JP2019137623A - Thickened composition - Google Patents

Abstract

To provide a thickened composition having a novel feeling of use.SOLUTION: A thickened composition contains an oil-in-water emulsion having oil droplets, blended with hydrophobic modified polyether urethane.SELECTED DRAWING: None

Description

  The present invention relates to a mash-like composition that exhibits a novel feel to use.

  At present, in the field of cosmetics, various cosmetics have been developed. For example, cosmetics that can give a smooth feeling or gel-like cosmetics that can exhibit a moisturizing action are provided.

  Patent Document 1 discloses an elastic gel-like composition having a peculiar tactile sensation in which a hydrophobic modified polyether urethane is contained in an oil-in-water emulsion having oil droplets having an average particle diameter of 150 nm or less. .

  Patent Document 2 contains (A) silicone resin powder, (B) amphoteric polymer, (C) nonionic surfactant, and (D) water, and (A) silicone resin powder and (B) amphoteric. A cosmetic having an excellent feeling of smoothness and having a polymer mass ratio [(A) / (B)] of 5 to 40 is disclosed.

  In Patent Document 3, (1) a carboxyvinyl polymer and / or a salt thereof which may have a C10-30 alkyl group or a cross-linked structure, and (2) is sulfated Further, a gel-like cosmetic material having a moisturizing action and containing a good trehalose and / or salt thereof and (3) a water-absorbing polymer is disclosed.

JP 2006-088868 A JP 2013-112680 A JP 2005-225769 A

  For example, in the field of cosmetics, there are various cosmetics that provide a smooth and elastic touch, but there is a need for cosmetics that exhibit a new feeling of use that is different from the past. It is rare.

  Accordingly, the subject of the present invention is to provide a composition that exhibits a new and different feel in use.

<Aspect 1>
A thick composition comprising an oil-in-water emulsion having oil droplets and a hydrophobic modified polyether urethane.
<Aspect 2>
The composition according to aspect 1, wherein an average particle diameter of the oil droplets is 150 nm or less.
<Aspect 3>
The composition according to embodiment 1 or 2, wherein the oil droplets contain an oil and a surfactant.
<Aspect 4>
The composition according to any one of Embodiments 1 to 3, wherein the hydrophobically modified polyether urethane is represented by Formula 1 below:
R ⁱ — {(O—R ⁱⁱ ) _k —OCONH—R ⁱⁱⁱ [—NHCOO— (R ^iv —O) _p —R ^v ] _h } _q Formula 1
In Formula 1,
R ⁱ , R ⁱⁱ and R ^iv each independently represent a hydrocarbon group having 2 to 4 carbon atoms,
R ⁱⁱⁱ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a urethane bond,
R ^v represents a hydrocarbon group having 8 to 36 carbon atoms,
k is an integer of 1 to 500;
p is an integer of 1 to 200;
h is an integer of 1 or more, and q is an integer of 2 or more.
<Aspect 5>
The composition according to embodiment 4, wherein the hydrophobically modified polyether urethane is a polyethylene glycol-decyltetradeces-hexamethylene diisocyanate copolymer.
<Aspect 6>
The viscosity at a shear rate of 1 / s is 5.00 mPa · s to 100 mPa · s, the viscosity at a shear rate of 1000 / s is 1.80 mPa · s to 10 mPa · s, and The composition according to any one of aspects 1 to 5, wherein the viscosity ratio is 2.0 or more and 30 or less.
<Aspect 7>
The composition as described in any one of aspects 1-6 which contains 0.08 mass% or more and 0.3 mass% or less of the said hydrophobic modified polyether urethane with respect to the whole quantity of a composition.
<Aspect 8>
A cosmetic base comprising the composition according to any one of aspects 1 to 7.

  ADVANTAGE OF THE INVENTION According to this invention, the composition which exhibits the novel use feeling different from the former can be provided. In particular, in addition to being excellent in applicability, it is possible to provide a thick composition that can exhibit a smooth feel.

  Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the invention.

  The thick composition of the present invention is a composition obtained by blending a hydrophobic modified polyether urethane with an oil-in-water emulsion having oil droplets.

  Although not limited by the principle, it is considered that the operation principle of the present invention is as follows.

