JP6284757B2 - Hairdressing composition - Google Patents

Description

  The present invention relates to a hairdressing composition.

  In recent hair styling agents, the amount of adhesive polymer and the set polymer that forms a strong film is increased in order to increase the hairstyle set retention, and the hairstyle is fixed by the adhesiveness of the polymer and the strong polymer film. Is common.

  Hairdressing agents that contain a large amount of adhesive polymer adhere to each other by the adhesiveness of the polymer to create and fix the hairstyle, and provide long-lasting hairstyle. In many cases, it was difficult to maintain the touch, which was a problem. On the other hand, hair styling agents that form a strong film can suppress stickiness, but because the hair style is maintained by the strong film, it is stiff and still insufficient in terms of giving the hair a natural feel. . Therefore, in addition to fixing and maintaining the hair in the desired shape, there is a need to keep the hair in a natural and non-sticky feel at the same time. Among them, when creating a wave style, you can not only simply adjust the wave, but also enhance the three-dimensional wave feeling in the desired part and give a soft volume, and a non-sticky hair styling Has been sought in recent years.

  In contrast, various hair styling compositions using poly (N-acylalkylenimine) -modified organopolysiloxane have been proposed. For example, as a hair styling composition suitable for the purpose of making a wave style, Patent Document 1 discloses a hair using a specific cationic thickener together with a specific poly (N-acylalkylenimine) -modified organopolysiloxane. A hair styling composition that is easy to stretch, can give a smooth feel, has excellent hair styling power, and is capable of re-styling is disclosed. In addition, as a hair styling composition suitable for the purpose of creating a voluminous style, Patent Document 2 uses a specific cationic film-forming polymer and a specific poly (N-acylalkylenimine) -modified organopolysiloxane in combination. Further, a hair styling composition having a finished flexibility, a long hair styling ability and capable of re-styling is disclosed.

JP 2010-138099 JP 2011-105660

  However, with the hairdressing composition described in Patent Document 1, the effect of adjusting the wave after styling and the feel are good, but a soft volume could not be imparted. Further, the hair styling composition described in Patent Document 2 has a problem that even if a volume can be imparted after styling, a wave having a three-dimensional effect cannot be imparted.

  Furthermore, in any of the hair styling compositions of Patent Documents 1 and 2, the ease of spreading the hair with no chemical treatment history and the ease of hair styling are sufficient, but it is hydrophilic to receive damage such as permanent waves. The wave hair that has become difficult to stretch when applied, and the hair is easily entangled and caught even when it is swallowed to produce a wave.

  In this way, the conventional hair styling composition has a three-dimensional effect on the wave hair damaged by chemical treatment such as permanent wave, and gives a soft volume while having a clear ridge wave. There is no technology that can finish into a hairstyle, and furthermore, the ease of spreading and hair-styling at the time of application, and the feel of the hair after hair-setting are all compatible.

  Therefore, the present invention is easy to stretch even when applied to healthy hair and wavy hair with a history of chemical treatment such as permanent wave. The present invention relates to a hair styling composition that has a three-dimensional feeling, can be finished into a hairstyle with a soft volume while having a clear wave of ridges, and has a good touch.

  By using a specific poly (N-acylalkylenimine) -modified organopolysiloxane and a specific liquid oil in a certain amount ratio, and further using a specific cationic thickener, Contains a certain amount of specific poly (N-acylalkyleneimine) -modified organopolysiloxane to produce volume and ridges (a tight and firm wave) to wave hair damaged by chemical treatment such as permanent wave Even in this case, it has been found that a hair styling composition that is easy to spread when applied to damaged hair can be obtained.

The present invention contains the following components (A) to (C), the content of component (A) is 2.5% by mass or more and 8% by mass or less, and the content of component (A) relative to the content of component (B) A hair styling composition having a mass ratio (A) / (B) of 1 to 4 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 n represents 2 or 3. ]
An organopolysiloxane formed by bonding poly (N-acylalkyleneimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 800 or more and 1,600 or less,
The mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (A) is from 65/35 to 82/18,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 10,000 or more and 100,000 or less,
Organopolysiloxane
(B) One or two or more oils selected from silicone oil, ester oil and hydrocarbon oil that are liquid at 25 ° C
(C) Cationic thickener

The hair styling composition of the present invention is easy to stretch even for wave hair damaged by chemical treatment such as permanent wave, and it is easy to squeeze into hair without tangling hair, and finish into a wave with good ridge. In addition, a volume can be given to a desired part. Also, stickiness after finishing can be suppressed.
Here, the ridge-like wave is a state where the wave has a clear sense of bunch.

