WO2013192515A1 - Radiation-curable, stable nail gel compositions and methods of preparation and use - Google Patents

Radiation-curable, stable nail gel compositions and methods of preparation and use Download PDF

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Publication number
WO2013192515A1
WO2013192515A1 PCT/US2013/047032 US2013047032W WO2013192515A1 WO 2013192515 A1 WO2013192515 A1 WO 2013192515A1 US 2013047032 W US2013047032 W US 2013047032W WO 2013192515 A1 WO2013192515 A1 WO 2013192515A1
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Prior art keywords
meth
acrylate
composition
hydroxyl
nail
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PCT/US2013/047032
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English (en)
French (fr)
Inventor
George Lein
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Mycone Dental Supply Co Inc
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Mycone Dental Supply Co Inc
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Publication date
Priority to KR20157001757A priority Critical patent/KR20150028995A/ko
Priority to BR112014032271A priority patent/BR112014032271A2/pt
Priority to EP13807308.5A priority patent/EP2863883A4/en
Priority to CA2877559A priority patent/CA2877559C/en
Priority to EP18198909.6A priority patent/EP3449905A1/en
Priority to US14/410,313 priority patent/US20150335568A1/en
Application filed by Mycone Dental Supply Co Inc filed Critical Mycone Dental Supply Co Inc
Priority to CN201380037663.4A priority patent/CN104470495A/zh
Priority to JP2015518607A priority patent/JP2015520242A/ja
Publication of WO2013192515A1 publication Critical patent/WO2013192515A1/en
Anticipated expiration legal-status Critical
Priority to ZA2015/00099A priority patent/ZA201500099B/en
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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
    • A61K8/87—Polyurethanes
    • 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
    • A61K8/35—Ketones, e.g. benzophenone
    • 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
    • A61K8/55—Phosphorus compounds
    • 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
    • A61K8/8141—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00—Manicure or pedicure preparations
    • A61Q3/02—Nail coatings
    • 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
    • A61K2800/81—Preparation or application process involves irradiation
    • 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
    • A61K2800/95—Involves in-situ formation or cross-linking of polymers

Definitions

  • This invention relates to the field of radiation-curable gels useful for cosmetic adornment of natural fingernails and toenails, artificial fingernails and toenails, and artificial nail extensions.
  • Such radiation-curable gels are often comprised of a hydroxyl-containing monomer and a vinyl functional urethane prepared by reacting a hydroxyl compound such as a polyester, polyether, and/or hydroxyl-containing unsaturated monomer with an isocyanate in the presence of a tin catalyst such as dibutyltin dilaurate (DBTL).
  • DBTL dibutyltin dilaurate
  • Reaction products of polyhydric polyesters, polyethers, diisocyanates, and hydroxyl-containing acrylic or methacrylic monomers represent the most commonly used polyester urethanes.
  • Polyether-based polyurethanes can be prepared by reacting polyhydric polyethers, diisocyanates, and hydroxyl-containing acrylic or methacrylic monomers.
  • vinyl polyesters and polyethers can also be produced by the direct reaction of hydroxyl-containing polyethers, polyols, polyacids or polyesters, and acid- or ester-containing monomers. This reaction is often catalyzed by DBTL as well.
  • the radiation- curable gels are either colorless or pigmented and are usually applied by professional nail technicians and cured by holding the hands or toes under actinic radiation. Such radiation- curable gels can be applied directly to natural fingernails or toenails, or alternatively can be applied to nail extensions bonded to fingernails. In some cases, the artificial nails are coated with conventional nail polish after they are cured.
  • It is another object to improve the stability of radiation curable nail gel compositions comprising ethylenically unsaturated hydroxyl-functional monomers or oligomers and vinyl functional polyester, polyethers, and/or vinyl functional urethanes.
  • a radiation-curable gel composition comprising a radiation-curable gel nail coating composition
  • a radiation-curable gel nail coating composition comprising (a) one or more of the following: a vinyl functional urethane; a vinyl containing polyester; and/or a compound containing ester functionality which does not contain a hydroxyl group; (b) at least one hydroxyl-containing monomer, oligomer, or solvent; and (c) a photo initiator; the radiation- curable gel nail coating composition comprising less than 10 ppm tin, preferably less than 5 ppm tin, and most preferably comprising less than 1 ppm tin.
  • the components of the composition are preferably prepared either with no catalyst or in the presence of a catalyst other than tin.
  • the radiation curable gel composition comprises a vinyl containing ester prepared by reaction of an alcohol, a polyol, a polyacid, an anhydride, polyether, or polyester, and acid-, anhydride-, or ester-containing monomers such as an acrylic or methacrylic monomer, the vinyl containing ester having been prepared in the absence of tin or, in some cases, in the presence of tin followed by a tin removal or reduction step.