  The thick composition of the present invention can obtain excellent coating properties and smooth tactile sensation by blending a hydrophobically modified polyether urethane with an oil-in-water emulsion having oil droplets. This is considered to be a synergistic action effect based on the combined use of an oil-in-water emulsion and a hydrophobically modified polyether urethane.

  Hydrophobically modified polyether urethane is known as an associative thickener that can be associated with a hydrophobic structure at both ends to exhibit a loop structure and / or a bridge structure. Since the thick composition of the present invention has oil droplets, it is considered that at least a part of the hydrophobic portion of the hydrophobic modified polyether urethane forms a bonding point or the like with at least a part of the oil droplets. Such a structure is considered to be one of the causes for a new feeling of use.

  The definitions of terms in the present invention are as follows.

  In the present invention, the term “thick” means that the viscosity is lower and more viscous than a general gel composition, but it is in a liquid state having a higher viscosity than water such as ion-exchanged water. Intended. Therefore, the thick composition of the present invention has a form different from a general gel composition or ion-exchanged water.

  The “thickness” in the present invention is, for example, the viscosity at the shear rate of 1 / s when the measurement object is measured at 32 ° C. and 1 atm using MCR-302 (manufactured by Anton-Paar) as a rheometer. However, the viscosity may include those having a value of 100 mPa · s or less, 90 mPa · s or less, or 80 mPa · s or less, and the viscosity is 5.00 mPa · s or more, 5.50 mPa · s or more, 6.00 mPa S or more, 10.0 mPa · s or more, or 20.0 mPa · s or more.

  The “thickness” in the present invention indicates that the viscosity of the object to be measured when measured under the same conditions is a value of 10 mPa · s or less, 9 mPa · s or less, or 8 mPa · s or less. The viscosity can be 1.80 mPa · s or more, 1.85 mPa · s or more, or 1.90 mPa · s or more.

  The “thickness” in the present invention is 2.0 or more, 2.1 or more, as a viscosity ratio defined as a ratio of viscosity at shear rate 1 / s to viscosity at shear rate 1000 / s, or Those having a value of 2.4 or more, 30 or less, 25 or less, or 20 or less can be included.

  The “thickness” in the present invention is 0.050 Pa or more, 0.060 Pa or more, 1.00 Pa or less, or 0.00 as the storage elastic modulus (G ′) in the linear region of the measurement object when measured under the same conditions. The range can be 90 Pa or less.

  In the “thickness” in the present invention, the loss elastic modulus (G ″) in the linear region of the measurement object when measured under the same conditions is 0.10 Pa or more, 0.15 Pa or more, 1.00 Pa or less, or 0.00. The range can be 90 Pa or less.

  “Thickness” in the present invention is a vis-elastic ratio (tan δ = (G ″ / G ′)) in the linear region of the measurement object when measured under the same conditions, 1.00 or more, or 1.10 or more, The range may be 5.00 or less or 4.00 or less.

  In the present invention, the “bonding point” means a site where at least one hydrophobic part of at least one hydrophobically modified polyether urethane is taken into the oil droplet or adsorbed in the vicinity of the surface of the oil droplet. .

<< Oil-in-water emulsion >>
The thick composition of the present invention includes an oil-in-water emulsion having oil droplets. Such an oil-in-water emulsion is an emulsion composition in which oil droplets as a dispersed phase are dispersed in water which is a continuous phase.

<Oil drops>
The oil droplets as an oil phase or a dispersed phase in the oil-in-water emulsion can contain an oil component and a surfactant, and can optionally contain a higher alcohol.

  The blending amount of the oil in the thick composition of the present invention is not limited to the following, but from the standpoint of expression of the thick form, for example, 1.0% by mass or more and 1. It can be 2 mass% or more, or 1.5 mass% or more. The upper limit of the oil content can be 20% by mass or less or 18% by mass or less from the viewpoint of stability. The oil content is preferably in the range of 2.0 to 15% by mass for exhibiting the expression of the thick form, the dispersibility, or the effective action as the oil content.

