WO2018181899A1 - ポリウレタンゲル組成物及びその利用 - Google Patents
ポリウレタンゲル組成物及びその利用 Download PDFInfo
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- WO2018181899A1 WO2018181899A1 PCT/JP2018/013607 JP2018013607W WO2018181899A1 WO 2018181899 A1 WO2018181899 A1 WO 2018181899A1 JP 2018013607 W JP2018013607 W JP 2018013607W WO 2018181899 A1 WO2018181899 A1 WO 2018181899A1
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- polyurethane
- oil
- gel
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
- C08G18/6208—Hydrogenated polymers of conjugated dienes
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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Definitions
- the present invention relates to a novel polyurethane gel composition having both strength and flexibility and having high elasticity, and its use, particularly to cosmetics.
- thermoplastic resin for example, it has been proposed to use a resin sheet produced using a polyurethane acrylate having a hydrogenated polybutadiene skeleton or a polyurethane acrylate having a polybutadiene skeleton as a strong glossy sheet for printing (Patent Document 1). .
- thermoplastic polyurethanes having good physical properties and excellent weather resistance, comprising low molecular weight chain extenders having two hydroxyl groups per one (Patent Document 2).
- the adhesive examples include a decorative plate in which an adhesive layer or an adhesive layer and a base coat layer, and a transfer layer are provided on a base material, and the adhesive layer is a hydroxyl group-containing polybutadiene polymer.
- a decorative plate characterized in that it is obtained from an adhesive composed of an organic polyisocyanate, and the adhesive is, if necessary, a hydroxyl group-containing resin (other than the hydroxyl group-containing polybutadiene polymer).
- a resin starting from ethylene glycol can be included (Patent Document 3).
- water-soluble gelling agent examples are derived from a water-soluble polyoxyalkylene polyol (A), a water-insoluble polyol (B) having a number average molecular weight of 500 to 2,000, and an organic polyisocyanate (C),
- An automatic fragrance cleaner group for flush toilets comprising a water-soluble solid polyurethane resin (D) in which the weight ratio of A) :( B) is (99.9-85.0) :( 0.1-15.0)
- a material has been proposed (Patent Document 4).
- Polyurethane has been used for various applications in the cosmetic field.
- a cosmetic composition comprising an associative thickener (a copolymer having a hydrophilic group as a skeleton and a hydrophobic moiety at the end) made of a hydrophilic compound having a urethane bond has been proposed (patent) Reference 5).
- a mascara product comprising a reservoir containing a composition having a viscosity in the range of s and containing no wax, and a sealing means equipped with an applicator has been proposed (Patent Document 6).
- composition comprising a physiologically acceptable medium thickened by associative polyurethane, the medium comprising an aqueous phase and a liquid fatty phase in an emulsion, the human face as well as the body skin , Keratin fibers such as eyelashes, eyebrows, and hair, or an emulsion type composition having a viscous consistency for lip care, treatment or makeup (Patent Document 7), hydrophilic alkylene oxide A cosmetic patch comprising a segment and a hydrophobic alkylene oxide segment, wherein a vitamin is contained in a gel layer comprising an adhesive polyurethane gel in which most or all of the segment is liquid at room temperature.
- Patent Document 8 partially crosslinked organopolysiloxane polymer, solid oil and powder (for example, polyurethane powder)
- An elastic gel-like oily cosmetic (Patent Document 9) characterized in that the cosmetic particle contains polyurethane gel particles containing a functional component and / or a designable component, and the gel particles are at least one of A polyisocyanate having a trifunctional or higher functionality, a compound having an active hydrogen group in the molecule, a polysiloxane having an active hydrogen group in the molecule and / or a reaction product of the polysiloxane and a lactone
- the surface of the three-dimensionally cross-linked polyurethane gel particles (particles A) is polyurethane gel particles (particles C) coated with polyurea colloid particles (particles B) precipitated from a polyurea colloid non-aqueous solvent solution.
- a characteristic cosmetic (Patent Document 10) and the like have also been proposed.
- JP-A-9-228294 Japanese National Patent Publication No. 11-507975 JP 2001-287309 A JP-A-8-218097 JP 2000-239120 A JP 2000-178137 A JP 2000-63235 A JP 2005-15457 A JP 2008-88099 A Japanese Patent No. 4802136
- the inventors of the present invention have repeatedly studied the prior art in order to solve problems such as wrinkles on skin and wrinkles, sagging, bears and dullness.
- problems such as wrinkles on skin and wrinkles, sagging, bears and dullness.
- various dosage forms such as powder solids and oily solid dosage forms.
- powdered solids containing pearl agents have the disadvantages of unnatural glare, emphasizing irregularities, conspicuous wrinkles and the like, and poor pearl adhesion.
- the oil-based solid dosage form has a drawback that gloss is insufficient due to a large amount of crystal components, and that irregularities (double grooves) occur with time.
- silicone rubber is a soft and soft gel, but has a drawback that it lacks gloss and lacks restoring force.
- Polysaccharide gels have high transparency and gel strength, but have the disadvantage of low elasticity and resilience.
- Aqueous polyurethane gels are transparent and have strong elasticity and resilience. However, they require water and have a serious drawback in that the color gamut is limited, and the lasting effect of gloss and decorative film is insufficient.
- polyurethane is known to be obtained by reacting diisocyanate and polyol, and polyurethane comprising hydrogenated polybutene and polyhydric alcohol is within the well-known art.
- polyurethane as an oil-soluble gelling agent.
- the present inventors have conducted intensive research and development in order to obtain a cosmetic film that is transparent, high in gloss, elastic and resilient, and has an excellent makeup sustaining effect.
- the present inventors have (a) hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO—R 3 —OH (wherein R 3 is a straight chain which may have an ether bond or Or A represents (c) a hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) a diisocyanate compound, and (b) (representing a branched C2 to C6 alkylene group).
- a polyurethane gel composition containing A and B is (a) hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO—R 3 —OH (wherein R 3 is a linear or branched C 2 to C 2 which may have an ether bond). Or C represents a hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) a diisocyanate compound, and (b) HO—R.
- composition according to (1) wherein (a) of A is an isocyanate compound obtained by a reaction between (c) a hydrogenated polybutadiene having a hydroxyl group at the terminal and (d) a diisocyanate compound.
- (3) The composition according to (1) or (2), wherein (d) of A is a diisocyanate compound represented by OCN—R 2 —NCO (wherein R 2 is C2 to C6 alkylene).
- (a) of A is the formula (1) (Wherein R 1 and R 2 are each independently a C 1 to C 6 alkylene group, n is an integer of 10 to 100, and n 1 and n 2 each independently represents 0 or 1)
- A is the formula (2) (Wherein n represents an integer of 10 to 100), and the composition according to any one of (1) to (4).
- (6) (c) Hydrogenated polybutadiene having a hydroxyl group at the terminal (Wherein n represents an integer of 10 to 100), (D) a diisocyanate compound And (B) A glycol represented by HO—R 3 —OH The composition as described in (2).
- the composition according to (1), wherein the polyurethane of A is an oil-soluble polyurethane.
- the composition according to (1), wherein the polyurethane of A has an average molecular weight (Mw) of 10,000 to 100,000.
- composition according to (1), wherein the oil agent B is a liquid oil agent at 25 ° C.
- oil agent B is at least one selected from hydrocarbon oils, ester oils having 0 or 1 hydroxyl groups, and silicone oils.
- (11) The composition according to (1), wherein the polyurethane content of A is 1 to 35% by mass.
- (13) A gel obtained by dissolving 30 parts of the polyurethane gel composition described in any one of (1) to (12) and 70 parts of liquid paraffin at 85 ° C. and cooling is obtained.
- a cosmetic comprising the composition according to any one of (1) to (15).
- a method for producing a polyurethane gel composition containing A and B (where A is a polyurethane and B is an oil agent), and in the B oil agent, at the (a) end of A A glycol represented by hydrogenated polybutadiene having an isocyanate group and (b) HO—R 3 —OH (wherein R 3 represents a linear or branched C2 to C6 alkylene group optionally having an ether bond).
- a method for producing a polyurethane gel composition comprising adding a polyaddition reaction.
- a in (a) is the formula (1) (Wherein R 1 and R 2 are each independently a C 1 to C 6 alkylene group, n is an integer of 10 to 100, and n 1 and n 2 each independently represents 0 or 1)
- a in (a) is the formula (2) (Wherein n represents an integer of 10 to 100), and the production method according to (17), (18), (20) or (21).
- the polyurethane gel composition of the present invention is extremely excellent in terms of transparency, glossiness, elasticity, and resilience, the polyurethane gel composition of the present invention is applied to a portion with a lot of skin movement. It is useful as a base material for cosmetics such as body oils, makeup bases, sunscreens and eye colors to be applied.
- the polyurethane gel composition containing A and B of the present invention includes the following composition.
- Composition 1 A is (a) hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO—R 3 —OH (wherein R 3 is a linear or branched C2-C6 alkylene group optionally having an ether bond)
- Composition 2 A is (c) a hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) a diisocyanate compound, and (b) HO—R 3 —OH (wherein R 3 is a linear or branched C 2 which may have an ether bond)
- a polyurethane obtained by reaction with a glycol represented by (-C6 alkylene group) and a composition containing an oil as B.
- terminal means “both ends”.
- the (a) of A used in the composition 1 is not particularly limited as long as it is a hydrogenated polybutadiene having an isocyanate group at the terminal.
- a compound represented by the following formula (1) is shown.
- R 1 and R 2 are each independently a C 1 to C 6 alkylene group, n is an integer of 10 to 100, and n 1 and n 2 each independently represents 0 or 1)
- R 1 and R 2 are each independently, that is, the same or different and each represents a C 1 to C 6 alkylene group, and the alkylene may be linear or branched.
- the C 1 -C 6 alkylene group include methylene, ethylene, n-propylene, n-butylene, n-hexylene and the like.
- n represents an integer of 10 to 100, and a more preferable range of n is 15 to 55.
- n 1 and n 2 each independently represent 0 or 1 independently, that is, the same or different.
- a hydrogenated polybutadiene moiety of the above formula (1) (the following formula (6)), There are various types of structures of the repeating unit “C 4 H 8 ” in FIG.
- the hydrogenated polybutadiene portion in the hydrogenated polybutadiene having an isocyanate group at the terminal used in the present invention may be composed of only one type of repeating unit as exemplified above, or two or more types of repeating units may be used. It may be included regularly or randomly. Regardless of whether the three-dimensional structure of the repeating unit “C 4 H 8 ” constituting the hydrogenated polybutadiene portion is the same or different, all structures in which the hydrogenated polybutadiene portion is represented by the formula (6) are included in the present invention. Is done.
- Examples of the hydrogenated polybutadiene having an isocyanate group at the terminal represented by the formula (1) include a compound represented by the following formula (2).
- n an integer of 10 to 100
- glycols that can be used include ethylene glycol (HOCH 2 CH 2 OH), propylene glycol (HOCH 2 CH (OH) CH 3 ), 1,3-butylene glycol (HOCH 2 CH 2 CH (OH) CH 3 ), diethylene glucose (HOCH 2 CH 2 OCH 2 CH 2 OH) , and the like.
- the hydrogenated polybutadiene having a hydroxyl group at the (c) terminal of A used in the composition 2 is not particularly limited.
- a compound represented by the following formula (3) is shown.
- n an integer of 10 to 100
- the hydrogenated polybutadiene part (formula (6)) has the same meaning as described above.
- the (d) diisocyanate compound used in the composition 2 include hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) benzene, 1,3-bis (isocyanatomethyl) cyclohexane, 2,4- Examples thereof include toluene diisocyanate and 2,6-toluene diisocyanate. Of these, hexamethylene diisocyanate represented by the following formula (4) is preferable.
- composition 1 (a) hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO—R 3 —OH (wherein R 3 is a linear or branched C 2 to C 2 which may have an ether bond).
- R 3 is a linear or branched C 2 to C 2 which may have an ether bond.
- R 3 represents a linear or branched C2-C6 alkylene group which may have an ether bond
- R 3 represents a linear or branched C2-C6 alkylene group which may have an ether bond
- the molar ratio (a) :( b) included in this range is 2: 3 to 3: 2, 3: 4 to 4: 3, 4: 5 to 5: 4, 4: 5 to 4: 3, 9 : 10 to 10: 9.
- the average molecular weight (Mw) of (a) is preferably 1000 to 3000.
- the molecular weight included in this range is 1200-2800, 1200-2600, 1200-2400, 1200-2000, 1200-1800, 1300-2700, 1300-2500, 1300-2100, 1300-1800. Examples are 1500-2500, 1500-2100, 1800-2800, 1800-2600, 1800-2400, 1800-2100, and the like.
- R 3 represents a linear or branched C2-C6 alkylene group which may have an ether bond
- R 3 represents a linear or branched C2-C6 alkylene group which may have an ether bond
- the molar ratio (c) :( b) included in this range is 2: 3 to 3: 2, 3: 4 to 4: 3, 4: 5 to 5: 4, 4: 5 to 4: 3, 9 : 10 to 10: 9.
- the average molecular weight (Mw) of (c) is preferably 1000 to 3000.
- the molecular weight included in this range is 1200-2800, 1200-2600, 1200-2400, 1200-2000, 1200-1800, 1300-2700, 1300-2500, 1300-2100, 1300-1800. Examples are 1500-2500, 1500-2100, 1800-2800, 1800-2600, 1800-2400, 1800-2100, and the like.
- the average molecular weight (Mw) of the polyurethane obtained by polyaddition is preferably 10,000 to 100,000.
- the molecular weights included in this range are 10,000 to 100,000, 10,000 to 90,000, 10,000 to 80,000, 10,000 to 70,000, 10,000 to 60,000, 10,000 to 50,000, 20000 to 90,000, 20000 to 80,000, 20000 to 70,000, 20000 to 60,000, 20000.
- 50,000, 30,000 to 90,000, 30,000 to 80,000, 30,000 to 70,000, 30,000 to 60,000, 30,000 to 50,000, 40,000 to 90,000, 40,000 to 80,000, 40,000 to 70,000, 40,000 to 60,000, 50,000 to 90,000, 50,000 to 80,000, 50,000 to 70,000 Are exemplified.
- the polyurethane of A used in the present invention is more preferably oil-soluble.
- oil-soluble means “at least 1% by mass or more can be dissolved in cetyl 2-ethylhexanoate at 30 ° C.”.
- the content of the polyurethane of A in the composition 1 is more preferably 1 to 35% by mass. When the concentration of the polyurethane polymer is lower than this range, the transparency is high, but the elasticity (load value) is inferior, and the elasticity is inferior to the cosmetic.
- the content of polyurethane included in this range is 1 to 35% by mass, 1 to 30% by mass, 1 to 25% by mass, 1 to 20% by mass, 1 to 15% by mass, 1 to 10% by mass, 1 to 5%, 5-30%, 5-25%, 5-20%, 5-15%, 5-10%, 10-30%, 10-25%, 10-20% %, 10 to 15% by mass.
- the content of the oil agent B in the composition 1 is preferably 65 to 99% by mass.
- the content of the oil agent included in this range is 65 to 99% by weight, 70 to 99% by weight, 80 to 99% by weight, 85 to 99% by weight, 90 to 99% by weight, 95 to 99% by weight, 70 to 99% by weight.
- the content of polyurethane A in the composition 2 is more preferably 1 to 35% by mass.
- concentration of the polyurethane polymer is lower than this range, the transparency is high, but the elasticity (load value) is inferior, and the elasticity is inferior to the cosmetic.