  • the radiation curable nail gel containing compositions in some embodiments comprise 5- 80 wt. % of the urethanes and/or esters, 2-80 wt. % of the hydroxyl-containing monomer, oligomer, or solvent, and 0.1 to 10 wt. % photo initiator.
  • the balance to make 100% by weight can be from other components.
  • oligomers prepared in the absence of tin are used. These oligomers may include polyether urethanes and/or polyester urethanes. [0011] In some embodiments poly ether urethanes prepared in the absence of tin can be used in the absence of polyester urethanes.
  • aliphatic or aromatic urethanes may be used.
  • urethanes are prepared, in the absence of tin, from the reaction of isocyanate-terminated prepolymers containing polyesters and/or polyethers or from isocyanates which do not contain polyester or polyether groups with hydroxyl-containing (meth)acrylate monomers.
  • polyurethanes or aliphatic or aromatic urethanes the tin causes unwanted decomposition of the hydroxyl-containing monomers, other monomers, or additives which contain ester functionality.
  • the monomer and the urethane are each ethylenically unsaturated since the compositions of such embodiments are cured by copolymerization through the ethylenic unsaturation of the monomer and oligomer.
  • the ethylenic unsaturation of the urethane is preferably provided by a vinyl group of a (meth)acrylate unit.
  • the ethylenic unsaturation of the hydroxy functional monomer or oligomer is preferably provided by (meth)acrylate unit, for example hydroxy alkyl (meth)acrylates are suitable.
  • the vinyl functional urethane is preferably prepared by reaction of the hydroxyl- containing polyester, polyether and/or hydroxyl-containing (meth)acrylate monomer and the isocyanate in the presence of a catalyst selected from the salts or complexes of the group consisting of bismuth, zinc, hafnium, zirconium, copper, iron, chromium, aluminum, cerium, titanium, manganese, nickel, potassium, and cobalt. Amine catalysts may also be used.
  • Such catalysts include metal based catalysts such as carboxylate complexes and salts of Bi, Zn, Ce, Co, K, and Pb including complexes with 2-ethylhexanoic acid, neodecanoic acid, acetic acid, napthanoic acid, n-octanoic acid, butyric acid, pivalic acid, and other carboxylic acids, dione complexes of Zr, Ti, Zn, Mn, Ni, Fe, Cu, and Cr, including complexes with 2,4- pentanedione, 6-methyl-2,4-heptadione, 2,2,6,6,-tetramethyl-3,5,-heptanedione, 1 -benzoyl acetone, ethyl acetoacetate, 3-ethyl-2,4-pentanedione, l,l,l-trifluoro-2,4,-pentanedione, triacetyl methane and other beta carbonyl
  • Amine based catalysts when used, may be selected from any tertiary amine, for example l,4-diazabicyclo[2.2.2]octane.
  • amine based catalysts include Bis-(2-dimethylaminoethyl)ether, benzyldimethylamine, N,N- dimethylcyclohexylamine, pentamethyldiethylenetriamine, N,N,N'-trimethyl-N'- hydroxyethylbisaminoethylether, 1 ,3-propanediamine, N'-(3-(dimethylamino)propyl)-N,N- dimethyl, N-ethylmorpholine, N-methylmorpholine, 2,2'-dimorpholinodiethylether, l,3,5-tris(3- (dimethylamino)propyl)-hexahydro-s-triazine available from Huntsman Corporation as well as catalysts available from Air Products such
  • the urethanes may contain one or more ester groups.
  • Bismuth, zinc, and amine-based catalysts are preferred with bismuth based catalysts being most preferred.
  • the vinyl functional urethane is prepared by reaction of a hydroxyl- containing monomer, polyester, and/or polyether with an isocyanate in the absence of catalyst.
  • Hydroxyl containing polyesters useful in the invention may be prepared by conventional methods known in the art such as condensation polymerization, ring opening polymerization, reaction with anhydrides and other methods.
  • Preferably the hydroxyl containing polyesters are prepared in the absence of a tin catalyst.
  • Vinyl containing polyesters can be prepared from the reaction of a (A) diol, polyol, or polyether polyol with (B) a diacid-, anhydride-, polyacid-, and/or an acid-, anhydride-, or ester- containing monomer with vinyl groups, with the ratio of (A) to (B) adjusted to give the desired molecular weight.
  • Other vinyl containing polyesters can be prepared from the ring opening polymerization of, for example, caprolactone.
  • the vinyl containing polyesters are prepared in the absence of any tin catalyst.
