JP5945164B2 - Hairdressing composition - Google Patents

Description

  The present invention relates to a hairdressing composition.

  The hair styling composition has various objectives and performance aspects, such as the hairstyle to be stipulated, improved touch after styling, maintaining the hairstyle, and re-styling properties once the hairstyle has collapsed. Proposals have been made so far.

  For example, Patent Document 1 discloses a hair cosmetic containing a specific poly (N-acylalkylenimine) -modified organopolysiloxane together with an organic carboxylic acid and an organic solvent. Patent Document 2 discloses a hair styling composition containing the same poly (N-acylalkylenimine) -modified organopolysiloxane as in Patent Document 1 together with a specific branched fatty acid.

JP 2009-46466 A JP 2009-149597

  However, the hair styling compositions described in Patent Documents 1 and 2 do not have a moist feeling on the set hair, and sometimes give a squeaky feeling when applied to the hair. Furthermore, these hair styling compositions have not been considered in terms of the fact that when a wave wave with wave perm is broken by sleeping or the like, the wave is restored to the state before being disturbed.

  Therefore, the present invention does not feel squeaky when applied to dry hair and is well-familiar with the hair. It is an object of the present invention to provide a hair styling composition that is excellent in the effect of recovering to a state before being disturbed and that is excellent in the feel of the set hair.

  The present inventors have found that polyoxyalkylene alkyl ether can give a moist feeling to hair without lowering the dispersibility of poly (N-acylalkylenimine) -modified organopolysiloxane, and is one of the surfactants. It has been found that by using a small amount of a cationic surfactant as a part, it is possible to suppress a squeaky feeling during coating.

The present invention contains the following components (A) to (E), the content of the component (A) is 0.1 to 10% by mass, the content of the component (B) is 0.1 to 10% by mass, the component (C) A hairdressing composition having a content of 0.4 to 5% by mass and a content of component (D) of 0.05 to 0.4% by mass is provided.
(A) 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 (1);

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aralkyl group or an aryl group, and a 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 800-1600,
The mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain to the poly (N-acylalkylenimine) segment (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

  (B) an alkylene oxide addition polymer represented by the following general formula (5)

[Wherein R ⁸ and R ⁹ represent a hydrogen atom, or a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms, m represents an integer of 1 or more, and n represents an integer of 0 or more, m + n is 3 or more. However, R ⁸ and R ⁹ are not simultaneously hydrogen atoms. ]
(C) Anionic, amphoteric or nonionic surfactants (except those corresponding to component (B))
(D) Cationic surfactant
(E) Water

  Furthermore, the present invention provides a hair styling method in which the hair styling composition is discharged from a former container in the form of foam and applied to dry hair.

  The hair styling composition of the present invention has no squeaky feeling when applied to dry hair, and is well-familiar with the hair. Excellent in restoring the bundles to their original state, and in addition, the hair feels excellent.

[Component (A): Organopolysiloxane]
The organopolysiloxane of component (A) contributes to the effect of returning the wave to the state prior to disturbance. In component (A), at least two poly (N-acylalkyleneimine) segments can be bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a hetero atom. In addition, 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 intervening in the bond between an organopolysiloxane segment and poly (N-acylalkyleneimine) has 2 to 20 carbon atoms containing 1 to 3 nitrogen atoms, oxygen atoms and / or sulfur atoms. An alkylene group is mentioned. As a specific example,

The N-acylalkyleneimine unit constituting the poly (N-acylalkylenimine) segment is represented by the general formula (1). In the general formula (1), R ¹ has 1 to 22 carbon atoms. Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 22 carbon atoms, and specifically include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl, nonadecyl, eicosyl, docosyl, etc. The Among these, an alkyl group having 1 to 10 carbon atoms, particularly 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, particularly 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, particularly 6 to 9 carbon atoms is more preferable.

Among these, R ^1, particularly preferably an alkyl group having 1 to 6 carbon atoms.

  The mass ratio (a / b) between the organopolysiloxane segment (a) and the poly (N-acylalkylenimine) segment (A) is 65/35 to 82/18, but it is not sticky and moist on the hair. From the viewpoint of providing an excellent effect of restoring the state before the wave curl and bundle alignment is disturbed, preferably 68/32 to 80/20, more preferably 70/30 to 79 / 21 and more preferably 73/27 to 79/21.