  The blending amount of the surfactant and the higher alcohol is not limited to the following, but from the viewpoint of the expression of the thickened form, the stability, etc., for example, the total blending amount of the surfactant and the higher alcohol is in the aqueous phase. On the other hand, it can be 0.2 mass% or more, 0.5 mass% or more, or 1.0 mass% or more. Although an upper limit is not specifically limited, It can be 10 mass% or less, 9 mass% or less, or 8 mass% or less. The amount of oil relative to the total amount of surfactant and higher alcohol can be 1/3 or more. The upper limit is not particularly limited, but can be 5 or less.

  The oil-in-water emulsion used in the present invention is preferably an ultrafine emulsion containing nanometer-order oil droplets from the viewpoints of expression of thickened form, stability, and the like. The average particle diameter of the oil droplets that are the dispersed phase can be, for example, 150 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, or 110 nm or less, and when a transparent or translucent composition is used. The thickness is preferably 100 nm or less, 90 nm or less, or 80 nm or less. The lower limit value of the average particle diameter is not particularly limited, and can be, for example, 5 nm or more, 10 nm or more, 20 nm or more, or 50 nm or more. The average particle diameter of the oil droplets can be defined, for example, as an average value of the diameter of the oil droplets optically measured by a dynamic light scattering method or the like when the particle shape of the oil droplets is assumed to be spherical.

  Here, the oil-in-water emulsion containing ultrafine oil droplets having an average particle diameter of 150 nm or less can be prepared by a method such as a coagulation method or a dispersion method.

  The agglomeration method is a colloid preparation method utilizing interfacial chemical characteristics, and is a method in which a uniform phase is brought into a supersaturated state by some means and a dispersed phase appears. As specific methods, an HLB temperature emulsification method, a phase inversion emulsification method, a non-aqueous emulsification method, a D phase emulsification method, a liquid crystal emulsification method, and the like are known.

  The dispersion method is a method of refining a lump of dispersed phase by force. Specifically, it is a method of emulsifying using the crushing force of an emulsifier. A dispersion method preferably used in the present invention is a dispersion method by high-pressure emulsification as described in Japanese Patent No. 3398171. Here, high-pressure emulsification means preliminarily emulsifying the water phase component and the oil phase component with a homomixer or the like, if necessary, for example, emulsification having fine emulsified particles by high shearing force using a high pressure homogenizer under high pressure. It is a way to get things.

(Oil)
The oil may be any of liquid oil, solid oil, semi-solid oil, such as avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, Persic oil, wheat germ oil, sasanqua oil, castor oil, flaxseed oil, safflower oil, cottonseed oil, evening primrose oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil , Jojoba oil, germ oil, triglycerin, glyceryl trioctanoate, glycerin triisopalmitate, hydrogenated polydecene, etc., cocoa butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, beef tallow, sheep fat, hardened Solid fats such as beef tallow, palm kernel oil, pork tallow, beef bone fat, owl kernel oil, hydrogenated oil, beef leg oil, owl, hydrogenated castor oil, beeswax, candelilla wax, cotton ball , Carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kabok wax, lanolin acetate, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, jojoballow, hard lanolin, shellac wax, POE lanolin alcohol ether , Waxes such as POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, hydrocarbons such as liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalane, petrolatum, microcrystalline wax, isopropyl myristate , Cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate Hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearylate, di-2-ethylhexyl acid Ethylene glycol, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, triisostearin Trimethylolpropane acid, pentaerythritol tetra-2-ethylhexylate, glycerin tri-2-ethylhexylate, triisostearic acid Trimethylolpropane, cetyl-2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleic acid oil, cetostearyl alcohol, acetoglyceride, Palmitic acid-2-heptylundecyl, diisopropyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sepatate, myristic 2-hexyldecyl acid, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, Synthetic esters such as triethyl enoate, silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane, perfluorocarbons such as perfluorodecalin, perfluorohexane and triperfluoro-n-butylamine, perfluoropolyether, vitamin A and the like Derivatives, vitamin D and its derivatives, vitamin E and its derivatives, vitamins such as vitamin K and its derivatives, sterols, natural and synthetic fragrances and the like.

(Surfactant)
The surfactant is not particularly limited, and anionic, cationic or amphoteric ionic surfactants or nonionic surfactants can be used. Of these, anionic or cationic ionic surfactants are preferred.

