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WO2018194129A1 - Procédé de production d'un film de revêtement - Google Patents

Procédé de production d'un film de revêtement Download PDF

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Publication number
WO2018194129A1
WO2018194129A1 PCT/JP2018/016183 JP2018016183W WO2018194129A1 WO 2018194129 A1 WO2018194129 A1 WO 2018194129A1 JP 2018016183 W JP2018016183 W JP 2018016183W WO 2018194129 A1 WO2018194129 A1 WO 2018194129A1
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WO
WIPO (PCT)
Prior art keywords
component
mass
less
producing
coating film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/016183
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English (en)
Japanese (ja)
Inventor
奈緒美 甘利
健太 向井
智成 岡田
浅見　信之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to CN201880025348.2A priority Critical patent/CN110545786A/zh
Publication of WO2018194129A1 publication Critical patent/WO2018194129A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/16—Arrangements for supplying liquids or other fluent material
    • B05B5/1691—Apparatus to be carried on or by a person or with a container fixed to the discharge device
    • 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
    • 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
    • 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
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • 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
    • 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
    • A61Q19/00—Preparations for care of the skin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • 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
    • A61K2800/805—Corresponding aspects not provided for by any of codes A61K2800/81 - A61K2800/95

Definitions

  • the present invention relates to a method for producing a coating.
  • Patent Document 1 describes a cosmetic sheet in which cosmetics or cosmetic ingredients are held.
  • Patent Documents 2 and 3 describe a method of forming a film by electrostatic spraying.
  • the present inventors have used a water-insoluble polymer as a polymer having a film-forming ability, and in combination with an adhesive polymer, It has been found that the adhesion and friction resistance of the coating when it is directly electrostatic sprayed are significantly improved.
  • the present invention provides a method for producing a film on the skin, which comprises electrostatically spraying a composition containing the component (a), the component (b) and the component (c) directly onto the skin.
  • a composition containing the component (a), the component (b) and the component (c) directly onto the skin comprises electrostatically spraying a composition containing the component (a), the component (b) and the component (c) directly onto the skin.
  • B a water-insoluble polymer having a film-forming ability,
  • FIG. 1 is a schematic view showing the configuration of an electrostatic spray apparatus suitably used in the present invention.
  • FIG. 2 is a schematic diagram illustrating a state where an electrostatic spray method is performed using an electrostatic spray apparatus.
  • the cosmetic sheet described in Patent Document 1 holds cosmetics or cosmetic ingredients, the cosmetics and the like can be used effectively on the skin.
  • the cosmetic sheet described in Patent Document 1 contains cosmetics or the like in a sheet prepared in advance, it easily peels off from the sheet when frictional force is applied during wearing.
  • the fiber of the sheet prepared in advance in addition to cosmetics etc., when stored in a state containing non-volatile oil or polyol such as almond oil, avocado oil, olive oil or the like, the fiber form of the constituent fibers of the sheet is The collapsed sheet form tends to collapse, and the storage stability deteriorates.
  • the skin treatment method by electrostatic spray described in Patent Document 2 is a method of treating skin by electrostatic application of particles that are particulate powder substances. Therefore, since the film is not a fiber deposit, it is difficult to maintain the form of a single film, and the durability is inferior, for example, particles are partially dropped during use, and it is difficult to peel off after use.
  • the method of forming a coating by electrostatic spray described in Patent Document 3 can be handled as a single film because the formed coating is a fiber deposit, and is easy to peel off after use.
  • the adhesion between the film formed by electrostatic spraying and the substrate is not sufficient, and the film may be damaged or peeled due to external force such as friction.
  • the present invention relates to a method for producing a highly adhesive coating film that is difficult to be damaged or peeled off by an external force such as friction.
  • the adhesion between the skin and the film formed by electrostatic spraying becomes high, and even if the film is rubbed, it becomes difficult to peel off and the friction resistance can be improved.
  • the production method of the present invention is a method for producing a film that forms a film on the surface of the skin.
  • a composition containing predetermined components is applied directly to the skin to form a film.
  • an electrostatic spray method is employed as a method for forming a coating film.
  • the electrostatic spray method is a method in which a positive or negative high voltage is applied to the composition to charge the composition, and the charged composition is sprayed toward the skin.
  • the sprayed composition spreads into the space while being repeatedly miniaturized by Coulomb repulsion, and forms a film on the surface of the skin by drying the solvent, which is a volatile substance, in the process or after adhering to the skin .
  • composition used in the present invention is a liquid in an environment where an electrostatic spray method is performed.
  • This composition contains the following component (a), component (b), and component (c).
  • each component will be described.
  • the volatile substance of component (a) is a substance that is volatile in the liquid state.
  • the component (a) is discharged from the tip of the nozzle toward the skin after the spray composition placed in an electric field is sufficiently charged, and the component (a) evaporates.
  • the charge density of the spray composition becomes excessive, and the component (a) further evaporates while being further refined by 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. It is still more preferably 67 kPa or more and 40.00 kPa or less, and further preferably 1.33 kPa or more and 40.00 kPa or less.
  • a monovalent chain aliphatic alcohol for example, a monovalent chain aliphatic alcohol, a monovalent cyclic aliphatic alcohol, or a monovalent aromatic alcohol is preferably used.
  • monovalent chain aliphatic alcohols include C 1 -C 6 alcohols
  • examples of monovalent cyclic alcohols include C 4 -C 6 cyclic alcohols
  • examples of monovalent aromatic alcohols include benzyl alcohol and phenylethyl alcohol.
  • ketone examples include di-C 1 -C 4 alkyl ketones 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 component (a) is more preferably one or more selected from ethanol, isopropyl alcohol, and butyl alcohol, more preferably one or more selected from ethanol and butyl alcohol. Yes, more preferably it contains ethanol.
  • the content of the component (a) in the spray composition is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. Moreover, it is preferable that it is 98 mass% or less, it is still more preferable that it is 96 mass% or less, and it is still more preferable that it is 94 mass% or less.
  • the content of the component (a) in the spray composition is preferably 50% by mass to 98% by mass, more preferably 55% by mass to 96% by mass, and 60% by mass to 94% by mass. More preferably, it is as follows. By containing the component (a) in the spray composition at this ratio, the spray composition can be sufficiently volatilized when the electrostatic spray method is performed.
  • ethanol is preferably 50% by mass or more, more preferably 65% by mass or more, and still more preferably 80% by mass or more based on the total amount of the volatile substance of component (a). Moreover, it is preferable that it is 100 mass% or less. Ethanol is preferably 50% by mass or more and 100% by mass or less, more preferably 65% by mass or more and 100% by mass or less, and more preferably 80% by mass or more and 100% by mass or less with respect to the total amount of the volatile substance of component (a). More preferably, it is at most mass%.
  • the water-insoluble polymer having a film-forming ability as the component (b) is generally a substance that can be dissolved in the volatile substance of the component (a).
  • dissolution means that the dispersion is in a dispersed state at 20 ° C., and the dispersed state is a visually uniform state, preferably a visually transparent or translucent state.
  • water-insoluble polymer having film-forming ability an appropriate one is used according to the nature of the volatile substance of component (a).
  • the “water-soluble polymer” means that 1 g of a polymer is weighed in an environment of 1 atm and 23 ° C. and then immersed in 10 g of ion-exchanged water. The thing which has the property which 5g or more melt
  • water-insoluble polymer means that 1 g of a polymer is weighed in an environment of 1 atm and 23 ° C. and then immersed in 10 g of ion-exchanged water. .5g or more is a property that does not dissolve, that is, a property that the dissolution amount is less than 0.5g.
  • water-insoluble polymer having film-forming ability examples include, for example, completely saponified polyvinyl alcohol (saponification degree: 98 mol% or more) that can be insolubilized after film formation, partially saponified polyvinyl alcohol that can be crosslinked after film formation by using in combination with a crosslinking agent ( Saponification degree 60 mol% or more and 98 mol% or less), polyvinyl acetal diethylaminoacetate, twein (main component of corn protein), polyester, polylactic acid (PLA), polyacrylonitrile resin, polystyrene resin, polyvinyl butyral resin, polyurethane resin, polyethylene terephthalate resin, Examples include polybutylene terephthalate resin, polyamide resin, polyimide resin, and polyamideimide resin.
  • saponification degree 60 mol% or more and 98 mol% or less partially saponified polyvinyl alcohol that can be crosslinked after film formation by using in combination with a crosslinking agent (
  • water-insoluble polymers can be used alone or in combination of two or more.
