WO2006009798A1 - Composition and method for producing colored bubbles - Google Patents

Composition and method for producing colored bubbles Download PDF

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Publication number
WO2006009798A1
WO2006009798A1 PCT/US2005/021362 US2005021362W WO2006009798A1 WO 2006009798 A1 WO2006009798 A1 WO 2006009798A1 US 2005021362 W US2005021362 W US 2005021362W WO 2006009798 A1 WO2006009798 A1 WO 2006009798A1
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WO
WIPO (PCT)
Prior art keywords
surfactant
bubble
dye
colorant
substantially uniformly
Prior art date
Application number
PCT/US2005/021362
Other languages
French (fr)
Inventor
Ram W. Sabnis
Timothy D. Kehoe
Original Assignee
C2C Technologies Llc
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Publication date
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Application filed by C2C Technologies Llc filed Critical C2C Technologies Llc
Priority to CA2570703A priority Critical patent/CA2570703C/en
Priority to EP05760290A priority patent/EP1794273A1/en
Publication of WO2006009798A1 publication Critical patent/WO2006009798A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • This invention relates generally to colored bubbles, and more specifically to a composition and method for producing substantially uniformly colored bubbles.
  • the compositions are non-toxic and, if necessary, are washable.
  • bubble blowing involves dipping a shaped article having an opening into a liquid soap solution followed by blowing into the opening to form one or more b ubbles.
  • a bubble is g enerally defined as a small volume of gas contained within a thin liquid spherical envelop.
  • a wand for example, is generally immersed into a bubble solution and air is blown through spherical opening to generate bubbles. Surface tension causes the bubble solution to for a film across the opening. Upon application of a sufficient force or pressure upon one side of the film, a bubble is formed and expelled from the opening.
  • a variety of bubble solutions have been marketed over the years, many of them claiming to have special features like longer lasting bubbles, solutions that produce greater numbers of bubbles, or solution that provide bubbles having a colorful in appearance.
  • Some manufacturers adorn their bubble packaging with illustrations of colored bubbles, or add colorants to tint their bubble solution, in an effort to provoke the illusion of a colored bubble.
  • Some manufactures have added modifying agents like glycerin to produce a transparent bubble with a transparent iridescent rainbow effect.
  • One manufacturer added color directly to the bubble and/or the bubble solution in an effort to create designs on a piece of paper with what they labeled a colored bubble.
  • This composition of liquid solution does not produce a visually colored bubble, but rather a bubble that is used as a vehicle to transport the color to the marking surface.
  • the bubble wall is transparent and does not produce a uniformly colored bubble. Rather the color runs to the bottom of the bubble wall.
  • Others manufacturers claim to produce bubble that is illuminated when viewed in the dark with infrared radiation or black light, but transparent in regular light. [005] Therefore, a need exists for the development of a solution, and a resultant bubble, that provides a substantially uniform color.
  • the present invention surprisingly provides colored bubble compositions, that have a uniform coloration about the bubble.
  • compositions of the present invention can also be used in, but not limited to, other fields such as toys, toothpaste, bath bubbles, shampoo, soaps, creams, lotions, diapers, lenses, paint, inks, adhesives, displays, semiconductors, biomedical, photonics, face masks, hair colors, plastics, and textiles.
  • the present invention provides an aqueous composition that includes a surfactant and a colorant.
  • the compositions provide a bubble that is a uniformly colored bubble.
  • Suitable colorants include dyes, polymeric dyes, fluorescent dyes, pigments, and/or colorants.
  • the compositions are non-toxic and/or washable, if necessary.
  • the substantially uniformly colored bubble includes a surfactant that is a polyether, an alkyl metal sulfate, a betaine, an alkanolamide or a combination thereof, hi one embodiment, the polyether surfactant is a cellulose ether surfactant., hi another embodiment, the alkyl metal sulfate is sodium lauryl sulfate.
  • the substantially uniformly colored bubble includes a surfactant that is a combination of a polyether surfactant and an alkyl metal sulfate.
  • the substantially uniformly colored bubble includes a polyether surfactant that is a cellulose ether surfactant and the alkyl metal sulfate is sodium lauryl sulfate.
  • the substantially uniformly colored bubble includes a surfactant that is a combination of an alkyl metal sulfate, a betaine and an alkanolamide.
  • the present invention provides methods to prepare compositions that provide the various bubble producing solutions used throughout the present specification.
  • the method to prepare a solution for a substantially uniformly colored bubble solution includes the steps of heating a mixture of glycerin, colorant and water to a temperature between about 50°C and about
  • Typical colorants include acid dyes, FD&C dyes, food dyes, polymeric dyes, fluorescent dyes, pigments, or combinations thereof.
  • the surfactant is a polyether, an alkyl metal sulfate, or a combination thereof.
  • Suitable polyether surfactants include cellulosic polyethers and suitable alkyl metal sulfates include lauryl sulfates having a metal counterion.
  • methods to prepare a solution for a substantially uniformly colored bubble solution include combining glycerin, colorant, water, an alkanolamide and an alkyl metal sulfate to form a mixture. The mixture is then heated to a temperature below about 6O 0 C and is then cooled to room temperature.
  • Typical colorants include acid dyes, FD&C dyes, food dyes, polymeric dyes, fluorescent dyes, pigments, or combinations thereof.
  • kits that include the compositions of the invention and instructions how to prepare bubbles from the compositions.
  • the present invention surprisingly provides bubble compositions that have substantially uniform coloration about the bubble.
  • the bubbles can have a wide range of opacity, colors and scents.
  • the compositions and resultant bubbles are non-toxic and/or washable.
  • the present invention further provides compositions and methods for producing bubbles, as described herein, having a wide range of opacities, ranging from essentially translucent to semi-transparent to opaque.
  • the bubbles can be intrinsically colored; the composition from which the bubbles are formed itself is colored.
  • the bubbles have substantially uniform color intensity. In other embodiments, the bubbles can have non-uniform color intensity and/or dispersion.
  • substantially uniform or “substantially uniformly” are intended to refer to coloration about the bubble such that the coloration intensity is approximately equal from the top of the bubble to the bottom of the bubble.
  • the coloration in the bubble is dispersed evenly throughout the bubble and coloration streaking or having an increased concentration of color at the bottom of the bubble is substantially avoided.
  • the coloration throughout the bubble can be such that a swirling pattern, random or non-random, can be seen on the surface of the bubble's film, but yet not having an increased concentration of color at the bottom of the bubble.
  • the substantially uniform color could be considered “solid” or could have a swirled aspect.
  • non-uniform or “non-uniformly” are intended to refer to coloration about the bubble such that the coloration intensity is concentrated, for example, more at the top and bottom of the bubble. Such fanciful bubbles can be very interesting to children.
  • colored bubble is intended to refer to a bubble that can be uniformly or non-uniformly colored, as described herein, but does not have a change in coloration over a given period of time and does not have the coloration disappear from the bubble. Colored bubbles retain their coloration throughout the period of time the bubble exists, generally from about a few seconds to about a few minutes.
  • compositions of the invention include a surfactant.
  • Suitable surfactants include anionic, cationic, nonionic or zwitterionic compounds and combinations thereof.
  • the surfactant can be either polymeric or non-polymeric.
  • surfactant is recognized in the relevant art to include those compounds which modify the nature of surfaces, e.g. reducing the surface tension of water. Surfactants are generally classified into four types: cationic (e.g.
  • modified onium salts where part of the molecule is hydrophilic and the other consists of straight or branches long hydrocarbon chains such as hexadecyltrimethyl bromide
  • anionic also known as amphiphatic agents (e.g., alkyl or aryl or alkylarylsulfonates, carboxylates, phosphates), nonionic (e.g., polyethylene oxides, alcohols) and ampholytic or amphoteric (e.g. dodecyl-beta- alanine, such that the surfactant contains a zwitterionic group).
  • anionic also known as amphiphatic agents (e.g., alkyl or aryl or alkylarylsulfonates, carboxylates, phosphates), nonionic (e.g., polyethylene oxides, alcohols) and ampholytic or amphoteric (e.g. dodecyl-beta- alanine, such that the surfactant contains a z
  • Cationic surfactants useful as surface tension reducing agents in the present invention include long chain hydrocarbons which contain quaternarized heteroatoms, such as nitrogen.
  • Suitable cationic surfactants include quaternary ammonium compounds in which typically one of the groups linked to the nitrogen atom is a C 12-Cl 8 alkyl group and the other three groups are short chained alkyl groups.
  • Anionic surfactants are characterized by a single lipophilic chain and a polar head group which can include sulfate, sulfonate, phosphate, phosphonate and carboxylate.
  • exemplary compounds include linear sodium alkyl benzene sulfonate (LAS), linear alkyl sulfates and phosphates, such as sodium lauryl sulfate (SLS) and linear alkyl ethoxy sulfates.
  • anionic surfactants include substituted ammonium (e.g., mono-, di-, and tri-ethanolammonium), alkali metal and alkaline earth metal salts of C6-C20 fatty acids and rosin acids, linear and branched alkyl benzene sulfonates, alkyl ether sulfates, alkane sulfonates, olefin sulfonates, hydroxyalkane sulfonates, fatty acid monoglyceride sulfates, alkyl glyceryl ether sulfates, acyl sarcosinates. acyl N-methyltaurides, and alkylaryl sulfonated surfactants, such as alkylbenezene sulfonates.
  • substituted ammonium e.g., mono-, di-, and tri-ethanolammonium
  • Nonionic surfactants do not dissociate but commonly derive their hydrophilic portion from polyhydroxy or polyalkyloxy structures.
  • Suitable examples of polyhydroxy (polyhydric) compounds include ethylene glycol, butylene glycol, 1,3-butylene glycol, propylene glycol, glycerine, 2-methyl-l,3- propane diol, glycerol, mannitol, corn syrup, beta-cyclodextrin, and amylodextrin.
  • Suitable examples of polyalkyloxy compounds include diethylene glycol, dipropylene glycol, polyethylene glycols, polypropylene glycols and glycol derivatives.
  • Suitable nonionic surfactants include other linear ethoxylated alcohols with an average length of 6 to 16 carbon atoms and averaging about 2 to 20 moles of ethylene oxide per mole of alcohol; linear and branched, primary and secondary ethoxylated, propoxylated alcohols with an average length of about 6 to 16 carbon atoms and averaging 0-10 moles of ethylene oxide and about 1 to 10 ⁇ moles of propylene oxide per mole of alcohol; linear and branched alkylphenoxy (polyethoxy) alcohols, otherwise known as ethoxylated alkylphenols, with an average chain length of 8 to 16 carbon atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; and mixtures thereof.
  • suitable nonionic surfactants include polyoxyethylene carboxylic acid esters, fatty acid glycerol esters, fatty acid and ethoxylated fatty acid alkanolamides.
  • Block copolymers of propylene oxide and ethylene oxide, and block polymers of propylene oxide and ethylene oxide with propoxylated ethylene diamine are also included as acceptable nonionic surfactants.
  • Semi-polar nonionic surfactants like amine oxides, phosphine oxides, sulfoxides, and their ethoxylated derivatives are included within the scope of the invention.
  • Suitable amphoteric and zwitterionic surfactants which contain an anionic water-solubilizing group, a cationic group and a hydrophobic organic group include amino carboxylic acids and their salts, amino dicarboxylic acids and their salts, alkylbetaines, alkyl aminopropylbetaines, sulfobetaines, alkyl imidazolinium derivatives, certain quaternary ammonium compounds, certain quaternary phosphonium compounds and certain tertiary sulfonium compounds [037] Examples of anionic, nonionic, cationic and amphoteric surfactants that are suitable for use in the present invention are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 22, pages 347- 387, and McCutcheon's Detergents and Emulsifiers, North American Edition,
  • Typical concentration ranges of surfactant that are useful in the present compositions are from about 0.01 parts by weight to about 90 parts by weight, from about 0.5 part by weight to about 50 parts by weight, and from about
  • surfactants useful in the compositions of the invention include, but are not limited to, cellulose ethers or mixtures with other surfactants, which are water soluble.
  • Cellulose ether surfactants have unique foaming and bubble forming properties which make them ideal of colored bubble applications.
  • Cellulose ethers used in the present invention include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, higher alkyl, aryl, alkoxy, cycloalkyl celluloses, hydroxypropyl cellulose, hydroxybutyl cellulose or mixtures thereof.
  • cellulose ether surfactants include, but are not limited to, Methocel A4M, methyl cellulose, Methocel F4M, hydroxypropyl methylcellulose, Methocel K4M, hydroxypropyl methylcellulose, manufactured by Dow Chemical Co., Mildland, MI; Natrosol, hydroxyethyl cellulose, Klucel, hydroxypropyl cellulose, Aqualon Cellulose Gum, sodium carboxymethyl cellulose, Hercules Inc., Wilmington, DE; Elfacos CD 481, ethyl 2-hydroxyethyl ether cellulose, manufactured by Akzo Nobel, Chicago, IL.
  • Cellulose ether surfactants are generally present in amounts from about 1% up to about 40% by weight in the compositions of the invention.
  • Suitable concentrations of cellulose ether surfactants are in the range of about 2% to about 30% by weight and from about 3% to about 8% by weight.
  • a particularly useful cellulosic ether surfactant in the compositions is Methocel
  • alkanolamide or a mixture with other surfactants can be used in the compositions of the invention.
  • Alkanolamides are commercially available and are the reaction products of one or more fatty acids having 12 or more carbon atoms and a lower alkanolamime. Typical alkanolamides are formed by reaction between stearic, mystiric, lauric acid or mixtures thereof with mono-, di-, and/or iso-propanolamine.
  • Alkanolamides can be present in the compositions of the invention in the ranges generally described throughout the application but generally are present in amounts from about 0% up to about 10% by weight. Suitable ranges include from about 1% to about 6% by weight and in particular from about 1.5% to about 4% by weight.
  • the alkanolamide surfactants of the present invention include, but are not limited to, Ninol 55LL, diethanolamine, Ninol 40CO, cocamide DEA, Ninol 30LL, lauramide DEA, manufactured by Stepan Co., Northfield, IL; Colamid C, cocamide DEA, Colamid 0071-J, alkanolamide, manufactured by Colonial Chemical Inc., S. Pittsburgh, TN.
  • the alkanolamides are Ninol 55LL, and Colamid C.
  • Exemplary sulfosuccinates that can be employed in the present compositions include, but are not limited to, Stepan-Mild SL3-BA, disodium laureth sulfosuccinate, Stepan-Mild LSB, sodium lauryl sulfosuccinate, manufactured by Stepan Co., Northfield, IL, Lankropol 4161L, sodium fatty alkanolamide sulfosuccinate and Colamate-DSLS, disodium laureth sulfosuccinate, manufactured by Colonial Chemical Inc., S. Pittsburgh, TN.
  • Suitable betaines that can be employed in the present compositions include, but are not limited to, Miracare BC-27, cocamidopropyl betaine and Miranol Ultra C-37, sodium cocoampho acetate, manufactured by J & S Chemical Co., Weston, FL.
  • Suitable sulfates that can be employed in the present compositions include Rhodapex ES-2, sodium laureth sulfate, J & S Chemical Co., Weston, FL; Witcolate WAQ, sodium alkyl sulfate, manufactured by Akzo Nobel, Chicago, I and Colonial-SLS, sodium lauryl sulfate, manufactured by Colonial Chemical
  • a suitable nonionic surfactant that can be employed in the present compositions is Triton H-66, alkyl aryl alkoxy potassium salt, manufactured by
  • the surfactant used is a combination of an ether based surfactant, such as a cellulose ether surfactant and an sodium alkyl sulfate, such as sodium lauryl sulfate.
  • the surfactant is a combination of
  • Methocel A4M (4 weight percent in aqueous solution) and sodium lauryl sulfate
  • the total weight of the ether surfactant and the alkyl sulfate surfactant of the total weight of the composition is between about
  • 3 percent and about 8 percent by weight more particularly between about 3 percent and about 5 percent by weight, and in particular about 5 percent by weight.
  • the surfactant used is a combination of an alkanolamide and a mixture of an alkyl betaine and/or an alkyl sulfonate.
  • the surfactant is a combination of
  • Colamid C and Miracare B C27 which is a mixture of Surfactant blend include sodium trideceyl sulfate, water, PEG 80 sorbitant laurate, cocamidopropyl betaine, sodium lauroamphoacetate, PEG 150 distearate, sodium laureth-13 carboxylate, glycerin, citric acid, tetrasodium EDTA, quaternium-15.
