JP5543114B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic containing a specific polymer.

  In hair cosmetics, in order to increase the holding power of a hairstyle, it is common to increase the blending amount of a set polymer or oil. However, if the amount of the set polymer is simply increased, the hair that has been set is hard and stiff. Moreover, in the hair cosmetics which mix | blended the polymer for a set, it is common that after a hair styling, once a hairstyle collapses, it cannot re-hair. On the other hand, in the case of hair cosmetics containing an oil agent, it is possible to re-hair after the hairstyle has collapsed, but the set retention strength is extremely low compared to the set polymer, and the oil agent is used to increase the set retention strength. Increasing the amount causes sticky hair to become sticky.

  Therefore, hair cosmetics that enable re-styling by using a specific set polymer have been proposed (for example, Patent Document 1). However, even with such a set polymer that can be re-haired, use of a polymer having a sufficient set holding force causes stickiness, while use of a non-sticky polymer provides a sufficient set holding force. Therefore, it is difficult to achieve both performances.

  In addition, it adheres to its own polymer, but has low adhesiveness to other objects (hereinafter referred to as “self-selective adhesiveness”). And hair cosmetics with little stickiness are proposed (for example, patent document 2). However, this polymer cannot be dissolved unless it is a specific solvent, and there are restrictions on the preparation of hair cosmetics by dissolving it in a general-purpose solvent such as water or lower alcohol. Even when it adheres, there is a problem that it is difficult to wash it off.

Special table 2001-507368 gazette JP 2008-162945 A

  Accordingly, there has been a demand for a hair cosmetic that has sufficient set holding power, can be re-haired, and can use a general-purpose solvent.

  The present inventors have found that a polyether polycarbonate having a specific polycarbonate structure having an alkyleneoxy chain as a constituent unit satisfies the above requirements and is suitable as a set polymer used in hair cosmetics.

  The present invention provides a hair cosmetic containing a polyether polycarbonate having a structural unit represented by the general formula (1).

[In the formula, A represents an alkylene group having 2 to 6 carbon atoms, n represents an average value of 5 to 1000, p represents an average value of 5 to 100, and (n × p) AO may be the same or different. ]

  The hair cosmetic composition of the present invention is not sticky, has a sufficient set holding power, has little stickiness, and can be restyled. Further, even when it is attached to a finger or the like during handling, it can be easily washed off.

[Polyether polycarbonate]
The polyether polycarbonate used in the present invention has a structural unit represented by the general formula (1). In the general formula (1), A represents an alkylene group having 2 to 6 carbon atoms, and (n × p) AOs may be the same or different, but are preferably composed of at least two alkyleneoxy groups. . A is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and (n × p) AOs further comprising a combination of an ethyleneoxy group and a propyleneoxy group. preferable. When (AO) _n is composed of different alkyleneoxy groups, these may be block structures or random structures, but are preferably random structures.

In the general formula (1), n is a number of 5 to 1000 indicating the average number of added moles of an alkyleneoxy group, and a number of 10 to 500 is preferable. p is a number of 5 to 100 indicating the average number of repeats of the [(AO) _n COO] group, and a number of 5 to 50 is preferred.

The polyether polycarbonate can be produced by the method shown in the following (A) or (B), and the method (A) is preferable.
(A) A method comprising a step of transesterifying a carbonate ester and a polyether diol.
(B) A method comprising a step of reacting phosgene and polyether diol.

  In the method (a), examples of the carbonate used for the production of the polyether polycarbonate include dimethyl carbonate, diphenyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and the like, and dimethyl carbonate and diphenyl carbonate are preferred.

  Polyether diol used in the production of polyether polycarbonate is preferably polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a copolymer of ethylene oxide and propylene oxide, and a random copolymer obtained by copolymerization of ethylene oxide and propylene oxide. Is more preferable. Commercially available products may be used as the polyether diol, and examples thereof include ADEKA polyether PR-3005, 3007, PR-5007 (manufactured by ADEKA Co., Ltd.) and the like.

