WO1998023695A2

WO1998023695A2 - Improved substrates and colorant stabilizers

Info

Publication number: WO1998023695A2
Application number: PCT/US1997/021700
Authority: WO
Inventors: Ronald S. Nohr; John G. Macdonald; Alison S. Bagwell; Kelly D. Branham; Bruce G. Stokes; Leonid A. Turkevich
Original assignee: Kimberly-Clark Worldwide, Inc.
Priority date: 1996-11-27
Filing date: 1997-11-26
Publication date: 1998-06-04
Also published as: KR20000069137A; SK67499A3; EP0941293A2; CA2269700A1; WO1998023695A3; PL336328A1; AU5589698A; JP2002511893A

Abstract

The present invention relates to improved substrates for use with colorants, and especially with a family of colorants and colorant stabilizers. The colorant stabilizers, according to the present invention, are capable of stabilizing a colorant when it is exposed to electromagnetic radiation. The colorant stabilizers enable the production of an ink set wherein each ink of the ink set, regardless of color, possesses substantially similar light fastness properties. The present invention further relates to improved substrates for use with colorants, and especially with the colorants and colorant stabilizers of the present invention. The improved substrates enable the production of a printed substrate having superior print quality compared to conventional substrates.

Description

IMPROVED SUBSTRATES AND COLORANT STABILIZERS

Technical Field

Background of the Invention

A major problem with colorants is that they tend to fade when exposed to electromagnetic radiation such as sunlight or artificial light and the like. It is believed that most of the fading of colorants when exposed to light is due to photodegradation mechanisms. These degradation mechanisms include oxidation or reduction of the colorants depending upon the environmental conditions in which the colorant is placed. Fading of a colorant also depends upon the substrate upon which they reside.

Product analysis of stable photoproducts and intermediates has revealed several important modes of photodecomposition. These include electron ejection from the colorant, reaction with ground-state or excited singlet state oxygen, cleavage of the central carbon-phenyl ring bonds to form amino substituted benzophenones, such as triphenylmethane dyes, reduction to form the colorless leuco dyes and electron or hydrogen atom abstraction to form radical intermediates.

Various factors such as temperature, humidity, gaseous reactants, including Cb, O3, SO2, and NCb, and water soluble, nonvolatile photodegradation products have been shown to influence fading of colorants. The factors that effect colorant fading appear to exhibit a certain amount of interdependence. It is due to this complex behavior that observations for the fading of a particular colorant on a particular substrate cannot be applied to colorants 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 colorant for a variety of colorant-substrate systems (e.g., McLaren, K., /. Soc. Dyers Colour, 1956, 72, 527). For example, as the relative humidity of the atmosphere increases, a fiber may swell because the moisture content of the fiber increases. This aids diffusion of gaseous reactants through the substrate structure.

The ability of a light source to cause photochemical change in a colorant is also dependent upon the spectral distribution of the light source, in particular the proportion of radiation of wavelengths most effective in causing a change in the colorant and the quantum yield of colorant degradation as a function of wavelength. On the basis of photochemical principles, it would be expected that light of higher energy (short wavelengths) would be more effective at causing fading than light of lower energy (long wavelengths). Studies have revealed that this is not always the case. Over 100 colorants of different classes were studied and found that generally the most unstable were faded more efficiently by visible light while those of higher lightfastness were degraded mainly by ultraviolet light (McLaren, K., J. Soc. Dyers Colour, 1956, 72, 86).

The influence of a substrate on colorant stability can be extremely important. Colorant fading may be retarded or promoted by one or more chemical groups within the substrate. Such a group can be a ground-state species or an excited-state species. The porosity of the substrate is also an important factor in colorant stability. A high porosity can promote fading of a colorant by facilitating penetration of moisture and gaseous reactants into the substrate. A substrate may also act as a protective agent by screening the colorant from light of wavelengths capable of causing degradation.

The purity of the substrate is also an important consideration whenever the photochemistry of dyed technical polymers is considered. For example, technical-grade cotton, viscose rayon, polyethylene, polypropylene, and polyisoprene are known to contain carbonyl group impurities. These impurities absorb light of wavelengths greater than 300 nm, which are present in sunlight, and so, excitation of these impurities may lead to reactive species capable of causing colorant fading (van Beek, H.C.A., Col Res. Appl, 1983, 8(3), 176).

Conventional print substrates result in acceptable print quality; however, certain print defects still exist resulting in less than desirable print quality. Printing defects, such as

"feathering" and "wicking", undesirably spread the colorant or colorant composition beyond the desired print pattern and/or pull the colorant or colorant composition into the print substrate. The result is a smeared print pattern, wherein a substantial portion of the colorant or colorant composition migrates below and beyond the intended area of the print substrate.

Therefore, there exists a need for methods and compositions which are capable of stabilizing a wide variety of colorants from the effects of both sunlight and artificial light.

There also exists a need for improved substrates which are capable of providing superior print quality, which minimizes print defects, such as "feathering" and "wicking" of a colorant composition. Further, there exists a need for such an improved substrate, which minimizes print defects while providing significant light stability from the effects of both sunlight and artificial light for a wide variety of colorants and colorant compositions.

Summary of the Invention

The present invention addresses the needs described above by providing compositions and methods for stabilizing colorants against radiation including radiation in the visible wavelength range. The present invention also provides an improved substrate for colorants and colorant compositions.

The improved substrates enable the production of superior print quality while providing enhanced lightfastness for colorants and colorant compositions against radiation including radiation in the visible wavelength range. The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with a colorant stabilizer. In one embodiment, the colorant stabilizer comprises one or more porphines that have an extremely short triplet state lifetime. (See e.g., Kubat, et al, Photophysical properties of metal complexes of meso- tetrakis (4-sulphonatophenyl) porphyrin, J. Photochem. and Photbio. A: Chemistry 96 (1996), pgs 93-97 which is incorporated herein by reference). Particularly suitable porphines include, but are not limited to, porphines having the following general structure:

wherein R is any proton-donating moiety and M is iron, cobalt or copper. Desirably, R is SO3H,

COOH, or RiCOOH wherein Ri is an alkyl group of from 1 to 6 carbons.

Examples of such porphines are Cu-meso-tetra-(4- sulfanatophenyl)-porphine (designated CuTPPS4) and Cu- meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures:

and

The copper ion can also be substituted with an iron or cobalt ion. Other metal ions can be substituted in the porphine molecule as long as the molecule has a relatively short-lived triplet state.

In a further embodiment of the present invention, the colorant stabilizer comprises at least one porphine in combination with at least one metal or metal salt. Unexpectedly, it has been discovered that the incorporation of a relatively small concentration of metal or metal salt into a po hine-containing composition results in superior colorant stability. Preferred metals or metal salts include, but are not limited to, lanthanides and lanthanide salts. Lanthanide elements include scandium, yttium, lanthanum, cerium praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

In order to improve the solubility of the metal or metal salt in solution, metal solubility-enhancing agents may be added. Particularly useful metal solubility-enhancing agents include, but are not limited to, chelating agents. Optionally, a surfactant can be added to the metal/porphine composition to increase the interaction of the metal or metal salt and the porphine. In addition to surfactants, other additives such as TINUVIN® compounds (Ciba-Geigy Corporation) may be incorporated into the colorant composition. The substrates to which the colorant stabilizers are applied include, but are not limited to, paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, metal, or any other substrate that would benefit from having a stabilized colorant thereon. In another embodiment, a colorant stabilizer is present in a polymer coating of a heat transfer product, such as is used for transferring graphic images onto clothing.

Accordingly, each of the embodiments of the present invention provide stabilizing molecules that, when one or more of the stabilizing molecules are associated with a colorant, stabilizes the colorant. Therefore, the stabilizing molecules can be used as an additive to any colorant composition. For example, as certain of the stabilizing molecules are poorly soluble in water, they can be directly added to solvent or oil based (not water based) colorant compositions. Additionally, the stabilizing molecules can be added to other colorant compositions that contain additives enabling the solubilization of the stabilizing molecule therein. Further, the stabilizing molecules can be solubilized in an aqueous solution by attaching the molecule to a large water soluble molecule, such as a cyclodextrin.

The colorant stabilizers are particularly effective in ink jet inks. Use of the colorant stabilizers, as described herein, intensifies the colors and stabilizes the colors when exposed to light. Additionally, the colorant stabilizers are particularly effective in paper such as paper designed for use with ink jet printers. Use of the colorant stabilizers in a substrate, as described herein, stabilizes a colorant to which it is applied. Also, colorant stabilizers in a substrate has been found to have the unexpected result of reducing the yellowing of the substrate itself upon exposure to light.