  • fully saponified polyvinyl alcohol (saponification degree: 98 mol% or more) that can be insolubilized after film formation
  • partially saponified polyvinyl alcohol (saponification degree: 60 mol% or more and 98 mol%) that can be crosslinked after film formation by using in combination with a crosslinking agent. % Or less)
  • polyvinyl butyral resin, polyurethane resin, polyvinyl acetal diethylaminoacetate, polylactic acid, twein and the like are preferably used.
  • one or more water-insoluble polymers selected from polyvinyl butyral resins and polyurethane resins are preferred.
  • the content of the component (b) in the spray composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and 5% by mass. It is even more preferable that it is at least%. Further, it is preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
  • the content of the component (b) in the spray composition is preferably 0.5% by mass or more and 45% by mass or less, more preferably 1% by mass or more and 40% by mass or less, and more preferably 2% by mass or more and 30% by mass. More preferably, it is more preferably 5% by mass or more and 25% by mass or less.
  • the ratio ((a) / (b)) of the content of component (a) and component (b) in the spray composition is sufficient to volatilize component (a) when performing electrostatic spraying. From the viewpoint of being able to form a target film, it is preferably from 0.5 to 40, more preferably from 1 to 30, and even more preferably from 2 to 25. Moreover, the ratio ((a) / (b)) of the content of ethanol (a) and component (b) in the spray composition sufficiently volatilizes ethanol (a) when performing the electrostatic spray method. From the viewpoint of being able to form a target film, it is preferably 0.5 or more and 40 or less, more preferably 1 or more and 30 or less, and further preferably 2 or more and 25 or less.
  • the adhesive polymer other than the component (b) contributes to the improvement of the adhesion and the friction resistance of the film formed on the skin by electrostatic spraying.
  • an adhesive polymer what is generally used as an adhesive can be used.
  • a rubber-based adhesive, a silicone-based adhesive, an acrylic-based adhesive, and a urethane-based adhesive can be used, and one or more selected from these can be used.
  • adhesive polymer at least 1 sort (s) selected from a nonionic polymer, an anionic polymer, a cationic polymer, and an amphoteric polymer can be used.
  • the rubber-based adhesive examples include natural rubber; polyisoprene rubber, styrene / butadiene (SB) rubber, styrene / isoprene (SI) rubber, styrene / isoprene / styrene block copolymer (SIS) rubber, styrene / butadiene / Styrene block copolymer (SBS) rubber, Styrene / ethylene / butylene / styrene block copolymer (SEBS) rubber, Styrene / ethylene / propylene / styrene block copolymer (SEPS) rubber, Styrene / ethylene / propylene block copolymer Synthetic rubbers such as coalesced (SEP) rubber, reclaimed rubber, butyl rubber, polyisobutylene, and modified products thereof; Of these rubber-based adhesives, at least one selected from styrene
  • acrylic pressure-sensitive adhesive examples include an acrylic pressure-sensitive adhesive based on an acrylic polymer (homopolymer or copolymer) using one or more (meth) acrylic acid alkyl esters as monomer components.
  • alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, 2-eth
  • silicone-based pressure-sensitive adhesive for example, a silicone-based pressure-sensitive adhesive having a base polymer such as a silicone rubber containing organopolysiloxane or a silicone resin is preferably used.
  • a base polymer such as a silicone rubber containing organopolysiloxane or a silicone resin
  • the base polymer constituting the silicone-based pressure-sensitive adhesive a base polymer obtained by crosslinking the above silicone rubber or silicone resin may be used.
  • the silicone rubber include organopolysiloxane containing dimethylsiloxane as a structural unit.
  • a functional group for example, vinyl group
  • the silicone resin examples include organopolysiloxanes containing at least one constituent unit selected from R 3 SiO 1/2 constituent units, SiO 2 constituent units, RSiO 3/2 constituent units, and R 2 SiO constituent units.
  • the silicone-based pressure-sensitive adhesive may contain a crosslinking agent.
  • the crosslinking agent include a siloxane crosslinking agent and a peroxide crosslinking agent. Any appropriate crosslinking agent may be used as the peroxide-based crosslinking agent.
  • Examples of the peroxide-based crosslinking agent include benzoyl peroxide, t-butyl peroxybenzoate, and dicumyl peroxide.
  • Examples of the siloxane-based crosslinking agent include polyorganohydrogensiloxane.
  • organopolysiloxane the following poly (N-acylalkylenimine) -modified organopolysiloxane (hereinafter also simply referred to as “modified organopolysiloxane”) can be used.
  • the modified organopolysiloxane has the following general formula (1) through an alkylene group containing a hetero atom in at least two silicon atoms of the organopolysiloxane segment constituting the main chain;
  • the imine) segment (B) has a mass ratio (A / B) of 40/60 or more and 98/2 or less, and the weight average molecular weight of the organopolysiloxane segment constituting the main chain is 30,000 or more and 100,000 or less.
  • a modified organopolysiloxane is a mass ratio (A / B) of 40/60 or more and 98/2 or less, and the weight average molecular weight of the organopolysiloxane segment constituting the main chain is 30,000 or more and 100,000 or less.
  • the mass ratio (A / B) between the organopolysiloxane segment (A) of the modified organopolysiloxane and the poly (N-acylalkyleneimine) segment (B) is 40/40 from the viewpoint of improving the friction resistance of the coating. 60 or more is preferable, 55/45 or more is more preferable, and 65/35 or more is more preferable. Further, from the viewpoint of forming the film in a fibrous form, 98/2 or less is preferable, 90/10 or less is more preferable, and 82/18 or less is still more preferable.
  • At least two poly (N-acylalkyleneimine) segments can be bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a hetero atom.
  • it is preferably bonded to one or more silicon atoms excluding both ends via the alkylene group, and more preferably bonded to two or more silicon atoms excluding both ends via the alkylene group.
  • the alkylene group containing a hetero atom intervening in the bond between the organopolysiloxane segment and poly includes 2 to 20 carbon atoms containing 1 to 3 nitrogen atoms, oxygen atoms and / or sulfur atoms.
  • An alkylene group is mentioned. Specific examples thereof include the following.
  • the N-acylalkyleneimine unit constituting the poly (N-acylalkylenimine) segment is represented by the general formula (1).
  • R 1 has 1 to 22 carbon atoms.
  • the alkyl group include linear, branched or cyclic alkyl groups having 1 to 22 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • aralkyl group examples include an aralkyl group having 7 to 15 carbon atoms, and specific examples include a benzyl group, a phenethyl group, a trityl group, a naphthylmethyl group, and an anthracenylmethyl group.
  • aryl group examples include aryl groups having 6 to 14 carbon atoms, and specific examples include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group.
  • the mass ratio (A / B) of the organopolysiloxane segment (A) to the poly (N-acylalkyleneimine) segment (B) in the modified organopolysiloxane is preferably 40/60 or more, more preferably 55/45 or more.
  • 65/35 or more is more preferable, 98/2 or less is preferable, 90/10 or less is more preferable, and 82/18 or less is still more preferable.
  • the mass ratio (A / B) is determined by dissolving 5 mass% of organopolysiloxane in deuterated chloroform and analyzing the alkyl group in the organopolysiloxane segment by nuclear magnetic resonance ( 1 H-NMR) analysis. Or the value calculated
  • the weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is preferably 1,300 or more, more preferably 1,500 or more, Preferably it is 1,800 or more, Preferably it is 32,000 or less, More preferably, it is 10,000 or less, More preferably, it is 5,000 or less.
  • organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments means an organopolysiloxane of a poly (N-acylalkyleneimine) segment as shown in the following formula (2): A portion surrounded by a broken line between two points from a bonding point (bonding point A) to a segment to a bonding point (bonding point B) of a poly (N-acylalkylenimine) segment adjacent thereto, A segment composed of an R 2 SiO unit, one R 6 , and y + 1 R 2 2 SiO units.
  • the “poly (N-acylalkylenimine) segment” refers to —ZR 7 bonded to R 6 .
  • each R 2 independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group
  • R 6 represents an alkylene group containing a hetero atom
  • R 7 represents a residue of a polymerization initiator.
  • -ZR 7 represents a poly (N-acylalkylenimine) segment
  • y represents a positive number.
  • MWg is the molecular weight of the portion surrounded by the broken line in the above general formula (2), but is understood as the mass (g / mol) of the organopolysiloxane segment per mole of the poly (N-acylalkyleneimine) segment.
  • the functional group of the organopolysiloxane that is the raw material compound is 100% substituted with poly (N-acylalkyleneimine), it matches the functional group equivalent (g / mol) of the modified organopolysiloxane.
  • MWg is the value when the functional group is not 100% substituted with poly (N-acylalkylenimine). Even if it exists, it is computable by the following formula
  • MWg [functional group equivalent of organopolysiloxane (g / mol)] ⁇ [substitution rate (%) / 100 (%)]
  • MWg is calculated using the content of organopolysiloxane segment (Csi) constituting the main chain and the molecular weight (MWox) of the poly (N-acylalkyleneimine) segment. Can be obtained by the following equation.