  The number average molecular weight of the polyether diol used in the present invention is preferably 200 to 50,000, more preferably 400 to 20,000, from the viewpoint of obtaining good solubility in water or alcohol.

  In the production of the polyether polycarbonate, other polyols may coexist in addition to the polyether diol. Other polyols include diols such as ethylene glycol, propylene glycol, butanediol, tetramethylene glycol, 2,2-dimethyl-1,3-propanediol, pentanediol and hexanediol; polyols such as glycerin and pentaerythritol; bisphenol A, aromatic group-containing diols such as ethylene oxide adducts of bisphenol A, and the like.

When the above-mentioned glycerin, pentaerythritol, bisphenol A, ethylene oxide adduct of bisphenol A, etc. coexist as other polyols in the transesterification of carbonate ester and polyether diol, Will contain structural parts derived from these other polyols. In this case, such a structure portion may be a block structure or a random structure, similar to the above-described (AO) _n .

  The ratio of the polyether diol to the total polyol is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

  The reaction molar ratio between the carbonate ester and the polyether diol when transesterifying the carbonate ester and the polyether diol is preferably 1 / 0.9 to 1 / 1.1, and more preferably 1 / 0.95 to 1 / 1.05.

  When transesterifying the carbonate ester and the polyether diol, a normal ester exchange reaction catalyst can be used. Examples of such catalysts include alkali metals, alkaline earth metals, and their alkoxides, hydrides, hydroxides, carbonates, acetates, oxides, and the like. Also, use alkoxides, hydrides, hydroxides, carbonates, acetates, oxides, etc. of metals such as zinc, aluminum, tin, titanium, lead, germanium, antimony, bismuth, nickel, iron, manganese, zirconium, etc. You can also. Moreover, organic base compounds, such as a triethylamine and imidazole, can also be used. Among these catalysts, alkoxides of alkali metals such as sodium, potassium, rubidium and cesium, hydrides, hydroxides, carbonates, acetates, oxides, alkoxides and hydroxides of metals such as tin and titanium Carbonate, acetate, oxide and the like are preferable.

  The reaction temperature in the transesterification reaction between the carbonate ester and the polyether diol is preferably 100 to 300 ° C, more preferably 120 to 250 ° C, still more preferably 120 to 200 ° C. The reaction pressure may be normal pressure, but is preferably under reduced pressure.

  In the transesterification reaction, it is desirable to prepare a carbonate ester, a polyether diol, and a catalyst, and stir at the above temperature to remove alcohol released from the carbonate ester from the reaction system. In the case of normal pressure, desorbed alcohol can be effectively removed by circulating an inert gas such as nitrogen. In the case of reduced pressure, the volatilized elimination alcohol can be easily removed out of the system.

  The product obtained by transesterification is preferably subjected to a purification step excluding low molecular weight components. By removing the low molecular weight component, it is possible to reduce the adhesion (adhesive strength to other things) and to obtain a more excellent hair cosmetic with less stickiness.

  The removal of the low molecular weight component can be performed, for example, by solvent purification. More specifically, the product obtained by the transesterification reaction is dissolved in a water-soluble solvent, and a polyether polycarbonate having a small amount of low molecular weight components can be precipitated by adding a hydrophobic solvent.

  Examples of the water-soluble solvent include alcohol solvents such as methanol, ethanol and 2-propanol, acetone and methyl ethyl ketone, and ethanol is preferable. Examples of the hydrophobic solvent include hydrocarbon solvents such as hexane and heptane, and hexane is preferable. By adjusting the amount of the hydrophobic solvent added to the water-soluble solvent, a polyether polycarbonate having a desired molecular weight distribution can be obtained. The amount of the hydrophobic solvent added to the water-soluble solvent is preferably 0.1 to 50 times by volume, more preferably 0.5 to 10 times by volume.

