JP2008162945A - Hair cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair cosmetic having a sufficient set retention power without forming a stiffened hair, giving little stickiness and enabling redressing of the hair. <P>SOLUTION: The hair cosmetic contains a polymer containing a polycarbonate structure having a repeating unit expressed by general formula (1) -(R-O-CO-O)- (R is a 2-20C bivalent hydrocarbon group) bonded with each other or with a structure having different repeating unit through one or more bonds selected from an ester bond, ether bond, urethane bond, urea bond, carbon-silicon bond, amide bond, bond (A) and bond (B) (R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each a hydrogen atom or a 1-4C alkyl group). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hair cosmetic for styling.

  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, simply increasing the blending amount of the set polymer causes a stiff and stiff condition. Moreover, in the hair cosmetics which mix | blended the polymer for a set, after styling, once a hairstyle collapses once, it is common that it cannot re-hair. On the other hand, in the case of hair cosmetics formulated with an oil agent, it is possible to re-hair after the hairstyle has collapsed, but the set holding power is extremely low compared to the set polymer, and the oil agent is used to increase the set holding power. Increasing the amount causes stickiness.

  On the other hand, there has been proposed a hair cosmetic capable of re-hairing by using a specific set polymer (for example, Patent Document 1). However, even with specific set polymers that can be re-haired, those with sufficient set retention will cause stickiness, and those with less stickiness will not have sufficient set retention and both performance will be reduced. There was nothing to make it compatible.

Special table 2001-507368 gazette

  SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a hair cosmetic that is not sticky, has a sufficient set retention force, has less stickiness, and can be restyled.

  The present inventors have found that the above object can be achieved by using a polymer having a specific structure for hair cosmetics.

  The present invention relates to general formula (1)

〔式中、Ｒは炭素数２〜20の２価の炭化水素基を示す。〕
で表される繰り返し単位を有するポリカーボネート構造が、エステル結合、エーテル結合、ウレタン結合、尿素結合、炭素−ケイ素結合、アミド結合、下記結合(A)及び結合(B)

[In formula, R shows a C2-C20 bivalent hydrocarbon group. ]
A polycarbonate structure having a repeating unit represented by the following formula is an ester bond, an ether bond, a urethane bond, a urea bond, a carbon-silicon bond, an amide bond, the following bond (A) and bond (B):

（Ｒ¹、Ｒ²及びＲ³は、それぞれ水素原子又は炭素数１〜４のアルキル基を示す）
からなる群から選ばれる一種以上の結合を介して、該ポリカーボネート構造同士で連結され、又は他の繰り返し単位を有する構造と連結されてなるポリマーを含有する毛髪化粧料を提供するものである。

(R ¹ , R ² and R ³ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
The present invention provides a hair cosmetic containing a polymer which is connected to each other through one or more bonds selected from the group consisting of the above, or is connected to a structure having another repeating unit.

  The hair cosmetic composition of the present invention is not sticky, has a sufficient set holding power, has little stickiness, and can be restyled.

(General formula (1))
In the general formula (1), the repeating degree of the repeating unit is not particularly limited and can be appropriately selected according to the purpose.

  In the general formula (1), the divalent hydrocarbon group having 2 to 20 carbon atoms represented by R may be any one of linear, branched, cyclic, saturated and unsaturated. Examples thereof include an alkylene group and an arylene group, and an alkylene group is particularly preferable. As the alkylene group, for example, linear or branched alkylene groups such as ethylene, trimethylene, propylene, tetramethylene, hexamethylene, 3-methylpentamethylene and octamethylene groups are preferable.

[Linking group]
The polycarbonate structures having a repeating structure represented by the general formula (1), or the polycarbonate structure and a structure having another repeating unit are an ester bond, an ether bond, a urethane bond, a urea bond, a carbon-silicon bond, and a bond. They are linked via one or more bonds selected from the group consisting of (A) and bond (B). Examples of R ¹ , R ^2, and R ^{3 in the} general formulas (A) and (B) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group.

  Among the above linking groups, ester bonds, urethane bonds, and urea bonds are preferable, and ester bonds are particularly preferable. Accordingly, polycarbonate polyester is most preferable as the polymer used in the present invention.