  • the molecular weight (MWox) of the poly (N-acylalkyleneimine) segment can be measured by a method of calculating from the molecular weight of N-acylalkyleneimine units and the degree of polymerization, or a gel permeation chromatography (GPC) measurement method described later. Although it is possible, in the present invention, it means the number average molecular weight measured by the GPC measurement method.
  • the MWox of the modified organopolysiloxane is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, and preferably 5,500 or less, more preferably 3,500 or less, from the viewpoint of excellent friction resistance. More preferably, it is 3,000 or less.
  • the weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is 7,000 or more, preferably 10,000 or more, more preferably 20,000 or more, from the viewpoint of excellent friction resistance. Moreover, it is 120,000 or less, Preferably it is 80,000 or less, More preferably, it is 60,000 or less. Since the organopolysiloxane segment constituting the main chain has a skeleton common to the organopolysiloxane that is the raw material compound, MWsi is substantially the same as the weight average molecular weight of the organopolysiloxane that is the raw material compound. In addition, the weight average molecular weight of organopolysiloxane which is a raw material compound is measured by GPC under the following measurement conditions, and is converted to polystyrene.
  • the weight average molecular weight (MWt) of the modified organopolysiloxane is preferably 10,000 or more, more preferably 12,000 or more, further preferably 24,000 or more, and preferably 2000,000 or less, more preferably It is 150,000 or less, more preferably 120,000 or less, further preferably 92,000 or less, and further preferably 80,000 or less. Thereby, it becomes a film which has sufficient film strength and is excellent in friction resistance.
  • MWt can be determined from the weight average molecular weight of the modified organopolysiloxane that is a raw material compound and the aforementioned mass ratio (A / B).
  • the modified organopolysiloxane can be produced by a known production method such as the method disclosed in JP 2009-024114 A or WO 2011/062210 pamphlet.
  • Examples of the urethane-based pressure-sensitive adhesive include those made of a urethane resin obtained by reacting a polyol and a polyisocyanate compound.
  • Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol.
  • Examples of the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and the like.
  • the nonionic polymer is not particularly limited, and any nonionic polymer that is usually used in the field of cosmetics can be used.
  • the solution may contain one or more nonionic polymers, and may further contain one or more anionic, cationic and / or amphoteric polymers in combination with the nonionic polymer. .
  • nonionic polymers include (meth) acrylic water-soluble nonionic polymers, (meth) acrylic water-insoluble nonionic polymers, polyvinylpyrrolidone, polyacrylamide, low saponified polyvinyl alcohol (saponification degree 60 mol% or less), Neutral polysaccharides and derivatives thereof (such as ethers and esters thereof).
  • Neutral sugars and derivatives thereof include neutral gums (guar gum, hydroxypropyl guar, etc.), cellulose ether (hydroxyethylcellulose (HEC), methylhydroxyethylcellulose (MHEC), ethylhydroxyethylcellulose (EHEC), methylethylhydroxyethylcellulose ( MEHEC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), hydrophobized derivatives thereof (such as HM-EHEC)), starch and derivatives thereof (such as dextrin), and the like.
  • HEC hydroxyethylcellulose
  • MHEC methylhydroxyethylcellulose
  • EHEC ethylhydroxyethylcellulose
  • MEHEC methylethylhydroxyethylcellulose
  • HPMC hydroxypropylmethylcellulose
  • hydrophobized derivatives thereof such as HM-EHEC
  • starch and derivatives thereof such as dextrin
  • nonionic polymers such as the (meth) acrylic water-soluble nonionic polymer, (meth) acrylic water-insoluble nonionic polymer, polyvinylpyrrolidone, polyacrylamide, low saponified polyvinyl alcohol (saponification degree 60 mol% or less)
  • nonionic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, (n-propyl) (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate.
  • one or more selected from (meth) acrylic water-insoluble nonionic polymers, polyvinylpyrrolidone, and low saponified polyvinyl alcohol (saponification degree of 60 mol% or less) are preferable.
  • examples of commercially available products include MAS683 (manufactured by Kosmedy Pharmaceutical), polyvinylpyrrolidone K-90 (manufactured by BASF) and JMR-150L (manufactured by Nippon Vinegar Bipovar).
  • (meth) acrylic means “acrylic or methacrylic”.
  • the anionic polymer is not particularly limited, and any anionic polymer usually used in the cosmetics field can be used.
  • the liquid agent may contain one or more anionic polymers, and may further contain one or more nonionic, cationic and / or amphoteric polymers in combination with the anionic polymer.
  • anionic polymers include, for example, anionic polysaccharides and derivatives thereof (alginate, pectin, hyaluronate, etc.), anionic gums (xanthan gum, dehydroxanthan gum, hydroxypropyl xanthan gum, gum arabic, karaya gum, gum tragacanth, etc.), Anionic cellulose derivatives (carboxymethyl cellulose (CMC) and the like), (meth) acrylic water-soluble anionic polymers, acrylamide-based water-soluble anionic polymers, and the like.
  • anionic polysaccharides and derivatives thereof alginate, pectin, hyaluronate, etc.
  • anionic gums xanthan gum, dehydroxanthan gum, hydroxypropyl xanthan gum, gum arabic, karaya gum, gum tragacanth, etc.
  • Anionic cellulose derivatives carboxymethyl cellulose (CMC) and the like
  • Examples of compounds having an ethylenically unsaturated bond capable of constituting an anionic polymer such as the (meth) acrylic water-soluble anionic polymer will be given below, but the present invention is not limited in any way by the following specific examples. Absent.
  • anionic monomers include unsaturated carboxylic acid compounds such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, and crotonic acid; unsaturated polybasic acid anhydrides (eg, succinic anhydride).
  • anionic unsaturated monomers can be used in the form of acid or partially neutralized or completely neutralized, or may be used in the state of acid copolymerization before partial neutralization or complete neutralization. it can.
  • the basic compound used for neutralization include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and amine compounds such as ammonia water, mono-, di-, tri-ethanolamine and trimethylamine.
  • acrylic water-insoluble anionic polymers are particularly preferred.
  • commercially available products include MASCOS10 (manufactured by Kosmedy Pharmaceutical) and HiPAS10 (manufactured by Kosmedy Pharmaceutical).
  • an emulsifying thickener containing these nonionic polymers and anionic polymers can be used.
  • examples thereof include polyacrylamide / (C13, C14) isoparaffin / laureth-7 (Seppic 305, Sepigel 305).
  • the cationic polymer is not particularly limited, and any cationic thickening polymer usually used in the cosmetic field can be used.
  • the solution may contain one or more cationic polymers, and may further contain one or more nonionic, anionic and / or amphoteric polymers in combination with the cationic polymer.
  • the cationic polymer is a polymer having a cationic group such as a quaternary ammonium group or a group such as a primary, secondary, or tertiary amino group that can be ionized to a cationic group.
  • the cationic polymer is typically a polymer containing an amine group or an ammonium group in the side chain of a polymer chain or a polymer containing a diallyl quaternary ammonium salt as a structural unit.
  • Preferred cationic polymers include, for example, cationized cellulose, cationic starch, cationic guar gum, vinyl-based or (meth) acrylic polymers or copolymers having quaternary ammonium side chains, quaternized polyvinyl pyrrolidone, (meth) Examples thereof include acrylate / aminoacrylate copolymers, amine-substituted poly (meth) acrylate crosspolymers, (meth) acrylic water-soluble cationic polymers, and acrylamide-based water-soluble cationic polymers.
  • Examples of cationic monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (Meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide P-dimethylaminomethyl styrene, p-dimethylaminoethyl styrene, p-diethylaminomethyl styrene, p-diethylaminoethyl styrene, etc.
  • the cationized cellulose include a quaternary ammonium salt polymer (polyquaternium-10) obtained by adding glycidyltrimethylammonium chloride to hydroxyethylcellulose, a hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer (polyquaternium-4), And a polymer of quaternary ammonium salt (polyquaternium-67) obtained by reacting hydroxyethyl cellulose with trimethylammonium substituted epoxide and lauryldimethylammonium substituted epoxide.
  • polyquaternium-10 quaternary ammonium salt polymer
  • polyquaternium-4 hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer
  • polyquaternium-67 polymer of quaternary ammonium salt obtained by reacting hydroxyethyl cellulose with trimethylammonium substituted epoxide and lauryldimethylammonium
  • vinyl or (meth) acrylic polymers or copolymers having quaternary ammonium side chains examples include poly (2-methacryloxyethyltrimethylammonium chloride) (polyquaternium-37).