  • Examples of polyether polyols include any hydroxyl-containing polyether. In some embodiments the poly ethers are made via opening of epoxides.
  • Vinyl containing esters containing polyethers may be prepared via known methods including reaction of hydroxyl-containing polyethers with acid-, anhydride-, or ester containing- monomers, vinyl containing anhydrides and other methods known in the art.
  • the vinyl containing esters containing polyethers may contain one or more ester groups.
  • Examples of other hydroxyl-containing monomers, oligomers, and solvents include polyacrylates made by incorporating hydroxyl-containing monomers in the polymer. It has been discovered that a hydroxyl-containing monomer, oligomer, or solvent causes side reactions when it reacts with an ester and causes decomposition.
  • isocyanates useful in the invention include isophorone diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4'-methylene dicyclohexyl diisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, tetramethylxylylene diisocyanate, triisocyanurate, isocyanatoethyl methacrylate, isophorone diisocyanate trimer, hexamethylenediisocyanate trimer, hexamethylene diisocyanate biuret, and hexamethylene diisocyanate uretdione.
  • Isocyanate terminated prepolymers prepared from polyester, polyether or other hydroxyl functional materials may also be used. Mixtures of materials containing isocyanate groups may also be used,
  • the gel have an initial viscosity of 5 to 2500 poise.
  • the initial viscosity is preferably about 250 to 2500 poise.
  • the initial viscosity is preferably about 5-25 poise.
  • the initial viscosity is preferably about 10-40 poise. In general these viscosity differences are achieved by varying the ratio of the polyurethane or oligomers and the hydroxyl- containing monomer and other monomers.
  • these viscosity differences can be achieved by the use of thixotropic additives.
  • the improved stability of the gel compositions results in their maintaining at least 85% of their initial viscosity over one year of storage, and more preferred compositions do not lose more than 10% of their initial viscosity over a year. Most preferred compositions lose no more than 5% of their initial viscosity over one year. In cases where thixotropic additives are used to adjust the initial viscosity, the loss in viscosity on storage is observed at higher shear rates
  • decomposition of the ester containing monomers and lower levels of formation of byproducts such as crosslinkers For example, decomposition of hydroxyethyl methacrylate results in the formation of the unwanted by-product ethylene glycol dimethacrylate which can negatively affect the balance of properties of the final cured material. It is preferable that less than 10% of the ester containing monomer is decomposed over one year, more preferably less than 5% and most preferably less than 1%.
  • hydroxyl-containing monomers examples include 2-hydroxyethyl acrylate, 2- hydroxyethyl methacrylate, diethylene glycol monoacrylate, diethylene glycol
  • (meth)acrylamides such as n-methylol acrylamide.
  • the most preferred hydroxyl-containing monomers are hydroxyethyl methacrylate (HEM A) and hydroxypropyl methacrylate (HPMA). Mixtures of more than one hydroxyl-containing monomer can be used. It is preferable that the hydroxyl functional monomers be present as greater than 5% of the formulation.
  • Hydroxy functional polyurethane, polyester, and/or polyether oligomers may also be used.
  • compositions can include a hydroxyl containing solvent, an ester containing solvent, and/or a solvent containing neither hydroxyl nor ester.
  • Typical such solvents are butyl acetate and ethyl acetate.
  • examples of other such solvents are isopropanol, toluene, methyl ethyl ketone, acetone, xylene, propyl acetate, butanol, and diacetone alcohol, propylene glycol, and butyl carbitol.
  • the composition can also include typical ingredients found in commercial nail polish such as cellulose and its derivatives, for example cellulose acetate butyrate, cellulose acetate propionate, and nitrocellulose, and/or polyester resins, polymers containing acid groups, aliphatic solvents, aromatic solvents, commercial nail polish, nail polish concentrates, and the like.
  • cellulose and its derivatives for example cellulose acetate butyrate, cellulose acetate propionate, and nitrocellulose
  • polyester resins polymers containing acid groups, aliphatic solvents, aromatic solvents, commercial nail polish, nail polish concentrates, and the like.
  • compositions can be applied to a human finger nail or toe nail as a coating or can be applied to artificial nails.
  • the radiation curing step can be conducted using any conventional ultraviolet (UV) cure apparatus and cure conditions known for use in the nail coating industry.
  • UV ultraviolet
  • non-conventional catalysts i.e., catalysts other than tin, to prepare the vinyl functional urethane does not significantly affect the UV cure rate or conditions.
  • the present invention comprises in one aspect a radiation-curable gel composition
  • a radiation-curable gel composition comprising a radiation-curable gel nail coating composition comprising (a) one or more of the following: a vinyl functional urethane; a vinyl containing polyester; and/or a compound containing ester functionality which does not contain a hydroxyl group; (b) at least one hydroxyl- containing monomer, oligomer, or solvent; and (c) a photo initiator; the radiation-curable gel nail coating composition comprising less than 10 ppm tin, preferably less than 5 ppm tin, and most preferably comprising less than 1 ppm tin.