[Polycarbonate polyester]
Polycarbonate polyester comprises a polycarbonate component containing at least one kind of polycarbonate having two reactive functional groups and an aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 20 carbon atoms as a molecular skeleton, and the reaction described above. It can be obtained by dehydrating and condensing a raw material containing a compound having two other reactive functional groups that can form an ester bond with the functional group.

  Since polyester is obtained by dehydration condensation of a compound having a hydroxyl group and a compound having a carboxy group, the above-mentioned “polycarbonate having two reactive functional groups” includes a polycarbonate having two hydroxyl groups or carboxy groups. Can be used. In addition, as the “compound having two other reactive functional groups”, a compound having two carboxy groups or two hydroxyl groups can be appropriately used corresponding to the kind of the reactive functional group of the polycarbonate. Further, a polycarbonate having one hydroxyl group and one carboxyl group may be subjected to dehydration condensation.

Therefore, by dehydrating and condensing a compound having a hydroxyl group and a compound having a carboxy group,
(i) a polyester having an ester structure formed by dehydration condensation between a polycarbonate having a hydroxyl group at both ends of the molecular chain (polycarbonate diol) and a compound having two carboxy groups in one molecule (dicarboxylic acid);
(ii) a polyester having an ester structure formed by dehydration condensation between a polycarbonate having a carboxy group at both ends of the molecular chain (polycarbonate dicarboxylic acid) and a compound having two hydroxyl groups in one molecule;
(iii) a polyester further comprising an ester structure formed by dehydration condensation between molecules of a polycarbonate having one hydroxyl group and one carboxy group at the end of the molecular chain;
There can be. Of these, (i) and (ii) are preferred, and (i) is most preferred.

  As described above, the ester bond of the polycarbonate polyester can be obtained by a method in which a compound having a hydroxyl group and a compound having a carboxy group are directly subjected to dehydration condensation. It may be reacted with a compound having a carboxy group instead of an active structure such as an ester, or a compound having a carboxy group may be reacted with a compound having a hydroxyl group instead of its acid halide or alkyl ester. An ester bond may be formed by However, from the viewpoint of simplicity of the process and a small amount of by-products, the method of directly dehydrating and condensing a compound having a hydroxyl group and a compound having a carboxy group is most preferable.

[Polycarbonate diol]
Examples of the (poly) carbonate diol include (poly) trimethylene carbonate diol, (poly) hexamethylene carbonate diol, (poly) 3-methyl (pentamethylene) carbonate diol, and copolymers thereof. Examples of the (poly) carbonate diol include ethylene glycol, 1,3-trimethylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8- Dealcoholization reaction of polyhydric alcohols such as octanediol, 1,9-nonanediol, 1,10-decanediol and 1,18-octadecanediol with dialkyl carbonates such as diethylene carbonate, dimethyl carbonate and diphenyl carbonate or diaryl carbonates Polycarbonate diol obtained by the above can also be used. (Poly) carbonate diol can be used individually or in combination of 2 or more types.

  These polycarbonate diols are required to have a molecular length with which the components are sufficiently effective, that is, molecular weight, and from the viewpoint of productivity, the number average molecular weight of the polycarbonate diol is preferably 400 to 10,000, It is more preferable that Here, the number average molecular weight of the polycarbonate diol refers to a 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.

GPC measurement conditions and sample concentration: 0.25% by mass (chloroform solution)
・ Sample injection volume: 10μl
・ Eluent: Chloroform ・ Flow rate: 1.0 ml / min
・ Measurement temperature: 40 ℃
・ Column: Product name “TSKguardcolumn H _HR -H” (1) + Product name “TSKgel GMH _HR -H” (2) (above, Tosoh Corporation)
・ Detector: Differential refractometer (Attached to GPC device “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)

  Commercially available (poly) carbonate diols include, for example, “PLACCEL CD205PL”, “PLACCEL CD210PL”, “PLACCEL CD220PL” (above, Daicel Chemical Industries), “UM-CARB90 (1/1)” (Ube Industries, Ltd.) ) And the like.

