WO1990015848A1

WO1990015848A1 - Water soluble coloring compositions containing sparkle components

Info

Publication number: WO1990015848A1
Application number: PCT/US1989/002675
Authority: WO
Inventors: Paul M. Mandel, Jr.; Cleveland L. Hughes; Timothy N. Williams
Original assignee: Mandel Paul M Jr; Hughes Cleveland L; Williams Timothy N
Priority date: 1989-06-19
Filing date: 1989-06-19
Publication date: 1990-12-27

Abstract

Water soluble coloring compositions are provided that contain a stable and uniform suspension of color and sparkle or glitter components. The process for producing the coloring compositions employs a lower temperature range than the prior art; this reduces the need for equipment heating and enables the equipment to be more readily cleaned.

Description

WATER SOLUBLE COLORING COMPOSITIONS CONTAINING SPARKLE COMPONENTS

This application is a continuation-in-part of U.S. Serial Numbers 025,853; 025,854; and 026,477 all filed on March 16, 1987 and all entitled: "WATER SOLUBLE COLORING COMPOSITIONS CONTAINING SPARKLE COMPONENTS".

This invention relates to a new and improved composition and process for producing coloring compositions. These have use in water soluble solid paints, poster paints, for color brushes and for roller balls, crayons, and the like. The coloring compositions of this invention also contain sparkle components which are maintained as a stable and uniform solid suspension in the coloring system.

The present paint compositions containing such sparkle components are pleasing visually, and also tend to take on the appearance of a multi-dimension because they are usually applied in a non uniform fashion.

Prior art paint compositions are manufactured at comparatively high temperatures estimated at about 130°F, and produce a pairit that hardens rapidly. Consequently, heaters are generally used at various steps of the process, and this requirement makes it difficult to clean the equipment. Also, it is difficult to obtain water soluble paint compositions containing sparkle components that can be maintained as a stable and uniform suspension.

Water soluble paint compositions produced by prior art processes generally do not contain a smell or scent component because they are evaporated or volatized by the high processing temperature. However, if a lower processing temperature range was possible, smell components such as scents, fragrances and perfumes could be incorporated and retained in the composition. THE INVENTION:

According to the invention, a water soluble paint composition is provided containing: water; a polymeric thickener to maintain solid components such as the color and the sparkle or glitter in a uniform and permanent suspension; a water soluble wax to thicken and harden the composition; glycerin, and the like to increase the time span of hardening to enable the mixture to flow without undue heating; and adhesive thickener; and, glitter and coloring agents.

The polymeric thickener may include a polyacrylic or polymeth- acrylic acid having polyfunctional groups; the polymeric acid is thickened or cured with an activator, infra. A typical polymeric thickener is sold by B.F. Goodrich under the trade name of CARBOPOL. Another suitable polyacrylic acid is sold as CARBCMER 941. The function of the thickener is to solidify the composition as a gel near the termination of the mixing process, and this enables solids such as glitter, sparkle or color to be maintained as a uniform and permanent solid suspension.

Other thickeners included in the term 'polymeric thickener' are: nitrile latexes, styrene-butadiene latexes, polyisobutylene, acrylic latexes, rosin gum, food thickeners such as flours and starches, fumed silica, hydroxypropyl methyl cellulose, hydroxy- butyl methyl cellulose, and so forth.

The water soluble wax is employed to thicken and harden the composition. The use of the wax offsets the cost of the more expensive adhesive thickener such as gum arabic, and also functions as an adhesive itself. Typical water soluble waxes are of the microcrystalline variety, and include EMERWAX 1255 and METHOCEL. Glycerin is used to enable the composition to flow with little or no application of heat and to increase the time span of hardening (to say within 48 hours). The glycerin is usually employed as 99.57o U.S.P. The glycerin may be replaced with sorbitol, and to a certain extent with other alcohols such as cetyl, and mixtures thereof.

The combination of the glycerin, wax and polymer results in a coloring composition which is liquid and pourable at a temperature in excess of about 85°F. Hence, no expensive processing equipment is required. Moreover, upon contact with air, the surface of the coloring composition will harden, and this permits subsequent handling after the processing step to facilitate pouring into molds and curing in place.