  • the components of the composition are preferably prepared either with no catalyst or in the presence of a catalyst other than tin.
  • tin is at least in part responsible for instability and resultant loss of viscosity of radiation curable nail coating gel compositions over time. Such compositions are often stored for several months before they are used. Therefore the tin free and low tin gel compositions have improved retention of viscosity and improved stability versus conventional tin catalyzed oligomers.
  • the vinyl functional urethanes can have at least one, preferably two or more acryloyl, or methacryloyl groups and a urethane group.
  • examples include urethanes based on aliphatic, aromatic, polyester, and polyether polyols and aliphatic, aromatic, polyester, and polyether diisocyanates capped with (meth)acrylate end groups and urethane (meth)acrylates made from reaction of aliphatic or aromatic isocyanates with hydroxyl-containing (meth)acrylic monomers or oligomers.
  • Epoxy urethane (meth)acrylates useful in the present invention, have at least one, preferably two or more two or more acryloyl or methacryloyl groups and a urethane group.
  • examples include epoxy (meth)acrylates based on aliphatic or aromatic epoxy prepolymers capped with a urethane (meth)acrylate end group.
  • An aliphatic or aromatic urethane spacer can be optionally inserted between the epoxy and the (meth)acrylate end group(s).
  • (Meth)acrylated polyester oligomers, useful in the present invention have at least one, preferably two or more acryloyl or methacryloyl groups and a polyester core.
  • (Meth)acrylated acrylate oligomers useful in the present invention, have at least two or more acryloyl or methacryloyl groups and a polyacrylic core. These materials can be made by methods well known in the art. Compounds containing hydroxyl groups, including polyesters, polyethers, epoxies, aliphatic or aromatic compounds can be reacted with a diisocyanate to form an isocyanate prepolymer which is subsequently reacted with a hydroxyl-containing (meth)acrylate. Alternatively, a (meth)acrylic monomer containing an isocyanate group can be reacted with the compounds containing hydroxyl groups.
  • vinyl containing isocyanates such as 3- Isopropenyl-alpha, alpha dimethybenzyl isocyanate may also be used.
  • the hydroxyl-containing (meth)acrylic monomers can also be reacted with isocyanates to form the urethane. Examples of this latter group include urethane dimethacrylate, bis hydroxy ethyl methacrylate isophorone diurethane (bis-HEMA IPDI) and the reaction product of isophorone diisocyanate and hydroxethyl acrylate.
  • Suitable compounds containing ester functionality which do not contain a hydroxyl group comprise, for example, solvents such as butyl acetate, ethyl acetate, isopropyl acetate, iso butyl acetate, monomers such as ethyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, butoxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxy propyl (meth)acrylate, phenoxyethylene glycol (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate.
  • solvents such as butyl acetate, ethyl acetate, isopropyl acetate, iso butyl acetate
  • monomers such as ethyl (meth)acrylate, methyl (meth)acrylate, but
  • these materials are prepared in the absence of tin catalysts.
  • mono (meth)acryloyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, hydroxypropyl (meth)acrylate, butyl (meth)acrylates, hydroxy ethyl (meth)acrylates, butoxyethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethoxyethyl (meth)acrylate, t-butyl aminoethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, phosphoethyl (meth)acrylate, methoxy propyl (meth)acrylate, methoxy polyethylene glycol(meth)acrylate, phenoxyethylene glycol (meth)acrylate,
  • phenoxypolyethylene glycol (meth)acrylate 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2- (meth)acryloxyethylsuccinic acid, 2-(meth)acryloylethylphthalic acid, 2- (meth)acryloyloxypropylphthalic acid, stearyl (meth)acrylate, isobornyl (meth)acrylate, 3- chloro-2-hydroxypropyl (meth)acrylates, tetrahydrofufuryl (meth)acrylate, (meth)acrylamides and allyl monomers.
  • difunctional (meth)acryloyl esters include 1,4 butane diol di(meth)acrylate, 1,6 hexananediol di(meth)acrylate, 1,9 nonanediol di(meth)acrylate, 1,10 decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl- 1,8-octane diol di(meth)acrylate, glycerin di(meth)acrylate, ethylene glycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxylated propylene glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, polyethoxypropoxy di(meth)acrylate, polye
  • Examples of tri and or higher (meth)acryloyl esters include trimethylol propane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ditrimethylol propane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylates. These monomers may contain an acidic group to improve adhesion.