In the present specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of component (A) in deuterated chloroform and analyzing it by nuclear magnetic resonance ( ¹ H-NMR) analysis. The value obtained from the integral ratio of the alkyl group or phenyl group in the segment and the methylene group in the poly (N-acylalkylenimine) segment.

  In addition, the weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is preferably 1500-3500, and is not sticky and is in a state before disturbing the curl and bundle alignment of the wave. From the viewpoint of excellent recovery effect, it is preferably 1600 to 3200, more preferably 1700 to 3000.

In the present 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 (2): A portion surrounded by a broken line between two points from a bonding point to the segment (bonding point A) to a bonding point (bonding point B) of the poly (N-acylalkyleneimine) segment adjacent thereto, A segment composed of an R ² SiO unit, one R ⁶ , and b + 1 R ² ₂ SiO units. The “poly (N-acylalkylenimine) segment” refers to —Z—R ⁷ bonded to the above R ⁶ .

In the general formula (2), each R ² independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group, R ⁶ represents an alkylene group containing a hetero atom, and R ⁷ represents a residue of a polymerization initiator. shows, -Z-R ⁷ is a poly (N- acylalkyleneimine) indicates a segment, b represents a positive number.

  MWg is the molecular weight of the portion surrounded by the broken line in the above general formula (2), 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 refers to the number average molecular weight measured by the GPC measurement method, which is 800 to 1600, preferably 850 to 1500, and more preferably 900 to 1400. As a result, the effect of recovering to the state before the wave curl or bundle alignment is disturbed without stickiness can be further improved.

  Further, MWg can be obtained by the following formula 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, which is preferable from the viewpoint of sufficient film strength, solubility in polar solvents such as water and ease of handling after dissolution. Is from 20,000 to 80,000, more preferably from 30,000 to 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. In addition, the weight average molecular weight of the modified organopolysiloxane which is a raw material compound is measured by GPC under the following measurement conditions and is converted to polystyrene.

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

  The weight average molecular weight (MWt) of the component (A) is preferably from 12,000 to 150,000, more preferably from 24,000 to 120,000, and even more preferably from 37,000 to 92,000. Thereby, sufficient film | membrane intensity | strength can be ensured and the solubility with respect to polar solvents, such as water, will become excellent. In addition, the effect of recovering to a state before the wave curl or bundle alignment is disturbed can be further improved. 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 aforementioned mass ratio (a / b).

  The organopolysiloxane of component (A) includes, for example, a modified organopolysiloxane represented by the following general formula (3) and a cyclic imino ether represented by the following general formula (4) (hereinafter referred to as “cyclic imino ether (4) And a terminal-reactive poly (N-acylalkylenimine) obtained by ring-opening polymerization.

[Wherein R ² has the same meaning as above, and R ³ and R ⁴ each represent the same group as R ² , or

R ⁵ represents a monovalent group represented by the above formula, d represents an integer of 135 to 1350, and e represents an integer of 3 to 57. ]

[Wherein, R ¹ and a are as defined above. ]

  The modified organopolysiloxane preferably has a functional group equivalent of 1700-3500, more preferably 1800-3200, particularly preferably 2000-3000, and a weight average molecular weight of preferably 10,000-100,000, more preferably 20,000-80,000. In particular, it is desirable to use one having a viscosity of 30,000 to 60,000.

  The terminal reactive poly (N-acylalkylenimine) is preferably adjusted to have a molecular weight of 800 to 1600, more preferably 850 to 1500, and still more preferably 900 to 1400.

  A polymerization initiator can be used for the ring-opening polymerization of the cyclic imino ether (4). As the polymerization initiator, a compound having strong electrophilic reactivity, for example, a strong acid such as benzenesulfonic acid alkyl ester, p-toluenesulfonic acid alkyl ester, trifluoromethanesulfonic acid alkyl ester, trifluoroacetic acid alkyl ester, sulfuric acid dialkyl ester, etc. Alkyl esters can be used, and among them, dialkyl sulfate is preferably used. The amount of the polymerization initiator used is usually 1 mol of the polymerization initiator with respect to 2 to 100 mol of the cyclic imino ether (4).