The colorant stabilizers are of particular interest in the formation of ink sets, wherein each ink of the ink set, regardless of color, possesses substantially identical light fastness properties as the other inks in the ink set. The ink set enables the production of multi-color text and/or graphics, which uniformly retain their color over extended periods of time and/or upon extended exposure to light. The present invention is also directed to improved substrates having thereon colorant compositions, such as the colorant compositions described above. High print quality, print vibrance, and colorant stability is achieved by combining the aforementioned improved substrates and colorant compositions.

These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.

Detailed Description of the Invention

The present invention is directed to compositions and methods for stabilizing colorants against radiation including radiation in the visible wavelength range. The present invention is further directed to ink sets comprising one or more inks, each of which possesses substantially similar light stability upon exposure to radiation, including radiation in the visible wavelength range. The present invention is further directed to improved substrates for colorants and colorant compositions. The improved substrates enable the production of superior print quality while providing enhanced lightfastness for colorants and colorant compositions against radiation, including radiation in the visible wavelength range. The compositions and methods relating to stabilizing a colorant by admixing a stabilizing molecule with a colorant solution will first be addressed below. Subsequently, the compositions and methods relating to stabilizing a colorant by applying the colorant to a treated substrate containing a stabilizing molecule will be discussed. As used herein, the term "composition" and such variations as "colored composition" are used herein to mean a colorant and one or more colorant stabilizers of the present invention. The composition can optionally include a molecular includant. As used herein, the term "colorant" is meant to include, without limitation, any material which typically will be an organic material, such as an organic colorant or dye. The term is meant to include a single material or a mixture of two or more materials. The term "light-stable" is used herein to mean that the colorant, when associated with one of the colorant stabilizing molecules of the present invention, is more stable to electromagnetic radiation, including, but not limited to, sunlight or artificial light, than when the colorant is not associated with such a 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 meant 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 colorant stabilizer are covalently coupled to each molecule of the molecular includant. The term "degree of substitution" is used herein to refer to the number of these molecules or leaving 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 having more than two leaving groups covalently coupled to each molecule of molecular includant. The term "leaving group" is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction. Examples of molecular includants include, but are not limited to, the cyclodextrins.

The term "artificial light" is used herein to mean 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.

The term "thereon" is used herein to mean thereon or therein. For example, the present invention includes a substrate having a colored composition thereon. According to the definition of "thereon" the colored composition may be present on the substrate or it may be in the substrate.

Admixing Stabilizing Molecules Into Colorant Solutions.

The present invention relates to colorant compositions having improved stability, wherein the colorant stabilizer is associated with a colorant solution. Desirably, the colorant stabilizer is admixed with a colorant solution. The colorant stabilizer is desirably one or more porphines alone or in combination with at least one metal or metal salt. The colorant stabilizers of the present invention are admixed with a colorant to stabilize the colorant when the admixture is exposed to electromagnetic radiation such as artificial light or sunlight. The present invention further relates to a method of stabilizing a colorant comprising associating one or more of the colorant stabilizers with the colorant solution. Optionally, the colorant stabilizer may be associated with a molecular includant, chelating agent, or other material to improve solubility and/or interaction of the colorant stabilizer and the colorant.

In another embodiment of the present invention, a colorant stabilizer is represented by porphines having an extremely short triplet state lifetime. (See e.g., Kubat, et al., Photophysical properties of metal complexes of meso-tetrakis (4-sulphonatophenyl) porphyrin, J. Photochem. and Photbio. A: Chemistry 96 (1996), pgs 93-97 which is incorporated herein by reference). Particularly suitable porphines include, but are not limited to, porphines having the following structure:

COOH, or RiCOOH wherein Ri is an alkyl group of from 1 to 6 carbons.

Desirably, the colorant stabilizer is represented by the porphines Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) and Cu-meso-tetra-(N-methyl-4- pyridyl)-porphine (designated CuTMPS4), having the following structure:

The copper ion can also be substituted with an iron or cobalt ion. It is also understood that in the case of FeTPPS4, CuTPPS4 or CoTPPS4, the sulfuric acid moieties may be substituted with salts when in solution, such as sodium salts. The colorant solution may be stabilized with about 0.1% to 10% wt/wt porphine, more preferably about 0.3% to 1 % wt/wt porphine, and more preferably about 0.5% wt/wt porphine. In another embodiment, the colorant stabilizer comprises one or more porphines in combination with one or more metals or metal salts, such as lanthanides and lanthanide salts. Desirably, the amount of metal or metal salt in the colorant solution is from about 0.01% to 10% wt/wt metal, more desirably about 0.03% to 1 % wt/wt metal, and most desirably about 0.05% wt/wt metal. Although lanthanides and lanthanide salts are desired metals, other metals, may also be used such as magnesium, iron, zinc, and other transition metals. To improve the solubility of the metal or metal salt in solution, metal solubility-enhancing agents may 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 EGTA (ethylene glycol-bis(β-aminoethyl ether)).

In a further embodiment, the colorant stabilizer comprises a porphine and a lanthanide, such as europium. Desirably, the amount of porphine in the colorant solution is from about 0.1 % to 10% wt/wt porphine, more desirably about 0.3% to 1% wt/wt porphine, and most desirably about

0.5% wt/wt porphine. Desirably, the amount of lanthanide in the colorant solution is from about 0.01 % to 10% wt/wt lanthanide, more desirably about 0.03% to 1 % wt/wt lanthanide, and most desirably about 0.05% wt wt lanthanide. Although europium and europium salts are desired lanthanides, other metals in the lanthanides series may also be used.

Although not wanting to be limited by the following, it is theorized that the above stabilizing compounds of the present invention, either admixed with a colorant solution or on or in a substrate to which the colorant is applied, act by quenching the excited state of a dye molecule by efficiently returning it to a ground state. This reduces the likelihood of an oxidative or other chemical reaction occurring which would render the dye chromophore colorless. The quenching process can occur by a number of processes. One such process is referred to as the heavy atom effect (internal or external) 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 to fore forbidden electronic transitions to occur and by decreasing the excited state lifetimes. This effect permits the rapid return of the dye to its ground state.

Another quenching process involves back electron transfer. In this case, quenching of the excited dye molecule occurs through sequential electron transfer. The additive or quencher, and dye form an ion pair through electron donation within which back electron transfer leads to an overall deactivation of the excited energy donor, i.e., the dye. Another quenching process involves a condition in which the quencher (additive) molecule has an excited energy state lower than the excited dye. In this case, it may be possible to transfer the excited energy to the quencher thereby allowing the dye molecule to return to its ground state. These mechanisms are more fully discussed in Chemistry and Light,

Suppan, P., Published by The Royal Society of Chemistry, 1994, pgs 65 - 69 which is incorporated herein by reference.

The dye or colorant, for example, may be an organic dye. Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base {4-

(dimethylamino)-α-[4-(dimethylamino)phenyl]-α-phenyl- benzene-methanol}, Malachite Green Carbinol hydrochloride {N-4-[[4-(dimethylamino)ρhenyl]phenyl-methylene]-2,5- cyclohexyldien-l-ylidene]-N-methyl-methanaminium chloride or bis[/7-(dimethylamino)phenyl]phenylmethylium chloride }, and Malachite Green oxalate ( N-4-[[4-(dimethylamino)- phenyl]-phenylmethylene]-2,5-cyclohexyldien-l-ylidene]-N- methyl-methanaminium chloride or bis[/?-(dimethylamino)- phenyljphenylmethylium oxalate} ; monoazo dyes, such as Cyanine Black, Chrysoidine [Basic Orange 2; 4-(ρhenylazo)- 1 ,3-benzenediamine monohydrochloride], Victoria Pure Blue BO, Victoria Pure Blue B, basic fuschin and β-Naphthol Orange; thiazine dyes, such as Methylene Green, zinc chloride double salt [3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc chloride double salt]; oxazine dyes, such as

