Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0075—Preparations with cationic 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
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material 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
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
  • B41M5/282—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using thermochromic compounds
  • B41M5/284—Organic thermochromic compounds
• • 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
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
  • B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0009—Obliterating the printed matter; Non-destructive removal of the ink pattern, e.g. for repetitive use of the support
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
  • B43M—BUREAU ACCESSORIES NOT OTHERWISE PROVIDED FOR
  • B43M11/00—Hand or desk devices of the office or personal type for applying liquid, other than ink, by contact to surfaces, e.g. for applying adhesive
  • B43M11/06—Hand-held devices
  • B43M11/08—Hand-held devices of the fountain-pen type
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
  • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
  • C07C49/213—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings
  • C07C49/217—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
  • C07C49/794—Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring
  • C07C49/796—Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring polycyclic
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
  • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/58—Preparation of carboxylic acid halides
  • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
  • C07C65/32—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups
  • C07C65/38—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups having unsaturation outside the aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
  • C07C69/94—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
  • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
  • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
  • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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  • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
  • C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
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  • C09B67/0092—Dyes in solid form
• • 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
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• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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• • C—CHEMISTRY; METALLURGY
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• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31971—Of carbohydrate
  • Y10T428/31993—Of paper
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2582—Coating or impregnation contains an optical bleach or brightener or functions as an optical bleach or brightener [e.g., it masks fabric yellowing, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/259—Coating or impregnation provides protection from radiation [e.g., U.V., visible light, I.R., micscheme-change-itemave, high energy particle, etc.] or heat retention thru radiation absorption

Definitions

• the present invention relates to a family of colorants and colorant modifiers.
• the colorant modifiers are capable of stabilizing a color to ordinary light and/or rendering the colorant mutable when exposed to specific wavelengths of electromagnetic radiation.
• 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 ch?.nge 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 some chemical group 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). Therefore, there exists a great need for methods and compositions which are capable of stabilizing a wide variety of colorants from the effects of both sunlight and artificial light.
• the ideal colorant would be one that is stable in ordinary light and can be mutated to a colorless form when exposed to a specific predetermined wavelength of electromagnetic radiation.
• 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 provides certain embodiments in which the light-stable colorant system is mutable by exposure to certain narrow bandwidths of radiation.
• the colorant system is stable in ordinary visible light and is mutable when exposed to a specific wavelength of electromagnetic radiation.
• the present invention provides a composition comprising a colorant which, in the presence of a radiation transorber, is mutable when exposed to a specific wavelength of radiation, while at the same time, provides light stability to the colorant when the composition is exposed to sunlight or artificial light.
• the radiation transorber may be any material which is adapted to absorb radiation and interact with the colorant to effect the mutation of the colorant.
• the radiation transorber contains a photoreactor and a wavelength- specific sensitizer.
• the wavelength-specific sensitizer generally absorbs radiation having a specific wavelength, and therefore a specific amount of energy, and transfers the energy to the photoreactor. It is desirable that the mutation of the colorant be irreversible.
• the present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with a modified photoreactor. It has been determined that conventional photoreactors, which normally contain a carbonyl group with a functional group on the carbon alpha to the carbonyl group, acquire the ability to stabilize colorants when the functional group on the alpha carbon is removed via dehydration.
• the present invention also includes a novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group. This reaction is necessary to impart the colorant stabilizing capability to the photoreactor.
• the novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group can be used with a wide variety of photoreactors to provide the colorant stabilizing capability to the photoreactor.
• the resulting modified photoreactor can optionally be linked to wavelength-selective sensitizer to impart the capability of decolorizing a colorant when exposed to a predetermined narrow wavelength of electromagnetic radiation.
• the present invention provides a photoreactor capable of stabilizing a colorant that it is admixed with.
• the mixture of colorant and radiation transorber is mutable upon exposure to radiation.
• the photoreactor may or may not be modified as described above to impart stability when admixed to a colorant.
• an ultraviolet radiation transorber is adapted to absorb ultraviolet radiation and interact with the colorant to effect the irreversible mutation of the colorant. It is desirable that the ultraviolet radiation transorber absorb ultraviolet radiation at a wavelength of from about 4 to about 300 nanometers. It is even more desirable that the ultraviolet radiation transorber absorb ultraviolet radiation at a wavelength of 100 to 300 nanometers.
• the colorant in combination with the ultraviolet radiation transorber remains stable when exposed to sunlight or artificial light. If the photoreactor is modified as described above, the colorant has improved stability when exposed to sunlight or artificial light.
• Another stabilizer that is considered part of the present invention is an arylketoalkene having the following general formula:
• K ⁇ is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
• R 2 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
• R 3 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group
• R is an aryl, heteroaryl, or substituted aryl group.
• the alkene group is in the trans configuration.
• the arylketoalkene stabilizing compound has the following formula.
• arylketoalkene stabilizing compound of the present invention is in the trans configuration with respect to the double bond.
• the sensitizer may also be in the cis configuration across the double bond.
• this embodiment of the present invention provides a stabilizing molecule, the above arylketoalkene, which when associated with a colorant, stabilizes the colorant. Therefore, the above arylketoalkene can be used as an additive to any colorant composition. For example, as the arylketoalkene compound is poorly soluble in water, it can be directly added to solvent or oil based (not water based) colorant compositions. Additionally, the arylketoalkene compound can be added to other colorant compositions that contain additives enabling the solubilization of the compound therein. Further, the arylketoalkene stabilizing compounds can be solubilized in an aqueous solution by attaching the compound to a large water soluble molecule, such as a cyclodextrin.
• the colored composition of the present invention may also contain a molecular includant having a chemical structure which defines at least one cavity.
• the molecular includants include, but are not limited to, clathrates, zeolites, and cyclodextrins.
• Each of the colorant and ultraviolet radiation transorber or modified photoreactor or arylketoalkene stabilizing compound can be associated with one or more molecular includant.
• the includant can have multiple radiation transorbers associated therewith (see co-pending U.S. Patent Application Serial No. 08/359,670).
• the includant can have many modified photoreactors or arylketoalkene stabilizing compounds associated therewith.
• the colorant is at least partially included within a cavity of the molecular includant and the ultraviolet radiation transorber or modified photoreactor or arylketoalkene stabilizer is associated with the molecular includant outside of the cavity.
• the ultraviolet ra ⁇ iation transorber or modified photoreactor or arylketoalkene stabilizer is covalently coupled to the outside of the molecular includant.
• the present invention also relates to a method of mutating the colorant associated with the composition of the present invention.
