MXPA00001223A - Neonanoplasts and microemulsion technology for inks and ink jet printing - Google Patents

Abstract

The present invention relates to colorant compositions containing neonanoplasts. The colorant compositions exhibit improved color brightness and brilliance due to the incorporation of one or more colorants in the neonanoplasts. The colorant compositions may be printed onto virtually any substrate. The colorant compositions of the present invention have particular utility in the area of printed textiles.

Description

NEONANOPLASTOS AND MICROEMULSION TECHNOLOGY FOR INKS AND PRINTING WITH INK JET TECHNICAL FIELD The present invention relates to compositions of dyes containing neonanoplasts. The colorant compositions exhibit improved brightness and color brilliance due to the incorporation of one or more colorants in the neonanoplast. The coloring compositions can be printed on any substrate. The colorant compositions of the present invention have a particular utility in the area of printed textiles.

BACKGROUND OF THE INVENTION A major problem with dyes is that they tend to fade when exposed to electromagnetic radiation such as similar sunlight or artificial light. It is believed that the greater fading of colorants when exposed to light is due to photodegradation mechanisms. These degradation mechanisms include oxidation or reduction of the dyes depending on the environmental conditions in which the dye is placed. The fading of a color will also depend on the substrate on which it resides.

The product analysis of stable and intermediate photoproducts has revealed several important modes of photodecomposition. These include electronic dye injection, reaction with singlet-excited excited state oxygen, unfolding of central phenyl-carbon ring bonds to form amino-substituted benzophenones such as triphenylmethane dyes, reduction to form leuco dyes colorless and the abstraction of hydrogen atom or electron to form radical intermediates.

Various factors such as temperature, humidity, gaseous reactants, including 02, 03, S02, and N02 the water-soluble, non-volatile products of photodegradation have been shown to influence the fading of the dyes. Factors that effect dye fading appear to exhibit a "certain amount of interdependence." This is due to this complex behavior that observations for the fading of a particular dye on a particular substrate can not be applied to dyes and substrates in general .

Under conditions of constant temperature it has been observed that an increase in the relative humidity of the atmosphere increases the fading of a dye for a variety of substrate systems and dyes (e.g. McLaren, K., J. Soc. Dyers Color, 1956 , 72.527). For example, by increasing the relative humidity of the atmosphere, a fiber can swell because the moisture content of the fiber increases. It helps the diffusion of gaseous reactants through the substrate structure.

The ability of a light source to cause a photochemical change in a colorant will also depend on the spectral distribution of the light source in particular, the radiation ratio of the most effective wavelengths to cause a change in the colorant and the quantum yield. of the dye degradation as a function of the wavelength. On the basis of photochemical principles, it would be expected that light of a higher energy (short wavelengths) would be more effective in causing fading than lower energy light (long wavelengths). Studies have revealed that this is not always the case. Over 100 dyes of different classes were studied and it was found that generally the most unstable ones were more effectively vanished by visible light while those of higher light fastness were degraded mainly by ultraviolet light (McLaren, KJ Soc. Dyers Color, 1956 , 72.86).

The influence of a substrate on the stabilizer of the dye can be extremely important. The fading of the dye can be retarded or promoted by a chemical group within the substrate. Such a group can be a kind of state-earth or a kind of excited state. The porosity of the substrate is also an important factor in the stability of the dye. High porosity can promote dyeing of a dye by facilitating the penetration of gaseous reactants and moisture into the substrate. A substrate can also act as a protective agent by filtering the dye from the light of the wavelengths capable of causing degradation.

The purity of the substrate is also an important consideration as long as the photochemistry of dried polymers is considered. For example, it is known that technical grade cotton, viscose rayon, polyethylene, polypropylene and polyisoprene contain carbonyl group impurities. These impurities absorb light at wavelengths greater than 300 nm, which are present in sunlight, and in this way, the excitation of these impurities can lead to reactive species capable of causing the dye to fade (van Beek, HCA, Col. Res. Appl., 1983, 8 (3), 176.) Mother nature protects naturally occurring dyes from one or more of the photodegradation mechanisms described above by surrounding naturally occurring dyes with a cell wall. The cell wall prevents the destructive materials such as gas 02 from reaching the dye. The result is a dye which maintains its brilliance, brightness and beauty even when exposed to sunlight day by day.

