferable, and specific examples thereof include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, and alkylbenzalkonium chloride. Among them, at least one selected from stearyltrimethylammonium chloride and behenyltrimethylammonium chloride is 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, and polyoxyethylene sorbitan fatty acid. Examples thereof include esters, polyoxyethylene sorbit fatty acid esters, alkyl saccharide-based surfactants, alkylamine oxides, and alkylamide amine oxides. Of these, at least one selected from polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil is preferable, and at least one selected from polyoxyethylene alkyl ether and polyoxyethylene / polyoxypropylene alkyl ether is preferable. ..

Examples of amphoteric tenside agents include imidazoline-based, carbobetaine-based, amide betaine-based, sulfobetaine-based, hydroxysulfobetaine-based, and amide sulfobetaine-based. Of these, betaine-based surfactants such as alkyldimethylaminoacetate betaine and fatty acid amide propyl betaine are preferable, and fatty acid amide propyl betaine is particularly preferable. The fatty acid amide propyl betaine preferably has an acyl group having 8 to 18 carbon atoms and 10 to 16 carbon atoms, and among them, lauric acid amide propyl betaine, palm kernel oil fatty acid amide propyl betaine, and palm oil fatty acid amide propyl betaine. At least one selected from the above is preferable.

Anionic surfactants include alkylbenzene 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 thereof include α-sulfon fatty acid salt, N-acylamino acid type surfactant, phosphoric acid mono or diester type surfactant, sulfosuccinic acid ester and the like. Examples of the counterion 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. Examples thereof include alkanolamines having 1 to 3 alkanolamines (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). Examples of the counterion of the cationic residue include halide ions such as chloride ion, bromide ion and iodide ion, metosulfate ion and saccharide ion.

Of these, at least one selected from cationic surfactants and nonionic surfactants is preferable from the viewpoint of improving the feel at the time of coating. The surfactant can be used alone or in combination of two or more, and the content in the hair styling composition of the present invention is from the viewpoint of improving the stability of the system including solubilization of the solvent and emulsification of the oil agent. Therefore, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass. It is as follows.

In addition, the total mass ratio of component (A) and (B) to component (C) [(A) + (B)] / (C) is easy to curl, and ridges and shadows are clearly attached. From the viewpoint of finishing the hair in a three-dimensional wave style with the tips pointing in random directions and improving the durability of the set, it is 1.30 or more, preferably 1.35 or more, more preferably 1.50 or more, and also. From the viewpoint of improving the flexibility of the hair after setting, it is 30 or less, preferably 20 or less, and more preferably 10 or less.

[Component (D): Silicone]
The hair styling composition of the present invention may further contain a silicone other than the component (A) as the component (D). Silicones include dimethylpolysiloxane, polyether-modified silicone, amino-modified silicone, carboxy-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, polyglycerin-modified silicone, fatty alcohol-modified silicone, epoxy-modified silicone, fluorine-modified silicone, and cyclic. Examples thereof include silicone and alkyl-modified silicone. Among them, at least one selected from dimethylpolysiloxane, polyether-modified silicone, and amino-modified silicone is preferable.

Upon application to hair, dimethylpolysiloxane can impart good lubricity to the hair, polyether-modified silicone can impart smoothness to the hair, and amino-modified silicone can moisturize the hair. A feeling can be given. In the present invention, various silicones can be used alone or in combination of two or more, depending on the required performance.

^{Didimethylpolysiloxane can be used from a viscosity of about 5 mm 2} / s depending on the desired feel to a viscosity of about 10 million mm ² / s, which is often supplied as an emulsion. The viscosity of dimethylpolysiloxane is preferably 1,000 mm ² / s or more, more preferably 10,000 mm ² / s or more, and preferably 5 million mm ² / s or less, more preferably 1 million mm ² / s or more. It is as follows.

