WO2022124388A1 - 被膜形成用組成物 - Google Patents
被膜形成用組成物 Download PDFInfo
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- WO2022124388A1 WO2022124388A1 PCT/JP2021/045450 JP2021045450W WO2022124388A1 WO 2022124388 A1 WO2022124388 A1 WO 2022124388A1 JP 2021045450 W JP2021045450 W JP 2021045450W WO 2022124388 A1 WO2022124388 A1 WO 2022124388A1
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- film
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- component
- glycerin
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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
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8135—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers, e.g. vinyl esters (polyvinylacetate)
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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
- A61Q1/12—Face or body powders for grooming, adorning or absorbing
-
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/31—Hydrocarbons
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
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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
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8129—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
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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
- 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
- A61K8/89—Polysiloxanes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M35/00—Devices for applying media, e.g. remedies, on the human body
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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
-
- 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
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/83—Electrophoresis; Electrodes; Electrolytic phenomena
Definitions
- the present invention relates to a composition for forming a film on the skin.
- Patent Document 1 describes a method for treating the skin, which comprises electrostatically spraying the composition onto the skin.
- the composition used in this method comprises a liquid insulating material, a conductive material, a particulate powder material and a thickener.
- cosmetics and skin care compositions containing pigments are typically used.
- a cosmetic foundation is used as the composition. That is, the invention described in Patent Document 1 mainly assumes that a cosmetic foundation is electrostatically sprayed for the purpose of cosmetics to make up the skin.
- Patent Document 2 describes a disposable cartridge for use in an electrostatic spray device for cosmetics.
- This electrostatic spray device is a hand-held self-contained type.
- This electrostatic spraying device is used for spraying a cosmetic foundation in the same manner as in Patent Document 1 described above.
- Patent Document 3 a composition containing a volatile substance and a polymer having a film-forming ability and a solid oil at 20 ° C. is electrostatically sprayed directly onto the skin to form a film on the skin. The method of manufacturing is described.
- Patent Document 4 in order to form a film formed of fibers directly on the skin by electrostatic spraying, which contains a volatile substance and a polymer having a film-forming ability, as well as a plasticizer and a tactile regulator. The composition of is described.
- the present invention relates to a film-forming composition containing the following components (a), (b), (c) and (d).
- (c) Plasticizer (d) Except for component (c), the viscosity at 35 ° C. is 50 mP ⁇ s or more 3000 mP.
- -Non-volatile oil agent of s or less 3% by mass or more and 15% by mass or less
- the adhesion between the skin and the film formed by the electrostatic spray is not sufficient, and it is caused by an external force such as friction.
- the coating may be damaged or peeled off.
- the coating film on the skin formed by the compositions of Patent Documents 3 and 4 has excellent adhesion and scratch resistance, but the coating film formed on the skin becomes fragile over time. It was found that the phenomenon of conversion and dissolution occurs. Therefore, the present invention relates to a composition capable of forming a coating film formed on the skin, which not only has excellent adhesion and scratch resistance, but also does not weaken even after a long period of time and can protect the skin.
- the present inventor has investigated various causes of the film formed on the skin becoming weakened over a long period of time. As a result, the more sebum secreted into the skin after the film is formed, the faster the film weakens. I found. As a result of further studies, if a certain amount of a non-volatile oily component having a viscosity at 35 ° C. within a certain range is contained in addition to a polymer having a film forming ability, a volatile component and a plasticizer, the film is formed.
- the present invention has been completed by finding that a composition having strong resistance to sebum secreted on the formed skin surface and capable of forming a non-fragile film can be obtained.
- the obtained film not only has excellent skin compatibility, adhesion and scratch resistance, but also has excellent sebum resistance. Since the film on the skin does not weaken or dissolve even after a long period of time, the skin can be protected for a long time.
- the film-forming composition of the present invention contains the above-mentioned components (a), (b), (c) and (d).
- the coating film formed of fibers means a coating film containing fibers due to the component (a), and a liquid substance may be present around the fibers, for example, other than the fibers.
- the polymer capable of forming a film which is the component (a), is generally a substance that can be dissolved in the volatile substance of the component (b).
- to dissolve means that when the component (a) and the component (b) are mixed, the component (a) is in a dispersed state at 20 ° C. in the component (b), and the dispersed state is visually uniform. It preferably means that it is in a transparent or translucent state visually.
- polymers having a film-forming ability an appropriate polymer is used depending on the properties of the volatile substance of the component (b). Specifically, polymers having a film-forming ability are roughly classified into water-soluble polymers and water-insoluble polymers.
- water-soluble polymer refers to 0. A polymer having the property of dissolving 5 g or more in water.
- water-insoluble polymer refers to a polymer that is weighed in 1 g of the polymer at 1 atm and 23 ° C, then immersed in 10 g of ion-exchanged water, and after 24 hours have passed, the immersed polymer. A polymer having the property of dissolving less than 0.5 g in water.
- polymer having a water-soluble film-forming ability examples include purulan, hyaluronic acid, chondroitin sulfate, poly- ⁇ -glutamic acid, modified corn starch, ⁇ -glucan, glucooligosaccharide, heparin, keratosulfate and other mucopolysaccharides, cellulose and pectin.
- Xylan lignin, glucomannan, galacturonic acid, psyllium seed gum, tamarind seed gum, arabic gum, tragant gum, soybean water-soluble polysaccharide, alginic acid, carrageenan, laminaran, agarose, fucoidan, methylcellulose, hydroxypropylcellulose, hydroxypropyl Examples thereof include natural polymers such as methyl cellulose, partially saponified polyvinyl alcohol (when not used in combination with a cross-linking agent), low saponified polyvinyl alcohol, polyvinylpyrrolidone (PVP), polyethylene oxide, synthetic polymers such as sodium polyacrylate and the like. These water-soluble polymers can be used alone or in combination of two or more.
- water-soluble polymers it is preferable to use synthetic polymers such as pullulan, partially saponified polyvinyl alcohol, low saponified polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene oxide from the viewpoint of easy production of a coating film.
- synthetic polymers such as pullulan, partially saponified polyvinyl alcohol, low saponified polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene oxide from the viewpoint of easy production of a coating film.
- polyethylene oxide when polyethylene oxide is used as the water-soluble polymer, its number average molecular weight is preferably 50,000 or more and 3 million or less, and more preferably 100,000 or more and 2.5 million or less.
- examples of the water-insoluble polymer having a film-forming ability include fully saponified polyvinyl alcohol that can be insolubilized after film formation, partially saponified polyvinyl alcohol that can be cross-linked after film formation by using in combination with a cross-linking agent, and poly (N-propa).
- Graft-Oxazoline-modified silicone such as dimethylsiloxane / ⁇ -aminopropylmethylsiloxane copolymer, polyvinylacetal diethylaminoacetate, zein (main component of corn protein), polyester, polylactic acid (PLA), polyacrylonitrile resin, Examples thereof include acrylic resins such as polymethacrylic acid resins, polystyrene resins, polyvinyl butyral resins, polyethylene terephthalates, polybutylene terephthalates, polyurethane resins, polyamide resins, polyimide resins, and polyamideimide resins. These water-insoluble polymers can be used alone or in combination of two or more.
- water-insoluble polymers fully saponified polyvinyl alcohol that can be insolubilized after film formation, partially saponified polyvinyl alcohol that can be crosslinked after film formation when used in combination with a cross-linking agent, polyvinyl butyral resin, polyurethane resin, poly (N-propanoyl). It is preferable to use oxazoline-modified silicone such as ethyleneimine) graft-dimethylsiloxane / ⁇ -aminopropylmethylsiloxane copolymer, polyvinyl acetal diethylaminoacetate, zein and the like.
- oxazoline-modified silicone such as ethyleneimine
- graft-dimethylsiloxane / ⁇ -aminopropylmethylsiloxane copolymer polyvinyl acetal diethylaminoacetate, zein and the like.
- a polymer having a water-insoluble film-forming ability is preferable, and partially saponified polyvinyl alcohol, low saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, polyvinyl butyral resin, polyurethane resin, polymethacrylic acid resin, oxazoline-modified silicone, and the like.
- polyvinyl acetal diethylaminoacetate and polylactic acid are more preferable.
- the content of the component (a) in the film-forming composition of the present invention is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and 4.0% by mass or more. It is even more preferably 6.0% by mass or more, and even more preferably 8.0% by mass or more. Further, it is preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and further preferably 20% by mass or less.
- the content of the component (a) in the film-forming composition is preferably 1.0% by mass or more and 30% by mass or less, more preferably 2.0% by mass or more and 25% by mass or less.
- the component (a) in the film-forming composition at this ratio, the target film can be efficiently formed and the film formed of fibers can be stably formed. ..
- the volatile substance of component (b) is a substance that is volatile in the liquid state.
- the component (b) is sufficiently charged in the film-forming composition placed in an electric field and then discharged from the tip of the nozzle toward the skin, and the component (b) evaporates.
- the charge density of the film-forming composition becomes excessive, and the component (b) further evaporates while becoming finer due to Coulomb repulsion, and is finally blended for the purpose of forming a dry film.
- the vapor pressure of the volatile substance is preferably 0.01 kPa or more and 106.66 kPa or less, more preferably 0.13 kPa or more and 66.66 kPa or less at 20 ° C., and 0.
- a monovalent chain aliphatic alcohol for example, a monovalent chain aliphatic alcohol, a monovalent cyclic aliphatic alcohol, and a monovalent aromatic alcohol are preferably used as the alcohol.
- a monohydric chain fatty alcohol a linear or branched alcohol having 1 to 6 carbon atoms is used, and as a monovalent ring fatty alcohol, a cyclic aliphatic alcohol having 4 to 6 carbon atoms is used.
- the aromatic alcohol in the above include benzyl alcohol and phenylethyl alcohol.
- Specific examples thereof include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, 2-methyl-2-propyl alcohol, n-pentanol, and 2-pentanol.
- examples of the ketone include ketones having two alkyl groups having 1 to 4 carbon atoms, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These ketones can be used alone or in combination of two or more.
- the volatile substance of the component (b) can be used alone or in combination of two or more selected from the alcohol and the ketone.
- the volatile substance of the component (b) is more preferably one or more selected from ethanol, isopropyl alcohol and n-butyl alcohol, and further preferably one or more selected from ethanol and isopropyl alcohol. And even more preferably ethanol.
- the content of the component (b) in the film-forming composition is preferably 45% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and 60% by mass. The above is even more preferable. Further, it is preferably 98.8% by mass or less, more preferably 98% by mass or less, further preferably 97% by mass or less, further preferably 96% by mass or less, and 94% by mass. It is more preferably less than or equal to, more preferably 91% by mass or less, and even more preferably 88.5% by mass or less.
- the content of the component (b) in the film-forming composition is preferably 50% by mass or more and 98.8% by mass or less, more preferably 50% by mass or more and 98% by mass or less, and 55% by mass or more. It is more preferably 96% by mass or less, and even more preferably 60% by mass or more and 94% by mass or less. Further, it is preferably 45% by mass or more and 97% by mass or less, more preferably 50% by mass or more and 94% by mass or less, further preferably 50% by mass or more and 91% by mass or less, and 50% by mass or more. It is more preferably 88.5% by mass or less.
- the target film can be efficiently formed and the film formed of fibers can be stably formed. .. Further, by containing the component (b) in the film-forming composition at this ratio, the component (b) is efficiently and sufficiently volatilized from the film-forming composition when the electrostatic spray method is performed. Can be made to.
- the content mass ratio ((a) / (b)) of the component (a) to the component (b) in the film-forming composition stabilizes the film formed of fibers from the viewpoint of efficiently forming the target film.