  As the diol component, in addition to the (poly) carbonate diol, other diol components can be used in combination as required. As such a diol component, an aromatic diol can be used, but an aliphatic diol or an alicyclic diol (particularly an aliphatic diol) can be preferably used. Such other diol components used in combination can be used alone or in combination of two or more.

  Specifically, examples of diol components other than (poly) carbonate diol include side chains (particularly, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,6-hexanediol, etc.). An aliphatic diol having a hydrocarbon group-containing side chain); a linear aliphatic diol such as ethylene glycol, 1,3-trimethylene glycol, 1,4-butanediol, 1,5-pentanediol; And alicyclic diols such as 4-cyclohexanediol.

  Further, as the diol component, it is also possible to use a diol component in a polymer form such as a commercially available polyester diol, polycaprolactone diol, polyalkylene diol, or silicone diol (particularly a diol component in the form of an aliphatic polymer).

  Examples of the polyester diol include diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, succinic acid, methyl succinic acid, adipic acid, sebacic acid, and the like. And polyester diols obtained by dehydration reaction of these acid anhydrides or dicarboxylic acids such as lower alkyl esters or derivatives thereof alone or in a mixed state. Examples of commercially available products include 3-methyl Trade names `` Kuraray polyol P-510 '', `` Kuraray polyol P-1010 '', `` Kuraray polyol P-2010 '', `` Kuraray polyol P-3010 '' which are polyester diols of 1,5-pentanediol and adipic acid, “Kuraray polyol P-5010” (Kuraray)

  Examples of the polycaprolactone diol include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and δ-valerolactone, and examples of commercially available products include, for example, the trade name “Placcel L205AL”. "Placcel L212AL", "Placcel L220AL", "Placcel L220PL", "Placcel L230AL" (above, Daicel Chemical Industries, Ltd.) and the like.

  Examples of the polyalkylene diol include a polyalkylene diol in which both ends of polyalkylene such as polybutene and polyisoprene are substituted with hydroxyl groups, and a hydrogenated grade polyalkylene diol in which double bonds in the molecular chain are treated with hydrogen. Examples of commercially available products include “R-45HT”, “R-15HT”, “Epol” (above, Idemitsu Kosan Co., Ltd.) and the like.

  Examples of the silicone diol include trade names “X-22-160AS”, “KF-6001”, “KF-6002”, “KF-6003” (Shin-Etsu Chemical Co., Ltd.), and the like.

  Furthermore, components having a structure such as polysulfide, polyamide, polyimide, polyketone, polyurethane, polyurea and the like can also be used as diol components if both ends are substituted with hydroxyl groups.

  By using these, it is possible to add structures other than polycarbonate and polyester into the polymer chain.

[Dicarboxylic acid component]
Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and the like. Of these, aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferred. In addition, as the dicarboxylic acid component, these reactive derivatives (for example, acid chloride, acid anhydride, lower alkyl ester, etc.) can also be used. The dicarboxylic acid components can be used alone or in combination of two or more.

  Specifically, examples of the dicarboxylic acid component include aliphatics such as succinic acid, methyl succinic acid, adipic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, and dimer acid. Dicarboxylic acids; aromatic dicarboxylic acids such as phthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid; and reactive derivatives thereof (acid anhydrides, lower alkyl esters, etc.).

  As the dicarboxylic acid component, commercially available polyester dicarboxylic acid, polyether dicarboxylic acid, dicarboxylic acid in polymer form such as carboxy-modified silicone at both ends (particularly, dicarboxylic acid in aliphatic polymer form) and the like can also be used. is there.

  The carbonate polyester can be obtained by an esterification reaction by a polycondensation reaction according to a conventional method. In this reaction, it is desirable that the diol component and the dicarboxylic acid component be equimolar reactions, but in order to promote the esterification reaction, either may be used in excess.

  In addition, it is desirable to use a catalyst in this reaction in order to increase the polymerization rate. As a catalyst, the catalyst used for a general condensation reaction can be used. Specifically, metals such as zinc powder, aluminum, tin oxide, zinc oxide, germanium oxide, antimony trioxide, dibutyltin oxide and other metal oxides, zinc chloride, aluminum sulfate, magnesium carbonate, cesium carbonate, zinc acetate, Examples thereof include metal salt compounds such as tin sulfate, metal alkoxides such as tetraisopropyl titanate and tetrabutyl titanate, rare earth metal compounds such as scandium triflate, and acids such as hydrochloric acid, sulfuric acid and paratoluenesulfonic acid. These can be used alone or in combination of two or more.