  The weight average molecular weight of the polyether polycarbonate is preferably 50,000 or more, more preferably 100,000 or more, still more preferably 150,000 or more, and particularly preferably 200,000 or more from the viewpoint of good self-selective adhesiveness. Further, from the viewpoint of ease of blending into hair cosmetics, cleanability at the time of washing, etc., 1 million or less is preferable, 700,000 or less is more preferable, and 500,000 or less is more preferable.

  In addition, the weight average molecular weight of polyether polycarbonate and the number average molecular weight of the above-mentioned polyether diol shall mean the value measured by gel permeation chromatography (GPC). More specifically, the product name “HLC-8220GPC” (Tosoh Corporation) is used as the GPC device, and the value is obtained under the following GPC measurement conditions by polystyrene conversion value.

<Measurement method of average molecular weight>
Sample concentration: 0.25% by mass (chloroform solution)
・ Sample injection volume: 100μL
・ Eluent: Chloroform ・ Flow rate: 1.0 mL / min
・ Measurement temperature: 40 ℃
・ Column: Product name “KG” (1) + Product name “K-804L” (2) (above, Shodex)
・ Detector: Differential refractometer (attached to the GPC device trade name “HLC-8220GPC” (Tosoh Corporation))
Standard polystyrene samples: “TSKstandard POLYSTYRENE F-10” (molecular weight 102,000), F-1 (1020,000), A-1000 (870) (above, Tosoh Corporation), and “POLYSTYRENE STANDARD” (molecular weight 900,000, 3 10,000; Nishio Kogyo)

  When the self-selective adhesiveness of the polyether polycarbonate is expressed as a physical property value obtained by the measurement method shown below, the physical property value indicating the adhesiveness between the same measurement target polymers is “self-adhesion”, the measurement target polymer and other than this When the physical property value indicating the adhesion to others is defined as “adhesion strength”, the relative ratio of the adhesion strength / self-adhesion strength is desirably 0.7 or less, more preferably 0.5 or less, and still more preferably 0.3 or less. Further, it is desirable that the self-adhesion force is in a range of 200 gf or more. More preferably, the self-adhesion force is 200 gf or more, and the other adhesion force is 140 gf or less, more preferably 120 gf or less, and still more preferably 100 gf or less.

<Measurement method of adhesiveness (other adhesion and self-adhesion)>
A 20% by mass toluene solution of the polymer to be measured is prepared, cast on a PET sheet to a thickness of 500 μm with a bar coater, heated at 60 ° C. for 12 hours, and then left at 25 ° C. and 50% RH for 1 day. Using a tacking tester (Resca, TACIIUC-2006), the adhesive strength between the sheet and various materials attached to the probe of the tacking tester is measured.
The measurement conditions were a probe lowering speed of 600 mm / sec, a probe pressing load of 200 gf, and a pressing time of 0.5 sec. A polypropylene disk (engineering test service test piece: Mitsubishi Chemical Noblen NH-8) with an indenter area of 8 mm ² was attached to the tip of the probe, and the adhesive strength was measured. The obtained value was defined as “other adhesion”. On the other hand, the polymer to be measured was dissolved in a solution, cast and dried in the same manner as described above to obtain a PET disc having an indenter area of 8 mm ² , and this was attached to the probe tip to measure the adhesive force. The value was “self-adhesion”.

  When the polyether polycarbonate used in hair cosmetics has the above-mentioned self-selective tackiness, it has very little or no adhesion at room temperature, but it can be very strongly adhered and re-adhered when the adhesion sites are bonded to each other. By applying such a pressure-sensitive adhesive composition to a hair care agent, it becomes possible to formulate a set agent that realizes a strong set retention without stickiness to the hand, which was not possible with conventional set materials.

  Moreover, in order to obtain a higher setting property and resetting property, the adhesiveness between hair and an adhesive needs to be kept high. For example, in hair spray preparations, when applied to hair, the polymer adheres to the hair in a plasticized state with a solvent, spreads on the surface of the hair that is the adherend, and enters fine irregularities. The polymer can promote fixing adhesion on the hair in the course of drying due to solvent evaporation.