Lumichrome (7,8-dimethylalloxazine); naphthalimide dyes, such as Lucifer Yellow CH { 6-amino-2-[(hydrazino- carbonyl)amino]-2,3-dihydro- l,3-dioxo- lH-benz[de]iso- quinoline-5,8-disulfonic acid dilithium salt } ; azine dyes, such as Janus Green B { 3-(diethylamino)-7-[[4-(dimethyl- amino)phenyl]azo]-5-phenylphenazinium chloride } ; cyanine dyes, such as Indocyanine Green {Cardio-Green or Fox Green; 2-[7-[ l,3-dihydro- l,l-dimethyl-3-(4-sulfobutyl)-2H- benz[e]indol-2-ylidene]- 1 ,3,5-heptatrienyl]- 1 , l-dimethyl-3-(4- sulfobutyl)- lH-benz[e]indolium hydroxide inner salt sodium salt} ; indigo dyes, such as Indigo {Indigo Blue or Vat Blue 1 ; 2-( 1 ,3-dihydro-3-oxo-2H-indol-2-ylidene)- 1 ,2-dihydro-3H- indol-3-one } ; coumarin dyes, such as 7-hydroxy-4-methyl- coumarin (4-methylumbelliferone); benzimidazole dyes, such as Hoechst 33258 [bisbenzimide or 2-(4-hydroxyphenyl)-5-(4- methyl- l-piperazinyl)-2,5-bi- lH-benzimidazole trihydro- chloride pentahydrate] ; paraquinoidal dyes, such as Hematoxylin { Natural Black 1 ; 7, 1 lb-dihydrobenz[b]- indeno[l,2-d]pyran-3,4,6a,9, 10(6H)-pentol } ; fluorescein dyes, such as Fluoresceinamine (5-aminofluorescein); diazonium salt dyes, such as Diazo Red RC (Azoic Diazo No. 10 or Fast Red RC salt; 2-methoxy-5-chlorobenzenediazonium chloride, zinc chloride double salt); azoic diazo dyes, such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5-diethoxy- benzene diazonium chloride, zinc chloride double salt); phenylenediamine dyes, such as Disperse Yellow 9 [N-(2,4- dinitrophenyl)-l,4-phenylenediamine or Solvent Orange 53]; diazo dyes, such as Disperse Orange 13 [Solvent Orange 52; 1- phenylazo-4-(4-hydroxyphenylazo)naphthalene] ; anthra- quinone dyes, such as Disperse Blue 3 [Celliton Fast Blue FFR; l-methylamino-4-(2-hydroxyethylamino)-9,10-anthraquinone], Disperse Blue 14 [Celliton Fast Blue B; l,4-bis(methylamino)- 9, 10-anthraquinone], and Alizarin Blue Black B (Mordant Black 13); trisazo dyes, such as Direct Blue 71 { Benzo Light Blue FFL or Sirius Light Blue BRR; 3-[(4-[(4-[(6-amino- l- hydroxy-3-sulfo-2-naphthalenyl)azo]-6-sulfo- l-naphthalenyl)- azo]- l -naphthalenyl)azo]- l ,5-naphthalenedisulfonic acid tetrasodium salt} ; xanthene dyes, such as 2,7-dichloro- fluorescein; proflavine dyes, such as 3,6-diaminoacridine hemisulfate (Proflavine); sulfonaphthalein dyes, such as Cresol

Red (o-cresolsulfonaphthalein); phthalocyanine dyes, such as Copper Phthalocyanine {Pigment Blue 15; (SP-4- l)-[29H,31H- phthalocyanato(2-)-N ,N ,N ,N^J ]coρper} ; carotenoid dyes, such as trans-β-carotene (Food Orange 5); carminic acid dyes, such as Carmine, the aluminum or calcium-aluminum lake of carminic acid (7-a-D-glucopyranosyl-9, 10-dihydro- 3,5,6,8-tetrahydroxy-l-methyl-9, 10-dioxo-2-anthracene- carbonylic acid); azure dyes, such as Azure A [3-amino-7- (dimethylamino)phenothiazin-5-ium chloride or 7-(dimethyl- amino)-3-imino-3H-phenothiazine hydrochloride]; and acridine dyes, such as Acridine Orange [Basic Orange 14; 3,8- bis(dimethylamino)acridine hydrochloride, zinc chloride double salt] and Acriflavine (Acriflavine neutral; 3,6-diamino- 10-methylacridinium chloride mixture with 3,6-acridine- diamine).

In some embodiments of the present invention, the colorant and/or colorant stabilizer is associated with a molecular includant. The term "associated" in its broadest sense means that the colorant and/or colorant stabilizer is at least in close proximity to the molecular includant. For example, the colorant and/or colorant stabilizer may be maintained in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, or the like. Alternatively, the colorant and/or colorant stabilizer may be covalently bonded to the molecular includant, although this normally is neither desired nor necessary. As a further example, the colorant and/or colorant stabilizer may be at least partially included within the cavity of the molecular includant. The molecular includant can be added to the colorant solution or incorporated into a substrate, such as paper, which is subsequently coated with the colorant solution. The molecular includant can be inorganic or organic in nature. In certain embodiments, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. Examples of molecular includants are, by way of illustration only, clathrates or intercalates, zeolites, and cyclodextrins. Examples of cyclodextrins include, but are not limited to, α- cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β cyclodextrin and sulfated γ-cyclodextrin (Cerestar U.S.A., Incorporated, Hammond, Indiana).

The term "derivatized cyclodextrin" as used herein means a cyclodextrin having more than two leaving groups covalently coupled to each molecule of cyclodextrin. The term "leaving group" is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction. Examples of derivatized cyclodextrin includes, but is not limited to, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β and γ-cyclodextrin. A desired derivatized cyclodextrin is ethylhydroxy β-cyclodextrin. A desired molecular includant is γ-cyclodextrin. Another desirable molecular includant is β-cyclodextrin. In other embodiments, the molecular includant is an ethyl hydroxy β-cyclodextrin. Although not wanting to be bound by the following theory, it is believed that the molecular includant inhibits the aggregation of the colorant molecule in solution. Other aggregation inhibitors that can be used in practicing the present invention are starches, pectins, amyloses, clathrates and the crown ethers. It is to be understood that the addition of derivatized cyclodextrins to an ink formulation for the purpose of inhibiting aggregation and/or stabilizing the dyes in the inks is considered one aspect of the present invention.

As a practical matter, the colorant, the colorant stabilizer and molecular includant are likely to be solids depending upon the constituents used to prepare the molecules.

However, any or all of such materials can be a liquid. The colored composition can be a liquid either because one or more of its components is a liquid, or, when the molecular includant is organic in nature, a solvent is employed. Suitable solvents include, but are not limited to, amides, such as N,N- dimethylformamide; sulfoxides, such as dimethylsulfoxide; ketones, such as acetone, methyl ethyl ketone, and methyl butyl ketone; aliphatic and aromatic hydrocarbons, such as hexane, octane, benzene, toluene, and the xylenes; esters, such as ethyl acetate; water; and the like. When the molecular includant is a cyclodextrin, particularly suitable solvents are the amides and sulfoxides.

In an embodiment where the composition of the present invention is a solid, the effectiveness of the above compounds on the colorant is improved when the colorant and the selected compounds are in intimate contact or in an association that approaches van der Waals radii. To this end, the thorough blending of the components, along with other components which may be present, is desirable. Such blending generally is accomplished by any of the means known to those having ordinary skill in the art. When the colored composition includes a polymer, blending is facilitated if the colorant and the colorant stabilizer are at least partly soluble in softened or molten polymer. In such case, the composition is readily prepared in, for example, a two-roll mill. Alternatively, the composition of the present invention can be a liquid because one or more of its components is a liquid.

For some applications, the composition of the present invention typically will be utilized in particulate form. In other applications, the particles of the composition should be very small. Methods of forming such particles are well known to those having ordinary skill in the art.

The colored composition optionally may also contain a carrier, the nature of which is well known to those having 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 more common. Examples of thermoplastic polymers include, but are not limited to: end- capped polyacetals, such as poly(oxymethylene) or polyformaldehyde, poly(trichloroacetaldehyde), poly(n- valeraldehyde), poly(acetaldehyde), poly(propionaldehyde), and the like; acrylic polymers, such as polyacrylamide, poly(acrylic acid), poly(methacrylic acid), poly(ethyl acrylate), poly(methyl methacrylate), and the like ; fluorocarbon polymers, such as poly(tetrafluoroethylene), perfluorinated ethylenepropylene copolymers, ethylene- tetrafluoroethylene copolymers, poly-(chlorotrifluoro- ethylene), ethylene-chlorotrifluoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the like; epoxy resins, such as the condensation products of epichlorohydrin and bisphenol A; polyamides, such as poly(6- aminocaproic acid) or poly(ε-caprolactam), poly(hexa- methylene adipamide), poly(hexamethylene sebacamide), poly(l l-aminoundecanoic acid), and the like; polyaramides, such as poly(imino- l ,3-phenyleneiminoisophthaloyl) or poly( - phenylene isophthalamide), and the like; parylenes, such as poly- -xylylene, poly(chloro-/?-xylene), and the like; polyaryl ethers, such as poly(oxy-2,6-dimethyl-l ,4-phenylene) or poly( -phenylene oxide), and the like; polyaryl sulfones, such as poly(oxy- 1 ,4-phenylenesulfonyl- 1 ,4-phenyleneoxy- 1 ,4- phenylene-isopropylidene- 1 ,4-phenylene), poly(sulfonyl- 1 ,4- phenyleneoxy- l,4-phenylenesulfonyl-4,4-biphenylene), and the like; polycarbonates, such as poly(bisphenol A) or poly (carbony ldioxy- 1 ,4-pheny leneisopropylidene- 1 ,4- phenylene), and the like; polyesters, such as poly(ethylene terephthalate), poly(tetramethylene terephthalate), poly(cyclo- hexylene- l ,4-dimethylene terephthalate) or poly(oxy- methylene- 1 ,4-cyclohexylenemethyleneoxyterephthaloyl), and the like; polyaryl sulfides, such as poly(/ phenylene sulfide) or poly(thio- l,4-phenylene), and the like; polyimides, such as poly(pyromellitimido- l ,4-phenylene), and the like ; polyolefins, such as polyethylene, polypropylene, poly( l - butene), poly(2-butene), poly( l-pentene), poly(2-pentene), poly(3-methyl-l-pentene), poly(4-methyl- l-pentene), 1,2-poly- 1 ,3-butadiene, l ,4-poly- l ,3-butadiene, polyisoprene, polychloroprene, polyacrylonitrile, poly(vinyl acetate), poly(vinylidene chloride), polystyrene, and the like; and copolymers of the foregoing, such as acrylonitrile-buta- dienestyrene (ABS) copolymers, styrene-n-butylmethacrylate copolymers, ethylene-vinyl acetate copolymers, and the like.