(Higher alcohol)
For example, in the case of the microemulsion prepared by the high-pressure emulsification described above, the oil droplet is a surfactant selected from those capable of forming a gel at room temperature or higher in a surfactant, higher alcohol and water system, Alcohols and oils can be included. In particular, it is preferable that substantially higher amounts of the higher alcohol and the surfactant are present at the oil droplet interface. The gel is preferably α type from the viewpoint of stability, and the gel transition temperature is preferably 60 ° C. or higher. Such higher alcohols preferably have a carbon chain length of 16 or more. Specific examples include lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerene ether (batyl alcohol), 2-decyltetradecinol, lanolin alcohol, cholesterol, hexyldodecanol. And linear or branched higher alcohols such as isostearyl alcohol and octyldodecanol.

  As a combination of higher alcohol and surfactant (hereinafter referred to as higher alcohol-surfactant), behenyl alcohol (higher alcohol) -behenic acid (behenic acid) soap (surfactant), stearyl alcohol (Higher alcohol) -stearic acid soap (surfactant), stearyl alcohol (higher alcohol) -sodium cetyl sulfate (surfactant), behenyl alcohol (higher alcohol) -behenyltrimethylammonium chloride (surfactant), behenyl alcohol (higher alcohol) ) -Stearyltrimethylammonium chloride (surfactant), behenyl alcohol and / or stearyl alcohol (higher alcohol) -sodium stearoyl glutamate (surfactant) and the like are preferable examples. But it is not limited.

《Hydrophobic modified polyether urethane》
The hydrophobically modified polyether urethane of the present invention is a material also called an associative thickener, an associative polymer, and the like, and is not limited to the following, but the following formula 1
R ⁱ — {(O—R ⁱⁱ ) _k —OCONH—R ⁱⁱⁱ [—NHCOO— (R ^iv —O) _p —R ^v ] _h } _q Formula 1
And a preferable example of the hydrophobically modified polyether urethane is polyethylene glycol-decyltetradeces-hexamethylene diisocyanate copolymer. A particularly preferred example is a hydrophobically modified polyether urethane having the INCI name “(PEG-240 / decyltetradeceth-20 / HDI) copolymer (PEG-240 / HDI COPLYMER BISDECYLTETRADECET-20-20 ETHER)”. The copolymer is commercially available from ADEKA Corporation under the trade name “Adecanol GT-700”.

In Formula 1, R ⁱ , R ⁱⁱ and R ^iv are each independently a hydrocarbon group having 2 to 4 carbon atoms, preferably an alkyl group or alkylene group having 2 to 4 carbon atoms. R ⁱⁱⁱ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a urethane bond. R ^v represents a hydrocarbon group having 8 to 36 carbon atoms, preferably 12 to 24 carbon atoms. k is an integer of 1 to 500, preferably an integer of 100 to 300. p is an integer of 1 to 200, preferably an integer of 10 to 100. h is an integer of 1 or more, preferably 1. q is an integer of 2 or more, preferably 2.

The hydrophobically modified polyether urethane represented by Formula 1 is, for example, one or more polyether polyols represented by R ⁱ — [(O—R ⁱⁱ ) _k —OH] _q , R ⁱⁱⁱ — (NCO ) Reacting one or more polyisocyanates represented by _{h + 1} and one or more polyether monoalcohols represented by HO— (R ^iv —O) _p —R ^v Can be obtained. Here, R ⁱ , R ⁱⁱ , R ⁱⁱⁱ , R ^iv , R ^v , k, p, h, and q are as defined above.

In this production method, R ^{i to} R ^{v in} formula 1 are R ⁱ — [(O—R ⁱⁱ ) _k —OH] _q , R ⁱⁱⁱ — (NCO) _{h + 1} , HO— (R ^iv It is determined by -O) _p -R ^v. The mixing ratio of the three is not particularly limited, but the ratio of the hydroxyl group derived from polyether polyol and polyether monoalcohol to the isocyanate group derived from polyisocyanate is NCO / OH = 0.8: 1 to 1. Preferably it is 1.4: 1.

^{<R i - [(O-} R ii) k -OH] polyether polyol represented by _q>
^{R i - [(O-R} ii) k -OH] polyether polyol represented by _q, the ethylene oxide q polyols, propylene oxide, butylene oxide, alkylene oxide epichlorohydrin, addition polymerization of styrene oxide, etc. Can be obtained.