  • the combination of the alkanolamide and alkylsulfonate/betaine is in the range of between about 1:1 to about 1:7, more particularly between about 1:1 to about 2:7 and more particularly about 2:7.
  • the combination of the two surfactants comprises a concentration between about 3 and about 10 percent by weight of the total weight of the composition, and more particularly between about 5 and about 10 percent by weight of the total weight of the composition, and in particular about 9 percent of the total weight of the composition.
  • aqueous c ompositions of the invention can further include a solvent or other additives as described throughout the present application.
  • Suitable solvents include, for example, alcohols having a carbon chain length of from about 1 carbon atom to about 12 carbon atoms.
  • alcohols having a carbon chain length of from about 1 carbon atom to about 12 carbon atoms.
  • methanol and ethanol are not included due to their generally recognized properties, especially in view of use with children.
  • Suitable optional additives to the compositions of the invention include, humectants, preservatives, fragrance, dye blockers, cleaners, etc.
  • humectant helps to retard the evaporation of water from the composition of the invention, thus avoiding premature drying during the application. Not to be limited by theory, it is believed that the presence of a humectant helps to strengthen the bubble formation, enhances even distribution of the dye throughout the bubble and increases life of bubble in the air.
  • humectants include, but are not limited to, polyhydroxy alkyls, such as glycerin, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, hydroxylated starches and mixtures of these materials. Any effective amount of humectant may be used although a generally useful concentration range for these humectants is from about 5% to about 35% by weight of the total composition. Particular ranges of the humectant include a range of from about 8% to about 30% by weight of the composition and from about 10% to about 25% by weight of the composition. In one particular aspect, the humectant is glycerin.
  • preservatives include, but are not limited to, glutaraldehyde, bicyclic oxazolidones, hydroxybenzoic acid esters, 3- iodo-2-propynyl butyl carbamate, methyl p-hydroxybenzoate, and a biocide comprising 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin- 3-one.
  • the preservatives often serves as both a bactericide and a fungicide.
  • compositions of the invention include preservatives that are selected from, but not limited to, Liquid Germall Plus, iodopropynyl butyl carbamate, Germall II, diazolidinyl urea, Nuosept 95, bicyclic oxazolidines solution, manufactured by ISP (International Specialty Products), Wayne, NJ, Troysan 395, dihydroxy-dimethyl hydantoin, manufactured by Troy Chemical Corporation, Florham park, NJ and Kathon PFM, isothiazolinones, manufactured by Rohm & Haas Co., Philadelphia, PA
  • Preservatives when present in the compositions of the invention, are generally present in amounts from about 0.01% to about 6% by weight, in ' particular from about 0.05% to about 5% by weight, and particularly from about 0.1% to about 2.5% by weight.
  • the preservative is one of Liquid Germall Plus, Tryosan 395 or Nuosept 95.
  • fragrances include those pleasing to children such as flowers, candy, popcorn, fruit, bubble gum and the like.
  • a fragrance when present in the compositions of the invention, is generally present in amounts from about 0.1% to about 10% by weight of the total weight of the composition.
  • Dye blockers or cleaners can be optionally added in the compositions of the invention to remove dye from hard/porous surfaces such as wood, stone, brick, leather, cloth, concrete, skin, fabric, etc. Up until the present invention, contact with a solution having a dye could stain a surface.
  • Suitable dye blockers include, but are not limited to, Bio-Terge
  • PAS-8S sodium octane sulfonate, Stepanate SXS, sodium xylenesulfonate, Steposol DG, fatty alcohol ethoxylate, manufactured by Stepan Co., Northfield, IL, Dowfax 8390, disodium hexadecyldiphenyloxide disulfonate, Dowfax 2Al, benzene- 1,1-oxybis-tetrapropylene sulfonated sodium, Dowfax 3B2, decyl- sulfophenoxy-benzenesulfonic acid-disodium, Dowfax ClOL, decyl- sulfophenoxybenzenesulfonicacid disodium, Triton X- 15, octylphenoxypolyethoxyethanol, manufactured by Dow Chemical Co., Mildland, MI, Tamol SN, sodium salt of naphthalene-formaldehyde condensate, Tamol 731, sodium
  • Dye blockers or cleaners are usually effective in the compositions of the invention when present in any amount but generally are present in ranges from about 5% up to about 50% by weight, from 10% to about 40% by weight or from about 12% to about 25% by weight.
  • Suitable colorants can be selected from various dye/pigments classes that include, but are not limited to acid dyes, food dyes (FD&C)/cosmetic dyes (D & C), polymeric dyes, fluorescent dyes and pigments [066] Suitable dyes can be selected from various dye classes that include, but are not limited to acid dyes, basic dyes, direct dyes, reactive dyes, sulfur dyes, fluorescent dyes, food dyes (FD&C) cosmetic dyes (D & C), solvent dyes and polymeric dyes.
  • acid dye or “acidic dye” are recognized in the art and are intended to include those water soluble anionic dyes , that are applied to a material from neutral to acid solution. Attachment to the material is attributed, at least partly, to salt formation between anionic groups in the dyes and cationic groups in the material.
  • acid dyes have functional groups such as azo, triaryl methane or anthraquinone that include acid substituents such as nitro, carboxy or sulfonic acid groups.
  • Acid dyes useful in the present compositions include, but are not limited to, Acid Black 1, Acid Black 2, Acid Black 24, Acid Black 48, Acid Blue 1, Acid Blue 7, Acid Blue 9, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 74, Acid Blue 80, Acid Blue 83, Acid Blue 90, Acid Blue 92, Acid Blue 113, Acid Blue 120, Acid Blue 129, Acid Blue 147, Acid Green 1, Acid Green 3, Acid Green 5, Acid Green 25, Acid Green 27, Acid Green 50, Acid Orange 6, Acid Orange 7, Acid Orange 8, Acid Orange 10, Acid Orange 12, Acid Orange 51, Acid Orange 51, Acid Orange 63, Acid Orange 74, Acid Red 1, Acid Red 4, Acid Red 8, Acid Red 14, Acid Red 17, Acid Red 18, Acid Red 26, Acid Red 27, Acid Red 29, Acid Red 37, Acid Red 44, Acid Red 50, Acid Red 51, Acid Red 52, Acid Red 66, Acid Red 73, Acid Red 87, Acid Red 88, Acid Red 91, Acid Red 92, v Acid Red 94, Acid Red 97, Acid Red 103, Acid Red 114, Acid Red
  • base dye or “basic dye” are recognized in the art and are intended to include those water soluble cationic dyes that are applied to a material from neutral to basic solution.
  • basic dyes have functional groups such as sulfonium, oxonium, or quarternary ammonium functional groups. Attachment to the material is attributed, at least partly, to salt formation between cationic groups in the dyes and anionic groups in the material.
  • Basic Blue 2 useful in the present compositions include, but are not limited to, Basic Black 2, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 11, Basic Blue 12, Basic Blue 16, Basic Blue 17, Basic Blue 24, Basic Blue 26, Basic Blue 41, Basic Blue 66, Basic Blue 140, Basic Brown 1, Basic Brown 4, Basic fuchsin, Basic Green 1, Basic Green 4, Basic Green 5, Basic Orange 2, Basic Orange 14, Basic Orange 21, Basic Red 1, Basic Red 2, Basic Red 5, Basic Red 9, Basic Red 29, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Yellow 1 and Basic Yellow 2.
  • Basic Black 2 Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 11, Basic Blue 12, Basic Blue 16, Basic Blue 17, Basic Blue 24, Basic Blue 26, Basic Blue 41, Basic Blue 66, Basic Blue 140, Basic Brown 1, Basic Brown 4, Basic fuchsin, Basic Green 1, Basic Green 4, Basic Green 5, Basic Orange 2, Basic Orange 14, Basic Orange 21, Basic Red 1, Basic Red 2, Basic Red 5, Basic Red 9, Basic Red 29, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Yellow 1 and Basic Yellow 2.
  • direct dye is recognized in the art and is intended to include those water soluble dyes that adsorb onto a material. Bonding is believed to occur through hydrogen bonding and/or Van der Waals forces between the dye and the substrate.
  • Direct dyes useful in the present compositions include, but are not limited to, Direct Blue 1, Direct Blue 14, Direct
  • Direct Yellow 50 Direct Yellow 59
  • Direct Yellow 62 Direct Yellow 62
  • reactive dye is recognized in the art and is intended to include those dyes that contain a reactive group, for example, either a haloheterocycle or an activated double bond, that, when applied to a surface in a weakly alkaline solution, forms a chemical bond with a hydroxyl or amino group on the substrate.
  • reactive dye compounds useful in the present compositions include, but are not limited to, Procion red, blue, orange and yellow (ICI), Levafix E Yellow (Bayer), Remazol Yellow (Hoechst), Cibacron
  • sulfur dye is recognized in the art and is intended to include those dyes that contain sulfide linkages and are absorbed by a substrate and are insolubilised within or on the substrate by oxidation. During this process the sulfur dye forms complex larger molecules which are the basis of their good wash-fastness.
  • sulfur dyes useful in the present compositions include, but are not limited to, Sulfur Black 1 (Sulfur Black T) and Sulfur Blue (Patent Blue VF).
  • fluorescent dye is recognized in the art and is intended to include those dyes which give fluorescence either in solid phase or in liquid form. The color of compound can be different from the fluorescence in liquid form.
  • fluorescent dyes/pigments useful in the present compositions include, but are not limited to, Fluorescein, fluorescein diacetate, carboxyfluorescein, carboxyfluorescein diacetate, rhodamine B, sulforhodamine B, cotadecyl rhodamine B, rhodamine 6G, rhodamine 110, rhodaine 123, xanthene dyes, thioxanthene dyes, naphtholactam dyes, azlactone dyes, methane dyes, oxazine dyes, thiazine dyes, fluorol, coumarin, 7-N.N- dialkylamino-3-hetarylcoumarin dyes, resorufm, quinoxalines, pyrido[l,2- a]benzimidazoles, acridirie, acriflavin, acridine orange,
  • solvent dye is recognized in the art. Solubility in an organic solvent or solvents is a characteristics physical property of a solvent dye.
  • solvent dyes useful in the present compositions include, but are not limited to, Solvent Black 3, Solvent Black 5, Solvent Blue 14, Solvent Blue 35, Solvent Blue 38, Solvent Blue 43, Solvent Blue 59, Solvent Brown 1, Solvent Green 1, Solvent Green 3, Solvent Green 7, Solvent Green 11, Solvent Orange 1, Solvent Orange 2, Solvent Orange 7, Solvent Orange 15, Solvent Red 19, Solvent Red 23, Solvent Red 24, Solvent Red 26, Solvent Red 27, Solvent Red 41, Solvent Red 43, Solvent Red 45, Solvent Red 49, Solvent Red 72, Solvent Violet 8, Solvent Yellow 2, Solvent Yellow 3, Solvent Yellow 7, Solvent Yellow 14, Solvent Yellow 33, Solvent Yellow 94, manufactured by Sigma- Aldrich, St.
  • FD&C dyes useful in compositions of the invention include, but are not limited to FD&C Blue 1, FD&C Blue 2, FD&C Green 3, FD&C Red 3, FD&C Red 40, FD&C Yellow 5, FD&C Yellow 6, Fast Emerald Green, and mixtures thereof, manufactured by Sensient Colors Inc., St.
  • Vitasyn Tetrazine X 90 Vitasyn Orange RGL 90, Vitasyn Quinoline Yellow 70, Vitasyn Ponceau 4RC 82, Vitasyn Blue AE 90, Vitasyn Patent Blue V 85 01, Sanolin Flavin 8GZ, Sanolin Yellow BG, Sanolin Red NBG, Sanolin Rhodarnine B, Sanolin Violet E2R, Sanolin Violet FBL, Sanolin Blue NBL, Sanolin Blue EHRL, Sanolin Blue EHRL Liquid, and mixtures thereof, manufactured by Clariant Corp., Coventry, RI.
  • polymeric colorant is recognized in the art and polymeric colorants are a group of intermediate or high molar mass compounds that are intrinsically colored.
  • Polymeric dyes may be defined through their applications as polymers and dyes, which possess suitably high tinctorial strength. Polymeric dyes are characterized by having polymeric chains covalently bonded to a chromophore (dye) molecule.
  • polymeric dyes useful in compositions of the invention include, but are not limited to , Palmer Orange Bl 13, Palmer Blue B232, Palmer Magenta, Palmer Fluorescent Red, Palmer Yellow R, Palmer Scarlett, Palmer Black B57, Palmer Patent Blue, LiquiTone Magenta 418, Polytint Violet X80LT, Polytint Orange X96, Polytint Yellow Xl 5, Polytint Black X41LV, Polytint Red X64, Polytint Blue X3LV, & mixtures thereof, manufactured by Milliken & Co., Spartanburg, SC.
  • pigments can be incorporated into the compositions of the invention. Suitable examples of pigments include those known as HydrusTM (available from Salis International Inc./Dr. Ph. Martin's). Currently there are 24 HydrusTM colors that can be used within the scope of the present invention. [086] Colorants (dyes and pigments) are included in the compositions of the invention in ranges from about 1% to about 90% by weight, more particularly from about 3% to about 30% by weight and in particular from about 5% to about 15% by weight.
  • compositions of the present invention provide bubbles that have at least average bubble integrity and lifespan, m particular embodiments, the compositions provide bubbles that maintain integrity and/or lifespan for 1 second to about 30 minutes, more particularly from about 2 seconds to about 20 minutes and most particularly from about 5 seconds to about 5 minutes.
  • the compositions of the present invention can be prepared by the following g eneral m ethod. A s olution o f c olorant, h umectant ( glycerin) a nd/or water are stirred and heated at 5O 0 C for about 15 minutes and cooled to room temperature. Generally, additives such as deionized water, surfactant, preservatives, base and dye blockers are added and the reaction mixture further stirred for 2 hours at room temperature.
  • Methocel A4M and an alkyl metal sulfate such as Colonial SLS (sodium lauryl sulfate) was added and stirred for 2 hours at room temperature, hi generally, the solution should not be heated at 5O 0 C after the addition of the surfactant(s), otherwise the formulation may either precipitates out or may gel.
  • an alkyl metal sulfate such as Colonial SLS (sodium lauryl sulfate) was added and stirred for 2 hours at room temperature, hi generally, the solution should not be heated at 5O 0 C after the addition of the surfactant(s), otherwise the formulation may either precipitates out or may gel.
  • a mixture of glycerin, dye (colorant), deionized water, an alkyl sulfonate mixture with betaine, such as Miracare BC27 and an alkanolamide, such as Colamid C was stirred and heated at 50 0 C for about 15 minutes. The mixture was cooled to room temperature and stirred, generally for about 2 hours.
  • compositions may be bottled. Alternately, the solution may be bottled without cooling.
  • a dense, highly concentrated pigment or dye is used. It is desirable that the pigment or dye be non-toxic so that the bubble solution is suitable for use by children.
  • Some suitable colorants include food colors or Hydras (available from
  • a composition heavily loaded with pigment may be used to produce a colored bubble.
  • a composition can be formed by mixing a surfactant solution with a colorant.
  • a composition can be formed by mixing 10% Ultra IvoryTM (anionic and nonionic surfactant, ethyl alcohol, water, stabilizing agents, and perfume) and 90% HydrasTM.
  • Another composition can be formed using 2% Ultra Concentrated DawnTM (anioinic and nonionic surfactant, ethyl alcohol, water, stabilizing agents, and perfume) and 98% of any D&C color.
  • compositions can be formed using 2% Ultra Concentrated DawnTM (anionic and nonionic surfactant, ethyl alcohol, water, stabilizing agents, and perfume) and 98% D&C color. Such solutions are not typically completely washable from fabrics and/or skin.
  • Ultra Concentrated DawnTM anionic and nonionic surfactant, ethyl alcohol, water, stabilizing agents, and perfume
  • a second embodiment provides a composition having less colorant.
  • the composition is heated and mixed in a manner provided by the present invention.
  • a solution of water and surfactants is brought to a boil.
  • the solution is actively stirred to prevent foaming.
  • the colorant is added during continued stirring.
  • the solution is heated to approximately 9O 0 C.
  • the solution is kept at this temperature for approximately 3-10 minutes.