  Examples of the polymerization solvent include acetates such as ethyl acetate and propyl acetate, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, halogen solvents such as chloroform and methylene chloride, acetonitrile. , Nitrile solvents such as benzonitrile, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, etc., among which acetates are preferred Is done. The usage-amount of a solvent is 20-2000 mass parts normally with respect to 100 mass parts of cyclic imino ether (4).

  The polymerization temperature is usually 30 to 170 ° C., preferably 40 to 150 ° C., and the polymerization time is usually 1 to 60 hours, although it is not uniform depending on the polymerization temperature and the like.

  When, for example, 2-substituted-2-oxazoline is used as the cyclic imino ether (4), a poly (N-acylethyleneimine) having a = 2 in the general formula (1) is obtained, and 2-substituted-dihydro When 2-oxazine is used, a poly (N-acylpropyleneimine) having a = 3 in the general formula (1) is obtained.

Examples of a method for connecting poly (N-acylalkylenimine) and the organopolysiloxane segment include the following methods.
1) A method of reacting a terminally reactive poly (N-acylalkyleneimine) obtained by living polymerization of a cyclic imino ether with a modified organopolysiloxane represented by the above general formula (3) 2) A carboxyl group and a hydroxyl group 3) Formation of ester by condensation of carboxyl group and amino group 4) Formation of amide by condensation of carboxyl group and amino group 4) Secondary, tertiary or quaternary of alkyl halide group with primary, secondary or tertiary amino group Formation reaction of ammonium 5) Addition reaction of vinyl group to organopolysiloxane having Si-H group 6) Formation reaction of β-hydroxyamine between epoxy group and amino group

  In particular, the above method 1) is polymerized by using the cyclic imino ether (4) and the polymerization initiator as shown in the following theoretical formula (where MWi is the molecular weight of poly (N-acylalkyleneimine)). It is most effective in that a substantially monodispersed poly (N-acylalkylenimine) having a molecular weight distribution narrower than that of normal radical polymerization can be obtained.

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

  The organopolysiloxane of component (A) can be used alone or in combination of two or more, and the content thereof is the hair styling composition of the present invention from the viewpoint of the effect of returning the wave to the state before being disturbed and the suppression of stickiness Although it is 0.1-10 mass% in a thing, 0.1-7 mass%, Furthermore, 0.5-5 mass% is preferable.

[Component (B): alkylene oxide addition polymer]
Component (B) is used to give a moist feeling to the hair. In order to give a moist feeling, when a commonly used oil is blended, even if a surfactant is blended, sufficient dispersibility of component (A) cannot be ensured, but component (B) The hair can be moistened without reducing the dispersibility of (A).

  Component (B) is at least one selected from alkylene oxide addition polymers represented by the following general formula (5).

R ⁸ and R ⁹ in the general formula (5) each represent a hydrogen atom, or a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms, but they are not simultaneously hydrogen atoms. m is an integer of 1 or more, and n is an integer of 0 or more, but m ≧ n is preferable in terms of a set shape and a feeling of unity. In particular, n is preferably 1 or more. m + n is 3 or more, but is preferably 20 to 200, more preferably 30 to 200, and particularly preferably 30 to 150 in terms of setability and unity. Furthermore, when the hairdressing agent is foamy, the number of carbon atoms of the alkyl group or alkenyl group of R ⁸ and R ⁹ is preferably 1 to 16, more preferably 1 to 14, and further preferably 1 to 12 from the viewpoint of foaminess.

  Specific examples of component (B) include, for example, polyoxypropylene (30) butyl ether, polyoxypropylene (33) butyl ether, polyoxypropylene (40) butyl ether, polyoxypropylene (52) butyl ether, polyoxypropylene (30) oleyl Polyoxypropylene alkyl ethers such as ether, polyoxypropylene (40) ricinoyl ether, polyoxypropylene (30) isocetyl ether; polyoxyethylene (17) polyoxypropylene (17) butyl ether, polyoxyethylene (3) poly Polyoxyethylene polyoxypropylene alkyl ethers such as oxypropylene (35) stearyl ether, polyoxyethylene (3) polyoxypropylene (20) cetyl ether, polyoxyethylene (5) polyoxypropylene (40) behenyl ether; polyoxy Echile (14) polyoxypropylene (7) Polyoxyethylene polyoxypropylene dialkyl ethers such as dimethyl ether.