An activator for the polymeric thickener is used to polymerize and thereby thicken the polymer. In the case of the polyacrylic acid, suitable catalysts or activators include triethanolamine, and other amines such as ethyl, propyl and hexyl. In addition to causing the suspension to thicken and gel, the activator also serves as a pH buffer and to dissolve the preservative, if one is employed. In other cases, the polymeric thickener may be activated by hea , etc.

An adhesive thickener such as gum arabic or accacia gum is used to thicken the composition and act as an adhesive or binder. Other adhesive thickeners such as tragacinth gum, and plant mucilages are also suitable.

To the extent that the polymeric thickener, wax and adhesive thickener have similar properties, they may be used somewhat inter¬ changeably. Their function is to maintain the color and glitter in a permanent and solid suspension. Magnesium stearate may be used to increase the hardening time and to function as a plasticizer and/or dispersing agent for the composition following processing, and also to substitute in part for the gum arabic. Equivalent compounds are also available, such as Ca stearate, Na stearate, di-butyl phthalate, di-isobutyl phthalate, dioctyl adipate, etc.

Colors which may be employed are standard F.D. & C. colors, and non F.D. &. C colors, both water soluble, and water insoluble.

The sparkle or glitter ingredients include those which are light reflective; light absorptive; light absorptive and which transmit a single different color; and, light absorptive and which transmit two or more different colors. Suitable sparkle or glitter ingredients are sold under the generic names of TIMIRON, BIVIRON, C0L0R0NA, DICHRONA, and the like and contain varying amounts of mica and TiO^. Other sparkle or glitter ingredients may include Cr(OH)« and mica, castor oil and mica, iron oxides and mica, bismuth oxychlorides , etc. These materials are sold by Mearl Products, Rona and Mallingkrodt. Aluminum and other metal particles also may be used.

When preservatives or stabilizers are used, they may include: imidazolidienyl urea (0.25% - 0.35%); mehtyl or propyl paraben (0.757o - 1.0%, and 0.25% - 0.35%, respectively); DOWOCIL 200 (0.1% - 0.5%); and, so forth. Bactericides , slimicides, etc., also may be used in addition to the preservatives or stabilizers.

It will be appreciated that the compositions can be removed from the processing equipment and pouring equipment simply by washing with water. This enables the equipment to be changed over to a different coloring formulation without undue difficulty. DESCRIPTION OF THE PREFERRED EMBODIMENTS:

Typically, for a water soluble, solid coloring paint, a suitable approximate range of ingredients, by percentage weight, for the broadest and preferred range of ingredients, respectively, is as follows:

Water (deionized) 45% - % 45% - 55%

Polymeric thickener 0% - 0.5% ,05% - 0.5%

Water soluble wax 0% - 5% 1% - 5%

Glycerin and/or long chain alcohols 0% - 10% 1% 10%

Activator for polymeric thickener 0% - 0.5% 0% - 0.5%

Adhesive thickener 0% - 25% 8% - 25%

Hardener 0% - 0.5% 0% - 0.5%

Color 3% - 5% 3% - 5%

Sparkle or glitter 21% - 30% 21% - 30%

Preservative 0% - 1% 0.1% - 1%

A preferred composition is, as follows: Polyacrylic acid (CARBOMER 941): 0.12%: Water soluble microcrystalline wax (EMERWAX 1255): 2%; Glycerin (U.S.P. 99.5%): 6%; amine activator (triethanolamine) : 0.17o; Adhesive thickener (gum arabic) : 12%,; Hardener (Mg stearate): 0.3%; Color: 4%; Glitter: 24%; preservative: 0.467_o; and, Water (deionized): 517₀, or balance.

