WO2011093508A1 - Polyalkylene glycol derivative and cosmetic comprising same - Google Patents
Polyalkylene glycol derivative and cosmetic comprising same Download PDFInfo
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- WO2011093508A1 WO2011093508A1 PCT/JP2011/052028 JP2011052028W WO2011093508A1 WO 2011093508 A1 WO2011093508 A1 WO 2011093508A1 JP 2011052028 W JP2011052028 W JP 2011052028W WO 2011093508 A1 WO2011093508 A1 WO 2011093508A1
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- 0 C*OCC1OC(C)(*(C*)N)OC1C1OC(C)(*)OC1 Chemical compound C*OCC1OC(C)(*(C*)N)OC1C1OC(C)(*)OC1 0.000 description 1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
- C08G2650/26—Sugars or saccharides used as initiators
Definitions
- the present invention relates to a polyalkylene glycol derivative suitable for a nonionic surfactant and a cosmetic comprising the same.
- Surfactant has the effect of adsorbing to the interface, lowering the interface energy, and thermodynamically stabilizing the system.
- the structure has both hydrophilic and lipophilic groups in the molecule, and it is mainly used as an emulsifying solubilizer at the liquid-liquid interface, and it has various properties such as dispersion of particles and improved wettability at the solid-liquid interface. Demonstrate the characteristics.
- nonionic surfactants along with anionic surfactants such as soap, are indispensable to industry, and have a low critical micelle concentration and can be used at low concentrations. Widely used in the field.
- oils such as hydrocarbon oils such as liquid paraffin and squalane, fats and oils such as vegetable oils and triglycerides, ester oils having ester bonds, and silicone oils such as dimethylsiloxane are stably blended in the presence of water.
- hydrocarbon oils such as liquid paraffin and squalane
- fats and oils such as vegetable oils and triglycerides
- ester oils having ester bonds and silicone oils such as dimethylsiloxane
- silicone oils such as dimethylsiloxane
- Patent Documents 1 and 2 Focusing on conventionally used nonionic surface active lipophilic groups, many of them are long-chain alkyl alcohols derived from animal and vegetable fats and oils or synthetic alcohols based on them (for example, Patent Documents 1 and 2). Industrially, only a molecular weight of about several hundreds was obtained, and it was difficult to exhibit sufficient lipophilicity.
- a hydrophilic group is known to act as an adsorptive group to the solid surface at a solid-liquid interface in which a solid such as a metal oxide is dispersed in a liquid.
- a solid such as a metal oxide
- sorbitan fatty acid esters, polyglycerin fatty acid esters or ethers for example, Patent Documents 2 and 3
- Patent Documents 2 and 3 that are widely used industrially have a hydroxyl group derived from a polyhydric alcohol as a hydrophilic group. The molecular weight of the group was limited, and there was a problem in exhibiting sufficient effects.
- An object of the present invention is to provide a novel polyalkylene glycol derivative exhibiting excellent surface activity and a cosmetic having long-term blending stability by blending such a novel polyalkylene glycol derivative. That is.
- a polyoxyalkylene group capable of controlling the molecular weight as a lipophilic group of a polyalkylene glycol derivative.
- hydrophilic group attention was paid to xylitol in which four hydroxyl groups having excellent adsorptivity to the solid surface are adjacent. That is, a protecting group is introduced into xylitol, an oxyalkylene group having 2 to 4 carbon atoms is introduced, alkylation or acylation is performed as necessary, and then deprotection is performed to thereby remove four adjacent hydroxyl groups. It was found that the emulsion can be localized and the emulsification solubilization ability and dispersion ability are improved.
- EO is an oxyethylene group
- AO is an oxyalkylene group having 3 to 4 carbon atoms
- EO and AO are bonded in a block form.
- the plurality of AOs may be the same as or different from each other.
- a and b are the average addition moles of EO
- m is the average addition moles of AO
- a + b is 0 to 100
- m is 10 to 100
- the ratio of the mass of (AO) m to the total mass of (AO) m is 50 to 100 mass%.
- R 1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 4 carbon atoms.
- a cosmetic comprising the polyalkylene glycol derivative according to any one of (1) to (3).
- the polyalkylene glycol derivative of the present invention exhibits an excellent surface activity, and a cosmetic containing it is also very useful.
- polyalkylene glycol derivatives The polyalkylene glycol derivative according to the present invention is represented by the following general formula (1) and has a xylitol skeleton.
- EO is an oxyethylene group
- AO is an oxyalkylene group having 3 to 4 carbon atoms.
- examples of AO include an oxypropylene group having 3 carbon atoms and an oxybutylene group derived from 1,2-butylene oxide, an oxyisobutylene group, an oxyt-butylene group, and an oxytetramethylene group having 4 carbon atoms.
- the addition form of EO and AO is block-like, and is added to xylitol in the order of EO-AO-EO ((AO) m is added to the end to which (EO) a is added, and (EO) is added to the end (EO). ) b is added). If EO and AO are added in a random manner, the surface activity cannot be obtained, which is not preferable.
- xylitol and EO part act as a hydrophilic group as an emulsifying solubilizer and as an adsorption site as a dispersing agent.
- the AO part acts as a lipophilic group as an emulsifying solubilizer and as a dispersion site that brings about steric repulsion as a dispersing agent. That is, the polyalkylene glycol derivative represented by the formula (1) can be used as a nonionic surfactant.
- m is the average number of moles of AO added. When two or more kinds of AO are present, the total average number of moles added is 10 to 100.
- the AO site acts as a lipophilic group.
- m is more preferably 20 or more.
- m is more preferably 80 or less, more preferably 70 or less, and most preferably 50 or less.
- EO can be added as necessary to supplement the hydrophilicity of the xylitol skeleton.
- a + b is an average added mole number of EO of 0 to 100, preferably 50 or less, more preferably 30 or less.
- a + b is larger than 100, the compatibility with the oil agent cannot be sufficiently obtained, and a sufficient effect cannot be obtained when used as an emulsifying solubilizer, which is not preferable.
- the polyalkylene glycol derivative of the present invention has only a xylitol site as a hydrophilic group and becomes a lipophilic nonionic surfactant having an AO site as lipophilic.
- a a hydrophilic-lipophilic-hydrophilic triblock type nonionic surfactant having xylitol sites and EO sites on both sides of the AO site is obtained.
- b 0, the EO site functions to supplement the hydrophilicity of xylitol.
- the nonionic surfactant of the present invention can take various molecular forms by appropriately selecting a + b and m, and can control hydrophilicity and lipophilicity according to the purpose.
- a + b is 1 to 100, preferably 1 to 50, more preferably 1 to 30, still more preferably 1 to 20, and particularly preferably 1 to 10.
- the ratio of the mass of (AO) m to the total mass of (EO) a, (EO) b, and (AO) m is 50 to 100 mass%. If this is less than 50% by mass, the lipophilicity may not be sufficient when used as an emulsifying solubilizer, which is not preferable.
- the amount is preferably 80 to 100% by mass, and more preferably 90 to 100% by mass.
- R 1 is a hydrogen atom, an alkyl having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms.
- the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a mixed group thereof. It is a group.
- the acyl group include formyl group, acetyl group, propionyl group, butyryl group, and the like.
- a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable, and a hydrogen atom, a methyl group, and an ethyl group are particularly preferable.
- the xylitol site has four adjacent hydroxyl groups and acts as a hydrophilic group.
- the solid-liquid interface is essential as an adsorption site on the solid surface, and the liquid-liquid interface is essential as a hydrophilic group of the emulsification solubilizer.
- the polyalkylene glycol derivative represented by the general formula (1) can usually be produced by the following procedures (1) to (3).
- the xylitol diketalized product or diacetalized product of formula (2) may be purified by distillation or the like, if necessary.
- R 2 and R 3 are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 do not simultaneously become a hydrogen atom.
- the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group and an ethyl group are preferable.
- acetone and 2,2-dimethoxypropane can be exemplified as the ketalizing agent
- acetaldehyde can be exemplified as the acetalizing agent.
- the ketalization or acetalization catalyst examples include acid catalysts such as sulfuric acid and paratoluenesulfonic acid.
- the charge amount of the ketalizing agent or acetalizing agent is 200 to 400 mol% with respect to xylitol, and the charge amount of the acid catalyst is 5 ⁇ 10 ⁇ 6 to 15 ⁇ 10 ⁇ 3 mol% with respect to xylitol.
- the reaction temperature is generally 30 to 90 ° C.
- xylitol diacetalized product or diketalized product of formula (2) is used in the alkylene oxide addition reaction in the next step, there is no particular need to perform catalyst removal treatment, etc., but if necessary, neutralization treatment with alkali And acid adsorption treatment, filtration and the like.
- neutralizing agents such as potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium acetate, Kyowa Chemical Industry Co., Ltd. Kyoward 300, Kyoward 500, Kyoward 1000, Kyoward 2000, Adsorbents such as Tomix AD-500 manufactured by Tomita Pharmaceutical Co., Ltd., and other zeolites can be used.
- the reaction is usually performed at 40 to 180 ° C. in a pressure reaction kettle such as an autoclave.
- a pressure reaction kettle such as an autoclave.
- the alkali catalyst alkali metal or alkaline earth metal oxides, hydroxides, alcoholates and the like can be used.