  The content of the polyether polycarbonate in the hair cosmetic composition of the present invention (in the case of an aerosol type, the content in the stock solution; the same applies hereinafter) is not sticky, and from the viewpoint of good set holding power, 0.5 to 20% by mass, It is preferably 1 to 15% by mass, more preferably 1.5 to 10% by mass.

[Other set polymers]
In the hair cosmetic composition of the present invention, the set holding power can be further improved by adding another set polymer as an optional component in addition to the polyether polycarbonate. Examples of such a set polymer include alkyl acrylamide / acrylate / alkyl aminoalkyl acrylamide / polyethylene glycol methacrylate copolymers described in JP-A-2-809911, and alkyl acrylamide / alkylaminoalkyl described in JP-A-8-291206. Acrylamide / polyethylene glycol methacrylate copolymer, Yuka Former R205 (Mitsubishi Chemical Co., Ltd.), RAM Resin (Osaka Organic Chemical Co., Ltd.) and other (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymers, Diaformer Z-712 (Mitsubishi Chemical Co., Ltd.) (Acrylates / Lauryl Acrylate / Stearyl Acrylate / Ethylamine Oxide Methyl Oxide) Copolymer, etc. (vinylamine / vinyl alcohol) such as Diafix C-601 (Mitsubishi Chemical Corporation) ) Copolymers, (alkyl acrylate / diacetone acrylamide) copolymers such as plus size L-9540B (Kohyo Chemical Co., Ltd.), Ultrahold 8, Acrylic acid / amides / ethyl acrylates such as Strong (above BASF) Copolymers, alkyl acrylate / methacrylic acid / silicone copolymers such as Rubiflex Silk (BASF), polyurethanes such as Rubiset PUR (BASF), polyvinyl caprolactams such as Rubiscol Plus (BASF), Rubimer 100P, Alkyl acrylate copolymers such as 30E (above, BASF), Anformer SH-701, 28-4910, LV-71, LV-47 (above, National Starch & Chemical) (Octylacrylamide / Hydroxypropyl acrylate / Butylaminoethyl methacrylate) Copolymer, Anformer V-42 (Nationala (Alkyl starch / octylacrylamide) copolymers such as Le Starch & Chemical Co.), vinyl acetate / crotonic acid / vinyl neodecanoate) copolymers such as Resin 28-2930 (National Starch & Chemical Co.), Dynam X (National)・ Polyurethane-14 such as Starch & Chemical Co., Ltd. ・ AMP-Acrylates Copolymer, Divinyl Sulfate Quaternary (Polyquaternium-11) of (Vinylpyrrolidone / Dimethylaminoethyl Methacrylate) Copolymer such as Gaffcut 440 (ISP), Guffcut HS -100 (ISP) vinyl pyrrolidone / dimethylaminopropyl methacrylamide) methyl quaternized (polyquaternium-28), Gantrez ES-225 (ISP), etc. (vinyl methyl ether / ethyl maleate) copolymers, Aqua Flex PV-40 (ISP), etc. (PV P / vinyl caprolactam / DMAPA acrylate copolymer, (isobutylene / ethylmaleimide / hydroxyethylmaleimide) copolymer such as Aquaflex FX-64 (ISP), and (vinylpyrrolidone / dimethylamino) such as Stylase W-20 (ISP) Propyl methacrylamide / methacryloylaminopropyl lauryl dimethyl ammonium chloride) copolymer (Polyquaternium-55), Stylee CC-10 (ISP) and other (vinyl pyrrolidone / acrylic acid DMAPA) copolymers, PVP / VA735 (ISP) and Rubiscor VA64P (Vinyl pyrrolidone / vinyl acetate) copolymers such as (BASF).