[Self-selective adhesiveness]
The polymer used in the present invention preferably has a mass average molecular weight of 30,000 to 300,000 from the viewpoints of self-selective adhesiveness, ease of incorporation into hair cosmetics, detergency during hair washing, and the like. 10,000 to 250,000 is more preferable, and 70,000 to 200,000 is most preferable. Here, the self-selective adhesiveness refers to the property that the compounds themselves show high adhesiveness but do not show adhesiveness to other things such as fingers.

  Here, the mass average molecular weight of the polymer used in the present invention is measured by gel permeation chromatography (GPC) in the same manner as the number average molecular weight of the polycarbonate diol. More specifically, as the GPC apparatus, the above-mentioned GPC apparatus trade name “HLC-8220GPC” (Tosoh Corporation) is used, and is obtained under the same measurement conditions as described above by polystyrene conversion value.

  In order to obtain a polymer having the above molecular weight, it is necessary to appropriately control various conditions (catalyst amount, temperature, reaction time, etc.) during the polycondensation reaction. In general, the catalyst amount is 0.0001 to 1% by mass based on the total amount of components, and the molecular weight can be adjusted by adjusting the reaction time in the temperature range of 50 to 300 ° C., but these are used. It depends on the type of catalyst and the type of monomer unit to be reacted. Moreover, when the polymer used in the present invention is a carbonate polyester, a method of adding a compound having two functional groups capable of reacting with a hydroxyl group and / or a carboxy group contained in the carbonate polyester to extend the chain. In addition, a method of crosslinking by adding a compound having three or more compounds can be used. As a compound which can react, a polyisocyanate compound, an epoxy compound, an aziridine compound etc. are mentioned, for example. These can be used alone or in combination of two or more.

  The polymer obtained is preferably used after purification by removing the catalyst, low molecular weight components and the like for reasons such as polymer stability. As a purification method, a known method such as a reprecipitation method, solvent distillation, dialysis method, ultrafiltration method, chromatographic method, extraction method, or neutralization method when an acid catalyst is used can be used.

  When the above-mentioned self-selection adhesiveness is expressed as a physical property value obtained by a measurement method under a certain condition (described later), the physical property value indicating the adhesiveness between the same measurement target polymers is “self-adhesion force”, the measurement target polymer and other than this When the physical property value indicating the adhesiveness with the other is “other adhesion”, it is desirable that the relative ratio of other adhesion / self-adhesion is 1/5 or less. More preferably, the self-adhesion force is desirably in the range of 200 gf or more. More preferably, the other adhesion force is 40 gf or less and the self-adhesion force is 200 gf or more.

  When the polymer used in hair cosmetics has the above-mentioned self-selective tackiness, it has very little or no adhesion at room temperature, but can be very strong and re-adhesive when the adhesion sites are bonded to each other. By applying the agent composition to a hair care agent, it becomes possible to formulate a set agent that realizes 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 polymer contained in the hair cosmetic composition of the present invention is not sticky, non-sticky, and from the viewpoint of obtaining a sufficient set holding power, 0.1 to 20 mass%, particularly 0.4 to 10 mass% of the entire hair cosmetic composition. Is preferred.

[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. Of these, ethanol and γ-caprolactone are preferred from the viewpoint of good solubility of the polymer used in the present invention, and ethanol and γ-caprolactone are particularly preferably used in combination.

[Optional ingredients]
In addition to the polymer having the polycarbonate structure described above, the hair cosmetic composition of the present invention, in addition to the above-described polymer having a polycarbonate structure, other polyester-based pressure-sensitive adhesives (that is, polyester having no polycarbonate structure), acrylic Resins that are conventionally used as resin components for pressure-sensitive adhesives such as pressure-sensitive adhesives, polyurethane-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives can be used. Such a resin component can be appropriately selected from amphoteric polymers, anionic polymers, cationic polymers, and nonionic polymers that are film-forming polymers used in ordinary hair cosmetics.