- the ratio is preferably 0.010 or more. It is more preferably 060 or more, further preferably 0.080 or more, further preferably 0.10 or more, further preferably 0.11 or more, and 0.12 or more. Is even more preferable. Further, it is preferably 0.60 or less, more preferably 0.45 or less, further preferably 0.35 or less, further preferably 0.33 or less, and 0.30 or less.
- the (a) / (b) is preferably 0.010 or more and 0.60 or less, more preferably 0.060 or more and 0.33 or less, and 0.10 or more and 0.25 or less. Is even more preferable, 0.11 or more and 0.20 or less is even more preferable, and 0.12 or more and 0.18 or less is even more preferable. Further, it is preferably 0.060 or more and 0.45 or less, more preferably 0.080 or more and 0.35 or less, further preferably 0.10 or more and 0.33 or less, and 0.11 or more and 0. It is more preferably .30 or less, and even more preferably 0.12 or more and 0.25 or less.
- the component (c) and the component (d) are not particularly limited as long as they can be generally used in the field of cosmetics, and for example, polyols, polyoxyalkylene glycols, polyoxyalkylene alkyl ethers, ester oils, silicone oils, and the like.
- polyols polyoxyalkylene glycols
- polyoxyalkylene alkyl ethers polyoxyalkylene alkyl ethers
- ester oils silicone oils
- silicone oils and the like.
- hydrocarbon oils, liquid oils and fats, solid oils and fats, higher alcohols, nonionic surfactants and the like can be used.
- the plasticizer which is the component (c), imparts flexibility to the film formed of fibers by electrostatic spraying, thereby improving the adhesion and scratch resistance of the film to the skin and the movement of the skin of the film. It is a component that improves the followability to the skin and improves the skin compatibility of the film.
- the plasticizer of the component (c) is selected from those evaluated to have plasticizing performance for the polymer having the water-insoluble film forming ability of the component (a) according to the following evaluation criteria.
- the polymer is a minute piece of 3 mm ⁇ 3 mm ⁇ 3 mm or less at the time of precipitation, it is used as it is for evaluation.
- the polymer is in the form of a film, it is cut into small pieces of 3 mm ⁇ 3 mm ⁇ 3 mm or less and used for evaluation.
- (3) The vial of (2) is rotated and stirred using a mix rotor (MVR-3R (manufactured by AS ONE Corporation)) at a rotation speed of 100 r / min. For 1 week. (Room temperature: 25 ° C) (4) The vial of (3) is allowed to stand at 25 ° C. for 2 hours, and the state is visually observed.
- MVR-3R manufactured by AS ONE Corporation
- plasticizer of the component (c) a compound that easily interacts with functional groups such as hydroxyl groups, esters and acetals in the structure of the polymer having a film-forming ability is preferable, and specifically, polyols and polyoxyalkylene glycols (specifically, polyols and polyoxyalkylene glycols).
- polyethers polyoxyalkylene alkyl ethers, specific ester oils, specific silicone oils, nonionic (nonionic) surfactants, etc., but polyols and polyoxys from the viewpoint of improving scratch resistance and film feel.
- It preferably contains an alkylene glycol, a glycerin mono fatty acid ester, a glycerin di fatty acid ester, an apple acid diester, an N-acyl amino acid ester, ethylhexyl methoxycinnamate, and an alkyl benzoate.
- an alkylene glycol a glycerin mono fatty acid ester, a glycerin di fatty acid ester, an apple acid diester, an N-acyl amino acid ester, ethylhexyl methoxycinnamate, and an alkyl benzoate.
- polystyrene resin examples include 2- to hexavalent polyols, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, glycerin, and 1,3-butylene glycol.
- polyoxyalkylene glycol examples include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, tributylene glycol, polybutylene glycol, diglycerin, triglycerin and polyglycerin.
- Polyoxyalkylene glycol containing at least one alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide as a constituent unit of oxyalkylene
- polyoxyethylene glycerin polyoxypropylene glyceryl ether
- polyoxybutylene examples include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, tributylene glycol, polybutylene glycol, diglycerin, triglycerin and polyglycerin.
- Examples thereof include glyceryl ether, polyoxyalkylene glyceryl ether (which contains one or more alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide as a constituent unit of oxyalkylene) and mixtures thereof.
- polyoxyalkylene alkyl ether examples include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxypropylene lauryl ether, polyoxypropylene oleyl ether, polyoxybutylene lauryl ether, polyoxybutylene oleyl ether, and polyoxyalkylene alkyl.
- Ether an alkyl ether containing at least one alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide as a constituent unit of oxyalkylene, and having an alkyl group having a linear or branched chain having about 1 to 20 carbon atoms).
- Specific ester oils include, for example, glycerin monofatty acid esters such as glyceryl monostearate, glyceryl monoisostearate, glyceryl monooleate, and glyceryl monopalmitate, glyceryl distearate, glyceryl diisostearate, glyceryl dioleate, and dipalmitic acid.
- glycerin monofatty acid esters such as glyceryl monostearate, glyceryl monoisostearate, glyceryl monooleate, and glyceryl monopalmitate, glyceryl distearate, glyceryl diisostearate, glyceryl dioleate, and dipalmitic acid.
- Glycerindi fatty acid esters such as glyceryl, lactic acid esters such as cetyl lactate and myristyl lactate, apple acid diesters such as triethyl citrate and diisostearyl malate, amino acid esters such as amino acid ester-2, and acyl amino acid esters such as lauroyl sarcosine isopropyl.
- Ultraviolet absorbers such as ethylhexyl methoxycinnamate, alkyl benzoate and the like.
- Specific silicone oils include amodimethicone, aminoethylamonopropyl dimethicone, aminopropyl dimethicone, oxazoline-modified silicone, PEG-11 methyl ether dimethicone, PEG / PPG-20 / 22 butyl ether dimethicone, polyglyceryl-3 disiloxane dimethicone, polyglyceryl. Examples thereof include -3disiloxane ethyldimethicone and laurylpolyglyceryl-3disiloxane ethyldimethicone.
- nonionic surfactant examples include polyethylene glycol monofatty acid esters such as polyoxyethylene glycol monolaurate and polyoxyethylene glycol monostearate, and polypropylene glycol monofatty acid esters such as polyoxypropylene glycol monolaurate and polyoxypropylene glycol monostearate.
- the content of the component (c) in the film-forming composition is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, and more preferably 1.0% by mass or more. It is more preferably 1.5% by mass or more, and even more preferably 1.5% by mass or more. Further, it is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, still more preferably 15% by mass or less.
- the content of the component (c) in the film-forming composition is preferably 0.10% by mass or more and 30% by mass or less, more preferably 0.50% by mass or more and 25% by mass or less.
- the film formed of fibers by electrostatic spraying is given flexibility, the adhesion and scratch resistance of the film to the skin are improved, and the skin of the film is coated. The followability to movement is improved, and the skin compatibility of the film is improved.
- the content mass ratio ((a) / (c)) of the component (a) to the component (c) in the film forming composition is the flexibility, skin compatibility, adhesion and adhesion of the film formed of fibers by electrostatic spraying. From the viewpoint of scratch resistance, it is preferably 0.033 or more, more preferably 0.10 or more, further preferably 0.20 or more, and even more preferably 0.40 or more. , 0.80 or more, more preferably 1.0 or more, and even more preferably 1.5 or more. Further, it is preferably 300 or less, more preferably 60 or less, further preferably 30 or less, further preferably 20 or less, further preferably 15 or less, and even more preferably 10 or less.
- the (a) / (c) is preferably 0.033 or more and 300 or less, more preferably 0.10 or more and 60 or less, further preferably 0.20 or more and 30 or less, and 0. It is more preferably 40 or more and 10 or less, and further preferably 1.0 or more and 10 or less. Further, it is preferably 0.80 or more and 20 or less, more preferably 1.0 or more and 15 or less, further preferably 1.0 or more and 10 or less, and 1.5 or more and 8.0 or less. Is even more preferable.
- the component (d) is a non-volatile oil having a viscosity of 50 mP ⁇ s or more and 3000 mP ⁇ s or less at 35 ° C. other than the component (c).
- the non-volatile oil agent is a non-volatile oil agent at 20 ° C.
- the non-volatile oil having a viscosity at 35 ° C. of 50 mP ⁇ s or more and 3000 mP ⁇ s or less in the present invention means that the viscosity of the entire mixture containing one or more non-volatile oils is 50 mP ⁇ s at 35 ° C. It means that it is 3000 mP ⁇ s or less.
- the viscosity of one of the constituent non-volatile oils at 35 ° C. does not necessarily have to be in this range, and the viscosity at 35 ° C. of a mixture of two or more types of non-volatile oils may be in this range.
- a non-volatile oil having a viscosity at 35 ° C. of less than 50 mP ⁇ s and a non-volatile oil having a viscosity at 35 ° C. of more than 3000 mP ⁇ s are mixed, and the viscosity of the mixture at 35 ° C. is 50 mP ⁇ s or more and 3000 mP ⁇ s. It should be as follows.
- a thickener to a non-volatile oil having a viscosity at 35 ° C. of less than 50 mP ⁇ s to adjust the viscosity to 50 mP ⁇ s or more and 3000 mP ⁇ s or less.
- non-volatile oil agent used as the component (d) one or more selected from ester oils, silicone oils, hydrocarbon oils, liquid fats and oils, solid fats and oils, higher alcohols and the like other than the component (c) are combined. Can be used. When one or more of these non-volatile oils are contained, a combination having a viscosity at 35 ° C. of 50 mP ⁇ s or more and 3000 mP ⁇ s or less is used. From the viewpoint of obtaining excellent sebum resistance of the film, the viscosity at a preferable 35 ° C.
- ⁇ s or more and 2800 mP ⁇ s or less is 100 mP ⁇ s or more and 2800 mP ⁇ s or less, more preferably 150 mP ⁇ s or more and 2500 mP ⁇ s or less, still more preferably 170 mP ⁇ s or more and 2000 mP ⁇ s or less, and further. More preferably, it is 200 mP ⁇ s or more and 1700 mP ⁇ s or less.
- ester oil examples include an octanoic acid ester such as cetyl octanate, a lauric acid ester such as hexyl laurate, a myristic acid ester such as octyldodecyl myristate, a palmitic acid ester such as octyl palmitate, and a stearic acid ester such as isocetyl stearate.
- octanoic acid ester such as cetyl octanate
- lauric acid ester such as hexyl laurate
- myristic acid ester such as octyldodecyl myristate
- palmitic acid ester such as octyl palmitate
- stearic acid ester such as isocetyl stearate.
- Isostearic acid ester such as isopropyl isostearate, isostriatic acid ester such as octyl isopalmitate, oleic acid ester such as isodesyl oleate, adipic acid diester such as diisopropyl adipate, sebacic acid diester such as diethyl sevacinate, malic acid.
- Appleic acid diester such as diisostearyl, isononyl isononanoate, isononanoic acid ester such as isotorideyl isononanoate, ethylhexanoic acid ester such as cetyl ethylhexanoate, fatty acid ester such as neopentylglycol diethylhexanoate, pentaerythrityl tetraethylhexanoate.
- ester oils pentaerythrityl tetraethylhexarate, glyceryl diisostearate, triethylhexanoin, tetra (bechenic acid / benzoic acid / ethylhexanoic acid) pentaerythrityl from the viewpoint of obtaining a film having excellent oil resistance.
- glycerin Dipentaerythritol fatty acid ester, di2-heptylundecanoic acid glycerin, trioctanoate glycerin, triisopalmitate glycerin, tri2-ethylhexanoic acid glycerin, trimyristate glycerin, tri2-heptylundecanoic acid glyceride, acetoglyceride, glycerin It is more preferable to use one or more selected from glycerides such as mono fatty acid ester, glycerin di fatty acid ester and glycerin tri fatty acid ester, and acyl amino acid diester such as lauroyl glutamate di (phytosteryl / octyldodecyl).