- the content of polyurethane included in this range is 1 to 35% by mass, 1 to 30% by mass, 1 to 25% by mass, 1 to 20% by mass, 1 to 15% by mass, 1 to 10% by mass, 1 to 5%, 5-30%, 5-25%, 5-20%, 5-15%, 5-10%, 10-30%, 10-25%, 10-20% %, 10 to 15% by mass.
- the content of the oil agent B in the composition 2 is preferably 65 to 99% by mass.
- the content of the oil agent included in this range is 65 to 99% by mass, 70 to 99% by mass, 80 to 99% by mass, 85 to 99% by mass, 90 to 99% by mass, 95 to 99% by mass, 70 to 99% by mass. 95%, 75-95%, 80-95%, 85-95%, 90-95%, 70-90%, 75-90%, 80-90%, 85-90% % Is exemplified.
- the oil agent B in the polyurethane gel composition can be used without particular limitation as long as it is usually used in cosmetics.
- the property is not particularly limited, but it is preferably a liquid oil at 10 ° C. to 30 ° C., particularly 25 ° C.
- examples of the oil agent B used in the polyurethane gel composition include hydrocarbon oils, ester oils, oils and fats, silicone oils, fluorine-based oils and the like regardless of the origin of animal oils, vegetable oils, synthetic oils and the like.
- the lower polarity tends to increase the strength of the polyurethane gel composition, it is selected from hydrocarbon oils, ester oils having 0 or 1 hydroxyl groups, and silicone oils containing phenyl groups.
- hydrocarbons such as liquid paraffin, squalane, polybutene and polyisobutylene
- oils and fats such as olive oil, castor oil, mink oil, macadamian nut oil and jojoba oil
- cetyl isooctanoate cetyl 2-ethylhexanoate
- Isopropyl myristate isopropyl palmitate
- octyldodecyl myristate glyceryl trioctanoate
- polyglyceryl diisostearate diglyceryl isostearate, diisostearyl malate, glyceryl tribehenate
- pentaerythritol diphosphate neopentyl glycol dioctanoate
- esters such as methylphenyl polysiloxane and silicones such as diphenyl polysiloxane, and one
- the polyurethane gel composition of the present invention preferably has not only transparency and gloss, but also has a feature of extremely high elasticity / restorability.
- 30 parts of this polyurethane gel composition and 70 parts of liquid paraffin (kinematic viscosity at 40 ° C. according to ASTM D445 measuring method is 8 mm 2 / s) are heated and dissolved at 85 ° C.
- the gel obtained after cooling to 1 ° C. exhibited excellent characteristics with a load value of 0.20 to 10.00 N when a 2 cm ⁇ spherical adapter was inserted 10 mm at 2 cm / min. This indicates that the polyurethane gel composition of the present invention has elasticity and resilience.
- the polyurethane gel composition of the present invention has a transmittance at a wavelength of 700 nm of 90% or more. That is, the polyurethane gel composition of the present invention has extremely high transparency.
- the polyurethane gel composition 1 of the present invention can be produced using a known polyurethane production method. That is, the polyurethane gel composition 1 according to the present invention comprises hydrogenated polybutadiene having an isocyanate group at the (a) end of A and (b) HO—R 3 —OH (wherein R 3 is an ether bond) It represents a linear or branched C2-C6 alkylene group which may have a glycan group) and is subjected to a polyaddition reaction.
- the polyurethane gel composition 2 of the present invention can be produced using a known polyurethane production method.
- the polyurethane gel composition 2 of the invention comprises (c) hydrogenated polybutadiene having a hydroxyl group at the terminal, and (b) HO—R 3 —OH (wherein R 3 is a straight chain which may have an ether bond or It can be produced by charging a glycol represented by a branched C2-C6 alkylene group) and a B oil agent, mixing them uniformly, and adding (d) a diisocyanate compound to react.
- the name “Hydrogenated Polybutadiene / Glycol / HDI Copolymer” is given in INCI (International Nomenclature of Cosmetic Ingredient).
- INCI International Nomenclature of Cosmetic Ingredient
- various components that can be contained can be used as needed.
- Such components include volatile components, surfactants, oils, powders, aqueous components, alcohols, water-soluble polymers, UV absorbers, humectants, gelling agents and thickeners, anti-fading agents, oxidation Preventive agent, antifoaming agent, cosmetic ingredients (whitening agent, cell activator, anti-inflammatory agent, blood circulation promoter, skin astringent, antiseborrheic agent, etc.), antiseptic, antibacterial agent, fragrance, vitamins, amino acids, Examples include nucleic acids and hormones.
- the aqueous component is not particularly limited, and any component can be used as long as it is a liquid component at room temperature and is usually used in cosmetics.
- any component can be used as long as it is a liquid component at room temperature and is usually used in cosmetics.
- glycerols such as glycerin, diglycerin, polyglycerin, aloe vera, hammamels, cucumber, lemon, lavender, rose, etc.
- These aqueous components can be used alone or in combination of two or more as necessary.
- the content of the aqueous component used in the present invention varies depending on the usability, feeling of use, and dosage form, and is not particularly limited, but is 10% by mass or less, further 5% by mass or less, particularly 0.1% by mass in the composition. Is preferable in terms of makeup effect, usability, and feeling of use.
- the surfactant is not particularly limited as long as it is usually used in cosmetics, and any surfactant can be used.
- the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. These may be used alone or in combination of two or more as required. be able to.
- anionic surfactants include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and salts thereof, carboxylates such as condensation of amino acids and fatty acids, alkyl sulfonic acids, and alkene sulfones.
- Acid salts sulfonates of fatty acid esters, sulfonates of fatty acid amides, sulfonates of alkyl sulfonates and their formalin condensates, alkyl sulfate esters, secondary higher alcohol sulfates, alkyl and allyl ether sulfates
- Ester salts fatty acid ester sulfates, fatty acid alkylolamide sulfates, polyoxyethylene alkyl sulfates, sulfate salts such as funnel oil, alkyl phosphates, ether phosphates, alkyl allyl ether phosphates , Mydrin salts, such as N- acylamino acid-based active agents.
- Cationic surfactants include long chain alkyltrimethylammonium salts, dilong chain alkyldimethylammonium salts, long chain alkyldimethylbenzylammonium salts, dipolyoxyethylene alkylmethylammonium salts, dipolyoxyethylene alkyl ether dimethylammonium salts, poly Alkyl quaternary ammonium salts such as oxypropylene methyl diethyl ammonium salt and aromatic quaternary ammonium salts, pyridinium salts such as alkyl pyridinium salts, imidazoline salts such as alkyl dihydroxyethyl imidazoline salts, N-acyl basic amino acid lower alkyl esters And amine salts such as alkylamine salts, polyamines, amino alcohol fatty acid derivatives and the like.
- Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxy Ethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene cured Castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxye Renphytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolys
- amphoteric surfactants include carbobetaine-type amphoteric surfactants such as alkyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, alkyldihydroxyethylaminoacetic acid betaine, and sulfobetaine-type amphoteric surfactants such as alkylsulfobetaine, N Amidoamine type (imidazoline type) amphoteric surfactants such as fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine salt, N-fatty acid acyl-N-carboxymethoxyethyl-N-carboxymethylethylenediamine di-salt, N- [ Examples include amino acid type amphoteric surfactants such as 3-alkyloxy-2-hydroxypropyl] arginine salts, and alkyliminodicarboxylate type amphoteric surfactants.
- humectant examples include urea, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate and the like.
- gelling agents those that are aqueous include gum arabic, gum tragacanth, galactan, carob gum, guar gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), starch (rice, corn, potato, wheat), alge colloid Plant polymers such as Tant gum and locust bean gum, microbial polymers such as xanthan gum, dextran, succinoglucan and pullulan, animal polymers such as collagen, casein, albumin and gelatin, carboxymethyl starch and methylhydroxypropyl Starch polymers such as starch, methylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, cellulose sulfate Cellulose polymers such as thorium and sodium carboxymethyl
- Vinyl polymer polyethylene glycol, ethylene oxide propylene oxide copolymer, acrylic acid / acryloyldimethyltaurine sodium copolymer, acrylic polymer such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, bentonite, silicic acid Inorganic gelling agents and thickeners such as aluminum magnesium, laponite, hectorite, silicic anhydride, etc. Chiren'imin, cationic polymers.
- natural rubber natural cellulose, cationized cellulose, various acrylic resins (including copolymers), various alkyd resins, polyvinyl alcohol, polyvinyl pyrrolidone, nitrocellulose, various silicone resins (copolymers) ), Urea resin, modified corn starch and the like are used.
- Specific film forming agents include acrylic amide / alkyl acrylate / methacrylic acid methoxypolyethylene glycol copolymer, methacrylic acid methoxypolyethylene glycol, eicosene / vinylpyrrolidone polymer, 1,1′-methylenebis (4-isocyanatocyclohexane ) Polypropylene glycol copolymer, perfluoropolyether, (acrylate / polytrimethylsiloxy methacrylate) copolymer, polypropylsilsesquioxane, (eicosene / vinylpyrrolidone) copolymer, (vinylpyrrolidone / hexadecene) copolymer , Hydroxyethyl cellulose, silicone-modified norbornene and the like.
- the colorant is a colorant usually used in cosmetics, it has a spherical shape, a plate shape, a spindle shape, a needle shape, or a particle size such as a fume shape, a fine particle, or a pigment grade, or a porous or nonporous material.
- the particle structure and the like thereof are not particularly limited, and inorganic pigments, organic pigments, glitter pigments, metals and the like can be used.
- Specific powders include white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide, and barium sulfate, colored inorganic pigments such as iron oxide, carbon black, chromium oxide, chromium hydroxide, bitumen, ultramarine, and bengara, mica Titanium, bismuth oxychloride, organic pigment-treated mica titanium, titanium dioxide-coated mica, titanium dioxide-coated synthetic phlogopite, titanium dioxide-coated bismuth oxychloride, iron oxide mica titanium, bituminized mica titanium, carmine-treated mica titanium, fish scale foil, dioxide Luminous pigments such as titanium coated glass powder, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / polymethyl methacrylate laminated film powder, etc., red 201, red 202, Red 205 Organic pigment powders such as red 226, red 228, orange 203, orange 204,
- metal powders such as aluminum powder, gold powder and silver powder, titanium oxide coated mica titanium, fine particle oxidation
- metal powders such as aluminum powder, gold powder and silver powder, titanium oxide coated mica titanium, fine particle oxidation
- examples include zinc-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide, and the like.
- natural pigments include carmine, laccaic acid, calsamine, bradylin, and crocin. 1 type or 2 types or more can be used as needed. These use one or more of fluorine compounds, silicone compounds, metal soap, lecithin, hydrogenated lecithin, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes, surfactants, etc. And may be surface-treated.
- a powder other than the colorant if it is usually used as a raw material for cosmetics, a plate shape, a spindle shape, a needle shape, a fume shape, a particle size such as a fine particle class, a porous material, a nonporous material, etc.
- the particle structure such as inorganic powders, aluminum oxide, cerium oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthesis Inorganic powders such as mica, synthetic sericite, sericite, talc, kaolin, silica, silicon carbide, boron nitride, and organic powders such as magnesium stearate, zinc stearate, N-acyl lysine, nylon, etc. These 1 type (s) or 2 or more types can be used. These powders may be used singly or in combination of two or more, and the surface treatment may be performed with an oil agent treatment, a silicone compound treatment, a water-soluble polymer treatment or the like.
- oils examples include solid oils, semi-solid oils, liquid oils, and examples include natural animal and vegetable oils and semi-synthetic oils, hydrocarbon oils, ester oils, glyceride oils, silicone oils, higher alcohols, higher fatty acids, organic solvents, and the like. Is done.
- Solid oils include carnauba wax, candelilla wax, cotton wax, shellac wax, natural waxes such as hardened oil, mineral waxes such as ozokerite, ceresin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, ethylene propylene copolymer And the like, synthetic alcohols such as behenyl alcohol, cetyl alcohol, stearyl alcohol, cholesterol and phytosterols, higher fatty acids such as stearic acid and behenic acid, and the like.
- Liquid oils including natural animal and vegetable oils and semi-synthetic oils, specifically avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, kaya oil, liver oil, kyounin oil, wheat germ oil, sesame oil, rice germ oil , Rice bran oil, sasanqua oil, safflower oil, cinnamon oil, cinnamon oil, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, rapeseed oil, Japanese kiri oil, nukarou, germ oil, persic oil , Palm oil, palm kernel oil, castor oil, sunflower oil, grape oil, jojoba oil, macadamia nut oil, cottonseed oil, coconut oil, tricoconut oil fatty acid glyceride, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, lanolin acetate, Lanolin fatty acid isopropyl, POE lanolin alcohol ether
- hydrocarbon oil examples include squalane, squalene, liquid paraffin, pristane, polyisobutylene and the like.
- Ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkylglycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, 2-ethylhexanoic acid Cetyl, ethylene glycol di-2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl Gum ester, oleyl ole
- glyceride oil examples include acetoglyceride, triisooctanoic acid glyceride, triisostearic acid glyceride, triisopalmitic acid glyceride, tri-2-ethylhexanoic acid glyceride, monostearic acid glyceride, di-2-heptylundecanoic acid glyceride, and trimyristic acid.
- a glyceride etc. are mentioned.
- Silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, alkyl-modified silicone.
- Etc. Examples of the higher alcohol include oleyl alcohol, lauryl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol and the like.
- Examples of the higher fatty acid include oleic acid, palmitic acid, myristic acid, stearic acid, and isostearic acid.
- Examples of the organic solvent include hydrocarbons such as n-hexane and cyclohexane, aromatic compounds such as benzene, toluene and xylene, non-aromatic compounds such as ethyl acetate and butyl acetate, chlorine compounds such as chloroform, dichloromethane and dichloroethane, Examples include ether compounds such as dioxane and tetrahydrofuran, 2-propanol, benzyl alcohol, phenoxyethanol, carbitols, cellosolves, spindle oil and the like.
- alcohols include lower alcohols such as ethanol and isopropanol, glycerol, diglycerol, polyglycerol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, erythritol, and the like.
- examples include monohydric alcohols, sugar alcohols such as sorbitol, maltose, xylitol, maltitol, benzyl alcohol, and the like.
- Beauty ingredients include whitening agents such as arbutin, glutathione, and yukinoshita extract, royal jelly, photosensitizer, cholesterol derivatives, cell activators such as calf blood extract, rough skin improver, nonyl acid wallenyl amide, nicotinic acid benzyl ester, Nicotinic acid ⁇ -butoxyethyl ester, capsaicin, zingerone, cantalis tincture, ictamol, caffeine, tannic acid, ⁇ -borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin , Blood circulation promoters such as ⁇ -oryzanol, skin astringents such as zinc oxide and tannic acid, and antiseborrheic agents such as sulfur and thianthol.
- cell activators such as
- Preservatives and antibacterials include paraoxybenzoic acid esters, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, salicylic acid, coalic acid, sorbic acid, parachlormetacresol, hexachlorophene, benzalkonium chloride, chloride Examples include chlorhexidine, trichlorocarbanilide, photosensitizer, and isopropylmethylphenol.
- Perfumes include natural fragrances (animal fragrances, vegetable fragrances), synthetic fragrances, and blended fragrances (blends of natural and synthetic fragrances). Current cosmetics include blended fragrances that blend natural and synthetic fragrances. Is the most commonly used.