Another suitable composition is, as follows: Polyacrylic acid; 0.15%; Wax: 2.8%;Glycerin: 7.25%; activator: 0.15%; Adhesive thickener: 10%; Hardener: 0.3%; Color: 4.5%; Glitter: 29.5%; Preservative: 0. 357o; and, Water: 45%, or balance. Another suitable composition is, as follows: Polymeric thickener: 0.15%; Wax: 2%; Glycerin: 8.75%; Activator: 0.15%; Adhesive: 10.25%; Hardener: 0.35%; Color: 3%; Sparkle: 21%; Preservative: 0.35%; and, Water: 547o, or balance.

The use of the formulation for poster paints, color brushes and roller balls requires the omission of the adhesive (gum arabic or gum tragacinth, mucilage, etc.) and the hardening agent (Mg stearate, etc.), and a decrease in the glitter or sparkle components. A suitable, approximate range of component concentrations, by percentage weight is, as follows:

Water (deionized) 75% - 65%

Polymeric thickener 0% - 1%

Water soluble wax 3% - 8%

Glycerin and/or long chain alcohols 5% - 12%

Activator for polymeric thickener 0% - 1%

Preservative 0.25%-0.35%

Color 1% - 5%

Sparkle or Glitter 8% - 15%.

A typical composition is, as follows: Water: 727_D; CARBOMER 941: 0.76%; EMERWAX 1255: 4%; Glycerin: 8%; Activator: 0.76%; Preservative: 0.15% - 0.35%; Color: 3%; and, Glitter: 12%, A suitable crayon composition is, as follows:

Water soluble wax 30% - 70%

Polymeric thickener 0% - 4%

Color 3% - 10%

Sparkle or glitter 20% - 35%

Preservative 0% - 3%

A preferred crayon composition is, as follows: Water soluble wax (EMERWAX 1255): 54.5%; Water soluble wax(MULTIWAX W 445): 5.9%; Polymeric thickener(CAB-0-SIL H55) silica gel: 1.2%; Polymeric thickener (non-ionic, water soluble, cellulose ethers: METHOCEL - Dow Chemical) 1.2%; Color: 6.0%; Sparkle: 30%; and, Preservative: 1.2%. This composition, as in the other compositions, has a processing temperature which is in the same range. Also, following application to a surface, such as paper, the sparkle appearance can be enhanced simply by rubbing.

For solid color paints, a suitable process for their manufacture includes: 1. adding CARBOMER and water to a high speed shear blender and mixing for about 10 minutes to obtain a uniform blend; 2. the blend is heated to about 130°F for about 20 minutes to hour with added glycerin and EMERWAX. This heating will melt the wax, and blending is continued for an additional hour to 40 minutes to obtain a blending time of about 1 hour for the mixture of CARBOMER, water, glycering and EMERWAX; 3. the balance of the ingredients (except the activator) are added, and the blending is continued at a reduced temperature of about 115°F - 120°F for about hour; 4. the activator is then added last and the blending is continued for about 15 minutes; 5. the ingredients are poured to a machine filler at about 90°F - 115°F, and poured and then hardened in situ for up to about 48 hours. A similar procedure is followed in the case of poster paints, color brushes and roller balls. In the case of the crayons, the ingredients are heated and blended for a sufficient time to obtain a uniform melt, the components being added in the same order as for color paints, where appropriate. If it is desired to incorporate scents, perfumes, flavors, etc., into the composition, these may be added in step 3. These can include licorice, chocolate, lemon, lime, fragrances, etc.

While the components disclosed are of the water soluble type, water insoluble components may be used and still produce a phase compatable compound. This is obtained by linking components such as water insoluble thickeners, waxes, colors and adhesives to the water soluble components using dispersing agents such as quaternary ammonium compounds, polysorbates , polyethylene glycols (PEG compounds), etc. This technique enables compounds such as stearic acid and cetyl alcohol to be substituted in place of or used in conjunction with the microcrystalline wax.

In general, waxes may be employed provided they are either in an emulsion form, or if they are emulsifyable. Preferably, these waxes are non toxic, such as cosmetic and/or petroleum waxes, and these include paraffin, polyethylene, polymerized and microcrystalline waxes. The most preferred waxes are both non toxic and edible, and these waxes are usually derived from edible products; examples include beeswax, candelilla, carnauba (Brazil), vegetable waxes, etc.