  Among the above set polymers, alkyl acrylamide / acrylate / alkyl amino alkyl acrylamide / polyethylene glycol methacrylate copolymer, alkyl acrylamide / alkyl amino alkyl acrylamide / polyethylene glycol methacrylate copolymer, (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) Copolymer, (methyl acrylate / diacetone acrylamide) copolymer neutralized aminomethyl propanol, (octyl acrylamide / hydroxypropyl acrylate / butyl aminoethyl methacrylate) copolymer, acrylic acid / acrylic acid amide / alkyl acid ethyl copolymer , Polyvinyl caprolactam, (alkyl acrylate / octylacrylamide) copo Mer Preferably, furthermore, the alkyl acrylamide / acrylate / alkylaminoalkyl acrylamide / polyethylene glycol methacrylate copolymers, alkyl acrylamide / alkylaminoalkyl acrylamide / polyethylene glycol methacrylate copolymer.

  Two or more kinds of these setting polymers can be used in combination, and the content thereof is 0.5 to 20% by mass, further 1 to 15% by mass in the hair cosmetic composition of the present invention, from the viewpoint of improving the setting power, It is preferably 1.5 to 10% by mass.

[Medium]
As the solvent (supporting medium), water, lower alcohols (ethanol, isopropanol, etc.), lactones, etc. can be used, and these can be used alone or in combination. Among these, from the viewpoint of versatility, water and ethanol are preferable, and ethanol is particularly preferable.

[Optional ingredients]
In addition to the above components, a cosmetic oil can be added to the hair cosmetic of the present invention within the limits that do not interfere with the effects of the present invention (0.1 to 10% by mass). Such cosmetic oils include glycerides such as castor oil, cacao oil, mink oil, avocado oil, olive oil; waxes such as beeswax, whale wax, lanolin, carnauba wax; cetyl alcohol, oleyl alcohol, hexadecyl alcohol Higher alcohols such as lauryl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol; isopropyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, Esters of myristic acid octyldodecyl acid; liquid oils such as liquid paraffin, petrolatum, squalane, hydrogenated polyisobutene; dimethylpolysiloxane, methylphenylpolysiloxane, polyether modified Examples include silicone derivatives such as silicone oil, epoxy-modified silicone oil, amino-modified silicone oil, and alkyl-modified silicone oil; polypropylene glycol and the like. Furthermore, an emulsifier can be added in order to stabilize the emulsification of these cosmetic oils. As the emulsifier, any of anionic, amphoteric, cationic and nonionic surfactants can be used.

  Further, the hair cosmetic composition of the present invention can be added with a fragrance, a pigment, and a preservative and an antioxidant to prevent daily deterioration of the hair cosmetic composition in order to increase commercial value. Depending on the humidity control agent such as glycerin and propylene glycol, curing agent, antistatic agent, surfactant, antifoaming agent, dispersant, thickener, ultraviolet absorber, antioxidant, preservative, colored dye, Dye fixing agents, propellants and the like can also be added.

[Drug type]
There is no restriction | limiting in particular as a dosage form of the hair cosmetics of this invention, Transparent liquid form, lotion form, emulsion, spray form (aerosol), mousse (foam aerosol), etc. are possible.

  The aerosol hair cosmetic is produced by filling the pressure cosmetic container with the above-described hair cosmetic together with a propellant. Examples of the propellant include liquefied petroleum gas (LPG), dimethyl ether (DME), carbon dioxide gas, nitrogen gas, and mixtures thereof. Alternatively, alternative CFCs such as HFC-152a can be used. The amount of the propellant is the mass ratio of the stock solution to the propellant in order to obtain good jetting properties and good adhesive properties, and the stock solution / propellant = 5/95 to 99/1, especially 20/80 to 95/5. The range of is preferable. Moreover, in order to obtain a good injection characteristic and a good adhesive characteristic, the pressure in the pressure vessel is preferably adjusted to be 0.12 to 0.45 MPa at a temperature of 25 ° C.