- flavors include jasmine, tadget, rosemary, vanilla, ginger oil, rose oil, jasmine oil, lavender oil, ylang ylang oil, peppermint oil, geranium oil, lemon oil, orange oil, star anise oil, grapefruit oil, eucalyptus Oil, sandalwood oil, black pepper oil, basil oil, ylang ylang oil, patchouli oil, coumarin, musk ketone, heliotropin, 1-octen-3-ol, and blends thereof.
- Antioxidants include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, and pH adjusters include lactic acid, lactate, citric acid, citrate, glycolic acid, succinic acid, tartaric acid, malic acid, potassium carbonate, hydrogen carbonate Sodium, ammonium bicarbonate, etc., chelating agents such as alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, phosphate, hydroxyethane diphosphone, etc., and refreshing agents such as L-menthol, camphor, thin cargo oil, peppermint
- anti-inflammatory agents such as oil and eucalyptus oil include allantoin, glycyrrhetinate, glycyrrhetin derivatives, tranexamic acid, and azulene.
- Vitamins such as vitamin A oil, retinol, retinol acetate, retinol palmitate, etc., vitamin B2 such as riboflavin, riboflavin butyrate, flavin adenine nucleotide, vitamin B6 such as pyridoxine hydrochloride, pyridoxine dioctanoate Vitamins such as L-ascorbic acid, L-ascorbic acid dipalmitate, L-ascorbic acid-2-sodium sulfate, dl- ⁇ -tocopherol-L-ascorbic acid diester dipotassium, calcium pantothenate, Pantothenic acids such as D-pantothenyl alcohol, pantothenyl ethyl ether, acetyl pantothenyl ethyl ether, vitamin Ds such as ergocalciferol and cholecalciferol, nicotinic acid, nicotinic acid
- amino acids examples include arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine, isoleucine, tryptophan, alanine, glycine, and proline, nucleic acids such as deoxyribonucleic acid, and hormones such as estradiol and ethinylestradiol.
- the polyurethane gel composition of the present invention can also be used to produce a surface-treated powder (hereinafter referred to as “polyurethane gel-treated powder”) by coating the surface of the powder as a surface treating agent.
- the powder to be coated with the polyurethane gel composition of the present invention is usually a powder used in cosmetics, such as a spherical shape, a plate shape, a needle shape, a fume shape, a fine particle, a pigment grade, etc.
- Species or two or more can be used.
- the inorganic powders include titanium oxide, black titanium oxide, conger, ultramarine blue, bengara, yellow iron oxide, black iron oxide, zinc oxide, aluminum oxide, silica, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, and oxidation. Selected from chromium, chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic mica, sericite, talc, kaolin, silicon carbide, barium sulfate, bentonite, smectite, boron nitride, etc. 1 type (s) or 2 or more types can be used. These may be prepared as fine particles of about 10 to 100 nm.
- Examples of the glitter powder include bismuth oxychloride, titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated mica titanium, organic pigment-coated mica titanium, titanium oxide-coated glass powder, and aluminum powder. Two or more kinds can be used.
- organic powders examples include nylon powder, polymethyl methacrylate powder, acrylonitrile-methacrylic acid copolymer powder, vinylidene chloride-methacrylic acid copolymer powder, PET resin powder, polyethylene powder, polystyrene powder, and organopolysiloxane elastomer powder.
- One or more selected from polymethylsilsesquioxane powder, polyurethane powder, wool powder, silk powder, crystalline cellulose powder, N-acyl lysine powder, and the like can be used.
- the dye powders one or more selected from organic tar pigments, lake pigments of organic dyes, and the like can be used.
- the composite powders one or more selected from fine titanium oxide-coated mica titanium, fine particle zinc oxide-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silica, zinc oxide-containing silica, and the like are used. Can do.
- titanium powder, bengara, talc, sericite, and mica which are inorganic powders, are particularly suitable as the powder to be coated. Since these powders are widely used in cosmetics and are contained in a large amount, they can exhibit remarkable effects when used in cosmetics by coating them.
- the method for coating these powders with the above-mentioned polyurethane gel is not particularly limited and is usually produced by a known method.
- a method of directly mixing polyurethane gel with powder dry treatment method
- a method using a solvent wet method
- a wet solution in which a dispersion obtained by dispersing polyurethane gel in a solvent and a powder are kneaded, and then the solvent is removed by evaporation to dry completely.
- the method is preferred, and by further pulverizing this, it is possible to produce a polyurethane gel-treated powder that is more homogeneous and excellent in usability.
- the pulverization method is not particularly limited.
- the compound used as the solvent is not particularly limited as long as it can disperse the polyurethane gel, and examples thereof include water, ethanol, n-propyl alcohol, isopropyl alcohol, n-hexane, isoparaffin, benzene, toluene and the like. 1 type or 2 types or more can be used. From the viewpoint of obtaining a polyurethane gel-treated powder that is more homogeneous and excellent in usability, it is preferable to use one or more of isopropyl alcohol and n-hexane.
- the polyurethane gel-treated powder is further used for the purpose of improving dispersibility to cosmetic base materials, improving touch, etc., such as silicone compounds, fluorine compounds, oils, fats and oils, higher alcohols, waxes, polymers, resins, etc.
- cosmetic base materials such as silicone compounds, fluorine compounds, oils, fats and oils, higher alcohols, waxes, polymers, resins, etc.
- surface treatment agents may be used after coating.
- the polyurethane gel-treated powder has a powder surface treated with the polyurethane gel, and the polyurethane gel exists on the powder surface.
- the coating amount is not particularly limited, but is preferably 0.1 to 10% by mass based on the total mass of the coated powder from the viewpoint that the effects of the present invention are more remarkably exhibited.
- the coating amount included in this range is 0.1 to 10% by mass, 0.1 to 7.5% by mass, 0.1 to 5% by mass, 0.5 to 10% by mass, 0.5 to 7%.
- a cosmetic can be produced by using one or more of the polyurethane gel-treated powders in combination with a known cosmetic ingredient according to a conventional method.
- the content of the treated powder in the cosmetic is not particularly limited, and is 1 to 99% by mass, preferably 5 to 95% by mass, depending on the cosmetic dosage form.
- the cosmetic using the polyurethane gel-treated powder is a powder cosmetic mainly composed of powder and can exhibit a remarkable effect. In that case, 1 to 70% by mass, and further 5 to 50%. It is preferable that the content be 10% by mass, particularly 10 to 30% by mass.
- components that can be contained can be used as needed.
- the volatile components for example, the volatile components, surfactants, oils, powders, aqueous components, alcohols, water-soluble polymers, ultraviolet absorbers, humectants, gelling agents and thickeners, antifading agents, antioxidants , Antifoaming agents, cosmetic ingredients (whitening agents, cell activators, anti-inflammatory agents, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), antiseptics, antibacterial agents, fragrances, vitamins, amino acids, nucleic acids, In order to impart various effects, such as hormones, other components that are usually used in cosmetics can be used as appropriate.
- Cosmetics can be produced by using the polyurethane gel composition of the present invention in combination with known cosmetic ingredients according to a conventional method.
- the content of the polyurethane gel composition in the cosmetic is not particularly limited, and is 0.1 to 99% by mass, preferably 1 to 95% by mass, although it varies depending on the cosmetic dosage form. .
- components that can be contained can be used as needed.
- the volatile components for example, as such components, the volatile components, surfactants, oils, powders, aqueous components, alcohols, water-soluble polymers, UV absorbers, humectants, gelling agents and thickeners, amber Antioxidants, antioxidants, antifoaming agents, beauty ingredients (whitening agents, cell activators, anti-inflammatory agents, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), antiseptics, antibacterial agents, fragrances, vitamins And amino acids, nucleic acids, hormones and the like.
- the polyurethane gel composition of the present invention has various dosage forms such as liquid, emulsion, cream, solid, paste, gel, powder, press, multilayer, mousse, spray, or stick.
- the polyurethane gel composition of the present invention can be used to produce cosmetics for various application sites, such as makeup cosmetics, skin care cosmetics, hair cosmetics, antiperspirants, or UV protection cosmetics.
- Cosmetic items containing the polyurethane gel composition of the present invention include skin lotion, milky lotion, serum, pack, all-in-one gel, cream, body milk, oil cleansing, cleansing cream, sunscreen and other basic cosmetics, styling water, Examples include cosmetics for hair such as hair wax, makeup cosmetics such as mascara, lip gloss, lipstick, eye shadow, eyeliner, foundation, face color, concealer, and makeup base.
- the present invention will be described in more detail with reference to examples. In addition, these do not limit this invention at all.
- the following Production Examples 1 to 5 all relate to the composition 2, but the same applies when the composition 1 is used by replacing the hydrogenated polybutadiene having a terminal hydroxyl group with a hydrogenated polybutadiene having an isocyanate group at the terminal.
- a polyurethane gel can be produced.
- the polyurethane in the composition 2 has (c) a hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) a diisocyanate compound, and (b) HO—R 3 —OH (wherein R 3 has an ether bond).
- the polyurethane in composition 1 is obtained by replacing (a) hydrogenated polybutadiene having a hydroxyl group at the terminal of composition 2 with (a) hydrogenated polybutadiene having an isocyanate group at the terminal. Obtained by reacting polybutadiene with a glycol represented by (b) HO—R 3 —OH (wherein R 3 represents a linear or branched C2 to C6 alkylene group optionally having an ether bond).
- Polyurethane polyurethane.
- the same polyurethane can be manufactured by making the molar ratio of (a) and (b) the same as the molar ratio of (c) and (b).
- the weight average molecular weight of the polyurethane in the obtained polyurethane gel was 10,000 by GPC measurement (polystyrene conversion). Further, 30 parts of the gel obtained was dissolved in 70 parts of liquid paraffin, heated and melted at 85 ° C., and cooled to 30 ° C. The load value of the gel was 2 cm ⁇ spherical adapter, 2 cm / cm by a load measuring machine (manufactured by FUDOH). In the case of min, 10 mm penetration condition, it was 2.50N.
- the weight average molecular weight of the polyurethane in the obtained polyurethane gel was 50000 in GPC measurement (polystyrene conversion). Further, 30 parts of the obtained gel, 70 parts of liquid paraffin, heat-dissolved at 85 ° C., and the gel loaded after cooling to 30 ° C. have a load value of 2 cm ⁇ spherical adapter, 2 cm / In the case of min, 10 mm penetration condition, it was 5.00N.
- the weight average molecular weight of the polyurethane in the obtained polyurethane gel was 100,000 by GPC measurement (polystyrene conversion). Further, 30 parts of the gel obtained was dissolved in 70 parts of liquid paraffin, heated and melted at 85 ° C., and cooled to 30 ° C. The load value of the gel was 2 cm ⁇ spherical adapter, 2 cm / cm by a load measuring machine (manufactured by FUDOH). In the case of min, 10 mm penetration conditions, it was 7.50 N.
- a polysaccharide gel was prepared by heating and cooling 35 parts of dextrin fatty acid ester (Leopard ISK, manufactured by Chiba Flour Mills) and 65 parts of cetyl 2-ethylhexanoate at 90 ° C.
- a wax oil gel was prepared by heating and cooling 35 parts of crystalline polyethylene wax (PERFORMALENE 655 New Phase Technology) and 65 parts of cetyl 2-ethylhexanoate at 90 ° C.
- the polyurethane gel composition of the present invention is a highly novel gel having excellent transparency, high elasticity, and excellent self-restoring ability.
- the molar ratio of (c) :( b) (molar ratio of (c) / (b)) is more preferably 2: 3 to 3: 2 (0.66 to 1.5).
- the content (mass%) of A (polyurethane) is 1 to 35 mass%, and the content (mass%) of B (cetyl 2-ethylhexanoate (oil agent)) may satisfy 65 to 99 mass%. preferable.
- Oily body oils having the composition shown in Table 3 were prepared by the following manufacturing method, and each sample was prepared with the following characteristics: “Ease of spreading”, “Smooth”, “Glossy”, “No stickiness”, “Long makeup effect” Was evaluated by the following evaluation method, and the results are also shown in Table 3.
- the oil-based body oils of Examples 1 to 7 were oil-based body oils having excellent spreadability, firmness, glossiness, non-stickiness, and excellent makeup lasting effects. Compared with the oily body oils of Examples 1 to 7, it was confirmed that the oily body oils of Comparative Examples 1 to 5 were inferior in the following points.
- the oil-based body oil of Comparative Example 1 is particularly inferior in elasticity and gloss because the cross-linked silicone gel has low elasticity and transparency, and the oil-based body oil of Comparative Example 2 is rich in dextrin fatty acid esters.
- the saccharide gel has a relatively high transparency, it has a sticky feeling peculiar to saccharides, and since it has low elasticity, it is poorly stretched and inferior in firmness and stickiness.
- the oily body oil of Comparative Example 3 was inferior and hard to the transparency and elasticity of the wax oil gel, it was poor in spreading and glossy.
- the oily body oil of Comparative Example 4 using polyurethane powder and polysaccharide gel instead of the polyurethane gel of the present invention is insufficient in terms of spreading and stickiness, and has a feeling of elasticity, gloss and makeup lasting effect. It was inferior in respect.
- Comparative Example 5 using polyurethane powder was difficult to evaluate because the polyurethane powder settled.
- Example 8 Emulsion type lotion (component) (mass%) 1. Cetyl alcohol 0.2 2. Polyurethane gel of Production Example 1 0.2 3. Phospholipid / phytosterol mixture (15:85) (Note 8) 0.5 4). Polyoxyethylene (40 mol) hydrogenated castor oil 0.1 5). Tocopherol acetate 0.5 6). Stearic acid triethanolamine 0.5 7). Purified water remaining amount 8. Ethanol 10.0 9. Fragrance 0.1 (Note 8): Made by Nippon Seika Co., Ltd.
- the emulsified lotion of Example 8 was an emulsified lotion excellent in “goodness of spreading”, “feel of elasticity”, “feel of gloss”, “no stickiness”, and “makeup lasting effect”.
- Latex (component) (mass%) 1. Stearic acid 0.5 2. Polyoxyethylene sorbitan monostearate (20EO) 1.0 3. Tetraoleic acid polyoxypropylene sorbitol (40EO) 1.0 4). Behenyl alcohol 1.5 5). Liquid paraffin 2.0 6). Glyceryl tri-2-ethylhexanoate 5.0 7). Polyurethane gel of Production Example 2 2.0 8). Acrylic acid / methacrylic acid alkyl ester copolymer 0.1 9. Xanthan gum 0.1 10. Sodium hydroxide 0.05 11.1,3-butylene glycol 8.0 12 Preservative appropriate amount13. Fragrance 0.1 14 Purified water remaining
- the emulsion of Example 9 was an emulsion excellent in “goodness of spreading”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Example 10 O / W type cream (component) (mass%) 1. Decaglyceryl pentaoleate 2.5 2. Behenyl alcohol 1.5 3. Vaseline 3.0 4). Heavy liquid isoparaffin 1.0 5). Glyceryl tri-2-ethylhexanoate 1.0 6). Polyurethane gel of Production Example 3 4.0 7). Purified water remaining amount 8. Glycerin 7.0 9. Acrylic acid / methacrylic acid alkyl ester copolymer 0.2 10. Sodium hydroxide 0.09 11. Preservative appropriate amount 12. Fragrance 0.1
- the O / W type cream of Example 10 was an O / W type cream excellent in “goodness of spreading”, “feel of elasticity”, “feel of gloss”, “no stickiness”, and “makeup lasting effect”. .