Some of the more commonly used thermoplastic polymers include styrene-n-butyl methacrylate copolymers, polystyrene, styrene-n-butyl acrylate copolymers, styrene- butadiene copolymers, polycarbonates, poly(methyl methacrylate), poly(vinylidene fluoride), polyamides (nylon-

12), polyethylene, polypropylene, ethylene-vinyl acetate copolymers, and epoxy resins.

Examples of thermosetting polymers include, but are not limited to, alkyd resins, such as phthalic anhydride-glycerol resins, maleic acid-glycerol resins, adipic acid-glycerol resins, and phthalic anhydride-pentaerythritol resins; allylic resins, in which such monomers as diallyl phthalate, diallyl isophthalate diallyl maleate, and diallyl chlorendate serve as nonvolatile cross-linking agents in polyester compounds; amino resins, such as aniline-formaldehyde resins, ethylene urea- formaldehyde resins, dicyandiamide-formaldehyde resins, melamine-formaldehyde resins, sulfonamide-formaldehyde resins, and urea-formaldehyde resins; epoxy resins, such as cross-linked epichlorohydrin-bisphenol A resins; phenolic resins, such as phenol-formaldehyde resins, including Novolacs and resols; and thermosetting polyesters, silicones, and urethanes.

In addition to the colorant, colorant stabilizer, and optional molecular includant, the colored composition of the present invention also can contain additional components, depending upon the application for which it is intended. Examples of such additional components include, but are not limited to, charge carriers; stabilizers against thermal oxidation; viscoelastic properties modifiers; cross-linking agents; plasticizers; charge control additives such as a quaternary ammonium salt; flow control additives such as hydrophobic silica, zinc stearate, calcium stearate, lithium stearate, polyvinylstearate, and polyethylene powders; fillers such as calcium carbonate, clay and talc; surfactants; buffer/pH adjusters; chelating agents; wetting agents; corrosion inhibitors; biocides; and TINUVIN® compounds; among other additives used by those having ordinary skill in the art. Charge carriers are well known to those having ordinary skill in the art and typically are polymer-coated metal particles. Desirable surfactants include, but are not limited to, Cj2 to

C i 8 surfactants such as cetyl trimethyl ammonium chloride, carboxymethylamylose, and acetylene glycols such as SURFYNOL® 104E. Desirable buffer/pH adjusters include, but are not limited to, borax, hydrochloric acid and sodium hydroxide. Desirable chelating agents include, but are not limited to, EDTA and EDTA complexes or salts. Desirable wetting agents include, but are not limited to, ethylene glycol and glycerine. Desirable corrosion inhibitors include, but are not limited to, a benzotriazole sold under the tradename COBRATEC® 99. Desirable biocides include, but are not limited to, 2,6-dimethyl-m-dioxan-4-ol acetate sold under the tradename GIV-GARD DXN®. TINUVIN® compounds are a class of compounds produced by Ciba-Geigy Corporation, which includes benzophenones, benzotriazoles and hindered amines. Desirable TINUVIN® compounds include, but are not limited to, 2-(2'-hydroxy-3'-.9έ'c-butyl-5'-tert-butylphenyl)- benzo-triazole, poly-(N-β-hydroxyethyl-2,2,6,6-tetramethyl- 4-hydroxy-piperidyl succinate and 2-(2'-hydroxy-3',5'-diteτt butylphenyl)-5-chloro-benzotriazole. The identities and amounts of such additional components in the colored composition are well known to one of ordinary skill in the art.

When the colorant stabilizers of the present invention are used to stabilize the dyes in ink jet inks, it is desirable to filter the compositions through a small pore filter (0.45 μ) such as a Millipore® filter before the ink formulation is placed in an ink jet cartridge. This will reduce or eliminate clogging of the cartridge ink nozzles due to particulate matter.

The colorant stabilizers of the present invention enable the formation of ink sets comprising one or more inks, wherein each ink of the ink set, regardless of color, possesses similar light fastness properties as the other inks in the ink set. Such ink sets may be used to produce multi-color text and/or graphics, which uniformly retain their color over extended periods of time and/or upon extended exposure to light. One desirable ink set includes cyan, magenta, yellow and black inks, wherein the magenta ink contains colorant stabilizers in the form of a porphine and a metal, such as europium, and the yellow ink contains a colorant stabilizer in the form of a porphine without the metal. Another desirable ink set includes cyan, magenta, yellow and black inks, wherein the cyan ink contains a colorant stabilizer in the form of a benzophenone, and the magenta and yellow inks contain colorant stabilizers in the form of a porphine and a metal, such as europium.

It is to be understood that in any desired ink set, a single ink may be stabilized according to the present invention or several of the inks may be stabilized utilizing one or more of the stabilizing agents described herein. Other ink sets are within the scope of the present invention. Included in the present invention are ink sets wherein the black color is a pigment and the other colors in the ink set are dyes. Although ink sets wherein the inks possess substantially identical light fastness properties are desirable, in some embodiments, it may be desirable to produce ink sets wherein the inks within the ink set have specifically controlled, varying light fastness properties.

The substrates to which the colorant and colorant stabilizers are applied include, but are not limited to, paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, metal, or any other substrate that would benefit from having a stabilized colorant thereon. A plastic substrate includes, but is not limited to, a plastic film, a plastic nonwoven web, or a plastic woven web. A preferred substrate is paper. Any existing or future type of paper or paper products may be used in the present invention. Examples of paper or paper products include, but not limited to, printing and writing papers, packaging and industrial papers, paperboard, and tissue papers. Examples of printing and writing papers include, but are not limited to the following: wood-free coated papers; wood-containing coated papers; wood-free uncoated papers such as bond and writing paper, envelopes, offset and opaque circular, carbonless, tablet, forms bond, ledger, mimeograph, and manifold, duplication, fax base, thermal base, technical papers, supercalandered, and specialty papers; uncoated wood- containing papers such as supercalandered, directory, specialty converting and publishing; bristols such as coated bristols, uncoated bleached bristols, tag, coated tag papers, file folders, and tabulating; and thin papers such as cigarette paper, bible paper, lightweight paper, lightweight specialty, manifold, cotton fiber papers, and specialty thin papers.

Examples of packaging and industrial papers include, but are not limited to the following: breached Kraft paper such as grocers bags, shipping sacks, wrapping paper, and converting paper; unbleached Kraft paper such as grocers bags, shipping sacks converting paper, wrapping paper, and envelopes. Examples of paperboard include, but are not limited to the following: containerboard such as unbleached linerboard, bleached linerboard, corrugated medium, and chip and filler board; folding boxboard/folding cartonboard such as solid bleached sulfite, bleached and unbleached bristols, coated recycled board, coated unbleached Kraft, milk, cup, plate and foodservice stock (coated or uncoated), and folding board; gypsum wallboard; and tube/can and drum paperboard. Examples of tissue papers include, but are not limited to, sanitary tissues such as bathroom tissue, facial tissue, napkins, toweling, wiper stock, and other sanitary tissue papers.

Improved substrates of the present invention are particularly suitable for colorants and colorant compositions. The improved substrates enable the production of superior print quality while providing enhanced lightfastness for colorants and colorant compositions against radiation including radiation in the visible wavelength range. The improved substrates are suitable for use with any colorant or colorant composition, and especially colorant or colorant compositions containing one or more light stabilizers as described above.

The improved substrate of the present invention comprises a base layer coated with a binder composition containing one or more polymeric binders in combination with one or more cyclodextrins. The base layer, to which the binder composition is applied, includes, but is not limited to, paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, metal, or any other substrate capable of maintaining the binder composition thereon. Examples of suitable substrates are disclosed above. The base layer may comprise one or more of the above- mentioned layers. Desirably, the base layer is a coated or uncoated fiber-containing substrate such as Photoglossy Base, Presentation Matte Photobase, and High Quality Matte papers and Wetstrength Media; a film such as White Opaque Films (e.g. KIMDURA®, K-C), Clears Films (e.g. MELINEX®,

ICI) Backlit Films, and Vinyl; or a nonwoven such as TYVEK® . More desirably, the base layer is a coated or uncoated paper. Most desirably, the base layer is a coated paper comprising a cellulose sheet coated with a polymeric film, such as polyethylene.