- the amount of the catalyst used is not particularly limited, but is generally 0.01 to 5.0% by mass with respect to the mass after completion of the addition reaction.
- the compound of the formula (3) after the addition reaction of alkylene oxide can be reacted with an alkyl halide having 1 to 4 carbon atoms in the presence of an alkali to form an alkyl ether.
- alkyl halides include methyl chloride, ethyl chloride, propyl chloride, butyl chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide and the like.
- an alkali metal or alkaline earth metal oxide, hydroxide, alcoholate, or the like can be used as an alkali at this time.
- the amount of alkali halide charged is generally 100 to 400 mol% with respect to the number of hydroxyl groups to be reacted, the alkali amount is 100 to 500 mol% with respect to the number of hydroxyl groups to be reacted, and the reaction temperature is generally 60 to 180 ° C. It is.
- an acylating agent such as a carboxylic acid having 1 to 4 carbon atoms, a carboxylic acid halide, a carboxylic acid anhydride, It can also be esterified.
- carboxylic acids include acetic acid, propionic acid, butyric acid, etc.
- carboxylic acid halides include acetic acid chloride, propionic acid chloride, butyric acid chloride, and acid anhydrides include acetic anhydride, propionic anhydride, and the like.
- the amount of acylating agent charged is 100 to 400 mol% with respect to the number of hydroxyl groups to be reacted, the amount of alkali or acid catalyst is 0.01 to 500 mol% with respect to the number of hydroxyl groups to be reacted, and the reaction temperature is 60 to 180 ° C. It is common to do in.
- the deketalization or deacetalization reaction in the oxyalkylenated compound of the compound of formula (3) is performed in the presence of an acid.
- the acid include hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, acetic acid, citric acid, succinic acid, tartaric acid, paratoluenesulfonic acid, other solid acids, cation exchange resins, and acid clay.
- the amount of the acid used is 0.001 to 6.0% by mass with respect to the oxyalkylenated product of the compound of formula (3). Further, if necessary, the reaction can be carried out by adding water, and the amount used is 0.01 to 100% by mass.
- the reaction temperature is generally 60 to 150 ° C.
- neutralization treatment with an alkali, acid adsorbent treatment, filtration, or the like can be performed.
- neutralizers such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate, Kyowa Chemical Industry Co., Ltd. Kyoward 300, Kyoward 500, Kyoward 1000, Kyoward 2000, Adsorbents such as Tomix AD-500 manufactured by Tomita Pharmaceutical Co., Ltd., and other zeolites can be used.
- the polyalkylene glycol derivative represented by the general formula (1) protects the hydroxyl group of xylitol by diketalization or diacetalization in advance, and performs an oxyalkylenation reaction of the hydroxyl group in this state. After etherification / esterification, a series of steps of deprotection by deketalization or deacetalization reaction is performed. Thereby, a polyalkylene glycol derivative in which one hydroxyl group of xylitol is modified as shown in the formula (1) can be obtained.
- the polyalkylene glycol derivative of the present invention is particularly good as an emulsifying solubilizing agent and dispersing agent, but the application is not limited thereto. Applications can be used for emulsifiers, solubilizers, dispersants, antifoaming agents, lubricants, penetrants, cleaning agents, and the like.
- the blending amount of the polyalkylene glycol derivative in the cosmetic of the present invention is not particularly limited, but is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass.
- various components generally used in cosmetics, pharmaceuticals and the like can be blended as needed, as long as the effects of the present invention are not impaired.
- hydrocarbons, higher alcohols, higher fatty acids and their triglycerides, ester oils, animal and vegetable oils, silicones, vitamins, UV absorbers, water-soluble polymers, antioxidants, cationic surfactants, anionic interfaces examples include activators, amphoteric surfactants, nonionic surfactants, sequestering agents, ethanol, thickeners, preservatives, dyes, pigments, and fragrances.
- the product form of the cosmetic comprising the polyalkylene glycol derivative of the present invention is not particularly limited, and W / O emulsion cosmetic, O / W emulsion cosmetic, W / O / W emulsion cosmetic.
- Any of cosmetics composed of a bicontinuous phase of oil and water, oily cosmetics and the like may be used, but it can be suitably used as a W / O emulsified cosmetic.
- the polyalkylene glycol derivative of the present invention acts as a W / O type emulsifier.
- the polyalkylene glycol derivative is preferably contained in an amount of 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total mass of the cosmetic.
- the cosmetic preferably contains 5 to 95% by mass of an oil agent, more preferably 10 to 90% by mass.
- hydrocarbon oils higher alcohols, higher fatty acids, ester oils, triglycerides including fats and oils, and silicone oils in combination.
- Hydrocarbon oils include liquid paraffin, polybutene, hydrogenated polyisobutene, hydrogenated polydecene, squalane, squalene, pristane, light isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, liquid isoparaffin, tetradecene, isohexadecane, isododecane, ⁇ -olefin.
- Examples include oligomers, petrolatum, microcrystalline wax, paraffin, polyethylene, and ceresin.
- the higher alcohol may be linear, branched, saturated or unsaturated.
- Such higher alcohols include octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol, isocetyl alcohol, stearyl alcohol, oleyl alcohol, isostearyl alcohol, aralkyl.
- Alcohol, behenyl alcohol, jojoba alcohol and the like can be exemplified by higher alcohols having 8 or more carbon atoms. These can be used alone or in combination of two or more.
- the higher fatty acid may be any of linear, branched, saturated, unsaturated, and hydroxyl group-containing types.
- Such higher fatty acids include caprylic acid, capric acid, 2-ethylhexanoic acid, lauric acid, myristic acid, myristoleic acid, coconut oil fatty acid, beef tallow fatty acid, palm oil fatty acid, palmitic acid, palmitoleic acid, stearic acid
- higher fatty acids having 8 or more carbon atoms such as oleic acid, isostearic acid, ricinoleic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, arachidonic acid and erucic acid. These can be used alone or in combination of two or more.
- Ester oils include diethyl sebacate, cetyl 2-ethylhexanoate, isocetyl 2-ethylhexanoate, isopropyl palmitate, octyl palmitate, 2-ethylhexyl palmitate, isopropyl isostearate, 2-hexyldecyl isostearate, isostearic acid Isostearyl, trimethylolpropane triisostearate, octyldodecyl myristate, isopropyl myristate, isostearyl myristate, isocetyl myristate, hexyl laurate, ethyl oleate, decyl oleate, isostearyl pivalate, butyl stearate, stearin Octyl acid, stearyl stearate, isopropyl isostearate, isononyl isononanoate, 2-
- triglycerides containing fats and oils include caproic acid, caprylic acid, capric acid, 2-ethylhexanoic acid, lauric acid, myristic acid, myristoleic acid, coconut oil fatty acid, beef tallow fatty acid, palm oil fatty acid, palmitic acid, palmitoleic acid, stearin Triglycerides of higher fatty acids having 6 or more carbon atoms such as acid, oleic acid, isostearic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, arachidonic acid, erucic acid, glyceryl trioxystearate, tri (Myristin stearic acid) glyceride, trilanolin fatty acid glyceryl, olive oil, corn oil, peanut oil, rapeseed oil, sesame oil, soybean oil, palm oil, palm oil, palm kernel oil, castor oil, flaxseed oil, jojoba oil
- Silicone oils include linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetrahydrotetramethylcyclotetrasiloxane. Examples thereof include cyclic polysiloxanes such as polyoxyethylene polyalkylsiloxane. One or more of these can be used.
- oils hydrocarbon oils, ester oils, and silicone oils are particularly preferable.
- the polyalkylene glycol derivative of the present invention when used as a W / O type emulsified cosmetic, can stably disperse inorganic pigments.
- an emulsified cosmetic (particularly preferably a W / O type cosmetic) comprising the composition of the following component (a), component (b), component (c), component (d) and component (e): ) Is preferred.
- a Polyalkylene glycol derivative of formula (1)
- Inorganic pigment (c) Hydrocarbon oil liquid at 25 ° C.
- (d) Silicone oil (e) Water
- the component (a) is contained in an amount of 0.01 to 30% by mass (preferably 0.1 to 20% by mass), and the component (b) is contained in an amount of 0.1 to 50% by mass (preferably 1 to 50% by mass). %)contains. Further, the total of the component (c) and the component (d) is 10 to 95% by mass, and the component (e) is 5 to 80% by mass. Further, when the total amount of component (c) and component (d) is 100 parts by weight, the ratio of component (c) is 10 parts by mass or more (ratio of component (d) is 90 parts by mass or less), preferably The ratio of the component (c) is 90 parts by mass or less (the ratio of the component (d) is 10 parts by mass or more).
- the component is an inorganic pigment.
- inorganic reds such as titanium oxide, zinc oxide, anhydrous silicic acid, aluminum silicate, magnesium silicate, calcium silicate, talc, mica, sericite, kaolin, bentonite, red iron oxide (Bengara), iron titanate, etc.
- Pigments inorganic brown pigments such as ⁇ -iron oxide, inorganic yellow pigments such as yellow iron oxide and ocher, inorganic black pigments such as black iron oxide and carbon black, inorganic purple pigments such as mango violet and cobalt violet, Examples thereof include inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate, inorganic blue pigments such as ultramarine and bitumen, and pearl pigments such as titanium oxide-coated mica, bismuth oxychloride and oxybismuth oxide-coated titanium oxide. One or more of these can be used.