- Example 11 W / O type cream (component) (mass%) 1. Microcrystalline wax 1.5 2. Beeswax 1.5 3. Cetyl alcohol 3.0 4). Polyurethane gel of Production Example 4 3.0 5). Hydrogenated soybean phospholipid 1.0 6). Squalane 35.0 7). Sorbitan sesquioleate 3.0 8). Propylene glycol 10.0 9. Preservative appropriate amount10. Fragrance 0.1 11. Purified water remaining
- the W / O type cream of Example 11 was a W / O type cream excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”. .
- Example 12 Oil cleansing (component) (mass%) 1. Tetraoleic acid polyoxyethylene sorbit 8.0 2. Polyglyceryl diisostearate 0.5 3. 3. Liquid paraffin remaining Glyceryl tri-2-ethylhexanoate 25.0 5). Polyurethane gel of Production Example 5 1.0 6). Preservative appropriate amount 7. Fragrance 0.1
- the oil cleansing of Example 12 was an oil cleansing excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Example 13 Cleansing cream (ingredient) (mass%) 1. Stearic acid 3.0 2. Cetanol 2.0 3. Tetraoleic acid polyoxypropylene sorbitol (40EO) 1.0 4). Polyoxyethylene sorbitan monostearate (20EO) 1.0 5). Glyceryl tri-2-ethylhexanoate 20.0 6). Liquid paraffin 20.0 7). Polyurethane gel of Production Example 1 2.0 8). Acrylic acid / methacrylic acid alkyl ester copolymer 0.1 9. 1,3-Butylene glycol 7.0 10. Sodium hydroxide 0.05 11. Purified water remaining amount 12. Preservative appropriate amount13. Fragrance 0.1
- the cleansing cream of Example 13 was a cleansing cream excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Example 14 Styling water (component) (mass%) 1. Ethanol 15.0 2. Stearyltrimethylammonium chloride 0.2 3. Isostearic acid polyoxyethylene hydrogenated castor oil 0.2 4). Polyurethane gel of Production Example 2 0.1 5). Purified water remaining amount 6. Hydroxypropylcellulose 0.01 7). Highly polymerized methylpolysiloxane emulsion (Note 9) 2.0 8). Preservative appropriate amount 9. Fragrance 0.1 (Note 9) BY11-007 (made by Toray Dow Corning)
- the styling water of Example 14 was a styling water excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “no stickiness”, and “makeup lasting effect”.
- Example 15 Hair wax (ingredient) (mass%) 1.
- Purified water remaining amount Propylene glycol 10.0 3. Polyethylene glycol monostearate 3.0 4). Vaseline 10.0 5). Paraffin wax 3.0 6). Cetostearyl alcohol 3.0 7). Behenyl alcohol 3.0 8).
- Ethanol 5.0 Purified water 15.0
- Sodium hydroxide 0.05 14 Preservative appropriate amount15. Fragrance 0.1
- the hair wax of Example 15 was a hair wax excellent in “goodness of spreading”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Example 16 O / W type mascara (component) (mass%) 1. Stearic acid 2.0 2. Beeswax 10.0 3. Cetostearyl alcohol 1.0 4). Monooleic acid polyoxyethylene sorbitan (20EO) 1.5 5). Sorbitan sesquioleate 0.5 6). Polyurethane gel of Production Example 4 3.0 7). Black iron oxide 5.0 8). Silicic anhydride 3.0 9. Purified water remaining 10.1,3-butylene glycol 10.0 11. Triethanolamine 1.5 12 Alkyl acrylate copolymer emulsion (Note 10) 30.0 13. Preservative appropriate amount14. Fragrance 0.1 (Note 10) Iodosol 32A707 (45% by mass solids) (NSC Japan)
- the O / W type mascara of Example 16 was an O / W type mascara excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “no stickiness”, and “makeup lasting effect”. .
- Example 17 Pasty Lip Gloss (Component) (mass%) 1. Polyurethane gel of Production Example 5 2.0 2. Diisostearyl malate 10.0 3. Stearyl lactate 10.0 4). Hydrogenated polyisobutene 30.0 5). 5. Triethylhexanoin remaining amount Liquid paraffin 5.0 7). Microcrystalline wax 2.0 8.12-hydroxystearic acid 0.1 9. ⁇ -olefin-vinylpyrrolidone copolymer (Note 11) 0.5 10. Silicic anhydride (Note 12) 3.5 11. Bengala 0.1 12 Red 201 No. 0.3 13. Black iron oxide 0.05 14 Titanium oxide 0.2 15. Soy phospholipid 0.01 16.
- the paste-like lip gloss of Example 17 was a paste-like lip gloss excellent in “goodness of spreading”, “feel”, “feel”, “non-stickiness”, and “makeup lasting effect”.
- Example 18 Stick-shaped lipstick (component) (mass%) 1. Polyethylene wax 10.0 2. Carnauba wax 5.0 3. Paraffin wax 2.0 4. Cetyl 2-ethylhexanoate 5 Polyurethane gel of Production Example 1 2.0 6). Liquid paraffin 10.0 7). Isotridecyl isononanoate 10.0 8). Red 202 0.5 9. Yellow 4 2.0 10. Titanium oxide 0.5 11. Black iron oxide 0.1 12 ⁇ -Tocopherol 0.5 13. Fragrance 0.1
- the stick-shaped lipstick of Example 18 was a stick-shaped lipstick that was excellent in “goodness of spreading”, “harshness”, “shininess”, “no stickiness”, and “makeup lasting effect”.
- Example 19 Oily eye shadow (component) (mass%) 1. Dextrin fatty acid ester (Note 13) 2.0 2. Polyurethane gel of Production Example 2 1.0 3. Diisostearyl malate 2.5 4.2 Cetyl 2-ethylhexanoate 13.0 5). Dextrin laurate 2.0 6). Dextrin myristate 5.0 7). Dextrin behenate 5.0 8). 8. Liquid paraffin remaining Hydrogenated polyisobutene 1.5 10. Silica anhydride 6.0 11. Nylon powder 5.0 12 Silicone-treated talc (Note 14) 5.5 13. Red No. 202 0.05 14 Yellow No. 4 aluminum lake 0.05 15. Blue No. 1 aluminum rake 0.05 16. Mica titanium 1.5 17. Preservative appropriate amount 18. Fragrance 0.1 (Note 13) Spirit TT (Chiba Flour Mills) (Note 14) Dimethylpolysiloxane 5% by mass treatment
- the oily eye shadow of Example 19 was an oily eye shadow excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Example 20 Solid powder foundation (component) (mass%) 1. Dimethylpolysiloxane-treated talc 30.0 2. Mica treated with dimethylpolysiloxane 15.0 3. Dimethylpolysiloxane treated titanium oxide 15.0 4). 4. Sericite treated with dimethylpolysiloxane Synthetic phlogopite 5.0 6). Yellow iron oxide 2.0 7). Bengala 0.5 8). Black iron oxide 0.2 9. Preservative appropriate amount10. Polyurethane gel of Production Example 3 1.0 11. Liquid paraffin 3.0 12 Dimethylpolysiloxane 1.0 13. Glyceryl 2-ethylhexanoate 2.0 14 Fragrance 0.1
- the solid powder foundation of Example 20 was a solid powder foundation excellent in “goodness of spreading”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Example 21 Solid powder eye shadow (component) (mass%) 1. Synthetic gold mica treated with dimethylpolysiloxane 10.0 2. 2. Dimethylpolysiloxane-treated talc Titanium oxide coated mica 30.0 4). Boron nitride 5.0 5). Polyethylene terephthalate / aluminum / epoxy laminated powder 5.0 6). Ultramarine 2.0 7). Red 202 0.5 8). Polyalkyl acrylate 1.0 9. Preservative appropriate amount10. Polyurethane gel of Production Example 4 1.0 11. Liquid paraffin 3.0 12 Dimethylpolysiloxane 2.0 13. Glyceryl 2-ethylhexanoate 2.0 14 Fragrance 0.1
- the solid powder eye shadow of Example 21 was a solid powder eye shadow excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”. .
- Example 22 Solid powder face color (component) (mass%) 1. Mica 20.0 2. 2. Talc remaining amount Titanium oxide coated mica 10.0 4). Ultramarine 0.5 5). Red 226 0.2 6). Polyalkyl acrylate 1.0 7). Preservative appropriate amount 8. Polyurethane gel of Production Example 5 1.0 9. Liquid paraffin 2.0 10. Dimethylpolysiloxane 1.0 11.2-Glyceryl ethylhexanoate 1.0 12 Fragrance 0.1
- the solid powder face color of Example 22 was a solid powder face color excellent in “excellent spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”. .
- Example 23 Stick concealer (component) (mass%) 1. Paraffin wax 5.0 2. Polyethylene wax 5.0 3. Candelilla Row 2.0 4). Polyurethane gel of Production Example 1 2.0 5). Glyceryl tri-2-ethylhexanoate 15.0 6). Methylphenylpolysiloxane 5.0 7). Acetic acid liquid lanolin 10.0 8). 2-Ethylhexyl paramethoxycinnamate 5.0 9. Titanium oxide 20.0 10. Yellow iron oxide 2.0 11. Bengala 0.5 12 Black iron oxide 0.2 13. Mica 7.0 14 Preservative appropriate amount
- the stick-like concealer of Example 23 was a stick-like concealer excellent in “goodness of spreading”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Example 24 W / O type sunscreen (component) (mass%) 1.
- Zinc oxide 2.0 Silicone coated fine particle titanium oxide 5.0 3.
- Polyurethane gel of Production Example 2 1.0 10. Preservative appropriate amount11. Sodium chloride 0.3 12 Purified water remaining amount 13.
- Dipropylene glycol 5.0 Ethanol 5.0 15.
- Fragrance 0.1 (Note 15)
- the W / O type sunscreen of Example 24 is a W / O type sunscreen excellent in “goodness of spread”, “feel of elasticity”, “feel of luster”, “non-stickiness”, and “makeup lasting effect”. It was a fee.
- Example 25 W / O type foundation (component) (mass%) 1. Polyoxyethylene methylsiloxane / polyoxypropylene oleyl methylsiloxane / dimethylsiloxane copolymer (Note 16) 2.0 2. PEG-3 Dimethicone (Note 17) 1.0 3. Cyclopentasiloxane 20.0 4). Silicone-treated red iron oxide 1.0 5). Silicone-treated yellow iron oxide 1.5 6). Silicone-treated black iron oxide 0.5 7). Silicone-treated titanium oxide 10.0 8). Silicone-treated talc 5.0 9. Glyceryl tri-2-ethylhexanoate 5.0 10. Polyurethane gel of Production Example 3 1.0 11. Sorbitan sesquioleate 0.5 12 Purified water remaining 13.1,3-butylene glycol 15.0 14 Sodium chloride 0.5 15. Preservative appropriate amount 16. Fragrance 0.1
- KF-6026 (manufactured by Shin-Etsu Chemical Co., Ltd.)
- KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.)
- the W / O type foundation of Example 25 was a W / O type foundation excellent in “goodness of spreading”, “feel of elasticity”, “feel of gloss”, “no stickiness”, and “makeup lasting effect”. .
- Example 26 O / W type foundation (component) (mass%) 1. Monooleic acid polyoxyethylene sorbitan (20EO) 0.5 2. Sorbitan sesquioleate 0.5 3. 1,3-butylene glycol 10.0 4). Silicone-treated titanium oxide 10.0 5). Silicone treatment Bengala 0.4 6). Silicone-treated yellow iron oxide 2.0 7). Silicone-treated black iron oxide 0.1 8). Silicone-treated talc 5.0 9. Carboxyvinyl polymer 0.3 10. Triethanolamine 1.0 11. Purified water remaining amount 12. Ethanol 2.0 13. Stearic acid 1.0 14 Behenyl alcohol 0.5 15. Liquid paraffin 5.0 16. Polyurethane gel of Production Example 4 1.0 17. Glyceryl tri-2-ethylhexanoate 1.0 18. 2-Methylhexyl paramethoxycinnamate 2.0 19. Vaseline 0.5 20. Antiseptic suitable amount 21. Fragrance 0.1
- the O / W type foundation of Example 26 was an O / W type foundation excellent in “goodness of spreading”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”. .
- Example 27 Oily solid foundation (component) (mass%) 1. Talc 15.0 2. Mica 10.0 3. Silicone-treated titanium oxide 15.0 4). Silicone-treated Bengala 1.0 5). Silicone-treated yellow iron oxide 3.0 6). Silicone-treated black iron oxide 0.2 7). Polyethylene wax 7.0 8). Microcrystalline wax 6.0 9. 10. Glyceryl tri-2-ethylhexanoate remaining 10. Polyurethane gel of Production Example 5 3.0 11. Dimethylpolysiloxane 5.0 12 Liquid paraffin 20.0 13. Polyoxyethylene methylsiloxane / polyoxypropylene oleyl methylsiloxane / dimethylsiloxane copolymer (Note 16) 2.0 14 Preservative appropriate amount15. Fragrance 0.1 (Note 16) KF-6026 (manufactured by Shin-Etsu Chemical Co., Ltd.)
- the oily solid foundation of Example 27 was an oily solid foundation excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Example 28 Makeup Base (Ingredient) (mass%) 1. Cetostearyl alcohol 2.0 2. 2-Ethylhexyl paramethoxycinnamate 5.0 3. Polyurethane gel of Production Example 1 2.0 4). Glyceryl tri-2-ethylhexanoate 3.0 5). Purified water remaining amount 6. N-stearoyl-N-methyltaurine sodium 0.5 7). Carboxyvinyl polymer 0.1 8). Acrylic acid / methacrylic acid alkyl ester copolymer 0.1 9. Sodium hydroxide 0.05 10. Ethanol 10.0 11.1,3-butylene glycol 10.0 12 Preservative appropriate amount13. Fragrance 0.1
- the makeup base of Example 28 was a makeup base excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Example 29 Body milk (ingredient) (mass%) 1. Stearic acid 1.0 2. Monooleic acid polyoxyethylene sorbitan (20EO) 0.5 3. Sorbitan sesquioleate 0.5 4). Behenyl alcohol 0.5 5.2 Glyceryl 2-ethylhexanoate 2.0 6). Liquid paraffin 2.0 7). Polyurethane gel of Production Example 2 2.0 8). Ethanol 10.0 9. Dipropylene glycol 10.0 10. Triethanolamine 1.0 11. Purified water remaining amount 12. Glycerin 5.0 13.1,3-Butylene glycol 5.0 14 Acrylic acid / methacrylic acid alkyl ester copolymer 0.2 15. Preservative appropriate amount 16. Fragrance 0.1
- the body milk of Example 29 was a body milk excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Example 30 Remover (ingredient) (mass%) 1. 1,3-butylene glycol 15.0 2. Alkyl acrylate copolymer emulsion (Note 18) 2.5 3. L-Arginine 0.5 4). 4. Purified water remaining amount Light liquid isoparaffin 3.0 6). Polyurethane gel of Production Example 3 0.5 7). Preservative appropriate amount 8. Fragrance 0.1 (Note 18) Iodosol 32A707 (45 mass% solid content) (manufactured by NSC Japan)
- the remover of Example 30 was a remover excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- Non-aqueous mascara (component) (mass%) 1. Rosin acid pentaerythritol 10.0 2. Candelilla resin 3.0 3. Beeswax 2.0 4). Ceresin wax 2.0 5). Dextrin palmitate 2.0 6). Trimethylsiloxysilicic acid 3.0 7). Dimethyl distearyl ammonium hectorite 5.0 8). Propion carbonate 1.0 9. Light liquid isoparaffin remaining amount 10. Polyurethane gel of Production Example 4 2.0 11. Black iron oxide 5.0 12 Silica 3.0 13. Talc 5.0
- the non-aqueous mascara of Example 31 was a non-aqueous mascara excellent in “goodness of spreading”, “harshness”, “shininess”, “no stickiness”, and “makeup lasting effect”.