  Here, as the polyol, those having 2 to 8 valences are preferable. For example, dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol and neopentyl glycol; glycerin, trioxyisobutane, 1,2,3- Butanetriol, 1,2,3-pentatriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin , Pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetri , Trimethylol ethane, trimethylol propane and other trihydric alcohols; pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5 -Tetravalent alcohols such as pentanetetrol, 1,3,4,5-hexanetetrol; pentavalent alcohols such as adnit, arabit and xylit; hexavalent alcohols such as dipentaerythritol, sorbit, mannitol and exit; Examples include octahydric alcohols such as sucrose.

R ⁱⁱ is determined by the alkylene oxide, styrene oxide or the like to be added. In particular, alkylene oxides or styrene oxides having 2 to 4 carbon atoms are preferable because they are easily available and can exhibit excellent effects. The alkylene oxide, styrene oxide and the like to be added may be homopolymerization, two or more kinds of random polymerization, or block polymerization. The addition method may be a normal method. The degree of polymerization k is an integer of 1 to 500. The proportion of ethylene groups in R ⁱⁱ is preferably 50 to 100% by mass of the total R ⁱⁱ .

The molecular weight of R ⁱ — [(O—R ⁱⁱ ) _k —OH] _q is preferably 500 to 100,000, more preferably 1,000 to 50,000.

<Polyisocyanate represented by R ^iii- (NCO) _{h + 1} >
The polyisocyanate represented by R ^iii- (NCO) _{h + 1} is not particularly limited as long as it has two or more isocyanate groups in the molecule. For example, aliphatic diisocyanate, aromatic diisocyanate, alicyclic Diisocyanate, biphenyl diisocyanate, di-, tri- or tetra-isocyanate of phenylmethane can be used.

  Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, Octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, paraxylylene Range isocyanine DOO, tetramethylxylylene diisocyanate, and the like.

  Examples of the aromatic diisocyanate include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4- Examples include naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, and 2,7-naphthalene diisocyanate.

  Examples of the alicyclic diisocyanate include hydrogenated xylylene diisocyanate and isophorone diisocyanate.

  Examples of the biphenyl diisocyanate include biphenyl diisocyanate, 3,3′-dimethylbiphenyl diisocyanate, and 3,3′-dimethoxybiphenyl diisocyanate.

  Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2 ′. , 5′-tetramethyldiphenylmethane-4,4′-diisocyanate, cyclohexylbis (4-isothiontphenyl) methane, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane 3,3′-diisocyanate, 4,4′-diethoxydiphenylmethane-3,3′-diisocyanate, 2,2′-dimethyl-5,5′-dimethoxydiphenylmethane-4,4′-diisocyanate, 3,3′- Dichlorodiphenyldimethyl Tan-4,4'-diisocyanate, benzophenone-3,3'-diisocyanate, and the like.

  Examples of the triisocyanate of phenylmethane include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, and 1,3,7-naphthalenetriisocyanate. Isocyanate, biphenyl-2,4,4′-triisocyanate, diphenylmethane-2,4,4′-triisocyanate, 3-methyldiphenylmethane-4,6,4′-triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenyl) Such as thiophosphate It is below.

  These polyisocyanate compounds may be used in the form of a trimer based on a dimer, isocyanurate bond or the like, or may be used as a biuret by reacting with an amine.

Polyisocyanates having urethane bonds obtained by reacting these polyisocyanate compounds and polyols can also be used. As a polyol, the thing of 2-8 valence is preferable, and the above-mentioned polyol is preferable. When using a polyisocyanate having 3 or more valences as R ^iii- (NCO) _{h + 1} , this polyisocyanate having a urethane bond is preferred.

_{^{<HO- (R iv -O) p}} -R v polyether monoalcohol represented by>
The polyether monoalcohol represented by HO— (R ^iv —O) _p —R ^v is not particularly limited as long as it is a monohydric alcohol polyether. Such a compound can be obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin, styrene oxide and the like to monohydric alcohol.