- Preferred are titanium oxide, zinc oxide, anhydrous silicic acid, aluminum silicate, magnesium silicate, calcium silicate, talc, mica, sericite, kaolin and bentonite, and more preferred are titanium oxide and zinc oxide.
- inorganic pigments are known surface treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, N-acylated lysine treatment, Surface treatment may be performed by acrylic acid treatment, metal soap treatment, amino acid treatment, lecithin treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, or the like.
- Component is hydrocarbon oil which is liquid at 25 ° C.
- the hydrocarbon oil has an action of improving the compatibility between the polyalkylene glycol derivative represented by the formula (1) and the silicone oil of the component (d), and brings about dispersion stability.
- the hydrocarbon oil which is liquid at 25 ° C. is not particularly limited, and liquid paraffin, polybutene, hydrogenated polyisobutene, hydrogenated polydecene, squalane, squalene, pristane, light isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, liquid isoparaffin, tetradecene, Examples thereof include isohexadecane, isododecane and ⁇ -olefin oligomer. One or more of these can be used.
- Component (d) is silicone oil, which is an essential component for improving smoothness when applied to skin and hair.
- linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetrahydrotetramethylcyclotetrasiloxane
- Examples thereof include cyclic polysiloxanes such as polyoxyethylene polyalkylsiloxane, and one or more of these can be used. Cyclic polysiloxane is preferable.
- the total amount of component (c) and component (d) is 10 to 95% by mass, particularly preferably 20 to 90% by mass, based on the total amount of the cosmetic. Further, when the total amount of the component (c) and the component (d) is 100 parts by weight, the amount of the component (c) is 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts. More than part by mass. By making this 10 parts by mass or more, the above effect becomes remarkable. Further, when the total amount of the component (c) and the component (d) is 100 parts by weight, the amount of the component (c) is preferably 90 parts by weight or less, more preferably 80 parts by weight or less, and the effect is remarkable. Become.
- the water of component (e) is not particularly limited as long as it is generally used as an aqueous phase of W / O emulsified cosmetics.
- purified water such as distilled water or ion exchange water, physiological saline, phosphoric acid A citrate buffer aqueous solution or the like can be preferably used.
- the amount of water is 5 to 80% by mass, more preferably 10% by mass or more, and further preferably 75% by mass or less.
- the preferable ranges of the parts by mass of the components (a) to (e) are as follows: It is. Component (a): 0.01 to 30 parts by mass (more preferably 0.1 to 20 parts by mass) Component (b): 0.1 to 50 parts by mass (more preferably 1 to 50 parts by mass) Total amount of component (c) and component (d): 10 to 95 parts by mass (more preferably 15 to 90 parts by mass) Component (e): 5 to 80 parts by mass (more preferably 10 to 80 parts by mass)
- This cosmetic is preferably used as a sunscreen cosmetic such as a sunscreen lotion as a product form.
- a sunscreen cosmetic such as a sunscreen lotion
- the form of the cosmetic of the present invention can take any form of liquid, semi-solid, or solid at room temperature, and other components can be contained within a range that does not impair the performance of the present invention.
- the product form of the cosmetic comprising the polyalkylene glycol derivative of the present invention is not particularly limited to the aforementioned form, but is preferably a skin external preparation.
- Skin external preparations include skin care cosmetics such as lotions, emulsions, creams and packs; makeup cosmetics such as foundations, lipsticks and eye shadows; sunscreen cosmetics (sunscreen agents); body cosmetics; aromatic cosmetics Skin cosmetics such as make-up removers and body shampoos; hair cosmetics such as hair liquids, hair tonics, hair conditioners, hair shampoos, rinses, hair restorers; ointments and the like.
- Synthesis Example 2 Polyoxyethylene (5 mol) Polyoxybutylene (40 mol) Xylitol (Compound 2)
- the ketalization reaction was changed as follows, and synthesis was performed to obtain polyoxyethylene (5 mol) polyoxybutylene (40 mol) xylitol (Compound 2).
- (1) Ketalization reaction 700 g of xylitol, 1050 g of acetone, and 10 mg of paratoluenesulfonic acid monohydrate were added to a 3 liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, a cooling tube and an oil-water separation tube. The reaction system was charged at 60 to 90 ° C.
- the present inventors prepared polyalkylene glycol derivatives having the compositions shown in Table 1 below in accordance with Synthesis Examples 1 and 2 above.
- Example 11 A W / O type emulsion was prepared using the polyalkylene glycol derivative of the present invention.
- the base comprising the following composition
- the oil phase and the water phase were each dissolved by heating at 70 ° C. to dissolve uniformly, and then the water phase was slowly added to the oil phase while stirring to the room temperature. Until cooled.
- Oil phase Liquid paraffin 25.0% by mass Lanolin 2.0% by mass Beeswax 2.0% by mass Hydrogenated polyisobutene 20.0% by mass Compound 1 5.0% by mass Perfume Appropriate amount Preservative Appropriate amount
- Aqueous phase Glycerin 5.0% by mass Water balance
- Example 12 An O / W type skin cream was prepared using the polyalkylene glycol derivative of the present invention. After heating and dissolving the oil phase and the aqueous phase at 70 ° C. in a base composed of the following composition uniformly, the oil phase is slowly added to the water phase while stirring and the mixture is allowed to reach room temperature. Cooled down. Oil phase: Liquid paraffin 10.0% by mass Vaseline 3.0% by mass Compound 4 5.0% by mass Perfume appropriate amount Preservative appropriate amount Aqueous phase: Glycerin 5.0% by mass PEG # 4000 5.0 mass% Water balance
- Example 13 A W / O type emulsion was prepared using the polyalkylene glycol derivative of the present invention. After heating and dissolving the oil phase and the water phase at 70 ° C. in a base comprising the following composition uniformly, the water phase is slowly added to the oil phase while stirring, until the temperature reaches room temperature. Cooled down.
- Oil phase 2-ethylhexyl palmitate 20.0% by mass Liquid paraffin 30.0% by mass Lanolin 1.0% by mass Beeswax 0.5 mass Compound 1 3.0 mass% Polyoxyethylene (20 mol) sorbitan monooleate 2.0% by mass Perfume Appropriate amount Preservative Appropriate amount
- Aqueous phase Glycerin 4.0% by mass 1,3-butanediol 1.0% by mass Water balance
- Example 14 A cosmetic (sunscreen lotion) of the present invention was prepared.
- the A phase was mixed at room temperature, the B phase and the C phase were dissolved at room temperature, respectively, and then the B phase and the C phase were added to the A phase while stirring to emulsify.
- the content of the components is described as mass%, but the parts by weight of each component when the total amount of the components (a) to (e) is 100 parts by weight are also described. The same applies to Comparative Example 18.
- Phase A Compound 1 (a) component 2.0 mass% (2.4 weight part) Titanium oxide (b) component 10.0% by mass (12.1 parts by weight) Zinc oxide (b) component 10.0% by mass (12.1 parts by weight) Decamethylcyclopentasiloxane (c) component 10.0% by mass (12.1 parts by weight) Squalane (d) component 3.0 mass% (3.6 parts by weight) Octyldodecyl myristate 5.0% by mass Polyoxyethylene (75 mol) monostearate 0.5% by mass Polyoxyethylene (20 mol) sorbitan monostearate 0.5% by mass Ethylhexyl methoxycinnamate 5.0% by mass Phase B: Butylene glycol 5.0% by mass Water (e) Component 47.5% by mass (57.7 parts by weight) Phase C: Ethanol 1.0% by mass Preservative appropriate amount Fragrance proper amount
- a sunscreen lotion having the following composition was prepared in the same manner as in Example 14.
- Phase A Compound 6 2.0 mass% (2.4 parts by weight) Titanium oxide (b) component 10.0% by mass (12.1 parts by weight) Zinc oxide (b) component 10.0% by mass (12.1 parts by weight) Decamethylcyclopentasiloxane (c) component 10.0% by mass (12.1 parts by weight) Squalane (d) component 3.0 mass% (3.6 parts by weight) Octyldodecyl myristate 5.0% by mass Polyoxyethylene (75 mol) monostearate 0.5% by mass Polyoxyethylene (20 mol) sorbitan monostearate 0.5% by mass Ethylhexyl methoxycinnamate 5.0% by mass Phase B: Butylene glycol 5.0% by mass Water (e) Component 47.5% by mass (57.7 parts by weight) Phase C: Ethanol 1.0 mass% (1.2 parts by weight) Preservative appropriate amount Fragrance proper amount
- Example 14 cosmetics (sunscreen lotions) of Examples 15 to 20 and Comparative Examples 19 to 23 were prepared. Table 6 shows. The emulsified state immediately after emulsification and after storage for 1 month at 40 ° C. was judged visually according to the following criteria. The results are also shown in Table 6. ⁇ : Stable emulsion state. X: Precipitate or phase separation is observed.
- the polyalkylene glycol derivative of the present invention exhibits an excellent surface activity, and a cosmetic containing it is also very useful.