In what is required in the art is a coloring system which provides protection to a dye in more the same way that nature protects dyes. There is a need for methods and compositions which are capable of stabilizing a wide variety of dyes, whether importing the dye's stability from the effects of both sunlight and artificial light.

S NTESIS OF THE INVENTION The present invention relates to the needs described above by providing compositions and methods for stabilizing colorants against radiation including radiation in the visible wavelength range. The present invention provides a system for shielding a colorant from destructive forces, such as oxidants and reducing agents. By providing a protective shield for the colorant, highly unstable color dyes can be used in a wide variety of printing applications which were believed to be impossible applications due to rapid degradation of the dye.

The present invention is directed to the neonanoplasts formed by the microemulsion technology. The neonanoplasts contain one or more dye and optionally dye stabilizers. The neonanoplast comprises a polymeric membrane which prevents degradable materials from reaching the dye. The neonanoplast can be incorporated into a variety of liquid media to form coloring compositions.

The present invention is further directed to a method for stabilizing a dye by encapsulating the dye in a polymeric membrane, forming a neonanoplast. In one embodiment of the present invention, one or more dye stabilizers are also encapsulated in the polymeric membrane, creating multiple levels of dye protection of the photodegradable mechanisms.

The present invention is also directed to coloring compositions containing the neonanoplasts described above. The coloring compositions can be applied to any substrate to impart a color to the substrate. In one embodiment of the present invention, a coloring composition comprising neonanoplasts, a liquid medium and a prepolymer is coated on a substrate and subsequently exposed to radiation to fix the neonanoplast to the substrate through polymerization of the prepolymer.

In another embodiment of the present invention, neonanoplasts are present in a polymer coating of a heat transfer product, such as used to transfer graphic images onto clothing.

The neonanoplastos are particularly effective in the application with ink jet of the inks. The use of neonanoplasts as described herein, intensifies colore and stabilizes dyes when exposed to light and other potentially degradable conditions. Additionally, neonanoplasts are particularly effective in coatings for paper and textile products.

These and other features and advantages of the present invention will become apparent upon review of the following detailed description of the written entries and the appended claims.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to neonanoplasts formed by microemulsion technology. Neonanoplasts are spherically shaped polymeric membranes which encapsulate a colorant, and optionally other materials, to prevent degradable materials from reaching the colorant. The neonanoplastos can be formed by a process of microemulsion. The neonanoplastos can have an average particle size of less than about d 1000 nanometers (nm), desirably less than 500 nanometers. The neonanoplasts can be incorporated into a variety of medium to form coloring compositions.

The present invention is further directed to a method for stabilizing a dye by encapsulating the dye in a polymeric membrane, forming a neonanoplast. In one embodiment of the present invention, one or more dye stabilizers are encapsulated in the polymeric membrane, creating multiple levels of dye protection of the photodegradable mechanisms. . Suitable dye stabilizers include any dye stabilizer which does not adversely affect the neonanoplast polymer membrane. In order to describe the various embodiments of the present invention, the following definitions are provided. As used herein, the term "microemulsion" is used herein to mean a multi-phase system that contains, at a minimum, an aqueous phase and a non-aqueous phase in physical contact with each other.

As used herein, the term "colorant" means that it includes, without limitation, any material which will typically be an organic material, such as an organic dye or dye. The term is intended to include a single material or a mixture of two or more materials.

The term "light stable" is used herein to mean that the dye, when encapsulated within a neonanoplast and / or associated with dye stabilizing molecules, is more stable to electromagnetic radiation, including, but not limited to, sunlight or artificial lu, which when the dye is not encapsulated by a neonanoplast and / or is associated with such compound.

The term "molecular includant" as used herein is intended to mean any substance having a chemical structure which defines at least one cavity. That is, the molecular includant is a cavity-containing structure. As used herein the term "cavity" is intended to include any opening or space of a size sufficient to accept at least a portion of the colorant.

The term "functionalized molecular includant" is used herein to mean a molecular includant to which one or more molecules of a dye stabilizer are covalently coupled to each molecule of the molecular includant. The term "degree of substitution" is used here to refer to the number of these leaving molecules or groups (defined below) which are covalently coupled to each molecule of the molecular includant.

The term "derivatized molecular includant" is used herein to mean a molecular includant that has more than two groups of derivatives covalently coupled to each molecule of the molecular includant. The term "derogatory group" is used herein to mean any derogatory group capable of participating in a bimolecular nucleophilic substitution reaction. Examples of molecular inclusives include, but are not limited to, cyclodextrins.