  The above alkylene oxide addition polymers are commercially available, for example, Adeka Pluronic L series sold by ADEKA Co., Ltd., New Pole PE series sold by Sanyo Chemical Industries, Ltd., and Nippon Oil & Fats Co., Ltd. Use commercially available products such as the UNILOVE 10MS series, UNISafe series, UNILOVE 50MB series, Bepol series sold by Toho Chemical Co., Ltd., and Macbio Obride E series sold by NOF America. be able to.

  The content of the component (B) is 0.1 to 10% by mass in the hair styling composition of the present invention, from the viewpoints of imparting a good moist feeling to the hair, and suppressing stickiness and squeaking, but 0.1 to 10% by mass. 10 mass%, Furthermore, 0.1-7 mass%, Furthermore, 0.5-5 mass% is preferable. In the general formula (5), those in which m + n is 30 or more and m ≧ n are particularly excellent in the effect of imparting a good setting property and a feeling of unity.

[Component (C): Surfactant other than Component (B) and Component (D)]
Component (C) is an anionic, amphoteric or nonionic surfactant (excluding those corresponding to component (B)), that is, a surfactant other than component (B) and component (D). In order to disperse (A) well, it is blended in the hairdressing composition of the present invention.

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

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series. Among these, betaine surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amidopropyl betaine are preferred, and fatty acid amidopropyl betaine is particularly preferred. The fatty acid amidopropyl betaine is preferably one having an acyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and in particular, lauric acid amidopropyl betaine, palm kernel oil fatty acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine and the like. preferable.

  Non-ionic surfactants other than component (B) include polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, alkyl saccharide surfactant, alkyl amine oxide, alkyl amido amine oxide and the like. Of these, polyoxyethylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether is particularly preferable.

  Component (C) can be used alone or in combination of two or more, and among them, it is preferable to use a nonionic surfactant. In addition, from the viewpoint of good dispersibility of component (A) and suppression of squeaky sensation during application, the content thereof is 0.4 to 5% by mass in the hairdressing composition of the present invention, further 0.4 to 4% by mass, Furthermore, 0.4-3 mass% is preferable.

[Component (D): Cationic surfactant]
In the present invention, by adding a small amount of the component (D) cationic surfactant, the squeaky feeling due to the component (C) can be alleviated. Examples of the cationic surfactant include quaternary ammonium salts represented by the following general formula (6).

[Wherein, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms, or a benzyl group, and at the same time, a hydrogen atom, a benzyl group, a lower alkyl group having 1 to 3 carbon atoms, or these Except when combined. An ^- is as defined above. ]

Here, one of R ¹⁰ and R ¹¹ is preferably an alkyl group having 16 to 24 carbon atoms, more preferably 22 alkyl groups, particularly a linear alkyl group, and the other is a lower alkyl group having 1 to 3 carbon atoms, particularly A methyl group is preferred.

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

Component (D) can be used alone or in combination of two or more thereof, and its content is 0.05% by mass or more in the hairdressing composition of the present invention from the viewpoint of sufficiently suppressing the squeaky sensation due to component (C). Yes, 0.1 mass% or more is preferable. Further, from the viewpoint of suppressing the squeaky feeling due to the component (D) itself when the component (D) is excessive, the content thereof is 0.4% by mass or less in the hairdressing composition of the present invention.
Furthermore, from the viewpoint of suppressing dispersibility of component (A) and squeaky sensation when applying the hairdressing composition, the mass ratio of the content of component (C) to component (D) is (C) / (D) = 1.2 to 80 is preferable, 1.25 to 80 is more preferable, and 1.3 to 70 is particularly preferable.