- Example 32 Oily eyeliner (component) (mass%) 1. Ceresin wax 11.0 2. Polyisobutylene 16.0 3. Polyethylene wax 8.0 4). Light liquid isoparaffin 5 Polyurethane gel of Production Example 5 2.0 6). Silicone-treated black iron oxide 15.0 7). Silicone-treated talc 5.0 8). Preservative appropriate amount 9. Fragrance 0.1
- the oily eyeliner of Example 32 was an oily eyeliner excellent in “goodness of spread”, “feel of elasticity”, “feel of gloss”, “non-stickiness”, and “makeup lasting effect”.
- the polyurethane gel composition of the present invention can provide an oil-soluble gel film that is extremely excellent in transparency, glossiness, elasticity, and resilience. It is an extremely useful invention in the field.
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Abstract
Description
(1)動きに柔軟であり、自己修復性がある。凹凸が発生しても自然に修復して、常に化粧膜表面が平滑である。即ち、膜がよれない。
(2)膜自体にツヤと厚みがある。即ち、濡れヅヤによる明るさがある。
(3)化粧膜の持続効果に優れる。
一般的にポリウレタンは、ジイソシアネートとポリオールとを反応させて得られることが知られており、水添ポリブテンと多価アルコールから成るポリウレタンは周知技術の範疇である。しかしながら、ポリウレタンを油溶性のゲル化剤として用いている例はない。
その結果、本発明者らは、(a)末端にイソシアネート基を持つ水添ポリブタジエンと(b)HO-R3-OH(式中、R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールとの反応によって得られるポリウレタンであるか、または、Aは(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物と(b)HO-R3-OH(式中R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールとの反応によって得られるポリウレタン、に油剤を混合すると、弾力性、復元性のあるポリウレタンゲル組成物が得られることを見出した。本ポリウレタンゲル組成物を化粧料に用いると、ツヤに優れた化粧膜が得られ、肌や瞼などの動きによる経時での化粧崩れ等を抑制する効果(化粧持続効果)が高くなることを見出した。本発明は、かかる知見に基づいて完成されたものである。
(1)AとBとを含有するポリウレタンゲル組成物。
ここで、Aは(a)末端にイソシアネート基を持つ水添ポリブタジエンと(b)HO-R3-OH(式中、R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールとの反応によって得られるポリウレタンであるか、または、Aは(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物と(b)HO-R3-OH(式中R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールとの反応によって得られるポリウレタンであり、Bは油剤である。
(2)Aの(a)が(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物との反応によって得られるイソシアネート化合物である(1)に記載の組成物。
(3)Aの(d)がOCN-R2-NCO(式中、R2はC2~C6アルキレン)で表されるジイソシアネート化合物である(1)又は(2)に記載の組成物。
(4)Aの(a)が式(1)
(5)Aの(a)が式(2)
(6)(c)末端に水酸基を持つ水添ポリブタジエンが
(d)ジイソシアネート化合物が
(b)HO-R3-OHで表されるグリコールが
(7)Aのポリウレタンが油溶性のポリウレタンである、(1)に記載の組成物。
(8)Aのポリウレタンの平均分子量(Mw)が、10000~100000である、(1)に記載の組成物。
(9)Bの油剤が25℃で液状の油剤である、(1)に記載の組成物。
(10)Bの油剤が、炭化水素油、水酸基の数が0又は1個であるエステル油、シリコーン油から選ばれる1種以上である、(1)に記載の組成物。
(11)Aのポリウレタンの含有量が1~35質量%である、(1)に記載の組成物。
(12)Bの油剤の含有量が65~99質量%である、(1)に記載の組成物。
(13)(1)~(12)のいずれかに記載されたポリウレタンゲル組成物30部と流動パラフィン70部とを、85℃にて加熱溶解し、冷却し得られたゲルが、2cmφ球状アダプタを2cm/minで10mm針入させた時の荷重値が0.20-10.00N(ニュートン)である、(1)~(12)のいずれかに記載の組成物。
(14)ゲル復元性を有する、(1)~(13)のいずれかに記載の組成物。
(15)700nmの波長の透過率が90%以上である、(1)~(14)のいずれかに記載の組成物。
(16)(1)~(15)のいずれかに記載の組成物を含有する化粧料。
(17)AとBとを含有するポリウレタンゲル組成物(ここでAはポリウレタンであり、Bは油剤である。)の製造方法であって、Bの油剤中において、Aの(a)末端にイソシアネート基を持つ水添ポリブタジエンと(b)HO-R3-OH(式中R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールを加えて重付加反応を行うことを含む、ポリウレタンゲル組成物の製造方法。
(18)Aの(a)が(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物との反応によって得られるイソシアネート化合物である、(17)に記載の製造方法。
(19)Aのポリウレタンが(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物と(b)HO-R3-OHで表されるグリコールとの反応によって得られるポリウレタン(式中R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)である、(17)に記載の製造方法。
(20)Aの(d)がOCN-R2-NCOで表されるジイソシアネート化合物(式中、R2はC2~C6アルキレン)である(18)又は(19)に記載の製造方法。
(21)Aの(a)が式(1)
(22)Aの(a)が式(2)
(23)(c)末端に水酸基を持つ水添ポリブタジエンが
(d)ジイソシアネート化合物が
(b)HO-R3-OHで表されるグリコールが
(24)Aのポリウレタンが油溶性のポリウレタンである、(17)又は(19)に記載の製造方法。
(25)Aのポリウレタンの平均分子量(Mw)が、10000~100000である、(17)又は(19)に記載の製造方法。
(26)Bの油剤が25℃で液状の油剤である、(17)に記載の製造方法。
(27)Bの油剤が、炭化水素油、水酸基の数が0又は1個であるエステル油、シリコーン油から選ばれる1種以上である、(26)に記載の製造方法。
(28)Aのポリウレタンの含有量が1~35質量%である、(17)又は(19)に記載の製造方法。
(29)Bの油剤の含有量が65~99質量%である、(17)に記載の製造方法。
(30)(1)~(12)のいずれかに記載されたポリウレタンゲル組成物30部と流動パラフィン70部とを、85℃にて加熱溶解し、冷却し得られたゲルが、2cmφ球状アダプタを2cm/minで10mm針入させた時のポリウレタンゲル組成物の荷重値が0.20-10.00Nである、(17)~(29)のいずれかに記載の製造方法。
(31)ポリウレタンゲル組成物がゲル復元性を有する、(17)~(30)のいずれか1項に記載の製造方法。
(32)ポリウレタンゲル組成物に対する700nmの波長の透過率が90%以上である、(17)~(31)のいずれかに記載の製造方法。
組成物1
Aとして(a)末端にイソシアネート基を持つ水添ポリブタジエンと(b)HO-R3-OH(式中、R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールとの反応によって得られるポリウレタン、Bとして油剤を含有する組成物。
組成物2
Aとして(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物と(b)HO-R3-OH(式中R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールとの反応によって得られるポリウレタン、Bとして油剤を含有する組成物。
本発明において「末端」とは「両末端」を意味する。
組成物1において用いられるAの(a)は、末端にイソシアネート基を持つ水添ポリブタジエンであれば、特に限定されない。例えば、下記式(1)で示される化合物が示される。
nは10~100の整数を表し、nのより好ましい範囲は、15~55である。
n1、n2は各々独立して、即ち、同一若しくは異なって0又は1を表す。
式(1)で表される末端にイソシアネート基を持つ水添ポリブタジエンとして、例えば、下記式(2)で表される化合物が例示される。
式(2)の化合物は、式(1)の末端にイソシアネート基を持つ水添ポリブタジエンにおいて、R1がエチレン基、R2がヘキサメチレン基、n1=n2=1である場合に相当する。
また、組成物2において用いられる(d)ジイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネート、1,3-ビス(イソシアナトメチル)ベンゼン、1,3-ビス(イソシアナトメチル)シクロヘキサン、2,4-トルエンジイソシアネート、2,6-トルエンジイソシアネートなどを挙げることができる。これらのうち、下記式(4)で示されるヘキサメチレンジイソシアネートが好ましい。
また、重付加によって得られるポリウレタンの平均分子量(Mw)は10000~100000であることが好ましい。この範囲に包含される分子量として、10000~100000、10000~90000、10000~80000、10000~70000、10000~60000、10000~50000、20000~90000、20000~80000、20000~70000、20000~60000、20000~50000、30000~90000、30000~80000、30000~70000、30000~60000、30000~50000、40000~90000、40000~80000、40000~70000、40000~60000、50000~90000、50000~80000、50000~70000、が例示される。
組成物1中のAのポリウレタンの含有量は1~35質量%であることがより好ましい。ポリウレタンポリマーの濃度がこの範囲より低い場合、透明性は高いものの弾力感(荷重値)に劣り、化粧料へのハリ感付与に劣る。この範囲に包含されるポリウレタンの含有量として、1~35質量%、1~30質量%、1~25質量%、1~20質量%、1~15質量%、1~10質量%、1~5質量%、5~30質量%、5~25質量%、5~20質量%、5~15質量%、5~10質量%、10~30質量%、10~25質量%、10~20質量%、10~15質量%、が例示される。また、組成物1中のBの油剤の含有量は65~99質量%であることが好ましい。この範囲に包含される油剤の含有量として、65~99重量%、70~99質量%、80~99質量%、85~99質量%、90~99質量%、95~99質量%、70~95質量%、75~95質量%、80~95質量%、85~95質量%、90~95質量%、70~90質量%、75~90質量%、80~90質量%、85~90質量%、が例示される。
組成物2中のAのポリウレタンの含有量は1~35質量%であることがより好ましい。ポリウレタンポリマーの濃度がこの範囲より低い場合、透明性は高いものの弾力感(荷重値)に劣り、化粧料へのハリ感付与に劣る。この範囲に包含されるポリウレタンの含有量として、1~35質量%、1~30質量%、1~25質量%、1~20質量%、1~15質量%、1~10質量%、1~5質量%、5~30質量%、5~25質量%、5~20質量%、5~15質量%、5~10質量%、10~30質量%、10~25質量%、10~20質量%、10~15質量%、が例示される。また、組成物2中のBの油剤の含有量は65~99質量%であることが好ましい。この範囲に包含される油剤の含有量として、65~99質量%、70~99質量%、80~99質量%、85~99質量%、90~99質量%、95~99質量%、70~95質量%、75~95質量%、80~95質量%、85~95質量%、90~95質量%、70~90質量%、75~90質量%、80~90質量%、85~90質量%、が例示される。
ポリウレタンゲル組成物において用いられるBの油剤としては、動物油、植物油、合成油等の起源を問わず、炭化水素油、エステル油、油脂類、シリコーン油、フッ素系油類等が挙げられる。これらのうち、極性が低い方がポリウレタンゲル組成物の強度が高くなる傾向にあることから、炭化水素油、水酸基の数が0又は1個であるエステル油、フェニル基を含有するシリコーン油から選ばれる1種以上を使用することが例示される。具体的には、流動パラフィン、スクワラン、ポリブテン、ポリイソブチレン等の炭化水素類、オリーブ油、ヒマシ油、ミンク油、マカデミアンナッツ油、ホホバ油等の油脂類、イソオクタン酸セチル(2-エチルヘキサン酸セチル)、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、ミリスチン酸オクチルドデシル、トリオクタン酸グリセリル、ジイソステアリン酸ポリグリセリル、イソステアリン酸ジグリセリル、リンゴ酸ジイソステアリル、トリベヘン酸グリセリル、ロジン酸ペンタエリトリットエステル、ジオクタン酸ネオペンチルグリコール等のエステル類、メチルフェニルポリシロキサン、ジフェニルポリシロキサン等のシリコーン類、が挙げられ、これらを1種又は2種以上用いることができる。
本発明のポリウレタンゲル組成物2は、公知のポリウレタン製造方法を利用して製造することができる。即ち、発明のポリウレタンゲル組成物2は、(c)末端に水酸基を持つ水添ポリブタジエン、(b)HO-R3-OH(式中R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコール、Bの油剤を仕込んで均一に混合し、(d)ジイソシアネート化合物を投入して反応させることによって製造することができる。
本発明のポリウレタンゲル組成物1及びポリウレタンゲル組成物2におけるポリウレタンの一例として、INCI(International Nomenclature of Cosmetic Ingredient(化粧品原料国際命名法))において、「Hydrogenated Polybutadiene/Glycol/HDI Copolymer」という名称が付与されているポリウレタンが挙げられる。