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Abstract
Description
このように、液-液界面および固-液界面において効果的に作用する非イオン性界面活性剤は必要不可欠である。 Particularly in the cosmetics field, various oils such as hydrocarbon oils such as liquid paraffin and squalane, fats and oils such as vegetable oils and triglycerides, ester oils having ester bonds, and silicone oils such as dimethylsiloxane are stably blended in the presence of water. There is a need. Furthermore, in order to protect the skin from external factors such as ultraviolet rays, it is also necessary to ensure the dispersion stability of inorganic powders such as titanium oxide and zinc oxide.
Thus, a nonionic surfactant that works effectively at the liquid-liquid interface and the solid-liquid interface is indispensable.
(1)下記一般式(1)により示されるポリアルキレングリコール誘導体 That is, the present invention is as follows.
(1) A polyalkylene glycol derivative represented by the following general formula (1)
aおよびbはEOの平均付加モル数であり、mはAOの平均付加モル数であり、a+bは0~100であり、mは10~100であり、(EO)aと(EO)bと(AO)mの合計質量に対する(AO)mの質量の割合は50~100質量%である。
R1は、水素原子、炭素数1~4のアルキル基、または炭素数1~4のアシル基である。 In the formula, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, and EO and AO are bonded in a block form. The plurality of AOs may be the same as or different from each other.
a and b are the average addition moles of EO, m is the average addition moles of AO, a + b is 0 to 100, m is 10 to 100, (EO) a and (EO) b The ratio of the mass of (AO) m to the total mass of (AO) m is 50 to 100 mass%.
R 1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 4 carbon atoms.
(a)前記ポリアルキレングリコール誘導体
(b)無機顔料
(c)25℃で液状の炭化水素油
(d)シリコーン油
(e)水 (5) 0.01 to 30% by mass of the following component (a), 0.1 to 50% by mass of component (b), 5 to 80 of component (c), component (d), and component (e) The total amount of the component (c) and the component (d) is 10 to 95% by mass, and the total amount of the component (c) and the component (d) is 100 parts by mass. The cosmetic according to (4), wherein the amount of the component (c) is sometimes 10 parts by mass or more.
(A) Polyalkylene glycol derivative (b) Inorganic pigment (c) Hydrocarbon oil liquid at 25 ° C. (d) Silicone oil (e) Water
本発明に係るポリアルキレングリコール誘導体は、下記一般式(1)により示され、キシリトール骨格を有することを特徴とする。 [Polyalkylene glycol derivatives]
The polyalkylene glycol derivative according to the present invention is represented by the following general formula (1) and has a xylitol skeleton.
mはAOの平均付加モル数であり、AOが2種以上の場合は、合計平均付加モル数を示し、10~100である。本発明のポリアルキレングリコール誘導体において、AO部位は、親油基として作用するが、mが10より小さい場合は、親油基として十分な分子量ではなく、乳化可溶化剤として用いた場合、十分な効果を発揮しない場合があり、また、分散剤として用いたときは、十分な立体反発が得られず好ましくない。こうした観点からは、mは、20以上が更に好ましい。また、mが100を超えると、副反応生成物の影響のために十分な効果を発揮しない場合があり、好ましくない。こうした観点からは、mは80以下が更に好ましく、70以下がより好ましく、50以下が最も好ましい。 Here, in formula (1), xylitol and EO part act as a hydrophilic group as an emulsifying solubilizer and as an adsorption site as a dispersing agent. On the other hand, the AO part acts as a lipophilic group as an emulsifying solubilizer and as a dispersion site that brings about steric repulsion as a dispersing agent. That is, the polyalkylene glycol derivative represented by the formula (1) can be used as a nonionic surfactant.
m is the average number of moles of AO added. When two or more kinds of AO are present, the total average number of moles added is 10 to 100. In the polyalkylene glycol derivative of the present invention, the AO site acts as a lipophilic group. However, when m is less than 10, the molecular weight is not sufficient as a lipophilic group, and sufficient when used as an emulsifying solubilizer. The effect may not be exhibited, and when used as a dispersant, sufficient steric repulsion cannot be obtained, which is not preferable. From such a viewpoint, m is more preferably 20 or more. On the other hand, if m exceeds 100, a sufficient effect may not be exhibited due to the influence of side reaction products, which is not preferable. From such a viewpoint, m is more preferably 80 or less, more preferably 70 or less, and most preferably 50 or less.
親水性を補うためにEOが必要であれば、a+bは、1~100、好ましくは1~50、より好ましくは1~30、更に好ましくは1~20、特に好ましくは1~10である。 Thus, the nonionic surfactant of the present invention can take various molecular forms by appropriately selecting a + b and m, and can control hydrophilicity and lipophilicity according to the purpose. However, the case where a = b = 0, which acts as a lipophilic nonionic surfactant, is particularly preferred.
If EO is required to supplement hydrophilicity, a + b is 1 to 100, preferably 1 to 50, more preferably 1 to 30, still more preferably 1 to 20, and particularly preferably 1 to 10.
一般式(1)に示されるポリアルキレングリコール誘導体は、通常、以下の(1)~(3)の手順により製造することができる。
(1)キシリトールを酸触媒の存在下、ケタール化剤もしくはアセタール化剤と反応させ、下記一般式(2)に示すキシリトールジケタール化合物もしくはジアセタール化合物を得る。
式(2)のキシリトールジケタール化物もしくはジアセタール化物は、必要に応じて、蒸留等で精製しても構わない。 [Production method of polyalkylene glycol derivative]
The polyalkylene glycol derivative represented by the general formula (1) can usually be produced by the following procedures (1) to (3).
(1) Xylitol is reacted with a ketalizing agent or acetalizing agent in the presence of an acid catalyst to obtain a xylitol diketal compound or diacetal compound represented by the following general formula (2).
The xylitol diketalized product or diacetalized product of formula (2) may be purified by distillation or the like, if necessary.
(3)その後、酸の存在下で脱ケタール化もしくは脱アセタール化を行う。 (2) Subsequently, an addition reaction of an oxyethylene group and an oxyalkylene group having 3 to 4 carbon atoms is carried out under an alkali catalyst, and if necessary, an alkyl halide, an acyl halide, an acid anhydride, etc. under an alkali catalyst. The terminal hydroxyl group can be etherified or esterified by reacting.
(3) Thereafter, deketalization or deacetalization is performed in the presence of an acid.
本発明のポリアルキレングリコール誘導体は、乳化可溶化剤、分散剤として特に良好であるが、用途はそれらに限定されるものではない。用途としては例えば、乳化剤、可溶化剤、分散剤、消泡剤、潤滑剤、浸透剤、洗浄剤等に用いることできる。 As described above, the polyalkylene glycol derivative represented by the general formula (1) protects the hydroxyl group of xylitol by diketalization or diacetalization in advance, and performs an oxyalkylenation reaction of the hydroxyl group in this state. After etherification / esterification, a series of steps of deprotection by deketalization or deacetalization reaction is performed. Thereby, a polyalkylene glycol derivative in which one hydroxyl group of xylitol is modified as shown in the formula (1) can be obtained.
The polyalkylene glycol derivative of the present invention is particularly good as an emulsifying solubilizing agent and dispersing agent, but the application is not limited thereto. Applications can be used for emulsifiers, solubilizers, dispersants, antifoaming agents, lubricants, penetrants, cleaning agents, and the like.
本発明の化粧料中へのポリアルキレングリコール誘導体の配合量は特には限定されないが、好ましくは0.001~50質量%、より好ましくは0.01~30質量%配合される。 [Cosmetics]
The blending amount of the polyalkylene glycol derivative in the cosmetic of the present invention is not particularly limited, but is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass.
(a) 式(1)のポリアルキレングリコール誘導体
(b) 無機顔料
(c) 25℃で液状の炭化水素油
(d) シリコーン油
(e) 水 That is, in this embodiment, an emulsified cosmetic (particularly preferably a W / O type cosmetic) comprising the composition of the following component (a), component (b), component (c), component (d) and component (e): ) Is preferred.
(A) Polyalkylene glycol derivative of formula (1) (b) Inorganic pigment (c) Hydrocarbon oil liquid at 25 ° C. (d) Silicone oil (e) Water
成分(e)の水としては、一般にW/O乳化化粧料の水相として用いられるものであれば特に限定されず、例えば、蒸留水やイオン交換水等の精製水、生理食塩水、リン酸やクエン酸緩衝水溶液等を好ましく用いることができる。また、本組成物では水の量は5~80質量%であるが、10質量%以上であることが更に好ましく、75質量%以下であることが更に好ましい。 The total amount of component (c) and component (d) is 10 to 95% by mass, particularly preferably 20 to 90% by mass, based on the total amount of the cosmetic. Further, when the total amount of the component (c) and the component (d) is 100 parts by weight, the amount of the component (c) is 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts. More than part by mass. By making this 10 parts by mass or more, the above effect becomes remarkable. Further, when the total amount of the component (c) and the component (d) is 100 parts by weight, the amount of the component (c) is preferably 90 parts by weight or less, more preferably 80 parts by weight or less, and the effect is remarkable. Become.
The water of component (e) is not particularly limited as long as it is generally used as an aqueous phase of W / O emulsified cosmetics. For example, purified water such as distilled water or ion exchange water, physiological saline, phosphoric acid A citrate buffer aqueous solution or the like can be preferably used. In the present composition, the amount of water is 5 to 80% by mass, more preferably 10% by mass or more, and further preferably 75% by mass or less.