• the method comprises irradiating a composition containing a mutable colorant and an ultraviolet radiation transorber with ultraviolet radiation at a dosage level sufficient to mutate the colorant.
• the composition further includes a molecular includant.
• the composition is applied to a substrate before being irradiated with ultraviolet radiation. It is desirable that the mutated colorant is stable.
• the present invention is also related to a substrate having an image thereon that is formed by the composition of the present invention.
• the colorant in the presence of the radiation transorber or modified photoreactor or arylketoalkene compound, is more stable to sunlight or artificial light.
• a molecular includant is included in the composition, the colorant is stabilized by a lower ratio of radiation transorbers to colorant.
• the present invention also includes a dry imaging process wherein the imaging process utilizes, for example, the following three mutable colorants: cyan, magenta, and yellow. These mutable colorants can be layered on the substrate or can be mixed together and applied as a single layer. Using, for example, laser technology with three lasers at different wavelengths, an image can be created by selectively "erasing" colorants. A further advantage of the present invention is that the remaining colorants are stable when exposed to ordinary light.
• the present invention also includes a method of storing data utilizing the mutable colorant on a substrate, such as a disc. The colorant is selectively mutated using a laser at the appropriate wavelength to provide the binary information required for storing the information. The present invention is particularly useful for this purpose because the unmutated colorant is stabilized to ordinary light by the radiation transorber and can be further stabilized by the optionally included molecular includant.
• the present invention also includes data processing forms for use with photo-sensing apparatus that detect the presence of indicia at indicia-receiving locations of the form.
• the data processing forms are composed of a sheet of carrier material and a plurality of indicia-receiving locations on the surface of the sheet.
• the indicia-receiving locations are defined by a colored composition including a mutable colorant and a radiation transorber.
• Figure 1 illustrates an ultraviolet radiation transorber/ mutable colorant/ molecular includant complex wherein the mutable colorant is malachite green, the ultraviolet radiation transorber is IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone), and the molecular includant is ⁇ -cyclodextrin.
• Figure 2 illustrates an ultraviolet radiation transorber/ mutable colorant/ molecular includant complex wherein the mutable colorant is Victoria Pure Blue BO (Basic Blue 7), the ultraviolet radiation transorber is IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone), and the molecular includant is ⁇ -cyclodextrin.
• Figure 3 is a plot of the average number of ultraviolet radiation transorber molecules which are covalently coupled to each molecule of a molecular includant in several colored compositions, which number also is referred to by the term, "degree of substitution,” versus the decolorization time upon exposure to 222-nanometer excimer lamp ultraviolet radiation.
• Figure 4 is an illustration of several 222 nanometer excimer lamps arranged in four parallel columns wherein the twelve numbers represent the locations where twelve intensity measurements were obtained approximately 5.5 centimeters from the excimer lamps.
• Figure 5 is an illustration of several 222 nanometer excimer lamps arranged in four parallel columns wherein the nine numbers represent the locations where nine intensity measurements were obtained approximately 5.5 centimeters from the excimer lamps.
• Figure 6 is an illustration of several 222 nanometer excimer lamps arranged in four parallel columns wherein the location of the number " 1" denotes the location where ten intensity measurements were obtained from increasing distances from the lamps at that location. (The measurements and their distances from the lamp are summarized in Table 12.)
• the present invention relates in general to a light-stable colorant system that is optionally mutable by exposure to narrow band-width radiation.
• the present invention more particularly relates to a composition comprising a colorant which, in the presence of a radiation transorber, is stable under ordinary light but is mutable when exposed to specific, narrow band-width radiation.
• the radiation transorber is capable of absorbing radiation and interacting with the colorant to effect a mutation of the colorant.
• the radiation transorber may be any material which is adapted to absorb radiation and interact with the colorant to effect the mutation of the colorant.
• the radiation transorber contains a photoreactor and a wavelength-specific sensitizer.
• the wavelength-specific sensitizer generally absorbs radiation having a specific wavelength, and therefore a specific amount of energy, and transfers the energy to the photoreactor. It is desirable that the mutation of the colorant be irreversible.
• the present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with a modified photoreactor. It has been determined that conventional photoreactors which normally contain a carbonyl group with a functional group on the carbon alpha to the carbonyl group acquire the ability to stabilize colorants when the functional group on the alpha carbon is removed. Accordingly, the present invention also includes a novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group.
• the novel method of dehydrating photoreactors that have a hydroxyl group in the alpha position to a carbonyl group can be used with a wide variety of photoreactors to provide the colorant stabilizing capability to the photoreactor.
• the resulting modified photoreactor can optionally be linked to a wavelength-selective sensitizer to impart the capability of decolorizing a colorant when exposed to a predetermined narrow wavelength of electromagnetic radiation. Accordingly, the present invention provides a photoreactor capable of stabilizing a colorant with which it is admixed.
• the colorant and radiation transorber is mutable upon exposure to radiation.
• the photoreactor may or may not be modified as described above to impart stability when admixed to a colorant.
• an ultraviolet radiation transorber is adapted to absorb ultraviolet radiation and interact with the colorant to effect the irreversible mutation of the colorant. It is desirable that the ultraviolet radiation transorber absorb ultraviolet radiation at a wavelength of from about 4 to about 300 nanometers. If the photoreactor in the radiation transorber is modified as described above, the colorant has improved stability when exposed to sunlight or artificial light.
• the present invention also relates to a method of mutating the colorant in the composition of the present invention.
• the method comprises irradiating a composition containing a mutable colorant and a radiation transorber with radiation at a dosage level sufficient to mutate the colorant.
• the present invention further relates to a method of stabilizing a colorant comprising associating the modified photoreactor described above with the colorant.
• the photoreactor may be associated with a wavelength-selective sensitizer, or the photoreactor may be associated with a molecular includant, or both.
• the stabilizing composition produced by the process of dehydrating a tertiary alcohol that is alpha to a carbonyl group on a photoreactor is shown in the following general formula:
• R is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
• R is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group
• R 3 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group; and R is an aryl, heteroaryl, or substituted aryl group.
• the alkene group is in the trans configuration.
• the arylketoalkene stabilizing compound is represented by the following formulas:
• this embodiment of the present invention provides a stabilizing molecule, the above arylketoalkene, which when associated with a colorant, stabilizes the colorant. Therefore, the above arylketoalkene can be used as an additive to any colorant composition.
• the arylketoalkene compound can be directly added to solvent or oil based (not water based) colorant compositions.
• the arylketoalkene compound can be added to other colorant compositions that contain additives enabling the solubilization of the compound therein.