- hydrocarbon oil examples include liquid paraffin, squalane, squalane, paraffin, isoparaffin, ceresin, isohexadecane, isododecane, ozokerite, pristane, paraffin wax, petrolatum, microcrystalline wax and the like.
- these hydrocarbons it is more preferable to use one or more selected from liquid paraffin, isododecane, paraffin wax, and petrolatum from the viewpoint of obtaining a film having excellent sebum resistance.
- Liquid fats and oils include flaxseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, southern ka oil, castor oil, safflower oil, rapeseed oil, soybean oil, peanut oil, triglycerin, trioctanoic acid.
- Examples thereof include oil, cow leg oil, liver oil, and pentaerythrit tetraoctanoate.
- solid fats and oils examples include coconut oil, palm oil, palm oil, palm kernel oil, beef tallow, sheep fat, pork fat, horse fat, hydrogenated oil, hardened castor oil, mokurou, and shea butter.
- saturated linear monohydric alcohols examples include saturated linear monohydric alcohols and unsaturated monohydric alcohols.
- Saturated linear monohydric alcohols include dodecanol (lauryl alcohol), tridodecanol, tetradodecanol (myristyl alcohol), pentadecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol).
- Nonadecanol Nonadecanol, Icosanol (Arakil alcohol), Henicosanol, Docosanol (Behenyl alcohol), Tricosanol, Tetracosanol (Carnervir alcohol), Pentacosanol, Hexacosanol (Ceryl alcohol) and the like.
- unsaturated monohydric alcohols include oleyl alcohol and eridyl alcohol.
- silicone oil examples include chain silicones such as dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, diphenylpolysiloxane (diphenyldimethicone), diphenylsiloxyphenyltrimethicone, and methylhydrogenpolysiloxane, cyclopentasiloxane methyltrimethicone, and octa.
- Cyclic silicones such as methylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, silicone resins forming a three-dimensional network structure, silicone rubber, and the like can be mentioned.
- the content of the component (d) in the film-forming composition is 3% by mass or more and 15% by mass or less from the viewpoint of obtaining a film having excellent sebum resistance. Further, it is preferably 3.5% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 15% by mass or less, and further preferably 5% by mass or more and 15% by mass or less.
- the content mass ratio ((c) / (d)) of the component (c) to the component (d) in the film forming composition is the flexibility, skin compatibility, adhesion and adhesion of the film formed of fibers by electrostatic spraying. From the viewpoint of scratch resistance and further, from the viewpoint of obtaining excellent skin oil resistance of the coating film, it is preferably 0.0033 or more, more preferably 0.0050 or more, and further preferably 0.0066 or more. Preferably, it is more preferably 0.01 or more, further preferably 0.03 or more, further preferably 0.05 or more, further preferably 0.066 or more, and 0. .1 or more is even more preferable, and 0.2 or more is even more preferable.
- the (c) / (d) is preferably 0.0033 or more and 30 or less, more preferably 0.0050 or more and 25 or less, further preferably 0.0066 or more and 20 or less, and 0. It is more preferably 01 or more and 15 or less. Further, it is preferably 0.03 or more and 10 or less, more preferably 0.05 or more and 7.0 or less, further preferably 0.066 or more and 5 or less, and 0.1 or more and 5 or less. Is even more preferable, and 0.2 or more and 3 or less is even more preferable.
- the content mass ratio ((a) / (d)) of the component (a) to the component (d) in the film-forming composition is from the viewpoint of obtaining excellent skin oil resistance of the film formed of fibers by electrostatic spraying. , 0.0033 or more, more preferably 0.005 or more, further preferably 0.0066 or more, further preferably 0.01 or more, and 0.02 or more. It is more preferably 0.03 or more, further preferably 0.066 or more, further preferably 0.1 or more, and even more preferably 0.3 or more. Even more preferably, it is even more preferably 0.5 or more, and even more preferably 0.8 or more.
- the (a) / (d) is preferably 0.0033 or more and 30 or less, more preferably 0.005 or more and 25 or less, further preferably 0.0066 or more and 20 or less, and 0. It is more preferably 01 or more and 15 or less, and further preferably 0.02 or more and 13 or less.
- it is preferably 0.03 or more and 10 or less, more preferably 0.066 or more and 10 or less, further preferably 0.10 or more and 8.0 or less, and 0.30 or more and 8.0 or less. It is even more preferably 0.50 or more and 8.0 or less, and even more preferably 0.80 or more and 8.0 or less.
- the film-forming composition includes a conductivity control agent, an oil agent other than the components (c) and (d), a coloring pigment, an extender pigment, a dye, a fragrance, a repellent, an antioxidant, a stabilizer, and the like. It may contain preservatives, various vitamins, water and the like.
- the conductivity control agent is preferably an alkali metal salt or an ammonium salt, more preferably an ionic surfactant, and further preferably a cationic surfactant and an anionic surfactant from the viewpoint of improving conductivity.
- One or more selected from the agents are selected from the agents.
- the content of the conductivity control agent in the film-forming composition is not limited as long as it is an amount that keeps the conductivity of the composition within the above range, but from the viewpoint of stably forming the film and excessively increasing the conductivity. From the viewpoint of preventing The following is further preferable, 2.5% by mass or less is further preferable, and 2% by mass or less is further preferable.
- the viscosity of the film-forming composition is 25 ° C. from the viewpoint of stably forming a film formed of fibers on the skin, spinnability during electrostatic spraying, drying of fibers, and reduction of the diameter of fibers. It is preferably 2 mPa ⁇ s or more, more preferably 5 mPa ⁇ s or more, further preferably 10 mPa ⁇ s or more, further preferably 30 mPa ⁇ s or more, and 50 mPa ⁇ s or more. It is even more preferable that the content is 80 mPa ⁇ s or more, and it is even more preferable that the content is 80 mPa ⁇ s or more.
- it is preferably 3000 mPa ⁇ s or less, more preferably 2000 mPa ⁇ s or less, further preferably 1500 mPa ⁇ s or less, further preferably 1000 mPa ⁇ s or less, and 800 mPa ⁇ s or less. It is more preferably present, and even more preferably 500 mPa ⁇ s or less.
- the viscosity range of the film-forming composition is preferably 2 mPa ⁇ s or more and 3000 mPa ⁇ s or less, more preferably 5 mPa ⁇ s or more and 2000 mPa ⁇ s or less, and 10 mPa ⁇ s or more and 1500 mPa ⁇ s or less. Is more preferably 30 mPa ⁇ s or more and 1000 mPa ⁇ s or less, further preferably 50 mPa ⁇ s or more and 800 mPa ⁇ s or less, and even more preferably 80 mPa ⁇ s or more and 500 mPa ⁇ s or less. ..
- the viscosity of the film-forming composition is measured at 25 ° C. using a B-type viscometer.
- a B-type viscometer for example, a B-type viscometer (TVB-10M) manufactured by Toki Sangyo Co., Ltd. can be used.
- the measurement condition is that the measurement temperature is 25 ° C.
- the measured temperature is the temperature of the film-forming composition.
- the type of rotor and the number of revolutions of the rotor are selected according to the specifications of the measuring equipment to be used, depending on the viscosity of the coating composition. For example, when a B-type viscometer (TVB-10M) manufactured by Toki Sangyo Co., Ltd.
- a M2 rotor is used at 6 rpm and 1000 mPa ⁇ s or more 2500 mPa. ⁇ Less than s is 12 rpm using an M2 rotor, 500 mPa ⁇ s or more and less than 1000 mPa ⁇ s is 30 rpm using an M2 rotor, and 100 mPa ⁇ s or more and less than 500 mPa ⁇ s is 60 rpm using an M2 rotor and less than 100 mPa ⁇ s. Can be measured at 60 rpm using an M1 rotor.
- the specification manual of the B-type viscometer (TVB-10M) manufactured by Toki Sangyo Co., Ltd. also describes measurement conditions other than the above measurement conditions, and other measurement conditions are described depending on the viscosity of the film-forming composition. Viscosity can also be measured under measurement conditions.
- a method of forming a film formed of fibers directly on the skin by electrostatic spraying and an electrostatic spraying method are used. There is a method of forming a film formed of fibers on a substrate and applying the film onto the skin. Next, a method of forming a film formed of fibers directly on the skin by electrostatic spraying will be described.
- the film-forming composition is sprayed directly onto the site of human skin where the film is to be formed by the electrostatic spray method.
- the electrostatic spray method includes a step of electrostatically spraying a film-forming composition onto the skin using an electrostatic spray device.
- the electrostatic spray device basically includes a container for containing the composition, a nozzle for discharging the composition, a supply device for supplying the composition contained in the container to the nozzle, and the above. It has a power supply that applies a voltage to the nozzle.
- FIG. 1 shows a schematic diagram showing the configuration of an electrostatic spray device preferably used in the present invention.
- the electrostatic spray device 10 shown in the figure includes a low voltage power supply 11.
- the low voltage power supply 11 can generate a voltage of several V to a dozen V.
- the low voltage power supply 11 is preferably composed of one or two or more batteries. Further, by using the battery as the low voltage power source 11, there is an advantage that the battery can be easily replaced as needed. Instead of the battery, an AC adapter or the like can be used as the low voltage power supply 11.
- the electrostatic spray device 10 also includes a high voltage power supply 12.
- the high voltage power supply 12 is connected to the low voltage power supply 11 and includes an electric circuit (not shown) that boosts the voltage generated by the low voltage power supply 11 to a high voltage.
- the step-up electric circuit is generally composed of a transformer, a capacitor, a semiconductor element, and the like.
- the electrostatic spray device 10 further includes an auxiliary electric circuit 13.
- the auxiliary electric circuit 13 is interposed between the low voltage power supply 11 and the high voltage power supply 12 described above, and has a function of adjusting the voltage of the low voltage power supply 11 to stably operate the high voltage power supply 12. Further, the auxiliary electric circuit 13 has a function of controlling the rotation speed of the motor provided in the micro gear pump 14 described later. By controlling the rotation speed of the motor, the supply amount of the film-forming composition from the container 15 of the film-forming composition to the micro gear pump 14 is controlled.
- a switch SW is attached between the auxiliary electric circuit 13 and the low-voltage power supply 11, and the electrostatic spray device 10 can be started / stopped by turning the switch SW on and off.
- the electrostatic spray device 10 further includes a nozzle 16.
- the nozzle 16 is made of various conductors such as metal and non-conductors such as plastic, rubber, and ceramic, and has a shape capable of ejecting a film-forming composition from the tip thereof.
- a minute space through which the film-forming composition flows is formed in the nozzle 16 along the longitudinal direction of the nozzle 16.
- the size of the cross section of this microspace is preferably 100 ⁇ m or more and 1000 ⁇ m or less in terms of diameter.
- the nozzle 16 communicates with the micro gear pump 14 via a conduit 17.
- the conduit 17 may be a conductor or a non-conductor.
- the nozzle 16 is electrically connected to the high voltage power supply 12. This makes it possible to apply a high voltage to the nozzle 16. In this case, in order to prevent an excessive current from flowing when the human body directly touches the nozzle 16, the nozzle 16 and the high voltage power supply 12 are electrically connected via a current limiting resistance 19.
- the micro gear pump 14 communicating with the nozzle 16 via the pipeline 17 functions as a supply device for supplying the film-forming composition contained in the container 15 to the nozzle 16.
- the micro gear pump 14 operates by receiving power supplied from the low voltage power supply 11. Further, the micro gear pump 14 is configured to supply a predetermined amount of the film-forming composition to the nozzle 16 under the control of the auxiliary electric circuit 13.
- a container 15 is connected to the micro gear pump 14 via a flexible pipeline 18.