  Specific examples of the amphoteric polymer include a monochloroacetic acid amphoteric product of a dimethylaminoethyl methacrylate / methacrylic acid alkyl ester copolymer such as Yucaformer AM-75, AM75S / SM (Mitsubishi Chemical Corporation); Anformer 28-4910, Examples thereof include hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymers such as LV-71 (National Starch).

  Specific examples of anionic polymers include methyl vinyl ether / maleic anhydride alkyl half ester copolymers such as Gantrez ES-225, ES-425, and SP-215 (above ISP); Resin 28-1310 (National Starch) ), Vinyl acetate / crotonic acid copolymers such as Ruby Set CA (BASF); vinyl acetate / crotonic acid / vinyl neodecanoate copolymers such as Resin 28-2930 (National Starch); Ruby Set CAP (BASF) Such as vinyl acetate / crotonic acid / vinyl propionate copolymer; vinyl acetate / maleic acid monobutyl ester / isoboronyl acrylate copolymer such as ADVANTAGE-CP (ISP); plus size L53P (Kohyo Chemical Co.), (Meth) acrylic acid / (meth) acrylic acid ester copolymers such as Diamond Hold (Mitsubishi Chemical); Ultrahold 8, Ultrahold Acrylic acid / alkyl acrylate / alkyl acrylamide copolymers such as Strong (above BASF), Anformer V-42 (National Starch); Polyvinylpyrrolidone / Acrylate / Rubiflex VBM35 (BASF), etc. (Meth) acrylic acid copolymer; carrageenan (MRC polysaccharide company) such as Soagina LX-22.

  Specific examples of the cationic polymer include vinyl imidazolium trichloride / vinyl pyrrolidone copolymers such as Rubycut FC370, FC550, FC905, HM552, MonoCP (above, BASF); Cellcut H-100, L-200 (above, National Starch Co., Ltd.) hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer; Gaffcut 734, 755N, 755 (above, ISP Co.) vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer; Rubiflex (BASF) Polyvinylpyrrolidone / dimethylaminoethyl methacrylate copolymer such as Co., Ltd .; Polyvinyl pyrrolidone / alkylamino acrylate / vinyl caprolactam copolymer such as Copolymer 845, 937, 958 (above, GAF); Guffcut HS-100 (ISP) Vinylpyrrolidone / methacrylamidopropyl salts such as Trimethylammonium copolymer; water-soluble polymer compound such as an alkyl acrylamide / acrylate / alkylaminoalkyl acrylamide / polyethylene glycol methacrylate copolymers as described in JP-A-2-180911 and the like.

  Specific examples of nonionic polymers include polyvinylpyrrolidone such as Rubiscol K-12, 17, 30, 60, 80, 90 (above, BASF), PVP K-15, 30, 60, 90 (above, ISP), etc. ; Polyvinylpyrrolidone / vinyl acetate copolymers such as Rubiscol VA28, 37, 55, 64, 73 (above, BASF), PVP / VA-735, 535, 335, 235, S-630 (above, ISP) ; Polyvinylpyrrolidone / vinyl acetate / vinyl propionate terpolymer such as Rubiscol VAP343 (BASF); Vinyl acetate / N-vinyl-5-methyl-2-oxazoline copolymer such as Dowlex (Dow Chemical) Examples include coalescence.

  The content of the film-forming polymer is preferably from 0.01 to 25% by mass, particularly from 0.01 to 10% by mass, based on the entire hair cosmetic composition, from the viewpoint of sufficient setting power and good touch.

  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 , Lauryl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, polypropylene glycol, etc .; isopropyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, 2-ethylhexanoic acid Hexadecyl, esters of myristic acid octyldodecyl acid; dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone oil, epoxy-modified silicone oil, amino And silicone derivatives such as non-modified silicone oil and alkyl-modified silicone oil. 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.

When the dosage form is aerosol, the propellant is hydrofluorocarbon, liquefied petroleum gas, dimethyl ether, etc. alone or as a mixture at a rate of 1 to 20% by mass, that is, the internal pressure is 2.0 to 6.0 kg / cm ² G It is preferable to use it.