• the arylketoalkene stabilizing compounds can be solubilized in an aqueous solution by attaching the compound to a large water soluble molecule, such as a cyclodextrin.
• composition and such variations as “colored composition” are used herein to mean a colorant, and a radiation transorber or a modified photoreactor or an arylketoalkene stabilizer. Where the colored composition includes the modified photoreactor, it may further comprise a wavelength-selective sensitizer. Where the colored composition includes the arylketoalkene stabilizer, it may further comprise a photoreactor. When reference is being made to a colored composition which is adapted for a specific application, the term "composition-based" is used as a modifier to indicate that the material includes a colorant, an ultraviolet radiation transorber or a modified photoreactor or an arylketoalkene stabilizer, and, optionally, 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 pigment. Desirably, the colorant will be substantially transparent to, that is, will not significantly interact with, the ultraviolet radiation to which it is exposed.
• the term is meant to include a single material or a mixture of two or more materials.
• the term “irreversible” means that the colorant will not revert to its original color when it no longer is exposed to ultraviolet radiation.
• radiation transorber is used herein to mean any material which is adapted to absorb radiation at a specific wavelength and interact with the colorant to affect the mutation of the colorant and, at the same time, protect the colorant from fading in sunlight or artificial light.
• ultraviolet radiation transorber is used herein to mean any material which is adapted to absorb ultraviolet radiation and interact with the colorant to effect the mutation of the colorant.
• the ultraviolet radiation transorber may be an organic compound. Where the radiation transorber is comprised of a wavelength-selective sensitizer and a photoreactor, the photoreactor may optionally be modified as described below.
• a radiation transorber is comprised of a photoreactor and a wavelength selective sensitizer.
• the radiation transorber has the additional property of making the colorant with which the radiation transorber is associated light stable to sunlight or aidficial light.
• light-stable is used herein to mean that the colorant, when associated with the radiation transorber or modified photoreactor or arylketoalkene stabilizer molecule, is more stable to light, including, but not limited to, sunlight or artificial light, than when the colorant is not associated with these compounds.
• 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.
• the term “cavity” is meant to include any opening or space of a size sufficient to accept at least a portion of one or both of the colorant and the ultraviolet radiation transorber.
• functionalized molecular includant is used herein to mean a molecular includant to which one or more molecules of an ultraviolet radiation transorber or modified photoreactor or arylketoalkene 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.
• leaving group is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction.
• 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.
• ultraviolet radiation is used herein to mean electromagnetic radiation having wavelengths in the range of from about 4 to about 400 nanometers.
• the especially desirable ultraviolet radiation range for the present invention is between approximately 100 to 375 nanometers.
• the term includes the regions commonly referred to as ultraviolet and vacuum ultraviolet.
• the wavelength ranges typically assigned to these two regions are from about 180 to about 400 nanometers and from about 100 to about 180 nanometers, respectively.
• 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.
• mutable with reference to the colorant, is used to mean that the abso ⁇ tion maximum of the colorant in the visible region of the electromagnetic spectrum is capable of being mutated or changed by exposure to radiation, preferably ultraviolet radiation, when in the presence of the radiation transorber.
• radiation preferably ultraviolet radiation
• the new abso ⁇ tion maximum can be within or outside of the visible region of the electromagnetic spectrum.
• the colorant can mutate to a different color or be rendered colorless. The latter is also desirable when the colorant is used in data processing forms for use with photo-sensing apparatus that detect the presence of indicia at indicia-receiving locations of the form.
• the radiation transorber molecule, the wavelength-selective sensitizer, the photoreactor, or the arylketoalkene stabilizer may be associated with a molecular includant. It is to be noted that in all the formulas, the number of such molecules can be between approximately 1 and approximately 21 molecules per molecular includant. Of course, in certain situations, there can be more than 21 molecules per molecular includant molecule. Desirably, there are more than three of such molecules per molecular includant.
• the degree of substitution of the functionalized molecular includant may be in a range of from 1 to approximately 21. As another example, the degree of substitution may be in a range of from 3 to about 10. As a further example, the degree of substitution may be in a range of from about 4 to about 9.
• the colorant is associated with the functionalized molecular includant.
• the term "associated" in its broadest sense means that the colorant is at least in close proximity to the functionalized molecular includant.
• the colorant may be maintained in close proximity to the functionalized molecular includant by hydrogen bonding, van der Waals forces, or the like.
• the colorant may be covalently bonded to the functionalized molecular includant, although this normally is neither desired nor necessary.
• the colorant may be at least partially included within the cavity of the functionalized molecular includant.
• Examples 1, 2, 6, and 7 disclose one or more methods of preparing and associating colorants and ultraviolet radiation transorbers to cyclodextrins.
• the efficiency of energy transfer from the ultraviolet radiation transorber to the colorant is, at least in part, a function of the number of ultraviolet radiation transorber molecules which are attached to the molecular includant. It now is known that the synthetic methods described above result in covalently coupling an average of two transorber molecules to each molecule of the molecular includant.
• the time required to mutate the colorant should, at least in part, be a function of the number of ultraviolet radiation transorber molecules coupled to each molecule of molecular includant, there is a need for an improved colored composition in which an average of more than two ultraviolet radiation transorber molecules are covalently coupled to each molecule of the molecular includant.
• the present invention also relates to a composition which includes a colorant and a functionalized molecular includant.
• a composition which includes a colorant and a functionalized molecular includant.
• Examples 12 through 19, and 21 through 22 disclose other methods of preparing and associating colorants and ultraviolet radiation transorbers to cyclodextrins, wherein more than two molecules of the ultraviolet radiation transorber are covalently coupled to each molecule of the molecular includant.
• Examples 29 and 31 disclose methods of preparing and associating arylketoalkene stabilizers with cyclodextrin, wherein the cyclodextrin has an average of approximately 3 or 4 stabilizer molecules attached thereto.
• the present invention also provides a method of making a functionalized molecular includant.
• the method of making a functionalized molecular includant involves the steps of providing a derivatized ultraviolet radiation transorber having a nucleophilic group, providing a derivatized molecular includant having more than two leaving groups per molecule, and reacting the derivatized ultraviolet radiation transorber with the derivatized molecular includant under conditions sufficient to result in the covalent coupling of an average of more than two ultraviolet radiation transorber molecules to each molecular includant molecule.
• the derivatized ultraviolet radiation transorber may be 2-[p-(2-methyl-2- mercaptomethylpropionyl)phenoxy]ethyl 1 ,3-dioxo-2-isoindoline- acetate.
• the derivatized ultraviolet radiation transorber may be 2-mercaptomethyl-2-methyl-4'-[2-[/>-(3- oxobutyl)phenoxy]ethoxy]propiophenone.