  • Examples of these include Sarbox® monomers available from Sartomer Company.
  • a compound having at least one free radical polymerizable group includes not only a single component but also a mixture of polymerizable monomers. Thus combinations of two or more materials containing free radical polymerizable groups may be used.
  • the gels also contain a photo initiator.
  • a photo initiator examples include benzyl ketones, monomeric hydroxyl ketones, polymeric hydroxyl ketones, alpha-amino ketones, acyl phosphine oxides, phosphinates, metallocenes, benzophenone, benzophenone derivatives, and the like.
  • gel we mean a radiation-curable composition comprising photo initiator, ethylenically unsaturated monomers and/or oligomers, having a viscosity suitable for coating natural or artificial nails, or forming artificial nails and extensions, as well as adorning such nails.
  • Pigments and dyes may be used to color the gels. These may be added directly to the formulation.
  • Pigment concentrates can be used to provide color to the composition and when used generally contain 10-50% pigment which may be dispersed in an organic liquid comprised of one or more chemicals selected from solvents, ethylenically unsaturated monomers, and ethylenically unsaturated oligomers.
  • the organic liquid may also comprise non-reactive polymer, filler, and dispersant.
  • the organic liquid may comprise nitrocellulose.
  • the organic liquid has one continuous phase whereas the pigment is a discontinuous phase of the pigment concentrate. Examples of suitable solvents are ethyl acetate and butyl acetate.
  • ethylenically unsaturated monomers are (meth)acrylic esters
  • examples of ethylenically unsaturated oligomers are urethane (meth)acrylates.
  • the concentrates may be dispersed in the same UV- curable monomers and/or oligomers as used in the gel formulation by any means, for example by shearing of the pigment directly into the organic liquid.
  • the organic liquid comprises ethyl acetate, butyl acetate, and nitrocellulose.
  • Suitable pigments which can be incorporated into the concentrates include barium, calcium and aluminum lakes, iron oxides, chromates, molybdates, cadmiums, metallic or mixed metallic oxides, talcs, carmine, titanium dioxide, chromium hydroxides, ferric ferrocyanide, ultramarines, titanium dioxide coated mica platelets, and/or bismuth oxychlorides.
  • Preferred pigments include D&C Black No. 2, D&C Black No. 3., FD&C Blue No. 1, D&C Blue No. 4, D&C Brown No. 1, FD&C Green No. 3, D&C Green No. 5, D&C Green No. 6, D&C Green No. 8, D&C Orange No. 4, D&C Orange No.
  • D&C Orange No. 10 D&C Orange No. 11, FD&C Red No. 4.
  • D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, FD&C Red No. 40 D&C Violet No. 2, Ext. D&C Violet No. 2, FD&C Yellow No. 5, FD&C Yellow No. 6, D&C Yellow No. 7, Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, as well as others listed on the FDA color additives website, and Annex IV of the Cosmetic Directive 76/768/EEC, Coloring Agents Permitted in Cosmetics.
  • Thixotropic additives may also be used in the compositions.
  • a thixotropic additive is defined herein as an additive that when mixed with a relatively low viscosity gel imparts shelf stability to the pigmented gel. The pigment does not readily fall out of the gel to form a hard pack.
  • the thixotropic additive also imparts shear thinning properties such that a viscosity reduction of at least a factor of 2 occurs over the range of shear from l/2sec to l/70sec, i.e.- the gel is thick (viscous) under normal storage conditions, but flows (becomes thin, less viscous) when stressed such as applying the gel to nails.
  • the thixotropic additive changes the rheological properties of the gel.
  • Thixotropic additives useful in this invention include inorganic and organic materials.
  • inorganic materials useful in the invention include but are not limited to calcium, zinc or aluminum stearate, silica, fumed silica such as that available as Aerosil ® from Evonik Industries or Cab-O-Sil® available from Cabot Corporation, diatomaceous earth, bentonite clay, kaolinite, pyrophyllite, sericite, saponite, smectic/vermiculites (montmorillinite, beidillite, nontronite, hectorite and saponite), organic modified bentonite and hectorite such as stearyl alkonium hectorite and others that are available from Elementis Specialties under the trade name of Bentone®, talc, mica, zirconium oxide, zinc oxide, and magnesium oxide.
  • organic materials useful in the invention include but are not limited to hydrogenated castor oils, hydrogenated castor oil waxes, inorganically modified castor oils, organically modified castor oils such as those sold by Elementis Specialties under the Thixcin® trademark, triglycerides such as glyceryl tri-12-hydroxy stearate, polyamides and modified polyamides such as 12- hydroxystearic acid diamide of ethylene diamine, 12-hydroxystearicacid diglycolamide, N- stearyl ricinoleamide, N-stearyl stearamide and other polyamide waxes.