- the film-forming composition is contained in the container 15.
- the container 15 preferably has a cartridge-type replaceable form.
- the electrostatic spray device 10 having the above configuration can be used, for example, as shown in FIG. FIG. 2 shows a handy type electrostatic spray device 10 having dimensions that can be gripped with one hand.
- all the members in the configuration diagram shown in FIG. 1 are housed in a cylindrical housing 20.
- a nozzle (not shown) is arranged at one end 10a of the housing 20 in the longitudinal direction.
- the nozzles are arranged in the housing 20 so that the blowing direction of the composition coincides with the vertical direction of the housing 20 and becomes convex toward the skin side. Since the tip of the nozzle is arranged so as to be convex toward the skin in the vertical direction of the housing 20, the film-forming composition is less likely to adhere to the housing, and a film can be stably formed. can.
- FIG. 2 shows a state in which one end 10a of the electrostatic spray device 10 is directed toward the inside of the forearm portion of the user. Under this state, the switch of the device 10 is turned on to perform the electrostatic spray method. When the device 10 is turned on, an electric field is generated between the nozzle and the skin. In the embodiment shown in FIG. 2, a positive high voltage is applied to the nozzle, and the skin becomes the negative electrode.
- the film-forming composition at the tip of the nozzle is polarized by electrostatic induction to form a cone at the tip, and the liquid of the film-forming composition charged from the tip of the cone. Drops are ejected into the air toward the skin along the electric field.
- the component (b) which is a solvent, evaporates from the film-forming composition discharged and charged into the space, the charge density on the surface of the film-forming composition becomes excessive, and the space is repeatedly miniaturized by the Coulomb repulsive force. Proceed to reach the skin.
- a volatile substance as a solvent is volatilized from the droplets while being discharged into the space, and a component having a film-forming ability as a solute (a component having a film-forming ability as a solute).
- a fiber while solidifying the polymer of a) and stretching and deforming it by a potential difference, and deposit the fiber at the application site.
- increasing the viscosity of the film-forming composition facilitates the deposition of the composition in the form of fibers at the application site.
- a porous film made of such a deposit of fibers can also be formed by adjusting the distance between the nozzle and the skin and the voltage applied to the nozzle.
- the present inventors have confirmed that the current flowing through the human body during the electrostatic spray method is several orders of magnitude smaller than the current flowing through the human body due to static electricity generated in normal life.
- the thickness of the fiber is preferably 10 nm or more, more preferably 50 nm or more when expressed in terms of the diameter equivalent to a circle. Further, it is preferably 3000 nm or less, more preferably 1000 nm or less, and further preferably 800 nm or less.
- the thickness of the fiber is determined by observing the fiber at a magnification of 10,000 times, for example, by observing with a scanning electron microscope (SEM), and removing defects (fiber mass, fiber intersection, droplet) from the two-dimensional image. It can be measured by arbitrarily selecting 10 fibers, drawing a line orthogonal to the longitudinal direction of the fibers, and directly reading the fiber diameter.
- the fiber of the present invention is preferably a continuous fiber, and preferably has a length of at least 100 times the thickness of the fiber.
- the formed film preferably contains a fiber having a length of 10 ⁇ m or more, more preferably 50 ⁇ m or more, still more preferably 100 ⁇ m or more, containing the component (a).
- a fiber having a length of 100 times or more the thickness of the fiber is defined as a "continuous fiber”.
- the cross-sectional shape of the fiber is preferably circular or elliptical, and the thickness of the fiber is the diameter when it is circular and the length of the major axis when it is elliptical.
- the coating produced by the electrostatic spray method is preferably a porous discontinuous coating composed of deposits of one or more continuous fibers.
- the film-forming composition is charged and sprayed, and when the humidity is high, it is affected by the moisture in the atmosphere, but it is less affected by the inclusion of the conductivity control agent. can do.
- the mixed solution containing all the components may be stirred, but after the step 1 in which the mixed solution 1 containing the components other than the component (a) is stirred, the component (a) is used. It is preferable to include the step 2 of adding and stirring and mixing. Further, a mixture of step 1 of mixing the component (a) and a part of the component (b), step 2 of mixing the rest of the component (b) with the component (c) and the component (d), and step 1. And step 3 for mixing the mixture of step 2 may be provided. It is preferable that these steps 1, 2, and 3 are performed at room temperature of 10 ° C to 30 ° C.
- the distance between the nozzle and the skin depends on the voltage applied to the nozzle, but is preferably 10 mm or more, more preferably 20 mm or more, and even more preferably 40 mm or more. Further, it is preferably 160 mm or less, more preferably 140 mm or less, and further preferably 120 mm or less. When the distance between the nozzle and the skin is within this range, the formability of the film can be improved.
- the distance between the nozzle and the skin can be measured by a commonly used non-contact sensor or the like.
- the basis weight of the film is preferably 0.10 g / m 2 or more, and 1.0 g / m 2 or more. It is more preferable to have. Further, it is preferably 50 g / m 2 or less, and more preferably 40 g / m 2 or less.
- the basis weight of the formed coating film is preferably 0.10 g / m 2 or more and 50 g / m 2 or less, and more preferably 1.0 g / m 2 or more and 40 g / m 2 or less.
- the present invention further discloses the following compositions and methods.
- a film-forming composition containing the following components (a), (b), (c) and (d).
- (A) Polymer having film-forming ability (b) One or more volatile substances selected from alcohols and ketones (c) Plasticizer (d) Except for component (c), the viscosity at 35 ° C. is 50 mP ⁇ s or more 3000 mP. -Non-volatile oil agent of s or less 3% by mass or more and 15% by mass or less
- the component (a) is a polymer having a film-forming ability that is water-insoluble, preferably completely saponified polyvinyl alcohol that can be insolubilized after film formation, and partial saponification that can be cross-linked after film formation by using in combination with a cross-linking agent.
- Polyvinyl alcohol such as poly (N-propanoylethyleneimine) graft-dimethylsiloxane / ⁇ -aminopropylmethylsiloxane copolymer, polyvinyl acetal diethylaminoacetate, zein (main component of corn protein), polyester, polylactic acid (PLA), polyacrylonitrile resin, acrylic resin such as polymethacrylic acid resin, polystyrene resin, polyvinyl butyral resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyurethane resin, polyamide resin, polyimide resin and polyamideimide resin.
- PVA polylactic acid
- acrylic resin such as polymethacrylic acid resin
- polystyrene resin polyvinyl butyral resin
- polyethylene terephthalate resin polybutylene terephthalate resin
- polyurethane resin polyamide resin
- polyimide resin polyimide resin and polyamideimide resin.
- composition for forming a film according to ⁇ 1> which is one or more selected from polyvinyl acetal diethylaminoacetate and zein.
- the content of the component (a) is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, still more preferably 4.0% by mass or more.
- the film-forming composition according to the above. ⁇ 4> The composition for forming a film according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the component (a) is 2.0% by mass or more and 25% by mass or less.
- ⁇ 5> The composition for forming a film according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the component (a) is 6.0% by mass or more and 30% by mass or less.
- the vapor pressure of the component (b) is preferably 0.01 kPa or more and 106.66 kPa or less, more preferably 0.13 kPa or more and 66.66 kPa or less, and 0.67 kPa or less at 20 ° C. As mentioned above, it is more preferably 40.00 kPa or less, further preferably 1.33 kPa or more and 40.00 kPa or less, and further preferably 2.40 kPa or more and 40.00 kPa or less ⁇ 1> to ⁇ .
- the alcohol of the component (b) is preferably one or more selected from monohydric chain-type aliphatic alcohols, monovalent ring-type aliphatic alcohols and monovalent aromatic alcohols, and has a carbon number of carbon.
- two or more are preferable, and one or two or more selected from ethanol, isopropyl alcohol, n-butyl alcohol, phenylethyl alcohol, n-propanol and n-pentanol are preferable.
- the ketone of the component (b) is preferably a ketone having two alkyl groups having 1 to 4 carbon atoms, and more preferably one or more selected from acetone, methyl ethyl ketone and methyl isobutyl ketone ⁇ 1>.
- the component (b) is preferably one or more selected from ethanol, isopropyl alcohol and n-butyl alcohol, and more preferably one or more selected from ethanol and isopropyl alcohol.
- the content of the component (b) is preferably 45% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and more preferably 60% by mass or more. It is more preferably 98.8% by mass or less, more preferably 98% by mass or less, further preferably 97% by mass or less, and further preferably 96% by mass or less. Further, it is more preferably 94% by mass or less, further preferably 91% by mass or less, further preferably 88.5% by mass or less, and 50% by mass or more and 98.8% by mass.
- ⁇ 11> The film-forming composition according to any one of ⁇ 1> to ⁇ 10>, wherein the content of the component (b) is 50% by mass or more and 98% by mass or less.
- ⁇ 12> The composition for forming a film according to any one of ⁇ 1> to ⁇ 10>, wherein the content of the component (b) is 50% by mass or more and 91% by mass or less.
- One of the components (c) selected from polyols, polyoxyalkylene glycols, polyoxyalkylene alkyl ethers, ester oils, silicone oils, hydrocarbon oils, liquid fats and oils, solid fats and oils, higher alcohols and nonionic surfactants.
- the component (c) is a compound that easily interacts with a hydroxyl group, an ester, and an acetal moiety in the structure of a polymer having a film-forming ability, and is preferably a polyol, a polyoxyalkylene glycol, a polyoxyalkylene alkyl ether, and the like.
- composition for forming a film according to any one of ⁇ 1> to ⁇ 13> which is one or more selected from an acyl amino acid ester, ethylhexyl methoxycinnamate, and alkyl benzoate.
- the content of the component (c) is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, still more preferably 1.0% by mass or more. It is more preferably 1.5% by mass or more, more preferably 30% by mass or less, further preferably 25% by mass or less, further preferably 20% by mass or less, and 15% by mass.
- ⁇ 16> The composition for forming a film according to any one of ⁇ 1> to ⁇ 15>, wherein the content of the component (c) is 0.50% by mass or more and 25% by mass or less.
- ⁇ 17> The film-forming composition according to any one of ⁇ 1> to ⁇ 15>, wherein the content of the component (c) is 1.0% by mass or more and 20% by mass or less.
- ⁇ 18> The preferable viscosity of the component (d) at 35 ° C.
- the film-forming composition according to any one of ⁇ 1> to ⁇ 17>. ⁇ 19> The composition for forming a film according to any one of ⁇ 1> to ⁇ 18>, wherein the component (d) is one or more selected from an ester oil and a hydrocarbon oil.
- the component (d) is pentaerythrityl tetraethylhexarate, glyceryl diisostearate, triethylhexanoin, tetra (bechenic acid / benzoic acid / ethylhexanoic acid) pentaerythrityl, dipentaerythritol fatty acid ester, di2-heptyl.
- glycerides such as fatty acid esters, acyl amino acid diesters such as di (phytosteryl / octyldodecy
- the film-forming composition according to any one of ⁇ 1> to ⁇ 19>.
- the content of the component (d) is preferably 3% by mass or more and 15% by mass or less, more preferably 3.5% by mass or more and 15% by mass or less, and further preferably 4% by mass or more and 15% by mass or less. %, More preferably 5% by mass or more and 15% by mass or less, according to any one of ⁇ 1> to ⁇ 20>.
- the content mass ratio ((a) / (c)) of the component (a) to the component (c) is preferably 0.033 or more, more preferably 0.10 or more, and 0.
- compositions Is more preferable, 1.0 or more and 15 or less is more preferable, 1.0 or more and 10 or less is further preferable, and 1.5 or more and 8.0 or less is further preferable.
- the film-forming composition according to any one of. ⁇ 23> The film formation according to any one of ⁇ 1> to ⁇ 22>, wherein the content mass ratio ((a) / (c)) of the component (a) to the component (c) is 0.2 or more and 30 or less.