The viscosity of the polyether-modified silicone is preferably 50 mm ² / s or more, more preferably 1000 mm ² / s or more, and preferably 500,000 mm ² / s or less, more preferably 100,000 mm ² / s or less. is there. The polyether-modified silicone may be any silicone having a polyoxyalkylene group, and examples of the group constituting the polyoxyalkylene group include an oxyethylene group and an oxypropylene group. Commercially available products include, for example, "KF-6015", "KF-945A", "KF-6005", "KF-6009", "KF-6013", "KF-6019", "KF-6029", " KF-6017 "," KF-6043 "," KF-353A "," KF-354A "," KF-355A "(all manufactured by Shin-Etsu Chemical Co., Ltd.)," FZ-2404 "," SS-2805 ", "FZ-2411", "FZ-2412", "SH3771M", "SH3772M", "SH3773M", "SH3775M", "SH3749", "SS-280X series", "BY22-008M", "BY11-030" , "BY25-337" (above, manufactured by Toray Dow Corning), etc.

Amino-modified silicones with an average molecular weight of about 3,000 or more and 100,000 or less are listed in the 16th edition of ICID (International Cosmetic Ingredient Dictionary and Handbook) under the name of Amodimethicone. preferable. This amino-modified silicone is preferably used as an aqueous emulsion, and commercially available products include "SM 8904", "CB-1002" (manufactured by Toray Dow Corning), and "XF42-B8922" (momentive performance materials). Z), etc.

These silicones can be contained 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 0.05% by mass or more, still more preferably, from the viewpoint of improving finger passage and non-stickiness. Is 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, still more preferably 2% by mass or less. ..

[Ingredient (E): Oil]
The hair styling composition of the present invention may further contain an oil agent as a component (E) in order to improve the cohesiveness of the hair after drying. Oil agents include hydrocarbons such as squalane, squalane, liquid isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, liquid paraffin, cycloparaffin, hydrogenated polyisobutene; castor oil, cacao oil, mink oil, avocado. Fatty acids such as oil and olive oil; waxes such as beeswax, whale wax, lanolin, microcrystallin wax, selecin wax and carnauba wax; higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol and 2-octyldodecanol. Kinds: Esters such as octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridecyl isononanoate; capric acid, laurate, myristin Higher fatty acids such as acids, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acids, lanolin fatty acids, isostearlic acid, isoparmitic acid; solid fats such as cholesterol, vaseline, cholesteryl isostearate, sphingolipid; In addition, jojoba oil, isostearyl glyceryl ether, polyoxypropylene butyl ether, bismethoxypropylamide isodocosan and the like can be mentioned. At least one selected from these is preferable.

The content of the oil agent in the hair styling composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, from the viewpoint of good cohesiveness and non-stickiness. It is more preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 2% by mass or less.

[Other optional ingredients]
Furthermore, fragrances and pigments can be added to the hair styling composition of the present invention in order to increase the commercial value, and preservatives and antioxidants can be added to prevent aging deterioration of the hair styling composition. Further, if necessary, a humidity control agent, a curing agent, an antistatic agent, a defoaming 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 (support medium), water, lower alcohol (ethanol, isopropanol, etc.), lactones, etc. can be used, and these can be used alone or in combination. Of these, water, ethanol, or a mixed system of water and ethanol is preferable from the viewpoint of versatility and ensuring the solubility and dispersibility of the hair styling composition. When water is contained in the solvent, the content of water in the hair styling composition is preferably 60% by mass or more, more preferably 65% by mass or more, and further preferably 70% by mass or more.

[Dosage form]
The dosage form of the hair styling composition of the present invention is not particularly limited, and can be a transparent liquid, a lotion, a milky liquid, a gel, a foam (aerosol, non-aerosol) or the like.

The hair styling composition of the present invention has an aerosol containing a propellant because it has a firm curl, clear ridges and shadows, and a three-dimensional wave style in which the tips of the hair are oriented in random directions. It is preferable to use a hair styling product as a hair styling product.