In the following examples, the weight average molecular weight and tackiness (other adhesion force and self-adhesion force) of the polyether polycarbonate were measured by the above-described methods.
For Comparative Polymer 1, the column was changed to the product name “TSKguardcolumn HHR-H” (1) + product name “TSKgel GMHHR-H” (2) (above, Tosoh Corporation) among the measurement conditions described above. And measured.

Synthesis example 1
In a reaction vessel equipped with a stirrer, a fractionation condenser and a thermometer, a random copolymer of ethylene oxide and propylene oxide (number average molecular weight 5000, hydroxyl value 22.0 mg KOH / g, manufactured by ADEKA Corporation, trade name ADEKA polyether PR-5007) 27.1 g (0.005 mol), 1.15 g (0.005 mol) of diphenyl carbonate and 4 mg (0.01 mmol) of cesium carbonate were added.

While stirring in the reaction vessel, the temperature was raised to 160 ° C., and heating was continued for 2 hours as it was, and the phenol produced by the reaction was discharged out of the system. Furthermore, vacuum suction was started using a vacuum pump, and the reaction was carried out for about 4 hours while gradually raising the temperature to 180 ° C. to obtain a polyether polycarbonate (hereinafter referred to as polymer 1). The weight average molecular weight of this polymer 1 was 180,000.
The other attachment strength was 106 gf, the self-adhesion strength was 233 gf, and the other attachment strength / self-adhesion strength was 0.45.

Synthesis example 2
10 g of the polymer 1 obtained in Synthesis Example 1 was dissolved in 100 mL of ethanol, 2 times the amount of hexane was added and shaken, and the resulting precipitate was collected. The recovered polymer (hereinafter referred to as polymer 2) had a weight average molecular weight of 257,000.
Further, the other attachment strength was 25 gf, the self-adhesion strength was 381 gf, and the other attachment strength / self-adhesion strength was 0.07.

Synthesis example 3
99 g of a random copolymer of ethylene oxide and propylene oxide (number average molecular weight 5000, hydroxyl value 22.0 mg KOH / g, manufactured by ADEKA, trade name ADEKA polyether PR-5007) in a reaction vessel equipped with a stirrer, a fractionation condenser and a thermometer (0.02 mol), 4.2 g (0.02 mol) of diphenyl carbonate and 16 mg (0.1 mmol) of potassium carbonate were added.

The temperature inside the reaction vessel was raised to 120 ° C. while stirring, and vacuum suction was started using a vacuum pump. The temperature was further raised to 145 ° C., and the phenol produced by the reaction was discharged out of the system. The mixture was continuously heated for 4.5 hours to obtain a polyether polycarbonate (hereinafter referred to as polymer 3). The weight average molecular weight of this polymer 3 was 210,000.
Further, the other attachment strength was 70 gf, the self-adhesion strength was 324 gf, and the other attachment strength / self-adhesion strength was 0.22.

  7.5g of each of the polymers 1 to 3 obtained in Synthesis Examples 1 to 3 can be sealed in a glass container that can be sealed (transparent wide-mouth standard bottle, No. 13, mouth inner diameter 31.9mm x body diameter 58.0mm x height 115.0mm) Ethanol was added to make a total amount of 100 g, and the mixture was stirred (800 r / m) with a magnetic stirrer (length 30 mm × diameter 8 mm) at room temperature (25 ° C.) for 24 hours. Then, it was left still for 24 hours, and the solubility in ethanol was evaluated using the presence or absence of solid content in the solution as an evaluation criterion. As a result, all the polymers 1 to 3 were dissolved in ethanol.