- Composition for. ⁇ 24> The film forming according to any one of ⁇ 1> to ⁇ 22>, wherein the content mass ratio ((a) / (c)) of the component (a) to the component (c) is 1.0 or more and 10 or less.
- the content mass ratio ((c) / (d)) of the component (c) to the component (d) is preferably 0.0033 or more, more preferably 0.0050 or more, and 0. It is more preferably 0066 or more, further preferably 0.01 or more, further preferably 0.03 or more, further preferably 0.05 or more, and 0.066 or more. It is even more preferably 0.1 or more, even more preferably 0.2 or more, still more preferably 30 or less, still more preferably 25 or less, and 20 or less.
- the film-forming composition according to any one of ⁇ 1> to ⁇ 24>, preferably 0.10 or more and 5 or less, and even more preferably 0.2 or more and 3 or less.
- composition for. ⁇ 26> The film forming according to any one of ⁇ 1> to ⁇ 25>, wherein the content mass ratio ((c) / (d)) of the component (c) to the component (d) is 0.03 or more and 10 or less.
- Composition for. ⁇ 27> The film formation according to any one of ⁇ 1> to ⁇ 25>, wherein the content mass ratio ((c) / (d)) of the component (c) to the component (d) is 0.2 or more and 3 or less.
- Composition for. ⁇ 28> The content mass ratio ((a) / (b)) of the component (a) to the component (b) is preferably 0.010 or more, more preferably 0.060 or more, and 0.
- the content mass ratio ((a) / (d)) of the component (a) to the component (d) is preferably 0.0033 or more, more preferably 0.005 or more, and 0. It is more preferably 0066 or more, further preferably 0.01 or more, further preferably 0.02 or more, further preferably 0.03 or more, and even more preferably 0.066 or more.
- ⁇ 32> The film forming according to any one of ⁇ 1> to ⁇ 31>, wherein the content mass ratio ((a) / (d)) of the component (a) to the component (d) is 0.02 or more and 13 or less. Composition for.
- ⁇ 33> The description according to any one of ⁇ 1> to ⁇ 31>, wherein the content mass ratio ((a) / (d)) of the component (a) to the component (d) is 0.80 or more and 8.0 or less.
- Composition for film formation. ⁇ 34> Selected from conductivity control agents, oils other than the components (c) and (d), coloring pigments, extender pigments, dyes, fragrances, repellents, antioxidants, stabilizers, preservatives, various vitamins and water.
- the conductivity control agent is preferably an alkali metal salt or an ammonium salt, more preferably an ionic surfactant, and further preferably one selected from a cationic surfactant and an anionic surfactant.
- the composition for forming a film according to ⁇ 34> or ⁇ 35> which is two or more kinds.
- the content of the conductivity control agent is preferably 0.010% by mass or more, more preferably 0.050% by mass or more, further preferably 0.10% by mass or more, and further. It is preferably 10% by mass or less, more preferably 8.0% by mass or less, further preferably 6.0% by mass or less, and even more preferably 2.5% by mass or less.
- composition for forming a film according to any one of ⁇ 34> to ⁇ 37> which is more preferably as follows.
- the viscosity of the film-forming composition is preferably 2 mPa ⁇ s or more, more preferably 5 mPa ⁇ s or more, still more preferably 10 mPa ⁇ s or more, and 30 mPa ⁇ s at 25 ° C. More preferably, it is more preferably 50 mPa ⁇ s or more, further preferably 80 mPa ⁇ s or more, further preferably 3000 mPa ⁇ s or less, still more preferably 2000 mPa ⁇ s or less, 1500 mPa ⁇ s.
- the coating composition according to any one of ⁇ 1> to ⁇ 38> further preferably 50 mPa ⁇ s or more and 800 mPa ⁇ s or less, and even more preferably 80 mPa ⁇ s or more and 500 mPa ⁇ s or less. .. ⁇ 40>
- the composition for forming a film according to any one of ⁇ 1> to ⁇ 39> which is a composition for forming a film formed of fibers directly on the skin by electrostatic spraying.
- a skin sheet-like composition obtained by electrostatically spraying a composition containing the following components (a), (b), (c) and (d).
- the viscosity at 35 ° C. is 50 mP ⁇ s or more 3000 mP.
- the component (d) is pentaerythrityl tetraethylhexanoate, glyceryl diisostearate, triethylhexanoin, tetra (bechenic acid / benzoic acid / ethylhexane).
- the sheet-like composition for skin according to ⁇ 41> which is two or more kinds of non-volatile oils.
- the plasticizer is selected from polyols, polyoxyalkylene glycols, glycerin monofatty acid esters, glycerin difatty acid esters, malic acid diesters, N-acylamino acid esters, ethylhexyl methoxycinnamate, and alkyl benzoate 1
- the sheet-like composition for skin according to ⁇ 41> or ⁇ 42> which is a seed or two or more kinds.
- Viscosity of component (d) The viscosity of component (d) is measured at a measurement temperature of 35 ° C using a B-type viscometer after mixing two types of oils and storing them in a water bath at 35 ° C for 24 hours. Was measured. Here, the measured temperature is the temperature of the component (d).
- a B-type viscometer a B-type viscometer (TVB-10M) manufactured by Toki Sangyo Co., Ltd. was used, the rotor types were M1, M2, M4, and the rotation speed was measured at 3.0 rpm to 60 rpm.
- Electrostatic spraying process Using an electrostatic spraying device 10 having the configuration shown in FIG. 1 and having the appearance shown in FIG. 2, a 3x8 cm portion was cut out from a 5x10 cm aluminum foil in a hole portion (frame portion). The film-forming composition was electrostatically sprayed for 30 seconds to form a film formed of fibers. The amount of polymer was 6.6 mg (0.275 mg / cm 2 ).
- the sebum resistance is excellent when the viscosity of the component (d) at 35 ° C. is 50 mP ⁇ s or more and 3000 mP ⁇ s or less. Further, from Table 2, it can be seen that the sebum resistance is excellent when the content of the component (d) is 3% by mass or more and 15% by mass or less.
- the film-forming compositions of Examples in Tables 1 and 2 were electrostatically sprayed directly onto the skin to form a film composed of fibers, and the adhesion and scratch resistance of the film were evaluated. The coating film also had excellent adhesion and scratch resistance.
- Example 2 [Examples 8 to 11]
- Polyvinyl butyral was used as the component (a) of the film-forming composition, and 99-degree synthetic alcohol (manufactured by Nippon Synthetic Alcohol Co., Ltd.) was used as the component (b).
- component (c) polyethylene glycol (average molecular weight 400), glycerin, PEG / PPG / polybutylene glycol-8 / 5/3 glycerin, 1,3-butylene glycol, or ethylhexyl methoxycinnamate, as the component (d).