The propellant is not particularly limited as long as it is usually used for aerosol-type cosmetics, and is, for example, a lower saturated hydrocarbon such as propane, butane or a mixture thereof (including liquefied petroleum gas). Ethers such as dimethyl ether, nitrogen gas, carbon dioxide gas, hydrocarbon gas, and the like can be used. These can be used alone or in combination of two or more. The mass ratio of the stock solution to the propellant (stock solution / propellant) is preferably 10/90 or more, more preferably 40/60 or more, and preferably 99/1 or less, more preferably 90/10 or less. ..

Synthesis Example 1 Synthesis of Polysilicone-28 (polymer of component (A))
(1) Synthesis of radically reactive organopolysiloxane As an organopolysiloxane having a reactive functional group in a separable flask equipped with a reflux cooling tube, a thermometer, a nitrogen introduction tube, and a stirrer, a side chain primary aminopropyl-modified organopoly 100 g of siloxane (weight average molecular weight 30,000, number of moles 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. The temperature was raised to 100 ° C. under a nitrogen atmosphere, and the mixture was stirred for 3 hours to synthesize a radical-reactive organopolysiloxane A having a sulfanil 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). Base conversion rate 99%). Therefore, the number of moles of sulfanyl groups per unit mass of radically reactive organopolysiloxane is 1/2,210 mol / g. The weight average molecular weight of the radically 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 stirrer. While stirring ethanol under reflux at 80 ° C. under a nitrogen atmosphere, the following solutions (a) and solution (b) were placed in separate dropping funnels and simultaneously added dropwise over 1 hour.
Solution (a): A solution in which 76.8 g of N, N-dimethylacrylamide (DMAAm), 19.2 g of N-tert-butylacrylamide (tBuAAm), and 96.0 g of ethanol are mixed.
Solution (b): Radical-reactive organopolysiloxane A 64.0 g, 2,2'-azobis (2,4-dimethylvaleronitrile) "V-65B" (manufactured by Wako Pure Chemical Industries, Ltd.) synthesized in (1) above. , Azo-based polymerization initiator) 0.03 g, ethanol 43.0 g mixed solution.

After completion of the dropping, 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.) and under reduced pressure (20 kPa) for 4 hours to obtain a mixture containing the organopolysiloxane graft polymer B as a white solid. When the residual rate of the sulfanil group was measured by the method described later, it was 3%.
With respect to the obtained mixture, 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 completion of the reaction is measured according to the method described later. As a result, it was 29% by mass.
The mass ratio (a / b) of the organopolysiloxane segment (a) to the polymer segment (b) derived from the unsaturated monomer was calculated by the above formula (I) and found to be 56/44.

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

(Method for measuring the content of a polymer derived from an unsaturated monomer that is not bound to an organopolysiloxane graft polymer)
After completion of the reaction, the content of the polymer derived from the unsaturated monomer not bonded to the organopolysiloxane graft polymer was measured 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: Ultraviolet absorptiometer (measurement wavelength: 230 nm)
Column: ODS column "L-column ODS" (manufactured by Chemical Substances Evaluation and Research Institute, size: 4.6 x 150 mm, 5 μm)
Column temperature: Constant temperature around 30 ° C Mobile phase A: 2% aqueous phosphoric acid solution, mobile phase B: 2% ethanol phosphate solution Flow velocity: 0.5 mL / min
Sample concentration and sample volume: 1-2 mg / mL, 10.0 μL

Synthesis Example 2 Synthesis of Polysilicone-28 (polymer of component (A)) 96.0 g of ethanol was charged into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirrer. While stirring ethanol under reflux at 80 ° C. under a nitrogen atmosphere, the following solutions (a) and solution (b) were placed in separate dropping funnels and simultaneously added dropwise over 1 hour.
Solution (a): A solution in which 78.4 g of N, N-dimethylacrylamide (DMAAm), 33.6 g of N-tert-butylacrylamide (tBuAAm), and 112.0 g of ethanol are mixed.
Solution (b): Radical-reactive organopolysiloxane A 48.0 g, 2,2'-azobis (2,4-dimethylvaleronitrile) "V-65B" (Wako Pure Chemical Industries, Ltd.) synthesized in Synthesis Example 1 (1). A solution in which 0.027 g of an azo-based polymerization initiator manufactured by Kogyo Co., Ltd. and 32.0 g of ethanol are mixed.