The binder composition contains one or more polymeric binders. Suitable binder materials include, but are not limited to, naturally-occurring polymers, synthetically-modified naturally-occurring polymers or synthetic polymers as exemplified in Water-Soluble Polymers, C. L. McCormick, J.

Bock, and D. N. Schulz, in Vol. 17, Encyclopedia of Polvmer Science and Engineering. John Wiley and Sons, Publishers (1989), pgs. 730-84. Desirably, the binder composition contains one or more of the following polymers: polyvinylpyrrolidone (PVP), polyvinylalcohol (PVOH), polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate, polyacrylamide, polymethacrylamide, polyethylene glycol, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, polyacrylic acid and polyacrylic acid salts, polymethacrylic acid and polymethacrylic acid salts, polyvinylsulfonate and polyvinylsulfonate salts , poly-2- acrylamido- 2 - methylpropanesulfonic acid and poly-2-acrylamido-2- methylpropanesulfonic acid salts, polyacryloxy- trimethylammonium chloride, polymethacryloxytrimethyl- ammonium chloride, and polydiallyldimethylammonium chloride. Desirably, the binder composition contains sodium carboxymethyl cellulose, polyvinylpyrrolidone (PVP), polyvinylalcohol (PVOH) or a combination thereof. The binder composition also contains one or more cyclodextrins. Suitable cyclodextrins include, but are not limited to, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ- cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β- cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β cyclodextrin and sulfated γ-cyclodextrin (Cerestar USA Incorporated, Hammond, Indiana). Desirably, the binder composition contains β-cyclodextrin (β-CD), hydroxypropyl β-cyclodextrin (hp-β-CD), or a combination thereof.

In one embodiment of the present invention, the binder composition contains from about 90 to about 10 weight percent polymeric binder and from about 10 to about 90 weight percent cyclodextrin. More desirably, the binder composition contains from about 75 to about 25 weight percent polymeric binder and from about 25 to about 75 weight percent cyclodextrin. Most desirably, the binder composition contains from about 65 to about 25 weight percent polymeric binder and from about 35 to about 75 weight percent cyclodextrin.

In addition to the polymeric binder and the cyclodextrin, the binder composition of the present invention may also contain additional components. Examples of such additional components include, but are not limited to, charge carriers; stabilizers against thermal oxidation; viscoelastic properties modifiers; cross-linking agents; plasticizers; charge control additives such as a quaternary ammonium salt; flow control additives such as hydrophobic silica, zinc stearate, calcium stearate, lithium stearate, polyvinylstearate, and polyethylene powders; fillers such as calcium carbonate, clay and talc; surfactants; detacktifiers; chelating agents; and TINUVIN® compounds; among other additives used by those having ordinary skill in the art. Charge carriers are well known to those having ordinary skill in the art and typically are polymer-coated metal particles. Desirable surfactants include, but are not limited to, C l 2 to C l 8 surfactants such as cetyl trimethyl ammonium chloride and carboxymethylamylose, and other surfactants such as Triton X- 100 and SURFYNOL® 420. TINUVIN® compounds are a class of compounds produced by Ciba-Geigy Corporation, which includes benzophenones, benzotriazoles and hindered amines. Desirable TINUVIN® compounds include, but are not limited to, 2-(2'-hydroxy-3'- s.?c-butyl-5'-t -butylphenyl)-benzo-triazole, poly-(N-β- hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate and 2-(2'-hydroxy-3',5'-dit<?r butylphenyl)-5- chloro-benzotriazole. The identities and amounts of such additional components in the colored composition are well known to one of ordinary skill in the art. Typically, one or more of the above additives are present in the binder composition in an amount of from about 1 to 14 weight percent based on the total weight of the binder composition.

In one embodiment of the present invention, the binder composition contains filler material in the form of particles. The incorporation of selected particulate material in the binder composition results in a rougher outer coating surface, which improves processibility (i.e., printer rolls grab the substrate more readily), and prevents "set-off" (i.e., prevents extensive contact between the printed image and an adjacent sheet or substrate). Particles having a particle size than less or equal to the coating thickness have been found to provide desirable print quality. Any particle may be used in the binder composition provided that the particle does not dull the gloss of the improved substrate. Suitable particles include, but are not limited to, starch particles, polyamide particles, polyethylene particles and aluminum trihydrate particles. Desirably, the particles comprise polyamide particles having a particle size of about 12 to about 50 microns.

The binder composition is coated onto the base layer by any conventional coating method including, but not limited to, rod coating, dip coating, spray coating, gravure coating, knife coating, slot coating, and roller coating. Desirably, the binder composition is applied to the base layer by a process wherein the binder composition is transferred from a bath onto a roller which extends into the bath, and onto at least one surface of the base layer. Optionally, the same or a different coating may be provided on the same or an opposite side of the base layer. The coated base layer then passes under or over a rod, which meters excess coating from the base layer. Once coated, the base layer is dried in a conventional oven or by any other means.

The amount of binder composition coated onto a surface of the base layer may vary depending upon the type of base layer used and the application of the final product. For example, a base layer in the form of an uncoated paper may require more binder composition coating than a base layer in the form of a coated paper or film due to the increased porosity of the base layer. Desirably, the binder composition is applied to a base layer to produce a coating weight of from about 3.0 to about 60.0 g/m² of base layer surface area. More desirably, the coating weight is from about 9.0 to about 23.0 g/m² of base layer surface area. More desirably, the coating weight is from about 15.0 to about 20.0 g/m² of base layer surface area.

Although not wanting to be limited by the following, it is theorized that the improved substrates of the present invention and the above stabilizing compounds act by quenching the excited state of a dye molecule by efficiently returning it to a ground state. This reduces the likelihood of an oxidative or other chemical reaction occurring which would render the dye chromophore colorless. The improved substrates of the present invention, alone or in combination with the above stabilizing compounds, provide stability to any dye or colorant, including those mentioned above.

The improved substrate of the present invention may also be suitable for use with colored compositions within a carrier. For many applications, the carrier will be a polymer, typically a thermosetting or thermoplastic polymer, with the latter being the more common. Examples of suitable thermosetting and thermoplastic polymers are disclosed above. The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or scope of the present invention. In the examples, all parts are parts by weight unless stated otherwise.

EXAMPLE 1 Preparation and Testing of Inks Containing Porphine Colorant Stabilizers

This example reports the results of fade testing of various inks, either with or without the stabilizing additives of the present invention, on treated or untreated paper. More particularly, the paper is untreated Hewlett-Packard premium paper, or treated Hewlett-Packard premium paper prepared using a solution of about 50% wt/wt hydroxypropyl γ- cyclodextrin to ink, in or on the paper in a concentration of about 5 to 15 % wt/wt solution to paper.

The stabilizing additives of this example are porphines. Specifically, the porphines Cu-meso-tetra-(4-sulfanatophenyl)- porphine (designated CuTPPS4) and Cu-meso-tetra-(N-methyl- 4-pyridyl)-porphine (designated CuTMPS4) (available from

Porphyrin Products, Inc., Logan, UT) were used, which are represented by the following structures, respectively:

and

The invention provides that the metal ions Cu, Co or Fe may be used interchangeably in the porphine structures of the present invention. Additional background on the chemistry of porphines can be found in Kubat et al. "Photophysical properties of metal complexes of meso-tetrakis (4- sulphonatophenyl) Porphyrin," Journal of Photochemistry and Photobiology A:Chemistry 96 (1996) 93-97, and references cited therein, hereby incorporated by reference.

Printed sheets of paper were placed in the Atlas weatherometer and exposed for the designated number of hours under the following conditions: 0.54 W/m² at 440 nm,

55% humidity, 45°C black panel temperature, borosilicate filters.

The change in magenta color is measured by the Xrite

Colorimeter (Model 938, SpectroDensitometer, Grandville, Michigan) which measures the ΔE* values, based on the L, a*, b* as described by Cielab, D-50-2. The results are reported in the tables below.