  • quaternized polyvinylpyrrolidone examples include quaternary ammonium salt (polyquaternium-11) synthesized from vinylpyrrolidone (VP) and a copolymer of dimethylaminoethyl methacrylate and diethyl sulfate.
  • Examples of (meth) acrylate / aminoacrylate copolymers include (acrylates / aminoacrylates / C10-30 alkyl PEG-20 itaconic acid) copolymers.
  • Examples of amine-substituted poly (meth) acrylate crosspolymers include polyacrylate-1 crosspolymer and polyquaternium-52.
  • acrylamide-based water-soluble cationic polymers are particularly preferable.
  • examples of commercially available products include t-butyl acrylamide / ethyl acrylate / dimethylaminopropyl acrylamide / methoxypolyethylene glycol methacrylate copolymer (RP77S, manufactured by Kao Corporation).
  • the amphoteric polymer is a polymer containing both a cationic group and an anionic group. From a structural point of view, the amphoteric polymer can be derived by further introducing an anionic group or comonomer into any of the aforementioned cationic polymers.
  • amphoteric polymer any amphoteric polymer usually used in the field of cosmetics can be used.
  • the liquid agent may contain one or more amphoteric polymers, and may further contain a nonionic, anionic and / or cationic polymer in combination with the amphoteric polymer.
  • amphoteric polymers include carboxyl-modified or sulfonic acid-modified cationic polysaccharides (such as carboxymethyl chitosan), (meth) acrylate polymers having a phosphobetaine group or sulfobetaine group in the side chain, and (meth) acrylic zwitterions For example.
  • amphoteric monomer examples include compounds obtained by allowing a modifying agent such as sodium or potassium haloacetate to act on the specific examples of the cationic monomer precursor described above.
  • polarizable monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl And amine oxides such as (meth) acrylamide, vinyl N, N-dimethylaminopropionate, p-dimethylaminomethylstyrene, p-dimethylaminoethylstyrene, p-diethylaminomethylstyren
  • copolymers of cationic vinyl or (meth) acrylic monomers and (meth) acrylic acid such as dimethyldiallylammonium chloride / acrylic acid copolymer (polyquaternium-22)).
  • the adhesive polymer is appropriately selected from the viewpoint of improving the friction resistance of the coating.
  • the adhesive strength of the adhesive polymer is preferably such that the adhesive strength of the polymer at a concentration of 30% by mass using the component (a) as a solvent measured by the following method is 0.1 N / 10 mm or more, 0.2 N / It is more preferably 10 mm or more, further preferably 0.5 N / 10 mm or more, and particularly preferably 1.0 N / 10 mm or more.
  • the adhesive force of the polymer is preferably 100 N / 10 mm or less, more preferably 50 N / 10 mm or less, and further preferably 40 N / 10 mm or less. .
  • the specific range is preferably 0.2 N / 10 mm to 100 N / 10 mm, more preferably 0.5 N / 10 mm to 50 N / 10 mm, and still more preferably 1.0 N / 10 mm to 40 N / 10 mm.
  • ⁇ Polymer adhesive evaluation method> At room temperature (20 ° C.), the polymer of component (c) is dissolved in component (a) at a concentration of 30% by mass, and wet film thickness is measured with a bar coater on a polyethylene terephthalate (PET) film (Teijin, Tetron G2, thickness 25 ⁇ m). Apply to 41 ⁇ m. After drying for 10 minutes in a normal temperature and humidity environment, the PET film cut out to 150 mm ⁇ 150 mm is pressed against the coated surface at a pressure of 0.01 kgf / cm 2 for 3 minutes.
  • PET polyethylene terephthalate
  • the film is cut into a strip with a width of 10 mm, the end face is peeled off by about 20 mm, and both ends of the peeled film are picked and pulled in a 180 ° direction by a 180 ° peel tester (IPT200-5N, manufactured by Imada Co., Ltd.).
  • the adhesion was measured.
  • the tensile speed was 500 mm / min, and the maximum load point was defined as the polymer adhesive strength (N / 10 mm).
  • all the adhesive force of the polymer of the Example described in Table 1 and the comparative example was evaluated using ethanol (the Wako Pure Chemical Industries Ltd. make: brand name ethanol (99.5)) as a component (a). .
  • the content of the adhesive polymer other than the component (b) which is the component (c) in the spray composition is such that the adhesion of the coating is improved, the friction resistance of the coating is improved, and the feel of the coating.
  • 0.5 mass% or more is preferable, 1 mass% or more is more preferable, and 1.5 mass% or more is further more preferable.
  • 30 mass% or less is preferable from the same viewpoint, 25 mass% or less is more preferable, and 20 mass% or less is further more preferable.
  • 0.5 mass% or more and 30 mass% or less are preferable, 1 mass% or more and 25 mass% or less are more preferable, and 1.5 mass% or more and 20 mass% or less are more preferable.
  • the mass ratio (b / c) of the content of the component (b) and the component (c) in the spray composition increases the adhesiveness between the polymers of the component (b) to improve the adhesion of the film to the skin, From the viewpoint of improving the friction resistance of the coating, it is preferably 0.5 or more, more preferably 1 or more, still more preferably 2 or more, particularly preferably 3 or more, and preferably from the same viewpoint. Is 20 or less, more preferably 15 or less, even more preferably 10 or less, and even more preferably 5 or less.
  • the composition for spraying improves dispersibility of the component (c), and balance between the ease of charging and the fiber-forming property when electrostatic spraying is performed, and improves the adhesion of the coating film by the combined use with the component (b).
  • the content of the component (d) in the spray composition is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.35% by mass. % Or more, more preferably 0.4% by mass or more.
  • the content of the component (c) in the spray composition is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 19% by mass or less, from the viewpoint of fiber formation. More preferably, it is 18 mass% or less, More preferably, it is 10 mass% or less.
  • the mass ratio (c / d) of the content of component (c) and component (d) in the spray composition is preferably 1 or more from the viewpoint of further improving the adhesion and friction resistance of the coating.
  • it is 2 or more, More preferably, it is 4 or more, Preferably it is 50 or less, More preferably, it is 40 or less, More preferably, it is 30 or less.
  • the spray composition may contain only the component (a), component (b) and component (c) described above, or in addition to the component (a), component (b) and component (c). And other components may be included.
  • other components include (d) water, a plasticizer of a polymer having a film-forming ability of component (b), a color pigment, an extender pigment, a dye, a surfactant, a fragrance, a repellent, an antioxidant, and a stabilizer. , Preservatives, various vitamins and the like.
  • the content of the other components is preferably 0.1% by mass or more and 30% by mass or less, and 0.5% by mass or more and 20% by mass or less. More preferably it is.
  • glycol can be contained in the spray composition.
  • examples of the glycol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, and polypropylene glycol.
  • the component (a) can be sufficiently volatilized when the electrostatic spray method is performed, and from the viewpoint of suppressing secondary aggregation of the powder, 10% by mass or less is preferable in the spray composition, and 3% by mass or less. Is more preferable, 1 mass% or less is preferable, and it is preferable not to contain substantially.
  • the spraying composition may contain powders such as color pigments and extender pigments, but the content of the powder having a particle diameter of 0.1 ⁇ m or more at 20 ° C. has a uniform film-forming property, From the viewpoint of the durability and adhesion of the coating, it is preferably 1% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.01% by mass or less. It is preferable not to contain except.
  • the spray composition is directly sprayed onto the skin.
  • a spray composition having a viscosity of preferably 1 mPa ⁇ s or more, more preferably 10 mPa ⁇ s or more, more preferably 50 mPa ⁇ s or more at 25 ° C. is used.
  • a material having a viscosity at 25 ° C. of preferably 5000 mPa ⁇ s or less, more preferably 2000 mPa ⁇ s or less, and still more preferably 1500 mPa ⁇ s or less is used.
  • the viscosity of the spray composition is preferably 1 mPa ⁇ s or more and 5000 mPa ⁇ s or less, more preferably 10 mPa ⁇ s or more and 2000 mPa ⁇ s or less, more preferably 50 mPa ⁇ s or more and 1500 mPa ⁇ s or less at 25 ° C. It is.
  • a porous coating particularly a porous coating composed of a fiber deposit, can be successfully formed by electrostatic spraying. Formation of the porous coating is advantageous from the viewpoints of coating adhesion, friction resistance, coating transparency, suppression of coating feeling, prevention of skin stuffiness, and the like.
  • the viscosity of the spray composition is measured at 25 ° C. using an E-type viscometer.
  • E type viscometer for example, an E type viscometer manufactured by Tokyo Keiki Co., Ltd. can be used. In this case, the rotor No. 43 can be used.