After completion of the dropping, 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.) and under reduced pressure (20 kPa) for 4 hours to obtain a mixture containing the organopolysiloxane graft polymer C as a white solid. When the residual rate of the sulfanil group was measured by the above-mentioned method, it was 3%.
For the obtained mixture, 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 C after completion of the reaction was measured according to the above-mentioned method. As a result, it was 29% by mass.
The mass ratio (a / b) of the organopolysiloxane segment (a) to the polymer segment (b) derived from the unsaturated monomer was calculated by the above formula (I) and found to be 42/58.

Examples 1 to 13, Comparative Examples 1 to 3
The raw materials shown in Tables 1 and 2 were mixed at room temperature (25 ° C.) to prepare an aerosol hair styling product stock solution. Using this aerosol hair styling agent stock solution and LPG (0.39MPa, 20 ° C) as a propellant, the pressure inside the pressure resistant container is 0.46MPa at 25 ° C, and the undiluted solution / propellant (mass ratio) = 93/7, the aerosol The container was filled. As the aerosol container, a container equipped with the following valves and nozzles was used. Valve: Stem diameter φ0.5mm, Housing diameter φ0.3mm, Vapor tap diameter 0mm Nozzle: Diameter φ0.5mm

● Evaluation (1)-(5)
(Hair bundle treatment conditions)
Japanese wave perm hair with a length of 30 cm and a weight of 1.5 g was used for evaluation. Wet the entire hair bundle with water so that it gets wet, apply 0.1 g of the sample, knead it to create a wave, and then let it air dry. Place the sample directly under a white light in the room and evaluate (1). )-(5) were sensory evaluated.
This series of treatments was subjected to sensory evaluation according to the following criteria. The evaluation shows the average value by 5 panelists (rounded to the first decimal place).

(Evaluation criteria)
(1) Ease of curling Under the above hair bundle treatment conditions, the state of the hair bundle after drying was visually evaluated according to the following criteria.
5: The curl is firmer than the perm on the hair 4: The curl is slightly higher than the perm on the hair 3: The curl is on the same level as the perm on the hair 2: There is a weaker curl than the perm on the hair 1: There is no curl on the perm on the hair

(2) Ridge appearance Under the above hair bundle treatment conditions, the state of the hair bundle after drying was visually evaluated according to the following criteria.
5: Wave ridge is clearly visible 4: Wave ridge is slightly clear 3: Neither can be said 2: Wave ridge is slightly out 1: Wave ridge is not out The ridge here means a proper sense of bunch that the perm wave is clear and not too thick and not too thin.

(3) Clarity of shadow Under the above hair bundle treatment conditions, the state of the hair bundle after drying was visually evaluated according to the following criteria.
5: Shading is clearer than unapplied 4: Slightly shading than unapplied 3: Shading similar to unapplied 2: Slightly less shading than unapplied 1: Shading than unapplied Absent

(4) Randomness of hair tips Under the above hair bundle treatment conditions, the state of hair bundles after drying was visually evaluated according to the following criteria.
5: The tips of the hair are facing in various directions more than the perm on the hair 4: The hair is facing in various directions more than the perm on the hair 3: Same as the perm on the hair The direction of the tip of the hair is constant to a certain extent 2: The direction of the tip of the hair is slightly aligned with the perm applied to the hair 1: The direction of the tip of the hair is completely aligned