The treated and untreated paper is printed with inks designated Al, A2, A3, A4, B l, B2, B3, B4, Cl , C2, C3, and C4, prepared as follows:

Al Ink DI Water 84.80%

2 Pyrrolidone 10.00

GIV-GARD DXN® 00.20

COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 4.00

Acid Red 52 0.40

A2 Ink DI Water 85.40%

2 Pyrrolidone 10.00

GIV-GARD DXN® 00.20

COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 3.00

Acid Red 52 0.80 A3 Ink DI Water 86.00%

2 Pyrrolidone 10.00 GIV-GARD DXN® 00.20 COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 2.00

Acid Red 52 1.20

A4 Ink DI Water 86.60%

2 Pyrrolidone 10.00 GIV-GARD DXN® 00.20 COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 1.00

Acid Red 52 1.60

B l Ink DI Water 83.02%

2 Pyrrolidone 10.00 GIV-GARD DXN® 00.20 COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 5.78

Acid Red 52 0.40

B2 Ink DI Water 84.07%

2 Pyrrolidone 10.00 GIV-GARD DXN® 00.20 COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 4.33

Acid Red 52 0.80 B3 Ink DI Water 85.1 1 %

2 Pyrrolidone 10.00 GIV-GARD DXN® 00.20 COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 2.89

Acid Red 52 1.20

B4 Ink DI Water 86.16%

2 Pyrrolidone 10.00 GIV-GARD DXN® 00.20 COBRATEC®.99 00.10

Triethanolamine 00.50

Reactive Red 120 1.44

Acid Red 52 1.60

Cl Ink DI Water 82.62%

2 Pyrrolidone 10.00 GIV-GARD DXN® 00.20 COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 6.18

Acid Red 52 0.40

C2 Ink DI Water 82.62%

2 Pyrrolidone 10.00 GIV-GARD DXN® 00.20 COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 4.63

Acid Red 52 0.80 C3 Ink DI Water 84.91 %

2 Pyrrolidone 10.00 GIV-GARD DXN® 00.20 COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 3.09

Acid Red 52 1.20

C4 Ink DI Water 86.06%

2 Pyrrolidone 10.00 GIV-GARD DXN® 00.20 COBRATEC® 99 00.10

Triethanolamine 00.50

Reactive Red 120 1.54

Acid Red 52 1.60

The above inks were fade tested with the following results.

Inks Without Additives

The inks were prepared with about 0.5% CuTPPS₄ stabilizing additive and fade tested on HP paper and HP γ-CD paper with the following results.

Additionally, HP- 1600 magenta ink was prepared with about 0.5% CuTPPS₄ stabilizing additive and fade tested on HP paper and HP γ-CD paper with the following results.

15 Hour Multi le Sam les

The HP- 1600 magenta ink was also prepared with about 0.5% CuTMPS₄ stabilizing additive and fade tested on HP paper and HP γ-CD paper with the following results.

EXAMPLE 2 Preparation and Testing of Inks Containing Porphine and Lanthanide Colorant Stabilizers

This example reports the results of fade testing of various inks, either with or without the stabilizing additives of the present invention, on untreated paper. More particularly, the paper is untreated QIS Photo Glossy paper.

The stabilizing additives of this example are porphines and europium salts. Specifically, the porphine Cu-meso-tetra- (4-sulfanatophenyl)-porphine (designated CuTPPS4) (available from Porphyrin Products, Inc., Logan, UT) is used, as in Example 1 above. The europium salt, europium nitrate (designated EuN) (Strem Chemical Co., Newburyport, MA) is used.

A forty-eight hour accelerated fade test of various magenta ink composition was performed. A magenta control without stabilizing additives was applied to the QIS paper medium. After subjecting the ink composition and paper medium to the forty-eight hour test, ΔE* and ΔH* values were measured. Similar measurements were taken using the following ink formulations: a) magenta + 0.5 wt% CuTPPS4 b) magenta + 0.05 wt% EuN c) magenta + 0.5 wt% CuTPPS4 + 0.05 wt% EuN. The resulting measurements are given below.

EXAMPLE 3

A coating composition was formulated by adding 7.0 parts polyvinylpyrrolidone (PVP K-90, International Specialty Products) to 63.4 part deionized water. The composition was heated and agitated to dissolve the PVP. To this solution was added: 1.4 parts Triton X- 100 (Rohm and Haas), 0.1 parts

SURFYNOL® 420 (Air Products), and 3.5 parts glycerol

(Fisher Scientific). Beta-cyclodextrin, β-CD, and hydroxypropyl-beta-cyclodextrin, hp-β-CD, (Cerestar) were added to the composition as 1.8 parts and 22.9 parts, respectively. The composition was agitated and heated, as necessary, to obtain a clear solution. The solution was allowed to cool to room temperature before being applied to a substrate.

EXAMPLE 4 A coating composition was formulated by placing 2.8 parts of a poly(sodium acrylate) solution (Polysciences, 140,000 M.W. 25% in water) in a container and diluting with

61.2 parts deionized water. To this solution, 6.3 parts polyvinylpyrrolidone (PVP K-90, International Specialty Products) was added. The composition was heated and agitated to dissolve the PVP. To this solution was added: 1.4 parts Triton X-100 (Rohm and Haas), 0.1 parts SURFYNOL® 420

(Air Products), and 3.5 parts glycerol (Fisher Scientific). Beta-Cyclodextrin, β-CD, and hydroxypropyl-beta- cyclodextrin, hp- β-CD, (Cerestar) were added to the composition as 1.8 parts and 22.9 parts, respectively. The composition was agitated and heated, as necessary, to obtain a clear solution. The solution was allowed to cool to room temperature before being applied to a substrate. EXAMPLE 5 A coating composition was formulated by placing 3.5 parts of a poly(sodium acrylate) solution (Polysciences, 225,000 M.W. 20% in water) in a container and diluting with 60.5 parts deionized water. To this solution 6.3 parts polyvinylpyrrolidone (PVP K-90, International Specialty Products) was added. The composition was heated and agitated to dissolve the PVP. 1.4 parts Triton X- 100 (Rohm and Haas), 0.1 parts SURFYNOL® 420 (Air Products), and 3.5 parts glycerol (Fisher Scientific) were added to the composition.

Beta-Cyclodextrin, β-CD, and hydroxypropyl-beta- cyclodextrin, hp-β-CD, (Cerestar) were added to the composition as 1.8 parts and 22.9 parts, respectively. The composition was agitated and heated, as necessary, to obtain a clear solution. The solution was allowed to cool to room temperature before being applied to a substrate.

EXAMPLE 6 A coating composition was formulated as in Example 4, except that 2.0 parts Dow Corning Super Wetter (Dow

Corning, Q2-5211) was substituted for Triton X-100 (Rohm and Haas).

EXAMPLE 7 A coating composition was formulated by dissolving 3.3 parts poly(vinylalcohol) (Airvol 523, Air Products) in 62.0 parts hot deionized water. 3.7 parts of a poly (sodium acrylate) solution (Polysciences, 225,000 M.W. 20% in water) was added, followed by 6.3 parts polyvinylpyrrolidone (PVP K-90, International Specialty Products). The composition was heated and agitated to dissolve the PVP. 1.4 parts Triton X- 100 (Rohm and Haas) and 0.1 parts SURFYNOL® 420 (Air Products) were added to the composition. Beta-cyclodextrin, β-CD, and hydroxypropyl-beta-cyclodextrin, hp-β-CD, (Cerestar) were added to the composition as 1.8 parts and 22.9 parts, respectively. The composition was agitated and heated, as necessary, to obtain a clear solution. The solution was allowed to cool to room temperature before being applied to a substrate.

EXAMPLE 8 A coating composition was formulated as in Example 7, substituting polyvinylpyrrolidone (PVP K- 120, International Specialty Products) for polyvinylpyrrolidone (PVP K-90).

EXAMPLE 9 A coating composition was formulated as in Example 7, substituting poly(sodium acrylate) solution (PARAGUM® 231 , Para-Chem Southern Inc.) for poly(sodium acrylate) solution (Polysciences, 225,000 M.W. 20% in water).

EXAMPLE 10 A coating composition was formulated by mixing 500 g of a 10% solution of poly(vinylalcohol) (Airvol 523, Air Products) and 250 g of a 20% solution of polyvinylpyrrolidone (PVP K-90, International Specialty Products). 3.0 g of a 33% solution of Triton X- 100 (Rohm and Haas) and 1.0 g of ORGASOL® polyamide particles ( 18 microns) were added to the composition. 150 g of a 50% solution of Hydroxypropyl-beta-cyclodextrin, hp-β-CD,

(Cerestar) was added to the composition. The composition was agitated and heated, as necessary, to obtain a clear solution. The solution was allowed to cool to room temperature before being applied to a substrate.

EXAMPLE 11

A coating composition was formulated by mixing 250 g of a 10% solution of poly(vinylalcohol) (Airvol 523, Air

Products); 6.1 g of a 33% solution of Triton X-100 (Rohm and Haas); and 0.5 g of SURFYNOL® 420 (Air Products). 1500 g of a 5% solution of Sodium carboxymethyl cellulose (Catalog No. 41927-3, Aldrich Chemicals, Inc.) and 150 g of a 50% solution of Hydroxypropyl-beta-cyclodextrin, hp-β-CD, (Cerestar) was added to the composition. The composition was agitated and heated, as necessary, to obtain a clear solution.

The solution was allowed to cool to room temperature before being applied to a substrate.