[Measurement method of adhesiveness (other adhesion and self-adhesion)]
In this specification, the measurement of the adhesiveness (self-adhesion force and other adhesion force) of a polymer shall be performed by the following method.
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 is dissolved in a solution, cast, and dried as described above to form a PET disc with an indenter area of 8 mm ² , which is attached to the probe tip to measure the adhesive force. The value was determined as “self-adhesion”.

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) 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. After the toluene was completely discharged, the water separation tube was removed and replaced with a cold trap, and further connected to a vacuum pump. While maintaining the temperature at 150 ° C., vacuum suction was started, and the reaction was carried out for about 6 hours to obtain polymer 1.
The mass average molecular weight of the polymer 1 was measured by gel filtration chromatography (GPC) using polystyrene gel. The molecular weight was calibrated with a polystyrene standard sample, and the mass average molecular weight was 102000.
In addition, the other attachment force was 25 gf, the self-adhesion force was 420 gf, and the other attachment force / self-adhesion force was 0.06.

Synthesis example 2
Polymer 2 was obtained by carrying out the same raw materials and the same operations as in Synthesis Example 1 except that the reaction time under vacuum suction with a vacuum pump was about 2 hours.
The mass average molecular weight of the polymer 2 was measured by gel filtration chromatography (GPC) using polystyrene gel. The molecular weight was calibrated with a polystyrene standard sample, and the mass average molecular weight was 75000.
In addition, the other attachment force was 35 gf, the self-adhesion force was 400 gf, and the other attachment force / self-adhesion force was 0.09.

Synthesis example 3
The same raw material as in Synthesis Example 1 and the same operation as in Synthesis Example 1 were performed except that the reaction was not performed while suctioning under reduced pressure with a vacuum pump to obtain Polymer 3.
The mass average molecular weight of this polymer 3 was measured by gel filtration chromatography (GPC) using polystyrene gel. The molecular weight was calibrated with a polystyrene standard sample, and the mass 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.

Examples 1-6 and Comparative Examples 1-2
Using the polymers synthesized in Synthesis Examples 1 to 3, hair cosmetics shown in Table 1 were prepared, and “no stickiness”, “no stickiness”, “setting power” and “resetting power” were obtained. evaluated.

〔Evaluation methods〕
・ Evaluation of feeling of stickiness on the finger Create a dry adhesive surface on the resin sheet, press the index finger for a short time (about 1 second), pull it away, and evaluate the degree of stickiness by touching the index finger surface at that time according to the following criteria did.
◎: No sticky feeling ○: Almost no sticky feeling △: Slightly sticky feeling ×: There is a sticky feeling

・ Evaluation of the feeling of stickiness A hair bundle having a length of 10 cm and a width of 2 cm was wetted with water, towel-dried, wound on a rod with a diameter of 4 cm and dried naturally. After applying a certain amount of the preparation and drying, the degree of stiffness immediately after removing the hair bundle from the rod was evaluated according to the following criteria.
◎: No wrinkle feeling ○: Almost no wrinkle feeling △: Slightly stiff feeling ×: Stiff feeling

-Evaluation of setting power A hair bundle having a length of 10 cm and a width of 2 cm was wetted with water, towel-dried, wound on a rod having a diameter of 4 cm and naturally dried. After a predetermined amount of the preparation was applied and dried, the hair bundle was removed from the rod. The upper end of the hair bundle was fixed, and the difference L ₀ between the upper end immediately after removal and the height of the hair tip was measured. According to the following formula, the case where the length of the original hair without curl was the same as L was evaluated as a setting force of 0%.
Setting force (%) = (L−L ₀ ) / L

-Evaluation of resetting force A hair bundle having a length of 10 cm and a width of 2 cm was wetted with water, dried with a towel, and then wound on a rod with a diameter of 4 cm to be naturally dried. After applying a certain amount of the preparation and drying at room temperature for 1 hour, the hair bundle was removed from the rod. The upper end of the hair bundle was fixed, and the difference L ₀ between the upper end immediately after removal and the height of the hair tip was measured. The hair bundle broken through the comb was wound around a rod having a diameter of 4 cm again and left at room temperature for 1 hour, and then the rod was removed from the hair bundle. The upper end of the hair bundle was fixed, and the difference L ₁ between the upper end immediately after removal and the height of the hair tip was measured. According to the following formula, the length of the original hair without curling was set as L, and the case where curling was achieved after combing as in the first curling was evaluated as 100%.
Reset force (%) = (L−L ₁ ) / (L−L ₀ )