ゲル化剤のうち、水性のものとしては、アラビアガム、トラガカントガム、ガラクタン、キャロブガム、グァーガム、カラヤガム、カラギーナン、ペクチン、寒天、クインスシード(マルメロ)、デンプン(コメ、トウモロコシ、バレイショ、コムギ)、アルゲコロイド、トラントガム、ローカストビーンガム等の植物系高分子、キサンタンガム、デキストラン、サクシノグルカン、プルラン等の微生物系高分子、コラーゲン、カゼイン、アルブミン、ゼラチン等の動物系高分子、カルボキシメチルデンプン、メチルヒドロキシプロピルデンプン等のデンプン系高分子、メチルセルロース、ヒドロキシプロピルメチルセルロース、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシプロピルセルロース、セルロース硫酸ナトリウム、カルボキシメチルセルロースナトリウム等のセルロース系高分子、アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル等のアルギン酸系高分子、ポリアクリル酸ナトリウム、カルボキシビニルポリマー、アルキル変性カルボキシビニルポリマー、ポリアクリルアミド、ポリビニルアルコール、ポリビニルピロリドン等のビニル系高分子、ポリエチレングリコール、エチレンオキサイドプロピレンオキサイド共重合体、アクリル酸・アクリロイルジメチルタウリンナトリウム共重合体、ポリアクリル酸ナトリウム、ポリエチルアクリレート、ポリアクリルアミド等のアクリル系高分子、ベントナイト、ケイ酸アルミニウムマグネシウム、ラポナイト、ヘクトライト、無水ケイ酸等の無機系ゲル化剤及び増粘剤、ポリエチレンイミン、カチオンポリマー等が挙げられる。
皮膜形成剤としては、天然ゴム、天然セルロース、カチオン化セルロース、種々のアクリル樹脂(共重合体を含む)、種々のアルキド樹脂、ポリビニルアルコール、ポリビニルピロリドン、ニトロセルロース、種々のシリコーン樹脂(共重合体を含む)、尿素樹脂、変性コーンスターチ等が用いられる。具体的な皮膜形成剤として、アクリル酸アミド・アクリル酸アルキル・メタクリル酸メトキシポリエチレングリコール共重合体、メタクリル酸メトキシポリエチレングリコール、エイコセン・ビニルピロリドン重合体、1,1’-メチレンビス(4-イソシアナトシクロヘキサン)ポリプロピレングリコール共重合体、パーフルオロポリエーテル、(アクリレート/メタクリル酸ポリトリメチルシロキシ)共重合体、ポリプロピルシルセスキオキサン、(エイコセン/ビニルピロリドン)共重合体、(ビニルピロリドン/ヘキサデセン)共重合体、ヒドロキシエチルセルロース、シリコーン変性ノルボルネン等が挙げられる。
固形油としてはカルナウバロウ、キャンデリラロウ、綿ロウ、セラックロウ、硬化油等の天然ロウ類、オゾケライト、セレシン、パラフィンワックス、マイクロクリスタリンワックス等の鉱物系ワックス、ポリエチレンワックス、フィッシャートロプシュワックス、エチレン・プロピレンコポリマー等の合成ワックス、ベヘニルアルコール、セチルアルコール、ステアリルアルコール、コレステロール、フィトステロールなどの高級アルコール、ステアリン酸、ベヘン酸などの高級脂肪酸等を例示することができる。
液状油で、天然動植物油及び半合成油としては、具体的にアボガド油、アマニ油、アーモンド油、イボタロウ、エノ油、オリーブ油、カヤ油、肝油、キョウニン油、小麦胚芽油、ゴマ油、コメ胚芽油、コメヌカ油、サザンカ油、サフラワー油、シナギリ油、シナモン油、タートル油、大豆油、茶実油、ツバキ油、月見草油、トウモロコシ油、ナタネ油、日本キリ油、ヌカロウ、胚芽油、パーシック油、パーム油、パーム核油、ヒマシ油、ヒマワリ油、ブドウ油、ホホバ油、マカデミアナッツ油、綿実油、ヤシ油、トリヤシ油脂肪酸グリセライド、落花生油、ラノリン、液状ラノリン、還元ラノリン、ラノリンアルコール、酢酸ラノリン、ラノリン脂肪酸イソプロピル、POEラノリンアルコールエーテル、POEラノリンアルコールアセテート、ラノリン脂肪酸ポリエチレングリコール、POE水素添加ラノリンアルコールエーテル、卵黄油等が挙げられる。
炭化水素油としては、スクワラン、スクワレン、流動パラフィン、プリスタン、ポリイソブチレン等が挙げられる。
エステル油としては、アジピン酸ジイソブチル、アジピン酸2-ヘキシルデシル、アジピン酸ジ-2-ヘプチルウンデシル、モノイソステアリン酸N-アルキルグリコール、イソステアリン酸イソセチル、トリイソステアリン酸トリメチロールプロパン、2-エチルヘキサン酸セチル、ジ-2-エチルヘキサン酸エチレングリコール、ジ-2-エチルヘキサン酸ネオペンチルグリコール、トリ-2-エチルヘキサン酸トリメチロールプロパン、テトラ-2-エチルヘキサン酸ペンタエリスリトール、オクタン酸セチル、オクチルドデシルガムエステル、オレイン酸オレイル、オレイン酸オクチルドデシル、オレイン酸デシル、ジカプリン酸ネオペンチルグリコール、クエン酸トリエチル、コハク酸2-エチルヘキシル、酢酸アミル、酢酸エチル、酢酸ブチル、ステアリン酸イソセチル、ステアリン酸ブチル、セバシン酸ジイソプロピル、セバシン酸ジ-2-エチルヘキシル、乳酸セチル、乳酸ミリスチル、パルミチン酸イソプロピル、パルミチン酸2-エチルヘキシル、パルミチン酸2-ヘキシルデシル、パルミチン酸2-ヘプチルウンデシル、12-ヒドロキシステアリル酸コレステリル、ジペンタエリスリトール脂肪酸エステル、ミリスチン酸イソプロピル、ミリスチン酸2-オクチルドデシル、ミリスチン酸2-ヘキシルデシル、ミリスチン酸ミリスチル、ジメチルオクタン酸ヘキシルデシル、ラウリン酸エチル、ラウリン酸ヘキシル、N-ラウロイル-L-グルタミン酸-2-オクチルドデシルエステル、リンゴ酸ジイソステアリル等が挙げられる。
グリセライド油としては、アセトグリセライド、トリイソオクタン酸グリセライド、トリイソステアリン酸グリセライド、トリイソパルミチン酸グリセライド、トリ-2-エチルヘキサン酸グリセライド、モノステアリン酸グリセライド、ジ-2-ヘプチルウンデカン酸グリセライド、トリミリスチン酸グリセライド等が挙げられる。
シリコーン油としては、ジメチルポリシロキサン、メチルフェニルポリシロキサン、メチルハイドロジェンポリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン、テトラメチルテトラハイドロジェンシクロテトラシロキサン、アルキル変性シリコーン等が挙げられる。
高級アルコールとしては、オレイルアルコール、ラウリルアルコール、ステアリルアルコール、イソステアリルアルコール、2-オクチルドデカノール等が挙げられる。
高級脂肪酸としては、オレイン酸、パルミチン酸、ミリスチン酸、ステアリン酸、イソステアリン酸等が挙げられる。
有機溶媒としては、n-ヘキサン、シクロヘキサンなどの炭化水素、ベンゼン、トルエン、キシレン等の芳香族化合物、酢酸エチル、酢酸ブチル等の非芳香族系化合物、クロロホルム、ジクロロメタン、ジクロロエタン等の塩素系化合物、ジオキサン、テトラハイドロフラン等のエーテル系化合物、2-プロパノール、ベンジルアルコール、フェノキシエタノール、カービトール類、セロソルブ類、スピンドル油等が挙げられる。
香料には、天然香料(動物性香料、植物性香料)、合成香料、及び調合香料(天然香料と合成香料のブレンド)があり、現在の化粧品には、天然香料と合成香料をブレンドした調合香料がもっともよく使われている。香料として、例えば、ジャスミン、タジェット、ローズマリー、バニラ、ジンジャーオイル、ローズオイル、ジャスミンオイル、ラベンダーオイル、イランイランオイル、ペパーミントオイル、ゼラニウムオイル、レモンオイル、オレンジオイル、スターアニスオイル、グレープフルーツオイル、ユーカリオイル、サンダルウッドオイル、ブラックペッパーオイル、バジルオイル、イランイランオイル、パチュリオイル、クマリン、ムスクケトン、ヘリオトロピン、1-オクテン-3-オール、及びこれらのブレンド等が挙げられる。
前記複合粉体類としては、微粒子酸化チタン被覆マイカチタン、微粒子酸化亜鉛被覆マイカチタン、硫酸バリウム被覆マイカチタン、酸化チタン含有シリカ、酸化亜鉛含有シリカ等から選ばれる1種又は2種以上を用いることができる。
前記ポリウレタンゲル処理粉体を含む化粧料には、必要に応じて含有可能な成分を適宜用いることができる。
例えば、前記の揮発性成分、界面活性剤、油剤、粉体、水性成分、アルコール類、水溶性高分子、紫外線吸収剤、保湿剤、ゲル化剤及び増粘剤、褪色防止剤、酸化防止剤、消泡剤、美容成分(美白剤、細胞賦活剤、抗炎症剤、血行促進剤、皮膚収斂剤、抗脂漏剤等)、防腐剤、抗菌剤、香料、ビタミン類、アミノ酸類、核酸、ホルモン等、各種の効果を付与するために通常化粧品に用いられる他の成分を適宜用いることができる。
前記ポリウレタンゲル組成物を含む化粧料には、必要に応じて含有可能な成分を適宜用いることができる。
例えば、そのような成分として、前記の揮発性成分、界面活性剤、油剤、粉体、水性成分、アルコール類、水溶性高分子、紫外線吸収剤、保湿剤、ゲル化剤及び増粘剤、褪色防止剤、酸化防止剤、消泡剤、美容成分(美白剤、細胞賦活剤、抗炎症剤、血行促進剤、皮膚収斂剤、抗脂漏剤等)、防腐剤、抗菌剤、香料、ビタミン類、アミノ酸類、核酸、ホルモン等が例示される。
本発明のポリウレタンゲル組成物は、種々の剤型、例えば、液状、乳液状、クリーム状、固形状、ペースト状、ゲル状、粉末状、プレス状、多層状、ムース状、スプレー状、又はスティック状等の剤型の化粧料の製造に使用することができる。また、本発明のポリウレタンゲル組成物は、種々の適用部位を対象とした化粧料、例えば、メイクアップ化粧料、スキンケア化粧料、頭髪化粧料、制汗剤、又は紫外線防御用化粧料等の製造に使用することができる。
本発明のポリウレタンゲル組成物を含有する化粧料アイテムとして、化粧水、乳液、美容液、パック、オールインワンジェル、クリーム、ボディミルク、オイルクレンジング、クレンジングクリーム、日焼け止め等の基礎化粧料、スタイリングウォーター、ヘアワックス等の頭髪用化粧料、マスカラ、リップグロス、口紅、アイシャドウ、アイライナー、ファンデーション、フェイスカラー、コンシーラー、化粧下地等のメイクアップ化粧料等が例示される。
以下の製造実施例1~5はいずれも組成物2に関するものであるが、末端水酸基水素化ポリブタジエンを、末端にイソシアネート基を持つ水添ポリブタジエンに置き換えることによって、組成物1を用いた場合も同様にしてポリウレタンゲルを製造することができる。
具体的には以下のようになる。即ち、組成物2におけるポリウレタンは、(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物と(b)HO-R3-OH(式中R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールとの反応によって得られるポリウレタンである。これに対して、組成物1におけるポリウレタンは、組成物2の(c)末端に水酸基を持つ水添ポリブタジエンを、(a)末端にイソシアネート基を持つ水添ポリブタジエンに置き換えて、(a)水添ポリブタジエンと(b)HO-R3-OH(式中、R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールとの反応によって得られるポリウレタンである。この場合、(a)と(b)のモル比を(c)と(b)のモル比と同じにすることによって、同様のポリウレタンを製造することができる。
3Lの三口フラスコに末端水酸基水素化ポリブタジエン899部(分子量2200)と、2-エチルヘキサン酸セチル2450部、ヘキサメチレンジイソシアネート128部を仕込み、均一に混合した。
60℃に制御しながらジブチル錫ジラウレート0.9部を投入し、3時間攪拌後、エチレングリコールを24部投入した。
投入終了後、80℃で5時間攪拌後、エタノールを18部添加して反応を完結させた。
得られたポリウレタンゲル中のポリウレタンの重量平均分子量は、GPC測定(ポリスチレン換算)にて10000であった。また、得られたゲル30部を、流動パラフィン70部と、85℃にて加熱溶解、30℃に冷却したゲルの荷重値は、荷重測定機(FUDOH社製)による、2cmφ球状アダプター、2cm/min、10mm針入の条件の場合、2.50Nであった。
3Lの三口フラスコに末端水酸基水素化ポリブタジエン899部(分子量2200)と、2-エチルヘキサン酸セチル2450部、ヘキサメチレンジイソシアネート128部を仕込み、均一に混合した。
60℃に制御しながらジブチル錫ジラウレート0.9部を投入し、3時間攪拌後、エチレングリコールを24部投入した。
投入終了後、80℃で10時間攪拌後、エタノールを18部添加して反応を完結させた。
得られたポリウレタンゲル中のポリウレタンの重量平均分子量は、GPC測定(ポリスチレン換算)にて50000であった。また、得られたゲル30部を、流動パラフィン70部と、85℃にて加熱溶解、30℃に冷却したゲルの荷重値は、荷重測定機(FUDOH社製)による、2cmφ球状アダプター、2cm/min、10mm針入の条件の場合、5.00Nであった。
3Lの三口フラスコに末端水酸基水素化ポリブタジエン899部(分子量2200)と、2-エチルヘキサン酸セチル2450部、ヘキサメチレンジイソシアネート128部を仕込み、均一に混合した。
60℃に制御しながらジブチル錫ジラウレート0.9部を投入し、3時間攪拌後、2-エチルヘキサン酸セチルで希釈しながら、エチレングリコールを24部投入した。
投入終了後、80℃で15時間攪拌後、エタノールを18部添加して反応を完結させた。
得られたポリウレタンゲル中のポリウレタンの重量平均分子量は、GPC測定(ポリスチレン換算)にて100000であった。また、得られたゲル30部を、流動パラフィン70部と、85℃にて加熱溶解、30℃に冷却したゲルの荷重値は、荷重測定機(FUDOH社製)による、2cmφ球状アダプター、2cm/min、10mm針入の条件の場合、7.50Nであった。
3Lの三口フラスコに末端水酸基水素化ポリブタジエン899部(分子量2200)、エチレングリコール24部、ジブチル錫ジラウレート0.9部、2-エチルヘキサン酸セチル2450部を仕込み、均一に混合した。
60℃に制御しながらヘキサエチレンジイソシアネート128部を投入し、投入終了後80℃で10時間攪拌し、その後、エタノールを18部添加して反応を完結させた。
得られたポリウレタンゲル中のポリウレタンの重量平均分子量は、GPC測定(ポリスチレン換算)にて50000であった。また、得られたゲル30部を、流動パラフィン70部と、85℃にて加熱溶解、30℃に冷却したゲルの荷重値は、荷重測定機(FUDOH社製)による、2cmφ球状アダプター、2cm/min、10mm針入の条件の場合、3.00Nであった。
3Lの三口フラスコに末端水酸基水素化ポリブタジエン899部(分子量2200)、エチレングリコール24部、ジブチル錫ジラウレート0.9部、2-エチルヘキサン酸セチル2450部を仕込み、均一に混合した。
60℃に制御しながら、ヘキサエチレンジイソシアネート128部を投入し、投入終了後80℃で15時間攪拌し、その後、エタノールを18部添加して反応を完結させた。
得られたポリウレタンゲル中のポリウレタンの重量平均分子量は、GPC測定(ポリスチレン換算)にて100000であった。また、得られたゲル30部を、流動パラフィン70部と、85℃にて加熱溶解、30℃に冷却したゲルの荷重値は、荷重測定機(FUDOH社製)による、2cmφ球状アダプター、2cm/min、10mm針入の条件の場合、4.50Nであった。
架橋型シリコーンゲル(KSG-43 信越化学工業社製)100部を用いる。