- Dicaprate neopentyl glycol, dipentaerythrit fatty acid ester (melting point 50 ° C.), isononyl isononanoate, or isododecane was mixed with dextrin palmitate to adjust the viscosity at 35 ° C. and used.
- the content of each component shown in Table 3 is an effective amount, and the unit is mass%.
- Viscosity of component (d) The viscosity of component (d) is measured by using a B-type viscometer after mixing a non-volatile oil agent and dextrin palmitate and storing in a water bath at 35 ° C. for 24 hours. It was measured at 35 ° C. Here, the measured temperature is the temperature of the component (d).
- a B-type viscometer As the B-type viscometer, a B-type viscometer (TVB-10M) manufactured by Toki Sangyo Co., Ltd. was used, the rotor types were M1, M2, M4, and the rotation speed was measured at 3.0 rpm to 60 rpm.
- Electrostatic spraying process Using an electrostatic spraying device 10 having the configuration shown in FIG. 1 and having the appearance shown in FIG. 2, a 3x8 cm portion was cut out from a 5x10 cm aluminum foil in a hole portion (frame portion). The film-forming composition was electrostatically sprayed for 30 seconds to form a film formed of fibers. The amount of polymer was 6.6 mg (0.275 mg / cm 2 ).
- Electrostatic spray device 11 Low voltage power supply 12 High voltage power supply 13 Auxiliary electric circuit 14
- Micro gear pump 15 Container 16 Nozzle 17 Pipe line 18 Flexible line line 19 Current limiting resistance 20 Housing
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Abstract
Description
また、特許文献3には、揮発性物質、被膜形成能を有するポリマーに加えて、20℃で固体状の油を含有する組成物を、直接皮膚上に静電スプレーして皮膚上に被膜を製造する方法が記載されている。
さらに、特許文献4には、揮発性物質、被膜形成能を有するポリマーに加えて、可塑剤及び感触調節剤を含有する、静電スプレーにより直接皮膚上に繊維で形成された被膜を形成するための組成物が記載されている。
(a)被膜形成能を有するポリマー
(b)アルコール及びケトンから選ばれる1種以上の揮発性物質
(c)可塑剤
(d)成分(c)以外の、35℃における粘度が50mP・s以上3000mP・s以下である不揮発性油剤3質量%以上15質量%以下
従って、本発明は、皮膚上に形成された被膜が密着性や耐擦過性に優れるだけでなく、長時間経過後も脆弱化せず、皮膚を保護できる被膜を形成できる組成物に関する。
これらの水不溶性ポリマーのうち、被膜形成後に不溶化処理できる完全鹸化ポリビニルアルコール、架橋剤と併用することで被膜形成後に架橋処理できる部分鹸化ポリビニルアルコール、ポリビニルブチラール樹脂、ポリウレタン樹脂、ポリ(N-プロパノイルエチレンイミン)グラフト-ジメチルシロキサン/γ-アミノプロピルメチルシロキサン共重合体等のオキサゾリン変性シリコーン、ポリビニルアセタールジエチルアミノアセテート、ツエイン等を用いることが好ましい。
成分(b)の揮発性物質は、より好ましくはエタノール、イソプロピルアルコール及びn-ブチルアルコールから選ばれる1種又は2種以上であり、さらに好ましくはエタノール及びイソプロピルアルコールから選ばれる1種又は2種以上であり、よりさらに好ましくはエタノールである。
(1)マイティバイアル No.4(株式会社マルエム製)に評価する油剤等を8.8g加える。
(2)(1)のバイアルに特定の成分(a)被膜形成能を有するポリマーを1.2g加え、スパチュラでかき混ぜ、ポリマーを油剤中に良く分散させ、マイティバイアルに蓋をする。尚、ポリマーが紛体状の場合は、そのまま評価に用いる。ポリマーが溶液状の場合は、溶媒を除去してポリマーを析出させた後、3mm×3mm×3mm以下の微小片に切断して評価に用いる。ポリマーを析出させた時点で3mm×3mm×3mm以下の微小片となっている場合には、そのまま評価に用いる。ポリマーがフィルム状の場合は、3mm×3mm×3mm以下の微小片に切断して評価に用いる。
(3)(2)のバイアルをミックスローター(MVR-3R(アズワン株式会社製))を用いて100r/min.の回転速度で、1週間回転攪拌する。(室温:25℃)
(4)(3)のバイアルを25℃で2時間、静置し、状態を目視観察する。
・可塑性能有り:ポリマーが油剤等に完全に溶解している(透明な1相の溶液)、又はポリマーと油剤等が混和してゲル状である。ただし、油剤等の一部が分離(ポリマー+油剤相と油剤相)している場合は、ポリマー+油剤相がゲル状である。(評価前のポリマーの形状を維持していない。)
・可塑性能無し:静置後にポリマーが沈降し、振り混ぜるとポリマーが再分散する。さらに静置するとポリマーが再沈降する。ポリマーの溶解やゲル化は起こらない。(評価前のポリマーの形状を維持している。)
これらのエステル油のうち、優れた耐皮脂性を有する被膜を得る観点から、テトラエチルヘキサン酸ペンタエリスリチル、ジイソステアリン酸グリセリル、トリエチルヘキサノイン、テトラ(ベヘン酸/安息香酸/エチルヘキサン酸)ペンタエリスリチル、ジペンタエリスリトール脂肪酸エステル、ジ2-ヘプチルウンデカン酸グリセリン、トリオクタン酸グリセリン、トリイソパルミチン酸グリセリン、トリ2-エチルヘキサン酸グリセリン、トリミリスチン酸グリセリン、トリ2-ヘプチルウンデカン酸グリセライド、アセトグリセライド、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、グリセリントリ脂肪酸エステル等のグリセリド類、ラウロイルグルタミン酸ジ(フィトステリル/オクチルドデシル)等のアシルアミノ酸ジエステルから選ばれる1種又は2種以上を用いるのがより好ましい。
これらの炭化水素のうち、優れた耐皮脂性を有する被膜を得る観点から、流動パラフィン、イソドデカン、パラフィンワックス、ワセリンから選ばれる1種又は2種以上を用いるのがより好ましい。
ノズル16は、管路17を介してマイクロギヤポンプ14と連通している。管路17は導電体でもよく、あるいは非導電体でもよい。また、ノズル16は、高電圧電源12と電気的に接続されている。これによって、ノズル16に高電圧を印加することが可能になっている。この場合、ノズル16に人体が直接触れた場合に過大な電流が流れることを防止するために、ノズル16と高電圧電源12とは、電流制限抵抗19を介して電気的に接続されている。
図2に示す実施形態では、ノズルに正の高電圧が印加され、皮膚が負極となる。ノズルと皮膚との間に電界が生じると、ノズル先端部の被膜形成用組成物は、静電誘導によって分極して先端部分がコーン状になり、コーン先端から帯電した被膜形成用組成物の液滴が電界に沿って、皮膚に向かって空中に吐出される。空間に吐出され且つ帯電した被膜形成用組成物から溶媒である成分(b)が蒸発していくと、被膜形成用組成物表面の電荷密度が過剰となり、クーロン反発力によって微細化を繰り返しながら空間をすすみ、皮膚に到達する。この場合、被膜形成用組成物の粘度を適切に調整することで、空間に吐出されている間に、溶媒である揮発性物質を液滴から揮発させ、溶質である被膜形成能を有する成分(a)のポリマーを固化させつつ、電位差によって伸長変形させながら繊維を形成し、その繊維を適用部位に堆積させることもできる。例えば、被膜形成用組成物の粘度を高めると、該組成物を繊維の形態で適用部位に堆積させやすい。これによって、繊維の堆積物からなる多孔性被膜が適用部位の表面に形成される。このような繊維の堆積物からなる多孔性被膜は、ノズルと皮膚との間の距離や、ノズルに印加する電圧を調整することでも形成することが可能である。
本発明の繊維は、連続繊維であることが好ましく、少なくとも繊維の太さの100倍以上の長さを有することが好ましい。例えば、形成された被膜は、成分(a)を含む、好ましくは10μm以上の長さ、より好ましくは50μm以上の長さ、さらに好ましくは100μm以上の長さの繊維を含有することが好ましい。
本明細書においては、繊維の太さの100倍以上の長さを有する繊維のことを「連続繊維」と定義する。繊維の断面形状は好ましくは円形、又は楕円形であり、繊維の太さは円形の場合は直径、楕円形の場合は長径の長さである。そして、静電スプレー法によって製造される被膜は、1本又は2本以上の連続繊維の堆積物からなる多孔性の不連続被膜であることが好ましい。
(a)被膜形成能を有するポリマー
(b)アルコール及びケトンから選ばれる1種以上の揮発性物質
(c)可塑剤
(d)成分(c)以外の、35℃における粘度が50mP・s以上3000mP・s以下である不揮発性油剤3質量%以上15質量%以下
<3>成分(a)の含有量が、1.0質量%以上であることが好ましく、2.0質量%以上であることがより好ましく、4.0質量%以上であることがさらに好ましく、6.0質量%以上であることがよりさらに好ましく、8.0質量%以上であることがよりさらに好ましく、また35質量%以下であることが好ましく、30質量%以下であることがより好ましく、25質量%以下であることがさらに好ましく、20質量%以下であることがよりさらに好ましく、また1.0質量%以上30質量%以下であることが好ましく、2.0質量%以上25質量%以下であることがより好ましく、4.0質量%以上20質量%以下であることがさらに好ましく、6.0質量%以上20質量%以下であることがよりさらに好ましく、また2.0質量%以上35質量%以下であることが好ましく、4.0質量%以上30質量%以下であることがより好ましく、6.0質量%以上30質量%以下であることがさらに好ましく、6.0質量%以上25質量%以下であることがよりさらに好ましく、8.0質量%以上25質量%以下が一層好ましく、8.0質量%以上20質量%以下であることがより一層好ましい<1>又は<2>に記載の被膜形成用組成物。
<4>成分(a)の含有量が、2.0質量%以上25質量%以下である<1>~<3>のいずれかに記載の被膜形成用組成物。
<5>成分(a)の含有量が、6.0質量%以上30質量%以下である<1>~<3>のいずれかに記載の被膜形成用組成物。
<6>成分(b)は、その蒸気圧が20℃において0.01kPa以上、106.66kPa以下であることが好ましく、0.13kPa以上、66.66kPa以下であることがより好ましく、0.67kPa以上、40.00kPa以下であることがさらに好ましく、1.33kPa以上、40.00kPa以下であることがよりさらに好ましく、2.40kPa以上、40.00kPa以下であることが一層好ましい<1>~<5>のいずれかに記載の被膜形成用組成物。
<7>成分(b)のアルコールは、一価の鎖式脂肪族アルコール、一価の環式脂肪族アルコール及び一価の芳香族アルコールから選ばれる1種又は2種以上が好ましく、炭素数が1~6の鎖状で直鎖または分岐鎖を有する一価の鎖式脂肪族アルコール、炭素数が4~6の一価の環式脂肪族アルコール、ベンジルアルコール及びフェニルエチルアルコールから選ばれる1種又は2種以上が好ましく、さらにエタノール、イソプロピルアルコール、n-ブチルアルコール、フェニルエチルアルコール、n-プロパノール及びn-ペンタノールから選ばれる1種又は2種以上が好ましい<1>~<6>のいずれかに記載の被膜形成用組成物。
<8>成分(b)のケトンが、炭素数が1~4のアルキル基を2つ有するケトンが好ましく、さらにアセトン、メチルエチルケトン及びメチルイソブチルケトンから選ばれる1種又は2種以上が好ましい<1>~<7>のいずれかに記載の被膜形成用組成物。
<9>成分(b)が、好ましくはエタノール、イソプロピルアルコール及びn-ブチルアルコールから選ばれる1種又は2種以上であり、より好ましくはエタノール及びイソプロピルアルコールから選ばれる1種又は2種以上であり、さらに好ましくはエタノールである<1>~<8>のいずれかに記載の被膜形成用組成物。
<10>成分(b)の含有量が、45質量%以上であることが好ましく、50質量%以上であることがより好ましく、55質量%以上であることがさらに好ましく、60質量%以上であることがよりさらに好ましく、また98.8質量%以下であることが好ましく、98質量%以下であることがより好ましく、97質量%以下であることがさらに好ましく、96質量%以下であることがよりさらに好ましく、94質量%以下であることが一層好ましく、91質量%以下であることがより一層好ましく、88.5質量%以下であることがさらに一層好ましく、また50質量%以上98.8質量%以下であることが好ましく、50質量%以上98質量%以下であることがより好ましく、55質量%以上96質量%以下であることがさらに好ましく、60質量%以上94質量%以下であることがよりさらに好ましく、また、45質量%以上97質量%以下であることが好ましく、50質量%以上94質量%以下であることがより好ましく、50質量%以上91質量%以下であることがさらに好ましく、50質量%以上88.5質量%以下であることがよりさらに好ましい<1>~<9>のいずれかに記載の被膜形成用組成物。
<11>成分(b)の含有量が、50質量%以上98質量%以下である<1>~<10>のいずれかに記載の被膜形成用組成物。