  • the solution is then cooled. After cooling, the solution may be bottled.
  • One composition uses 50% water, 25% colorant and 25% surfactant. However, these percentages may be varied and as little as approximately 10% colorant may be used.
  • a composition may use 80% water, 10% colorant, and 10% surfactant.
  • the present invention further includes kits that include the compositions of the invention and instructions how to use the compositions to form bubbles.
  • the present invention provides compositions and methods for producing substantially uniformly colored bubbles having a wide variety of opacities ranging from semi-transparent to opaque.
  • the bubbles are substantially uniformly colored, or solidly colored, with approximately equal amounts of color on the top and the bottom of the bubble.
  • the present invention does not produce bubbles having colorant streaking or a concentration of color at the bottom of the bubble as currently available solutions provide.
  • FD & C Red 3 C. I. Food Red 14
  • a mixture of glycerin, FD & C Red 3, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
  • FD & C Blue 2 C. I. Food Blue 1 [0121] A mixture of glycerin, FD & C Blue 2, Colamid C, Miracare BC-
  • FD & C Green 3 C. I. Food Green 3
  • Table 1 shows color of the colored bubbles using food dyes/acid dyes in various Examples 1 through 19 as given below: Table 1: Color of the colored bubbles using food dyes/acid dyes
  • Example 1 Bright Blue Example 2 Dull Blue Example 3 Bright Red Example 4 Pale Red Example 5 Bright Yellow Example 6 Bright Orange Example 7 Dull Green Example 8 Bright Green Example 9 Light Black Example 10 Bright Blue Example 11 Dull Blue Example 12 Bright Red Example 13 Pale Red Example 14 Bright Yellow Example 15 Bright Orange Example 16 Dull Green Example 17 Bright Green Example 18 Light Black Example 19 Light Blue
  • Liquid Germall Plus 0.2 [0138] A mixture of glycerin, Palmer Blue B232, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
  • Liquid Germall Plus 0.2 [0140] A mixture of glycerin, Palmer Yellow R, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
  • Liquid Germall Plus 0.2 [0142] A mixture of glycerin, Palmer FL Red, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
  • Liquid Germall Plus 0.2 [0144] A mixture of glycerin, Palmer Black B57, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
  • Liquid Germall Plus 0.2 [0146] A m ixture o f glycerin, LiquiTone M agenta 418, d eionized w ater was stirred and heated at 5O 0 C for 15 minutes, cooled to room temperature, followed by addition of Metliocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
  • Liquid Germall Plus 0.2 A mixture of glycerin, Palmer Scarlett, Colamid C, Miracare BC-
  • a soap solution was formed by mixing 20 ml of Ivory dishwashing detergent, 1 ml triethanolamine, 9 ml water and 1 ml glycerin. 30 ml National Ink, LLC Super washable blue and 10 ml of the soap solution were added to the soap solution. The resulting composition produced bubbles that were vividly colored. The formula washed easily from skin and out of cotton, polyester, linen, knit and cotton/poly blends.
  • Table 2 shows color of the colored bubbles using polymeric dyes in various Examples 1 through 20 as given below: Table 2: Color of the colored bubbles using polymeric dyes
  • Methocel A4M (4% solution in water) 2.5 Colonial SLS 2.5
  • Methocel A4M (4% solution in water) 2.5 Colonial SLS 2.5
  • Table 3 shows color of the colored bubbles using fluorescent dyes in various Examples 1 through 12 as given below: Table 3: Color of the colored bubbles using fluorescent dyes
  • Example 1 Lightly colored bubbles of various colors
  • Example 2 Vividly colored bubbles of various colors
  • Example 3 Lightly tinted bubbles of various colors
  • Example 4 Lightly colored bubbles of various colors
  • Example 5 Vividly colored bubbles of various colors
  • Example 6 Vividly colored bubbles of various colors
  • the resulting composition produced bubbles that were vividly colored in the color of Hydras used (currently available . in 24 colors) that smelled like buttered popcorn.

Abstract

Compositions and methods for producing substantially uniformly colored bubbles are described. The composition comprises at least one surfactant mixed with at least one colorant, the colorant forming at least approximately 10% of the composition. The surfactant, or surface-active agent, forms the bubble while the colorant, or pigment, provides the color. Generally, the composition may comprise 10-99% colorant to produce varying degrees of opacity. In addition, glycerin, fragrance, propylene glycol, sodium lauryl sulfate, potassium hydroxide, or other additives may be included.

Description

COMPOSITION AND METHOD FOR PRODUCING COLORED
BUBBLES
CROSS REFERENCE TO RELATED APPLICATIONS
[001] This application claims benefit under 35 U.S. C. § 119(e) to application Serial No. 60/581,294, filed on June 17, 2004, by Tim Kehoe entitled "Composition and Method for Producing Colored Bubbles (attorney docket No. 34469/US) the contents of which are incorporated herein by reference in their entirety for all purposes.
FIELD OF THE INVENTION
[002] This invention relates generally to colored bubbles, and more specifically to a composition and method for producing substantially uniformly colored bubbles. The compositions are non-toxic and, if necessary, are washable.
BACKGROUND OF THE INVENTION
[003] Bubbles have long fascinated children, adults, and scientists alike.
The formation of bubbles for recreation and entertainment is a well-recognized and widely practiced past-time. In its simplest form, bubble blowing involves dipping a shaped article having an opening into a liquid soap solution followed by blowing into the opening to form one or more b ubbles. A bubble is g enerally defined as a small volume of gas contained within a thin liquid spherical envelop. A wand, for example, is generally immersed into a bubble solution and air is blown through spherical opening to generate bubbles. Surface tension causes the bubble solution to for a film across the opening. Upon application of a sufficient force or pressure upon one side of the film, a bubble is formed and expelled from the opening. [004] A variety of bubble solutions have been marketed over the years, many of them claiming to have special features like longer lasting bubbles, solutions that produce greater numbers of bubbles, or solution that provide bubbles having a colorful in appearance. Some manufacturers adorn their bubble packaging with illustrations of colored bubbles, or add colorants to tint their bubble solution, in an effort to provoke the illusion of a colored bubble. Some manufactures have added modifying agents like glycerin to produce a transparent bubble with a transparent iridescent rainbow effect. One manufacturer added color directly to the bubble and/or the bubble solution in an effort to create designs on a piece of paper with what they labeled a colored bubble. This composition of liquid solution does not produce a visually colored bubble, but rather a bubble that is used as a vehicle to transport the color to the marking surface. The bubble wall is transparent and does not produce a uniformly colored bubble. Rather the color runs to the bottom of the bubble wall. Others manufacturers claim to produce bubble that is illuminated when viewed in the dark with infrared radiation or black light, but transparent in regular light. [005] Therefore, a need exists for the development of a solution, and a resultant bubble, that provides a substantially uniform color.
BRIEF SUMMARY OF THE INVENTION
[006] The present invention surprisingly provides colored bubble compositions, that have a uniform coloration about the bubble.
[007] The compositions of the present invention can also be used in, but not limited to, other fields such as toys, toothpaste, bath bubbles, shampoo, soaps, creams, lotions, diapers, lenses, paint, inks, adhesives, displays, semiconductors, biomedical, photonics, face masks, hair colors, plastics, and textiles.
[008] In one embodiment, the present invention provides an aqueous composition that includes a surfactant and a colorant. The compositions provide a bubble that is a uniformly colored bubble. Suitable colorants include dyes, polymeric dyes, fluorescent dyes, pigments, and/or colorants. The compositions are non-toxic and/or washable, if necessary.
[009] hi one aspect, the substantially uniformly colored bubble includes a surfactant that is a polyether, an alkyl metal sulfate, a betaine, an alkanolamide or a combination thereof, hi one embodiment, the polyether surfactant is a cellulose ether surfactant., hi another embodiment, the alkyl metal sulfate is sodium lauryl sulfate.
[010] hi another aspect, the substantially uniformly colored bubble includes a surfactant that is a combination of a polyether surfactant and an alkyl metal sulfate.
[011] hi still another aspect, the substantially uniformly colored bubble includes a polyether surfactant that is a cellulose ether surfactant and the alkyl metal sulfate is sodium lauryl sulfate.
[012] hi still yet another aspect, the substantially uniformly colored bubble includes a surfactant that is a combination of an alkyl metal sulfate, a betaine and an alkanolamide.
[013] hi still another embodiment, the present invention provides methods to prepare compositions that provide the various bubble producing solutions used throughout the present specification.
[014] In one aspect, the method to prepare a solution for a substantially uniformly colored bubble solution includes the steps of heating a mixture of glycerin, colorant and water to a temperature between about 50°C and about
60°C, followed by cooling the mixture and then adding a surfactant to the cooled mixture. Generally the solution is cooled to room temperature prior to the addition of the surfactant. Typical colorants include acid dyes, FD&C dyes, food dyes, polymeric dyes, fluorescent dyes, pigments, or combinations thereof.
[015] hi particular, the surfactant is a polyether, an alkyl metal sulfate, or a combination thereof. Suitable polyether surfactants include cellulosic polyethers and suitable alkyl metal sulfates include lauryl sulfates having a metal counterion.
[016] In another aspect, methods to prepare a solution for a substantially uniformly colored bubble solution include combining glycerin, colorant, water, an alkanolamide and an alkyl metal sulfate to form a mixture. The mixture is then heated to a temperature below about 6O0C and is then cooled to room temperature.
Typical colorants include acid dyes, FD&C dyes, food dyes, polymeric dyes, fluorescent dyes, pigments, or combinations thereof.
[017] In still yet another embodiment, the present invention provides kits that include the compositions of the invention and instructions how to prepare bubbles from the compositions.
[018] While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description. As will be apparent, the invention is capable of modifications in various obvious aspects, all without departing from the spirit and scope of the present invention. Accordingly, the detailed descriptions are to be regarded as illustrative in nature and not restrictive.
DETAILED DESCRIPTION
[019] Prior to the present invention, it was generally considered extremely difficult if not impossible to make a colored bubble with uniform color intensity throughout the bubble: A bubble's wall is only a few millionths of an inch thick and up until the present invention it was considered that the bubble wall was incapable of being colored.
[020] Traditionally, when a light waves hits the surface of a bubble, part of the light is reflected back to a viewer's eye from the outer surface and part of the light is reflected from the inner surface which is a few millionths of an inch further. As the two waves of light travel back, they interfere with one another causing what we visualize as color. When the waves reinforce each other, the color is more intense. When the waves get close to canceling each other out, there is almost no color. As a bubble wall gets thinner, either from a weakened solution or because gravity has pulled the additives to the bottom of the bubble, the distance between the inner surface and the outer surface of the bubble becomes less and less until the two reflected waves of light start to coincide and cancel each other out. The result is that the bubble loses its color and can become nearly invisible.
[021] Prior to the present invention, it has proven extremely difficult, if not impossible, to develop a colored bubble composition with uniform color intensity throughout the bubble. When the dyes are added to the soap/bubble solution, they form colored solution but when the bubbles are blown, the resulting bubbles are colorless.
[022] The present invention surprisingly provides bubble compositions that have substantially uniform coloration about the bubble. The bubbles can have a wide range of opacity, colors and scents. The compositions and resultant bubbles are non-toxic and/or washable.
[023] The present invention further provides compositions and methods for producing bubbles, as described herein, having a wide range of opacities, ranging from essentially translucent to semi-transparent to opaque. The bubbles can be intrinsically colored; the composition from which the bubbles are formed itself is colored.
[024] In some embodiments, the bubbles have substantially uniform color intensity. In other embodiments, the bubbles can have non-uniform color intensity and/or dispersion.
[025] The 'phrases "substantially uniform" or "substantially uniformly" are intended to refer to coloration about the bubble such that the coloration intensity is approximately equal from the top of the bubble to the bottom of the bubble. Li such an embodiment, the coloration in the bubble is dispersed evenly throughout the bubble and coloration streaking or having an increased concentration of color at the bottom of the bubble is substantially avoided. It should be understood that the coloration throughout the bubble can be such that a swirling pattern, random or non-random, can be seen on the surface of the bubble's film, but yet not having an increased concentration of color at the bottom of the bubble. For example, the substantially uniform color could be considered "solid" or could have a swirled aspect.
[026] The phrases "non-uniform" or "non-uniformly" are intended to refer to coloration about the bubble such that the coloration intensity is concentrated, for example, more at the top and bottom of the bubble. Such fanciful bubbles can be very interesting to children.
[027] The phrase "colored bubble" is intended to refer to a bubble that can be uniformly or non-uniformly colored, as described herein, but does not have a change in coloration over a given period of time and does not have the coloration disappear from the bubble. Colored bubbles retain their coloration throughout the period of time the bubble exists, generally from about a few seconds to about a few minutes.
[028] The a queous s olutions o f t he p resent i nvention g enerally c ontain between about 1 and about 9 O p arts w ater, in p articular b etween about 10 and about 80, and more particularly between about 20 and about 70 percent based on a total weight percentage of the final composition, hi one aspect, the water utilized can b e o rdinary t ap w ater o r s pring w ater. In a nother a spect t he w ater can b e deionized water or water purified by reverse osmosis.
[029] The compositions of the invention include a surfactant. Suitable surfactants include anionic, cationic, nonionic or zwitterionic compounds and combinations thereof. The surfactant can be either polymeric or non-polymeric. [030] The term "surfactant" is recognized in the relevant art to include those compounds which modify the nature of surfaces, e.g. reducing the surface tension of water. Surfactants are generally classified into four types: cationic (e.g. modified onium salts, where part of the molecule is hydrophilic and the other consists of straight or branches long hydrocarbon chains such as hexadecyltrimethyl bromide), anionic, also known as amphiphatic agents (e.g., alkyl or aryl or alkylarylsulfonates, carboxylates, phosphates), nonionic (e.g., polyethylene oxides, alcohols) and ampholytic or amphoteric (e.g. dodecyl-beta- alanine, such that the surfactant contains a zwitterionic group). One or more surfactants can be used in the present invention.
[031] Cationic surfactants useful as surface tension reducing agents in the present invention include long chain hydrocarbons which contain quaternarized heteroatoms, such as nitrogen. Suitable cationic surfactants include quaternary ammonium compounds in which typically one of the groups linked to the nitrogen atom is a C 12-Cl 8 alkyl group and the other three groups are short chained alkyl groups.
[032] Anionic surfactants (amphiphatic agents) are characterized by a single lipophilic chain and a polar head group which can include sulfate, sulfonate, phosphate, phosphonate and carboxylate. Exemplary compounds include linear sodium alkyl benzene sulfonate (LAS), linear alkyl sulfates and phosphates, such as sodium lauryl sulfate (SLS) and linear alkyl ethoxy sulfates. Additional examples of anionic surfactants include substituted ammonium (e.g., mono-, di-, and tri-ethanolammonium), alkali metal and alkaline earth metal salts of C6-C20 fatty acids and rosin acids, linear and branched alkyl benzene sulfonates, alkyl ether sulfates, alkane sulfonates, olefin sulfonates, hydroxyalkane sulfonates, fatty acid monoglyceride sulfates, alkyl glyceryl ether sulfates, acyl sarcosinates. acyl N-methyltaurides, and alkylaryl sulfonated surfactants, such as alkylbenezene sulfonates.
[033] Nonionic surfactants do not dissociate but commonly derive their hydrophilic portion from polyhydroxy or polyalkyloxy structures. Suitable examples of polyhydroxy (polyhydric) compounds include ethylene glycol, butylene glycol, 1,3-butylene glycol, propylene glycol, glycerine, 2-methyl-l,3- propane diol, glycerol, mannitol, corn syrup, beta-cyclodextrin, and amylodextrin. Suitable examples of polyalkyloxy compounds include diethylene glycol, dipropylene glycol, polyethylene glycols, polypropylene glycols and glycol derivatives.
[034] Other suitable nonionic surfactants include other linear ethoxylated alcohols with an average length of 6 to 16 carbon atoms and averaging about 2 to 20 moles of ethylene oxide per mole of alcohol; linear and branched, primary and secondary ethoxylated, propoxylated alcohols with an average length of about 6 to 16 carbon atoms and averaging 0-10 moles of ethylene oxide and about 1 to 10 ■ moles of propylene oxide per mole of alcohol; linear and branched alkylphenoxy (polyethoxy) alcohols, otherwise known as ethoxylated alkylphenols, with an average chain length of 8 to 16 carbon atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; and mixtures thereof.