Comparative Synthesis Example 1
Prepare a reaction vessel equipped with a stirrer, a reflux condenser through a water separation tube, and a thermometer. Polycarbonate diol (PLACCEL CD220PL; number average molecular weight 2000, hydroxyl value 58.4 mgKOH / g, Daicel Chemical Industries, Ltd.) 51.4 g (0.027 mol), 5.4 g (0.027 mol) of sebacic acid, 0.2 g (0.001 mol) of p-toluenesulfonic acid and 120 mL of toluene were added.
While stirring the inside of the reaction vessel, the temperature was raised to 150 ° C., and heating was continued as it was for 5 hours, and water produced by the reaction was discharged out of the system together with toluene. Comparative polymer 1 was obtained.
The weight average molecular weight of this comparative polymer 1 was measured by gel filtration chromatography (GPC) using polystyrene gel. The molecular weight was calibrated with a polystyrene standard sample, and the weight average molecular weight was 50700.
The other attachment strength was 50 gf, the self-adhesion strength was 350 gf, and the other attachment strength / self-adhesion strength was 0.14.

  Comparative polymer 1 obtained in Comparative Synthesis Example 1 was evaluated for solubility in ethanol in the same manner as described above. As a result, the comparative polymer 1 was not dissolved in ethanol.

Examples 1-3 and Comparative Examples 1-3
Using the polymers 1 to 3 obtained in Synthesis Examples 1 to 3 and the comparative polymer 1 obtained in Comparative Synthesis Example 1, pump mists having the formulations shown in Table 1 were prepared. These pump mists were evaluated according to the following evaluation method.

〔Evaluation method〕
・ Evaluation of stickiness to fingers A hair bundle having a length of 10 cm and a width of 2 cm was wetted with water, towel-dried, wound around a 4 cm diameter rod, and allowed to stand in an environment of 25 ° C. and 65% RH for 24 hours. A 2 g amount of the hair cosmetic composition of each formulation was applied to this hair bundle by a pump mist, left to dry in an environment of 25 ° C. and 65% RH for 2 hours, and then the rod was removed to prepare an evaluation sample. A specialized panelist evaluated the feel of these evaluation samples according to the following criteria.

◎: No sticky feeling ○: Almost no sticky feeling △: Slightly sticky feeling ×: There is a sticky feeling

・ Evaluation of the feeling of stickiness The expert panelist evaluated the feel of the evaluation sample produced in the same manner as described above according to the following criteria.

◎: No wrinkle feeling ○: Almost no wrinkle feeling △: Slightly stiff feeling ×: Stiff feeling

・ Evaluation of set power The expert panelists evaluated the set power of evaluation samples prepared in the same manner as described above according to the following criteria.

◎: Setting power is strong ○: Setting power is slightly strong △: Setting power is slightly weak ×: Setting power is weak or absent

・ Evaluation of resetting force After passing through the evaluation sample prepared in the same manner as described above five times (Dellin Smooth Comb # 802 (straight); Takikawa Co., Ltd.), it was wound again on a 4 cm diameter rod and 25 ° C. The set was fixed for 1 hour in an environment of 65% RH. A specialized panelist evaluated the resetting power of the reset evaluation sample according to the following criteria.

◎: Reset force is strong ○: Reset force is slightly strong △: Reset force is slightly weak ×: Reset force is weak or absent

Example 4
A hair cream having the following composition was produced by a conventional method.
Self-selective adhesive polymer (Synthesis example 3) 1.0 (mass%)
Polyoxyethylene (EO6) stearyl ether 1.5
Beeswax 1.0
Perfume appropriate amount Preservative appropriate amount
Water balance meter 100.0

Example 5
A hair liquid having the following composition was produced by a conventional method.
Self-selective adhesive polymer (Synthesis example 2) 1.0 (mass%)
Propylene glycol 2.0
Ethanol 45.0
Perfume appropriate amount Colorant appropriate amount
Water balance <br/> 100.0 in total

Example 6
A hair conditioner having the composition shown below was produced by a conventional method.
Self-selective adhesive polymer (Synthesis example 2) 1.0 (mass%)
Cetyltrimethylammonium chloride 0.75
Cetostearyl alcohol 1.0
Glyceryl monostearate 0.5
Perfume
Water balance meter 100.0