デキストリン脂肪酸エステル(レオパールISK 千葉製粉社製)35部と、2-エチルヘキサン酸セチル65部を、90℃にて加熱、冷却し、多糖類ゲルを調製した。
結晶性ポリエチレンワックス(PERFORMALENE655 ニューフェーズテクノロジー社製)35部と、2-エチルヘキサン酸セチル65部を、90℃にて加熱、冷却し、ワックスオイルゲルを調製した。
[ゲルの評価]
前記製法により得られたポリウレタンゲルの中から、製造実施例2のポリウレタンゲルに対して、化粧品に汎用される各種油剤に対するゲル荷重値、並びにゲルの透明性に関して評価した。その結果を表1に示す。また、種々の評価方法は、以下となる。
製造実施例2のポリウレタンゲルと、表1に記載の各種油剤を85℃にて加熱溶解、30℃に冷却し、弾力性のあるゲルを調製した。ゲルの荷重値に関しては、荷重測定機(FUDOH社製)を用いて、2cmφ球状アダプター)、2cm/min、10mm針入の条件にて測定した。実施例1~4の結果、分子中の水酸基数が少ない油剤ほど、荷重値が高い傾向にあることを確認した。これは、ポリウレタンゲルの親水基会合性増粘機構における、親水基部分に、油剤中の水酸基が影響を与え、増粘低下をもたらしたと考えられる。
表1に記載の各種ゲルに対する透明性は、透過度測定機(島津製作所社製)を用いて、700nmにおける透過率を測定した。その結果、実施例1~6全てのゲルにおいて、90%以上と、良好な透明性(A)を示した。
製造実施例2のポリウレタンゲル、及び製造比較例2のデキストリン脂肪酸エステルゲルを用いて、自己復元力の評価を実施した。測定サンプルは、各々、純分が10.5質量%になる様に2-エチルヘキサン酸セチルで希釈し、85℃にて加熱後、ジャー容器に流し込み、30℃に冷却することで弾力性のあるゲルを調製した。調製したサンプルに対し、テクスチュアアナライザー(英栄精機社製)を用いて、2cmφ球状アダプターにて5gの荷重をかけた時点から、1mm/minの速度、5mm針入する条件にて、7回、同じ動作を繰り返すことで、荷重によりゲル構造が破壊されず、復元力があるか確認した。測定の模式図を図1に示す。その結果(図2)、製造比較例2のデキストリン脂肪酸エステルゲルは、繰り返しの荷重で、ゲル構造が破壊し、同じ曲線にならないのに対し、製造実施例2のポリウレタンゲルは、繰り返しの荷重でゲルが崩壊することなく、同じ曲線を辿ることから、ゲルの復元性が高いことが分かった。また、荷重値自体の値も、製造比較例2のデキストリン脂肪酸エステルゲルと比較して高いことから、弾力性に優れることが分かった。
[ゲルの評価]
末端水酸基水素化ポリブタジエン、ヘキサメチレンジイソシアネート、2-エチルヘキサン酸セチル及びエチレングリコールの各成分の混合比率を変更した以外は、製造実施例2と同様にして、表2に示す通り、製造実施例6~16のポリウレタンゲルを製造した。これらのポリウレタンゲルの荷重値、並びに透明性に関して評価した。その結果を表2に示す。なお、参考のために、製造実施例2のポリウレタンゲルのデータも表2に記載した。評価方法は以下に記載する。
(b)エチレングリコール:分子量(Mw)=62とし、当該分子量を1モルとして算出
(c)末端水酸基水素化ポリブタジエン:分子量(Mw)=2200とし、当該分子量を1モルとして算出
表2に記載の各製造実施例のポリウレタンゲル30部を、流動パラフィン70部と、85℃にて加熱溶解し、30℃に冷却したゲルの荷重値は、荷重測定機(FUDOH社製)を用いて、2cmφ球状アダプター、2cm/min、10mm針入の条件にて測定した。評価は以下の基準に基づき行った。
A:4.50N以上
B:2.50N以上4.50N未満
C:0.50N以上2.50N未満
D:0.50N未満
表2に記載のポリウレタンゲルに対する透明性は、透過度測定機(島津製作所社製)を用いて、700nmにおける透過率を測定した。評価は以下の基準に基づき行った。
A:90%以上
B:85%以上90%未満
C:80%以上85%未満
D:80%未満
(c):(b)のモル比((c)/(b)のモル比率)は、2:3~3:2(0.66~1.5)がより好ましい。
A(ポリウレタン)の含有量(質量%)は、1~35質量%で、B(2-エチルヘキサン酸セチル(油剤))の含有量(質量%)は65~99質量%を満たす場合がより好ましい。
表3に示す組成の油性ボディオイルを下記の製造方法により調製し、各試料を、「伸び広がりの良さ」、「ハリ感」、「ツヤ感」、「べたつきのなさ」、「化粧持続効果」について下記評価方法にて評価し、その結果も併せて表3に示した。
(1)成分1~16をデスパーにて均一に混合する。
(2)(1)に成分17を添加、脱泡、容器に充填し、油性型ボディオイルを得た。
実施例1~7、及び比較例1~5の油性型ボディオイルに対して、化粧品評価専門パネル20名に、「伸び広がりの良さ」、「ハリ感」、「ツヤ感」、「べたつきのなさ」、「化粧持続効果」の其々の項目について、各自が以下の評価基準に従って7段階評価し、更に全パネルの評点の平均点を用いて、以下の判定基準に従って判定した。
[評価基準]
(評価結果) :(評点)
非常に良好 : 6点
良好 : 5点
やや良好 : 4点
普通 : 3点
やや不良 : 2点
不良 : 1点
非常に不良 : 0点
[判定基準]
(評点の平均点) :(判定)
5.0以上 : A
3.5以上~5.0未満 : B
1.5以上~3.5未満 : C
1.5未満 : D
(成分) (質量%)
1.セチルアルコール 0.2
2.製造実施例1のポリウレタンゲル 0.2
3.リン脂質・フィトステロール混合物(15:85)(注8) 0.5
4.ポリオキシエチレン(40モル)硬化ヒマシ油 0.1
5.酢酸トコフェロール 0.5
6.ステアリン酸トリエタノールアミン 0.5
7.精製水 残量
8.エタノール 10.0
9.香料 0.1
(注8):日本精化株式会社製
(1)成分1~6を75℃に加熱し、均一に混合溶解する。
(2)成分7、8を75℃に加熱し、均一に混合溶解する。
(3)(1)に(2)を添加し、乳化する。
(4)(3)を冷却し、成分9を添加し、乳化型化粧水を得た。
(成分) (質量%)
1.ステアリン酸 0.5
2.モノステアリン酸ポリオキシエチレンソルビタン(20EO)1.0
3.テトラオレイン酸ポリオキシプロピレンソルビトール
(40EO) 1.0
4.ベヘニルアルコール 1.5
5.流動パラフィン 2.0
6.トリ2-エチルヘキサン酸グリセリル 5.0
7.製造実施例2のポリウレタンゲル 2.0
8.アクリル酸/メタクリル酸アルキルエステル共重合体 0.1
9.キサンタンガム 0.1
10.水酸化ナトリウム 0.05
11.1,3-ブチレングリコール 8.0
12.防腐剤 適量
13.香料 0.1
14.精製水 残量
(1)成分1~7を80℃にて均一に混合する。
(2)成分8~14を80℃にて均一に混合する。
(3)(1)に(2)を添加し、乳化する。
(4)(3)を攪拌しながら冷却し、乳液を得た。
(成分) (質量%)
1.ペンタオレイン酸デカグリセリル 2.5
2.ベヘニルアルコール 1.5
3.ワセリン 3.0
4.重質流動イソパラフィン 1.0
5.トリ2-エチルヘキサン酸グリセリル 1.0
6.製造実施例3のポリウレタンゲル 4.0
7.精製水 残量
8.グリセリン 7.0
9.アクリル酸/メタクリル酸アルキルエステル共重合体 0.2
10.水酸化ナトリウム 0.09
11.防腐剤 適量
12.香料 0.1
(1)成分1~6を80℃にて均一に混合する。
(2)成分7~12を80℃にて均一に混合する。
(3)(1)に(2)を添加し、乳化する。
(4)(3)を攪拌しながら冷却し、クリームを得た。
(成分) (質量%)
1.マイクロクリスタリンワックス 1.5
2.ミツロウ 1.5
3.セチルアルコール 3.0
4.製造実施例4のポリウレタンゲル 3.0
5.水素添加大豆リン脂質 1.0
6.スクワラン 35.0
7.ソルビタンセスキオレイン酸エステル 3.0
8.プロピレングリコール 10.0
9.防腐剤 適量
10.香料 0.1
11.精製水 残量
(1)成分1~7を75℃に加熱し、均一に混合溶解する。
(2)成分8、11を75℃に加熱し、均一に混合溶解する。
(3)(1)に(2)を添加し、乳化する。
(4)(3)を冷却し、成分9、10を添加し、W/O型クリームを得た。
(成分) (質量%)
1.テトラオレイン酸ポリオキシエチレンソルビット 8.0
2.ジイソステアリン酸ポリグリセリル 0.5
3.流動パラフィン 残量
4.トリ2-エチルヘキサン酸グリセリル 25.0
5.製造実施例5のポリウレタンゲル 1.0
6.防腐剤 適量
7.香料 0.1
(1)成分1~7を常温にて均一に混合し、オイルクレンジングを得た。
(成分) (質量%)
1.ステアリン酸 3.0
2.セタノール 2.0
3.テトラオレイン酸ポリオキシプロピレンソルビトール
(40EO) 1.0
4.モノステアリン酸ポリオキシエチレンソルビタン(20EO)1.0
5.トリ2-エチルヘキサン酸グリセリル 20.0
6.流動パラフィン 20.0
7.製造実施例1のポリウレタンゲル 2.0
8.アクリル酸/メタクリル酸アルキルエステル共重合体 0.1
9.1,3-ブチレングリコール 7.0
10.水酸化ナトリウム 0.05
11.精製水 残量
12.防腐剤 適量
13.香料 0.1
(1)成分1~7を80℃にて均一に混合する。
(2)成分8~13を80℃にて均一に混合する。
(3)(2)に(1)を添加し、乳化する。
(4)(3)を攪拌しながら冷却し、クレンジングクリームを得た。
(成分) (質量%)
1.エタノール 15.0
2.塩化ステアリルトリメチルアンモニウム 0.2
3.イソステアリン酸ポリオキシエチレン硬化ヒマシ油 0.2
4.製造実施例2のポリウレタンゲル 0.1
5.精製水 残量
6.ヒドロキシプロピルセルロース 0.01
7.高重合メチルポリシロキサンエマルション(注9) 2.0
8.防腐剤 適量
9.香料 0.1
(注9)BY11-007(東レ・ダウコーニング社製)
(1)成分1~9を常温にて均一に混合し、スタイリングウォーターを得た。
(成分) (質量%)
1.精製水 残量
2.プロピレングリコール 10.0
3.モノステアリン酸ポリエチレングリコール 3.0
4.ワセリン 10.0
5.パラフィンワックス 3.0
6.セトステアリルアルコール 3.0
7.ベヘニルアルコール 3.0
8.製造実施例3のポリウレタンゲル 2.0
9.エタノール 5.0
10.精製水 15.0
11.ビニルピロリドン 1.0
12.アクリル酸/メタクリル酸アルキルエステル共重合体 0.15
13.水酸化ナトリウム 0.05
14.防腐剤 適量
15.香料 0.1
(1)成分1~3を80℃にて均一に混合する。
(2)成分4~8を80℃にて均一に混合する。
(3)(1)に(2)を添加し、乳化する。
(4)(3)に成分9~15を添加後、攪拌しながら冷却し、ヘアワックスを得た。
(成分) (質量%)
1.ステアリン酸 2.0
2.ミツロウ 10.0
3.セトステアリルアルコール 1.0
4.モノオレイン酸ポリオキシエチレンソルビタン(20EO) 1.5
5.セスキオレイン酸ソルビタン 0.5
6.製造実施例4のポリウレタンゲル 3.0
7.黒酸化鉄 5.0
8.無水ケイ酸 3.0
9.精製水 残量
10.1,3-ブチレングリコール 10.0
11.トリエタノールアミン 1.5
12.アクリル酸アルキル共重合体エマルション(注10) 30.0
13.防腐剤 適量
14.香料 0.1
(注10)ヨドゾール32A707(45質量%固形分)(日本NSC社製)
(1)成分1~3を80℃にて均一に混合する。
(2)成分4~8をローラーにて処理する。
(3)成分9~14を80℃にて均一に混合する。
(4)(1)、(2)を混合後、(3)を添加し、乳化する。
(5)(4)を冷却し、O/W型マスカラを得た。
(成分) (質量%)
1.製造実施例5のポリウレタンゲル 2.0
2.リンゴ酸ジイソステアリル 10.0
3.乳酸ステアリル 10.0
4.水添ポリイソブテン 30.0
5.トリエチルヘキサノイン 残量
6.流動パラフィン 5.0
7.マイクロクリスタリンワックス 2.0
8.12-ヒドロキシステアリン酸 0.1
9.αオレフィン・ビニルピロリドン共重合体(注11) 0.5
10.無水ケイ酸(注12) 3.5
11.ベンガラ 0.1
12.赤色201号 0.3
13.黒酸化鉄 0.05
14.酸化チタン 0.2
15.大豆リン脂質 0.01
16.p-メトキシケイ皮酸-2-エチルヘキシル 3.0
17.防腐剤 適量
18.香料 0.1
(注11)ANTARON V-220(ISP社製)
(注12)AEROSIL 200 (日本アエロジル社製)
(1)成分1~9を100℃で溶解混合する。
(2)(1)に成分10~18を加え、均一に混合分散する。
(3)(2)をチューブに流し込み、冷却してペースト状リップグロスを得た。
(成分) (質量%)
1.ポリエチレンワックス 10.0
2.カルナウバワックス 5.0
3.パラフィンワックス 2.0
4.2-エチルへキサン酸セチル 残量
5.製造実施例1のポリウレタンゲル 2.0
6.流動パラフィン 10.0
7.イソノナン酸イソトリデシル 10.0
8.赤202号 0.5
9.黄色4号 2.0
10.酸化チタン 0.5
11.黒酸化鉄 0.1
12.α-トコフェロール 0.5
13.香料 0.1
(1)成分1~7を100℃で均一に溶解混合する。
(2)(1)に成分8~13を添加し均一に混合する。
(3)(2)を容器に流し込み、冷却してスティック状口紅を得た。
(成分) (質量%)
1.デキストリン脂肪酸エステル(注13) 2.0
2.製造実施例2のポリウレタンゲル 1.0
3.リンゴ酸ジイソステアリル 2.5
4.2-エチルヘキサン酸セチル 13.0
5.ラウリン酸デキストリン 2.0
6.ミリスチン酸デキストリン 5.0
7.ベヘニン酸デキストリン 5.0
8.流動パラフィン 残量
9.水添ポリイソブテン 1.5
10.無水ケイ酸 6.0
11.ナイロン末 5.0
12.シリコーン処理タルク(注14) 5.5
13.赤色202号 0.05
14.黄色4号アルミニウムレーキ 0.05
15.青色1号アルミニウムレーキ 0.05
16.雲母チタン 1.5
17.防腐剤 適量
18.香料 0.1
(注13)レオパールTT(千葉製粉社製)
(注14)ジメチルポリシロキサン 5質量%処理
(1)成分1~9を100℃で溶解混合する。
(2)(1)に成分10~18を加え、均一に混合分散する。
(3)(2)を容器に流し込み、冷却固化して油性アイカラーを得た。
(成分) (質量%)
1.ジメチルポリシロキサン処理タルク 30.0
2.ジメチルポリシロキサン処理マイカ 15.0
3.ジメチルポリシロキサン処理酸化チタン 15.0
4.ジメチルポリシロキサン処理セリサイト 残量
5.合成金雲母 5.0
6.黄酸化鉄 2.0
7.ベンガラ 0.5
8.黒酸化鉄 0.2
9.防腐剤 適量
10.製造実施例3のポリウレタンゲル 1.0
11.流動パラフィン 3.0
12.ジメチルポリシロキサン 1.0
13.2-エチルヘキサン酸グリセリル 2.0
14.香料 0.1
(1)成分1~9をヘンシェルミキサー(三井三池社製)75℃で均一に分散する。
(2)成分10~13を均一に混合溶解する。
(3)(1)をヘンシェルミキサーにて攪拌しながら、(2)及び14を添加し、均一分散する。
(4)(3)をパルベライザーにて粉砕する。
(5)(4)を金皿に充填し、圧縮成型し、固形粉末状のファンデーションを得た。
(成分) (質量%)
1.ジメチルポリシロキサン処理合成金マイカ 10.0