[035] Additionally, suitable nonionic surfactants include polyoxyethylene carboxylic acid esters, fatty acid glycerol esters, fatty acid and ethoxylated fatty acid alkanolamides. Block copolymers of propylene oxide and ethylene oxide, and block polymers of propylene oxide and ethylene oxide with propoxylated ethylene diamine are also included as acceptable nonionic surfactants. Semi-polar nonionic surfactants like amine oxides, phosphine oxides, sulfoxides, and their ethoxylated derivatives are included within the scope of the invention.
[036] Suitable amphoteric and zwitterionic surfactants which contain an anionic water-solubilizing group, a cationic group and a hydrophobic organic group include amino carboxylic acids and their salts, amino dicarboxylic acids and their salts, alkylbetaines, alkyl aminopropylbetaines, sulfobetaines, alkyl imidazolinium derivatives, certain quaternary ammonium compounds, certain quaternary phosphonium compounds and certain tertiary sulfonium compounds [037] Examples of anionic, nonionic, cationic and amphoteric surfactants that are suitable for use in the present invention are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 22, pages 347- 387, and McCutcheon's Detergents and Emulsifiers, North American Edition,
1983, both of which are incorporated herein by reference.
[038] Typical concentration ranges of surfactant that are useful in the present compositions are from about 0.01 parts by weight to about 90 parts by weight, from about 0.5 part by weight to about 50 parts by weight, and from about
1 parts by weight to about 10 parts by weight.
[039] hi one aspect, surfactants useful in the compositions of the invention include, but are not limited to, cellulose ethers or mixtures with other surfactants,, which are water soluble. Cellulose ether surfactants have unique foaming and bubble forming properties which make them ideal of colored bubble applications. Cellulose ethers used in the present invention include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, higher alkyl, aryl, alkoxy, cycloalkyl celluloses, hydroxypropyl cellulose, hydroxybutyl cellulose or mixtures thereof.
[040] Commercial cellulose ether surfactants include, but are not limited to, Methocel A4M, methyl cellulose, Methocel F4M, hydroxypropyl methylcellulose, Methocel K4M, hydroxypropyl methylcellulose, manufactured by Dow Chemical Co., Mildland, MI; Natrosol, hydroxyethyl cellulose, Klucel, hydroxypropyl cellulose, Aqualon Cellulose Gum, sodium carboxymethyl cellulose, Hercules Inc., Wilmington, DE; Elfacos CD 481, ethyl 2-hydroxyethyl ether cellulose, manufactured by Akzo Nobel, Chicago, IL.
[041] Cellulose ether surfactants are generally present in amounts from about 1% up to about 40% by weight in the compositions of the invention.
Suitable concentrations of cellulose ether surfactants are in the range of about 2% to about 30% by weight and from about 3% to about 8% by weight. A particularly useful cellulosic ether surfactant in the compositions is Methocel
A4M.
[042] In another aspect, alkanolamide or a mixture with other surfactants can be used in the compositions of the invention. Alkanolamides are commercially available and are the reaction products of one or more fatty acids having 12 or more carbon atoms and a lower alkanolamime. Typical alkanolamides are formed by reaction between stearic, mystiric, lauric acid or mixtures thereof with mono-, di-, and/or iso-propanolamine. [043] Alkanolamides can be present in the compositions of the invention in the ranges generally described throughout the application but generally are present in amounts from about 0% up to about 10% by weight. Suitable ranges include from about 1% to about 6% by weight and in particular from about 1.5% to about 4% by weight.
[044] In one embodiment, the alkanolamide surfactants of the present invention include, but are not limited to, Ninol 55LL, diethanolamine, Ninol 40CO, cocamide DEA, Ninol 30LL, lauramide DEA, manufactured by Stepan Co., Northfield, IL; Colamid C, cocamide DEA, Colamid 0071-J, alkanolamide, manufactured by Colonial Chemical Inc., S. Pittsburgh, TN. In one aspect, the alkanolamides are Ninol 55LL, and Colamid C.
[045] Exemplary sulfosuccinates that can be employed in the present compositions include, but are not limited to, Stepan-Mild SL3-BA, disodium laureth sulfosuccinate, Stepan-Mild LSB, sodium lauryl sulfosuccinate, manufactured by Stepan Co., Northfield, IL, Lankropol 4161L, sodium fatty alkanolamide sulfosuccinate and Colamate-DSLS, disodium laureth sulfosuccinate, manufactured by Colonial Chemical Inc., S. Pittsburgh, TN. [046] Suitable betaines that can be employed in the present compositions include, but are not limited to, Miracare BC-27, cocamidopropyl betaine and Miranol Ultra C-37, sodium cocoampho acetate, manufactured by J & S Chemical Co., Weston, FL.
[047] Suitable sulfates that can be employed in the present compositions include Rhodapex ES-2, sodium laureth sulfate, J & S Chemical Co., Weston, FL; Witcolate WAQ, sodium alkyl sulfate, manufactured by Akzo Nobel, Chicago, I and Colonial-SLS, sodium lauryl sulfate, manufactured by Colonial Chemical
Inc., S. Pittsburgh, TN.
[048] A suitable nonionic surfactant that can be employed in the present compositions is Triton H-66, alkyl aryl alkoxy potassium salt, manufactured by
Dow Chemical Co., Mildland, MI.
[049] hi one particular embodiment, the surfactant used is a combination of an ether based surfactant, such as a cellulose ether surfactant and an sodium alkyl sulfate, such as sodium lauryl sulfate.
[050] hi a particular embodiment, the surfactant is a combination of
Methocel A4M (4 weight percent in aqueous solution) and sodium lauryl sulfate
(30 weight percent in aqueous solution) in a (1:1 ratio) with a concentration range of from about 1 part by weight to about 10 parts by weight of the total weight of the composition, hi particular aspects, the total weight of the ether surfactant and the alkyl sulfate surfactant of the total weight of the composition is between about
3 percent and about 8 percent by weight, more particularly between about 3 percent and about 5 percent by weight, and in particular about 5 percent by weight.
[051] hi another embodiment, the surfactant used is a combination of an alkanolamide and a mixture of an alkyl betaine and/or an alkyl sulfonate.
[052] hi a particular embodiment, the surfactant is a combination of
Colamid C and Miracare B C27 which is a mixture of Surfactant blend include sodium trideceyl sulfate, water, PEG 80 sorbitant laurate, cocamidopropyl betaine, sodium lauroamphoacetate, PEG 150 distearate, sodium laureth-13 carboxylate, glycerin, citric acid, tetrasodium EDTA, quaternium-15. Generally, the combination of the alkanolamide and alkylsulfonate/betaine is in the range of between about 1:1 to about 1:7, more particularly between about 1:1 to about 2:7 and more particularly about 2:7. Generally, the combination of the two surfactants comprises a concentration between about 3 and about 10 percent by weight of the total weight of the composition, and more particularly between about 5 and about 10 percent by weight of the total weight of the composition, and in particular about 9 percent of the total weight of the composition.
[053] The aqueous c ompositions of the invention can further include a solvent or other additives as described throughout the present application.
Suitable solvents include, for example, alcohols having a carbon chain length of from about 1 carbon atom to about 12 carbon atoms. Typically, methanol and ethanol are not included due to their generally recognized properties, especially in view of use with children.
[054] Suitable optional additives to the compositions of the invention include, humectants, preservatives, fragrance, dye blockers, cleaners, etc.
[055] The term "humectant" is known and helps to retard the evaporation of water from the composition of the invention, thus avoiding premature drying during the application. Not to be limited by theory, it is believed that the presence of a humectant helps to strengthen the bubble formation, enhances even distribution of the dye throughout the bubble and increases life of bubble in the air.
[056] Representative examples of humectants include, but are not limited to, polyhydroxy alkyls, such as glycerin, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, hydroxylated starches and mixtures of these materials. Any effective amount of humectant may be used although a generally useful concentration range for these humectants is from about 5% to about 35% by weight of the total composition. Particular ranges of the humectant include a range of from about 8% to about 30% by weight of the composition and from about 10% to about 25% by weight of the composition. In one particular aspect, the humectant is glycerin.
[057] Not to be limited by theory, it is believed that in some application glycerin helps to evenly distribute the colorant within the bubble film.
[058] Representative examples of preservatives include, but are not limited to, glutaraldehyde, bicyclic oxazolidones, hydroxybenzoic acid esters, 3- iodo-2-propynyl butyl carbamate, methyl p-hydroxybenzoate, and a biocide comprising 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin- 3-one. The preservatives often serves as both a bactericide and a fungicide. [059] In particular, compositions of the invention include preservatives that are selected from, but not limited to, Liquid Germall Plus, iodopropynyl butyl carbamate, Germall II, diazolidinyl urea, Nuosept 95, bicyclic oxazolidines solution, manufactured by ISP (International Specialty Products), Wayne, NJ, Troysan 395, dihydroxy-dimethyl hydantoin, manufactured by Troy Chemical Corporation, Florham park, NJ and Kathon PFM, isothiazolinones, manufactured by Rohm & Haas Co., Philadelphia, PA
[060] Preservatives, when present in the compositions of the invention, are generally present in amounts from about 0.01% to about 6% by weight, in ' particular from about 0.05% to about 5% by weight, and particularly from about 0.1% to about 2.5% by weight. In one aspect, the preservative is one of Liquid Germall Plus, Tryosan 395 or Nuosept 95.
[061] Representative fragrances include those pleasing to children such as flowers, candy, popcorn, fruit, bubble gum and the like. A fragrance, when present in the compositions of the invention, is generally present in amounts from about 0.1% to about 10% by weight of the total weight of the composition. [062] Dye blockers or cleaners can be optionally added in the compositions of the invention to remove dye from hard/porous surfaces such as wood, stone, brick, leather, cloth, concrete, skin, fabric, etc. Up until the present invention, contact with a solution having a dye could stain a surface. [063] Suitable dye blockers include, but are not limited to, Bio-Terge
PAS-8S, sodium octane sulfonate, Stepanate SXS, sodium xylenesulfonate, Steposol DG, fatty alcohol ethoxylate, manufactured by Stepan Co., Northfield, IL, Dowfax 8390, disodium hexadecyldiphenyloxide disulfonate, Dowfax 2Al, benzene- 1,1-oxybis-tetrapropylene sulfonated sodium, Dowfax 3B2, decyl- sulfophenoxy-benzenesulfonic acid-disodium, Dowfax ClOL, decyl- sulfophenoxybenzenesulfonicacid disodium, Triton X- 15, octylphenoxypolyethoxyethanol, manufactured by Dow Chemical Co., Mildland, MI, Tamol SN, sodium salt of naphthalene-formaldehyde condensate, Tamol 731, sodium salt of carboxylated polyelectrolyte, manufactured by Rohm & Haas Co., Philadelphia, PA, Darvan 2, sodium lignin sulfonate, manufactured by R. T. Vanderbilt & Co., Norwalk, CT, Aqua-Cleen GP, polyethoxylated tert-dodecyl sulfur compound, TZ-Paint Prep, phosphorous/sulfur containing builders, and TAZ-B300, , sulfur/oxygen/nitrogen containing surface active agents, manufactured by Chemical Products Industries, Oklahoma City, OK [064] Dye blockers or cleaners are usually effective in the compositions of the invention when present in any amount but generally are present in ranges from about 5% up to about 50% by weight, from 10% to about 40% by weight or from about 12% to about 25% by weight.
[065] Suitable colorants can be selected from various dye/pigments classes that include, but are not limited to acid dyes, food dyes (FD&C)/cosmetic dyes (D & C), polymeric dyes, fluorescent dyes and pigments [066] Suitable dyes can be selected from various dye classes that include, but are not limited to acid dyes, basic dyes, direct dyes, reactive dyes, sulfur dyes, fluorescent dyes, food dyes (FD&C) cosmetic dyes (D & C), solvent dyes and polymeric dyes.
[067] The terms "acid dye" or "acidic dye" are recognized in the art and are intended to include those water soluble anionic dyes , that are applied to a material from neutral to acid solution. Attachment to the material is attributed, at least partly, to salt formation between anionic groups in the dyes and cationic groups in the material. Generally, acid dyes have functional groups such as azo, triaryl methane or anthraquinone that include acid substituents such as nitro, carboxy or sulfonic acid groups.
[068] Representative examples of acid dyes useful in the present compositions include, but are not limited to, Acid Black 1, Acid Black 2, Acid Black 24, Acid Black 48, Acid Blue 1, Acid Blue 7, Acid Blue 9, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 74, Acid Blue 80, Acid Blue 83, Acid Blue 90, Acid Blue 92, Acid Blue 113, Acid Blue 120, Acid Blue 129, Acid Blue 147, Acid Green 1, Acid Green 3, Acid Green 5, Acid Green 25, Acid Green 27, Acid Green 50, Acid Orange 6, Acid Orange 7, Acid Orange 8, Acid Orange 10, Acid Orange 12, Acid Orange 51, Acid Orange 51, Acid Orange 63, Acid Orange 74, Acid Red 1, Acid Red 4, Acid Red 8, Acid Red 14, Acid Red 17, Acid Red 18, Acid Red 26, Acid Red 27, Acid Red 29, Acid Red 37, Acid Red 44, Acid Red 50, Acid Red 51, Acid Red 52, Acid Red 66, Acid Red 73, Acid Red 87, Acid Red 88, Acid Red 91, Acid Red 92, v Acid Red 94, Acid Red 97, Acid Red 103, Acid Red 114, Acid Red 150, Acid Red 151, Acid Red 183, Acid V iolet 7 , A cid V iolet 9 , A cid V iolet 1 7, A cid V iolet 1 9, A cid Y ellow 1 , Acid Yellow 3, Acid Yellow 9, Acid Yellow 11, Acid Yellow 17, Acid Yellow 23, A cid Y ellow 25, A cid Y ellow 29, Acid Yellow 34, A cid Y ellow 3 6, A cid Yellow 42, Acid Yellow 54, Acid Yellow 73, Acid Yellow 76 and Acid Yellow 99.
[069] The terms "base dye" or "basic dye" are recognized in the art and are intended to include those water soluble cationic dyes that are applied to a material from neutral to basic solution. Generally, basic dyes have functional groups such as sulfonium, oxonium, or quarternary ammonium functional groups. Attachment to the material is attributed, at least partly, to salt formation between cationic groups in the dyes and anionic groups in the material. [070] Representative examples of basic dyes useful in the present compositions include, but are not limited to, Basic Black 2, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 11, Basic Blue 12, Basic Blue 16, Basic Blue 17, Basic Blue 24, Basic Blue 26, Basic Blue 41, Basic Blue 66, Basic Blue 140, Basic Brown 1, Basic Brown 4, Basic fuchsin, Basic Green 1, Basic Green 4, Basic Green 5, Basic Orange 2, Basic Orange 14, Basic Orange 21, Basic Red 1, Basic Red 2, Basic Red 5, Basic Red 9, Basic Red 29, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Yellow 1 and Basic Yellow 2.
[071] The term "direct dye" is recognized in the art and is intended to include those water soluble dyes that adsorb onto a material. Bonding is believed to occur through hydrogen bonding and/or Van der Waals forces between the dye and the substrate.
[072] Representative examples of direct dyes useful in the present compositions include, but are not limited to, Direct Blue 1, Direct Blue 14, Direct
Blue 53, Direct Blue 71, Direct Red 2, Direct Red 23, Direct Red 28, Direct Red
75, Direct Red 80, Direct Red 81, Direct Violet 51, Direct Yellow 4, Direct
Yellow 7, Direct Yellow 8, Direct Yellow 9, Direct Yellow 12, Direct Yellow 27,
Direct Yellow 50, Direct Yellow 59, Direct Yellow 62.
[073] The term "reactive dye" is recognized in the art and is intended to include those dyes that contain a reactive group, for example, either a haloheterocycle or an activated double bond, that, when applied to a surface in a weakly alkaline solution, forms a chemical bond with a hydroxyl or amino group on the substrate.
[074] Representative examples of reactive dye compounds useful in the present compositions include, but are not limited to, Procion red, blue, orange and yellow (ICI), Levafix E Yellow (Bayer), Remazol Yellow (Hoechst), Cibacron
(Ciba), Drimarene X, R, K (Sandoz), Reactive Black 5, Reactive Blue 2, Reactive
Blue 4, Reactive Blue 13, Reactive orange 16 and Reactive Yellow 4.