  • the number of rotations is selected according to the viscosity, the viscosity of 1300 mPa ⁇ S or more is 5 rpm, the viscosity of 250 mPa ⁇ S or more and less than 1300 mPa ⁇ S is 10 rpm, the viscosity of 25 mPa ⁇ S or more and less than 250 mPa ⁇ S is 50 rpm, The viscosity of less than 25 mPa ⁇ S is 100 rpm.
  • the spray composition is sprayed directly onto the target site of human skin by electrostatic spraying.
  • the skin includes nails.
  • the electrostatic spray method includes a step of electrostatic spraying the spray composition on the skin using an electrostatic spray device.
  • the electrostatic spray apparatus basically includes a container for storing the composition, a nozzle for discharging the composition, a supply device for supplying the composition stored in the container to the nozzle, A power source for applying a voltage to the nozzle.
  • FIG. 1 is a schematic diagram showing the configuration of an electrostatic spray apparatus suitably used in the present invention.
  • the electrostatic spray apparatus 10 shown in the figure includes a low voltage power supply 11.
  • the low voltage power supply 11 can generate a voltage of several volts to several tens of volts.
  • the low voltage power supply 11 is preferably composed of one or two or more batteries. Further, by using a battery as the low voltage power supply 11, there is an advantage that replacement can be easily performed as necessary. 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 and causing the high voltage power supply 12 to operate stably. Further, the auxiliary electric circuit 13 has a function of controlling the rotational speed of a motor provided in the micro gear pump 14 described later. By controlling the number of rotations of the motor, the amount of the spray composition supplied from the spray composition container 15 to be described later to the micro gear pump 14 is controlled.
  • a switch SW is attached between the auxiliary electric circuit 13 and the low voltage power source 11, and the electrostatic spray device 10 can be operated / stopped by turning on / off the switch SW.
  • the electrostatic spray device 10 further includes a nozzle 16.
  • the nozzle 16 is made of various conductors including metals and non-conductors such as plastic, rubber, and ceramic, and has a shape that allows the spray composition to be discharged from its tip.
  • a minute space through which the spraying composition flows is formed along the longitudinal direction of the nozzle 16.
  • the size of the cross section of the minute space 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 through a pipe line 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. As a result, a high voltage can be applied to the nozzle 16.
  • the nozzle 16 and the high voltage power supply 12 are electrically connected via the current limiting resistor 19 in order to prevent an excessive current from flowing when the human body directly touches the nozzle 16.
  • the micro gear pump 14 that communicates with the nozzle 16 via the pipe line 17 functions as a supply device that supplies the spray composition contained in the container 15 to the nozzle 16.
  • the micro gear pump 14 operates by receiving power from the low voltage power source 11. Further, the micro gear pump 14 is configured to supply a predetermined amount of the spray composition to the nozzle 16 under the control of the auxiliary electric circuit 13.
  • the container 15 is connected to the micro gear pump 14 through a flexible pipe 18.
  • the container 15 contains a spraying composition.
  • the container 15 is preferably in a cartridge-type replaceable form.
  • FIG. 2 shows a handy type electrostatic spray apparatus 10 having a size that can be held with one hand.
  • the electrostatic spray device 10 shown in the figure all members in the configuration diagram shown in FIG. 1 are accommodated in a cylindrical housing 20.
  • a nozzle (not shown) is disposed at one end 10 a in the longitudinal direction of the housing 20.
  • the nozzle is arranged in the casing 20 so that the blowing direction of the composition coincides with the vertical direction of the casing 20 and becomes convex toward the skin side.
  • FIG. 2 shows a state where one end 10a of the electrostatic spray device 10 is directed to the inner side of the user's forearm. Under this state, the apparatus 10 is turned on to perform the electrostatic spray method. When the apparatus 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 spray composition at the tip of the nozzle is polarized by electrostatic induction, the tip becomes a cone shape, and droplets of the spray composition charged from the tip of the cone are discharged. It is discharged into the air along the electric field toward the skin.
  • component (a) which is a solvent, evaporates from the spray composition charged and discharged into space, the charge density on the surface of the spray composition becomes excessive and spreads into the space while repeating miniaturization by Coulomb repulsion. Reach the skin.
  • the viscosity of the spray composition the sprayed composition can reach the application site in the form of droplets.
  • Fibers can also be deposited at the application site. For example, increasing the viscosity of the spray composition tends to deposit the composition at the application site in the form of fibers. As a result, a porous coating made of a fiber deposit is formed on the surface of the application site.
  • a porous film made of a fiber deposit containing an ultraviolet protective agent can also be formed by adjusting the distance between the nozzle and the skin and the voltage applied to the nozzle.
  • the electrostatic spray method a high potential difference is generated between the nozzle and the skin.
  • the impedance is very large, the current flowing through the human body is extremely small.
  • the present inventor has 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, and more preferably 50 nm or more, when expressed in terms of a circle-equivalent diameter. . Moreover, it is preferable that it is 3000 nm or less, and it is still more preferable that it is 1000 nm or less.
  • the thickness of the fiber is observed by, for example, scanning electron microscope (SEM) observation by magnifying the fiber 10,000 times, and removing defects (fiber clumps, fiber intersections, droplets) from the two-dimensional image, It can be measured by selecting 10 fibers arbitrarily, drawing a line perpendicular to the longitudinal direction of the fiber, and directly reading the fiber diameter.
  • SEM scanning electron microscope
  • the film which is a fiber deposit formed by electrostatic spraying, has a supported film in which component (c) is present on the surface side of the constituent fibers.
  • the surface side of the fiber means the surface or a part of the surface and between the fibers.
  • the content of the component (c) in the spray composition depends on the affinity between the water-insoluble polymer and the component (c). It is possible to prevent the coating from being broken or peeled off against external friction by the fact that the fiber is reinforced with the adhesive polymer in a flexible manner due to the presence of the component (c) between them. . In addition to these adhesion and friction resistance, the transparency is further enhanced by liquid application described later.
  • the component (c) is combined in the fiber, so that the fiber swells and is easily plasticized.
  • a thin film is produced by electrostatic spraying the same composition on a metal surface that does not contain moisture or oil and a skin surface that contains moisture or oil, such as the palm for 5 seconds, the change in fiber diameter is observed over time. Then, the fiber electrostatically sprayed on the skin surface becomes larger in diameter due to swelling than the fiber electrostatically sprayed on the metal surface. In this way, the coating film containing fibers formed by electrostatic spraying is plasticized with oil and moisture in the skin and becomes softer, so that the followability of the fibers themselves to the texture of the skin is improved.
  • the component (c) bleeds out and exists between the fiber surface and between the fibers, so that the coating film containing the fibers becomes translucent or transparent, and natural appearance is imparted.
  • the fiber diameter due to swelling satisfies the following formula (1). (Fiber diameter after 30 seconds of spinning on the skin)> (fiber diameter after 30 seconds of spinning on the metal plate) (1)
  • the content of the component (a), the component (b), and the component (c) that are the spray composition is measured as follows.
  • the component (a), which is a volatile substance, does not exist in the formed film or volatilizes even if it exists, so that the formed film contains only component (b) and component (c).
  • the content is measured as follows.
  • ⁇ Measurement method of content of component (a), component (b), component (c) of spray composition There are separation identification by liquid chromatograph (HPLC) in solution state and identification by infrared spectrophotometer (IR).
  • HPLC liquid chromatograph
  • IR infrared spectrophotometer
  • functional groups can be assigned and identified from individual absorbers.
  • identification can be performed by comparing a standard chart of commercially available additives with an IR chart of components.
  • ⁇ Method for measuring the content of component (b) and component (c) in the formed film A solvent capable of dissolving the film is searched, and after the film is dissolved in the solvent, separation and identification by liquid chromatography (HPLC) or infrared spectrophotometer (IR) is performed.
  • HPLC liquid chromatography
  • IR infrared spectrophotometer
  • the fiber forming the coating is a continuous fiber having an infinite length on the principle of production, but preferably has a length at least 100 times the thickness of the fiber.
  • a fiber having a length of 100 times or more the thickness of the fiber is defined as “continuous fiber”.
  • the film manufactured by the electrostatic spray method is a porous discontinuous film made of a continuous fiber deposit.
  • the coating in such a form has very soft characteristics, and even when shearing force is applied to it, it does not easily break apart, and can follow the movement of the body. There is an advantage of being excellent. There is also an advantage that the complete removal of the coating is easy.
  • the continuous film having no pores is not easily peeled off and has low sweat dissipation, so that there is a risk of stuffiness on the skin.
  • a porous discontinuous film composed of aggregates of particles is required to be completely removed without damaging the skin, for example, an operation such as rubbing the entire film is required to completely remove the film. Have difficulty.