• the derivatized ultraviolet radiation transorber and the derivatized molecular includant are selected to cause the covalent coupling of the ultraviolet radiation transorber to the molecular includant by means of a bimolecular nucleophilic substitution reaction.
• the nucleophilic group of the derivatized ultraviolet radiation transorber may be any nucleophilic group capable of participating in a bimolecular nucleophilic substitution reaction, provided, of course, that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular includant.
• the nucleophilic group generally will be a Lewis base, i.e., any group having an unshared pair of electrons.
• the group may be neutral or negatively charged. Examples of nucleophilic groups include, by way of illustration only, aliphatic hydroxy, aromatic hydroxy, alkoxides, carboxy, carboxylate, amino, and mercapto.
• the leaving group of the derivatized molecular includant may be any leaving group capable of participating in a bimolecular nucleophilic substitution reaction, again provided that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular includant.
• Examples of leaving groups include, also by way of illustration only, /?-tolu ⁇ n ⁇ sulfonates (tosylates), ?-bromobenzenesulf onates (brosylates), -nitrobenzenesulf onates (nosylates), methanesulfonates (mesylates), oxonium ions, alkyl perchlorates, ammonioalkane sulfonate esters (betylates), alkyl fluorosulf onates, trifluoromethanesulf onates (triflates), nonafluorobutanesulfonates (nonaflates), and 2,2,2- trifluoroethanesulf onates (tresy lates) .
• the reaction of the derivatized ultraviolet radiation transorber with the derivatized molecular includant is carried out in solution.
• the choice of solvent depends upon the solubilities of the two derivatized species.
• a particularly useful solvent is N,N-dimethylformamide (DMF).
• reaction conditions such as temperature, reaction time, and the like generally are matters of choice based upon the natures of the nucleophilic and leaving groups. Elevated temperatures usually are not required. For example, the reaction temperature may be in a range of from about 0°C to around ambient temperature, i.e., to 20°-25°C.
• the preparation of the functionalized molecular includant as described above generally is carried out in the absence of the colorant. However, the colorant may be associated with the derivatized molecular includant before reacting the derivatized ultraviolet radiation transorber with the derivatized molecular includant, particularly if a degree of substitution greater than about three is desired.
• the degree of substitution is about three, it is believed that the association of the colorant with the functionalized molecular includant still may permit the colorant to be at least partially included in a cavity of the functionalized molecular includant.
• steric hindrance may partially or completely prevent the colorant from being at least partially included in a cavity of the functionalized molecular includant. Consequently, the colorant may be associated with the derivatized molecular includant which normally will exhibit little, if any, steric hindrance. In this instance, the colorant will be at least partially included in a cavity of the derivatized molecular includant.
• the above-described bimolecular nucleophilic substitution reaction then may be carried out to give a colored composition of the present invention in which the colorant is at least partially included in a cavity of the functionalized molecular includant.
• the present invention provides compositions comprising a colorant which, in the presence of a radiation transorber, is mutable when exposed to a specific wavelength of radiation, while at the same time, provides light stability to the colorant with respect to sunlight and artificial light.
• the mutated colorant will be stable, i.e., not appreciably adversely affected by radiation normally encountered in the environment, such as natural or artificial light and heat.
• a colorant rendered colorless will remain colorless indefinitely.
• the dye may be an organic dye.
• Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base ⁇ 4-(dimethylamino)- ⁇ -[4- (dimethylamino)phenyl]- -phenylbenzene-methanol ⁇ , Malachite Green Carbinol hydrochloride ⁇ N-4-[[4-
• cyanine dyes such as Indocyanine Green ⁇ Cardio-Green or Fox Green
• indigo dyes such as Indigo ⁇ Indigo Blue or Vat Blue 1
• coumarin dyes such as 7-hydroxy-4-methylcoumarin (4-
• azoic diazo dyes such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5- diethoxybenzene 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] ; anthraquinone dyes, such as Disperse Blue 3 [Celliton Fast Blue FFR; 1- methylamino-4-(2-hydroxyethylamino)-9, 10-anthraquinone],
• Disperse Blue 14 [Celliton Fast Blue B; 1 ,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-naphtha- lenyl)azo]-l,5-naphthalenedisulfonic acid tetrasodium salt ⁇ ; xanthene dyes, such as 2,7-dichlorofluorescein; proflavine dyes, such as 3,6-diaminoacridine hemisulfate (Proflavine); sulfonaphthalein dyes, such as Cresol Red (o- cresolsulf
• the present invention includes unique compounds, namely, radiation transorbers, that are capable of absorbing narrow ultraviolet wavelength radiation, while at the same time, imparting light-stability to a colorant with which the compounds are associated.
• the compounds are synthesized by combining a wavelength-selective sensitizer and a photoreactor.
• the photoreactors oftentimes do not efficiently absorb high energy radiation.
• the resulting compound is a wavelength specific compound that efficiently absorbs a very narrow spectrum of radiation.
• the wavelength-selective sensitizer may be covalently coupled to the photoreactor.
• the wavelength-selective sensitizer may be selected from the group consisting of phthaloylglycine and 4- (4-oxyphenyl)-2-butanone.
• the photoreactor may be selected from the group consisting of l-[4-(2- hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-l-one and cyclohexyl-phenyl ketone ester.
• Other photoreactors are listed by way of example, in the detailed description below regarding the impoved stabilized composition of the present invention.
• the ultraviolet radiation transorber may be 2-[p- 2-methyllactoyl)phenoxy]ethyl l,3-dioxo-2-isoin-dolineacetate.
• the ultraviolet radiation transorber may be 2-hydroxy-2-methyl-4'-2-[p-(3-oxobutyl)phenoxy]- propiophenone.
• the colorant and the ultraviolet radiation transorber have been described as separate compounds, they can be part of the same molecule. For example, they can be covalently coupled to each other, either directly, or indirectly through a relatively small molecule, or spacer. Alternatively, the colorant and ultraviolet radiation transorber can be covalently coupled to a large molecule, such as an oligomer or a polymer.
• the colorant and ultraviolet radiation transorber may be associated with a large molecule by van der Waals forces, and hydrogen bonding, among other means.
• the composition further comprises a molecular includant.
• the cavity in the molecular includant can be a tunnel through the molecular includant or a cave-like space or a dented-in space in the molecular includant.
• the cavity can be isolated or independent, or connected to one or more other cavities.
• 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.
• molecular includants are, by way of illustration only, clathrates or intercalates, zeolites, and cyclodextrins.