[075] The term "sulfur dye" is recognized in the art and is intended to include those dyes that contain sulfide linkages and are absorbed by a substrate and are insolubilised within or on the substrate by oxidation. During this process the sulfur dye forms complex larger molecules which are the basis of their good wash-fastness. [076] Representative examples of sulfur dyes useful in the present compositions include, but are not limited to, Sulfur Black 1 (Sulfur Black T) and Sulfur Blue (Patent Blue VF).
[077] The term "fluorescent dye" is recognized in the art and is intended to include those dyes which give fluorescence either in solid phase or in liquid form. The color of compound can be different from the fluorescence in liquid form.
[078] Representative examples of fluorescent dyes/pigments useful in the present compositions include, but are not limited to, Fluorescein, fluorescein diacetate, carboxyfluorescein, carboxyfluorescein diacetate, rhodamine B, sulforhodamine B, cotadecyl rhodamine B, rhodamine 6G, rhodamine 110, rhodaine 123, xanthene dyes, thioxanthene dyes, naphtholactam dyes, azlactone dyes, methane dyes, oxazine dyes, thiazine dyes, fluorol, coumarin, 7-N.N- dialkylamino-3-hetarylcoumarin dyes, resorufm, quinoxalines, pyrido[l,2- a]benzimidazoles, acridirie, acriflavin, acridine orange, nonyl acridine orange, xanthene, eosin Y, pyronine Y, texas red, calcein, quinacrine, ethidium bromide, propidium iodide, resazurin, nile, crystal violet, DiO6(3), JC-I, YOYO-I, DAPI, Hoechst 33342, FM 1-43, thiazole orange, primuline, thioflavin T, calcein blue, morin, naphthol blue black, fura-2, 4-amino-3-sulfo-l,8-naphthalimide, naphthalimide dyes, fluorescent pigments, and their derivatives. [079] The term "solvent dye"" is recognized in the art. Solubility in an organic solvent or solvents is a characteristics physical property of a solvent dye. [080] Representative examples of solvent dyes useful in the present compositions include, but are not limited to, Solvent Black 3, Solvent Black 5, Solvent Blue 14, Solvent Blue 35, Solvent Blue 38, Solvent Blue 43, Solvent Blue 59, Solvent Brown 1, Solvent Green 1, Solvent Green 3, Solvent Green 7, Solvent Green 11, Solvent Orange 1, Solvent Orange 2, Solvent Orange 7, Solvent Orange 15, Solvent Red 19, Solvent Red 23, Solvent Red 24, Solvent Red 26, Solvent Red 27, Solvent Red 41, Solvent Red 43, Solvent Red 45, Solvent Red 49, Solvent Red 72, Solvent Violet 8, Solvent Yellow 2, Solvent Yellow 3, Solvent Yellow 7, Solvent Yellow 14, Solvent Yellow 33, Solvent Yellow 94, manufactured by Sigma- Aldrich, St. Louis, MO; and Special Fluorescent Yellow 3G (Solvent Green 7), manufactured by Lanxess Corporation, Pittsburgh, PA. [081] The terms "FD&C" and "D&C" dyes are recognized in the art. In the United States, colorants for food, drugs and cosmetics are regarded as "color additives". The Federal Food, Drug & Cosmetic (FD&C) Act of 1938 made food color additive certification mandatory. Since then the Food and Drug Administration (FDA) has been responsible for regulating all color additives used in food, drugs and cosmetics. Each batch to be sold in the United States has to be certified by the FDA. To avoid confusing color additives used in food with those manufactured for other uses, 3 categories of certifiable color additives were created: 1) FD&C (Food, Drug & Cosmetics) color additives with applications in food, drug & cosmetics; 2) D&C (Drug & Cosmetics) color additives with applications in drug & cosmetics; 3) External D&C (External Drug & Cosmetics) color additives with applications in externally applied drugs & in externally < applied cosmetics. The use of all food colors approved for use in the United States are listed in 2 1 CFR ( Code o f Federal Regulation), p arts 70 through 82 dealing with color additives.
[082] Representative examples of FD&C dyes useful in compositions of the invention include, but are not limited to FD&C Blue 1, FD&C Blue 2, FD&C Green 3, FD&C Red 3, FD&C Red 40, FD&C Yellow 5, FD&C Yellow 6, Fast Emerald Green, and mixtures thereof, manufactured by Sensient Colors Inc., St. Louis, MO, Vitasyn Tetrazine X 90, Vitasyn Orange RGL 90, Vitasyn Quinoline Yellow 70, Vitasyn Ponceau 4RC 82, Vitasyn Blue AE 90, Vitasyn Patent Blue V 85 01, Sanolin Flavin 8GZ, Sanolin Yellow BG, Sanolin Red NBG, Sanolin Rhodarnine B, Sanolin Violet E2R, Sanolin Violet FBL, Sanolin Blue NBL, Sanolin Blue EHRL, Sanolin Blue EHRL Liquid, and mixtures thereof, manufactured by Clariant Corp., Coventry, RI. [083] The term "polymeric colorant" is recognized in the art and polymeric colorants are a group of intermediate or high molar mass compounds that are intrinsically colored. Polymeric dyes may be defined through their applications as polymers and dyes, which possess suitably high tinctorial strength. Polymeric dyes are characterized by having polymeric chains covalently bonded to a chromophore (dye) molecule.
[084] Representative examples of polymeric dyes useful in compositions of the invention include, but are not limited to , Palmer Orange Bl 13, Palmer Blue B232, Palmer Magenta, Palmer Fluorescent Red, Palmer Yellow R, Palmer Scarlett, Palmer Black B57, Palmer Patent Blue, LiquiTone Magenta 418, Polytint Violet X80LT, Polytint Orange X96, Polytint Yellow Xl 5, Polytint Black X41LV, Polytint Red X64, Polytint Blue X3LV, & mixtures thereof, manufactured by Milliken & Co., Spartanburg, SC.
[085] Alternatively, pigments can be incorporated into the compositions of the invention. Suitable examples of pigments include those known as Hydrus™ (available from Salis International Inc./Dr. Ph. Martin's). Currently there are 24 Hydrus™ colors that can be used within the scope of the present invention. [086] Colorants (dyes and pigments) are included in the compositions of the invention in ranges from about 1% to about 90% by weight, more particularly from about 3% to about 30% by weight and in particular from about 5% to about 15% by weight.
[087] The c ompositions o f t he p resent i nvention c an b e u sed w ith a ny simple or complex bubble making device, apparatus or machine to generate bubbles.
[088] The compositions of the present invention provide bubbles that have at least average bubble integrity and lifespan, m particular embodiments, the compositions provide bubbles that maintain integrity and/or lifespan for 1 second to about 30 minutes, more particularly from about 2 seconds to about 20 minutes and most particularly from about 5 seconds to about 5 minutes. [089] The compositions of the present invention can be prepared by the following g eneral m ethod. A s olution o f c olorant, h umectant ( glycerin) a nd/or water are stirred and heated at 5O0C for about 15 minutes and cooled to room temperature. Generally, additives such as deionized water, surfactant, preservatives, base and dye blockers are added and the reaction mixture further stirred for 2 hours at room temperature.
[090] More particularly, a mixture of glycerin, dye (colorant) and deionized water was stirred and heated at 500C for about 15 minutes. The solution was cooled to room temperature, and a polyether surfactant, such as
Methocel A4M and an alkyl metal sulfate, such as Colonial SLS (sodium lauryl sulfate) was added and stirred for 2 hours at room temperature, hi generally, the solution should not be heated at 5O0C after the addition of the surfactant(s), otherwise the formulation may either precipitates out or may gel.
[091] In another aspect, a mixture of glycerin, dye (colorant), deionized water, an alkyl sulfonate mixture with betaine, such as Miracare BC27 and an alkanolamide, such as Colamid C, was stirred and heated at 500C for about 15 minutes. The mixture was cooled to room temperature and stirred, generally for about 2 hours.
[092] It has been found that is beneficial to add a preservative, such as
Liquid Germall Plus, at room temperature.
[093] After cooling, the compositions may be bottled. Alternately, the solution may be bottled without cooling.
[094] To produce a substantially uniformly colored bubble for example, a dense, highly concentrated pigment or dye is used. It is desirable that the pigment or dye be non-toxic so that the bubble solution is suitable for use by children. Some suitable colorants include food colors or Hydras (available from
Salis International rnc./Dr. Ph. Martin's).
[095] In a first embodiment, a composition heavily loaded with pigment may be used to produce a colored bubble. Such a composition can be formed by mixing a surfactant solution with a colorant. For example, a composition can be formed by mixing 10% Ultra Ivory™ (anionic and nonionic surfactant, ethyl alcohol, water, stabilizing agents, and perfume) and 90% Hydras™. Another composition can be formed using 2% Ultra Concentrated Dawn™ (anioinic and nonionic surfactant, ethyl alcohol, water, stabilizing agents, and perfume) and 98% of any D&C color. Yet another composition can be formed using 2% Ultra Concentrated Dawn™ (anionic and nonionic surfactant, ethyl alcohol, water, stabilizing agents, and perfume) and 98% D&C color. Such solutions are not typically completely washable from fabrics and/or skin.
[096] A second embodiment provides a composition having less colorant. To form such a composition, the composition is heated and mixed in a manner provided by the present invention. A solution of water and surfactants is brought to a boil. The solution is actively stirred to prevent foaming. When the solution has reached a boil, the colorant is added during continued stirring. The solution is heated to approximately 9O0C. The solution is kept at this temperature for approximately 3-10 minutes. The solution is then cooled. After cooling, the solution may be bottled. One composition uses 50% water, 25% colorant and 25% surfactant. However, these percentages may be varied and as little as approximately 10% colorant may be used. For example, a composition may use 80% water, 10% colorant, and 10% surfactant.
[097] The present invention further includes kits that include the compositions of the invention and instructions how to use the compositions to form bubbles.
[098] The present invention provides compositions and methods for producing substantially uniformly colored bubbles having a wide variety of opacities ranging from semi-transparent to opaque. The bubbles are substantially uniformly colored, or solidly colored, with approximately equal amounts of color on the top and the bottom of the bubble. Thus, the present invention does not produce bubbles having colorant streaking or a concentration of color at the bottom of the bubble as currently available solutions provide. [099] Aspects of the present teachings can be further understood in light of the following examples, which should not be construed as limiting the scope of the present teachings in any way.
[0100] Examples
1. Food Dyes/Acid Dyes
EXAMPLE 1
Chemical Component Weight in grams
Glycerin 10
FD & C Blue 1 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0101] FD & C Blue I = C I. Food Blue 2 = C. I. Acid Blue 9
[0102] A mixture of glycerin, FD & C Blue 1, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature. EXAMPLE 2
Chemical Component Weight in grams
Glycerin 10
FD & C Blue 2 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0103] FD & C Blue 2 = C. I. Food Blue 1
[0104] A mixture of glycerin, FD & C Blue 2, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 3
Chemical Component Weight in grams
Glycerin 10
FD & C Red 3 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0105] FD & C Red 3 = C. I. Food Red 14 [0106] A mixture of glycerin, FD & C Red 3, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 4
Chemical Component Weight in grams
Glycerin 10
FD & C Red 40 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0107] FD & C Red 40 = C. I. Food Red 17
[0108] A mixture of glycerin, FD & C Red 40, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 5
Chemical Component Weight in grams
Glycerin 10
Vitasyn Tetrazine X 90 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2 [0109] Vitasyn Tetrazine X 90 = FD & C Yellow 5 = C. I. Food Yellow 4
= C. I. Acid Yellow 23
[0110] A mixture of glycerin, Vitasyn Tetrazine X 90, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 6
Chemical Component Weight in grams
Glycerin 10
Vitasyn Orange RGL 90 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0111] Vitasyn Orange RGL 90 - FD & C Yellow 6 = C. I. Food Yellow
3
[0112] A mixture of glycerin, Vitasyn Orange RGL 90, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature. EXAMPLE 7
Chemical Component Weight in grams
Glycerin 10
FD & C Green 3 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0113] FD & C Green 3 = C. I. Food Green 3
[0114] A mixture of glycerin, FD & C Green 3, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 8
Chemical Component Weight in grams
Glycerin 10
Fast Emerald Green 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0115] A mixture of glycerin, Fast Emerald Green, deionized water was stirred and heated at 5O0C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 9
Chemical Component Weight in grams
Glycerin 10
Brilliant Black BN 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0116] Brilliant Black BN = C. I. Food Black 1
[0117] A mixture of glycerin, Brilliant Black BN, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 10
Chemical Component Weight in grams
Glycerin 5 FD & C Blue 1 5 Colamid C 2 Miracare BC-27 7 Deionized water 80.8 Liquid Germall Plus 0.2
[0118] FD & C Blue I = C I. Food Blue 2 = C. I. Acid Blue 9
[0119] A mixture of glycerin, FD & C Blue 1, Colamid C, Miracare BC-
27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 11
Chemical Component Weight in grams
Glycerin 5 FD & C Blue 2 5 Colamid C 2 Miracare BC-27 7 Deionized water 80.8 Liquid Germall Plus 0.2
[0120] FD & C Blue 2 = C. I. Food Blue 1 [0121] A mixture of glycerin, FD & C Blue 2, Colamid C, Miracare BC-
27, deionized water was stirred and heated at 500C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 12
Chemical Component Weight in grams
Glycerin 5
FD & C Red 3 5
Colamid C 2
Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2
[0122] FD & C Red 3 = C. I. Food Red 14
[0123] A mixture of glycerin, FD & C Red 3, Colamid C, Miracare BC-
27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 13
Chemical Component Weight in grams
Glycerin 5
FD & C Red 40 5
Colamid C 2
Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2 [0124] FD & C Red 40 = C. I. Food Red 17
[0125] A mixture of glycerin, FD & C Red 40, Colamid C, Miracare BC-
27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 14
Chemical Component Weight in grams
Glycerin 5
Vitasyn Tetrazine X 90 5
Colamid C 2
Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2
[0126] Vitasyn Tetrazine X 90 = FD & C Yellow 5 = C. I. Food Yellow 4
= C. I. Acid Yellow 23
[0127] A mixture of glycerin, Vitasyn Tetrazine X 90, Colamid C,
Miracare BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 15
Chemical Component Weight in grams
Glycerin 5
Vitasyn Orange RGL 90 5
Colamid C 2
Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2
[0128] Vitasyn Orange RGL 90 = FD & C Yellow 6 = C. I. Food Yellow 3
[0129] A mixture of glycerin, Vitasyn Orange RGL 90, Colamid C,
Miracare BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 16
Chemical Component Weight in grams
Glycerin 5 FD & C Green 3 5 Colamid C 2 Miracare BC-27 7 Deionized water 80.8 Liquid Germall Plus 0.2
[0130] FD & C Green 3 = C. I. Food Green 3 [0131] A mixture of glycerin, FD & C Green 3, Colamid C, Miracare BC-
27, deionized water was stirred and heated at 5O0C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 17
Chemical Component Weight in grams
Glycerin 5
Fast Emerald Green 5
Colamid C 2
Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2
[0132] A mixture of glycerin, Fast Emerald Green, Colamid C, Miracare
BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 18
Chemical Component Weight in grams
Glycerin 5
Brilliant Black BN 5
Colamid C 2
Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2
[0133] Brilliant Black BN = C. I. Food Black 1 [0134] A mixture of glycerin, B rilliant Black B N, Colamid C, Miracare
BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 19
Chemical Component Unites
Glycerin 5 ml
FD&C Blue No. 2 30 ml
Ivory Soap 5 ml
Deionized water 230 ml
[0135] FD&C Blue No. 2
[0136] 230 ml water, 5 ml Ivory soap, and 5 ml glycerin were mixed in a pan or other suitable container. The resultant solution was brought to a boil. 30 ml FD&C Blue No. 2 was then added and the solution was boiled and stirred for 4 minutes. The solution was quickly cooled by placing in a bowl of ice water. The resulting c omposition p roduced 1 ight b lue generally u niformly c olored b ubbles. The formula is somewhat difficult to remove from skin and washes out of cotton.