[(A): Organopolysiloxane]
Ingredient (A) is effective in giving a sense of bundle to the wave hair and improving the setability. 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. More preferably, it is 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. Specific examples thereof include the following groups.

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, and more preferably 1 to 6 carbon atoms is 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, and more preferably 7 to 10 carbon atoms is 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, more preferably 6 to 9 carbon atoms is preferable.

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

  The mass ratio (a / b) between the organopolysiloxane segment (a) and the poly (N-acylalkyleneimine) segment (b) is sticky but not sticky, and gives a bundled feeling to the perm wave hair. And, from the viewpoint of having excellent setability and re-styling properties, it is 65/35 or more, preferably 68/32 or more, more preferably 70/30 or more, still more preferably 73/27 or more, Further, it is 82/18 or less, preferably 80/20 or less, more preferably 79/21 or less.

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 sticky and non-sticky, and gives a bundled feel to the perm wave hair. And from the viewpoint of having excellent re-hair styling properties, preferably 1500 or more, more preferably 1600 or more, more preferably 1700 or more, preferably 3500 or less, more preferably 3200 or less, still more preferably 3000 or less. It is.

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 y + 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 —Z—R ⁷ represents poly (N— An acylalkylenimine) segment, R ⁷ represents a residue of a polymerization initiator, and y 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. For this reason, when the functional group equivalent of the modified organopolysiloxane which is a raw material compound is clear, MWg can be calculated by the following formula.
MWg = [functional group equivalent of raw material compound] × (100- [functional group residual ratio (%)]) / 100

  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 a gel permeation chromatography (GPC) measurement method described later. Although it is possible, in the present invention, it means the number average molecular weight measured by the GPC measurement method. In the present invention, the molecular weight of the poly (N-acylalkyleneimine) segment is 800 or more, preferably 850 or more, more preferably 900 or more, from the viewpoint that it is not sticky and is excellent in setting properties and re-styling properties. Also, it is 1,600 or less, preferably 1,500 or less, more preferably 1,400 or less.

  The weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is from the viewpoint of providing sufficient film strength, solubility in polar solvents such as water, ease of handling after dissolution, and good feel to the hair. 10,000 or more, preferably 20,000 or more, more preferably 30,000 or more, and 100,000 or less, preferably 80,000 or less, more preferably 60,000 or less. 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 organopolysiloxane of component (A) ensures sufficient film strength, and has excellent solubility in polar solvents such as water, from the viewpoint of imparting a good feel to the hair. Preferably, it is 12,000 or more, more preferably 24,000 or more, further preferably 37,000 or more, preferably 150,000 or less, more preferably 120,000 or less, and further preferably 92,000 or less. Moreover, it is not sticky, and both styling properties of setability and re-styling property 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) can be produced by a known method (for example, the method described in JP 2010-138099 A).

  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 in the hairdressing composition of the present invention is 2.5 mass from the viewpoint of producing the volume and ridge of perm wave hair. % Or more, preferably 2.55% by mass or more, more preferably 2.6% by mass or more, and 8% by mass from the viewpoint of easy extension to perm wave hair, ease of squeezing, and reduction of stickiness after finishing. Or less, preferably 7.7% by mass or less, more preferably 7.5% by mass or less, and still more preferably 5% by mass or less.