• cyclodextrins include, but are not limited to, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, hydroxypropyl ⁇ -cyclodextrin, hydroxyethyl ⁇ -cyclodextrin, sulfated ⁇ -cyclodextrin, hydroxyethyl ⁇ cyclodextrin, carboxymethyle ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin, carboxymethyl ⁇ cyclodextrin.
• octyl succinated ⁇ cyclodextrin octyl succinated ⁇ cyclodextrin, octyl succinated ⁇ cyclodextrin, octyl succinated ⁇ cyclodextrin and sulfated ⁇ and ⁇ -cyclodextrin (American Maize-Products Company, Hammond, Indiana).
• the desired molecular includant is ⁇ -cyclodextrin. More particularly, in some embodiments, the molecular includant is an ⁇ -cyclodextrin. In other embodiments, the molecular includant is a ⁇ -cyclodextrin.
• the molecular includant with functional groups that can react with and bind the transorber molecule and that are close to the binding site of the mutable colorant are the more desirable molecular includants.
• the colorant and the ultraviolet radiation transorber are associated with the molecular includant.
• association in its broadest sense, means that the colorant and the ultraviolet radiation transorber are at least in close proximity to the molecular includant.
• the colorant and/or the ultraviolet radiation transorber can be maintained in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, or the like.
• either or both of the colorant and the ultraviolet radiation transorber can be covalently bonded to the molecular includant.
• the colorant will be associated with the molecular includant by means of hydrogen bonding and/or van der Waals forces or the like, while the ultraviolet radiation transorber is covalently bonded to the molecular includant.
• the colorant is at least partially included within the cavity of the molecular includant, and the ultraviolet radiation transorber is located outside of the cavity of the molecular includant.
• the colorant and the ultraviolet radiation transorber are associated with the molecular includant, the colorant is crystal violet, the ultraviolet radiation transorber is a dehydrated phthaloylglycine-2959, and the molecular includant is ⁇ -cyclodextrin.
• the colorant and the ultraviolet radiation transorber are associated with the molecular includant
• the colorant is crystal violet
• the ultraviolet radiation transorber is 4(4-hydroxy ⁇ henyl) butan-2- one-2959 (chloro substimted)
• the molecular includant is ⁇ -cyclodextrin.
• the colorant and the ultraviolet radiation transorber are associated with the molecular includant
• the colorant is malachite green
• the ultraviolet radiation transorber is IRGACURE 184
• the molecular includant is ⁇ - cyclodextrin as shown in Figure 1.
• the colorant is Victoria Pure Blue BO
• the ultraviolet radiation transorber is IRGACURE 184
• the molecular includant is ⁇ -cyclodextrin as shown in Figure 2.
• the present invention also relates to a method of mutating the colorant in the composition of the present invention.
• the method comprises irradiating a composition containing a mutable colorant and a radiation transorber with radiation at a dosage level sufficient to mutate the colorant.
• the composition further includes a molecular includant.
• the composition is applied to a substrate before being inadiated with ultraviolet radiation.
• the composition of the present invention may be irradiated with radiation having a wavelength of between about 4 to about 1,000 nanometers.
• the radiation to which the composition of the present invention is exposed generally will have a wavelength of from about 4 to about 1,000 nanometers.
• the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation; visible radiation; and near infrared radiation.
• the composition is irradiated with radiation having a wavelength of from about 4 to about 700 nanometers. More desirably, the composition of the present invention is inadiated with ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. It is more desirable that the radiation has a wavelength of between about 100 to 375 nanometers.
• the dielectric barrier discharge lamp produces radiation having a narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers.
• the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers.
• the half width will be of the order of approximately 5 to 15 nanometers.
• the amount or dosage level of ultraviolet radiation that the colorant of the present invention is exposed to will generally be that amount which is necessary to mutate the colorant.
• the amount of ultraviolet radiation necessary to mutate the colorant can be determined by one of ordinary skill in the art using routine experimentation.
• Power density is the measure of the amount of radiated electromagnetic power traversing a unit area and is usually expressed in watts per centimeter squared (W/cm ).
• the power density level range is between approximately 5 mW/cm 2 and 15 mW/cm 2 , more particularly 8 to 10 mW/cm 2 .
• the dosage level typically is a function of the time of exposure and the intensity or flux of the radiation source which irradiates the colored composition.
• the latter is affected by the distance of the composition from the source and, depending upon the wavelength range of the ultraviolet radiation, can be affected by the atmosphere between the radiation source and the composition. Accordingly, in some instances it may be appropriate to expose the composition to the radiation in a controlled atmosphere or in a vacuum, although in general neither, approach is desired.
• photochemical processes involve the abso ⁇ tion of light quanta, or photons, by a molecule, e.g., the ultraviolet radiation transorber, to produce a highly reactive electronically excited state.
• a molecule e.g., the ultraviolet radiation transorber
• the photon energy which is proportional to the wavelength of the radiation, cannot be absorbed by the molecule unless it matches the energy difference between the unexcited, or original, state and an excited state. Consequently, while the wavelength range of the ultraviolet radiation to which the colored composition is exposed is not directly of concern, at least a portion of the radiation must have wavelengths wliich will provide the necessary energy to raise the ultraviolet radiation transorber to an energy level which is capable of interacting with the colorant.
• the abso ⁇ tion maximum of the ultraviolet radiation transorber ideally will be matched with the wavelength range of the ultraviolet radiation to increase the efficiency of the mutation of the colorant. Such efficiency also will be increased if the wavelength range of the ultraviolet radiation is relatively narrow, with the maximum of the ultraviolet radiation transorber coming within such range. For these reasons, especially suitable ultraviolet radiation has a wavelength of from about 100 to about 375 nanometers.
• Ultraviolet radiation within this range desirably may be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp.
• excimer lamp a dielectric barrier discharge excimer lamp
• excimer lamp a dielectric barrier discharge excimer lamp
• excimer lamp Such a lamp is described, for example, by U. Kogelschatz, "Silent discharges for the generation of ultraviolet and vacuum ultraviolet excimer radiation,” Pure & Appl. Chem., 62, No. 9, pp. 1667-1674 (1990); and E. Eliasson and U. Kogelschatz, "UV Excimer Radiation from Dielectric-Barrier Discharges," Appl. Phys. B, 46, pp. 299-303 (1988).
• Excimer lamps were developed originally by ABB Infocom Ltd., Lenzburg, Switzerland. The excimer lamp technology since has been acquired by Haraus Noblelight AG, Hanau, Germany.
• the excimer lamp emits radiation having a very narrow bandwidth, i.e., radiation in which the half width is of the order of 5-15 nanometers.