[0137] Table 1 shows color of the colored bubbles using food dyes/acid dyes in various Examples 1 through 19 as given below: Table 1: Color of the colored bubbles using food dyes/acid dyes
Color of the
Example # Colored Bubbles
Example 1 Bright Blue Example 2 Dull Blue Example 3 Bright Red Example 4 Pale Red Example 5 Bright Yellow Example 6 Bright Orange Example 7 Dull Green Example 8 Bright Green Example 9 Light Black Example 10 Bright Blue Example 11 Dull Blue Example 12 Bright Red Example 13 Pale Red Example 14 Bright Yellow Example 15 Bright Orange Example 16 Dull Green Example 17 Bright Green Example 18 Light Black Example 19 Light Blue
2. Polymeric Dyes
EXAMPLE 1
Chemical Component Weight in grams
Glycerin 10
Palmer Blue B232 25
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 59.8
Liquid Germall Plus 0.2 [0138] A mixture of glycerin, Palmer Blue B232, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 2
Chemical Component- Weight in grams
Glycerin 10
Palmer Scarlett 25
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 59.8
Liquid Germall Plus 0.2
[0139] A mixture of glycerin, Palmer Scarlett, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 3
Chemical Component Weight in grams
Glycerin 10
Palmer Yellow R 25
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 59.8
Liquid Germall Plus 0.2 [0140] A mixture of glycerin, Palmer Yellow R, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 4
Chemical Component Weight in grams
Glycerin 10
Palmer Magenta 25
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 59.8
Liquid Germall Plus 0.2
[0141] A mixture of glycerin, Palmer Magenta, deionized water was stirred and heated at 5O0C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 5
Chemical Component Weight in grams
Glycerin 10
Palmer FL Red 25
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 59.8
Liquid Germall Plus 0.2 [0142] A mixture of glycerin, Palmer FL Red, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 6
Chemical Component Weight in grams
Glycerin 10
Palmer Orange Bl 13 25
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 59.8
Liquid Germall Plus 0.2
[0143] A mixture of glycerin, Palmer Orange Bl 13, deionized water was stirred and heated at 5O0C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 7
Chemical Component Weight in grams
Glycerin 10
Palmer Black B57 25
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 59.8
Liquid Germall Plus 0.2 [0144] A mixture of glycerin, Palmer Black B57, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 8
Chemical Component Weight in grams
Figure imgf000039_0001
Palmer Patent Blue 25
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 59.8
Liquid Germall Plus 0.2
[0145] A mixture of glycerin, Palmer Patent Blue, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 9
Chemical Component Weight in grams
Glycerin 10
LiquiTone Magenta 418 25
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 59.8
Liquid Germall Plus 0.2 [0146] A m ixture o f glycerin, LiquiTone M agenta 418, d eionized w ater was stirred and heated at 5O0C for 15 minutes, cooled to room temperature, followed by addition of Metliocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 10
Chemical Component Weight in grams
Glycerin 5
Palmer Blue B232 25
Colamid C 2
Miracare BC-27 * 7
Deionized water 60.8
Liquid Germall Plus 0.2
[0147] A mixture of glycerin, Palmer Blue B232, Colamid C, Miracare
BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 11
Chemical Component Weight in grams
Glycerin 5
Palmer Scarlett 25
Colamid C 2
Miracare BC-27 7
Deionized water 60.8
Liquid Germall Plus 0.2 [0148] A mixture of glycerin, Palmer Scarlett, Colamid C, Miracare BC-
27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 12
Chemical Component Weight in grams
Glycerin 5
Palmer Yellow R 25
Colamid C 2
Miracare BC-27 7
Deionized water 60.8
Liquid Germall Plus 0.2
[0149] A mixture of glycerin, Palmer Yellow R, Colamid C, Miracare
BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 13
Chemical Component Weight in grams
Glycerin 5
Palmer Magenta 25
Colamid C 2
Miracare BC-27 7
Deionized water 60.8
Liquid Germall Plus 0.2
[0150] A mixture of glycerin, Palmer Magenta, Colamid C, Miracare BC-
27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 14
Chemical Component Weight in grams
Glycerin 5
Palmer FL Red 25
Colamid C 2
Miracare BC-27 7
Deionized water 60.8
Liquid Germall Plus 0.2
[0151] A mixture of glycerin, Palmer FL Red, Colamid C, Miracare BC-
27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 15
Chemical Component Weight in grams
Glycerin 5
Palmer Orange Bl 13 25
Colamid C 2
Miracare BC-27 7
Deionized water 60.8
Liquid Germall Plus 0.2
[0152] A mixture of glycerin, Palmer Orange Bl 13, Colamid C, Miracare
BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 16 Chemical Component Weight in grams
Glycerin 5
Palmer Black B57 25
Colamid C 2
Miracare BC-27 7
Deionized water 60.8
Liquid Germall Plus 0.2
[0153] A mixture of glycerin, Palmer Black B57, Colamid C, Miracare
BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 17
Chemical Component Weight in grams
Glycerin 5
Palmer Patent Blue 25
Colamid C 2
Miracare BC-27 7
Deionized water 60.8
Liquid Germall Plus 0.2
[0154] A mixture of glycerin, Palmer Patent Blue, Colamid C, Miracare
BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature. EXAMPLE 18
Chemical Component Weight in grams
Glycerin 5
LiquiTone Magenta 418 25
Colamid C 2
Miracare BC-27 7
Deionized water 60.8
Liquid Germall Plus 0.2
[0155] A mixture of glycerin, LiquiTone Magenta 418, Colamid C,
Miracare BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 19 Chemical Component Units
Glycerin I mI
Triethanolamine I mI
Deionized water 9 ml
Ivory Soap 20 ml
Soap solution total 31 ml
National Ink, LLC Super washable blue 30 ml
Soap solution 10 ml
[0156] A soap solution was formed by mixing 20 ml of Ivory dishwashing detergent, 1 ml triethanolamine, 9 ml water and 1 ml glycerin. 30 ml National Ink, LLC Super washable blue and 10 ml of the soap solution were added to the soap solution. The resulting composition produced bubbles that were vividly colored. The formula washed easily from skin and out of cotton, polyester, linen, knit and cotton/poly blends.
EXAMPLE 20
Chemical Component Units
National Ink, LLC. Super washable blue 30 ml
Ivory Soap 10 ml
[0157] 30 ml National Ink LLC Super washable blue and 10 ml Ivory soap were mixed. The resulting composition produced vividly colored bubbles. The formula washed easily from skin and out of cotton, polyester, and cotton/poly blends.
EXAMPLE 21
Chemical Component Units
National Ink, LLC. Super washable Magenta 20 ml
Ivory Soap 10 ml
[0158] 20 ml National Ink LLC Super washable Magenta and 10 ml Ivory soap were mixed. The solution was heated to about 90°C and stirred for approximately 7 minutes. T he solution was cooled to room temperature. T he resulting composition produced vividly colored bubbles that had a swirling pattern of magenta blotches patterned randomly about the bubble surface. The formula washed easily from skin and out of cotton, polyester, and cotton/poly blends.
[0159] Table 2 shows color of the colored bubbles using polymeric dyes in various Examples 1 through 20 as given below: Table 2: Color of the colored bubbles using polymeric dyes
Color of the
Example # Colored Bubbles
Example 1 Blue
Example 2 Scarlet
Example 3 Yellow
Example 4 Magenta
Example 5 Fluorescent Red
Example 6 Orange
Example 7 Pale Black
Example 8 Blue
Example 9 Magenta
Example 10 Blue
Example 11 Scarlet
Example 12 Yellow
Example 13 Magenta
Example 14 Fluorescent Red
Example 15 Orange
Example 16 Pale Black
Example 17 Blue
Example 18 Magenta
Example 19 Blue
Example 20 Blue
Magenta with random pools of
Example 21 magenta dots
3. Fluorescent Dyes
EXAMPLE 1
Chemical Component Weight in grams
Glycerin 10
Fluorescein (Na salt) 5
Methocel A4M (4% solution in water) 2.5 Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0160] A mixture of glycerin, Fluorescein (Na salt), deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 2
Chemical Component Weight in grams
Glycerin 10
Rhodamine B 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0161] A mixture of glycerin, Rhodamine B, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 3
Chemical Component Weight in grams
Glycerin 10
Rhodamine 6G 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5 Deionized water 79.8
Liquid Germall Plus 0.2
[0162] A mixture of glycerin, Rhodamine 6G, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 4
Chemical Component Weight in grams
Glycerin 10
Rhodamine 123 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0163] A mixture of glycerin, Rhodamine 123, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 5
Chemical Component Weight in grams
Glycerin 10
Eosin Y 5
Methocel A4M (4% solution in water) 2.5 Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0164] A mixture of glycerin, Eosin Y, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 6
Chemical Component Weight in grams
Glycerin 10
Naphthol Blue Black 5
Methocel A4M (4% solution in water) 2.5
Colonial SLS 2.5
Deionized water 79.8
Liquid Germall Plus 0.2
[0165] A mixture of glycerin, Naphthol Blue Black, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Methocel A4M, Colonial SLS, & Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 7
Chemical Component Weight in grams
Glycerin 5
Fluorescein (Na salt) 5
Colamid C 2
Miracare BC-27 7 Deionized water 80.8
Liquid Germall Plus 0.2
[0166] A mixture of glycerin, Fluorescein (Na salt), Colamid C, Miracare
BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 8
Chemical Component Weight in grams
Glycerin 5
Rhodamine B 5
Colamid C 2
Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2
[0167] A mixture of glycerin, Rhodamine B, Colamid C, Miracare BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 9
Chemical Component Weight in grams
Glycerin 5
Rhodamine 6G 5
Colamid C 2 Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2
[0168] A mixture of glycerin, Rhodamine 6G, Colamid C, Miracare BC-
27, deionized water was stirred and heated at 5O0C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 10
Chemical Component Weight in grams
Glycerin 5
Rhodamine 123 5
Colamid C 2
Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2
[0169] A mixture of glycerin, Rhodamine 123, Colamid C, Miracare BC-
27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 11
Chemical Component Weight in grams
Glycerin 5
Eosin Y 5 Colamid C 2
Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2
[0170] A mixture of glycerin, Eosin Y, Colamid C, Miracare BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
EXAMPLE 12
Chemical Component Weight in grams
Glycerin 5
Naphthol Blue Black 5
Colamid C 2
Miracare BC-27 7
Deionized water 80.8
Liquid Germall Plus 0.2
[0171] A mixture of glycerin, Naphthol Blue Black, Colamid C, Miracare
BC-27, deionized water was stirred and heated at 50°C for 15 minutes, cooled to room temperature, followed by addition of Liquid Germall Plus. The reaction mixture was further stirred for 2 hours at room temperature.
[0172] Table 3 shows color of the colored bubbles using fluorescent dyes in various Examples 1 through 12 as given below: Table 3: Color of the colored bubbles using fluorescent dyes
Example # Color of the Colored Bubbles
Example 1 Bright yellow with intense green fluorescence
Example 2 Pink with intense orange fluorescence
Example 3 Pink with intense yellow fluorescence
Example 4 Pink with intense yellow fluorescence
Example 5 Red with intense green fluorescence
Example 6 Bluish-green with blue fluorescence
Example 7 Bright yellow with intense green fluorescence
Example 8 Pink with intense orange fluorescence
Example 9 Pink with intense yellow fluorescence
Example 10 Pink with intense yellow fluorescence
Example 11 Red with intense green fluorescence
Example 12 Bluish-green with blue fluorescence
4. Pigments
[0173] Example 1 - Lightly colored bubbles of various colors
[0174] 230 ml water, 5 ml Ivory soap, and 5 ml glycerin were mixed in a pan or other suitable container. The resultant solution was brought to a boil. 30 ml Hydrus was then added and the solution was boiled and stirred for 4 minutes. The solution was quickly cooled by placing in a bowl of ice water. The resulting composition produced generally uniformly colored bubbles lightly shaded in the color of Hydrus used (currently available in 24 colors). The formula washed easily from skin but stains clothing.
[0175] Example 2 - Vividly colored bubbles of various colors
[0176] 230 ml water, 15 ml Ivory soap and 1 ml glycerin were mixed in a pan or other suitable container. The resultant solution was brought to a boil. 30 ml Hydrus was then added and the solution was boiled and stirred for 5 minutes. The solution was quickly cooled by placing in a bowl of ice water. The resulting composition produced generally uniformly colored bubbles lightly shaded in the color of Hydras used (currently available in 24 colors). The formula washes easily from skin but stains clothing. Bubbles produced using this composition do not typically pop immediately upon contact with a surface.
[0177] Example 3 - Lightly tinted bubbles of various colors
[0178] 345 ml water, 230 ml Ivory soap and 15 ml glycerin were mixed in a pan or other suitable container. The resultant solution was brought to a boil, 30 ml Hydras were added and then the solution was boiled and stirred for 7 minutes. The resulting composition produced bubbles that were color tinted in the color of Hydras used (currently available in 24 colors) but mostly transparent.
[0179] Example 4 - Lightly colored bubbles of various colors
[0180] 175 ml water, 60 ml Ivory soap and 30 ml glycerin were mixed in a pan or other suitable container. The resultant solution was brought to a boil, 30 ml Hydras were added and then the solution was boiled and stirred for 10 minutes. The resulting composition produced bubbles that were lightly colored in the color of Hydras used (currently available in 24 colors).
[0181] Example 5 — Vividly colored bubbles of various colors
[0182] 175 ml water, 50 ml Ivory soap and 2.5 ml glycerin were mixed in a pan or other suitable container. The resultant solution was brought to a boil, 60 ml Hydras were added and the solution was boiled and stirred for 7 minutes. The resulting composition produced bubbles that were vividly colored in the color of Hydras used (currently available in 24 colors).
[0183] Example 6 — Vividly colored bubbles of various colors
[0184] 30 ml Hydras and 4 ml Ivory were mixed. The resulting composition produced bubbles that were vividly colored in the color of Hydras used (currently available in 24 colors). [0185] Example 7 - Vividly colored bubbles of various colors with buttered popcorn scent
[0186] 30 ml Hydras, 4 ml Ivory and 1 ml popcorn scent were mixed.
The resulting composition produced bubbles that were vividly colored in the color of Hydras used (currently available . in 24 colors) that smelled like buttered popcorn.
[0187] Example 8 - Colored bubbles
[0188] 200 ml water and 60 ml Ivory soap were mixed in a pan or other suitable container. The resultant solution was brought to a boil, 30 ml Hydras were added and the solution was boiled and stirred for 3 minutes. The resulting composition produces bubbles in the color of Hydras used (currently available in 24 colors).
[0189] Although the present invention has been described with reference to preferred embodiments, persons skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. All references cited throughout the specification, including those in the background, are incorporated herein in their entirety. Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, many equivalents to specific embodiments of the invention described specifically herein. Such equivalents are intended to be encompassed in the scope of the following claim.

Claims

CLAIMSI claim:
1. A substantially uniformly colored bubble, comprising: water; a surfactant; and a colorant, wherein the bubble is substantially uniformly colored.
2. The substantially uniformly colored bubble of claim 1 , wherein the colorant is an acid dye, FD&C dye, food dye, a polymeric dye, a fluorescent dye, a pigment, or a combination thereof.
3. The substantially uniformly colored bubble of claim 2, wherein the surfactant is a polyether, an alkyl metal sulfate, a betaine, an alkanolamide or a combination thereof.
4. The substantially uniformly colored bubble of claim 3, wherein the polyether surfactant is a cellulose ether surfactant.
5. The substantially uniformly colored bubble of claim 3, wherein the alkyl metal sulfate is sodium lauryl sulfate.
6. The substantially uniformly colored bubble of claim ,3, wherein the surfactant is a combination of a polyether surfactant and an alkyl metal sulfate.
7. The substantially uniformly colored bubble of claim 6, wherein the polyether surfactant is a cellulose ether surfactant and the alkyl metal sulfate is sodium lauryl sulfate.
8. The substantially uniformly colored bubble of claim 3, wherein the surfactant is a combination of an alkyl metal sulfate, a betaine and an alkanolamide.
9. The substantially uniformly colored bubble of claim 2, wherein the colorant is an acid dye and the surfactant is a combination of a polyether surfactant and an alkyl metal sulfate.
10. The substantially uniformly colored bubble of claim 2, wherein the colorant is a pigment and the surfactant is a combination of a polyether surfactant and an alkyl metal sulfate. '
11. The substantially uniformly colored bubble of claim 2, wherein the colorant is an acid dye and the surfactant is a combination of an alkyl metal sulfate and an alkanolamide.