The term "artificial light" is used here to - meaning light having a relatively broad bandwidth that is produced from conventional light sources, including, but not limited to, conventional incandescent light bulbs and fluorescent light bulbs.

Neonanoplast formation The present invention is further directed to a method for forming neonanoplasts. A method for forming the neonanoplastos of the present invention comprises forming a non-aqueous solution containing an organic solvent and a surfactant. Suitable organic solvents include, but are not limited to n-hexane, heptane, octane, n-alkanes, branched alkanes. Suitable surfactants include but are not limited to aereosol OT or dioctyl sodium sulfosuccinate, TRITON® X 100 and fatty acid salts. In a separate vessel, an aqueous solution containing at least one monomer and at least one dye is prepared. Suitable monomers include, but are not limited to, acrylates, acrylamides. methacrylates.

Suitable colorants are included, but are not limited to dyes and pigments. The dye can be an organic tint. The organic dye class includes, by way of illustration only triarylmethyl dyes, such as base d Carbinol of Malachite Green. { 4- dimefilam-ino) -a- [4 (dimethylamino) phenyl] -a-phenyl-benzene-methanol), hydrochloride d Carbinol Verde from Malachite. { N-4 - '[[4- (dimethylamino) phenyl] phenyl methylene] -2,5-cyclohexyldiene-1-ylidiene] -N-methyl-chloride d-methanamine or bis [p- (dimethylamino) -phenyl] chloride d-phenylmethyl } , and green malachite oxalate. { N-4- [[4- (dimethylamino) -phenyl] -phenylmethylene] -2,5-cyclohexyl-diene-1-ylidene] -N-methyl-metanaminium chloride or bis [p (dimethylamino) phenyl] phenylmethyl oxalate}; Monoazo dyes, such as Black Cyanina, Chrysoidina [Basic Orange 2; 4- (phenylazo) 1,3-benzenediamine monohydrochloride], pure blue Victoria BO, pure azu Victoria B, basic fisquina and 3-naphthol Orange; dyes of thiazine, such as Methylene green, double salt of zin chloride [3,7-bis (dimethylamino) -6-nitrophenothiazine-5-chloride ium, double salt of zinc chloride]; oxazine dyes, such as Lumicrom (7, 8-dimethyloxazine); Naphthalimide dyes such as C Yellow Lucifer. { 6-amino-2- [(hydrazino-carbonyl) amino] -2,3-dihydro-1,3-dioxo-lH-benz [de] iso-quinoline-5,8-dilithium salt d-disulfonic acid}; dyes azine such as green Janus B. { 3- (diethylamino) -7- [[4- (dimethyl-amino) phenyl] azo] -5-d-phenylphenazinium chloride} , - cyanine dyes, such as Indocianin green. { Cardio-Green or Fox Green; 2- [7- [1,3-dihydro-l, l-dimethyl-3- (4-sulfobutyl) -2 H -benz [e] indol-2-ylidene] -1.3.5-heptatrienyl] -1,3, 5-heptatrienyl] -1, 1-dimethyl-3- (4-sulfobutyl) -1H sodium salt of benz [e] indole hydroxide inner salt}; indigo dyes, such as indigo. { Indigo Blue or Vat 1 Blue; 2 - (1,3-dihydro-3-oxo-2H-indyl-2-ylidene) -1,2-dihydro-3H-indol-3-one}; coumarin dyes, such as 7-hydroxy-4-methyl-coumarin- (-methylumbelliferone), - benzimidazole dyes, such as Hoechst 33258 [bisbenzimide or 2- (4-hydroxyphenyl) -5- (4-methyl-1-piperazinyl) -2,5-bi-lH-benzimidazole chloride-trihydro pentahydrate]; paraquinoidal dyes, such as Hematoxilin. { Natural Black 1; 7, 11b-dihridrobenz [b] -indeno [1,2-d] pyran-3, 4, 6a, 9, 10 (6H) -pentol}; fluoroescein dyes, such as Fluroroesceinamine (5-aminofluorostyline); diazonium salt dyes, such as Diazo Rojo RC (Diazo Azoico No. 10 or fast red RC salt; 2-methoxy-5-chlorobenzenediazonium chloride, double salt of zinc chloride); azoic diazo dyes, such as fast-blue BB salt (Diazo Azoic No. 20; 4-benzoylamino-2, 5-diethoxy-diazonium benzene chloride, double zinc chloride salt); phenylenediamine dyes, such as Scattered Yellow 9 [N (2,4-dinitrophenyl) -1,4-phenylenediamine or solvent orange 53] diazo dyes, such as Scattered Orange 13 [solvent orange 52 l-phenylazo-4- (4- hydroxyphenylazo) naptalene]; anthraquinone dyes such as Disperse Blue 3 [FFR Blue Fast Celiton: 1-methylamino 4- (2-hydroxyethylamino) -9, 10-anthraquinone], disperse blue 14 [fast azide Celiton B; 1, 4-bis (methylamino) -9, 10-anthraquinone], Alizarin blue black B (black mordant 13); dyes trisazo, ta as Azul Directo 71. { Light Blue Benzo FFL or Light Blue Siriu BRR; 3- [(4- [(4- [(6-amino-l-hydroxy-3-sulfo-2-naphthalenenoyl) azo] -6-sulfo-1-naphthalenyl) -azo] -1-naph-alenyl) azo] -1,5-azide naphthalene disulfonic salt tetrasodium}; xanthene dyes, such as 2, 7-dichloro-fluoroescein; proflavine dyes, such as 3,6 diaminoacridine-hemisulfate (Proflavine); sulfonaphthalein dyes, such as Roj-o Cresol (o-cresolculphonaphthalein); Phthalocyanine dye, such as copper phthalocyanine. { blue pigment 15; (SP-4-1) - [29H, 31H-phthalocyanoate (2-) -N29, N30, N31, N32] copper}; carotenoid dye, such as trans- / 5-carotene (Food Orange 5); carminic acid dyes, such as Carmine, aluminum or calcium-aluminum lacquer of carminic acid (7-aD-glucopyranosyl-9,10-dihydro-3,5,6,6-tet rahydro i-l-methyl- 9, 10-dioxo-2 -anthracene-carbonyl acid); celestial blue dyes, such as Celestial Blue A [3-amino-7 (dimethylamino) phenothiazine-5-chloride ium or 7- (dimethylamino) -3-imino-3 H -phenothiazine hydrochloride]; and acridine dyes, such as Orange Acridine [basic orange 14; 3,8-bis (dimethylamino) acridine hydrochloride, double salt of zinc chloruride] and Acriflavine (neutral acriflavine; 3,6-diamino-10 mixture of methylacridinium chloride with 3,6-acridine diamine).