Thus typical waxes which are usable include water insoluble waxes which can be used with linking compounds to form phase stable emulsions such as bayberry wax and bees waxes, and substit¬ utes for these myricyl esters such as palmitates, stearates and oleates; synthetic waxes; ceresin, otherwise known as earth wax, and which may contain paraffin, and substitutes such as mineral and ozacerite waxes; parffin waxes; polymer waxes such as low molecular weight polypropylene and polyethylenes; spermaceti wax (cetyl palmitate); candelilla wax; lanolin and lanesterol waxes; palm wax; carnauba and ouricury waxes; rice bean wax; vegetable waxes; lignit (montan) waxes; Japan wax, and mixtures or blends of these. Most of these waxes may be purchased as wax emulsions, i.e., the wax has been converted, by the manufacturer or processor, to an emulsion by blending with one or more liners causing them to emulsify. If the wax is not purchased as an emulsion, it must be converted to an emulsion by the purchaser by blending the wax with one or more suitable linkers.

A wide variety of linkers and/or emulsifiers which can be used to produce a wax emulsion include: alcohol ethoxylates; PEG esters, monostearates; phosphate esters; polysorbate esters; monoglycerides; polyglyceryl esters; sorbitol esters, etc. The linkers or emulsifiers should be non toxic, and preferably edible, such as polysorbates, glycerol and sorbitol esters, etc.

STITUTE SHEET Adhesives which are suitable are those which are non toxic, and which do not cure in air, in the case of water colors or crayons. Preferably, the adhesives employed in this invention are transparent or transluscent, and this enables less color and glitter to be used in the composition compared to those compositions which employ opaque adhesives.

Claims

original claims 1-6 cancelled; new cla ms

7-27 added (3 pages)]

CIAIM 7. fNEW) A water soluble crayon composition, consisting of: a polymeric thickener to maintain solid components in a uniform and permanent suspension in the composition; a water soluble wax to thicken the composition; color and glitter, the composition being pourable at about 95 .F - 130 F. , and formulated in the temperature range of about 90 F. - 130 F.

CIAIM 8. (NEW) The water soluble crayon composition of Claim 7, consisting of: water soluble wax: 30% - 70%; polymeric thickener: 0% - 8%; colorant: 3% - 10%; sparkle or glitter: 20% - 35%; and, preservative: 0% - 3%.

CIAIM 9. (NEW} The composition of Claim 7, consisting of: a silica gel polymeric thickener: 0% - 4%; a non-ionic, water soluble, cellulose ether thickener: 0% - 4%; a water soluble wax:

30% - 70%; sparkle or glitter: 20% - 30%; and, preservative:

0% - 3%.

CIAIM 10. (NEW) The composition of Claim 7, in which the silica gel polymeric thickener varies from about 1.2% - 8%.

CIAIM 11. fNEW) The composition of Claim 7, in which the polymeric thickener varies from about 2.4% - 8%.

CIAIM 12. (NEW. The composition of Claim 9, in which the silica gel polymeric thickener varies from about 1.2% - 4%; and the cellulose ether polymeric thickener varies from about 1.2% - 4%.

CIAIM 13. fNEW) The composition of Claim 1, in which the said wax is derived from a water insoluble wax which has been converted to a phase compatible, wax emulsion.

CIAIM 14. (NEW) The composition of Claim 13, in which the said phase compatible wax emulsion is obtained using linkers and/or emulsifiers.

CIAIM 15. fNEW) The composition of Claim 7, in which the said wax is a microcrystalline wax.

CIAIM 16. fNEW) A water soluble paint composition, including poster paints, color brushes, and roller balls consisting of: water; a thickener to maintain solid components in a uniform and permanent suspension in the composition, selected from the group consisting of a polyacrylic acid, nitrile latexes, styrene- butadiene latexes, polyisobutylene, acrylic latexes, rosin gum, flours, starches, fumed silica, hydroxypropyl methyl cellulose, hydroxy butyl methyl cellulose; glycerin, or alcohols selected from the rou consistin of sorbitol cet l, and mixtures thereof in liquid form to enable the mixture to flow at about 85 F. - 130 F. ; a water soluble wax to thicken the composition; and, glitter and color.