  • the spray composition that has been electrostatically sprayed into a fibrous form is charged with the component (b), the component (c), and the component (a) while the component (a) evaporates. Reach the skin directly.
  • the fibers adhere to the skin in the form of a single film by electrostatic force. Since fine irregularities such as texture are formed on the surface of the skin, the fibers are more closely attached to the surface of the skin in the form of a single film coupled with the anchor effect due to the irregularities.
  • electrostatic sprayer 10 is turned off.
  • the fiber which comprises a film contains the component (c), even if it does not apply
  • the component (c) is present in the fiber (on the surface of the fiber or between the fibers), so that the fiber itself becomes soft, or the adhesiveness between the fibers or the adhesion to the object to the skin or the like. This is considered to be because the followability to a fine uneven surface is increased by the above, and the presence of the component (c) on the fiber surface crosslinks the fiber and the skin.
  • the distance between the nozzle and the skin depends on the voltage applied to the nozzle, but is preferably 50 mm or more and 150 mm or less in order to successfully form the coating.
  • the distance between the nozzle and the skin can be measured by a generally used non-contact sensor or the like.
  • the basis weight of the coating is preferably 0.1 g / m 2 or more, and preferably 1 g / m 2 or more. Is more preferable. Moreover, it is preferable that it is 50 g / m ⁇ 2 > or less, and it is still more preferable that it is 40 g / m ⁇ 2 > or less.
  • the basis weight of the coating is preferably 0.1 g / m 2 or more 50 g / m 2 or less, further preferably 1 g / m 2 or more 40 g / m 2 or less.
  • the electrostatic spray process in which the composition is directly sprayed on the skin to form a film means the process in which the film is formed by electrostatic spraying on the skin.
  • the process of producing a sheet made of fibers by electrostatic spraying the composition on a place other than the skin, and forming the film by applying or sticking the sheet to the skin is different from the electrostatic spraying process.
  • a step of applying a liquid agent containing liquid oil at 20 ° C. to the skin by a method other than electrostatic spraying May be performed.
  • the coating formed in the electrostatic spraying step is easily adapted to the application site, the coating can be highly adhered to the skin, and can be made transparent. For example, it becomes difficult to produce a level
  • the coating when the coating is a porous coating made of a fiber deposit, it has high adhesion to the skin despite a high porosity, and a large capillary force tends to occur. Furthermore, when the fibers are fine, it is easy to increase the specific surface area of the porous coating.
  • the liquid agent is present between the fibers forming the porous film and / or on the fiber surface by performing the liquid agent application step after forming the porous film made of fiber deposits in the electrostatic spraying step. A film is formed.
  • the adhesion of the coating is improved, and the transparency of the coating is visually maintained or improved.
  • the coating is colorless and transparent or colored and transparent, the coating becomes more difficult to visually recognize, so that it can look like natural skin.
  • the coating is colored and transparent, the coating is transparent, so that it can be seen as a part of the skin.
  • liquid oil at 20 ° C. examples include linear or branched hydrocarbon oils such as liquid paraffin, light isoparaffin, liquid isoparaffin, squalane and squalene; triglycerin fatty ester, diglycerin fatty acid ester, monoglycerin fatty acid ester, monoalcohol Examples include ester oils such as fatty acid esters and polyhydric alcohol fatty acid esters; silicone oils such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher alcohol-modified organopolysiloxane.
  • linear or branched hydrocarbon oils such as liquid paraffin, light isoparaffin, liquid isoparaffin, squalane and squalene
  • triglycerin fatty ester diglycerin fatty acid ester, monoglycerin fatty acid ester, monoalcohol
  • ester oils such
  • hydrocarbon oils, ester oils, silicone oils and the like are preferable, and hydrocarbon oils and ester oils are more preferable from the viewpoint of feeling of use such as smoothness during application.
  • the liquid oil chosen from these can be used 1 type or in combination of 2 or more types.
  • jojoba oil containing two or more kinds of triglycerin fatty acid esters, vegetable oils such as olive oil, and animal oils such as liquid larin can also be used.
  • the hydrocarbon oil examples include liquid paraffin, squalane, squalene, n-octane, n-heptane, cyclohexane, light isoparaffin, liquid isoparaffin, and liquid paraffin and squalane are preferable from the viewpoint of feeling of use.
  • the viscosity of the hydrocarbon oil at 30 ° C. is preferably 10 mPa ⁇ s or more, and more preferably 30 mPa ⁇ s or more.
  • the total content in the liquid agent of isododecane, isohexadecane, and hydrogenated polyisobutene having a viscosity of less than 10 mPa ⁇ s at 30 ° C. is preferably 10% by mass or less, more preferably 5% by mass or less. More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less, and does not need to contain.
  • the viscosity of the ester oil and the silicone oil at 30 ° C. is preferably 10 mPa ⁇ s or more, more preferably 30 mPa ⁇ s or more.
  • the viscosity here is measured at 30 ° C. with a BM viscometer (manufactured by Tokimec, measurement conditions: rotor No. 1, 60 rpm, 1 minute).
  • a liquid agent of ether oil such as cetyl-1,3-dimethylbutyl ether, dicapryl ether, dilauryl ether, diisostearyl ether is preferably 10% by mass or less, More preferably, it is 5 mass% or less, More preferably, it is 1 mass% or less.
  • liquid oil an oil which is liquid at 20 ° C. can be preferably used.
  • examples thereof include ester oil, vegetable oil containing ester oil (triglyceride), higher fatty acid of branched fatty acid or unsaturated fatty acid, preservative, silicone Oil etc. are mentioned. These liquid oils can be used alone or in combination of two or more.
  • ester oil examples include esters composed of linear or branched fatty acids and linear or branched alcohols or polyhydric alcohols. Specifically, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, monoisostearic acid N-alkyl glycol, dicaprate neopentyl glycol, dimalate Isosteary
  • octyldodecyl myristate myristyl myristate, isocetyl stearate, isocetyl isostearate, and cetearyl isononylate are preferred because of the excellent adhesion to the skin and the sensation when applied to the skin.
  • glycerin is preferable, isopropyl myristate, isopropyl palmitate, diisostearyl malate, neopentyl glycol dicaprate, benzoic acid (C12-15) al
  • at least one selected from tri (caprylic acid / capric acid) glycerin more preferably selected from neopentyl glycol dicaprate, benzoic acid (12 to 15 carbon atoms) alkyl, tri (caprylic acid / capric acid) glycerin At least one is more preferred.
  • the triglyceride is preferably a fatty acid triglyceride, for example, olive oil, jojoba oil, macadamia nut oil, medfoam oil, castor oil, safflower oil, sunflower oil, avocado oil, canola oil, kyonin oil, rice germ oil, rice bran oil, etc. .
  • Examples of the higher alcohol include liquid higher alcohols having 12 to 20 carbon atoms, and specific examples include isostearyl alcohol and oleyl alcohol.
  • preservatives include phenoxyethanol, methyl paraoxybenzoate, ethyl paraaminobenzoate, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, ethyl paraoxybenzoate, butyl paraoxybenzoate, propyl paraoxybenzoate, benzyl paraoxybenzoate, and ethylhexanediol. Is mentioned.
  • silicone oil examples include dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher alcohol-modified organopolysiloxane.
  • Dynamic viscosity of the silicone oil, the electrostatic sprayed coating from the viewpoint of adhesion to the skin preferably 3 mm 2 / s, more preferably 4 mm 2 / s, more preferably not less than 5 mm 2 / s at 25 ° C., 30 mm 2 / S or less is preferable, 20 mm 2 / s or less is more preferable, and 10 mm 2 / s or less is more preferable.
  • the content of liquid oil in the liquid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 5% by mass or more. Moreover, Preferably it is 100 mass% or less.
  • the content of the liquid oil in the liquid is preferably 0.1% by mass or more and 100% by mass or less, and more preferably 0.5% by mass or more and 100% by mass or less.
  • the liquid may further contain a polyol.
  • a polyol examples include alkylene glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, and 1,3-butanediol; diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and the like.
  • ethylene glycol, propylene glycol, 1,3-butanediol, dipropylene glycol, polyethylene glycol, glycerin, and diglycerin are preferable from the viewpoint of feeling of use such as smoothness during coating, and propylene glycol, 1, 3-butanediol and glycerin are more preferable, and propylene glycol and 1,3-butanediol are more preferable.
  • the liquid agent preferably has a viscosity of about 5000 mPa ⁇ s or less at 25 ° C. from the viewpoint of improving the adhesion between the coating formed by the electrostatic spray method and the application site.
  • the method for measuring the viscosity of the liquid is as described above.