  • hydrogenated castor oils hydrogenated castor oil waxes
  • inorganically modified castor oils organically modified castor oils such as those sold by Elementis Specialties under the Thixcin® trademark
  • triglycerides such as glyceryl tri-12-hydroxy stearate
  • polyamides and modified polyamides such as 12- hydroxystearic acid diamide of ethylene diamine, 12-hydroxystearicacid
  • polyamide materials include those sold commercially by Kusumoto Chemicals Industries under the Disparlon® trademark, by Lehmann and Voss under the Luvotix® trademark, by Elementis Specialties under the Thixatrol® trademark, polyethylene oxide waxes, urea urethanes believed to be exemplified by those sold by Byk Incorporated as, for example, by Byk-410, Byk-411, and Byk-420, acrylic resins, amine salts of polymeric polyesters, salts of linear polyaminoamide and polymeric polyester, amide solutions of polycarboxylic acid, alkyl sulfonate, alkylallyl sulfonate, colloidal ester, polyester resin such as those sold by Elementis Specialties under the Thixatrol® trademark, phenol resin, melamine resin, epoxy resin, urethane resin, styrene butadiene polymers, polyimide resin, and polyester amides. Materials such as those sold by Byk under the trademark
  • Thixo tropic additives can be used at amounts from 0.1 to 10 wt.%. It is preferred to use quantities from 0.5 to 5.0 wt.% and more preferred to use amounts of 0.5 to 3.0 wt %.
  • the preferred thixotropic additives are polyamides, urea urethanes, and silica, or a mixture thereof.
  • Example 1 The procedure of Example 1 was used substituting 0.34g of Bicat 8108 (Shepherd Chemical) for the DBTDL.
  • Example 3 Preparation of Polyester oligomer with Diazobicycloundecene
  • the procedure of Example 1 was followed substituting 0.16g of diazobicycloundecene for the DBTDL.
  • polybutylene adipate diol prepared without catalyst (Fomrez 44-114U, Chemtura Co.) under dry air.
  • the reaction was heated to 50°C and 0.32g of DBTDL was added. After the exotherm the reaction was allowed to cool to 60°C and 0.8g BHT was added followed by addition of 0.6 moles of HEA over 35 minutes. The reaction was held at 85°C until no isocyanate peak remained in the infrared spectrum.
  • Example 5 The procedure of Example 5 was repeated substituting 0.5g of Bicat 8108 (Shepherd Chemical) for the DBTDL.
  • polybutylene adipate diol prepared without catalyst (Fomrez 44-114U) under dry air.
  • the reaction was heated to 50°C and 0.19g of Diazobicycloundecene was added. After the exotherm the reaction was allowed to cool to 60°C and 0.8g BHT was added followed by addition of 0.4 moles of HEA over 35 minutes. The reaction was held at 70°C until no isocyanate peak remained in the infrared spectrum.
  • Example 8 Preparation of Polyester oligomer with bismuth neodecanoate/zinc neodecanoate [0068] The procedure of Example 7 was repeated substituting 0.48g of Bicat 8 (Shepherd Chemical) for the diazobicycloundecene.
  • Curable nail formulations were prepared as shown in Table 1. All values are in weight percent.
  • Viscosities were measured at 25°C at shear rates of 2, 19, 36, 53, 70 sec "1 on a TA Instruments AR1500EX rheometer after initial preparation and after one month ageing at 50° C. One month accelerated ageing at 50° C. is equivalent to six months normal ageing at room temperature. Minimal ( ⁇ 1 unit) change in viscosity is seen over this range of shear and an average of all five values was used. Tin levels were measured using Inductively Coupled Plasma by Robertson Microlit Laboratories. Table 2 shows the results.
  • Viscosities were measured at 25°C at shear rates of 2, 19, 36, 53, 70 sec "1 on a TA Instruments AR1500EX rheometer after initial preparation and after two months ageing at 50°C. Two months accelerated ageing at 50° C. is approximately equivalent to one year normal ageing at room temperature. Minimal ( ⁇ 1 unit) change in viscosity is seen over this range of shear and an average of all five values was used. Tin levels were measured using Inductively Coupled Plasma by Robertson Micro lit Laboratories. Table 4 shows the results.
  • Curable nail formulations were prepared as shown in Table 5.
  • Viscosities were measured at 25°C at a shear rate of 70 sec "1 on a TA Instruments AR1500EX rheometer after initial preparation and after one month ageing at 50°C. Tin levels were measured using Inductively Coupled Plasma by Robertson Microlit Laboratories. Table 6 shows the results.
