WO1998023695A2 - Substrats ameliores et stabilisateurs de colorants - Google Patents

Substrats ameliores et stabilisateurs de colorants Download PDF

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Publication number
WO1998023695A2
WO1998023695A2 PCT/US1997/021700 US9721700W WO9823695A2 WO 1998023695 A2 WO1998023695 A2 WO 1998023695A2 US 9721700 W US9721700 W US 9721700W WO 9823695 A2 WO9823695 A2 WO 9823695A2
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WO
WIPO (PCT)
Prior art keywords
cyclodextrin
composition
colorant
porphine
ink set
Prior art date
Application number
PCT/US1997/021700
Other languages
English (en)
Other versions
WO1998023695A3 (fr
Inventor
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 (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/757,222 external-priority patent/US5782963A/en
Priority claimed from US08/788,863 external-priority patent/US6099628A/en
Priority claimed from US08/843,410 external-priority patent/US5855655A/en
Priority claimed from US08/903,911 external-priority patent/US5891229A/en
Priority to EP97952235A priority Critical patent/EP0941293A2/fr
Priority to CA002269700A priority patent/CA2269700A1/fr
Priority to BR9713151-2A priority patent/BR9713151A/pt
Priority to JP52484398A priority patent/JP2002511893A/ja
Application filed by Kimberly-Clark Worldwide, Inc. filed Critical Kimberly-Clark Worldwide, Inc.
Priority to AU55896/98A priority patent/AU5589698A/en
Priority to SK674-99A priority patent/SK67499A3/sk
Publication of WO1998023695A2 publication Critical patent/WO1998023695A2/fr
Publication of WO1998023695A3 publication Critical patent/WO1998023695A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023—Digital printing methods characterised by the inks used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates to improved substrates for use with colorants, and especially with a family of colorants and colorant stabilizers.
  • the colorant stabilizers 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.
  • 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.
  • 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.
  • light of higher energy short wavelengths
  • light of lower energy long wavelengths
  • 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.
  • 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).
  • 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.
  • the colorant stabilizer comprises one or more porphines that have an extremely short triplet state lifetime.
  • porphines include, but are not limited to, porphines having the following general structure:
  • R is any proton-donating moiety and M is iron, cobalt or copper. Desirably, R is SO3H,
  • Ri is an alkyl group of from 1 to 6 carbons.
  • porphines are Cu-meso-tetra-(4- sulfanatophenyl)-porphine (designated CuTPPS4) and Cu- meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures:
  • 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.
  • the colorant stabilizer comprises at least one porphine in combination with at least one metal or metal salt.
  • 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.
  • metal solubility-enhancing agents may be added.
  • Particularly useful metal solubility-enhancing agents include, but are not limited to, chelating agents.
  • a surfactant can be added to the metal/porphine composition to increase the interaction of the metal or metal salt and the porphine.
  • 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.
  • a colorant stabilizer is present in a polymer coating of a heat transfer product, such as is used for transferring graphic images onto clothing.
  • 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.
  • 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.
  • compositions and methods relating to stabilizing a colorant by applying the colorant to a treated substrate containing a stabilizing molecule will be discussed.
  • 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.
  • 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.
  • 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.
  • molecular includant 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present invention includes a substrate having a colored composition thereon.
  • the colored composition may be present on the substrate or it may be in the substrate.
  • the present invention relates to colorant compositions having improved stability, wherein the colorant stabilizer is associated with a colorant solution.
  • 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.
  • 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.
  • a colorant stabilizer is represented by porphines having an extremely short triplet state lifetime.
  • 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:
  • R is any proton-donating moiety and M is iron, cobalt or copper. Desirably, R is SO3H,
  • Ri is an alkyl group of from 1 to 6 carbons.
  • 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.
  • the colorant stabilizer comprises one or more porphines in combination with one or more metals or metal salts, such as lanthanides and lanthanide salts.
  • 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.
  • lanthanides and lanthanide salts are desired metals, other metals, may also be used such as magnesium, iron, zinc, and other transition metals.
  • 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( ⁇ -aminoethyl ether)).
  • chelating agents including, but not limited to, EDTA (ethylenediaminetetraacetic acid) or EGTA (ethylene glycol-bis( ⁇ -aminoethyl ether)).
  • the colorant stabilizer comprises a porphine and a lanthanide, such as europium.
  • 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
  • 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.
  • europium and europium salts are desired lanthanides, other metals in the lanthanides series may also be used.
  • the above stabilizing compounds of the present invention 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.
  • atoms with a high atomic number such as iodine, xenon and lanthanides
  • Another quenching process involves back electron transfer.
  • 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.
  • the dye or colorant may be an organic dye.
  • Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base ⁇ 4-
  • 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;
  • phthalocyanine dyes such as Copper Phthalocyanine ⁇ Pigment Blue 15; (SP-4- l)-[29H,31H- phthalocyanato(2-)-N ,N ,N ,N J ]co ⁇ per ⁇ ; carotenoid dyes, such as trans- ⁇ -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
  • the colorant and/or colorant stabilizer is associated with a molecular includant.
  • association in its broadest sense means that the colorant and/or colorant stabilizer is at least in close proximity to the molecular includant.
  • 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.
  • the colorant and/or colorant stabilizer may be covalently bonded to the molecular includant, although this normally is neither desired nor necessary.
  • 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.
  • 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.
  • cyclodextrins include, but are not limited to, ⁇ - cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, hydroxypropyl ⁇ -cyclodextrin, hydroxyethyl ⁇ -cyclodextrin, hydroxyethyl ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin, octyl succinated ⁇ cyclodextrin, octyl succinated ⁇ cyclodextrin, octyl succinated ⁇ cyclodextrin and sulfated ⁇ cyclodextrin and sulfated ⁇ -cyclodextrin (Cerestar U.S.A., Incorporated, Hammond, Indiana).