• This emitted radiation is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the alternating current power supply which typically is in the range of from about 20 to about 300 kHz.
• An excimer lamp typically is identified or referred to by the wavelength at which the maximum intensity of the radiation occurs, which convention is followed throughout this specification.
• excimer lamp radiation is substantially monochromatic.
• Excimers are unstable molecular complexes which occur only under extreme conditions, such as those temporarily existing in special types of gas discharge. Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom. Excimer complexes dissociate within less than a microsecond and, while they are dissociating, release their binding energy in the form of ultraviolet radiation.
• excimers in general, emit in the range of from about 125 to about 360 nanometers, depending upon the excimer gas mixture.
• the colorant of the present invention is mutated by exposure to 222 nanometer excimer lamps. More particularly, the colorant crystal violet is mutated by exposure to 222 nanometer lamps. Even more particularly, the colorant crystal violet is mutated by exposure to 222 nanometer excimer lamps located approximately 5 to 6 centimeters from the colorant, wherein the lamps are arranged in four parallel columns approximately 30 centimeters long. It is to be understood that the arrangement of the lamps is not critical to this aspect of the invention. Accordingly, one or more lamps may be arranged in any configuration and at any distance which results in the colorant mutating upon exposure to the lamp's ultraviolet radiation.
• the excimer lamp used to mutate a colorant associated with an ultraviolet radiation transorber should produce ultraviolet radiation of a wavelength that is absorbed by the ultraviolet radiation transorber.
• the molar ratio of ultraviolet radiation transorber to colorant generally will be equal to or greater than about 0.5.
• the more efficient the ultraviolet radiation transorber is in absorbing the ultraviolet radiation and interacting with, i.e., transfening absorbed energy to, the colorant to effect ineversible mutation of the colorant the lower such ratio can be.
• Cunent theories of molecular photo chemistry suggest that the lower limit to such ratio is 0.5, based on the generation of two free radicals per photon. As a practical matter, however, ratios higher than 1 are likely to be required, perhaps as high as about 10. However, the present invention is not bound by any specific molar ratio range. The important feature is that the transorber is present in an amount sufficient to effect mutation of the colorant.
• the ultraviolet radiation transorber may interact with the colorant in a variety of ways.
• the ultraviolet radiation transorber upon absorbing ultraviolet radiation, may be converted to one or more free radicals which interact with the colorant.
• Such free radical- generating compounds typically are hindered ketones, some examples of which include, but are not limited to: benzildimethyl ketal (available commercially as IRGACURE 651, Ciba-Geigy Co ⁇ oration, Hawthorne, New York); 1-hydroxycyclohexyl phenyl ketone (IRGACURE 500); 2-methyl-l -[4- (methylthio)phenyl] -2-mo ⁇ holino-propan- 1 -one] (IRGACURE 907); 2-benzyl-2-dimethy lamino- l-(4-mo ⁇ holinophenyl)butan-l- one (IRGACURE 369); and 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184).
• benzildimethyl ketal available commercially as IRGACURE 651, Ciba-Geigy Co ⁇ oration, Hawthorne, New York
• the ultraviolet radiation may initiate an electron transfer or reduction-oxidation reaction between the ultraviolet radiation transorber and the colorant.
• the ultraviolet radiation transorber may be, but is not limited to, Michler's ketone (p-dimethylaminophenyl ketone) or benzyl trimethyl stannate.
• a cationic mechanism may be involved, in which case the ultraviolet radiation transorber can be, for example, bis[4-(diphenylsulphonio)phenyl)] sulfide bis-
• the improved light stable composition of the present invention includes a colorant admixed with a photoreactor modified as described below.
• the modified photoreactor may or may not be combined with a wavelength-selective sensitizer.
• Many conventional photoreactor molecules have a functional group that is alpha to a carbonyl group.
• the functional group includes, but is not limited to, hydroxyl groups, ether groups, ketone groups, and phenyl groups.
• a preferred radiation transorber that can be used in the present invention is designated phthaloylglycine-2959 and is represented by the following formula:
• the photoreactor portion of the ultraviolet radiation transorber has a hydroxyl group (shaded portion) alpha to the carbonyl carbon.
• the above molecule does not light-stabilize a colorant.
• the hydroxyl group can be removed by dehydration (see Example 4 and 5) yielding the following compound:
• This dehydrated phthaloylglycine-2959 is capable of light- stabilizing a colorant.
• removal of the functional group alpha to the carbonyl carbon on any photoreactor molecule will impart the light- stabilizing capability to the molecule.
• the dehydrated ultraviolet radiation transorber can impart hght- stability to a colorant simply by mixing the molecule with the colorant, it has been found that the molecule is much more efficient at stabilizing colorants when it is attached to an includant, such as cyclodextrin, as described herein.
• stabilization of a colorant can be accomplished according to the present invention by utilizing only the modified photoreactor.
• a modified photoreactor without a wavelength selective sensitizer may be used to stabilize a colorant.
• An example of a photoreactor that is modified according to the present invention is DARCUR 2959. The unmodified DARCUR 2959 and the dehydrated DARCUR 2959 are shown below.
• photoreactors can be modified according to the present invention to provide stabilizers for dyes.
• photoreactors include, but are not limited to: 1-Hydroxy-cyclohexyl-phenyl ketone (“HCPK”) (IRGACURE 184, Ciba-Geigy); ⁇ , ⁇ - dimethoxy- ⁇ -hydroxy acetophenone (DAROCUR 1173, Merck); 1 -(4-Isopropylphenyl)-2-hydroxy-2-methyl-propan- 1 -one
• Benzoin ethyl ether (2-Ethoxy-l,2-diphenylethanone) (DAITOCURE EE, Siber Hegner); Benzoin isopropyl ether (2- Isopropoxy-l,2-diphenylethanone) (VICURE 30, Stauffer); Benzoin n-butyl ether (2-Butoxy-l,2-diphenylethanone) (ESACURE EBl, Fratelli Lamberti); mixture of benzoin butyl ethers (TRIGONAL 14, Akzo); Benzoin iso-butyl ether (2- Isobutoxy-l,2-diphenylethanone) (VICURE 10, Stauffer); blend of benzoin n-butyl ether and benzoin isobutyl ether (ESACURE EB3, ESACURE EB4, Fratelli Lamberti); Benzildimethyl ketal (2,2-Dimethoxy-l,2-diphenylethanone) (“BDK”)
• the groups on the carbon alpha to the carbonyl group can be groups other than methyl groups such as aryl or heterocychc groups. The only limitation on these groups are steric limitations.