The monohydric alcohol here is represented by the following formulas I to III.
R ^vi —OH Formula I
... Formula II
... Formula III

That is, R ^v is a group obtained by removing a hydroxyl group from the monohydric alcohol of the above formulas I to III. In the above formulas I to III, R ^vi , R ^vii , R ^viii , R ^x and R ^xi are hydrocarbon groups such as alkyl groups, alkenyl groups, alkylaryl groups, cycloalkyl groups, cycloalkenyl groups and the like. is there.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl. , Tridecyl, isotridecyl, myristyl, palmityl, stearyl, isostearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl branched-isostearyl and the like.

  Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

  Examples of alkylaryl groups include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonyl Examples include phenyl, α-naphthyl, β-naphthyl group and the like.

  Examples of the cycloalkyl group and the cycloalkenyl group include a cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl group. Etc.

In the above formula II, R ^ix is a hydrocarbon group, for example, an alkylene group, an alkenylene group, an alkylarylene group, a cycloalkylene group, a cycloalkenylene group or the like.

R ^v is a hydrocarbon group, preferably an alkyl group, more preferably 8 to 36 carbon atoms, and particularly preferably 12 to 24 carbon atoms.

The alkylene oxide, styrene oxide, etc. to be added may be homopolymerization, two or more kinds of random polymerization, or block polymerization. The addition method may be a normal method. The polymerization degree p is an integer of 0 to 1000, preferably an integer of 1 to 200, and more preferably an integer of 10 to 200. Ratio of ethylene groups to total R ^iv is preferably in the range of 50 to 100 wt% of the total R ^iv, more preferably in the range of 65 to 100 wt%.

(Method for producing copolymer represented by Formula 1)
The copolymer represented by the above formula 1 can be produced by, for example, reacting by heating at 80 to 90 ° C. for 1 to 3 hours in the same manner as the reaction of general polyether and isocyanate.

Polyether polyol D represented by R ⁱ — [(O—R ⁱⁱ ) _k —OH] _q , polyisocyanate E represented by R ⁱⁱⁱ — (NCO) _{h + 1} , and HO— (R ^iv —O ) when reacting a _p -R ^v polyether monoalcohol F represented by may also byproduct other than the copolymer of the structure of formula 1. For example, when a diisocyanate is used, as a main product, a FE-D-E-F type copolymer represented by Formula 1 is generated. Copolymers such as-(D-E) _x- D-E-F type may be by-produced. In this case, the copolymer of the formula 1 type can be used in the present invention in the form of a mixture containing the copolymer of the formula 1 type without separation.

(Amount of hydrophobically modified polyether urethane)
The blending amount of the hydrophobically modified polyether urethane in the thickened composition of the present invention can be set to 0.3% by mass or less based on the total amount of the composition from the viewpoint of obtaining a new feeling of use. The lower limit of the blending amount of ether urethane can be 0.08% by mass or more based on the viscosity at a shear rate of 1000 / s and the value of G ′ in the linear region.

"water"
Although the compounding quantity of the water in the thick composition of this invention is not specifically limited, For example, it is 70-95 mass% with respect to the composition whole quantity from viewpoints, such as thick form expression property. Is preferable, and it is more preferable that it is 75-90 mass%.

《Other ingredients》
In the thick composition of the present invention, various components can be appropriately blended in accordance with the intended use of the composition and the like as long as the effects of the present invention are not affected. As various components, additive components that can be usually blended in cosmetics, for example, lower alcohols, polyhydric alcohols, various extracts, moisturizers, antioxidants, buffers, preservatives, dyes, fragrances, chelating agents, Examples thereof include a pH adjuster and an ultraviolet absorber. Depending on the nature of the various components, for example, in the case of an oil-in-water emulsion, the various components can be blended in an aqueous phase as a continuous phase and / or an oil phase as a dispersed phase, that is, oil droplets.

  In the aqueous phase, in addition to water-soluble drugs that can be applied to pharmaceuticals, quasi drugs, cosmetics, etc., any aqueous component that is usually used for pharmaceuticals, cosmetics, etc. does not affect the effects of the present invention. You may mix | blend with the compounding quantity of. In particular, as an aqueous component, it is preferable that 1 type, or 2 or more types selected from ethanol and a polyol are mix | blended from viewpoints, such as a usability | use_condition.