  • Example 20 The procedure of Example 20 was repeated substituting 0.19g DBTDL for the bismuth neodeanoate.
  • Example 22 The procedure of Example 22 was repeated substituting 0.36 g of DBTDL for the bismuth neodecanoate.
  • Curable formulations were as shown in Table 7. Gas chromatography was used to analyze for HEMA, SR268 and TPO. Initial chromatograms showed no ethylene glycol dimethacrylate in any of the formulations. After ageing for two months at 50°C both samples, Ex. 21 and Ex. 23, containing oligomers made with DBTDL showed the formation of ethylene glycol dimethacrylate along with another material believed to be due to reaction with SR268, while those made with bismuth catalyst, Ex. 20 and Ex. 22, showed neither of these byproducts. Two months accelerated ageing at 50° C. is equivalent to one year normal ageing at room temperature.

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BR112014032271A BR112014032271A2 (pt) 2012-06-22 2013-06-21 composição para revestimento de unha de gel curável por radiação, método de revestimento da unha dos pés ou das mãos humanos, método de preparação de unha artificial
EP13807308.5A EP2863883A4 (en) 2012-06-22 2013-06-21 RADIATION-HARDENABLE, STABLE, NAIL-ANGLE COMPOSITIONS AND METHOD FOR THE PREPARATION AND USE THEREOF
CA2877559A CA2877559C (en) 2012-06-22 2013-06-21 Stable, tin-free radiation curable nail gel compositions and methods of preparation thereof
EP18198909.6A EP3449905A1 (en) 2012-06-22 2013-06-21 Radiation-curable, stable nail gel compositions and methods of preparation and use
US14/410,313 US20150335568A1 (en) 2012-06-22 2013-06-21 Radiation-curable, stable nail gel compositions and methods of preparation and use
KR20157001757A KR20150028995A (ko) 2012-06-22 2013-06-21 방사선-경화성의 안정한 손발톱 겔 조성물, 그의 제조방법 및 용도
CN201380037663.4A CN104470495A (zh) 2012-06-22 2013-06-21 可辐射固化的稳定的指甲凝胶组合物以及其制备和使用方法
JP2015518607A JP2015520242A (ja) 2012-06-22 2013-06-21 エネルギー線硬化性で安定なネイルゲル組成物、ならびに製造方法および使用方法
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015195659A1 (en) * 2014-06-16 2015-12-23 Elementis Specialties, Inc. Acrylate gel nail coating compositions
US20160303028A1 (en) * 2013-12-04 2016-10-20 L'oreal Photo-crosslinkable varnish compositions as base coating and application methods
WO2016179024A1 (en) * 2015-05-01 2016-11-10 Soo-Jin Yang Chemically minimized system for time reduced application of eyelash extensions
WO2017217983A1 (en) * 2016-06-15 2017-12-21 Mycone Dental Supply Co., Inc. One part acrylic nail formulation
US10639255B2 (en) * 2014-12-17 2020-05-05 L'oreal Nail treatment system
US11033482B2 (en) 2014-11-07 2021-06-15 Arkema France Removable coating systems and methods

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2998797B1 (fr) * 2012-12-05 2015-02-13 Oreal Composition cosmetique photoreticulable non collante
FR2998784B1 (fr) * 2012-12-05 2015-02-13 Oreal Composition cosmetique photoreticulable a haute brillance
FR2998790B1 (fr) * 2012-12-05 2015-01-09 Oreal Composition photoreticulable pour le maquillage des ongles
US11000469B1 (en) 2018-07-06 2021-05-11 Orly International, Inc. Nail gel builder composition
EP3744748A1 (de) * 2019-05-27 2020-12-02 Covestro Deutschland AG Verfahren zur herstellung eines gemischten silanterminierten polymers
CN113527628B (zh) * 2020-09-30 2022-12-30 南京聚发新材料有限公司 一种热固化聚氨酯丙烯酸树脂和应用
KR102266629B1 (ko) * 2021-01-21 2021-06-18 신성민 젤네일 스티커 및 그 제조방법
KR102384577B1 (ko) * 2021-09-23 2022-04-08 이미숙 내향성 손발톱 교정용 조성물
DE112022001357T5 (de) * 2022-02-15 2023-12-21 Taisei Kogyo Co., Ltd. Lichthärtender Urethan-Gelkörper und Verfahren zu dessen Herstellung
DE112023000051B4 (de) * 2022-04-22 2025-06-18 Taisei Kogyo Co., Ltd. Verfahren zur Herstellung einer Verbindungsstruktur

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6803394B2 (en) * 1999-12-17 2004-10-12 Gel Products, Inc. Radiation curable nail coatings and artificial nail tips and methods of using same