• the metal salt used in the Nohr-MacDonald ehmination reaction is ZnCl 2 . It is to be understood that other transition metal salts can be used in performing the Nohr-MacDonald elimination reaction but ZnCl 2 is the prefened metal salt.
• the amount of metal salt used in the Nohr-MacDonald elimination reaction is preferably approximately equimolar to the tertiary alcohol compound, such as the photoreactor.
• the concentration of tertiary alcohol in the reaction solution is between approximately 4%-and 50% w/v.
• the stabilizing composition produced by the process of dehydrating a tertiary alcohol that is alpha to a carbonyl group on a photoreactor is shown in the following general formula:
• R t is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
• R 2 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;
• R 3 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group
• R 4 is an aryl, heteroaryl, or substituted aryl group. Another requirement of the reaction is that it be run in a non-aqueous, non-polar solvent.
• the preferred solvents for running the Nohr-MacDonald elimination reaction are aromatic hydrocarbons including, but not limited to, xylene, benzene, toluene, cumene, mesitylene, p-cymene, butylbenzene, styrene, and divinylbenzene. It is to be understood that other substituted aromatic hydrocarbons can be used as solvents in the present invention.
• /?-Xylene is the preferred aromatic hydrocarbon solvent, but other isomers of xylene can be used in performing the Nohr-MacDonald elimination reaction.
• the reaction be run at a relatively high temperature.
• the reaction is desirably performed at a temperature of between approximately 80°C and 150°C.
• a suitable temperature for dehydrating phthaloylglycine-2959 is approximately 124°C.
• the time the reaction runs is not critical. The reaction should be run between approximately 30 minutes to
• the dehydrated phthaloylglycine- 2959 can be attached to the molecular includant in a variety of ways. In one embodiment, the dehydrated phthaloylglycine-2959 is covalently attached to the cyclodextrin as shown in the following structure:
• the dehydrated phthaloylglycine-2959 can be attached to the molecular includant via the opposite end of the molecule.
• One example of this embodiment is shown in the following formula:
• Another stabilizer that is considered part of the present invention is an arylketoalkene having the following general formula:
• R 2 is an aryl group
• R 2 is a hydrogen; heterocychc; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group
• Rj is hydrogen; heterocyclic; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group.
• the alkene group is in the trans configuration although it can be in the cis configuration.
• the arylketoalkene stabilizing compound has the following formula.
• the arylketoalkene may also function as a wavelength- specific sensitizer in the present invention, and it may be associated with any of the previously discussed photoreactors.
• the arylketoalkene compound may optionally be covalently bonded to the reactive species-generating photoinitiator. It is to be understood that the arylketoalkene compound of the present invention is not to be used with photoreactors in a composition where stability in natural sunlight is desired.
• arylketoalkene compounds absorb radiation in the range of about 270 to 310 depending on the identity of Ri and R 2 , then these compounds are capable of absorbing the appropriate radiation from sunlight. Accordingly, these compounds when admixed with a photoreactor can effect a mutation of the colorant upon exposure to sunlight. Where such a change in color is not desired, then a photoreactor is not to be admixed with the arylketoalkene compound of the present invention, and the arylketoalkene compound is to be used with a colorant without a photoreactor.
• the arylketoalkene stabilizing compound is represented by the following formula:
• the group attached to the aryl group is para to the remainder of the stabilizer molecule, the group may also be ortho or meta to the remainder of the molecule.
• arylketoalkene stabilizing compound can be an extended conjugated bond system arylketoalkene compound.
• R lt or R 2 , or both Rj and R 2 in the above general formula are phenyl groups substituted with one or more groups that extend the area of conjugation of the delocalized, pi electrons.
• R , or R 2 , or both R, ⁇ and R 2 are phenyl groups substituted with one or more carbonyl, ethylene, phenyl, ester, aryl, substituted aryl, or vinylic groups, wherein the groups are sequentially arranged such that only one of the groups is directly attached to the phenyl group, and the other groups are bonded to that attached group thereby extending the conjugation of the compound by forming a chain of unsaturated groups.
• the extended conjugated compound of the present invention includes any combination of the above groups, and any number of the above groups.
• a desirable extended conjugated arylketoalkene stabilizing compound of the present invention has the following formula:
• Another desirable arylketoalkene stabiUzing compound has the following formula:
• the extended stabiUzing compounds of the present invention may be produced by any method known to one of ordinary skill in the art. For example, one method is described in
• the hydroxy group on the phenyl group of the above intermediate may be substituted with any other group that will provide a linkage between the molecules shown in Examples 38 and 39 such that the product will have an extended conjugated bond system.
• a desirable Unkage is an ester Unkage.
• a desirable arylketoalkene stabilizing compound with a ketone linkage has the following formula:
• the extended conjugated arylketoalkene stabiUzing compound of the present invention is not Umited to only two of the compounds shown in Examples 38 and 39 Unked together. It is to be understood that the extended conjugated compound may include a multipUcity of the compounds shown in Examples 38 and 39 Unked together.
• the extended conjugated arylketoalkene stabiUzing compound of the present invention is extremely stable. Although not wanting to be Umited by the following, it is beUeved that the above extended conjugated compounds are low triplet state energy species, and are yellow in color. As the chain of conjugation is extended, it is believed that the color shifts to red or orange.
• this embodiment of the present invention provides a stabiUzing arylketoalkene which, when associated with a colorant, stabiUzes the colorant. Therefore, the above arylketoalkene can be used as an additive to any colorant composition. For example, as the arylketoalkene compound is not water soluble, it can be directly added to solvent or oil colorant compositions. Additionally, the arylketoalkene compound can be added to other colorant compositions that contain additives enabUng the solubiUzation of the compound therein.
• the arylketoalkene stabiUzing compounds can be solubiUzed in aqueous solution by a variety of means.
• One means of solubiUzing the arylketoalkene stabiUzing compound of the present invention is to attach the compound to a large water soluble molecule, such as a cyclodextrin, as described in Examples 28 through 31, and Examples 40 and 41.
• a large water soluble molecule such as a cyclodextrin, as described in Examples 28 through 31, and Examples 40 and 41.
• a cyclodextrin such as a cyclodextrin
• between about 4 to about 9 arylketoalkene molecules are attached to a cyclodextrin molecule.
• the arylketoalkene compound attached to cyclodextrin can be added to any aqueous colorant system to stabiUze the colorant therein. It is to be understood that the stabiUzing arylketoalkenes do not have to be attached to the molecular includants to exhibit their stabiUzing activity.