<12>成分(b)の含有量が、50質量%以上91質量%以下である<1>~<10>のいずれかに記載の被膜形成用組成物。
<13>成分(c)が、ポリオール、ポリオキシアルキレングリコール、ポリオキシアルキレンアルキルエーテル、エステル油、シリコーン油、炭化水素油、液体油脂、固体油脂、高級アルコール及びノニオン界面活性剤から選ばれる1種又は2種以上である<1>~<12>のいずれかに記載の被膜形成用組成物。
<14>成分(c)が、被膜形成能を有するポリマーの構造中の水酸基、エステル、アセタール部分と相互作用しやすい化合物であり、好ましくはポリオール、ポリオキシアルキレングリコール、ポリオキシアルキレンアルキルエーテル、特定のエステル油、特定のシリコーン油及びノニオン界面活性剤から選ばれる1種又は2種以上であり、より好ましくはポリオール、ポリオキシアルキレングリコール、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、リンゴ酸ジエステル、N-アシルアミノ酸エステル、メトキシケイヒ酸エチルヘキシル、及び安息香酸アルキルから選ばれる1種又は2種以上である<1>~<13>のいずれかに記載の被膜形成用組成物。
<15>成分(c)の含有量が、0.10質量%以上であることが好ましく、0.50質量%以上であることがより好ましく、1.0質量%以上であることがさらに好ましく、1.5質量%以上であることがよりさらに好ましく、また30質量%以下であることが好ましく、25質量%以下であることがより好ましく、20質量%以下であることがさらに好ましく、15質量%以下であることがよりさらに好ましく、また0.10質量%以上30質量%以下であることが好ましく、0.50質量%以上25質量%以下であることがより好ましく、1.0質量%以上20質量%以下であることがさらに好ましく、1.0質量%以上15質量%以下であることがよりさらに好ましく、また0.50質量%以上30質量%以下であることが好ましく、1.0質量%以上25質量%以下であることがより好ましく、1.0質量%以上20質量%以下であることがさらに好ましく、1.5質量%以上15質量%以下であることがよりさらに好ましい<1>~<14>のいずれかに記載の被膜形成用組成物。
<16>成分(c)の含有量が、0.50質量%以上25質量%以下である<1>~<15>のいずれかに記載の被膜形成用組成物。
<17>成分(c)の含有量が、1.0質量%以上20質量%以下である<1>~<15>のいずれかに記載の被膜形成用組成物。
<18>成分(d)の35℃における好ましい粘度が100mP・s以上2800mP・s以下であり、より好ましくは150mP・s以上2500mP・s以下であり、さらに好ましくは200mP・s以上2000mP・s以下である<1>~<17>のいずれかに記載の被膜形成用組成物。
<19>成分(d)が、エステル油及び炭化水素油から選ばれる1種又は2種以上である<1>~<18>のいずれかに記載の被膜形成用組成物。
<20>成分(d)が、テトラエチルヘキサン酸ペンタエリスリチル、ジイソステアリン酸グリセリル、トリエチルヘキサノイン、テトラ(ベヘン酸/安息香酸/エチルヘキサン酸)ペンタエリスリチル、ジペンタエリスリトール脂肪酸エステル、ジ2-ヘプチルウンデカン酸グリセリン、トリオクタン酸グリセリン、トリイソパルミチン酸グリセリン、トリ2-エチルヘキサン酸グリセリン、トリミリスチン酸グリセリン、トリ2-ヘプチルウンデカン酸グリセライド、アセトグリセライド、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、グリセリントリ脂肪酸エステル等のグリセリド類、ラウロイルグルタミン酸ジ(フィトステリル/オクチルドデシル)等のアシルアミノ酸ジエステル、ジカプリン酸ネオペンチルグリコール、流動パラフィン、イソドデカン、パラフィンワックス、ワセリンから選ばれる1種又は2種以上の不揮発性油剤である<1>~<19>のいずれかに記載の被膜形成用組成物。
<21>成分(d)の含有量が、好ましくは3質量%以上15質量%以下であり、より好ましくは3.5質量%以上15質量%以下であり、さらに好ましくは4質量%以上15質量%以下であり、さらにより好ましくは5質量%以上15質量%以下である<1>~<20>のいずれかに記載の被膜形成用組成物。
<22>成分(c)に対する成分(a)の含有質量比((a)/(c))が、0.033以上であることが好ましく、0.10以上であることがより好ましく、0.20以上であることがさらに好ましく、0.40以上であることがよりさらに好ましく、0.80以上であることが一層好ましく、1.0以上であることがより一層好ましく、1.5以上であることがさらに一層好ましく、また300以下であることが好ましく、60以下であることがより好ましく、30以下であることがさらに好ましく、20以下であることがよりさらに好ましく、15以下であることが一層好ましく、10以下であることがより一層好ましく、8.0以下であることがさらに一層好ましく、また0.033以上300以下であることが好ましく、0.10以上60以下であることがより好ましく、0.20以上30以下であることがさらに好ましく、0.40以上10以下であることがよりさらに好ましく、1.0以上10以下であることが一層好ましく、また0.80以上20以下であることが好ましく、1.0以上15以下であることがより好ましく、1.0以上10以下であることがさらに好ましく、1.5以上8.0以下であることがよりさらに好ましい<1>~<21>のいずれかに記載の被膜形成用組成物。
<23>成分(c)に対する成分(a)の含有質量比((a)/(c))が、0.2以上30以下である<1>~<22>のいずれかに記載の被膜形成用組成物。
<24>成分(c)に対する成分(a)の含有質量比((a)/(c))が、1.0以上10以下である<1>~<22>のいずれかに記載の被膜形成用組成物。
<25>成分(d)に対する成分(c)の含有質量比((c)/(d))が、0.0033以上であることが好ましく、0.0050以上であることがより好ましく、0.0066以上であることがさらに好ましく、0.01以上であることがよりさらに好ましく、0.03以上であることが一層好ましく、0.05以上であることがより一層好ましく、0.066以上であることがさらに一層好ましく、0.1以上であることがさらにより一層好ましく、0.2以上であることがさらにより一層好ましく、30以下であることが好ましく、25以下であることがより好ましく、20以下であることがさらに好ましく、15以下であることがよりさらに好ましく、10以下であることが一層好ましく、7.0以下であることがより一層好ましく、5以下であることがさらに一層好ましく、3以下であることがさらにより一層好ましく、0.0033以上30以下であることが好ましく、0.0050以上25以下であることがより好ましく、0.0066以上20以下であることがさらに好ましく、0.01以上15以下であることがよりさらに好ましく、0.03以上10以下であることが好ましく、0.05以上7.0以下であることがより好ましく、0.066以上5以下であることがさらに好ましく、0.10以上5以下であることがよりさらに好ましく、0.2以上3以下であることがさらにより一層好ましい<1>~<24>のいずれかに記載の被膜形成用組成物。
<26>成分(d)に対する成分(c)の含有質量比((c)/(d))が、0.03以上10以下である<1>~<25>のいずれかに記載の被膜形成用組成物。
<27>成分(d)に対する成分(c)の含有質量比((c)/(d))が、0.2以上3以下である<1>~<25>のいずれかに記載の被膜形成用組成物。
<28>成分(b)に対する成分(a)の含有質量比((a)/(b))が、0.010以上であることが好ましく、0.060以上であることがより好ましく、0.080以上であることがさらに好ましく、0.10以上であることがよりさらに好ましく、0.11以上であることが一層好ましく、0.12以上であることがより一層好ましく、また0.60以下であることが好ましく、0.45以下であることがより好ましく、0.35以下であることがさらに好ましく、0.33以下であることがよりさらに好ましく、0.30以下であることが一層好ましく、0.25以下であることがより一層好ましく、0.20以下であることがよりさらに一層好ましく、0.18以下であることがよりさらに一層好ましく、また0.010以上0.60以下であることが好ましく、0.060以上0.33以下であることがより好ましく、0.10以上0.25以下であることがさらに好ましく、0.11以上0.20以下であることがよりさらに好ましく、0.12以上0.18以下であることが一層好ましく、また0.060以上0.45以下であることが好ましく、0.080以上0.35以下であることがより好ましく、0.10以上0.33以下であることがさらに好ましく、0.11以上0.30以下であることがよりさらに好ましく、0.12以上0.25以下であることが一層好ましい<1>~<27>のいずれかに記載の被膜形成用組成物。
<29>成分(b)に対する成分(a)の含有質量比((a)/(b))が、0.10以上0.25以下である<1>~<28>のいずれかに記載の被膜形成用組成物。
<30>成分(b)に対する成分(a)の含有質量比((a)/(b))が、0.11以上0.30以下である<1>~<28>のいずれかに記載の被膜形成用組成物。
<31>成分(d)に対する成分(a)の含有質量比((a)/(d))が、0.0033以上であることが好ましく、0.005以上であることがより好ましく、0.0066以上であることがさらに好ましく、0.01以上であることがよりさらに好ましく、0.02以上であることが一層好ましく、0.03以上であることがより一層好ましく、0.066以上であることがより一層好ましく、0.1以上であることがより一層好ましく、0.3以上であることがより一層好ましく、0.5以上であることがより一層好ましく、0.8以上であることがより一層好ましく、30以下であることが好ましく、25以下であることがより好ましく、20以下であることがさらに好ましく、15以下であることがよりさらに好ましく、13以下であることが一層好ましく、10以下であることがより一層好ましく、8.0以下であることがさらに一層好ましく、0.0033以上30以下であることが好ましく、0.005以上25以下であることがより好ましく、0.0066以上20以下であることがさらに好ましく、0.01以上15以下であることがよりさらに好ましく、0.02以上13以下であることが一層好ましく、0.03以上10以下であることが好ましく、0.066以上10以下であることがより好ましく、0.10以上8.0以下であることがさらに好ましく、0.30以上8.0以下であることがよりさらに好ましく、0.50以上8.0以下であることがよりさらに好ましく、0.80以上8.0以下であることがよりさらに好ましい<1>~<30>のいずれかに記載の被膜形成用組成物。
<32>成分(d)に対する成分(a)の含有質量比((a)/(d))が、0.02以上13以下である<1>~<31>のいずれかに記載の被膜形成用組成物。
<33>成分(d)に対する成分(a)の含有質量比((a)/(d))が、0.80以上8.0以下である<1>~<31>のいずれかに記載の被膜形成用組成物。
<34>導電率制御剤、成分(c)及び(d)以外の油剤、着色顔料、体質顔料、染料、香料、忌避剤、酸化防止剤、安定剤、防腐剤、各種ビタミン及び水から選ばれる成分を含有する<1>~<33>のいずれかに記載の被膜形成用組成物。
<35>導電率制御剤が、25℃において被膜形成用組成物の導電率を10μS/cm以上300μS/cm以下とする成分が好ましい<34>に記載の被膜形成用組成物。
<36>導電率制御剤は、好ましくはアルカリ金属塩又はアンモニウム塩であり、より好ましくはイオン性界面活性剤であり、さらに好ましくはカチオン性界面活性剤及びアニオン性界面活性剤から選ばれる1種又は2種以上である<34>又は<35>に記載の被膜形成用組成物。
<37>導電率制御剤が、第4級アンモニウム塩及びアシルアミノ酸塩から選ばれる1種又は2種以上である<34>~<36>のいずれかに記載の被膜形成用組成物。
<38>導電率制御剤の含有量が0.010質量%以上であることが好ましく、0.050質量%以上であることがより好ましく、0.10質量%以上であることがさらに好ましく、また10質量%以下であることが好ましく、8.0質量%以下であることがより好ましく、6.0質量%以下であることがさらに好ましく、2.5質量%以下であることがよりさらに好まく、2.0質量%以下であることが一層好ましく、また0.010質量%以上10質量%以下であることが好ましく、0.050質量%以上8.0質量%以下であることがより好ましく、0.10質量%以上6.0質量%以下であることがさらに好ましく、0.10質量%以上2.5質量%以下であることがよりさらに好ましく、0.10質量%以上2.0質量%以下であることが一層好ましい<34>~<37>のいずれかに記載の被膜形成用組成物。
<39>被膜形成用組成物の粘度が、25℃で2mPa・s以上であることが好ましく、5mPa・s以上であることがより好ましく、10mPa・s以上であることがさらに好ましく、30mPa・s以上であることがよりさらに好ましく、50mPa・s以上が一層好ましく、80mPa・s以上がより一層好ましく、また3000mPa・s以下であることが好ましく、2000mPa・s以下であることがより好ましく、1500mPa・s以下であることがさらに好ましく、1000mPa・s以下であることがよりさらに好ましく、800mPa・s以下であることが一層好ましく、500mPa・s以下であることがより一層好ましく、また2mPa・s以上3000mPa・s以下であることが好ましく、5mPa・s以上2000mPa・s以下であることがより好ましく、10mPa・s以上1500mPa・s以下であることがさらに好ましく、30mPa・s以上1000mPa・s以下であることがよりさらに好ましく、50mPa・s以上800mPa・s以下であることが一層好ましく、80mPa・s以上500mPa・s以下がより一層好ましい<1>~<38>のいずれかに記載の被膜形成用組成物。
<40>静電スプレーにより直接皮膚上に繊維で形成された被膜を形成するための組成物である<1>~<39>のいずれかに記載の被膜形成用組成物。
<41>次の成分(a)、(b)、(c)及び(d)を含有する組成物を静電スプレーすることにより得られる皮膚用シート状組成物。
(a)被膜形成能を有するポリマー
(b)アルコール及びケトンから選ばれる1種以上の揮発性物質
(c)可塑剤
(d)成分(c)以外の、35℃における粘度が50mP・s以上3000mP・s以下である不揮発性油剤3質量%以上15質量%以下