[Component (E): Water]
The hairdressing composition of the present invention uses water as a medium. As a medium, in addition to water, an organic solvent other than the specific organic solvent can be used as necessary. Examples of such organic solvents include lower alkanols such as ethanol and 2-propanol, polyols such as propylene glycol, 1,3-butanediol, diethylene glycol, dipropylene glycol, and glycerin, ethyl cellosolve, butyl cellosolve, and benzyl cellosolve. Examples include cellosolves, carbitols such as ethyl carbitol and butyl carbitol.

[Other ingredients]
In the hairdressing composition of the present invention, various components usually used in hairdressing agents, such as chelating agents, vitamins, proteins, amino acids, herbal medicines, coolness-imparting agents (such as menthol), preservatives, ultraviolet absorption Agents, antioxidants, colorants, fragrances and the like can be blended depending on the purpose.

[Drug type]
The form of the hairdressing composition of the present invention can be appropriately selected from foam, liquid, mist, gel, paste, cream, etc., but is particularly suitable as a foamy hairdressing agent, and in particular, a non-aerosol foamer container It is preferable to be housed and discharged in the form of foam.

〔viscosity〕
When the hair styling composition of the present invention is contained in a non-aerosol foamer container, from the viewpoint that it can be suitably discharged as a foam from the non-aerosol foamer container, it is discharged in the state of being present in the non-aerosol container. In the previous liquid state), 1 to 100 mPa · s, 2 to 30 mPa · s, particularly 3 to 20 mPa · s are preferred. The viscosity here is 25 ° C. with a B-type rotational viscometer. When the viscosity is 1 to 20 mPa · s, the BL adapter is used and the rotational speed is measured at 30 rpm. And the rotation speed is measured at 60 rpm.

[Non-Aerosol Foamer Container]
The non-aerosol foamer container is used for mixing the hairdressing composition filled in the container with air without using a propellant and discharging it in the form of foam. By using the former container, an effect of preventing scattering of the discharged agent can be obtained. In particular, a non-aerosol type container can manufacture a product at a lower cost than an aerosol type container and does not require a high-pressure gas propellant. Therefore, the product can be handled more safely in distribution.

  As the former container, a known pump former container having a foam discharge means, a squeeze foamer container, an electric frother, a pressure accumulating pump former container or the like can be used. More specifically, for example, food and containers (vol. 35, No. 10, p588 to 593 (1994); vol. 35, No. 11, p624 to 627 (1994); vol. 36, No. 3, p154 ~ 158 (1995)) Pump former E3 type, F2 type (above, Daiwa Steel Co., Ltd.), squeeze foamer (Daiwa Steel Co., Ltd.), electric whisk (Matsushita Electric Works), air spray for Mar (Air Spray International). As the former container used in the hair styling agent of the present invention, a pump former container and a squeeze foamer container are preferable because they are inexpensive and easy to use.

  The pump former container or the squeeze foamer container has a foam homogenizing means such as a net, and preferably has a thin net from the viewpoint of preventing clogging. In this case, the net mesh is preferably 50 to 400 mesh, more preferably 70 to 350 mesh, and even more preferably 100 to 320 mesh. Here, the mesh means the number of eyes per inch. By using a mesh net in this range, creamy foam can be generated. Moreover, as a material of such a mesh, nylon, polyester, etc. can be illustrated preferably.

  In the non-aerosol foamer container containing the hairdressing composition of the present invention, at least one, preferably a plurality of such nets are disposed, and particularly economical, fineness of foam, difficulty in clogging, etc. It is preferable to arrange two from the point.

  The hair styling composition of the present invention is applied to dry hair by hand or a tool for hair styling, and hair styling is performed. From the viewpoint of hair styling properties, it is preferable that the hair styling composition of the present invention is applied to the hair and then applied to the hair. The hair styling method using the hair styling composition of the present invention is preferably performed on permanent wave-treated hair, and in particular, when the hair dries, the wave curl diameter increases and the alignment of the hair bundle is poor. It is preferable to carry out on the resulting hair. When applying this hair styling method to permanent wave-treated hair, after applying the hair styling composition of the present invention to the hair, hold the hair bundle with your hand and lift it up. It is preferable to incorporate.