  Examples of the polyol include ethylene glycol, propylene glycol, 1,3-butylene glycol, tetramethylene glycol, glycerin, sorbitol, diethylene glycol, dipropylene glycol, tetramethylene glycol, diglycerin, polyethylene glycol, and polypropylene glycol. In particular, propylene glycol, dipropylene glycol, and 1,3-butylene glycol are preferable. 1 type, or 2 or more types of aqueous components selected from ethanol and a polyol can be mix | blended in the range of 1-20 mass% with respect to the composition whole quantity, or 3-10 mass%.

《Use of thick composition》
Since the thick composition of the present invention has a low viscosity and exhibits a viscous behavior, it has excellent coatability and can exhibit a smooth tactile sensation. Moreover, the thick composition of this invention can also be made transparent or semi-transparent according to a use. Therefore, the thick composition of the present invention exhibiting such performance can be used, for example, as a base for cosmetics applied to skin and the like.

  Examples of the cosmetics include skin care cosmetics such as beauty essence, skin lotion, and emulsion, hair cosmetics such as sun care products and hair set agents, and hair dyes.

<< Production Method of Thick Composition >>
The thick composition of the present invention can be produced using a known method. For example, an oil-in-water emulsion having oil droplets is prepared by a coagulation method or a dispersion method, diluted with an aqueous medium such as ion-exchanged water as necessary, and then dissolved in an appropriate amount of an aqueous medium as necessary. It can be prepared by adding a hydrophobically modified polyether urethane solution.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, the blending amount is represented by mass%.

<< Examples 1 to 10 and Comparative Example 1 >>
For the composition of the present invention obtained by the formulation and manufacturing method shown in Table 1 below, and a composition not containing a hydrophobically modified polyether urethane for comparison, viscosity at shear rate 1 / s, shear rate 1000 / The viscosity at s, the viscoelastic ratio in the linear region, the storage elastic modulus (G ′) in the linear region, and the loss elastic modulus (G ″) were evaluated. The rheometer MCR302 manufactured by Anton Paar was used for these measurements. The viscosity ratio defined as the ratio of the viscosity at a shear rate of 1 / s to the viscosity at a shear rate of 1000 / s was calculated, and the results are shown in Table 1. Shown in

<Method for producing composition>
Example 1
Hydrogenated polydecene, behenyl alcohol, and stearyl alcohol as oil components were dissolved by heating at 80 ° C., and stirred to prepare a mixture A. While stirring and dissolving ion-exchanged water, sodium stearoyl glutamate, glycerin, dipropylene glycol, phenoxyethanol, and methylparaben at 75 ° C., the mixture A was added thereto, and high-pressure emulsification was performed under a pressure of about 100 MPa. An oil-in-water emulsion was prepared. Hydrophobic modified polyether urethane was added to the obtained oil-in-water emulsion, followed by stirring and mixing to prepare a composition. Here, the high-pressure emulsification was carried out using a high-pressure emulsifier Nanomizer mark II (manufactured by Yoshida Kikai Kogyo Co., Ltd.) and a homogenizer H-20 type (manufactured by Sanwa Engineering Co., Ltd.).

(Examples 2 to 10)
Except having employ | adopted the mixture ratio described in Table 1, it carried out similarly to Example 1, and produced the composition of Examples 2-10, respectively.

(Comparative Example 1)
A composition of Comparative Example 1 was produced in the same manner as in Example 1 except that the hydrophobic modified polyether urethane was not contained.

<result>
As is apparent from Table 1, the composition of Comparative Example 1 containing no hydrophobically modified polyether urethane had a very low viscosity of 3.2 mPa · s at a shear rate of 1 / s, and was as smooth as water. It was tactile. On the other hand, the compositions of Examples 1 to 10 had a viscosity of 7.6 to 35.8 mPa · s at a shear rate of 1 / s, and exhibited a thick, smooth feel. The compositions of Examples 1 to 10 were excellent in coatability because the viscosity at the shear rate of 1 / s was lower than that of a general gel composition. Moreover, since the composition of Examples 1-10 has the performance that a viscosity further falls when it is subjected to high shear such as a shear rate of 1000 / s, it can further improve applicability under high shear. It was confirmed.