The aqueous solution is added to the aqueous solution with stirring to form a mixture. To the mixture is added an initiator to polymerize the one or more monomers of the aqueous phase. When the polymerization reaction proceeds, the dye of the aqueous phase is encapsulated by the polymerization monomer d to form the microemulsion spheres within the nonaqueous phase. The non-aqueous phase is removed to give an aqueous phase containing the neonanoplastos. In order to remove the surfactant from the aqueous phase, the dialysis bags or some other separation means are used to separate the surfactant from the aqueous phase containing the neonanoplasts. The water is then removed to give neo-anoplasts. -The resulting neonanoplast can have an average particle size of less than about 1,000 nanometers. Desirably, the neonanoplasts have an average particle size of less than about 500 nanometers. Desirably, the neonanoplast have an average particle size of less than about 100 nanometers.

In one embodiment of the present invention, one or more dye stabilizers are associated with the dye. By incorporating one or more dye stabilizers into the aqueous solution described above, the dye stabilizers can be encapsulated within the neonanoplasts together with the dye. Suitable dye stabilizers for use in the present invention include but are not limited to the colorant stabilizers described in U.S. Patent Applications No. 08 / 627,693 filed March 29, 1996, 08 / 788,863 filed on October 23. of January of 1997, as well as the United States of America patents numbers 5,782,963 5,855,655; and 5,891,229; All of which were assigned to Kimberly-Clark World ide, Inc., whose entire entity is incorporated herein by reference. In a further embodiment of the present invention, suitable colorant stabilizers include, but are not limited to, porffin, a metal, a metal salt, a molecular includant or a combination thereof. Particularly suitable porphines include, -, but n are limited to porphines having the following structure: where R is a proton donor half and M is iron, cobalt or copper. Desirably R is S03H, - V-COOH JÍ-CH 3 COOH, R, COOH wherein R 1 is an alkyl group of from 1 to carbons or the corresponding salt thereof.