[(B): Oil agent liquid at 25 ° C]
The component (B), which is liquid at 25 ° C., is selected from silicone oil, ester oil, and hydrocarbon oil, improves the stretchability of hair whose surface is damaged by permanent wave treatment, etc. It is effective for reducing tangling and catching, ease of squeezing, and good feel of hair after styling. Among the component (B), as silicone oil, dimethylpolysiloxane, polyether-modified silicone, amino-modified silicone, carboxy-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, aliphatic alcohol-modified silicone, epoxy-modified Examples thereof include silicone, fluorine-modified silicone, cyclic silicone, and alkyl-modified silicone. Of these, dimethylpolysiloxane, polyether-modified silicone, cyclic silicone, and alkyl-modified silicone are preferable, and polyether-modified silicone is particularly preferable. Among the components (B), as ester oil, diisostearyl malate, isopropyl palmitate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, ethyl isostearate, oleyl oleate, 2- Hexadecyl ethylhexanoate, isononyl isononanoate, tridecyl isononanoate, cholesteryl isostearate, isopropyl myristate, olive oil, camellia oil, tea seed oil, sasanqua oil, safflower oil, sunflower oil, soybean oil, cottonseed oil, sesame oil, corn oil, Peanut oil, rapeseed oil, rice bran oil, rice germ oil, wheat germ oil, pearl barley oil, grape seed oil, almond oil, avocado oil, carrot oil, macadamia nut oil, castor oil, flaxseed oil, palm oil, mink oil, egg yolk oil , Jojoba Etc. The. Of these, isopropyl myristate and isopropyl palmitate are preferred. Among the component (B), examples of the hydrocarbon oil include liquid paraffin, liquid isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, cycloparaffin, α-olefin oligomer, squalane and the like. These can be used alone or in combination of two or more.

  As component (B), the interaction between the damaged hair surface and component (A) is alleviated, the elongation of hair cosmetics against damaged hair is improved, and the hair is firmly fixed while sticking to the hand. It is preferable to contain two or more kinds of oils from the viewpoint of reducing hair and preventing hairs from being entangled when squeezed, and shaping the hair into a squeezed form. It is preferable to contain more than one species in combination. When silicone oil and ester oil are combined, the ester oil is preferably a monohydric alcohol ester of a fatty acid, particularly isopropyl myristate. The mass ratio of silicone oil to ester oil (silicone oil) / (ester oil) is preferably 1/5 or more, more preferably 1/4 or more, still more preferably 1/3 or more, and even more preferably 1/2 or more. Moreover, it is preferably 5/1 or less, more preferably 4/1 or less, further preferably 3/1 or less, and further preferably 2/1 or less.

  The content of the component (B) in the hairdressing composition of the present invention is preferably 0.6% by mass or more, more preferably 0.7% by mass or more, and still more preferably, from the viewpoint of compatibility between style retention and elongation to hair. It is 0.8 mass% or more, preferably 5 mass% or less, more preferably 3.5 mass% or less, and still more preferably 2.5 mass% or less.

  The mass ratio (A) / (B) of the content of the component (A) to the content of the component (B) alleviates the interaction between the damaged hair surface and the component (A) and increases the damage to damaged hair. Is 1 or more, more preferably 1.2 or more, still more preferably 1.3 or more, still more preferably 1.5 or more, still more preferably 2 or more from the standpoint of improving From the viewpoint of absence, it is 4 or less, preferably 3.8 or less, more preferably 3.7 or less, and still more preferably 3.6 or less.

[(C): Cationic thickener]
As the cationic thickener of component (C), polymethacryloyloxyethyltrimethylammonium chloride is preferably used. A preferred example of polymethacryloyloxyethyltrimethylammonium chloride is a cationic polymer described in the 10th edition of the INCI Dictionary (USA, International Cosmetic Ingredient Dictionary and Handbook) under the name of polyquaternium-37. From the viewpoint of imparting an appropriate viscosity to the composition and making it easy to stretch on the hair, the weight average molecular weight of polyquaternium-37 is preferably 1 million or more, more preferably 1.2 million or more, and 10 million or less, and further 5 million. The following is preferred.

  The content of the component (C) in the hairdressing composition of the present invention obtains a high setting power and re-styling property, makes the expression of dry wrinkle adhesion moderately quick, and gives a smooth feel that is easy to extend to the hair. From the viewpoint, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, preferably 3% by mass or less, more preferably 1.5% by mass or less, and further preferably 1% by mass. % Or less.