Synthesis Example 1 Synthesis of Organopolysiloxane A 19.0 g (0.12 mol) of diethyl sulfate and 81.0 g (0.82 mol) of 2-ethyl-2-oxazoline were dissolved in 203.0 g of dehydrated ethyl acetate and heated to reflux for 8 hours in a nitrogen atmosphere. Terminal reactive poly (N-propionylethyleneimine) was synthesized. The number average molecular weight measured by GPC was 1100. A 33% ethyl acetate solution of 300 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32000, amine equivalent 2000) was added all at once and heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (390 g, yield 97%). The content of the silicone segment in the final product was 75% by mass, and the weight average molecular weight was 40000. According to the result of neutralization titration with hydrochloric acid using methanol as a solvent, about 20 mol% of amino groups remained.

Synthesis Example 2 Synthesis of Organopolysiloxane B 6.5 g (0.042 mol) of diethyl sulfate and 34.4 g (0.36 mol) of 2-ethyl-2-oxazoline were dissolved in 87 g of dehydrated ethyl acetate and heated under reflux for 8 hours under a nitrogen atmosphere. Poly (N-propionylethyleneimine) having a number average molecular weight of 1300 was synthesized. Here, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32000, amine equivalent 2000) was used, and N-propionylethyleneimine-dimethylsiloxane copolymer was converted into a pale yellow rubber-like semisolid (138 g, yield). 98%). The final product had an organopolysiloxane segment content of 71 mass% and a weight average molecular weight of 46000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that about 22% by mass of amino groups remained.

Synthesis Example 3 Synthesis of Organopolysiloxane C In the same manner as in Synthesis Example 1, 0.8 g (0.005 mol) of diethyl sulfate, 12.8 g (0.14 mol) of 2-ethyl-2-oxazoline and 29 g of dehydrated ethyl acetate Poly (N-propionylethyleneimine) having a molecular weight of 2700 was obtained. Further, using 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 100000, amine equivalent 20000), N-propionylethyleneimine-dimethylsiloxane copolymer was converted into a pale yellow rubbery solid (111 g, yield 98%). ). The content of the organopolysiloxane segment in the final product was 88% by mass, and the weight average molecular weight was 114,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Synthesis Example 4: Organopolysiloxane D
Diethyl sulfate (6.17 g, 0.04 mol) and 2-ethyl-2-oxazoline (93.8 g, 0.947 mol) were dissolved in dehydrated ethyl acetate (203 g), heated under reflux for 8 hours under a nitrogen atmosphere, and terminal-reactive poly (N-propionylethylene). Imine) was synthesized. The number average molecular weight measured by GPC was 2500. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30,000, amine equivalent 2,000) was added all at once, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (190 g, yield 95%). The final product had an organopolysiloxane segment content of 50 mass% and a weight average molecular weight of 60,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that about 20 mol% of amino groups remained.

Examples 1-9, Comparative Examples 1-13
Prepare hair styling compositions (solutions) shown in Tables 1 and 2 and take this solution in accordance with the following methods and criteria: “Familiarity with dry hair”, “No squeaky hair feel when applied” Performance evaluation was performed for "return of curled waves", "alignment of bundles of waves", "smooth / moist feeling of wave bundles", and "non-stickiness". However, the evaluation regarding the holding of the foam is that after preparing the hairdressing composition shown in Table 1 and Table 2, the pump former made by Yoshino Seisakusho Co., Ltd. The two-mesh product having a mesh of 200 and a mesh of 305 mesh that passes later was evaluated.
Note that Example 3 is a reference example and is not included in the scope of the claims.

<Evaluation hair bundle>
A hair bundle of Japanese hair perm treatment with a weight of 3 g, a width of 2.5 cm, and a length of 25 cm is washed with a model shampoo, towel dried, and then blown straight with a dryer and brush. What was completely dried was used as a hair bundle for evaluation.

<Evaluation method and evaluation criteria>
(Familiarity with dry hair)
Sensory evaluation was carried out in the following five stages with respect to “familiarity with dry hair” when the agent was spread on the evaluation hair bundle by five expert panelists, and the average value was shown.
5 points: Accommodates hair very quickly and evenly 4 points: Accommodates hair quickly and evenly 3 points: Accommodates hair quickly, but some parts cannot be applied evenly 2 Points: Some parts cannot be applied evenly and uniformly There are many 1 point: It is not very familiar with hair and it is not applied almost uniformly.