Desirably, the coloring stabilizer is represented by one or more porphines, such as Cu-meso-tetra (4-sulfonatophenyl) -porphine (designated CuTPPS4) and Cu-maso-tetra- (N-methyl-4-pyridyl) -porphine (designated CuTMPS4 ), which has the following structure: In the porphines described above, the cobr ion can also be substituted with the cobalt ion and iron. It is also understood that in the case of FeTPPS4, CuTPPS4 or CoTPPS4, the sulfuric acid moieties can be substituted with exits when in solution, such as the sodium salts. The colorant can be stabilized with about 0.1% to 10% wt / wt porffin, or more preferably about 0.3% to 1% wt / wt porffin, and more preferably about 0.5% wt / wt porffin based on the weight total of the solution containing the colorant.

In another embodiment of the present invention, the neonanoplasts contain a dye and a dye stabilizer in the form of a metal or a metal salt such as lanthanide or lanthanide salt. Desirably, the amount of metal or "salt" metal in the collorant solution is from about 0.01% to 10% wt / wt metal, more desirably about 0.03% to 1% wt / wt metal, and more desirably around 0.05% wt / wt metal. Although lanthanides and lanthanide salts are desired metals, other metals such as magnesium, iron, zinc and other transition metals can also be used. To improve the solubility of the metal or the metal salt in solution, the metal solubility enhancing agents can be added. Particularly useful metal solubility enhancing agents include, but are not limited to chelating agents including, but not limited to EDTA (ethylenediaminetetraacetic acid) or EGT (ethylene glycol bis (/ 3-aminoethyl ether)).

In a further embodiment of the present invention, the neonanoplasts comprise a dye and combination with a porphine and a lanthanide such as europium. Desirably, the amount of porphine in the dye solution is from about 0.1% to 10% wt / wt. more desirably from about 0.3% to 1% wt / wt porffin, and more desirably about 0.5% wt / wt porffin. Desirably, the amount of lanthanide in the dye solution is from about 0.01% to 10% wt / wt lanthanide, more desirably about 0.03 to 1% wt / wt lanthanide, and more desirably about 0.05 wt / wt lanthanide. Even when europium and salts, of europi are desired lanthanides, other lanthanides can also be used.

Although it is not desired to be limited by the following hypothesis, it is reasoned that in addition to the protection provided by the polymer membrane of the neonanoplasts, the aforementioned dye stabilizing compounds act by cooling the excited state of a dye molecule within of the neonanoplast by efficiently returning it to a ground state. This reduces the possibility of an oxidative or other chemical reaction occurring which could be to the colorless chromophore dye.

The cooling process can occur through a number of processes. One such process is mentioned as the heavy atom effect (internal or extreme) in which atoms with a high atomic number such as iodine, xenon and lanthanides, can effect the excited electronic transitions of the dye molecule by allowing here the occurrence of forbidden electronic transitions and by decreasing the lifetimes of the excited state. This effect allows the quick return of the dye to its ground state.

Another cooling process involves the transfer of the electron back. In this case, the cooling of. The excited dye molecule occurs through sequential electronic transfer. The additive or cooler, and the dye form a 'pair of' ion through the electronic donation within which the return electron transfer leads to a global deactivation of the excited energy donor for example the dye.

Another cooling process involves a condition in which the cooling molecule (additive) has a state of excited energy lower than the excited dye. In this case, it may be possible to transfer the excited energy to the cooler thereby allowing the dye molecule to return to its ground state. These mechanisms are more fully discussed in the work Química y Luz, by Suppan, P., published by the Royal Society of Chemistry, 1994, pages 65 - 6 which is incorporated herein by reference.

In some embodiments of the present invention, the colorant and / or the dye stabilizer within the neonanoplasts is associated with a molecular includant. The term "associated" in its broadest sense means that the dye and / or the dye stabilizer is at least a close proximity to the molecular includant. For example, the colorant and / or the colorant stabilizer can be maintained in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, or the like. Alternatively the dye and / or the dye stabilizer can be covalently linked to the molecularly inclusive, even though this is normally neither desired nor necessary. As a further example, the dye and / or the dye stabilizer can be at least partially included within the molecular inclusive cavity.