Example 7
A foam hair styling agent (mousse) having the composition shown below was produced by a conventional method.
Hair conditioner 90 of Example 6 (mass%)
Propellant (LPG 60% by mass, DME 40% by mass) 10
Total 100

Example 8
A hair liquid having the following composition was produced by a conventional method.
Self-selective adhesive polymer (Synthesis example 1) 2.5 (mass%)
Propylene glycol 3.0
Ethanol 40.0
Perfume
Water balance meter 100.0

Example 9
A stock solution having the following composition was filled in a pressure-resistant container at a ratio of propellant (LPG 60%, DME 40%) and stock solution / propellant = 50/50 to produce a mist-like hair styling agent (spray).
Self-selective adhesive polymer (Synthesis example 3) 7.5 (mass%)
Perfume
Ethanol balance meter 100.0

Example 10
A stock solution having the following composition was filled in a pressure-resistant container at a ratio of propellant (LPG 60%, DME 40%) and stock solution / propellant = 50/50 to produce a mist-like hair styling agent (spray).
Self-selective adhesive polymer (Synthesis example 1) 2.0 (mass%)
Perfume
Ethanol balance meter 100.0

Example 11
A hair gel having the composition shown below was produced by a conventional method.
Self-selective adhesive polymer (Synthesis example 3) 2.0 (mass%)
Carboxyvinyl polymer (* 1) 1.0
Concentrated glycerin 5.0
Triethanolamine solution (89% by mass) 1.3
Ethanol 10.0
Perfume
Water balance meter 100.0
* 1: Carbopol 940

Example 12
A hair wax having the following composition was produced by a conventional method.
Self-selective adhesive polymer (Synthesis Example 3) 10.0 (mass%)
Anionic polymer 1 5.0
Glycerin 5.0
Carbomer (* 2) 0.1
Cetanol 5.0
Glyceryl stearate 5.0
Polysorbate 60 1.0
Microcrystalline wax 0.5
Beeswax 0.5
Vaseline 0.5
Dimethicone 2.0
Octyldodecyl myristate 0.5
Ethanol 5.0
Fragrance 0.05
pH adjuster (sodium hydroxide) Adjusted to pH 6.5 Water remaining
* 2: Carbopol 981 manufactured by Lubrizol

  The hair cosmetic amounts obtained in the above examples all show excellent hair styling properties and re-styling properties when a normal dose is applied to the hair, and the hair is stiff during hair styling, sticky to the hand, etc. It did not give an unpleasant feel.

Claims (8)

Formula (1) it has a structural unit represented by weight average molecular weight of 50000-1000000 der Ru polyether polycarbonate hair styling hair cosmetic containing.

[In the formula, A represents an alkylene group having 2 to 6 carbon atoms, n represents an average value of 10 to 1000, p represents an average value of 5 to 100, and (n × p) AO may be the same or different. ] Polyether polycarbonate, number-average molecular weight of those prepared using a polyether diol of 400 to 50,000 claim 1 hair cosmetic according.   The hair cosmetic composition according to claim 1 or 2, wherein (n x p) AOs in the general formula (1) are composed of at least two alkyleneoxy groups.   The hair cosmetic composition according to claim 3, wherein (n x p) AOs in the general formula (1) are composed of a combination of an ethyleneoxy group and a propyleneoxy group. The hair cosmetic according to claim 3 or 4, wherein (AO) _n in the general formula (1) has a random structure.   The hair cosmetic according to any one of claims 1 to 5, wherein the polyether polycarbonate is produced by a production method comprising a step of transesterifying a carbonate ester and a polyether diol. The hair cosmetic composition according to claim 6 , wherein the polyether polycarbonate is produced through a purification step in which a low molecular weight component is removed from a product obtained by transesterification. The hair cosmetic according to any one of claims 1 to 7, further comprising a solvent selected from water, ethanol and isopropanol.