(No squeaky hair when applied)
Sensory evaluation was carried out by the following five stages and expressed as an average value for the “feel of squeaky hair during application” when the agent was spread on the evaluation hair bundle by five specialist panelists.
5 points: No hair squeaks when applied 4 points: Little squeaks on hair when applied 3 points: Some hair squeaks when applied 2 points: Hair squeaks when applied 1 point: During application I feel the squeaky hair

(Return of curled radius of stretched wave)
5 expert panelists spread the agent on the hair bundle for evaluation, hold the hair bundle with their hand and lift it up and swallow the agent 10 times. The sensory evaluation of “return of curl radius of” was performed in the following five stages, and the average value was shown.
For comparison, hair bundles after 12 hours of natural drying after shampoo / towel drying were used.
5 points: The curl diameter of the wave is about the same as the curl diameter during natural drying. 4 points: The curl diameter of the wave is slightly larger than the curl diameter during natural drying. 3 points: The curl diameter of the wave is larger than the curl diameter during natural drying. Slightly larger 2 points: The curl diameter of the wave is much larger than the curl diameter during natural drying. 1 point: The curl diameter of the wave is slightly wavy than the curl diameter during natural drying.

(A set of wave bundles)
Five expert panelists spread the agent on the hair bundle for evaluation, held the hair bundle by hand and lifted it up and swallowed the agent 10 times. Sensory evaluation was performed on the following five stages, and the average value was shown. For comparison, hair bundles after 12 hours of natural drying after shampoo / towel drying were used.
5 points: Wave bundles are much better aligned than naturally dried bundles 4 points: Wave bundles are slightly better aligned than naturally dried bundles 3 points: Wave bundles are naturally dried bundles 2 points: Wave bundles are a little worse than natural dry bundles 1 point: Wave bundles are much worse than natural dry bundles

(The smoothness and moist feeling of the wave bundle)
Five expert panelists spread the agent on the hair bundle for evaluation, held the hair bundle by hand and lifted it up and swallowed the agent 10 times. The “smoothness and moist feeling” was subjected to sensory evaluation in the following five stages, and the average value was shown.
5 points: Feeling the smoothness and moistness of the bunch of waves 4 points: Feeling the smoothness and moistness of the bunch of waves 3 points: Not enough I do not feel 1 point: I do not feel the smoothness and moistness of the bunch of waves

(No stickiness)
The “non-stickiness” of the hair bundle set by five professional panelists was subjected to sensory evaluation in the following five stages, and the average value was shown.
5 points: Not sticky 4 points: Not very sticky 3 points: Neither can be said 2 points: Slightly sticky 1 point: Sticky

(Holding bubbles)
5 points: Very good foam retention 4 points: Good foam retention 3 points: Neither point 2: Poor foam retention 1 point: Poor foam retention

Claims (3)

It contains the following components (A) to (E), the content of component (A) is 0.1 to 10% by mass, the content of component (B) is 0.1 to 10% by mass, and the content of component (C) is A foam hair styling composition that is contained in a non-aerosol foamer container and is used by being discharged in a foam form, having a content of 0.4 to 5 mass% and component (D) of 0.05 to 0.4 mass%.
(A) 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 (1);

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aralkyl group or an aryl group, and a 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 800-1600,
The mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain to the poly (N-acylalkylenimine) segment (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
(B) an alkylene oxide addition polymer represented by the following general formula (5)

[In the formula, one of R ⁸ and R ⁹ represents a linear or branched alkyl or alkenyl group having 4 to 12 carbon atoms, the other represents a hydrogen atom , m is an integer of 1 or more, and n is an integer of 0 or more. M + n is 3 or more . ]
(C) nonionic surface active agent (excluding those falling under the component (B))
(D) Cationic surfactant
(E) Water A hair styling method in which the foam hair styling composition according to claim 1 is applied to dry hair. The hair styling method according to claim 2 , wherein the dry hair is permanent wave-treated hair.