2.ジメチルポリシロキサン処理タルク 残量
3.酸化チタン被覆雲母 30.0
4.窒化ホウ素 5.0
5.ポリエチレンテレフタレート・アルミニウム・エポキシ積層末 5.0
6.群青 2.0
7.赤202号 0.5
8.ポリアクリル酸アルキル 1.0
9.防腐剤 適量
10.製造実施例4のポリウレタンゲル 1.0
11.流動パラフィン 3.0
12.ジメチルポリシロキサン 2.0
13.2-エチルヘキサン酸グリセリル 2.0
14.香料 0.1
(1)成分1~9をヘンシェルミキサー(三井三池社製)75℃で均一に分散する。
(2)成分10~13を均一に混合溶解する。
(3)(1)をヘンシェルミキサーにて攪拌しながら、(2)及び14を添加し、均一分散する。
(4)(3)をパルベライザーにて粉砕する。
(5)(4)を金皿に充填し、圧縮成型し、固形粉末状のアイシャドウを得た。
(成分) (質量%)
1.雲母 20.0
2.タルク 残量
3.酸化チタン被覆雲母 10.0
4.群青 0.5
5.赤226号 0.2
6.ポリアクリル酸アルキル 1.0
7.防腐剤 適量
8.製造実施例5のポリウレタンゲル 1.0
9.流動パラフィン 2.0
10.ジメチルポリシロキサン 1.0
11.2-エチルヘキサン酸グリセリル 1.0
12.香料 0.1
(1)成分1~7をヘンシェルミキサー(三井三池社製)75℃で均一に分散する。
(2)成分8~11を65℃に加熱し、均一に混合溶解する。
(3)(1)をヘンシェルミキサーにて攪拌しながら、(2)及び12を添加し、均一分散する。
(4)(3)をパルベライザーにて粉砕する。
(5)(4)を金皿に充填し、圧縮成型し、固形粉末状のフェイスカラーを得た。
(成分) (質量%)
1.パラフィンワックス 5.0
2.ポリエチレンワックス 5.0
3.キャンデリラロウ 2.0
4.製造実施例1のポリウレタンゲル 2.0
5.トリ-2-エチルヘキサン酸グリセリル 15.0
6.メチルフェニルポリシロキサン 5.0
7.酢酸液状ラノリン 10.0
8.パラメトキシケイ皮酸2-エチルヘキシル 5.0
9.酸化チタン 20.0
10.黄酸化鉄 2.0
11.ベンガラ 0.5
12.黒酸化鉄 0.2
13.マイカ 7.0
14.防腐剤 適量
(1)成分1~8を100℃にて混合溶解する。
(2)(1)に成分9~14を90℃にて均一に混合する。
(3)(2)を3本ローラーにて処理する。
(4)(3)を脱泡し、85℃にてカプセルに溶解充填後、4℃にて冷却して、スティック状コンシーラーを得た。
(成分) (質量%)
1.酸化亜鉛 2.0
2.シリコーン被覆微粒子酸化チタン 5.0
3.トリ(カプリル・カプリン酸)グリセリル 5.0
4.トリ2-エチルヘキサン酸グリセリル 3.0
5.パルミチン酸オクチル 3.0
6.パラメトキシケイ皮酸2-エチルヘキシル 10.0
7.デカメチルシクロペンタシロキサン 10.0
8.メチルポリシロキサン・セチルメチルポリシロキサン
・ポリ(オキシエチレン・オキシプロピレン)
メチルポリシロキサン共重合体(注15) 1.8
9.製造実施例2のポリウレタンゲル 1.0
10.防腐剤 適量
11.塩化ナトリウム 0.3
12.精製水 残量
13.ジプロピレングリコール 5.0
14.エタノール 5.0
15.香料 0.1
(注15)ABIL EM-90(EVONIC GOLDSCHMIDT GMBH社製)
(1)成分3、4を加温溶解した後、成分1、2を添加しローラーにて均一に分散する。
(2)成分5~10を70℃で溶解させた後、60℃で(1)を添加し均一に混合溶解する。
(3)成分11~13を混合溶解させた後、60℃で(2)へ添加し乳化する。
(4)(3)に成分14、15を添加し均一に混合し、W/O型日焼け止め料を得た。
(成分) (質量%)
1.ポリオキシエチレンメチルシロキサン・ポリオキプロピレンオレイル
メチルシロキサン・ジメチルシロキサン共重合体(注16) 2.0
2.PEG-3ジメチコン(注17) 1.0
3.シクロペンタシロキサン 20.0
4.シリコーン処理赤酸化鉄 1.0
5.シリコーン処理黄酸化鉄 1.5
6.シリコーン処理黒酸化鉄 0.5
7.シリコーン処理酸化チタン 10.0
8.シリコーン処理タルク 5.0
9.トリ2-エチルへキサン酸グリセリル 5.0
10.製造実施例3のポリウレタンゲル 1.0
11.セスキオレイン酸ソルビタン 0.5
12.精製水 残量
13.1,3-ブチレングリコール 15.0
14.塩化ナトリウム 0.5
15.防腐剤 適量
16.香料 0.1
(注17)KF-6015(信越化学工業社製)
(1)成分1~3を均一に混合する。
(2)成分4~11をローラーにて均一に分散する。
(3)(1)に(2)を添加し、均一混合する。
(4)(3)に成分12~16を添加、乳化し、W/O型ファンデーションを得た。
(成分) (質量%)
1.モノオレイン酸ポリオキシエチレンソルビタン(20EO) 0.5
2.セスキオレイン酸ソルビタン 0.5
3.1,3-ブチレングリコール 10.0
4.シリコーン処理酸化チタン 10.0
5.シリコーン処理ベンガラ 0.4
6.シリコーン処理黄酸化鉄 2.0
7.シリコーン処理黒酸化鉄 0.1
8.シリコーン処理タルク 5.0
9.カルボキシビニルポリマー 0.3
10.トリエタノールアミン 1.0
11.精製水 残量
12.エタノール 2.0
13.ステアリン酸 1.0
14.ベヘニルアルコール 0.5
15.流動パラフィン 5.0
16.製造実施例4のポリウレタンゲル 1.0
17.トリ2-エチルヘキサン酸グリセリル 1.0
18.パラメトキシケイ皮酸2-エチルへキシル 2.0
19.ワセリン 0.5
20.防腐剤 適量
21.香料 0.1
(1)成分1~8をローラーにて均一に分散する。
(2)成分9~12を均一に混合する。
(3)(2)に(1)を添加し、均一に混合する。
(4)成分13~20を80℃にて混合溶解する。
(5)(3)に(4)を80℃にて添加し、乳化する。
(6)(5)を冷却し、成分21を添加し、O/W型ファンデーションを得た。
(成分) (質量%)
1.タルク 15.0
2.マイカ 10.0
3.シリコーン処理酸化チタン 15.0
4.シリコーン処理ベンガラ 1.0
5.シリコーン処理黄酸化鉄 3.0
6.シリコーン処理黒酸化鉄 0.2
7.ポリエチレンワックス 7.0
8.マイクロクリスタリンワックス 6.0
9.トリ2-エチルへキサン酸グリセリル 残量
10.製造実施例5のポリウレタンゲル 3.0
11.ジメチルポリシロキサン 5.0
12.流動パラフィン 20.0
13.ポリオキシエチレンメチルシロキサン・ポリオキプロピレンオレイル
メチルシロキサン・ジメチルシロキサン共重合体(注16) 2.0
14.防腐剤 適量
15.香料 0.1
(注16)KF-6026(信越化学工業社製)
(1)成分7~14を90℃にて加熱溶解する。
(2)(1)に成分1~6を添加し、ローラーにて均一に分散する。
(3)(2)に成分15を添加し、80℃にて溶解後、金皿に充填し、油性固形ファンデーションを得た。
(成分) (質量%)
1.セトステアリルアルコール 2.0
2.パラメトキシケイ皮酸2-エチルヘキシル 5.0
3.製造実施例1のポリウレタンゲル 2.0
4.トリ2-エチルヘキサン酸グリセリル 3.0
5.精製水 残量
6.N-ステアロイル-N-メチルタウリンナトリウム 0.5
7.カルボキシビニルポリマー 0.1
8.アクリル酸/メタクリル酸アルキルエステル共重合体 0.1
9.水酸化ナトリウム 0.05
10.エタノール 10.0
11.1,3-ブチレングリコール 10.0
12.防腐剤 適量
13.香料 0.1
(1)成分1~4を80℃にて均一に溶解する。
(2)成分5~13を80℃にて均一に溶解する。
(3)(2)に(1)を添加し、乳化する。
(4)(3)に成分14を添加、冷却し、化粧下地を得た。
(成分) (質量%)
1.ステアリン酸 1.0
2.モノオレイン酸ポリオキシエチレンソルビタン(20EO) 0.5
3.セスキオレイン酸ソルビタン 0.5
4.ベヘニルアルコール 0.5
5.2-エチルヘキサン酸グリセリル 2.0
6.流動パラフィン 2.0
7.製造実施例2のポリウレタンゲル 2.0
8.エタノール 10.0
9.ジプロピレングリコール 10.0
10.トリエタノールアミン 1.0
11.精製水 残量
12.グリセリン 5.0
13.1,3-ブチレングリコール 5.0
14.アクリル酸/メタクリル酸アルキルエステル共重合体 0.2
15.防腐剤 適量
16.香料 0.1
(1)成分1~7を80℃にて均一に溶解する。
(2)成分8~16を80℃にて均一に溶解する。
(3)(2)に(1)を添加し、乳化する。
(4)(3)を攪拌冷却し、ボディミルクを得た。
(成分) (質量%)
1.1,3-ブチレングリコール 15.0
2.アクリル酸アルキル共重合体エマルション(注18) 2.5
3.L-アルギニン 0.5
4.精製水 残量
5.軽質流動イソパラフィン 3.0
6.製造実施例3のポリウレタンゲル 0.5
7.防腐剤 適量
8.香料 0.1
(注18)ヨドゾール32A707(45質量%固形分)(日本NSC社製)
(1)成分1~4を均一に混合する。
(2)(1)に成分5~8を60℃で添加し、乳化する。
(3)(2)を攪拌しながら冷却し、リムーバーを得た。
(成分) (質量%)
1.ロジン酸ペンタエリトリット 10.0
2.キャンデリラ樹脂 3.0
3.ミツロウ 2.0
4.セレシンワックス 2.0
5.パルミチン酸デキストリン 2.0
6.トリメチルシロキシケイ酸 3.0
7.ジメチルジステアリルアンモニウムヘクトライト 5.0
8.プロピオンカーボネート 1.0
9.軽質流動イソパラフィン 残量
10.製造実施例4のポリウレタンゲル 2.0
11.黒酸化鉄 5.0
12.シリカ 3.0
13.タルク 5.0
(1)成分1~5を110℃に加温する。
(2)(1)に成分6~10を添加混合する。
(3)(2)に成分11~13を添加混合する。
(4)(3)をローラーにて処理し、非水系マスカラを得た。
(成分) (質量%)
1.セレシンワックス 11.0
2.ポリイソブチレン 16.0
3.ポリエチレンワックス 8.0
4.軽質流動イソパラフィン 残量
5.製造実施例5のポリウレタンゲル 2.0
6.シリコーン処理黒酸化鉄 15.0
7.シリコーン処理タルク 5.0
8.防腐剤 適量
9.香料 0.1
(1)成分1~5を100℃に加温し、均一混合する。
(2)成分6~9を80℃に加温し、均一混合する。
(3)(1)に(2)を添加し、均一に混合する。
(4)(3)をローラーにて処理し、油性アイライナーを得た。
Claims (32)
- AとBとを含有するポリウレタンゲル組成物。
ここで、Aは(a)末端にイソシアネート基を持つ水添ポリブタジエンと(b)HO-R3-OH(式中、R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールとの反応によって得られるポリウレタンであるか、または、Aは(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物と(b)HO-R3-OH(式中R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールとの反応によって得られるポリウレタンであり、Bは油剤である。 - Aの(a)が(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物との反応によって得られるイソシアネート化合物である請求項1に記載の組成物。
- Aの(d)がOCN-R2-NCO(式中、R2はC2~C6アルキレン)で表されるジイソシアネート化合物である請求項1又は2に記載の組成物。
- Aのポリウレタンが油溶性のポリウレタンである、請求項1に記載の組成物。
- Aのポリウレタンの平均分子量(Mw)が、10000~100000である、請求項1に記載の組成物。
- Bの油剤が25℃で液状の油剤である、請求項1に記載の組成物。
- Bの油剤が、炭化水素油、水酸基の数が0又は1個であるエステル油、シリコーン油から選ばれる1種以上である、請求項1に記載の組成物。
- Aのポリウレタンの含有量が1~35質量%である、請求項1に記載の組成物。
- Bの油剤の含有量が65~99質量%である、請求項1に記載の組成物。
- 請求項1~12のいずれか1項に記載されたポリウレタンゲル組成物30部と流動パラフィン70部とを、85℃にて加熱溶解し、冷却し得られたゲルが、2cmφ球状アダプタを2cm/minで10mm針入させた時の荷重値が0.20-10.00Nである、請求項1~12のいずれか1項に記載の組成物。
- ゲル復元性を有する、請求項1~13のいずれか1項に記載の組成物。
- 700nmの波長の透過率が90%以上である、請求項1~14のいずれか1項に記載の組成物。
- 請求項1~15のいずれか1項に記載の組成物を含有する化粧料。
- AとBとを含有するポリウレタンゲル組成物(ここでAはポリウレタンであり、Bは油剤である。)の製造方法であって、Bの油剤中において、Aの(a)末端にイソシアネート基を持つ水添ポリブタジエンと(b)HO-R3-OH(式中R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)で表されるグリコールを加えて重付加反応を行うことを含む、ポリウレタンゲル組成物の製造方法。
- Aの(a)が(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物との反応によって得られるイソシアネート化合物である、請求項17に記載の製造方法。
- Aのポリウレタンが(c)末端に水酸基を持つ水添ポリブタジエンと(d)ジイソシアネート化合物と(b)HO-R3-OHで表されるグリコールとの反応によって得られるポリウレタン(式中R3はエーテル結合を有していてもよい直鎖若しくは分岐のC2~C6アルキレン基を表す)である、請求項17に記載の製造方法。
- Aの(d)がOCN-R2-NCOで表されるジイソシアネート化合物(式中、R2はC2~C6アルキレン)である請求項18又は19に記載の製造方法。
- Aのポリウレタンが油溶性のポリウレタンである、請求項17又は19に記載の製造方法。
- Aのポリウレタンの平均分子量(Mw)が、10000~100000である、請求項17又は19に記載の製造方法。
- Bの油剤が25℃で液状の油剤である、請求項17に記載の製造方法。
- Bの油剤が、炭化水素油、水酸基の数が0又は1個であるエステル油、シリコーン油から選ばれる1種以上である、請求項26に記載の製造方法。
- Aのポリウレタンの含有量が1~35質量%である、請求項17又は19に記載の製造方法。
- Bの油剤の含有量が65~99質量%である、請求項17に記載の製造方法。
- 請求項1~12のいずれか1項に記載されたポリウレタンゲル組成物30部と流動パラフィン70部とを、85℃にて加熱溶解し、冷却し得られたゲルが、2cmφ球状アダプタを2cm/minで10mm針入させた時のポリウレタンゲル組成物の荷重値が0.20-10.00Nである、請求項17~29のいずれか1項に記載の製造方法。
- ポリウレタンゲル組成物がゲル復元性を有する、請求項17~30のいずれか1項に記載の製造方法。
- ポリウレタンゲル組成物に対する700nmの波長の透過率が90%以上である、請求項17~31のいずれか1項に記載の製造方法。
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