成分(a): 0.01~30質量部(さらに好ましくは0.1~20質量部)
成分(b): 0.1~50質量部(さらに好ましくは1~50質量部)
成分(c)と成分(d)の合計量:10~95質量部(さらに好ましくは15~90質量部)
成分(e): 5~80質量部(さらに好ましくは10~80質量部) In addition, when the five components (a) to (e) are used as the composition and the total mass is set to 100 parts by mass, the preferable ranges of the parts by mass of the components (a) to (e) are as follows: It is.
Component (a): 0.01 to 30 parts by mass (more preferably 0.1 to 20 parts by mass)
Component (b): 0.1 to 50 parts by mass (more preferably 1 to 50 parts by mass)
Total amount of component (c) and component (d): 10 to 95 parts by mass (more preferably 15 to 90 parts by mass)
Component (e): 5 to 80 parts by mass (more preferably 10 to 80 parts by mass)
さらに、本発明の化粧料の形態は常温において液状、半固体、固体の何れかの形態をとることができ、他の成分を本発明の性能を損なわない範囲で含有することも可能である。例えば、低級アルコール、天然油脂類、合成トリグリセライド、エステル油、ロウ類、油性基剤、陰イオン性界面活性剤、両性界面活性剤、非イオン性界面活性剤、陽イオン性界面活性剤、半極性界面活性剤、水溶性高分子、有機または無機塩類、pH調整剤、殺菌剤、キレート剤、抗酸化剤、紫外線吸収剤、ビタミン類、動植物由来の天然エキス、色素、顔料、香料などが挙げられる。
また、本発明のポリアルキレングリコール誘導体を配合してなる化粧料の製品形態は、前述の形態に特に限定されるものではないが、皮膚外用剤であることが好ましい。皮膚外用剤としては、化粧水、乳液、クリーム、パック等のスキンケア化粧料;ファンデーション、口紅、アイシャドー等のメークアップ化粧料;日焼け止め化粧料(サンスクリーン剤);ボディー化粧料;芳香化粧料;メーク落とし、ボディーシャンプー等の皮膚化粧料;ヘアリキッド、ヘアトニック、ヘアコンディショナー、ヘアシャンプー、リンス、育毛剤等の毛髪化粧料;軟膏等が例示できる。 This cosmetic is preferably used as a sunscreen cosmetic such as a sunscreen lotion as a product form.
Furthermore, the form of the cosmetic of the present invention can take any form of liquid, semi-solid, or solid at room temperature, and other components can be contained within a range that does not impair the performance of the present invention. For example, lower alcohols, natural fats and oils, synthetic triglycerides, ester oils, waxes, oily bases, anionic surfactants, amphoteric surfactants, nonionic surfactants, cationic surfactants, semipolar Surfactants, water-soluble polymers, organic or inorganic salts, pH adjusters, bactericides, chelating agents, antioxidants, ultraviolet absorbers, vitamins, natural extracts derived from animals and plants, pigments, pigments, fragrances, etc. .
Moreover, the product form of the cosmetic comprising the polyalkylene glycol derivative of the present invention is not particularly limited to the aforementioned form, but is preferably a skin external preparation. Skin external preparations include skin care cosmetics such as lotions, emulsions, creams and packs; makeup cosmetics such as foundations, lipsticks and eye shadows; sunscreen cosmetics (sunscreen agents); body cosmetics; aromatic cosmetics Skin cosmetics such as make-up removers and body shampoos; hair cosmetics such as hair liquids, hair tonics, hair conditioners, hair shampoos, rinses, hair restorers; ointments and the like.
本発明にかかるポリアルキレングリコール誘導体の合成例を示す。水酸基価は、JISK1557 6.4に準じて測定した。
合成例1:ポリオキシブチレン(40モル)キシリトール(化合物1)
(1)ケタール化反応
撹拌羽根、窒素吹き込み管、熱電対、冷却管及び油水分離管を取り付けた3リットルの四つ口フラスコに、キシリトール700g、2,2-ジメトキシプロパン1291g、パラトルエンスルホン酸一水和物27mgを仕込み、反応系内を60~90℃に保持し、2時間反応させた。反応終了後、副生したメタノール及び過剰分の2,2-ジメトキシプロパンを除去し、1014gのジイソプロピリデンキシリトール(化合物1a、R2=R3=メチル基)を得た。水酸基価は、240KOHmg/gであった。原料のキシリトールと化合物1aのIRチャートを比較したところ、化合物1aには3500cm-1付近の水酸基のピークが小さくなっており、代わりに2960cm-1、2870cm-1、1460cm-1、1380cm-1付近のピークが出現していることを確認した。 [Synthesis example]
The synthesis example of the polyalkylene glycol derivative concerning this invention is shown. The hydroxyl value was measured according to JISK1557 6.4.
Synthesis Example 1: Polyoxybutylene (40 mol) xylitol (Compound 1)
(1)
化合物1aを235g、水酸化カリウム15.5gをオートクレーブ中に仕込み、オートクレーブ中の空気を乾燥窒素で置換した後、撹拌しながら140℃で触媒を完全に溶解した。次に滴下装置により1,2-ブチレンオキシド2900gを滴下させ、2時間撹拌した。その後、オートクレーブ内から、反応物を取り出し、塩酸で中和して、pH6~7とし、含有する水分を除去するため、100℃、1時間、減圧処理を行い、最後に濾過をして塩を除去して、2850gのポリオキシブチレン(40モル)ジイソプロピリデンキシリトール(化合物1b)を得た。水酸基価は、18.1KOHmg/gであった。 (2) Oxybutylene reaction 235 g of compound 1a and 15.5 g of potassium hydroxide were charged into an autoclave, and the air in the autoclave was replaced with dry nitrogen, and then the catalyst was completely dissolved at 140 ° C. with stirring. Next, 2900 g of 1,2-butylene oxide was added dropwise by a dropping device and stirred for 2 hours. Thereafter, the reaction product is taken out from the autoclave, neutralized with hydrochloric acid to pH 6-7, and subjected to reduced pressure treatment at 100 ° C. for 1 hour to remove the contained water. Finally, the salt is filtered to remove the salt. Removal of 2850 g of polyoxybutylene (40 mol) diisopropylidene xylitol (compound 1b) was obtained. The hydroxyl value was 18.1 KOHmg / g.
撹拌羽根、窒素吹き込み管、熱電対、冷却管を取り付けた1リットルの四つ口フラスコに、化合物1bを700g、水70g、36%塩酸10gを仕込み、密閉状態で80℃、2時間脱ケタール化反応を行った後、窒素バブリングで水及びアセトンを系外に留去した。続いて10%水酸化カリウム水溶液でpH6~7に合わせ、含有する水分を除去するために、100℃、1時間、減圧処理した。さらに処理後生成した塩を除去するため濾過を行い、650gのポリオキシブチレン(40モル)キシリトール(化合物1)を得た。 (3) Deketalization reaction Into a 1 liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, and a cooling tube were charged 700 g of Compound 1b, 70 g of water, and 10 g of 36% hydrochloric acid, and 80 in a sealed state. After the deketalization reaction at 2 ° C. for 2 hours, water and acetone were distilled out of the system by nitrogen bubbling. Subsequently, the solution was adjusted to pH 6 to 7 with a 10% aqueous potassium hydroxide solution and subjected to reduced pressure treatment at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and 650 g of polyoxybutylene (40 mol) xylitol (Compound 1) was obtained.
分析機器 :SHODEX GPC SYSTEM-11(昭和電工社製)
標準物質 :ポリエチレングリコール
サンプルサイズ :10%×100×0.001mL
溶離液 :THF
流速 :1.0mL/min
カラム :SHODEX KF804L(昭和電工社製)
カラムサイズ :I.D.8mm×30cm×3
カラム温度 :40℃
検出器 :RI×8
また、化合物1bと化合物1のIR分析を比較すると、化合物1では3500cm-1付近の水酸基のピークが大きくなっていることから、目的物質が得られていることを確認した。 In addition, when GPC analysis was performed about the
Analytical instrument: SHODEX GPC SYSTEM-11 (manufactured by Showa Denko)
Standard substance: Polyethylene glycol Sample size: 10% x 100 x 0.001 mL
Eluent: THF
Flow rate: 1.0 mL / min
Column: SHODEX KF804L (manufactured by Showa Denko)
Column size: I.D. D. 8mm
Column temperature: 40 ° C
Detector: RI x 8
Further, when the IR analysis of Compound 1b and
合成例1の手順のうち、ケタール化反応を以下の通りに変更し、合成を行い、ポリオキシエチレン(5モル)ポリオキシブチレン(40モル)キシリトール(化合物2)を得た。
(1) ケタール化反応
撹拌羽根、窒素吹き込み管、熱電対、冷却管及び油水分離管を取り付けた3リットルの四つ口フラスコに、キシリトール700g、アセトン1050g、パラトルエンスルホン酸一水和物10mgを仕込み、反応系内を60~90℃に保持し、4時間反応させた。反応終了後、副生した水及び過剰分のアセトンを除去し、1002gのジイソプロピリデンキシリトール(化合物1a、R2=R3=メチル基)を得た。水酸基価は、235KOHmg/gであった。原料のキシリトールと化合物1aのIRチャートを比較したところ、化合物1aには3500cm-1付近の水酸基のピークが小さくなっており、代わりに2960cm-1、2870cm-1、1460cm-1、1380cm-1付近のピークが出現していることを確認した。 Synthesis Example 2: Polyoxyethylene (5 mol) Polyoxybutylene (40 mol) Xylitol (Compound 2)
In the procedure of Synthesis Example 1, the ketalization reaction was changed as follows, and synthesis was performed to obtain polyoxyethylene (5 mol) polyoxybutylene (40 mol) xylitol (Compound 2).