EXAMPLE 12 A coating composition was formulated by mixing 1500 g of a 10% solution of poly(vinylalcohol) (Airvol 523, Air Products); 4 g of Triton X-100 (Rohm and Haas); and 1.0 g of SURFYNOL® 420 (Air Products). 1000 g of a 5% solution of Sodium carboxymethyl cellulose (Catalog No. 41927-3, Aldrich Chemicals, Inc.) and 300 g of a 50% solution of

Hydroxypropyl-beta-cyclodextrin, hp-β-CD, (Cerestar) was added to the composition. The composition was agitated and heated, as necessary, to obtain a clear solution. The solution was allowed to cool to room temperature before being applied to a substrate.

EXAMPLE 13 Preparation of Inks Containing Porphine Colorant Stabilizers This example reports the preparation of various inks, with one of the stabilizing additives of the present invention.

More particularly, the stabilizing additive of this example is the porphine, Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) (available from Porphyrin Products, Inc., Logan, UT), which is represented by the following structure:

In this example, an ink set comprising cyan, magenta, yellow and black inks was prepared using one or more of the following components: deionized water; borax, hydrochloric acid and/or sodium hydroxide as buffer/pH adjusters; EDTA or sodium salts thereof as a chelating agent; ethylene glycol and/or glycerine as wetting agents; GIV-GARD DXN® as a biocide; COBRATEC® 99 as a corrosion inhibitor; and Projet Cyan I, DB 168 Liquid, Reactive Red 187, Acid Red 52 and/or Acid Yellow 17 as dyes. In addition to the CuTPPS4 porphine, a lanthanide salt, europium nitride (EUNO3) was also used as a colorant stabilizer. The ink compositions prepared are given below, each component being given in weight percent.

EXAMPLE 14 Effect of Cyclodextrin on Coatings Made With Various

Binders In order to determine the effect of cyclodextrin (CD) content on the fading characteristics of images printed with the inks of Example 13 on photoglossy coatings made with different polymer binders, the following experiment was conducted.

Stock aqueous solutions of four binders: ( 1) CMC (sodium salt of carboxymethyl cellulose, catalog no. 42,927 from Aldrich Chemical Company) at 5 wt%; (2) PVOH (polyvinyl alcohol, Airvol 523 from Air Products and Chemicals, Inc.) at 10 wt%; (3) PAA (sodium polyacrylate = sodium salt of polyacrylic acid, PARAGUM® 13 1 from Polysciences, Inc.) at 5 wt%; and (4) PVP (polyvinyl pyrolidone, PVP-K90 from ISP Technologies) at 10 wt% were prepared. To each stock solution was added 3 wt% Triton X- 100 (from Union Carbide Chemicals). In addition a stock aqueous solution of hydroxypropyl-beta-cyclodextrin, hp-β- CD, (Cerestar) at 50 wt% and 3 wt% Triton X- 100 was prepared. The cyclodextrin and binder solutions were combined in the appropriate ratios to yield solutions containing a solid fraction of cyclodextrin, f_cd = _cd/( _cd+ polymer), where Mcd and Mpolymer are respectively the weights of cyclodextrin and polymer solids in the combined solution. The solutions were rod-coated onto 7 mil Jen-coat ink- jet photoglossy base sheets and oven dried. The rods used were chosen so as to obtain a relatively fixed dry coat weight of about 4 lbs/144.3 yd^. For example, by using a #20 Meyer rod, a fcd=100% (no polymer binder) coating of about 4.5 lbs/ 144.3 yd^ was achieved. Similarly, by using a #68 Meyer rod, a fcd=50% carboxymethyl cellulose coating of about 4.5 lbs/144.3 yd2 was achieved. By using a #60 Meyer rod, a f_c =50% polyvinyl alcohol coating of 3.9 lbs/144.3 yd2 was achieved. By using a #58 Meyer rod, a f_cd=50% polyvinyl pyrolidone coating of 3.7 lbs/144.3 yd2 was achieved. In order to achieve a coat weight of 3.8 lbs/144.3 yd2 for a sodium polyacrylate coating, two passes were required, wherein the first was with a #34 Meyer rod and the second pass was with a double-wound #60 Meyer rod. The above-prepared photoglossy media were then printed using the inks of Example 13. In particular, solid squares of the primary colors, magenta, cyan and yellow, were printed. The printed samples were then faded by irradiating with ultraviolet light from a xenon lamp in an Atlas Ci35 Weather-ometer (Atlas Electric Devices) for 43 hours at a nominal irradiance of 1.10 W/m- at 340 nm and a temperature of 63°C. Spectradensitometer (X-Rite) measurements were made before and after fading. Fading was quantified by ΔE values for the primary colors (magenta, cyan and yellow). The results are given below.

Binder f_cd(%) ΔEmagenta ΔEcyan ΔEyellow

PVP 0 43.9 34.3 16.5

10 27.4 34.4 16.1

20 22.3 32.6 12.3

30 21.5 31.6 13.4

40 16.1 28.3 10.9

50 12.5 25.3 9.6

60 9.0 22.6 9.9

70 4.9 18.6 5.7

80 2.9 16.1 4.6

90 1.8 11.5 4.1

100 3.7 5.1 3.0

CMC 0 - - -

10 22.1 5.5 32.7

20 30.7 4.6 14.7

30 22.3 4.3 14.6

40 14.6 3.5 10.4

50 7.9 2.0 6.7

60 6.8 1.9 6.7

70 7.6 1.5 3.2

80 5.1 3.5 5.5

90 4.3 2.6 5.5

100 3.7 5.1 3.0 Binder d(%) ΔEmagenta ΔEcyan ΔEyello

PVOH 0 5.0 3.3 21.7

10 10.1 3.3 16.6

20 5.9 2.6 13.3

30 5.5 3.1 11.0

40 5.5 2.4 8.7

50 4.5 2.5 6.5

60 3.9 3.0 4.8

70 4.6 2.8 3.5

80 4.6 3.2 3.6

90 4.4 3.4 3.5

100 3.7 5.1 3.0

PAA 0 _ _.

10 66.1 4.2 45.5

20 70.1 3.1 50.2

30 - - -

40 59.4 2.9 23.1

50 48.1 2.9 15.6

60 41.9 2.7 8.6

70 23.4 2.7 9.9

80 7.8 2.3 7.2

90 7.1 4.2 4.8

100 3.7 5.1 3.0

For the magenta, fading was suppressed in the PVOH binder, irrespective of CD content. CMC and PVP behaved similarly, with increased CD content inhibiting fading up to about 60%. Fading was most pronounced in the PAA binder, with large (80 %) amounts of CD necessary to inhibit fading. For the cyan, fading was suppressed for CMC, PVOH and PAA binders, irrespective of CD content. Fading was only significant in the PVP binder, with CD suppressing the fading most likely by displacing the PVP. For the yellow, PVOH and PVP behaved similarly, with increased CD content inhibiting fading up to about 60%. CMC was a little worse, while again fading was most pronounced in the PAA.

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

Claims

ClaimsWhat is claimed is:

1. An ink set comprising two or more inks, wherein the inks of the ink set possess substantially similar light fastness properties.

2. The ink set of claim 1, wherein one or more inks of the ink set contain a porphine.

3. The ink set of claim 2, wherein the porphine is represented by the following formula

wherein M is iron, cobalt or copper; and wherein R is SO3H,

COOH, or RiCOOH wherein Ri is an alkyl group of from 1 to 6 carbons.

4. The ink set of claim 3, wherein the porphine is Cu-meso-tetra-(4-sulfanatophenyl)-porphine or Cu-meso-tetra- (N-methyl-4-pyridyl)-porphine, having the following structures, respectively:

or the porphine is Co-meso-tetra-(4-sulfanatophenyl)- porphine or Co-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures, respectively:

5. The ink set of claim 2, wherein a metal or metal salt is added to one or more inks containing the porphine.

6. The ink set of claim 5, wherein the metal or metal salt is selected from Mg, Fe, Zn or lanthanides and their salts.

7. The ink set of claim 5, wherein the metal or metal salt comprises a lanthanide or lanthanide salt.

8. The ink set of claim 7, wherein the lanthanide or lanthanide salt comprises an europium or europium salt.

9. The ink set of claim 2, wherein the porphine is associated with a molecular includant.

10. The ink set of claim 9, wherein the molecular includant is one or more cyclodextrins.

1 1. The ink set of claim 10, wherein the one or more cyclodextrins comprise α-cyclodextrin, β-cyclodextrin, γ- cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, or hydroxyethyl β-cyclodextrin.

12. The ink set of claim 5, wherein one or more inks further comprise borax, hydrochloric acid, sodium hydroxide, EDTA or sodium salts thereof, ethylene glycol, glycerine, a biocide, a corrosion inhibitor or a combination thereof.