The molecular includants can be organic and inorganic in nature. In certain embodiments, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. Examples of molecular inclusions are, by way of illustration only, clathrates or intercalates, zeolites and cyclodextrins. Examples of cyclodextrins include but are not limited to cyclodextrin, b-cyclodextrin, g-cyclodextrin, d-cyclodextrin, hydroxypropyl b-cyclodextrin, hydroxyethyl b-cyclodextrin, hydroxyethyl-cyclodextrin, carboxymethyl-cyclodextrin, carboxymethyl-b-cyclodextrin, carboxymethyl-cyclodextrin, octyl-succinate-cyclodextrin, octy-succinate-b-cyclodextrin, octyl-succinate-b-cyclodextrin b sulfated cyclodextrin and sulfated cyclodextrin (Ceresta USA, Incoporated, Hammond, Indiana).

The term "derivatized cyclodextrin" as used herein means a cyclodextrin having more than two starting groups covalently coupled to each molecule of cyclodextrin. The term "starting group" is used here to mean any starting group capable of participating in a reaction of bimolecular nucleophilic substitution. Examples of the derivatized cyclodextrin include, but are not limited to, hydroxypropyl b-cyclodextrin, hydroxyethyl b cyclodextrin, hydroxyethyl cyclodextrin, carboxymethyl cyclodextrin, carboxymethyl b cyclodextrin, carboxymethyl cyclodextrin, octyl succinate to cyclodextrin, octy succinate b cyclodextrin, octyl succinate g cyclodextrin byg sulfated cyclodextrin. A desired derivatized cyclodextrin is ethyl hydroxy b-cyclodextrin.

A desired molecular includant is cyclodextrin g. Another desirable molecular includant is d-cyclodextrin. In other embodiments, the including molecule is ethyl hydroxy b-cyclodextrin. Although it is not desired to be bound by the following hypothesis, it is believed that the molecular incluyent inhibits the addition of the coloring molecule and solution. Other aggregate inhibitors that can be used in the practice of the present invention are starches, pectins, amyloses, clathrates and crown ethers. It is understood that the addition of the derivatized cyclodextrins to a neonanoplast-forming solution for the purpose of inhibiting the aggregation and / or stabilization of the dyes in the neonanoplast is considered an aspect of the present invention.

In addition to the dye, an optional dye stabilizer and an optional molecular includant, the neonanoplastics of the present invention may also contain additional components, depending on the application to which they are intended, provided that the additional component does not adversely affect the dye molecule . Examples of such additional components include, but are not limited to, charge carriers; to the stabilizers against thermal oxidation; to the modifiers of viscoelastic properties; to cross-linking agents; to plasticizers; to charge control additives, such as the quaternary ammonium salt; to flow control additives, such as hydrophobic silica, zinc stearate, calcium stearate, lithium stearate, polyvinyl stearate and polyethylene powders; the fillers such as calcium carbonate, clay and talc; the surfactants; the chelating agents; and TINUVIN® compounds among other additives registered by those with ordinary skill in the art. Charge carriers are well known to those who have ordinary skill in the art typically are polymer-coated metal particles. Desirable surfactants include, but are not limited to C12 to C18 surfactants such as cetyl trimethyl ammonium chloride and carboxymethylcellulose. TINUBIN® compounds are a class of compounds produced by Ciba-Geigy Corporation, which includes bezophenones, benzotriaols and hindered amine. Desirably, the TINUVIN® compounds include but are not limited to 2- (2'-hydroxy-3'-sec-butyl-5'-tert butylphenyl) -triazole, -. poly (N-5-hydroxyethyl-2,6,6,6-tetramethyl-4-hydroxy-piperidyl succinatoy 2- (2'-hydroxy-3 ', 5'-ditertbutylphenyl) -5-chloro-benzotriazole. Additional components in the colored composition are well known to those of ordinary skill in the art.

Applications for Neonanoplasts The present invention is also directed to the coloring compositions containing the above-described neonanoplasts. The coloring composition may comprise an aqueous or non-aqueous medium, even when an aqueous medium is desirable. The coloring compositions of the present invention contain neonanoplasts as well as any of the dye additive stabilizers described above. For example, the dye composition may contain the neonanoplasts arrib described in combination with any of the following additives: a second dye; a coloring stabilizer, ta as a porphine; a molecular includant; a pre-polymer; any additional components as described above. The present invention is particularly useful for inks to be used in inkjet printers. The inks used in ink jet printers are described in United States of America Patent No. 5,681,380 assigned to Kimberly Clark Worldwide, Inc., which is hereby incorporated by reference in its entirety.

The coloring compositions of the present invention can be applied to any substrate to impart a color to the substrate. The surface tension of the neonanoplast can be controlled to allow the monolayer coatings of the neonanoplasts on a substrate surface.