(5) Softness of Hair Under the above-mentioned hair bundle treatment conditions, the state of the hair bundle after drying was visually evaluated according to the following criteria.
5: I feel my hair is soft 4: I feel my hair is a little soft 3: I can't say either 2: I don't feel my hair is too soft 1: I don't feel my hair is soft

● Evaluation (6) Set persistence Hair is medium (length that the hair touches the shoulder) and is permed. The hair of 5 professional panelists is washed with model shampoo, dried with a hair dryer, and beauty. The teacher applied 3 g of the sample and prepared it.
After that, they were asked to live a daily life for 4 hours, and each panelist performed a sensory evaluation on the sustainability of the set according to the following criteria.
5: Good set holding 4: Somewhat good set holding 3: Neither can be said 2: Somewhat poor set holding 1: Not good set holding

* 1: Organopolysiloxane graft polymer synthesized in Production Example 1
* 2: Organopolysiloxane graft polymer synthesized in Production Example 2
* 3: Gaffcut 734, made by ISP
* 4: Gaffcut 755N-O, manufactured by ISP
* 5: Polymer described in JP-A-2015-13842
* 6: Rubiscoal K90, manufactured by BASF
* 7: Rubiscoal VA73W, manufactured by BASF
* 8: Plus size L-9540B, manufactured by GOO CHEMICAL CO., LTD.
* 9: Nikkor BC-20TX, manufactured by Nippon Surfactant Industry Co., Ltd.
* 10: GE-IS, manufactured by Kao Corporation
* 11: Softanol 90, manufactured by Nippon Shokubai Co., Ltd.
* 12: McBiobrite MG-10P, manufactured by NOF CORPORATION
* 13: Will Bride S-753, manufactured by NOF CORPORATION
* 14: Unilube 50MB-26, manufactured by NOF CORPORATION
* 15: Calcor 200GD, manufactured by Kao Corporation
* 16: Kotamin 86W, manufactured by Kao Corporation
* 17: SH3775M, manufactured by Toray Dow Corning
* 18: ELEMENT14 * PDMS 5K-JC (TSF451-5000A), manufactured by Momentive Performance Materials
* 19: Exepearl DG-MI, manufactured by Kao Corporation
* 20: Pearl Dream 4, manufactured by NOF CORPORATION
* 21: 18-MEA, manufactured by Croda Japan
* 22: BRS661, manufactured by Kao Corporation

Claims (4)

It contains the following components (A), (B) and (C), and the mass ratio (A) / (B) of the component (A) to the component (B) is 1 or more and 100 or less, and the component with respect to the component (C). An aerosol-type hair styling composition having a total mass ratio of (A) and (B) [(A) + (B)] / (C) of 1.30 or more and 30 or less.
(A) An organopolysiloxane graft polymer having an organopolysiloxane segment as a main chain and a polymer segment derived from an unsaturated monomer as a side chain, and N, N-dimethylacrylamide in the polymer segment. Organopolysiloxane graft polymer containing 50% by mass or more and 100% by mass or less of the derived repeating unit, and the ratio of organopolysiloxane segments in the whole is 10% by mass or more and 70% by mass or less.
(B) Non-crosslinked film-forming polymer without organosiloxane segment skeleton
(C) Surfactant The hair styling composition according to claim 1, wherein the component (B) is a film-forming polymer containing a structural unit derived from one or more monomers selected from the following (b-1) and (b-2). Stuff.
(b-1) Vinylpyrrolidone
(b-2) (Meta) acrylic acid or its ester or amide The polymer segment derived from the unsaturated monomer in the component (A) is derived from one or more unsaturated monomers selected from (meth) acrylamides and (meth) acrylates excluding N, N-dimethylacrylamide. The hair styling composition according to claim 1 or 2, which contains the repeating unit of. The hair styling composition according to any one of claims 1 to 3, further containing 0.01% by mass or more and 10% by mass or less of silicone other than the component (A) as the component (D).