<42>成分(d)が、テトラエチルヘキサン酸ペンタエリスリチル、ジイソステアリン酸グリセリル、トリエチルヘキサノイン、テトラ(ベヘン酸/安息香酸/エチルヘキサン酸)ペンタエリスリチル、ジペンタエリスリトール脂肪酸エステル、ジ2-ヘプチルウンデカン酸グリセリン、トリオクタン酸グリセリン、トリイソパルミチン酸グリセリン、トリ2-エチルヘキサン酸グリセリン、トリミリスチン酸グリセリン、トリ2-ヘプチルウンデカン酸グリセライド、アセトグリセライド、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、グリセリントリ脂肪酸エステル、ラウロイルグルタミン酸ジ(フィトステリル/オクチルドデシル)、ジカプリン酸ネオペンチルグリコール、流動パラフィン、イソドデカン、パラフィンワックス、及びワセリンから選ばれる1種又は2種以上の不揮発性油剤である<41>に記載の皮膚用シート状組成物。
<43>(c)可塑剤が、ポリオール、ポリオキシアルキレングリコール、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、リンゴ酸ジエステル、N-アシルアミノ酸エステル、メトキシケイヒ酸エチルヘキシル、及び安息香酸アルキルから選ばれる1種又は2種以上である、<41>又は<42>に記載の皮膚用シート状組成物。
〔実施例1~7、比較例1~4〕
(1)被膜形成用組成物の調製
被膜形成用組成物の成分(a)としてポリビニルブチラール(積水化学株式会社製:商品名;S-Lec B BM-1)を用い、成分(b)として99度合成アルコール(日本合成アルコール株式会社製)を用いた。また、成分(c)としてポリエチレングリコール(平均分子量400)、成分(d)として(d1)ジカプリン酸ネオペンチルグリコールと(d2)ジペンタエリトリット脂肪酸エステル(融点50℃)とを混合して、35℃における粘度を調整して用いた。なお、表1及び2に示す各成分の含有量は、有効量であり、単位は質量%である。
図1に示す構成を有し、図2に示す外観を有する静電スプレー装置10を用い、5x10cmのアルミ箔から3x8cm部分を切り抜いた穴の部分(枠部分)に、前記被膜形成用組成物を30秒間静電スプレーして繊維で形成された被膜を形成した。ポリマー量は、6.6mg(0.275mg/cm2)であった。
アルミ箔枠内に形成された繊維で形成された被膜上に皮脂モデルとしてオレイン酸(富士フイルム和光純薬株式会社製:和光一級)を10μL滴下して、被膜に穴があくまでの時間を計測した。
結果を表1及び表2に示す。
(b)エタノール(日本合成アルコール株式会社製:99度合成アルコール)
(c)ポリエチレングリコール(三洋化成工業株式会社製:PEG-400(-G))
(d1))ジカプリン酸ネオペンチルグリコール(日清オイリオグループ株式会社製:エステモール N-01)
(d2)ジペンタエリトリット脂肪酸エステル(日清オイリオグループ株式会社製:コスモール168EV)
揮発性シリコーン油(信越化学工業株式会社製:KF-96L-2CS(-G))
なお、表1及び表2の実施例の被膜形成用組成物を、皮膚上に直接静電スプレーして繊維からなる被膜を形成し、当該被膜の密着性及び耐擦過性を評価した結果、いずれの被膜も優れた密着性、耐擦過性を有していた。
〔実施例8~11〕
(1)被膜形成用組成物の調製
被膜形成用組成物の成分(a)としてポリビニルブチラールを用い、成分(b)として99度合成アルコール(日本合成アルコール株式会社製)を用いた。また、成分(c)としてポリエチレングリコール(平均分子量400)、グリセリン、PEG/PPG/ポリブチレングリコール-8/5/3グリセリン、1,3-ブチレングリコール、又はメトキシケイヒ酸エチルヘキシル、成分(d)として、ジカプリン酸ネオペンチルグリコール、ジペンタエリトリット脂肪酸エステル(融点50℃)、イソノナン酸イソノニル、又はイソドデカンと、パルミチン酸デキストリンとを混合して、35℃における粘度を調整して用いた。なお、表3に示す各成分の含有量は、有効量であり、単位は質量%である。
図1に示す構成を有し、図2に示す外観を有する静電スプレー装置10を用い、5x10cmのアルミ箔から3x8cm部分を切り抜いた穴の部分(枠部分)に、前記被膜形成用組成物を30秒間静電スプレーして繊維で形成された被膜を形成した。ポリマー量は、6.6mg(0.275mg/cm2)であった。
アルミ箔枠内に形成された繊維で形成された被膜上に皮脂モデルとしてオレイン酸(富士フイルム和光純薬株式会社製:和光一級)を10μL滴下して、被膜に穴があくまでの時間を計測した。
結果を表3に示す。
*2:Wilbride S-753(日油株式会社製)
*3:KF-96L-2CS(-G)(信越化学工業株式会社製)
*4:エステモール N-01(日清オイリオグループ株式会社製)
*5:コスモール168EV(日清オイリオグループ株式会社製)
*6:マルカゾールR(丸善石油化学株式会社製)
*7:99度合成アルコール(日本合成アルコール株式会社製)
11 低電圧電源
12 高電圧電源
13 補助的電気回路
14 マイクロギヤポンプ
15 容器
16 ノズル
17 管路
18 フレキシブル管路
19 電流制限抵抗
20 筐体
Claims (14)
- 次の成分(a)、(b)、(c)及び(d)を含有する被膜形成用組成物。
(a)被膜形成能を有するポリマー
(b)アルコール及びケトンから選ばれる1種以上の揮発性物質
(c)可塑剤
(d)成分(c)以外の、35℃における粘度が50mP・s以上3000mP・s以下である不揮発性油剤3質量%以上15質量%以下 - 成分(d)が、成分(c)以外のエステル油、シリコーン油、炭化水素油、液体油脂、固体油脂及び高級アルコールから選ばれる1種又は2種以上の不揮発性油剤を含む油性成分である請求項1に記載の被膜形成用組成物。
- 成分(d)の35℃における粘度が100mP・s以上3000mP・s以下である請求項1又は2に記載の被膜形成用組成物。
- 成分(d)の含有量が3.5質量%以上15質量%以下である請求項1~3のいずれか1項に記載の被膜形成用組成物。
- 成分(d)に対する成分(c)の含有質量比((c)/(d))が、0.03以上10以下である請求項1~4のいずれか1項に記載の被膜形成用組成物。
- 成分(d)に対する成分(c)の含有質量比((c)/(d))が、0.2以上3以下である請求項1~5のいずれか1項に記載の被膜形成用組成物。
- 成分(d)に対する成分(a)の含有質量比((a)/(d))が、0.02以上13以下である請求項1~6のいずれか1項に記載の被膜形成用組成物。
- 成分(d)に対する成分(a)の含有質量比((a)/(d))が、0.8以上8.0以下である請求項1~7のいずれか1項に記載の被膜形成用組成物。
- 成分(d)が、テトラエチルヘキサン酸ペンタエリスリチル、ジイソステアリン酸グリセリル、トリエチルヘキサノイン、テトラ(ベヘン酸/安息香酸/エチルヘキサン酸)ペンタエリスリチル、ジペンタエリスリトール脂肪酸エステル、ジ2-ヘプチルウンデカン酸グリセリン、トリオクタン酸グリセリン、トリイソパルミチン酸グリセリン、トリ2-エチルヘキサン酸グリセリン、トリミリスチン酸グリセリン、トリ2-ヘプチルウンデカン酸グリセライド、アセトグリセライド、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、グリセリントリ脂肪酸エステル、ラウロイルグルタミン酸ジ(フィトステリル/オクチルドデシル)、ジカプリン酸ネオペンチルグリコール、流動パラフィン、イソドデカン、パラフィンワックス、及びワセリンから選ばれる1種又は2種以上の不揮発性油剤である請求項1~8のいずれか1項に記載の被膜形成用組成物。
- (c)可塑剤が、ポリオール、ポリオキシアルキレングリコール、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、リンゴ酸ジエステル、N-アシルアミノ酸エステル、メトキシケイヒ酸エチルヘキシル、及び安息香酸アルキルから選ばれる1種又は2種以上である、請求項1~9のいずれか1項に記載の被膜形成用組成物。
- 静電スプレーにより直接皮膚上に繊維で形成された被膜を形成するための組成物である請求項1~10のいずれか1項に記載の被膜形成用組成物。
- 次の成分(a)、(b)、(c)及び(d)を含有する組成物を静電スプレーすることにより得られる皮膚用シート状組成物。
(a)被膜形成能を有するポリマー
(b)アルコール及びケトンから選ばれる1種以上の揮発性物質
(c)可塑剤
(d)成分(c)以外の、35℃における粘度が50mP・s以上3000mP・s以下である不揮発性油剤3質量%以上15質量%以下 - 成分(d)が、テトラエチルヘキサン酸ペンタエリスリチル、ジイソステアリン酸グリセリル、トリエチルヘキサノイン、テトラ(ベヘン酸/安息香酸/エチルヘキサン酸)ペンタエリスリチル、ジペンタエリスリトール脂肪酸エステル、ジ2-ヘプチルウンデカン酸グリセリン、トリオクタン酸グリセリン、トリイソパルミチン酸グリセリン、トリ2-エチルヘキサン酸グリセリン、トリミリスチン酸グリセリン、トリ2-ヘプチルウンデカン酸グリセライド、アセトグリセライド、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、グリセリントリ脂肪酸エステル、ラウロイルグルタミン酸ジ(フィトステリル/オクチルドデシル)、ジカプリン酸ネオペンチルグリコール、流動パラフィン、イソドデカン、パラフィンワックス、及びワセリンから選ばれる1種又は2種以上の不揮発性油剤である請求項12に記載の皮膚用シート状組成物。
- (c)可塑剤が、ポリオール、ポリオキシアルキレングリコール、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、リンゴ酸ジエステル、N-アシルアミノ酸エステル、メトキシケイヒ酸エチルヘキシル、及び安息香酸アルキルから選ばれる1種又は2種以上である、請求項12又は13に記載の皮膚用シート状組成物。
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| EP21903484.0A EP4260911A4 (en) | 2020-12-11 | 2021-12-10 | COMPOSITION INTENDED TO FORM A COATING |
| US18/256,584 US20240033204A1 (en) | 2020-12-11 | 2021-12-10 | Composition for forming coating |
| CN202180083203.XA CN116615179A (zh) | 2020-12-11 | 2021-12-10 | 覆膜形成用组合物 |
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| EP (1) | EP4260911A4 (ja) |
| JP (1) | JP2022093312A (ja) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003507165A (ja) | 1999-08-18 | 2003-02-25 | ザ、プロクター、エンド、ギャンブル、カンパニー | 手持ち式静電スプレー装置用の使い捨てカートリッジ |
| JP2006104211A (ja) | 1999-08-18 | 2006-04-20 | Procter & Gamble Co | 皮膚の処理方法 |
| WO2018194130A1 (ja) * | 2017-04-19 | 2018-10-25 | 花王株式会社 | 被膜形成用組成物 |
| JP2018177797A (ja) | 2017-04-18 | 2018-11-15 | 花王株式会社 | 化粧被膜の製造方法 |
| JP2020063226A (ja) | 2018-02-08 | 2020-04-23 | 花王株式会社 | 被膜形成用組成物 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5690779B2 (ja) * | 2012-07-10 | 2015-03-25 | 株式会社 資生堂 | 油中水型乳化化粧料 |
| CN110121391B (zh) * | 2016-12-28 | 2022-05-03 | 花王株式会社 | 覆膜的制造方法 |
| JP6903794B2 (ja) * | 2019-05-31 | 2021-07-14 | 花王株式会社 | 皮膜形成組成物 |
-
2021
- 2021-12-10 WO PCT/JP2021/045450 patent/WO2022124388A1/ja not_active Ceased
- 2021-12-10 CN CN202180083203.XA patent/CN116615179A/zh active Pending
- 2021-12-10 US US18/256,584 patent/US20240033204A1/en active Pending
- 2021-12-10 EP EP21903484.0A patent/EP4260911A4/en active Pending
- 2021-12-10 JP JP2021200557A patent/JP2022093312A/ja active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003507165A (ja) | 1999-08-18 | 2003-02-25 | ザ、プロクター、エンド、ギャンブル、カンパニー | 手持ち式静電スプレー装置用の使い捨てカートリッジ |
| JP2006104211A (ja) | 1999-08-18 | 2006-04-20 | Procter & Gamble Co | 皮膚の処理方法 |
| JP2018177797A (ja) | 2017-04-18 | 2018-11-15 | 花王株式会社 | 化粧被膜の製造方法 |
| WO2018194130A1 (ja) * | 2017-04-19 | 2018-10-25 | 花王株式会社 | 被膜形成用組成物 |
| JP2020063226A (ja) | 2018-02-08 | 2020-04-23 | 花王株式会社 | 被膜形成用組成物 |
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| Title |
|---|
| See also references of EP4260911A4 |
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| US20240033204A1 (en) | 2024-02-01 |
| EP4260911A1 (en) | 2023-10-18 |
| JP2022093312A (ja) | 2022-06-23 |
| CN116615179A (zh) | 2023-08-18 |
| EP4260911A4 (en) | 2025-04-16 |
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