[(D): Polyhydric alcohol]
The hair styling composition of the present invention preferably further contains a polyhydric alcohol from the viewpoint of ease of squeezing into the perm wave hair, ease of giving a ridge feel, suppression of stickiness after finishing, and imparting a good feel. . As the polyhydric alcohol, those having 2 to 20 carbon atoms, specifically, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,2-butylene glycol, 1, Alkylene glycols such as 3-butylene glycol, pentylene glycol and hexylene glycol; Glycerins such as glycerin, diglycerin and polyglycerin; Sugar alcohols such as xylit, mannitol, galactit and sorbit; Other trimethylolethane, triglycerides Examples include methylolpropane and pentaerythritol.

  Two or more polyhydric alcohols may be used in combination. In addition, the content of the polyhydric alcohol in the hairdressing composition of the present invention is easy to squeeze into perm wave hair, easy to give a ridge feeling, stickiness suppression after finishing, and imparting a good feel. It is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, and is preferably 10.0% by mass or less, more preferably 7.5% by mass or less, and further preferably 5.0% by mass or less.

  The mass ratio (D) / (A) of the content of the component (D) to the content of the component (A) suppresses stickiness after finishing, and makes it easy to produce a ridged feeling and a bundled feeling of the permanent wave hair. It is preferably at least 0.1, more preferably at least 0.2, even more preferably at least 0.5, preferably at most 2.0, more preferably at most 1.5, further preferably at most 1.0.

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

  Examples of the cationic surfactant include quaternary ammonium salts represented by the following general formula (5).

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

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

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

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

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

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

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

〔solvent〕
The hairdressing composition of the present invention preferably further contains ethanol and / or water as a solvent. The content of the medium in the hairdressing composition of the present invention is preferably 4% by mass or more, more preferably 30% by mass or more, from the viewpoint of improving the solubility of the polymer or plasticizer contained in the composition. Preferably, it is 50% by mass or more, preferably 98.4% by mass or less, more preferably 98% by mass or less, and still more preferably 95% by mass or less.

[Other optional ingredients]
In addition to the above-described components, the hair styling composition of the present invention may contain components used in normal hair cosmetics depending on the purpose. Examples of such components include film-forming polymers other than component (A) (such as carrageenan, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer), organic solvents other than ethanol (such as aromatic alcohol), Dandruff agents, vitamins, bactericides, anti-inflammatory agents, chelating agents, moisturizers (pantenol, etc.), pH adjusters, coloring agents such as dyes and pigments, plant extracts, pearling agents, fragrances, UV absorbers, oxidation Examples include inhibitors.

  The hairdressing composition of the present invention can be used in a jar, a pump dispenser, an aerosol can, or a pump mist. Among these, a pump dispenser is preferable.

[Viscosity, dosage form]
Since the hairdressing composition of the present invention can be filled in various containers, it can be suitably used in a wide viscosity range of 30 to 50,000 mPa · s. When used in a pump-type container (pump dispenser), the viscosity is preferably relatively low, and the viscosity is preferably 50 to 20,000 mPa · s, more preferably 100 to 10,000 mPa · s, It is preferably 200 to 5,000 mPa · s, more preferably 500 to 2,000 mPa · s. Here, the viscosity is measured with a B-type viscometer TVB-10 (Toki Sangyo Co., Ltd.) under the conditions after rotation at 30 ° C., 30 r / m for 60 seconds. For the rotor, use No. 2 for viscosity up to 1,000 mPa · s, No. 3 for higher viscosity up to 4,000 mPa · s, and No. 4 for higher viscosity.

  The form of the hairdressing composition of the present invention can be appropriately selected from liquid, gel, paste, cream and the like. In addition, as a method of styling hair using the hair styling composition of the present invention, the hair styling composition of the present invention is uniformly applied to wave hair, especially hair whose surface is hydrophilized by permanent wave treatment, Thereafter, a method of preparing a style while squeezing and styling hair is preferred.

In the following synthesis examples, the content of the organopolysiloxane segment is a value determined by nuclear magnetic resonance ( ¹ H-NMR), and the weight average molecular weight of the final product is a calculated value. The molecular weight of poly (N-propionylethyleneimine) is a number average molecular weight determined by gel permeation chromatography (GPC).