In an embodiment of the present invention, the coloring composition comprises neonanoplasts, a liquid medium, a pre-polymer and an initiator photo. The colorant composition is coated on a substrate and the radiation is subsequently exposed to light cure the prepolymer, fixing the neonanoplasts to the substrate through polymerization of the prepolymer. Suitably, the prepolymers include, but are not limited to acrylates, diacrylates, modified acrylates, triacrylates, pentaacrylates, methacrylates and cationic resins. Suitable photoinitiators include, but are not limited to, conventional photoinitiators, as well as photoinitiators described in U.S. Patent No. 5,739,175; U.S. Patent Application No. 08 / 625,737; provisional patent application of the United States of America reference number 11300-042OP, filed on May 7, 1998; and the provisional United States of America patent application, reference No. -11300-0450, filed June 1, 1998; all of which are assigned to Kimberly-Clark orldwide, Inc., whose "complete" content is incorporated herein by reference.

Substrates to which neonanoplasts can be applied include, but are not limited to, paper, wood, wood or composite product, woven fabric, nonwoven fabric, textile, plastic, glass, metal or any other substrate that could benefit from having a neonanoplast on it. Examples of suitable substrates are described in United States of America patent application parents series No. 08 / 843,410 assigned to Kimberly-Clark Worldwide, Inc., the entire contents of which are incorporated herein by reference in an embodiment of this invention, the neonanoplast is applied to a textile article, such as clothing. A very thin coating having a thickness of about one neonanoplast can be applied to a textile surface subsequently affixed to the surface using a pre-polymer as described above. The resulting textile has an excellent touch and drop as well as a bright color due to the thin coating of the textile neonanoplasts.

In still another embodiment of the present invention, neonanoplats are present in a carrier, the nature of which is well known to those of ordinary skill in the art. For many applications, the carrier will be a polymer, typically a thermosetting or thermoplastic polymer, with the latter being the most common. Examples of suitable thermosetting and thermoplastic polymers are described in the patent application of the United States of America parent series No. 08 / 843,410 assigned Kimberly-Clark Worldwide, Inc., the entire contents of which are incorporated herein by reference. A particularly suitable application is the incorporation of the neonanoplasts in the polymer coating of a heat transfer product, in order to transfer graphic images to the clothing.

The present invention is further described by the following examples. Such examples, however, should not be considered as limiting in any way, either the spirit or the scope of the present invention. Examples, all parts are by weight unless otherwise indicated.

Example 1 Preparation of Magenta Neonanoplastos To a 500 milliliter round bottom bottle with a stir bar was added 200 milliliters of hexane and 40 milliliters of aerosol or tea (dioctyl sodium sulfosuccinate available from American Cyanamid). To this mixture were added 1.0 milliliters of an 'acrylamide - 8 mg / ml) and: N, N' -methylene bisacrylamide (Aldrich Chemical Company, Milwaukee, Wisconsin) (2 mg / ml), solution in water. To this mixture was added 20 μl of N, N, N'N'-tetramethylene diamine (Aldrich Chemical Company, Milwaukee, Wisconsin). The mixture was stirred and flashed with argon gas to remove the oxygen.

In a separate vessel, an aqueous ink solution was prepared by adding 0.083 g of Rhodamine WT (Aldrich Chel Company, Milwaukee, Wisconsin) to 10 ml of water and stirring for about 30 minutes. The aqueous dye mixture was then added to the reaction mixture and re-scintillated with argon gas for one hour. Then, 20 μl of a solution of 80 mg / ml of ammonium persulfate was added to the bottle. The reaction mixture was stirred under argon gas for 8 hours.

The hexane was then removed under reduced pressure to give a syrup liquid. The liquid as jarab was placed in the dialysis bags (SIGMA, cut 10,000 d molecular weight) and underwent a continuous dialysis for 2 days to remove the surfactant and any non-encapsulated dye. The bags were then opened and the water was removed for gives the neonanoplastos in the form of a clear magenta powder.

Example 2 Preparation of Higher Concentrations of Magenta Neonanoplastos The procedure of Example 1 was repeated using the example three different concentrations of Rhodamine WT dye.

By increasing the concentration of dye, the resulting neonanoplasts had a dark magenta color. All the resulting neonanoplasts were filtered through a 0.45 μ filter without leaving a precipitate.