12. The substantially uniformly colored bubble of claim 2, wherein the colorant is a pigment and the surfactant is a combination of an alkyl metal sulfate and an alkanolamide.
13. A method to prepare a solution for a substantially uniformly colored bubble solution, comprising the steps of: heating a mixture of glycerin, colorant and water to a temperature below about 60°C; cooling the mixture; adding a surfactant to the cooled mixture.
14. The method of claim 13, wherein the colorant is an acid dye, FD&C dye, food dye, a polymeric dye, a fluorescent dye, a pigment, or a combination thereof.
15. The method of claim 14, wherein the surfactant is a polyether, an alkyl metal sulfate, or a combination thereof.
16. The method of claim 15 , wherein the polyether surfactant is a cellulose ether surfactant.
17. The method of claim 15, wherein the alkyl metal sulfate is sodium lauryl sulfate.
18. The method of claim 15, wherein the surfactant is a combination of a polyether surfactant and an alkyl metal sulfate.
19. The method of claim 18, wherein the polyether surfactant is a cellulose ether surfactant and the alkyl metal sulfate is sodium lauryl sulfate.
20. The method of claim 14, wherein the mixture of glycerin, colorant and water are heated for less than 30 minutes.
21. The method of claim 14, wherein the colorant is an acid dye, FD&C dye, food dye, a polymeric dye or a combination thereof.
22. The method of claim 21 , wherein the surfactant is a combination of a polyether surfactant and an alkyl metal sulfate.
23. The method of claim 22, wherein the polyether surfactant is a cellulosic ether surfactant and the alkyl metal sulfate is sodium lauryl sulfate.
24. A method to prepare a solution for a substantially uniformly colored bubble solution, comprising the steps of: combining glycerin, colorant, water, an alkanolamide and an alkyl metal sulfate to form a mixture; and heating the mixture to a temperature below about 60°C.
25. The method of claim 24, wherein the colorant is an acid dye, FD&C dye, food dye, a polymeric dye, a fluorescent dye, a pigment, or a combination thereof.
26. The method of claim 25, wherein the surfactant is an alkanolamide and at least an alkyl metal sulfate.
27. The method of claim 26, wherein the surfactant further comprises sodium trideceyl sulfate, water, PEG 80 sorbitant laurate, cocamidopropyl betaine, sodium lauroamphoacetate, PEG 150 distearate, sodium laureth-13 carboxylate, glycerin, citric acid, tetrasodium EDTA and quaternium-15.
28. A kit for producing substantially uniformly colored bubbles comprising; a container that contains water; a surfactant; and a colorant, wherein the solution produces a bubble that comprises a substantially uniformly colored bubble.
29. A kit for producing substantially uniformly colored bubbles comprising: a container that contains water, a surfactant and a colorant, wherein the solution produces a bubbles that comprises a substantially uniformly colored bubble, wherein the surfactant is a mixture of a polyether and an alkyl metal sulfate and the colorant is an acid dye.
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AU2008363988B2 (en) * 2008-11-11 2012-11-01 Colgate-Palmolive Company Composition with a color to indicate coverage
AU2008363987B2 (en) * 2008-11-11 2012-10-11 Colgate Palmolive Company Composition with a color marker
CN102286310B (en) * 2010-06-21 2013-02-13 金奇集团金奇日化有限公司 Method for preparing liquid detergent and product adopting same
US20120035311A1 (en) 2010-08-05 2012-02-09 Crayola, Llc Colored bubbles
CN102172434A (en) * 2011-01-27 2011-09-07 山西大学 Colored hubble-bubble liquid
US20120244777A1 (en) * 2011-03-22 2012-09-27 Sabnis Ram W Composition and method for producing colored bubbles
ITMI20110940A1 (en) * 2011-05-25 2012-11-26 Fra Ber S R L COMPOSITION FOR THE CARE OF VEHICLES
JP5899796B2 (en) * 2011-10-24 2016-04-06 日油株式会社 Soap bubble liquid composition
GB2537651A (en) * 2015-04-22 2016-10-26 Cosmetic Warriors Ltd Composition
WO2018038823A1 (en) 2016-08-24 2018-03-01 Tran Dat Q Formulations for edible bubble solution
CN106139619A (en) * 2016-08-31 2016-11-23 陈雄 A kind of stage preparation method rendering stage property
US10800924B2 (en) * 2017-11-27 2020-10-13 Cathy Cowan Toy bubble forming composition containing glitter
WO2019110092A1 (en) 2017-12-05 2019-06-13 Toys Trend Ltd. Bubble composition
CN108295490A (en) * 2018-01-17 2018-07-20 厦门卡拉风娱乐有限公司 A kind of colored hubble-bubble liquid and preparation method thereof with long preservation period that fades

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4511497A (en) * 1981-11-12 1985-04-16 Strombecker Corporation Bubble composition using multipurpose surfactant base
EP0155737A2 (en) * 1984-03-21 1985-09-25 Shionogi & Co., Ltd. Low irritating shampoo compositions
WO1995033387A1 (en) * 1994-06-09 1995-12-14 Oded Broshi Edible bubble solution
WO1997026076A2 (en) * 1996-01-19 1997-07-24 Oded Broshi A non-toxic, pleasant tasting bubble making composition
US5664947A (en) * 1995-02-10 1997-09-09 Binney & Smith Inc. Method, apparatus, and kit for marking a surface with colored bubbles
WO1997043012A1 (en) * 1996-05-14 1997-11-20 Eckhard Biller Fire suppressant foam dispersant and detergent eckhard iii-formula
US20030109392A1 (en) * 2001-12-06 2003-06-12 Hershey Entertainment & Resorts Company Whipped cocoa bath

Family Cites Families (191)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1112180A (en) 1913-03-08 1914-09-29 Charles W Westenfelter Dentifrice.
US1717723A (en) 1927-04-09 1929-06-18 Calsodent Company Inc Means for and method of detecting and correcting mouth acidity
US2451022A (en) 1944-02-28 1948-10-12 Frederick C Dohrmann Color changing antiseptic composition
US2445994A (en) 1944-09-06 1948-07-27 Benson Ellen Gay Toy
DE1767662U (en) 1958-03-28 1958-05-29 Schuechtermann & Kremer PROTECTIVE CAP FOR SCREW HEADS ON VIBRATING SCREENS.
US3332743A (en) 1963-06-27 1967-07-25 George H Green Diagnostic test for dental caries activity
US3382607A (en) 1965-01-04 1968-05-14 Mattel Inc Figure toy having fibers impregnated with indicator dye
US3454344A (en) 1965-12-15 1969-07-08 Matttel Inc Games employing ph-sensitive media
FR1499925A (en) 1966-04-05 1967-11-03 Marie Jeanne Niederhof Process for the preparation of a bubble bath intended for the maintenance of the skin and for combating the peripheral manifestations of fatigue, while slowing the effects of aging on the integuments
CH477207A (en) 1967-06-05 1969-08-31 Jacques Dr Assal Toothpaste for controlling tooth brushing time
US3443337A (en) * 1967-08-24 1969-05-13 Joseph R Ehrlich Toy for blowing bubbles
US3650831A (en) 1969-03-10 1972-03-21 Armour Dial Inc Method of cleaning surfaces
US3617325A (en) 1969-06-17 1971-11-02 Chem Rite Associates Writing
JPS5033816B1 (en) 1971-06-28 1975-11-04
US3899295A (en) 1973-11-23 1975-08-12 Bio Medical Sciences Inc Integrity indicator
US3957964A (en) 1974-01-30 1976-05-18 Colgate-Palmolive Company Dentifrice containing encapsulated flavoring
US3975405A (en) 1974-08-01 1976-08-17 Coulter Diagnostics, Inc. Monophosphate salt of o-cresolphthalein
US4016089A (en) 1974-11-11 1977-04-05 Regan Glen B Denture cleaning concentrate
US4071614A (en) 1975-06-03 1978-01-31 Colgate Palmolive Company Dentifrice containing encapsulated flavoring
US4071645A (en) 1976-03-12 1978-01-31 Acme Chemical Company Aqueous coating composition
US4206069A (en) 1976-04-22 1980-06-03 Colgate-Palmolive Company Transparent detergent pellets
US4139965A (en) 1977-09-12 1979-02-20 Mattel, Inc. Device using coated paper and chemical reactive marker
US4177300A (en) 1977-09-28 1979-12-04 Stauffer Chemical Company Phosphonoxycarboxamide flame retarding compositions
DE2747092C2 (en) 1977-10-20 1984-01-05 Württembergische Parfümerie - Fabrik GmbH, 7332 Eislingen Dentifrices containing dyes
US4229410A (en) 1978-02-13 1980-10-21 Kosti Carl M Bacteriostatic deodorant water coloring toilet element
DE2806049A1 (en) 1978-02-14 1979-08-16 Hoechst Ag ORGANIC PHOSPHORUS COMPOUNDS WITH 2-HYDROXYALKYLPHOSPHONIC ACID ESTER GROUPS
CH628808A5 (en) 1978-02-16 1982-03-31 Cooper Sa TOOTHPASTE ALLOWING CONTROL OF THE TOOTHBRUSHING TIME.
JPS54131428A (en) 1978-04-03 1979-10-12 Adger Kogyo Co Ltd Ink
US4431628A (en) 1978-04-07 1984-02-14 Colgate-Palmolive Company Natural dye indicator for dental plaque
US4248597A (en) 1978-12-12 1981-02-03 Akzona Incorporated Time watch or depletion indicator for removable substances
US4284534A (en) 1979-04-03 1981-08-18 Jack S. Wachtel Aqueous bubble blowing composition
US4246717A (en) * 1979-04-03 1981-01-27 Joseph R. Ehrlich Bubble pipe
US4359455A (en) 1979-10-30 1982-11-16 Sunstar Hamigaki Kabushiki Kaisha Diagnostic test composition for dental caries activity
US4321251A (en) 1979-12-19 1982-03-23 The United States Of America As Represented By The Department Of Health And Human Services Detection of malignant lesions of the oral cavity utilizing toluidine blue rinse
JPS5696700A (en) 1979-12-31 1981-08-04 Sankin Kogyo Kk Composition for diagnosing tooth decay activity
DE3011618A1 (en) 1980-03-26 1981-10-01 Württembergische Parfümerie - Fabrik GmbH, 7332 Eislingen TOOTH CREAM WITH HIGH FOAM RESISTANCE
JPS57146587A (en) 1981-03-06 1982-09-10 Akira Endo New physiologically active substance mutastein and preparation thereof
DE3206204A1 (en) 1982-02-20 1983-09-01 Wella Ag, 6100 Darmstadt PROTECTIVE CREAM FOR THE SCALP AND METHOD FOR CLEARING THE HAIR
US5192332A (en) 1983-10-14 1993-03-09 L'oreal Cosmetic temporary coloring compositions containing protein derivatives
CA1240620A (en) 1984-01-17 1988-08-16 Roger E. Stier Dentifrices
US4568534A (en) 1984-05-23 1986-02-04 Beecham Inc. Dentifrices
US4889559A (en) 1984-06-04 1989-12-26 Goldberg Murrell A Latent ink
JPS61110058A (en) 1984-11-02 1986-05-28 Fuji Photo Film Co Ltd Integrated type multilayer analysis element for measuring alkaline phosphatase activity
US4749508A (en) 1985-02-05 1988-06-07 Kay Chemical Company Floor cleaning compositions and their use
JPS61269067A (en) 1985-05-23 1986-11-28 Fuji Photo Film Co Ltd Monolithic multilayered analytical element for measuring activity of alkaline phosphatase
US5057303A (en) 1985-05-24 1991-10-15 Irene Casey Cleaner and disinfectant with dye
US4965063A (en) 1985-05-24 1990-10-23 Irene Casey Cleaner and disinfectant with dye
US5064635A (en) 1985-05-24 1991-11-12 Irene Casey Cleaner and disinfectant with dye
US4793988A (en) 1985-05-24 1988-12-27 Irene Casey Germicide and dye composition
US5110492A (en) 1985-05-24 1992-05-05 Irene Casey Cleaner and disinfectant with dye
US4877459A (en) 1985-08-08 1989-10-31 Kay Chemical Company Floor cleaning compositions and their use
FR2591102A1 (en) 1985-12-06 1987-06-12 Delaunay Francois Dentifrice
US4906395A (en) 1985-12-13 1990-03-06 The Dow Chemical Company Detergent package for laundering clothes
NL8503456A (en) 1985-12-16 1987-07-16 Naarden International Nv TIME INDICATOR SYSTEMS, AND SUCH INDICATOR SYSTEMS CONTAINING PRODUCTS OF LIMITED USE OR LIFE.