Column: K-804L + K-804L manufactured by Showa Denko KK Eluent: 1 mmol / L Pharmin DM20 (manufactured by Kao Corporation) / chloroform Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI
Sample amount: 5mg / mL, 100μL
Polystyrene conversion

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

Synthesis Example 2 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 to react with terminal reactive poly (N-propionylethylene). Imine) was synthesized. The number average molecular weight measured by GPC was 1300. A 33% ethyl acetate solution of 100 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 semi-solid (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 mol% of amino groups remained.

Examples 1-8 and Comparative Examples 1-8
Hair styling compositions shown in Tables 1 and 2 were prepared according to a conventional method, and evaluated according to the methods and criteria shown below.

(Evaluation tress)
Japanese hair tress weighing 5g, width 3cm, length 25cm is spirally wound around a cylindrical rod with a diameter of 14mm, and the first wave perm (gold) with a bath ratio (hair: agent, mass ratio) of 1: 1 Well Topform CNa) was applied and evenly blended and left at room temperature for 20 minutes. Next, the hair bundle wound on the rod is rinsed in running water at 40 ° C. for 30 seconds, and after removing moisture with a towel, Waveperm 2nd agent (Goldwell top form CNa) is used in a bath ratio (hair: agent, (Mass ratio) The coating was performed at a ratio of 1: 1. Finally, the hair bundle was removed from the rod and rinsed in running water at 40 ° C. for 30 seconds to complete the wave perm treatment. Thereafter, the product was washed three times with a model shampoo shown below, and then allowed to stand at room temperature for 12 hours and dried to obtain an evaluation tress.

Model shampoo composition (mass%)
Polyoxyethylene (2.5) sodium lauryl ether sulfate 25% by weight aqueous solution 62.00
Lauric acid diethanolamide 2.28
Edetate disodium 0.10
Sodium benzoate 0.50
Oxybenzone 0.03
Phosphoric acid (75 mass% aqueous solution) 0.10
Dibutylhydroxytoluene 0.01
Sodium chloride 0.80
Red No. 106 0.00012
Fragrance 0.26
Purified water balance

(Evaluation method)
"Easy extension to perm wave hair"
After taking 0.5 g of each hairdressing composition, it was evaluated from the viewpoint of ease of extension of the composition onto the hair when spread on a Japanese perm wave hair trace for evaluation.
In the evaluation, seven panelists were allowed to select either “easy to spread”, “neither”, or “difficult to spread” when each composition was processed by the above operation. It was. The number of panelists who answered “easy to spread” / “can't say either” / “difficult to spread” is shown in order.

"Ease of squeezing after applying to perm wave hair"
After taking 0.5g of each hair styling composition in hand and spreading it on the Japanese perm wave hair torches for evaluation, the “Ease of hair squeezing” is performed when the hair is swallowed to create a wave feeling. Evaluation was performed from the viewpoint of "."
Evaluation was performed by 7 panelists using the above-described operations with each of the compositions: “hair is not entangled and easy to squeeze” / “cannot say either” / “hair is entangled and difficult to squeeze” It was made to choose alternatively. The number of panelists who answered that “hair is not tangled and easy to squeeze” / “can't say either” / “hair is tangled and difficult to squeeze” is shown in order.

"Perm wave volume after permeation after perm wave hair application"
After picking up 0.5 g of each hairdressing composition, it was spread on an evaluation tress having a maximum width of 4.5 cm, and the maximum value (cm) of the width of the tress when the tress was suspended after swallowing was measured.

“Perm wave ridge after permeation after perm wave hair application”
After picking up 0.5g of each hairdressing composition and spreading it on Japanese perm wave hair torches for evaluation, after swallowing the hair to create a sense of wave, “Wave ridges appear? Evaluation was performed from the viewpoint of “no”.
The evaluation is whether 7 ridges are “Ridge clearly” / “Neither” or “Ridge is not out” when each composition is processed by the above operation. It was made to choose alternatively.
“Ridge” here means a clear sense of permawave.