13. The ink set of claim 1 , wherein the ink set comprises cyan, magenta, yellow and black inks.

14. The ink set of claim 13, wherein the magenta and yellow inks contain at least one colorant stabilizer.

15. The ink set of claim 14, wherein the at least one colorant stabilizer comprises a porphine.

16. The ink set of claim 15, wherein the porphine is represented by the following formula

wherein M is iron, cobalt or copper; and wherein R is SO3H,

COOH, or RiCOOH wherein Ri is an alkyl group of from 1 to 6 carbons.

17. The ink set of claim 16, wherein the porphine is Cu-meso-tetra-(4-sulfanatophenyl)-porphine or Cu-meso-tetra- (N-methyl-4-pyridyl)-porphine, having the following structures, respectively:

or

or

18. The ink set of claim 15, wherein the magenta ink further comprises a metal or metal salt.

19. The ink set of claim 18, wherein the metal or metal salt is selected from Mg, Fe, Zn or lanthanides and their salts.

20. The ink set of claim 18, wherein the metal or metal salt comprises europium or europium salt.

21. The ink set of claim 14, wherein the at least one colorant stabilizer comprises a benzophenone.

22. A method of making an ink set, wherein inks of the ink set possess substantially similar light fastness properties, the method comprising: providing an ink set comprising two or more inks; and adding one or more colorant stabilizers to one or more inks of the ink set.

23. The method of claim 22, wherein the one or more colorant stabilizers comprises a porphine.

24. The method of claim 23, wherein the porphine is represented by the following formula

wherein M is iron, cobalt or copper; and wherein R is SO3H,

COOH, or RiCOOH wherein Rj is an alkyl group of from 1 to 6 carbons.

25. The method of claim 24, wherein the porphine is Cu-meso-tetra-(4-sulfanatophenyl)-poφhine or Cu-meso-tetra- (N-methyl-4-pyridyl)-porphine, having the following structures, respectively:

or the porphine is Co-meso-tetra-(4-sulfanatophenyl)- porphine or Co-meso-tetra-(N-methyl-4-pyridyl)-ρorphine, having the following structures, respectively:

26. The method of claim 23, wherein a metal or metal salt is added to one or more inks containing the poφhine.

27. The method of claim 26, wherein the metal or metal salt is selected from Mg, Fe, Zn or lanthanides and their salts.

28. The method of claim 26, wherein the metal or metal salt comprises a lanthanide or lanthanide salt.

29. The method of claim 23, wherein the porphine is associated with a molecular includant.

30. The method of claim 29, wherein the molecular includant is one or more cyclodextrins.

31. The method of claim 30, wherein the one or more cyclodextrins comprise α-cyclodextrin, β-cyclodextrin, γ- cyciodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, or hydroxyethyl β-cyclodextrin.

32. The method of claim 26, wherein one or more inks further comprise borax, hydrochloric acid, sodium hydroxide, EDTA or sodium salts thereof, ethylene glycol, glycerine, a biocide, a corrosion inhibitor or a combination thereof.

33. The method of claim 22, wherein the ink set comprises cyan, magenta, yellow and black inks.

34. The method of claim 33, wherein the magenta and yellow inks contain at least one colorant stabilizer.

35. The method of claim 34, wherein the at least one colorant stabilizer comprises a poφhine.

36. The method of claim 35, wherein the porphine is represented by the following formula

wherein M is iron, cobalt or copper; and wherein R is SO3H,

COOH, or RiCOOH wherein Ri is an alkyl group of from 1 to 6 carbons.

37. The method of claim 36, wherein the poφhine is Cu-meso-tetra-(4-sulfanatophenyl)-poφhine or Cu-meso-tetra- (N-methyl-4-pyridyl)-porphme, having the following structures, respectively:

or

or

38. The method of claim 35, wherein the magenta ink further comprises a metal or metal salt.

39. The method of claim 38, wherein the metal or metal salt is selected from Mg, Fe, Zn or lanthanides and their salts.

40. The method of claim 38, wherein the metal or metal salt comprises europium or europium salt.

41. The method of claim 34, wherein the at least one colorant stabilizer comprises a benzophenone.

42. A composition comprising a colorant and at least one poφhine represented by the following formula

wherein M is iron, cobalt or copper; and wherein R is SO3H,

COOH, or RiCOOH wherein Ri is an alkyl group of from 1 to 6 carbons.

43. The composition of claim 42, further comprising a metal or a metal salt.

44. The composition of claim 43, wherein the metal or metal salt is selected from Mg, Fe, Zn or lanthanides and their salts.

45. The composition of claim 43, wherein the metal or metal salt comprises a lanthanide or lanthanide salt.

46. The composition of claim 45, wherein the lanthanide or lanthanide salt comprises europium or europium salt.

47. The composition of claim 42, wherein the at least one poφhine is associated with a molecular includant.

48. The composition of claim 47, wherein the molecular includant is one or more cyclodextrins.

49. The composition of claim 48, wherein the one or more cyclodextrins comprise -cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, or hydroxyethyl β-cyclodextrin.

50. The composition of claim 42, further comprising borax, hydrochloric acid, sodium hydroxide, EDTA or sodium salts thereof, ethylene glycol, glycerine, a biocide, a corrosion inhibitor or a combination thereof.

51. A method of stabilizing a colorant comprising associating a poφhine with the colorant, wherein at least one poφhine is represented by the following formula

wherein M is iron, cobalt or copper; and wherein R is SO3H,

COOH, or RiCOOH wherein Ri is an alkyl group of from 1 to 6 carbons.

52. The method of claim 51 , further comprising associating a metal or metal salt with the colorant.

53. The composition of claim 52, wherein the metal or metal salt is selected from Mg, Fe, Zn or lanthanides and their salts.

54. The method of claim 53, wherein the metal or metal salt comprises a lanthanide or lanthanide salt.

55. The method of claim 54, wherein the lanthanide or lanthanide salt comprises europium or europium salt.

56. The method of claim 51, wherein the at least one poφhine is associated with a molecular includant.

57. The method of claim 56, wherein the molecular includant is one or more cyclodextrins.

58. The method of claim 57, wherein the one or more cyclodextrins comprise α-cyclodextrin, β-cyclodextrin, γ- cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, or hydroxyethyl β-cyclodextrin.

59. The method of claim 51 , further associating borax, hydrochloric acid, sodium hydroxide, EDTA or sodium salts thereof, ethylene glycol, glycerine, a biocide, a corrosion inhibitor or a combination thereof with the colorant.

60. A composition comprising: a base layer; and a binder composition on the base layer, wherein the binder composition comprises one or more polymeric binders in combination with one or more cyclodextrins.

61. The composition of claim 60, wherein the one or more polymer binders comprise polyvinylpyrrolidone (PVP), polyvinylalcohol (PVOH), polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate , polyacrylamide , polymethacrylamide, polyethylene glycol, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, polyacrylic acid and polyacrylic acid salts, polymethacrylic acid and polymethacrylic acid salts, polyvinylsulfonate and polyvinylsulfonate salts , poly- 2 - acryl amido-2 - methylpropanesulfonic acid and poly-2-acrylamido-2- methylpropanesulfonic acid salts, polyacryloxy- trimethylammonium chloride, polymethacryloxytrimethyl- ammonium chloride, polydiallyldimethylammonium chloride or a combination thereof.

62. The composition of claim 61 , wherein the binder composition comprises sodium carboxymethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone (PVP), polyvinylalcohol (PVOH) or a combination thereof.

63. The composition of claim 60, wherein the one or more cyclodextrins comprise α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin, sulfated β cyclodextrin, sulfated γ-cyclodextrin or a combination thereof.

64. The composition of claim 63, wherein the one or more cyclodextrins comprise β-cyclodextrin (β-C D ) , hydroxypropyl β-cyclodextrin (hp-β-CD) or a combination thereof.

65. The composition of claim 60, wherein the binder composition comprises from about 90 to about 10 weight percent polymeric binder and from about 10 to about 90 weight percent cyclodextrin.

66. The composition of claim 65, wherein the binder composition comprises from about 65 to about 25 weight percent polymeric binder and from about 35 to about 75 weight percent cyclodextrin.

67. The composition of claim 65, wherein the base layer has a basis weight of from about 3.0 to about 60.0 g/m²

68. The composition of claim 67, wherein the base layer has a basis weight of from about 15.0 to about 20.0 g/m² of base layer surface area.

69. The composition of claim 60, wherein the base layer comprises one or more layers of paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, metal or a combination thereof.

70. The composition of claim 69, wherein the base layer comprises one or more layers of paper.

71. The composition of claim 70, wherein the base layer comprises a paper layer coated with a polyethylene film.

72. A method of light-stabilizing a colorant composition, comprising associating the colorant composition on a surface of the composition of Claim 60.

73. The method of light-stabilizing a colorant composition, wherein the colorant composition comprises the colorant composition of claim 42.