(1) Ketalization reaction 700 g of xylitol, 1050 g of acetone, and 10 mg of paratoluenesulfonic acid monohydrate were added to a 3 liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, a cooling tube and an oil-water separation tube. The reaction system was charged at 60 to 90 ° C. and reacted for 4 hours. After completion of the reaction, by-product water and excess acetone were removed to obtain 1002 g of diisopropylidenexylitol (compound 1a, R 2 = R 3 = methyl group). The hydroxyl value was 235 KOH mg / g. A comparison of xylitol and IR chart of a compound 1a of the raw material, the compound 1a is smaller peak of hydroxyl group in the vicinity of 3500 cm -1, 2960 cm -1 instead, 2870cm -1, 1460cm -1, 1380cm around -1 It was confirmed that the peak of.
化合物1aを235g、水酸化カリウム20gをオートクレーブ中に仕込み、オートクレーブ中の空気を乾燥窒素で置換した後、撹拌しながら140℃で触媒を完全に溶解した。次に滴下装置により、エチレンオキシド230gを滴下させ、2時間撹拌した。引き続き、1,2-ブチレンオキシド2900gを滴下させ、2時間撹拌した。その後、オートクレーブ内から、反応物を取り出し、塩酸で中和して、pH6~7とし、含有する水分を除去するため、100℃、1時間、減圧処理を行い、最後に濾過をして塩を除去して、3028gのポリオキシエチレン(5モル)ポリオキシブチレン(40モル)ジイソプロピリデンキシリトール(化合物2b)を得た。水酸基価は、17.0mgKOH/gであった。 (2) Oxyethylene and oxybutylene reaction 235 g of compound 1a and 20 g of potassium hydroxide were charged into an autoclave, and the air in the autoclave was replaced with dry nitrogen, and then the catalyst was completely dissolved at 140 ° C. with stirring. Next, 230 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 2900 g of 1,2-butylene oxide was added dropwise and stirred for 2 hours. Thereafter, the reaction product is taken out from the autoclave, neutralized with hydrochloric acid to pH 6-7, and subjected to reduced pressure treatment at 100 ° C. for 1 hour to remove the contained water. Finally, the salt is filtered to remove the salt. Removal gave 3028 g of polyoxyethylene (5 mol) polyoxybutylene (40 mol) diisopropylidene xylitol (compound 2b). The hydroxyl value was 17.0 mgKOH / g.
撹拌羽根、窒素吹き込み管、熱電対、冷却管を取り付けた1リットルの四つ口フラスコに、化合物2bを700g、水70g、36%塩酸10gを仕込み、密閉状態で80℃、2時間脱ケタール化反応を行った後、窒素バブリングで水及びアセトンを系外に留去した。続いて10%水酸化カリウム水溶液でpH6~7に合わせ、含有する水分を除去するために、100℃、1時間、減圧処理した。さらに処理後生成した塩を除去するため濾過を行い、670gのポリオキシエチレン(5モル)ポリオキシブチレン(40モル)キシリトール(化合物2)を得た。 (3) Ketalization reaction 700 g of compound 2b, 70 g of water, and 10 g of 36% hydrochloric acid were charged in a 1-liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, and a cooling tube, and sealed at 80 ° C. After performing the deketalization reaction for 2 hours, water and acetone were distilled out of the system by nitrogen bubbling. Subsequently, the solution was adjusted to pH 6 to 7 with a 10% aqueous potassium hydroxide solution and subjected to reduced pressure treatment at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt produced after the treatment, and 670 g of polyoxyethylene (5 mol) polyoxybutylene (40 mol) xylitol (compound 2) was obtained.
[調製方法]
酸化チタン1.0g、ポリアルキレングリコール誘導体など分散剤1.0gを量りとり、流動パラフィン(モレスコ製モレスコホワイトP-70)にて、全量40gとした(2.5%酸化チタン溶液)。これをディスパーにて撹拌(25℃、5000rpm×3min)した後、40℃にて1週間放置した。この分散液の上澄みを採取し、流動パラフィンにて100倍に希釈した溶液を試料溶液とした。 <Evaluation of dispersibility>
[Preparation method]
1.0 g of titanium oxide and 1.0 g of a dispersant such as a polyalkylene glycol derivative were weighed and made into a total amount of 40 g using liquid paraffin (Moleco White P-70 manufactured by Moresco) (2.5% titanium oxide solution). This was stirred with a disper (25 ° C., 5000 rpm × 3 min) and then allowed to stand at 40 ° C. for 1 week. The supernatant of this dispersion was collected, and a solution diluted 100 times with liquid paraffin was used as a sample solution.
得られた希釈溶液の300nmの吸光度を測定した。結果を表2および図1に示す。 [Transparency measurement]
The absorbance of the obtained diluted solution was measured at 300 nm. The results are shown in Table 2 and FIG.
[調製方法]
流動パラフィン 30.0 質量%
乳化剤 5.0 質量%
水 65.0 質量%
流動パラフィン(モレスコ製モレスコホワイトP-70)と乳化剤を、70℃にて均一に撹拌し、さらに同温度にて水をゆっくり添加して予備溶解した。これをホモミキサーにて撹拌して(5000rpm×5分間)、W/O型乳化剤組成物を得た。 <Evaluation of emulsion stability>
[Preparation method]
Liquid paraffin 30.0% by mass
Emulsifier 5.0% by mass
Water 65.0% by mass
Liquid paraffin (Molesco White P-70 manufactured by Moresco) and an emulsifier were uniformly stirred at 70 ° C., and water was slowly added at the same temperature to be preliminarily dissolved. This was stirred with a homomixer (5000 rpm × 5 minutes) to obtain a W / O type emulsifier composition.
作成した乳化剤組成物を乳化直後および40℃で1ヶ月間保管した後の乳化状態を下記の基準により、目視で判断した。結果を表4に示す。
○:安定なエマルジョン状態。
×:わずかに油浮きが見られる状態。
××:完全にクリーミングまたは分離している状態。 [Evaluation criteria]
The emulsified state of the prepared emulsifier composition was judged visually by the following criteria immediately after emulsification and after storage at 40 ° C. for 1 month. The results are shown in Table 4.
○: Stable emulsion state.
X: A state in which oil floating is slightly observed.
XX: completely creamed or separated.
本発明のポリアルキレングリコール誘導体を使用してW/O型乳液を調製した。以下の組成からなる基剤のうち油相および水相をそれぞれ70℃にて加温溶解して均一に溶解した後に、撹拌しながら油相に、水相を同温度にゆっくり添加して、室温まで冷却した。 (Example 11)
A W / O type emulsion was prepared using the polyalkylene glycol derivative of the present invention. Of the base comprising the following composition, the oil phase and the water phase were each dissolved by heating at 70 ° C. to dissolve uniformly, and then the water phase was slowly added to the oil phase while stirring to the room temperature. Until cooled.
流動パラフィン 25.0質量%
ラノリン 2.0質量%
ミツロウ 2.0質量%
水添ポリイソブテン 20.0質量%
化合物1 5.0質量%
香料 適量
防腐剤 適量
水相:
グリセリン 5.0質量%
水 残部 Oil phase:
Liquid paraffin 25.0% by mass
Lanolin 2.0% by mass
Beeswax 2.0% by mass
Hydrogenated polyisobutene 20.0% by mass
Perfume Appropriate amount Preservative Appropriate amount Aqueous phase:
Glycerin 5.0% by mass
Water balance
以下の組成からなるW/O型乳液を、実施例11と同様に調製した。
油相:
流動パラフィン 25.0質量%
ラノリン 2.0質量%
ミツロウ 2.0質量%
水添ポリイソブテン 20.0質量%
化合物6 5.0質量%
香料 適量
防腐剤 適量
水相:
グリセリン 5.0質量%
水 残部 (Comparative Example 15)
A W / O type emulsion having the following composition was prepared in the same manner as in Example 11.
Oil phase:
Liquid paraffin 25.0% by mass
Lanolin 2.0% by mass
Beeswax 2.0% by mass
Hydrogenated polyisobutene 20.0% by mass
Compound 6 5.0 mass%
Perfume Appropriate amount Preservative Appropriate amount Aqueous phase:
Glycerin 5.0% by mass
Water balance
本発明のポリアルキレングリコール誘導体を使用してO/W型スキンクリームを調製した。以下の組成からなる基剤のうち油相および水相をそれぞれ70℃にて加温溶解して均一に溶解した後に、撹拌しながら水相に、油相を同温度にゆっくり添加し、室温まで冷却した。
油相:
流動パラフィン 10.0質量%
ワセリン 3.0質量%
化合物4 5.0質量%
香料 適量
防腐剤 適量
水相:
グリセリン 5.0質量%
PEG#4000 5.0質量%
水 残部 (Example 12)
An O / W type skin cream was prepared using the polyalkylene glycol derivative of the present invention. After heating and dissolving the oil phase and the aqueous phase at 70 ° C. in a base composed of the following composition uniformly, the oil phase is slowly added to the water phase while stirring and the mixture is allowed to reach room temperature. Cooled down.