  • a liquid agent containing liquid oil can be used to apply a liquid agent containing liquid oil to the skin.
  • a solution for example, by applying a solution to the skin by a method such as dripping or sprinkling, and applying a step of spreading the solution, it is possible to adjust to the skin or film, and a thin layer of the solution can be formed.
  • a method such as rubbing using a user's finger or a tool such as an applicator can be employed.
  • the liquid agent may be simply dropped or sprinkled, it can be applied to the skin or the coating by providing a spreading step, and the adhesion of the coating can be sufficiently improved.
  • the solution can be sprayed onto the skin to form a thin layer of the solution.
  • the amount of the liquid applied to the skin may be an amount necessary and sufficient for improving the adhesion between the skin and the film.
  • the basis weight of the liquid oil is preferably 0.1 g / m 2 from the viewpoint of ensuring adhesion between the skin and the film. More preferably, the amount is 0.2 g / m 2 or more, preferably 40 g / m 2 or less, more preferably 35 g / m 2 or less.
  • the amount of liquid applied to the skin is such that the basis weight of the liquid oil is preferably from 0.1 g / m 2 to 40 g / m 2 , more preferably from 0.2 g / m 2 to 35 g / m 2. Amount.
  • the amount of the solution applied to the skin or the film is preferably 5 g / m 2 or more, more preferably 10 g / m 2 from the viewpoint of improving the adhesion between the skin and the film and the transparency. Or more, more preferably 15 g / m 2 or more, preferably 50 g / m 2 or less, more preferably 45 g / m 2 or less.
  • the coating film production method of the present invention as described above is useful as a cosmetic method not intended for human surgery, treatment, or diagnostic methods.
  • this invention was demonstrated based on the preferable embodiment, this invention is not restrict
  • a person who wants to form a film on his skin grips the electrostatic spray device 10 and generates an electric field between the conductive nozzle of the device 10 and his skin. As long as an electric field is generated between the two, it is not necessary for a person who wants to form a film on his skin to hold the electrostatic spray device 10.
  • the present invention further discloses the following method for producing a coating film.
  • a method for producing a film on the skin wherein the composition comprising the component (a), the component (b) and the component (c) is electrostatically sprayed directly onto the skin.
  • ⁇ 2> Furthermore, the manufacturing method of the film as described in ⁇ 1> which has the process of apply
  • ⁇ 3> (c) The method for producing a film according to ⁇ 1> or ⁇ 2>, wherein the adhesive polymer is at least one selected from a nonionic polymer, an anionic polymer, a cationic polymer, and an amphoteric polymer.
  • the adhesive polymer is any one of ⁇ 1> to ⁇ 3>, wherein the adhesive polymer is at least one selected from a rubber adhesive, a silicone adhesive, an acrylic adhesive, and a urethane adhesive.
  • the adhesive polymer is composed of poly (meth) acrylic acid C1-C20 alkyl ester or (meth) acrylic acid C1-C20 alkyl ester as a base monomer, and N-vinylpyrrolidone, methylvinylpyrrolidone, (meta )
  • the adhesive polymer is at least one selected from styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene butadiene rubber, polyisobutylene, isoprene rubber, and silicone rubber.
  • the adhesive strength of the adhesive polymer is preferably 0.1 N / 10 mm or more, more preferably 0.2 N / 10 mm or more, and further preferably 0.5 N / 10 mm or more.
  • it is 1.0 N / 10 mm or more, more preferably 100 N / 10 mm or less, more preferably 50 N / 10 mm or less, and further preferably 40 N / 10 mm or less.
  • the content of the adhesive polymer in the spray composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, and 30% by mass or less.
  • the mass ratio (b / c) of the content of component (b) and component (c) in the spray composition is preferably 0.05 or more, more preferably 0.1 or more, More preferably, it is 2 or more, particularly preferably 3 or more, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and even more preferably 5 or less.
  • 1> to ⁇ 10> The method for producing a coating film according to any one of ⁇ 10>.
  • the mass ratio (a / b) of the content of component (a) and component (b) in the spray composition is preferably 150 or less, more preferably 100 or less, and even more preferably 70.
  • the film according to any one of ⁇ 1> to ⁇ 11> which is more preferably 50 or less, preferably 2 or more, more preferably 3 or more, and still more preferably 5 or more.
  • Manufacturing method. ⁇ 13> The spray composition preferably further contains component (d) water, and the content of component (d) in the spray composition is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, more preferably 0.35% by mass or more, still more preferably 0.4% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass.
  • the method for producing a coating film according to any one of ⁇ 1> to ⁇ 12> which is more preferably 19% by mass or less, and still more preferably 18% by mass or less.
  • the mass ratio (c / d) of the content of the component (c) and the component (d) in the spray composition is preferably 1 or more, more preferably 2 or more, and further preferably 4 or more. Preferably, it is 50 or less, More preferably, it is 40 or less, More preferably, it is 30 or less,
  • ⁇ 15> A container in which the electrostatic spray stores the composition, a nozzle that discharges the composition, a supply device that supplies the composition stored in the container to the nozzle, and the nozzle The method for producing a coating film according to any one of ⁇ 1> to ⁇ 14>, which is carried out using an electrostatic spraying device having a power source for applying a voltage to.
  • the volatile substance of component (a) preferably has a vapor pressure of 0.01 kPa to 106.66 kPa at 20 ° C., more preferably 0.13 kPa to 66.66 kPa, The method for producing a coating film according to any one of ⁇ 1> to ⁇ 15>, further preferably 0.67 kPa or more and 40.00 kPa or less, and further preferably 1.33 kPa or more and 40.00 kPa or less. .
  • the volatile substance of component (a) is an alcohol, and the alcohol is a monovalent chain aliphatic alcohol, a monovalent cycloaliphatic alcohol, or a monovalent aromatic alcohol, or Two or more are preferable, and the alcohol is preferably one or two or more selected from ethanol, isopropyl alcohol, butyl alcohol, phenylethyl alcohol, propanol, and pentanol, and any one of the above items ⁇ 1> to ⁇ 16> A method for producing the film according to claim 1.
  • the volatile substance of component (a) is one or more selected from ethanol, isopropyl alcohol and butyl alcohol, more preferably one or two selected from ethanol and butyl alcohol.
  • the coating film contains ethanol.
  • Fully saponified polyvinyl alcohol water saponification degree: 98 mol% or more
  • partially saponified polyvinyl alcohol that can be crosslinked after film formation by using in combination with a crosslinking agent.
  • the content of the component (a) in the composition is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, and 98 It is preferably at most mass%, more preferably at most 96 mass%, further preferably at most 94 mass%, and the content of component (a) in the composition is 50 mass% or more and 98 mass% or less. % Or less, more preferably 55% by mass or more and 96% by mass or less, and further preferably 60% by mass or more and 94% by mass or less, in any one of the above items ⁇ 1> to ⁇ 19>.
  • the manufacturing method of the film of this is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, and 98 It is preferably at most mass%, more preferably at most 96 mass%, further preferably at most 94 mass%, and the content of component (a) in the composition is 50 mass% or more and 98 mass% or less. % Or less,
  • the content of the component (b) in the composition is preferably 0.5% by mass or more, more preferably 14% by mass or more, and even more preferably 2% by mass or more. It is further preferably 5% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, further preferably 30% by mass or less, and 25% by mass or less. More preferably, the content of the component (b) in the composition is preferably 0.5% by mass or more and 45% by mass or less, more preferably 1% by mass or more and 40% by mass or less.
  • An electrostatic spray method is performed using an electrostatic spray device,
  • the electrostatic spray device includes a nozzle,
  • the nozzle is made of various conductors including metal, or non-conductor such as plastic, rubber, ceramic, etc., and has a shape capable of discharging the composition from the tip thereof ⁇ 1> to ⁇ 21>
  • the manufacturing method of the film in any one of.
  • An electrostatic spray method is performed using an electrostatic spray device,
  • the electrostatic spray device includes a nozzle and a housing,
  • the nozzle is arranged at one end in the longitudinal direction of the housing, ⁇ 1> to ⁇ 22>, wherein the nozzle is disposed in the casing such that the blowing direction of the composition coincides with the longitudinal direction of the casing and is convex toward the skin side.
  • the manufacturing method of the film in any one.
  • the sprayed composition forms a fiber while volatilizing a volatile substance as a solvent from droplets and solidifying a polymer having a film-forming ability as a solute while stretching and deforming by a potential difference ⁇ [1]
  • An electrostatic spray method is performed using an electrostatic spray apparatus,
  • the electrostatic spray device includes a nozzle,
  • the basis weight of the film formed by the electrostatic spray method is preferably 0.1 g / m 2 or more, more preferably 1 g / m 2 or more, and 30 g / m 2 or less.