CIAIM 17. NEW) The composition of Claim 16, including poster paints, color brushes, and roller balls, consisting of: water: 75% - 65%; polymeric thickener: 0% - 1%; water soluble wax: 3% - 8%; glycerin, and /or long chain alcohols: 5% - 12%; activator for thickener: 0% - 1%; color: 1% - 5%; and, sparkle or glitter: 8% -15%.

CIAIM 18. fNEW) The composition of Claim 16, including poster paints, color brushes and roller balls, consisting of: water: 75% - 65%; polyacrylic acid: 0% - 1%; water soluble wax: 3% - 8%; glycerin and/or long chain alcohols: 5% - 12%; activator for polyacrylic acid: 0% - 1%; preservative: 0.25% - 0.35%; colorant: 1% - 5%; and, sparkle or glitter: 8% - 15%.

CIAIM 19. fNEW) The composition of Claim 16, in which the water soluble wax is a microcrystalline wax.

CIAIM 20. fNEW) The composition of Claim 16, in which the water soluble wax is derived from a water insoluble wax which has been converted into a phase compatible wax emulsion.

CIAIM 21. fNEW) The composition of Claim 20, in which the said compatible wax emulsion is formed using linkers and/or emulsifiers.

CIAIM 22. fNEW) A water soluble, solid coloring paint having an approximate range of ingredients, by percentage weight, consisting of: water: 45% - 55%; polymeric thickener selected from the group consisting of: polyacrylic acid, silica, nitrile latexes, styrene- butadiene latexes, polyisobutylene, acrylic latexes, rosin gum, food thickeners including flours and starches, and cellulose ethers: 0.05% - 0.5%; water soluble wax: 1% - 5%; glycerin, cetyl alcohol or sorbitol, and mixtures thereof: 1% - 10%; an activator to cure the polymeric thickener: 0% - 0.5%; adhesive thickener selected from the class consisting of gum arabic, acacia gum, tragacanth gum and plant mucilages: 8% - 25%; hardener: 0% - 0.5%; color: 3% - 5%; sparkle or glitter: 21% - 30%; and preservative: 0% - 1%; the mixture being pourable at about 90 F. - 130 F.

CIAIM 23. fNEW) The coloring paint of Claim 22, consisting of: water; 45% - 55%; polyacrylic acid: 0.05% - 0.5%; water soluble wax: 1% - 5%; glycerin: 1% - 10%; triethanolamine: 0% - 0.5%; sparkle or glitter: 21% - 30%; and, preservative: 0.1% - 1%. CLAIM 24. fNEW) The coloring paint of Claim 22, in which the said wax is derived from a water insoluble wax which has been converted to a phase compatible wax emulsion.

CIAIM 25. fNEW) The coloring paint of Claim 22, in which the said wax emulsion is derived using linkers and/or emulsions.

CIAIM 26. fNEW) The coloring paint of Claim 22, in which the said wax is a microcrystalline wax.

CIAIM 27. fNEW) A process for producing a water soluble paint composition, comprising mixing water and a polymeric thickener to form a uniform suspension, the polymeric thickener selected from the class consisting of: polyacrylic acid, silica, nitrile latexes, styrene-butadiene latexes, polyisobutylene, acrylic latexes, rosin gum, food thickeners, including flours and starches, and cellulose ethers; adding a water soluble wax to the suspension; heating the suspension to about 130 F. to melt the wax; continuing the mixing to produce a uniform composition; adding a thickener selected from the class consisting of gum arabic, acacia gum, tragacanth gum, and plant mucilages, hardeners, colorant and glitter and continuing the mixing at about 115 F. - 120 F. ; adding an activator to cure the thickener; pouring the composition at about 90 F. - 115 F. ; and, then hardening.