Oil phase:
Liquid paraffin 10.0% by mass
Vaseline 3.0% by mass
Compound 4 5.0% by mass
Perfume appropriate amount Preservative appropriate amount Aqueous phase:
Glycerin 5.0% by mass
PEG # 4000 5.0 mass%
Water balance
以下の組成からなるO/W型スキンクリームを、実施例12と同様に調製した。
油相:
流動パラフィン 10.0質量%
ワセリン 3.0質量%
化合物7 5.0質量%
香料 適量
防腐剤 適量
水相:
グリセリン 5.0質量%
PEG#4000 5.0質量%
水 残部 (Comparative Example 16)
An O / W type skin cream having the following composition was prepared in the same manner as in Example 12.
Oil phase:
Liquid paraffin 10.0% by mass
Vaseline 3.0% by mass
Compound 7 5.0 mass%
Perfume Appropriate amount Preservative Appropriate amount Aqueous phase:
Glycerin 5.0% by mass
PEG # 4000 5.0 mass%
Water balance
本発明のポリアルキレングリコール誘導体を使用してW/O型乳液を調製した。以下の組成からなる基剤のうち油相および水相をそれぞれ70℃にて加温溶解して均一に溶解した後に、撹拌しながら油相に、水相を同温度にゆっくり添加し、室温まで冷却した。
油相:
パルミチン酸2-エチルヘキシル 20.0質量%
流動パラフィン 30.0質量%
ラノリン 1.0質量%
ミツロウ 0.5質量
化合物1 3.0質量%
ポリオキシエチレン(20モル)ソルビタンモノオレート
2.0質量%
香料 適量
防腐剤 適量
水相:
グリセリン 4.0質量%
1,3-ブタンジオール 1.0質量%
水 残部 (Example 13)
A W / O type emulsion was prepared using the polyalkylene glycol derivative of the present invention. After heating and dissolving the oil phase and the water phase at 70 ° C. in a base comprising the following composition uniformly, the water phase is slowly added to the oil phase while stirring, until the temperature reaches room temperature. Cooled down.
Oil phase:
2-ethylhexyl palmitate 20.0% by mass
Liquid paraffin 30.0% by mass
Lanolin 1.0% by mass
Beeswax 0.5
Polyoxyethylene (20 mol) sorbitan monooleate 2.0% by mass
Perfume Appropriate amount Preservative Appropriate amount Aqueous phase:
Glycerin 4.0% by mass
1,3-butanediol 1.0% by mass
Water balance
以下の組成からなるW/O型乳液を、実施例13と同様に調製した。
油相:
パルミチン酸2-エチルヘキシル 20.0質量%
流動パラフィン 30.0質量%
ラノリン 1.0質量%
ミツロウ 0.5質量
化合物6 3.0質量%
ポリオキシエチレン(20モル)ソルビタンモノオレート
2.0質量%
香料 適量
防腐剤 適量
水相:
グリセリン 4.0質量%
1,3-ブタンジオール 1.0質量%
水 残部 (Comparative Example 17)
A W / O type emulsion having the following composition was prepared in the same manner as in Example 13.
Oil phase:
2-ethylhexyl palmitate 20.0% by mass
Liquid paraffin 30.0% by mass
Lanolin 1.0% by mass
Beeswax 0.5 mass Compound 6 3.0 mass%
Polyoxyethylene (20 mol) sorbitan monooleate 2.0% by mass
Perfume Appropriate amount Preservative Appropriate amount Aqueous phase:
Glycerin 4.0% by mass
1,3-butanediol 1.0% by mass
Water balance
○:安定なエマルジョン状態。
×:わずかに油浮きが見られる状態。
××:完全にクリーミングまたは分離している状態。 For Examples 11, 12, 13 and Comparative Examples 15, 16, and 17, the emulsified state immediately after emulsification and after storage for 1 month at 40 ° C. was judged visually according to the following criteria. The results are shown in Table 5.
○: Stable emulsion state.
X: A state in which oil floating is slightly observed.
XX: completely creamed or separated.
本発明の化粧料(サンスクリーンローション)を調製した。以下の組成において、A相を室温にて混合、B相およびC相も室温にてそれぞれ溶解させた後、撹拌しながらA相に、B相とC相を加え乳化した。
以下、成分の含有量は質量%として記載するが、(a)~(e)成分の合計量を100重量部とした場合の各成分の重量部を併記する。比較例18にも同様に併記する。
A相:
化合物1 (a)成分 2.0質量%(2.4重量部)
酸化チタン (b)成分 10.0質量%(12.1重量部)
酸化亜鉛 (b)成分 10.0質量%(12.1重量部)
デカメチルシクロペンタシロキサン (c)成分
10.0質量%(12.1重量部)
スクワラン (d)成分 3.0質量%(3.6重量部)
ミリスチン酸オクチルドデシル 5.0質量%
ポリオキシエチレン(75モル)モノステアレート
0.5質量%
ポリオキシエチレン(20モル)ソルビタンモノステアレート
0.5質量%
メトキシケイ皮酸エチルヘキシル 5.0質量%
B相:
ブチレングリコール 5.0質量%
水 (e)成分 47.5質量%(57.7重量部)
C相:
エタノール 1.0質量%
防腐剤 適量
香料 適量 (Example 14)
A cosmetic (sunscreen lotion) of the present invention was prepared. In the following composition, the A phase was mixed at room temperature, the B phase and the C phase were dissolved at room temperature, respectively, and then the B phase and the C phase were added to the A phase while stirring to emulsify.
Hereinafter, the content of the components is described as mass%, but the parts by weight of each component when the total amount of the components (a) to (e) is 100 parts by weight are also described. The same applies to Comparative Example 18.
Phase A:
Compound 1 (a) component 2.0 mass% (2.4 weight part)
Titanium oxide (b) component 10.0% by mass (12.1 parts by weight)
Zinc oxide (b) component 10.0% by mass (12.1 parts by weight)
Decamethylcyclopentasiloxane (c) component 10.0% by mass (12.1 parts by weight)
Squalane (d) component 3.0 mass% (3.6 parts by weight)
Octyldodecyl myristate 5.0% by mass
Polyoxyethylene (75 mol) monostearate
0.5% by mass
Polyoxyethylene (20 mol) sorbitan monostearate 0.5% by mass
Ethylhexyl methoxycinnamate 5.0% by mass
Phase B:
Butylene glycol 5.0% by mass
Water (e) Component 47.5% by mass (57.7 parts by weight)
Phase C:
Ethanol 1.0% by mass
Preservative appropriate amount Fragrance proper amount
以下の組成からなるサンスクリーンローションを、実施例14と同様に調製した。
A相:
化合物6 2.0質量%(2.4重量部)
酸化チタン (b)成分 10.0質量%(12.1重量部)
酸化亜鉛 (b)成分 10.0質量%(12.1重量部)
デカメチルシクロペンタシロキサン(c)成分
10.0質量%(12.1重量部)
スクワラン (d)成分 3.0質量%(3.6重量部)
ミリスチン酸オクチルドデシル 5.0質量%
ポリオキシエチレン(75モル)モノステアレート
0.5質量%
ポリオキシエチレン(20モル)ソルビタンモノステアレート
0.5質量%
メトキシケイ皮酸エチルヘキシル 5.0質量%
B相:
ブチレングリコール 5.0質量%
水 (e)成分 47.5質量%(57.7重量部)
C相:
エタノール 1.0質量%(1.2重量部)
防腐剤 適量
香料 適量 (Comparative Example 18)
A sunscreen lotion having the following composition was prepared in the same manner as in Example 14.
Phase A:
Compound 6 2.0 mass% (2.4 parts by weight)
Titanium oxide (b) component 10.0% by mass (12.1 parts by weight)
Zinc oxide (b) component 10.0% by mass (12.1 parts by weight)
Decamethylcyclopentasiloxane (c) component 10.0% by mass (12.1 parts by weight)
Squalane (d) component 3.0 mass% (3.6 parts by weight)
Octyldodecyl myristate 5.0% by mass
Polyoxyethylene (75 mol) monostearate 0.5% by mass
Polyoxyethylene (20 mol) sorbitan monostearate 0.5% by mass
Ethylhexyl methoxycinnamate 5.0% by mass
Phase B:
Butylene glycol 5.0% by mass
Water (e) Component 47.5% by mass (57.7 parts by weight)
Phase C:
Ethanol 1.0 mass% (1.2 parts by weight)
Preservative appropriate amount Fragrance proper amount
○:安定なエマルジョン状態。
×:沈殿物または、相分離が認められる。 Furthermore, according to Example 14, cosmetics (sunscreen lotions) of Examples 15 to 20 and Comparative Examples 19 to 23 were prepared. Table 6 shows. The emulsified state immediately after emulsification and after storage for 1 month at 40 ° C. was judged visually according to the following criteria. The results are also shown in Table 6.