Example 7
A hair cream having the following composition was produced by a conventional method.
Self-selective adhesive polymer (Synthesis example 3) 1.0 (mass%)
Polyoxyethylene stearyl ether (9E.O.) 1.5
Beeswax 1.0
Perfume appropriate amount Preservative appropriate amount
Water balance meter 100.0

Example 8
A hair liquid having the following composition was produced by a conventional method.
Self-selective adhesive polymer (Synthesis Example 2) 0.5 (mass%)
Propylene glycol 2.0
Ethanol 30.0
γ-Caprolactone 15.0
Perfume appropriate amount Colorant appropriate amount
Water balance <br/> 100.0 in total

Example 9
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 10
A foam hair styling agent (mousse) having the composition shown below was produced by a conventional method.
Hair conditioner 90 of Example 9 (mass%)
Propellant (LPG 90% by mass, DME 10% by mass) 10
Total 100

Example 11
A hair liquid having the following composition was produced by a conventional method.
Self-selective adhesive polymer (Synthesis example 1) 2.0 (mass%)
PVP K30 (GAF) ^{* 2} 1.5
Propylene glycol 3.0
Ethanol 25.0
γ-Caprolactone 15.0
Perfume
Water balance meter 100.0
* 2: Polyvinylpyrrolidone

Example 12
The stock solution having the composition shown below was filled into a pressure-resistant container at a ratio of propellant (LPG 90%, DME 10%) and stock solution / propellant = 90/10 to produce a foam hair styling agent (mousse).
Self-selective adhesive polymer (Synthesis example 1) 1.5 (%)
GANTREZ ES425 (ISP Japan) ^{* 3} 0.5
Cetyltrimethylammonium chloride 0.1
Ethanol 7.5
γ-Caprolactone 2.5
Perfume
Water balance meter 100.0
* 3: Methyl vinyl ether / maleic anhydride alkyl half ester copolymer

Example 13
A hair liquid having the following composition was produced by a conventional method.
Self-selective adhesive polymer (Synthesis example 3) 0.4 (%)
Resin 28-1310 (National Starch) ^{* 4} 2.0
Glycerin monostearate 1.2
Cetyltrimethylammonium chloride 0.5
Ethanol 30.0
γ-Caprolactone 15.0
Perfume
Water balance meter 100.0
* 4: Vinyl acetate / crotonic acid copolymer

  The hair cosmetics obtained in Examples 7 to 13 show excellent hair styling properties and re-styling properties when regular doses are applied to the hair, and the hair is stiff during hair styling, sticky to the hand, etc. Did not give an unpleasant feel.

Claims (5)

General formula (1)

[In formula, R shows a C2-C20 bivalent hydrocarbon group. ]
A polycarbonate structure having a repeating unit represented by the following formula is an ester bond, an ether bond, a urethane bond, a urea bond, a carbon-silicon bond, an amide bond, the following bond (A) and bond (B):

(R ¹ , R ² and R ³ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
A hair cosmetic comprising a polymer that is connected to each other through one or more bonds selected from the group consisting of the above, or connected to a structure having another repeating unit.   The hair cosmetic according to claim 1, comprising a polymer having a self-selective adhesiveness defined by "other adhesion / self-adhesion" of 1/5 or less.   The polymer contained is a polycarbonate skeleton containing at least one polycarbonate having two reactive functional groups, and an aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 20 carbon atoms as a molecular skeleton, The hair cosmetic according to claim 1 or 2, which is a polyester obtained by dehydrating and condensing a raw material containing a compound having two other reactive functional groups capable of forming an ester bond with the reactive functional group.   The hair cosmetic according to claim 3, wherein the polycarbonate having two reactive functional groups is a polycarbonate diol, and the compound having two other reactive functional groups is a dicarboxylic acid.   The hair cosmetic composition according to any one of claims 1 to 4, wherein the polymer contained has a mass average molecular weight of 30,000 to 300,000.