US7879994B2 (en) * 2003-11-28 2011-02-01 Eastman Chemical Company Cellulose interpolymers and method of oxidation
US20120004340A1 (en) * 2010-03-16 2012-01-05 Mycone Dental Supply Company, Inc. Method of preparation of radiation-curable colored artificial nail gels
US20120041131A1 (en) * 2009-10-31 2012-02-16 Bayer Materialscience Ag Tin-free aqueous polyurethane dispersions

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4178303A (en) * 1979-01-26 1979-12-11 Gaf Corporation (2-Cyano-3,3-diphenylacryloxy) alkylene acrylic acid esters
US4761363A (en) * 1985-06-20 1988-08-02 M&T Chemicals Inc. UV curable compositions for making improved solder mask coatings
US5550264A (en) * 1994-07-13 1996-08-27 Henkel Corporation Process for the removal of dissolved metallic catalyst from ester products
TWI237052B (en) * 2001-07-26 2005-08-01 Surface Specialties Sa Radiation curable powder coating compositions
JP2006057025A (ja) * 2004-08-20 2006-03-02 Sanyo Chem Ind Ltd 活性エネルギー線硬化型ウレタン（メタ）アクリレート組成物
US20070048441A1 (en) * 2005-08-31 2007-03-01 Basf Corporation Radiation curable clearcoat repair system and method for obtaining film build in thin film areas using the system
DE102007045944A1 (de) * 2007-09-25 2009-04-09 Evonik Degussa Gmbh Verfahren zur lösemittelfreien, kontinuierlichen Herstellung von zinnfreien, strahlungshärtbaren Urethanacrylaten auf Basis von carbonylhydrierten Keton-Aldehydharzen und/oder hydrierten Keton und/oder carbonylhydrierten und kernhydrierten Keton-Aldehydharzen auf Basis von aromatischen Ketonen, die hergestellten Produkte und deren Verwendung
WO2011016531A1 (ja) * 2009-08-05 2011-02-10 Jsr株式会社 爪装飾用硬化性組成物、爪装飾の形成方法、及び、爪装飾の除去方法
ES2699693T3 (es) * 2010-01-25 2019-02-12 Mycone Dental Supply Company Inc Formulaciones de recubrimiento de uñas curables por radiación ultravioleta a base de polioles renovables
US20110226271A1 (en) * 2010-03-16 2011-09-22 Mycone Dental Supply Company, Inc. Method of Preparation of Radiation-Curable Colored Artificial Nail Gels
US20130025617A1 (en) * 2010-03-16 2013-01-31 Mycone Dental Supply Co., Inc. Method of preparation of radiation-curable colored artificial nail gels
JP2011229725A (ja) * 2010-04-28 2011-11-17 Jsr Corp 爪装飾の形成方法およびその除去方法、並びに、爪装飾および爪装飾用キット

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6803394B2 (en) * 1999-12-17 2004-10-12 Gel Products, Inc. Radiation curable nail coatings and artificial nail tips and methods of using same
US7879994B2 (en) * 2003-11-28 2011-02-01 Eastman Chemical Company Cellulose interpolymers and method of oxidation
US20120041131A1 (en) * 2009-10-31 2012-02-16 Bayer Materialscience Ag Tin-free aqueous polyurethane dispersions
US20120004340A1 (en) * 2010-03-16 2012-01-05 Mycone Dental Supply Company, Inc. Method of preparation of radiation-curable colored artificial nail gels

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BLANK, WERNER J.: "Advances in catalysis for organic coatings", CHIMIA INTERNATIONAL JOURNAL FOR CHEMISTRY 0009-4293, vol. 56, no. 5, May 2002 (2002-05-01), pages 191 - 196, XP008175723 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160303028A1 (en) * 2013-12-04 2016-10-20 L'oreal Photo-crosslinkable varnish compositions as base coating and application methods
WO2015195659A1 (en) * 2014-06-16 2015-12-23 Elementis Specialties, Inc. Acrylate gel nail coating compositions
US11033482B2 (en) 2014-11-07 2021-06-15 Arkema France Removable coating systems and methods
US10639255B2 (en) * 2014-12-17 2020-05-05 L'oreal Nail treatment system
WO2016179024A1 (en) * 2015-05-01 2016-11-10 Soo-Jin Yang Chemically minimized system for time reduced application of eyelash extensions
US10907075B2 (en) 2015-05-01 2021-02-02 Cosmo Spa Lounge & Supply, Inc. Chemically minimized system for time reduced application of eyelash extensions
WO2017217983A1 (en) * 2016-06-15 2017-12-21 Mycone Dental Supply Co., Inc. One part acrylic nail formulation

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