  • cyclodextrin as used herein means a cyclodextrin having more than two leaving groups covalently coupled to each molecule of cyclodextrin.
  • 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 ⁇ -cyclodextrin, hydroxyethyl ⁇ -cyclodextrin, hydroxyethyl cyclodextrin, carboxymethyl ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin, octyl succinated ⁇ cyclodextrin, octyl succinated ⁇ cyclodextrin, octyl succinated ⁇ cyclodextrin and sulfated ⁇ and ⁇ -cyclodextrin.
  • a desired derivatized cyclodextrin is ethylhydroxy ⁇ -cyclodextrin.
  • a desired molecular includant is ⁇ -cyclodextrin.
  • Another desirable molecular includant is ⁇ -cyclodextrin.
  • the molecular includant is an ethyl hydroxy ⁇ -cyclodextrin.
  • 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.
  • the colorant, the colorant stabilizer and molecular includant are likely to be solids depending upon the constituents used to prepare the molecules.
  • 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.
  • amides such as N,N- dimethylformamide
  • sulfoxides such as dimethylsulfoxide
  • ketones such as acetone, methyl ethyl ketone, and methyl butyl ketone
  • 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.
  • 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.
  • 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.
  • the composition of the present invention can be a liquid because one or more of its components is a liquid.
  • composition of the present invention typically will be utilized in particulate form.
  • 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.
  • the carrier will be a polymer, typically a thermosetting or thermoplastic polymer, with the latter being the more common.
  • 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-
  • 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-
  • polyethylene polyethylene
  • polypropylene polypropylene
  • ethylene-vinyl acetate copolymers polypropylene
  • epoxy resins epoxy resins
  • 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
  • the colored composition of the present invention also can contain additional components, depending upon the application for which it is intended.
  • 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
  • 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'-.9 ⁇ 'c-butyl-5'-tert-butylphenyl)- benzo-triazole, poly-(N- ⁇ -hydroxyethyl-2,2,6,6-tetramethyl- 4-hydroxy-piperidyl succinate and 2-(2'-hydroxy-3',5'-dite ⁇ t 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.
  • 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 ⁇ ) 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • 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.
  • paperboard examples 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.
  • 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.
  • 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®,
  • 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®,
  • the base layer is a coated or uncoated paper.
  • 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.
  • 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- tri
  • 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, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ - cyclodextrin, hydroxypropyl ⁇ -cyclodextrin, hydroxyethyl ⁇ - cyclodextrin, hydroxyethyl ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin, octyl succinated cyclodextrin, octyl succinated ⁇ cyclodextrin, octyl succinated ⁇ cyclodextrin and sulfated ⁇ cyclodextrin and sulfated ⁇ -cyclodextrin (Cerestar USA Incorporated, Hammond, Indiana).
  • the binder composition contains
  • 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.
  • the binder composition of the present invention may also contain additional components.
  • 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.
  • 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- ⁇ - 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the binder composition is applied to a base layer to produce a coating weight of from about 3.0 to about 60.0 g/m 2 of base layer surface area. More desirably, the coating weight is from about 9.0 to about 23.0 g/m 2 of base layer surface area. More desirably, the coating weight is from about 15.0 to about 20.0 g/m 2 of base layer surface area.
  • 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.
  • the carrier will be a polymer, typically a thermosetting or thermoplastic polymer, with the latter being the more common.
  • 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.
  • 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.
  • the paper is untreated Hewlett-Packard premium paper, or treated Hewlett-Packard premium paper prepared using a solution of about 50% wt/wt hydroxypropyl ⁇ - 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.
  • 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:
  • 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.
  • the change in magenta color is measured by the Xrite
  • 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:
  • the inks were prepared with about 0.5% CuTPPS 4 stabilizing additive and fade tested on HP paper and HP ⁇ -CD paper with the following results.
  • HP- 1600 magenta ink was prepared with about 0.5% CuTPPS 4 stabilizing additive and fade tested on HP paper and HP ⁇ -CD paper with the following results.
  • HP- 1600 magenta ink was also prepared with about 0.5% CuTMPS 4 stabilizing additive and fade tested on HP paper and HP ⁇ -CD paper with the following results.
  • 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.
  • 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.
  • ⁇ E* and ⁇ H* 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.
  • 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
  • Beta-cyclodextrin, ⁇ -CD, and hydroxypropyl-beta-cyclodextrin, hp- ⁇ -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
  • 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.
  • polyvinylpyrrolidone PVP K-90, International Specialty Products
  • PVP K-90 polyvinylpyrrolidone
  • Triton X- 100 Rhm and Haas
  • SURFYNOL® 420 Air Products
  • glycerol Fisher Scientific
  • Beta-Cyclodextrin, ⁇ -CD, and hydroxypropyl-beta- cyclodextrin, hp- ⁇ -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).
  • 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, ⁇ -CD, and hydroxypropyl-beta-cyclodextrin, hp- ⁇ -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).
  • 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- ⁇ -CD,
  • a coating composition was formulated by mixing 250 g of a 10% solution of poly(vinylalcohol) (Airvol 523, Air
  • 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- ⁇ -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.
  • 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:
  • 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.
  • 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.
  • a stock aqueous solution of hydroxypropyl-beta-cyclodextrin, hp- ⁇ - CD, (Cerestar) at 50 wt% and 3 wt% Triton X- 100 was prepared.
  • 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 ⁇ .
  • a f c 50% polyvinyl alcohol coating of 3.9 lbs/144.3 yd2 was achieved.
  • 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.
  • Atlas Ci35 Weather-ometer Align Chemical Vaporometer
  • X-Rite Spectradensitometer