○: Stable emulsion state.
X: Precipitate or phase separation is observed.
本出願は、2010年2月1日出願の日本特許出願(特願2010-019955)、及び2010年2月1日出願の日本特許出願(特願2010-020008)に基づくものであり、その内容はここに参照として取り込まれる。
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on February 1, 2010 (Japanese Patent Application No. 2010-019955) and a Japanese patent application filed on February 1, 2010 (Japanese Patent Application No. 2010-020008). Is incorporated herein by reference.
Claims (5)
- 下記一般式(1)により示されるポリアルキレングリコール誘導体
aおよびbはEOの平均付加モル数であり、mはAOの平均付加モル数であり、a+bは0~100であり、mは10~100であり、(EO)aと(EO)bと(AO)mの合計質量に対する(AO)mの質量の割合は50~100質量%である。
R1は、水素原子、炭素数1~4のアルキル基、または炭素数1~4のアシル基である。 Polyalkylene glycol derivatives represented by the following general formula (1)
a and b are the average addition moles of EO, m is the average addition moles of AO, a + b is 0 to 100, m is 10 to 100, (EO) a and (EO) b The ratio of the mass of (AO) m to the total mass of (AO) m is 50 to 100 mass%.
R 1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 4 carbon atoms. - AOが、1,2-ブチレンオキシド由来のオキシブチレン基であることを特徴とする、請求項1記載のポリアルキレングリコール誘導体。 The polyalkylene glycol derivative according to claim 1, wherein AO is an oxybutylene group derived from 1,2-butylene oxide.
- 式(1)で示されるポリアルキレングリコール誘導体において、b=0であり、(EO)aと(AO)mの合計質量に対する (AO)mの質量の割合が80~100質量%であることを特徴とする、請求項1または2記載のポリアルキレングリコール誘導体。 In the polyalkylene glycol derivative represented by the formula (1), b = 0, and the ratio of the mass of (AO) m to the total mass of (EO) a and (AO) m is 80 to 100% by mass. The polyalkylene glycol derivative according to claim 1 or 2, characterized in that
- 請求項1~3のいずれか一つの請求項に記載のポリアルキレングリコール誘導体を含有する化粧料。 Cosmetics containing the polyalkylene glycol derivative according to any one of claims 1 to 3.
- 下記の成分(a)を0.01~30質量%、成分(b)を0.1~50質量%、成分(c)、成分(d)、および成分(e)を5~80質量%含有しており、前記成分(c)と前記成分(d)の合計量が10~95質量%であり、前記成分(c)と前記成分(d)の合計量を100質量部としたときに前記成分(c)の量が10質量部以上であることを特徴とする、請求項4記載の化粧料。
(a)前記ポリアルキレングリコール誘導体
(b)無機顔料
(c)25℃で液状の炭化水素油
(d)シリコーン油
(e)水
Contains 0.01 to 30% by mass of the following component (a), 0.1 to 50% by mass of component (b), 5 to 80% by mass of component (c), component (d), and component (e) The total amount of the component (c) and the component (d) is 10 to 95% by mass, and the total amount of the component (c) and the component (d) is 100 parts by mass. 5. The cosmetic according to claim 4, wherein the amount of the component (c) is 10 parts by mass or more.
(A) Polyalkylene glycol derivative (b) Inorganic pigment (c) Hydrocarbon oil liquid at 25 ° C. (d) Silicone oil (e) Water
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180008024.6A CN102741322B (en) | 2010-02-01 | 2011-02-01 | Polyalkylene glycol derivative and cosmetic comprising same |
KR1020127020309A KR101772720B1 (en) | 2010-02-01 | 2011-02-01 | Polyalkylene glycol derivative and cosmetic comprising same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP2010020008A JP5585863B2 (en) | 2010-02-01 | 2010-02-01 | Polyalkylene glycol derivatives |
JP2010-020008 | 2010-02-01 | ||
JP2010019955 | 2010-02-01 | ||
JP2010-019955 | 2010-02-01 |
Publications (1)
Publication Number | Publication Date |
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WO2011093508A1 true WO2011093508A1 (en) | 2011-08-04 |
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Family Applications (1)
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PCT/JP2011/052028 WO2011093508A1 (en) | 2010-02-01 | 2011-02-01 | Polyalkylene glycol derivative and cosmetic comprising same |
Country Status (3)
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KR (1) | KR101772720B1 (en) |
CN (1) | CN102741322B (en) |
WO (1) | WO2011093508A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011246403A (en) * | 2010-05-27 | 2011-12-08 | Nof Corp | Water-in-oil type emulsified composition |
KR20140148403A (en) * | 2012-03-30 | 2014-12-31 | 니치유 가부시키가이샤 | Multi-arm polyethylene glycol derivative, intermediate of same, and production method of same |
JP2018104399A (en) * | 2016-12-28 | 2018-07-05 | 花王株式会社 | Oil-in-water emulsion composition |
JP2019059798A (en) * | 2017-09-22 | 2019-04-18 | 株式会社大阪ソーダ | Polyether polymer and composition containing the same, and molding |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62127378A (en) * | 1985-11-28 | 1987-06-09 | New Japan Chem Co Ltd | Solidified alcohol composition |
JPH0420596A (en) * | 1990-05-15 | 1992-01-24 | Asahi Glass Co Ltd | Tetrafluoroethane composition for refrigerator |
US5288884A (en) * | 1992-10-22 | 1994-02-22 | Arco Chemical Technology, L.P. | Process for producing a reduced calorie fat mimetic composition |
JPH09328540A (en) * | 1996-06-12 | 1997-12-22 | Nof Corp | Alkenylated polyoxyalkylene compound |
WO2008105514A1 (en) * | 2007-02-28 | 2008-09-04 | Nof Corporation | Multibranched polyoxyalkylene derivative |
WO2010114074A1 (en) * | 2009-03-31 | 2010-10-07 | 日油株式会社 | Hyperbranched polyoxyalkylene compound and method for producing same |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4325463B2 (en) * | 2004-03-31 | 2009-09-02 | 日油株式会社 | Cleansing cosmetics |
KR101407750B1 (en) * | 2006-05-23 | 2014-06-16 | 니치유 가부시키가이샤 | External preparation for skin |
-
2011
- 2011-02-01 WO PCT/JP2011/052028 patent/WO2011093508A1/en active Application Filing
- 2011-02-01 CN CN201180008024.6A patent/CN102741322B/en not_active Expired - Fee Related
- 2011-02-01 KR KR1020127020309A patent/KR101772720B1/en active IP Right Grant
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62127378A (en) * | 1985-11-28 | 1987-06-09 | New Japan Chem Co Ltd | Solidified alcohol composition |
JPH0420596A (en) * | 1990-05-15 | 1992-01-24 | Asahi Glass Co Ltd | Tetrafluoroethane composition for refrigerator |
US5288884A (en) * | 1992-10-22 | 1994-02-22 | Arco Chemical Technology, L.P. | Process for producing a reduced calorie fat mimetic composition |
JPH09328540A (en) * | 1996-06-12 | 1997-12-22 | Nof Corp | Alkenylated polyoxyalkylene compound |
WO2008105514A1 (en) * | 2007-02-28 | 2008-09-04 | Nof Corporation | Multibranched polyoxyalkylene derivative |
WO2010114074A1 (en) * | 2009-03-31 | 2010-10-07 | 日油株式会社 | Hyperbranched polyoxyalkylene compound and method for producing same |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011246403A (en) * | 2010-05-27 | 2011-12-08 | Nof Corp | Water-in-oil type emulsified composition |
KR20140148403A (en) * | 2012-03-30 | 2014-12-31 | 니치유 가부시키가이샤 | Multi-arm polyethylene glycol derivative, intermediate of same, and production method of same |
EP2832765A4 (en) * | 2012-03-30 | 2016-01-06 | Nof Corp | Multi-arm polyethylene glycol derivative, intermediate thereof and method for producing same |
US9428609B2 (en) | 2012-03-30 | 2016-08-30 | Nof Corporation | Multi-arm polyethylene glycol derivative, intermediate thereof, and method for producing same |
US9908971B2 (en) | 2012-03-30 | 2018-03-06 | Nof Corporation | Multi-arm polyethylene glycol derivative, intermediate thereof, and method for producing same |
KR101918339B1 (en) * | 2012-03-30 | 2018-11-13 | 니치유 가부시키가이샤 | Multi-arm polyethylene glycol derivative, intermediate of same, and production method of same |
JP2018104399A (en) * | 2016-12-28 | 2018-07-05 | 花王株式会社 | Oil-in-water emulsion composition |
JP2019059798A (en) * | 2017-09-22 | 2019-04-18 | 株式会社大阪ソーダ | Polyether polymer and composition containing the same, and molding |
JP7081104B2 (en) | 2017-09-22 | 2022-06-07 | 株式会社大阪ソーダ | A polyether polymer, a composition containing the polyether polymer, and a molded product. |
Also Published As
Publication number | Publication date |
---|---|
KR101772720B1 (en) | 2017-08-29 |
KR20120112705A (en) | 2012-10-11 |
CN102741322B (en) | 2014-12-31 |
CN102741322A (en) | 2012-10-17 |
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