  • the basis weight of the coating is preferably 0.1 g / m 2 or more 30 g / m 2 or less, 1 g / m 2 or more 20 g / m 2 or less More preferably, the method for producing a coating film according to any one of ⁇ 1> to ⁇ 25>.
  • the component (a) is a volatile substance containing at least ethanol
  • the component (b) is one or more selected from polyvinyl butyral resins and polyurethane resins. The manufacturing method of the film in any one.
  • ⁇ 28> The method for producing a coating film according to any one of ⁇ 1> to ⁇ 27>, wherein the component (a) is a volatile substance containing at least ethanol and further contains 10% by mass or less of glycol.
  • the component (a) is a volatile substance containing at least ethanol, the ethanol content in the volatile substance is 50% by mass or more and 100% by mass, and contains 10% by mass or less of glycol ⁇ 1>
  • the content of component (a) is 30% by mass to 98% by mass in the composition, and the content of component (b) is 2% by mass to 50% by mass in the spray composition.
  • the content of component (a) is 55% by mass to 96% by mass in the composition, and the content of component (b) is 4% by mass to 45% by mass in the spray composition.
  • the content of component (a) is 60% by mass or more and 94% by mass or less in the composition, and the content of component (b) is 6% by mass or more and 40% by mass or less in the composition for spraying.
  • the component (a) is a volatile substance containing at least ethanol
  • the component (b) is one or more selected from polyvinyl butyral resins and polyurethane resins.
  • the manufacturing method of the film in any one.
  • ⁇ 34> The method for producing a coating film according to any one of ⁇ 1> to ⁇ 33>, wherein the component (a) is a volatile substance containing at least ethanol and further contains 10% by mass or less of glycol.
  • the component (a) is a volatile substance containing at least ethanol, and the ethanol content in the volatile substance is 50% by mass or more and 100% by mass, and contains 10% by mass or less of glycol ⁇ 1>
  • Example 1 (1) Preparation of spraying composition As component (a) of the spraying composition, ethanol (manufactured by Wako Pure Chemical Industries, Ltd .: trade name ethanol (99.5)) was used. Polyvinyl butyral (PVB, manufactured by Sekisui Chemical Co., Ltd .: trade name S-LEC B BM-1) was used as the component (b) of the spray composition. Modified organopolysiloxane 1 was used as component (c) of the spray composition.
  • ethanol manufactured by Wako Pure Chemical Industries, Ltd .: trade name ethanol (99.5)
  • PVB Polyvinyl butyral
  • S-LEC B BM-1 Modified organopolysiloxane 1 was used as component (c) of the spray composition.
  • the modified organopolysiloxane 1 has a mass ratio (A / B) of the organopolysiloxane segment (A) to the poly (N-acylalkyleneimine) segment (B) of 71/29, and Mwg, Mwox, Mwsi, Mwt was 2,500, 1,000, 50,000 and 70,000, respectively.
  • the blending ratio in the spray composition is as shown in Tables 1 and 2.
  • the amount of ethanol shown in Tables 1 and 2 is an effective amount and does not include water.
  • Electrostatic spray process Skin model (artificial leather, protein leather PBZ13001BK, Idemitsu Techno Fine Co., Ltd.) cut out to 50 mm ⁇ 50 mm using the electrostatic spray apparatus 10 having the configuration shown in FIG. 1 and the appearance shown in FIG. Electrostatic spraying was performed for 60 seconds.
  • the conditions of the electrostatic spray method were as shown below.
  • Discharge rate of spray composition 3 mL / h ⁇ Environment: 25 °C, 30% RH
  • Example 2 to Example 9 The electrostatic spraying process was performed in the same manner as in Example 1 except that the components (a), (b), and (c) in the spray composition were changed to the conditions shown in Table 1 below. A coating was obtained.
  • the component (c) described in Table 1 is as follows.
  • Modified organopolysiloxane 2 The mass ratio (A / B) of the organopolysiloxane segment (A) to the poly (N-acylalkyleneimine) segment (B) is 75/25, and Mwg, Mwox, Mwsi, Mwt Are respectively 2,500, 800, 50,000, 67,000 modified organopolysiloxane 3: mass ratio of organopolysiloxane segment (a) to poly (N-acylalkyleneimine) segment (b) (a / b ) Is 88/12, and Mwg, Mwox, Mwsi, and Mwt are 20000, 2700, 10,000, and 114,000, respectively.
  • Modified organopolysiloxane 4 The mass ratio (A / B) of the organopolysiloxane segment (A) to the poly (N-acylalkyleneimine) segment (B) is 50/50, and Mwg, Mwox, Mwsi, Mwt Are 2,500, 2,500, 30,000 and 60,000 respectively.
  • K-90 Polyvinylpyrrolidone, manufactured by BASF RP77S: Quaternary acrylamide-based water-soluble cationic polymer, manufactured by Kao JMR150L: Polyvinyl alcohol, Nihon Vinegar Bipoval Co., Ltd. MAS683: Acrylic water-insoluble polymer, Kosmedy Pharmaceutical Co., Ltd.
  • Example 10 to 12 An electrostatic spraying process was performed in the same manner as in Example 1 except that the component (c) in the spray composition was changed to the conditions shown in Table 2 below, to obtain a film made of fiber deposits.
  • the component (c) described in Table 2 is as follows.
  • MASCOS10 Acrylic water-insoluble polymer, Cosmedy Pharmaceutical Co., Ltd.
  • MAS811 Acrylic water-insoluble polymer, Cosmedy Pharmaceutical Co., Ltd.
  • HiPAS-PU Urethane polymer, Cosmedy Pharmaceutical Co., Ltd.
  • Example 1 An electrostatic spraying process was performed in the same manner as in Example 1 except that the spray composition did not contain the component (c) to obtain a coating film composed of fiber deposits.
  • Durability was evaluated by a rubbing test with a minute load of the coating. The skin model was fixed, and a 2 cm distance was rubbed 5 times in one direction while applying a load of about 50 gf from the top surface with the index finger. Durability was evaluated according to the following criteria from the adhesion state of the coating film and skin model and adhesion to the index finger. A: No peeling or tearing of the film, no adhesion to the index finger B: There is a tear on the surface of the film, but no adhesion to the index finger C: There is a tear on the surface of the film, and there is an adhesion to the index finger D: Torn and peel completely
  • Friction resistance was evaluated by a rubbing test under a heavy load of the coating.
  • the skin model on which the film is formed is fixed on a weight of 2.7 kg, and the film formed on the skin model is placed in a state of being in contact with a polyolefin resin substrate (JOINTEX B060J-S, manufactured by Jointex Company). At this time, a weight load is applied to the entire skin model.
  • a rubbing test was conducted with a horizontal movement of 10 cm, and the durability of the coating was evaluated according to the following criteria based on the peeled state from the skin model.
  • ⁇ Fibre structure of coating> Using a scanning electron microscope (for example, JSM-6510 manufactured by JEOL Ltd.), the upper surface of the coating was observed at an acceleration voltage of 20 kV and a magnification of 5000 times, and the fiber structure of the coating was evaluated according to the following criteria.
  • Example 13 to 19 An electrostatic spray process was performed in the same manner as in Example 1 except that the components (a), (b), and (c) in the spray composition were changed to the conditions shown in Table 2 below. A coating was obtained.
  • the component (c) described in Table 2 is as follows.
  • MAS683 Acrylic water-insoluble polymer, Kosmedy Pharmaceutical Co., Ltd.
  • Baycusan C2000 Urethane water-insoluble polymer
  • Covetro HPC-M Hydroxypropylcellulose, Nippon Soda Co., Ltd.
  • Yodosol GH41F Styrene-acrylic acid copolymer Akzo Nobel Corporation

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Abstract

L'invention concerne un procédé de production d'un film de revêtement présentant une excellente adhérence à la peau et une excellente transparence, par pulvérisation électrostatique. L'invention concerne également un procédé de production d'un film de revêtement sur la peau, le procédé étant caractérisé en ce qu'une composition comprenant un constituant (a), un constituant (b) et un constituant (c) est appliquée directement sur la peau par pulvérisation électrostatique. L'invention concerne en outre (a) une ou plusieurs substances volatiles choisies parmi les alcools et les cétones, (b) un polymère insoluble dans l'eau présentant une capacité de formation de film de revêtement et (c) un polymère adhésif autre que le constituant (b).
PCT/JP2018/016183 2017-04-19 2018-04-19 Procédé de production d'un film de revêtement Ceased WO2018194129A1 (fr)

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JP7137958B2 (ja) 2022-09-15
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CN110545786A (zh) 2019-12-06

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