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Abstract

Substrats améliorés destinés à être utilisés avec des colorants, en particulier avec une famille de colorants et de stabilisateurs de colorants. Selon l'invention, les stabilisateurs de colorants peuvent stabiliser un colorant exposé au rayonnement électromagnétique. Les stabilisateurs de colorants permettent de produire une série d'encres, où chaque encre, indépendamment de la couleur, a des propriétés de solidité à la lumière sensiblement analogues. On décrit aussi des substrats améliorés destinés à être utilisés avec des colorants, en particulier avec les colorants et stabilisateurs de colorants considérés dans l'invention. Les substrats améliorés permettent de produire un substrat imprimé dont la qualité de l'impression est supérieure à celle des substrats classiques.
PCT/US1997/021700 1996-11-27 1997-11-26 Substrats ameliores et stabilisateurs de colorants WO1998023695A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
SK674-99A SK67499A3 (en) 1996-11-27 1997-11-26 Sets of colorants, colorant compositions and substrates for intake of colorants containing colorant stabilizers, methods for making a set of colorants and methods for stabilizing colorant compositions
AU55896/98A AU5589698A (en) 1996-11-27 1997-11-26 Improved substrates and colorant stabilizers
EP97952235A EP0941293A2 (fr) 1996-11-27 1997-11-26 Substrats ameliores et stabilisateurs de colorants
JP52484398A JP2002511893A (ja) 1996-11-27 1997-11-26 改良された支持体及び着色剤の安定剤
CA002269700A CA2269700A1 (fr) 1996-11-27 1997-11-26 Substrats ameliores et stabilisateurs de colorants
BR9713151-2A BR9713151A (pt) 1996-11-27 1997-11-26 Substratos aperfeiçoados e estabilizadores de coloração.