US5143729A (en) 1986-07-29 1992-09-01 Fadeguard, Inc. Fade resistant water and soil repellent composition for fabric
US5055287A (en) 1986-12-29 1991-10-08 Kessler Jack H Methods to control color during disinfecting peroxidase reactions
US5270174A (en) 1987-04-03 1993-12-14 Assif Science And Technology Projects Development Ltd. Method and kit for indicating the level of oral microbial activity
FR2617709B1 (en) 1987-07-06 1991-04-26 Roch Romeo TOOTHPASTE WITH BRUSHING TIME INDICATOR
US5196243A (en) 1987-08-10 1993-03-23 Kiyoharu Kawashima Printed matter
US5124129A (en) 1988-07-29 1992-06-23 Mallinckrodt Medical, Inc. Carbon dioxide indicator
US5053339A (en) 1988-11-03 1991-10-01 J P Labs Inc. Color changing device for monitoring shelf-life of perishable products
JPH02187484A (en) 1989-01-13 1990-07-23 Okitsumo Kk Instantaneous adhesive for paper
US4954544A (en) 1989-03-23 1990-09-04 Conros Corporation Modified adhesive composition which undergoes color changes upon application
JP2770409B2 (en) 1989-04-28 1998-07-02 ソニー株式会社 Display composition, coloring pigment and recording material
US5032178A (en) 1990-02-02 1991-07-16 Demetron Research Corporation Dental composition system and method for bleaching teeth
US5015467A (en) 1990-06-26 1991-05-14 The Procter & Gamble Company Combined anticalculus and antiplaque compositions
US5154917A (en) 1990-09-11 1992-10-13 Beecham Inc. Color change mouthrinse
US5223245A (en) 1990-09-11 1993-06-29 Beecham Inc. Color change mouthrinse
CA2027518A1 (en) 1990-10-03 1992-04-04 Richard L. Tadsen Process for preparing high density detergent compositions containing particulate ph sensitive surfactant
US5143023A (en) 1990-10-16 1992-09-01 Kleanheart, Inc. Animal litter with chemically bound chemical indicators
US5246631A (en) * 1991-05-23 1993-09-21 Halbritter Martin J Self-illuminated bubbles
EP0597895A1 (en) 1991-08-09 1994-05-25 Minnesota Mining And Manufacturing Company Repositionable coated substrate adhesive
US5167952A (en) 1991-10-04 1992-12-01 Mchugh John E Therapeutic composition formulated as a dental rinse that stimulates Prostaglandin synthesis in the mouth to prevent plaque buildup on the teeth and Periodontal disease
US5565363A (en) 1991-10-21 1996-10-15 Wako Pure Chemical Industries, Ltd. Reagent composition for measuring ionic strength or specific gravity of aqueous solution samples
JP3549880B2 (en) 1991-10-31 2004-08-04 ジラ・インコーポレーテッド Biological dye compositions, methods of preparation and methods of use for depicting epithelial cancer
US5480925A (en) 1991-11-08 1996-01-02 Minnesota Mining And Manufacturing Company Self-fading color adhesive
EP0549145A1 (en) 1991-12-20 1993-06-30 Rohm And Haas Company Method for increasing the hiding power of paint
JPH07503772A (en) 1992-02-17 1995-04-20 シャブリー，アレクサンダー Internal combustion engine intake and exhaust system
US5486228A (en) 1992-07-31 1996-01-23 Binney & Smith Inc. Washable color changing compositions
US5346422A (en) 1992-12-08 1994-09-13 Eastman Chemical Company Toy articles of manufacture comprising spontaneously wettable fibers
US5523075A (en) 1993-05-13 1996-06-04 Fuerst; Ronnie S. Materials and methods utilizing a temporary visual indicator
US5532029A (en) 1993-05-13 1996-07-02 Fuerst; Ronnie S. Materials and methods utilizing a temporary visual indicator
GB9312219D0 (en) 1993-06-14 1993-07-28 Dow Deutschland Inc Purification of aqueous reaction or washing medium containing cellulose ethers
US5418013A (en) 1993-06-21 1995-05-23 Rohm And Haas Company Method for decreasing drying time
TW382635B (en) * 1993-12-20 2000-02-21 Canon Kk Liquid composition and ink set, and image-forming process and apparatus using the same
US5407665A (en) 1993-12-22 1995-04-18 The Procter & Gamble Company Ethanol substitutes
US6395551B1 (en) 1994-02-16 2002-05-28 3M Innovative Properties Company Indicator for liquid disinfection or sterilization solutions
US5753244A (en) 1994-05-09 1998-05-19 Reynolds; Taylor W. Method and product for applying skin treatments and ointments
US5482654A (en) 1994-11-09 1996-01-09 Warnaway Corporation Safety indicator system
US5599525A (en) 1994-11-14 1997-02-04 Colgate Palmolive Company Stabilized dentifrice compositions containing reactive ingredients
US5567420A (en) 1994-11-16 1996-10-22 Mceleney; John Lotion which is temporarily colored upon application
US5464470A (en) 1995-02-10 1995-11-07 Binney & Smith Inc. Color-changing marking composition system
DE69614843T2 (en) 1995-04-13 2002-04-11 United Color Mfg Inc COLORLESS PETROLEUM MARKING AGENT
US6419902B1 (en) 1995-12-11 2002-07-16 Howard W. Wright Color changing toothpaste
ATE253380T1 (en) 1996-01-16 2003-11-15 Zila Inc METHOD AND MEANS FOR IN VIVO DETECTION OF ORAL CANCER AND PRECANCEROUS CONDITIONS
US20030066096A1 (en) * 1996-02-06 2003-04-03 Bruce Bryan Bioluminescent novelty items
US6576633B1 (en) 1996-02-22 2003-06-10 The Dow Chemical Company Stable liquid antimicrobial suspension compositions containing quarternaries prepared from hexamethylenetetramine and certain halohydrocarbons
AU2424197A (en) 1996-03-26 1997-10-17 Colgate-Palmolive Company, The Simultaneous saponification and neutralization process
DE19632432A1 (en) 1996-08-12 1998-02-19 Boehringer Mannheim Gmbh Stable mixture for the detection of alkaline phosphatase with a salt of o-cresolphthalein monophosphoric acid
TW385307B (en) 1996-08-30 2000-03-21 Dsm Nv Process for the preparation of urea
BR9712987A (en) 1996-10-11 2000-04-18 Warner Lambert Co Sulfonamide interleukin-1beta conversion enzyme inhibitors
SE507437C2 (en) 1996-11-14 1998-06-08 Medi Team Dentalutveckling I G Preparations for use in the chemical-mechanical treatment of caries infestation and process for the preparation of the preparation
US5972869A (en) 1996-12-17 1999-10-26 Colgate-Palmolive Co Mildly acidic laundry detergent composition providing improved protection of fine fabrics during washing and enhanced rinsing in hand wash
FR2759087B1 (en) 1997-02-06 1999-07-30 Electricite De France POROUS COMPOSITE PRODUCT WITH HIGH SPECIFIC SURFACE, PREPARATION METHOD AND ELECTRODE FOR ELECTROCHEMICAL ASSEMBLY FORMED FROM POROUS COMPOSITE FILM
CN1246883A (en) 1997-02-14 2000-03-08 宾尼及史密斯公司 Washable colouring composition
US5885594A (en) 1997-03-27 1999-03-23 The Procter & Gamble Company Oral compositions having enhanced mouth-feel
US6066689A (en) 1997-04-23 2000-05-23 Elmer's Products, Inc. Adhesive applicator crayon
ID20406A (en) 1997-06-03 1998-12-10 Binney & Smith Inc LOW-OUT OUTDOOR COMPOSITION
JP2002500898A (en) 1997-08-15 2002-01-15 チルドレンズ メディカル センター コーポレーション Osteopontin coating surface and its use
US5853430A (en) 1997-09-03 1998-12-29 The Procter & Gamble Company Method for predissolving detergent compositions
US5929004A (en) 1997-10-10 1999-07-27 No Touch North America Detergent for cleaning tire wheels and cleaning method
US6667161B1 (en) 1997-10-27 2003-12-23 Ibbex, Inc. Chromogenic substrates of sialidase of bacterial, viral, protozoa, and vertebrate origin and methods of making and using the same
US5942438A (en) 1997-11-07 1999-08-24 Johnson & Johnson Medical, Inc. Chemical indicator for oxidation-type sterilization processes using bleachable dyes
US6965043B1 (en) 1997-11-10 2005-11-15 Procter + Gamble Co. Process for making high purity fatty acid lower alkyl esters
DE19756401A1 (en) 1997-12-18 1999-07-01 Faber Castell A W Color preparation, especially a solid lead or chalk
US6149895A (en) 1998-02-17 2000-11-21 Kreativ, Inc Dental bleaching compositions, kits & methods
US6152887A (en) 1998-02-27 2000-11-28 Blume; Richard Stephen Method and test kit for oral sampling and diagnosis
US6042813A (en) 1998-05-04 2000-03-28 Schering-Plough Healthcare Products, Inc. Sunscreen having disappearing color indicator
SE511331C2 (en) 1998-05-18 1999-09-13 Ekulf Ab System for optimized formation of fluorapatitis in teeth
US6677287B1 (en) 1998-05-18 2004-01-13 The Procter & Gamble Company Implement containing cleaning composition and disappearing dye
US6100226A (en) 1998-05-20 2000-08-08 The Lubrizol Corporation Simple metal grease compositions
US6124377A (en) 1998-07-01 2000-09-26 Binney & Smith Inc. Marking system
US6677129B1 (en) 1998-07-22 2004-01-13 Richard S. Blume Method for detecting Helicobacter pylori infection
US6036493A (en) 1998-07-23 2000-03-14 Ad Dent Inc. Dental bleaching system and method
US6030222A (en) 1998-12-01 2000-02-29 Tarver; Jeanna G. Dye compositions and methods for whitening teeth using same
US6126923A (en) 1998-12-11 2000-10-03 Colgate-Palmolive Company Magically appearing striped dentifrice
US6039797A (en) 1999-02-01 2000-03-21 Binney & Smith Inc. Washable marking composition
MXPA01011215A (en) 1999-05-05 2002-08-12 Dap Products Inc Ready to use spackle/repair product containing dryness indicator.
US6099825A (en) 1999-05-26 2000-08-08 Schering-Plough Healthcare Products, Inc. Sunscreen having disappearing color
US6501002B1 (en) 1999-06-29 2002-12-31 The Proctor & Gamble Company Disposable surface wipe article having a waste contamination sensor
US7067115B2 (en) 1999-07-07 2006-06-27 Scientific Pharmaceuticals, Inc. Process and composition for high efficacy teeth whitening
US6365134B1 (en) 1999-07-07 2002-04-02 Scientific Pharmaceuticals, Inc. Process and composition for high efficacy teeth whitening
WO2001055702A1 (en) 2000-01-31 2001-08-02 Board Of Regents, The University Of Texas System Portable sensor array system
GB0007654D0 (en) 2000-03-29 2000-05-17 Unilever Plc Laundry treatment for fabrics
GB2360793A (en) 2000-03-29 2001-10-03 Unilever Plc Improving perfume deposition or retention on fabrics
US6846512B2 (en) 2001-01-30 2005-01-25 The Procter & Gamble Company System and method for cleaning and/or treating vehicles and the surfaces of other objects
US7267728B2 (en) 2001-01-30 2007-09-11 The Procter & Gamble Company System and method for cleaning and/or treating vehicles and the surfaces of other objects
US6869028B2 (en) 2000-06-14 2005-03-22 The Procter & Gamble Company Spraying device
US20030103905A1 (en) 2000-06-23 2003-06-05 Ribi Hans O. Methods and compositions for preparing consumables with optical shifting properties
US6607744B1 (en) 2000-06-23 2003-08-19 Segan Industries Ingestibles possessing intrinsic color change
US6663902B1 (en) 2000-09-19 2003-12-16 Ecolab Inc. Method and composition for the generation of chlorine dioxide using Iodo-Compounds, and methods of use
EP1191084A2 (en) 2000-09-26 2002-03-27 Rohm And Haas Company Colorless petroleum marker dyes
US6447757B1 (en) 2000-11-08 2002-09-10 Scientific Pharmaceuticals, Inc. Teeth whitening composition with increased bleaching efficiency and storage stability
JP2002256291A (en) 2001-03-01 2002-09-11 Arutan Kk Detergent composition containing ph indicator and coloring cleansing composition
GB2374346B (en) 2001-04-10 2003-04-23 Mon-Sheng Lin Liquid bubble solution for producing luminous bubbles
ATE316916T1 (en) 2001-05-03 2006-02-15 Allied Domecq Spirits & Wine L ORIGINALITY CLOSURE
US20030211618A1 (en) 2001-05-07 2003-11-13 Patel Gordhandhai Nathalal Color changing steam sterilization indicator
ES2296684T3 (en) 2001-05-17 2008-05-01 KETTENBACH GMBH &amp; CO. KG CHEMICALLY HARMFUL DENTAL WHITENING MATERIAL.
DE60106586D1 (en) 2001-06-20 2004-11-25 Flit S A Process for controlling insecticide application and composition therefor
WO2003006025A1 (en) 2001-07-09 2003-01-23 Mayo Foundation For Medical Education And Research Methods and materials for treating bone conditions
US6960475B2 (en) 2001-07-11 2005-11-01 The Procter & Gamble Company Composition and process for indicating the presence of soluble fluoride ion in oral care compositions and method of making the same
US6331515B1 (en) 2001-08-06 2001-12-18 Colgate-Palmolive Co. Color changing liquid cleaning composition comprising red dyes
JP2003056782A (en) 2001-08-09 2003-02-26 Nissan Motor Co Ltd Connecting structure between resin-made connector and resin-made tube
WO2003026609A1 (en) 2001-09-20 2003-04-03 Stockhausen Gmbh & Co.Kg Skin and hand care agents
US6772708B2 (en) 2001-10-30 2004-08-10 The Procter And Gamble Company Wetness indicator having improved colorant retention
US6998113B1 (en) 2005-01-31 2006-02-14 Aquea Scientific Corporation Bodywashes containing additives
US6531118B1 (en) 2001-12-11 2003-03-11 Avon Products, Inc. Topical compositions with a reversible photochromic ingredient
US20030113266A1 (en) 2001-12-14 2003-06-19 Gc Corporation Material for evaluating dental caries activity
US6726584B2 (en) 2002-01-22 2004-04-27 Jerry Iggulden Method and apparatus for temporarily marking a point of contact
US6783991B1 (en) 2002-02-06 2004-08-31 The Standard Register Company Reversible and reusable authentication system for secure documents
CN100531692C (en) 2002-02-19 2009-08-26 宝洁公司 Wetness indicator composition and disposable absorbent article containing same
US7053029B2 (en) 2002-03-27 2006-05-30 Kimberly-Clark Worldwide, Inc. Use indicating soap
TW200405128A (en) 2002-05-01 2004-04-01 Shinetsu Chemical Co Novel sulfonyldiazomethanes, photoacid generators, resist compositions, and patterning process
DE10254337A1 (en) 2002-05-03 2003-11-27 Harald Wilkens Toothpaste has an integrated self-coloring indicator to show temporarily the presence and location of plaque for removal, to improve oral hygiene
US6733766B2 (en) 2002-05-06 2004-05-11 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Personal care composition with color change indicator
US20030220213A1 (en) 2002-05-24 2003-11-27 Bober Andrew M. Color changing floor finish stripper
US6894095B2 (en) 2002-07-17 2005-05-17 The Dial Corporation Color-changing wallpaper adhesive primer/activator
US20050187137A1 (en) 2002-08-14 2005-08-25 Ulrich Pegelow Portioned cleaning agents or detergents containing phosphate
US7448556B2 (en) 2002-08-16 2008-11-11 Henkel Kgaa Dispenser bottle for at least two active fluids
US20040053803A1 (en) 2002-09-13 2004-03-18 Kimberly-Clark Worldwide, Inc. Method for enhancing cleansing vehicles and cleansing vehicles utilizing such method
US20050163729A1 (en) 2002-09-27 2005-07-28 Zaidel Lynette A. Oral compositions containing peroxide and methods for use
GB0305222D0 (en) 2002-10-03 2003-04-09 Unilever Plc Indicator kit
US20040087922A1 (en) 2002-11-04 2004-05-06 Bobadilla Tory Leigh Method of making early indicator color changing diaper or plastic color changing training pants
EP1457529B1 (en) 2003-03-08 2007-06-20 Brillux GmbH & Co. KG Coating having colour indicator
US20040213698A1 (en) 2003-04-25 2004-10-28 Tennakoon Charles L.K. Electrochemical method and apparatus for generating a mouth rinse
JP2005008537A (en) 2003-06-17 2005-01-13 Tokuyama Corp Preliminarily treating material composition for dentistry
RU2246335C1 (en) 2003-06-24 2005-02-20 Гомзарь Игорь Михайлович Apparatus and composition for releasing of soap bubbles
US7651989B2 (en) 2003-08-29 2010-01-26 Kimberly-Clark Worldwide, Inc. Single phase color change agents
US7442725B2 (en) 2003-10-02 2008-10-28 Sanford, L.P. Color changing correction fluid
US7837663B2 (en) 2003-10-16 2010-11-23 Kimberly-Clark Worldwide, Inc. Odor controlling article including a visual indicating device for monitoring odor absorption
US20050090414A1 (en) 2003-10-23 2005-04-28 Sarah Rich Color changing hand soap composition
US7111933B2 (en) 2003-10-29 2006-09-26 Hewlett-Packard Development Company, Lp. Ink-jet systems and methods using visible and invisible ink
US20050103233A1 (en) 2003-11-14 2005-05-19 Rood Christopher T. Tint for drywall
JP4102739B2 (en) 2003-11-25 2008-06-18 株式会社日立ハイテクノロジーズ Automatic analyzer
US20050143505A1 (en) 2003-12-05 2005-06-30 Rosekelly George S. Paint with color change additive and method of application and painted substrate
US7390628B2 (en) 2003-12-23 2008-06-24 University Of Florida Research Foundation, Inc. Microparticle-based diagnostic methods
WO2005065406A2 (en) 2003-12-30 2005-07-21 Ep Acquisition, Inc. Protective eyewear
US20050154109A1 (en) 2004-01-12 2005-07-14 Minyu Li Floor finish with lightening agent
US20050191326A1 (en) 2004-02-27 2005-09-01 Melker Richard J. Materials and methods for creating customized compositions having a temporary visual indicator
ATE486563T1 (en) 2004-06-15 2010-11-15 Procter & Gamble SYSTEM FOR EVALUATION OF THE PH VALUE AND BUFFER CAPACITY OF MOISTURE CONTAINING CLEANING ITEMS
US20060008912A1 (en) 2004-07-09 2006-01-12 Simon Patrick L Temporary visual indicators for paint and other compositions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4511497A (en) * 1981-11-12 1985-04-16 Strombecker Corporation Bubble composition using multipurpose surfactant base
EP0155737A2 (en) * 1984-03-21 1985-09-25 Shionogi & Co., Ltd. Low irritating shampoo compositions
WO1995033387A1 (en) * 1994-06-09 1995-12-14 Oded Broshi Edible bubble solution
US5664947A (en) * 1995-02-10 1997-09-09 Binney & Smith Inc. Method, apparatus, and kit for marking a surface with colored bubbles
WO1997026076A2 (en) * 1996-01-19 1997-07-24 Oded Broshi A non-toxic, pleasant tasting bubble making composition
WO1997043012A1 (en) * 1996-05-14 1997-11-20 Eckhard Biller Fire suppressant foam dispersant and detergent eckhard iii-formula
US20030109392A1 (en) * 2001-12-06 2003-06-12 Hershey Entertainment & Resorts Company Whipped cocoa bath

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008147934A3 (en) * 2007-05-25 2010-05-27 Healthpro Brands Inc. Microorganism reduction methods and compositions for food with controlled foam generation
US10233171B2 (en) 2012-04-02 2019-03-19 The Trustees Of Columbia University In The City Of New York Compounds, compositions, and methods for modulating ferroptosis and treating excitotoxic disorders

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