  If the thickened form of the present invention is to be achieved with only the hydrophobic modified polyether urethane, it is necessary to use the hydrophobic modified polyether urethane at a high level, and a sticky feeling is generated after drying. The thickening composition of the present invention provides a material that is new compared to the system of only hydrophobically modified polyether urethane in order to achieve the same viscosity in addition to the above-described novel use feeling unprecedented. Since it can be used in a lower amount, it has been found that the moist feeling after drying can be exhibited while reducing the sticky feeling derived from the hydrophobically modified polyether urethane.

  In addition, it was 64 nm when the average particle diameter of the oil droplet in the composition in the comparative example 1 was measured using Zeta sizer nano (product made from Malvern) at 25 degreeC. Since the compositions in Examples 1 to 10 may also have peaks derived from polymer micelles due to hydrophobically modified polyether urethane, the average particle diameter of the oil droplets in these compositions varies slightly from that in Comparative Example 1. It is estimated that the particle size is similar.

<< Prescription example of thick composition >>
Although the formulation example of the cosmetics based on the thick composition of this invention is given to the following, it is not limited to this illustration. In addition, the cosmetics described in the following prescription examples were provided with a feeling of use based on the thick composition of the present invention, that is, a smooth texture.

<Prescription example 1 lotion>
(Ingredient) (mass%)
Purified water Appropriate amount Sodium stearoyl glutamate 0.6
Glycerin 3
Dipropylene glycol 3
Phenoxyethanol 0.3
Methylparaben 0.17
Behenyl alcohol 1
Stearyl alcohol 1
Hydrogenated polydecene 4.05
Perfume
(PEG-240 / decyltetradeceth-20 / HDI) copolymer 0.3

(Method for producing lotion)
Behenyl alcohol, stearyl alcohol, hydrogenated polydecene and perfume were heated and dissolved at 80 ° C. and mixed to prepare a mixture A. While stirring and dissolving ion-exchanged water, sodium stearoyl glutamate, glycerin, dipropylene glycol, phenoxyethanol, and methylparaben at 75 ° C., the mixture A was added thereto, and high-pressure emulsification was performed under a pressure of about 100 MPa. An oil-in-water emulsion was prepared. To the obtained oil-in-water emulsion, a hydrophobic modified polyether urethane (PEG-240 / decyltetradeceth-20 / HDI) copolymer was added, and then stirred and mixed to prepare a skin lotion. Here, the high-pressure emulsification was carried out using a high-pressure emulsifier Nanomizer mark II (manufactured by Yoshida Kikai Kogyo Co., Ltd.) and a homogenizer H-20 type (manufactured by Sanwa Engineering Co., Ltd.).

Claims (8)

  A thick composition comprising an oil-in-water emulsion having oil droplets and a hydrophobic modified polyether urethane.   The composition according to claim 1, wherein an average particle diameter of the oil droplets is 150 nm or less.   The composition of Claim 1 or 2 in which the said oil droplet contains an oil component and surfactant. The composition according to any one of claims 1 to 3, wherein the hydrophobically modified polyether urethane is represented by the following formula 1.
R ⁱ — {(O—R ⁱⁱ ) _k —OCONH—R ⁱⁱⁱ [—NHCOO— (R ^iv —O) _p —R ^v ] _h } _q Formula 1
In Formula 1,
R ⁱ , R ⁱⁱ and R ^iv each independently represent a hydrocarbon group having 2 to 4 carbon atoms,
R ⁱⁱⁱ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a urethane bond,
R ^v represents a hydrocarbon group having 8 to 36 carbon atoms,
k is an integer of 1 to 500;
p is an integer of 1 to 200;
h is an integer of 1 or more, and q is an integer of 2 or more.   The composition according to claim 4, wherein the hydrophobically modified polyether urethane is a polyethylene glycol-decyltetradeces-hexamethylene diisocyanate copolymer.   The viscosity at a shear rate of 1 / s is 5.00 mPa · s to 100 mPa · s, the viscosity at a shear rate of 1000 / s is 1.80 mPa · s to 10 mPa · s, and The composition as described in any one of Claims 1-5 whose viscosity ratio is 2.0 or more and 30 or less.   The composition as described in any one of Claims 1-6 which contains the said hydrophobic modified polyether urethane 0.08 mass% or more and 0.3 mass% or less with respect to the whole quantity of a composition.   A cosmetic base comprising the composition according to any one of claims 1 to 7.