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US08/757,222 US5782963A (en) 1996-03-29 1996-11-27 Colorant stabilizers
US08/788,863 US6099628A (en) 1996-03-29 1997-01-23 Colorant stabilizers
US08/843,410 US5855655A (en) 1996-03-29 1997-04-15 Colorant stabilizers
US08/903,911 US5891229A (en) 1996-03-29 1997-07-31 Colorant stabilizers
US5578597P 1997-08-15 1997-08-15
US6264397P 1997-10-22 1997-10-22
US60/062,643 1997-10-22
US08/843,410 1997-10-22
US08/757,222 1997-10-22
US08/903,911 1997-10-22
US08/788,863 1997-10-22
US60/055,785 1997-10-22

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999036476A2 (fr) * 1998-01-20 1999-07-22 Kimberly-Clark Worlwide, Inc. Procede ameliore de fabrication de porphines substituees par le sulfanatophenyl
WO1999063006A2 (fr) * 1998-06-03 1999-12-09 Kimberly-Clark Worldwide, Inc. Techniques recourant aux neonanoplastes et aux microemulsions relatives aux encres et a l'impression par jets d'encre
WO1999065700A1 (fr) * 1998-06-15 1999-12-23 Kimberly-Clark Worldwide, Inc. Substrat pour impression par jet d'encre revetu d'un enduit anti-tuilage
WO2000042110A1 (fr) * 1999-01-19 2000-07-20 Kimberly-Clark Worldwide, Inc. Nouveaux colorants,stabilisateurs de colorants, compositions d'encre, et leur procedes de preparation ameliores
US8551731B2 (en) 2007-03-15 2013-10-08 Ventana Medical Systems, Inc. Stabilized hematoxylin

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100498807B1 (ko) * 2001-12-04 2005-07-01 대한민국 휘발된 청색잉크 복원제 및 이의 제조방법
JP2005162770A (ja) * 2003-11-28 2005-06-23 Canon Inc 水性インク
US9683102B2 (en) * 2014-05-05 2017-06-20 Frontier Scientific, Inc. Photo-stable and thermally-stable dye compounds for selective blue light filtered optic

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0716929A1 (fr) * 1994-12-12 1996-06-19 Arkwright Inc. Matériau pour l'enregistrement par jet d'encre d'encre ayant un revêtement d'une matrice polymère
WO1997020000A2 (fr) * 1995-11-28 1997-06-05 Kimberly-Clark Worldwide, Inc. Stabilisants ameliores pour colorants

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55113036A (en) * 1979-02-24 1980-09-01 Ricoh Co Ltd Photosensitive and thermosensitive copying material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0716929A1 (fr) * 1994-12-12 1996-06-19 Arkwright Inc. Matériau pour l'enregistrement par jet d'encre d'encre ayant un revêtement d'une matrice polymère
WO1997020000A2 (fr) * 1995-11-28 1997-06-05 Kimberly-Clark Worldwide, Inc. Stabilisants ameliores pour colorants

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 8041 Derwent Publications Ltd., London, GB; Class A89, AN 80-72623C XP002072372 & JP 55 113 036 A (RICOH KK) *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999036476A2 (fr) * 1998-01-20 1999-07-22 Kimberly-Clark Worlwide, Inc. Procede ameliore de fabrication de porphines substituees par le sulfanatophenyl
WO1999036476A3 (fr) * 1998-01-20 2000-11-23 Kimberly Clark Co Procede ameliore de fabrication de porphines substituees par le sulfanatophenyl
US6399769B1 (en) 1998-01-20 2002-06-04 Kimberly-Clark Worldwide, Inc. Method of making sulfanatophenyl substituted porphines
WO1999063006A2 (fr) * 1998-06-03 1999-12-09 Kimberly-Clark Worldwide, Inc. Techniques recourant aux neonanoplastes et aux microemulsions relatives aux encres et a l'impression par jets d'encre
WO1999063006A3 (fr) * 1998-06-03 2000-09-21 Kimberly Clark Co Techniques recourant aux neonanoplastes et aux microemulsions relatives aux encres et a l'impression par jets d'encre
WO1999065700A1 (fr) * 1998-06-15 1999-12-23 Kimberly-Clark Worldwide, Inc. Substrat pour impression par jet d'encre revetu d'un enduit anti-tuilage
WO2000042110A1 (fr) * 1999-01-19 2000-07-20 Kimberly-Clark Worldwide, Inc. Nouveaux colorants,stabilisateurs de colorants, compositions d'encre, et leur procedes de preparation ameliores
US8551731B2 (en) 2007-03-15 2013-10-08 Ventana Medical Systems, Inc. Stabilized hematoxylin

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SK67499A3 (en) 2000-07-11
WO1998023695A3 (fr) 1998-10-01
EP0941293A2 (fr) 1999-09-15
CA2269700A1 (fr) 1998-06-04
KR20000069137A (ko) 2000-11-25
PL336328A1 (en) 2000-06-19
AU5589698A (en) 1998-06-22
JP2002511893A (ja) 2002-04-16

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