Example 3 Preparation of Neonanoplasts using different dyes The procedure of example 1 was repeated using other dyes, rida Dye Grams of Moles de tint Tintée eaag? 23f) ml 1 Victoria blue bo 0. 4 1. 33 x 10"3 2 Red Acid 52 0. 3 1 x 10'3 The resulting neonanoplasts in the powder form had a dark color. All the resulting neonanoplasts were filtered through a 0.44 μ filter after leaving a precipitate.

Having thus described the invention, numerous changes and modifications will be readily apparent to those having ordinary skill in the art, without departing from the spirit or scope of the invention.

Claims (24)

1. A neonanoplast that has an average particle size of less than 500 nanometers.

2. The neonanoplast as claimed in clause 1, characterized in that it comprises at least one dye encapsulated by a polymeric membrane.

3. The neonanoplast as claimed in clause 2, characterized in that it also comprises at least one coloring stabilizer associated with at least one dye.

4. The neonanoplast as claimed in clause 3, characterized in that at least one "decolorizing stabilizer selected from a porphine, a metal, a metal salt, a molecular includant or a combination thereof.

5. The neonanoplast as claimed in clause 4, characterized in that the porphine is represented by the following formula where M is iron, cobalt or copper; and where R is S03H, RiCOOH where R, from 1 to 6 carbons.

6. The neonanoplast as claimed in clause 5, characterized in that the porphine is Cu-meso-tetra (4 -sulfanofenyl) porcine or Cu-meso-etra- (N-methyl-4-pyridyl) porphine, having the following structures respectively: or the porf ina is Co-mesa-tetra- (4-sulfanatofenil porfine or Co-meso-tetra- (N-methyl-4-pyridyl) -porphine, having the following structures, respectively:

7. The neonanoplast as claimed in clause 4, characterized in that the metal salt or the target comprises a lanthanide or a lanthanide salt.

8. The neonanoplast as claimed in clause 4, characterized in that the molecular includant is one or more cyclodextrins.

9. The ink set as claimed in clause 8, characterized in that the one or more cyclodextrin comprises a-cyclodextrin, b-cyclodextrin, g-cyclodextrin, d-cyclodextrin, hydroxypropyl b-cyclodextrin or hydroxyethyl b-cyclodextrin.

10. A coloring composition comprising the neonanoplasts as claimed in clause 1.

11. The coloring composition "such" and as claimed in clause 10, further characterized as comprising a pre-polymer material.

12. A method for stabilizing a dye comprising: encapsulating the dye in a polymeric membrane to form a neonanoplast membrane.

13. The method as claimed in clause 12, further characterized in that it comprises associating at least one coloring stabilizer with the colorant.

14. The method as claimed in clause 12, characterized in that the at least one coloring stabilizer selected from a porphine, a metal, a metal salt, a molecular includant or a combination d thereof.

15. The method as claimed in clause 14, characterized in that the porphine is represented by the following formula where -M is iron, cobalt or copper; and where R -.- is S03H, RjCOOH wherein Rj is an alkyl group of from 1 to 6 carbons.

16. The method as claimed in clause 15, characterized in that the porphine is Cu-meso-tetra- (4-sulfonatophenyl) -porphine or Cu-meso-tetra- (N-methyl-4-pyridyl) -porphine which has the following structures, respectively: or the porphine is Co-meso-tetra- (4-sulfanatophenyl) -porfin or Co-meso-tetra- (N-methyl-4-pyridyl) -porphine, having the following structures respectively:

17. The method as claimed in clause 14, characterized in that the metal or metal salt comprises a lanthanide or a lanthanide salt.

18. The method as claimed in clause 14, characterized in that the molecular includant is one or more cyclodextrins.

19. The method as claimed in clause 18, characterized in that the one or more cyclodextrin comprises a-cyclodextrin, b-cyclodextrin, g-cyclodextrin, d-cyclodextrin, hydroxypropyl b-cyclodextrin or hydroxyethyl b-cyclodextrin.

20. A method for making a dye composition comprising incorporating the neonanoplast as claimed in clause 1 in a liquid medium.

21. The method as claimed in clause 20, further characterized in that it comprises adding a pre-polymer to the coloring composition.

22. A method for forming a colored textile comprising coating the coloring composition as claimed in clause 11 on a textile; Y exposing the pre-polymer to the ultraviolet radiation to fix the neonanoplast to the textile.

23. A substrate that has on it or there neonanoplasto as claimed in clause 1.

24. A substrate having on it or there the coloring composition as claimed in clause 10.