"No hair stickiness after finishing"
After taking 0.5 g of each hair styling composition in hand, it was evaluated from the viewpoint of “no stickiness of hair” after spreading, spreading and finishing on Japanese perm wave hair torches for evaluation.
In the evaluation, seven panelists were allowed to select one of “not sticky” / “neither” / “sticky” when each composition was treated by the above-described operation.

<Prescription Example 1>
(mass%)
Organopolysiloxane A 2.7
Isopropyl myristate 0.3
PEG-12 Dimethicone 0.5
Polyquaternium-37 0.9
Steartrimonium chloride 0.2
Concentrated glycerin 1.0
PEG-65M 0.1
(C12-14) s-Palace-9 0.25
Ethanol 17.5
Fragrance 0.1
Water remaining

  This hair styling composition is easy to stretch even when applied to both normal hair and wave hair with a history of chemical treatment such as permanent wave. It has a three-dimensional effect, and it can be finished into a hairstyle with a soft volume while having a clear wave of ridges.

<Prescription Example 2>
(mass%)
Organopolysiloxane A 2.5
Organopolysiloxane B 2.5
Isopropyl myristate 1.0
PEG-12 Dimethicone 1.0
Polyquaternium-37 0.6
Steartrimonium chloride 0.24
Dipropylene glycol 1.0
PEG-2M 0.1
(C12-14) s-Palace-9 0.3
Ethanol 15.0
Fragrance 0.1
Water remaining

  This hair styling composition is easy to stretch even when applied to both normal hair and wave hair with a history of chemical treatment such as permanent wave. It has a three-dimensional effect, and it can be finished into a hairstyle with a soft volume while having a clear wave of ridges.

<Prescription Example 3>
(mass)
Organopolysiloxane A 3.5
Isopropyl palmitate 0.7
PEG-9 Dimethicone 0.7
Polyquaternium-37 1.0
Steartrimonium chloride 0.24
Propylene glycol 1.5
(C12-14) s-Palace-9 0.25
Ethanol 18.0
Fragrance 0.1
Water remaining

  This hair styling composition is easy to stretch even when applied to both normal hair and wave hair with a history of chemical treatment such as permanent wave. It has a three-dimensional effect, and it can be finished into a hairstyle with a soft volume while having a clear wave of ridges.

Claims (8)

It contains the following components (A) to (D), the content of component (A) is 2.5% by mass or more and 8% by mass or less, the content of component (B) is 0.6% by mass or more and 5% by mass or less, The mass ratio (A) / (B) of the content of component (A) to the content of B) is 1 or more and 4 or less, and the mass ratio (D) of the content of component (D) to the content of component (A) / A hairdressing composition having (A) of 0.1 or more and 1.0 or less.
(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 n represents 2 or 3. ]
An organopolysiloxane formed by bonding poly (N-acylalkyleneimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 800 or more and 1,600 or less,
The mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is from 65/35 to 82/18,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 10,000 or more and 100,000 or less,
Organopolysiloxane
(B) One or two or more oils selected from silicone oil, ester oil and hydrocarbon oil that are liquid at 25 ° C
(C) Cationic thickener
(D) One or more polyhydric alcohols selected from glycerin, propylene glycol and dipropylene glycol   The hair styling composition according to claim 1, comprising a combination of at least one silicone oil and at least one ester oil as component (B).   The hair styling composition according to claim 2, wherein a mass ratio of the silicone oil to the ester oil (silicone oil) / (ester oil) is 1/5 or more and 5/1 or less.   The hair styling composition according to claim 2 or 3, wherein the component (B) is a combination of a polyether-modified silicone and a monohydric alcohol ester of a fatty acid.   The hairdressing composition according to claim 4, wherein the monohydric alcohol ester of fatty acid is isopropyl myristate.   The hair styling composition according to any one of claims 1 to 5, wherein the component (C) is polymethacryloyloxyethyltrimethylammonium chloride.   The hair styling composition according to claim 6, wherein the content of the component (C) is 0.05 mass% or more and 3 mass% or less.   The hairdressing composition according to any one of claims 1 to 7, which is used for permanent wave-treated hair.