• this embodiment provides a method for stabiUzing colorant compositions by admixing the aryketoalkene compound with the colorant composition in an amount effective to stabiUze the composition.
• the arylketoalkenes desirably should be present in the colorant medium or solution at a concentration of approximately OJ to 50% by weight, desirably between approximately 20% and 30% by weight. If no cyclodextrin is used, the desirable range is approximately 1 part dye to approximately 20 parts arylketoalkene.
• the arylketoalkene compound need only be associated with the colorant, in some embodiments of the present invention, the arylketoalkene compound may be covalently bonded to the colorant.
• the arylketoalkene compound of the present invention stabiUzes colorants through functioning as a singlet oxygen scavenger.
• the arylketoalkene compound functions as a stabilizer of a colorant via the resonance of the unshared electron pairs in the p orbitals, e.g., it functions as an energy sink.
• the colorant, ultraviolet radiation transorber, modified photoreactor, arylketoalkene stabiUzer, and molecular includant are Ukely to be soUds depending upon the constituents used to prepare the molecules.
• any or all of such materials can be a Uquid.
• the colored composition can be a Uquid either because one or more of its components is a Iiquid, or, when the molecular includant is organic in nature, a solvent is employed.
• Suitable solvents include, but are not Umited to, amides, such as N,N-dimethylformamide; sulfoxides, such as dimethylsulfoxide; ketones, such as acetone, methyl ethyl ketone, and methyl butyl ketone; aUphatic and aromatic hydrocarbons, such as hexane, octane, benzene, toluene, and the xylenes; esters, such as ethyl acetate; water; and the Uke.
• amides such as N,N-dimethylformamide
• sulfoxides such as dimethylsulfoxide
• ketones such as acetone, methyl ethyl ketone, and methyl butyl ketone
• aUphatic and aromatic hydrocarbons such as hexane, octane, benzene, toluene, and the xylenes
• esters such as
• the effectiveness of the above compounds on the colorant is improved when the colorant and the selected compounds are in intimate contact.
• the thorough blending of the components, along with other components which may be present, is desirable.
• Such blending generally is accomphshed by any of the means known to those having ordinary skill in the art.
• the colored composition includes a polymer
• blending is faciUtated if the colorant and the ultraviolet radiation transorber 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 Uquid because one or more of its components is a Uquid.
• the composition of the present invention typically will be utiUzed in particulate form.
• 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 of the present invention can be utiUzed on or in any substrate. If one desires to mutate the colored composition that is present in a substrate, however, the substrate should be substantially transparent to the ultraviolet radiation which is employed to mutate the colorant. That is, the ultraviolet radiation will not significantly interact with or be absorbed by the substrate. As a practical matter, the composition typically will be placed on a substrate, with the most common substrate being paper. Other substrates, including, but not Umited to, woven and nonwoven webs or fabrics, films, and the like, can be used, however.
• the colored composition optionally may also contain a carrier, the nature of which is well known to those having ordinary skill in the art.
• a carrier will be a polymer, typically a thermosetting or thermoplastic polymer, with the latter being the more common.
• thermoplastic polymers include, but are not Umited to: end-capped polyacetals, such as poly (oxymethy lene) or polyformaldehyde, poly(trichloroacetaldehyde), poly(n-valeraldehyde), poly(acetaldehyde), poly(propionaldehyde), and the Uke; acryUc polymers, such as polyacrylamide, poly(acryhc acid), poly(methacryUc acid), poly(ethyl acrylate), poly(methyl methacrylate), and the Uke; fluorocarbon polymers, such as poly(tetrafluoroethylene), perfluorinated ethylenepropylene copolymers, ethylenetetrafluoroethylene copolymers, poly- (chlorotrifluoroethylene), ethylene-chlorotrifluoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the Uke; epoxy resins,
• polystyrene pyromelUtimido-l,4-phenylene
• 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), l,2-poly-l,3-butadiene, l,4-poly-l,3- butadiene, polyisoprene, polychloroprene, polyacrylonitrile, poly(vinyl acetate), poly(vinyUdene chloride), polystyrene, and the Uke; and copolymers of the foregoing, such as acrylonitrile- butadienestyrene (ABS) copolymers, styrene-n-butylmethacrylate copolymers, ethylene-vinyl acetate copolymers
• thermoplastic polymers include styrene-n-butyl methacrylate copolymers, polystyrene, styrene-n-butyl acrylate copolymers, styrene-butadiene copolymers, polycarbonates, poly(methyl methacrylate), poly(vinyUdene fluoride), polyamides (nylon- 12), polyethylene, polypropylene, ethylene-vinyl acetate copolymers, and epoxy resins.
• thermosetting polymers include, but are not Umited to, alkyd resins, such as phthaUc anhydride-glycerol resins, maleic acid-glycerol resins, adipic acid-glycerol resins, and phthaUc anhydride-pentaerythritol resins; allyUc resins, in which such monomers as diallyl phthalate, diallyl isophthalate diallyl maleate, and diallyl chlorendate serve as nonvolatile cross- Unking agents in polyester compounds; amino resins, such as aniUne-formaldehyde resins, ethylene urea-formaldehyde resins, dicyandiamide-formaldehyde resins, melamine-formaldehyde resins, sulfonamide-formaldehyde resins, and urea-formaldehyde resins; epoxy resins, such as cross-Unked epichlorohydrin-
• the colored composition of the present invention also can contain additional components, depending upon the apphcation for which it is intended.
• additional components include, but are not Umited to, charge carriers, stabiUzers against thermal oxidation, viscoelastic properties modifiers, cross-Unking agents, plasticizers, charge control additives such as a quaternary ammonium salt; flow control additives such as hydrophobic siUca, zinc stearate, calcium stearate, Uthium stearate, polyvinylstearate, and polyethylene powders; and fillers such as calcium carbonate, clay and talc, 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. The identities and amounts of such additional components in the colored composition are well known to one of ordinary skill in the art.
• This example describes the preparation of a ⁇ -cyclodextrin molecular includant having (1) an ultraviolet radiation transorber covalently bonded to the cyclodextrin outside of the cavity of the cyclodextrin, and (2) a colorant associated with the cyclodextrin by means of hydrogen bonds and/or van der Waals forces.
• a 250-ml, three-necked, round-bottomed reaction flask was fitted with a condenser and a pressure-equaUzing addition funnel equipped with a nitrogen inlet tube.
• a magnetic stirring bar was -.6
• the resulting reaction mixture was maintained at about 0 ⁇ C in an ice bath for about one hour, after which the mixture was allowed to warm to ambient temperature for two hours.
• the reaction mixture then was poured into a mixture of 500 ml of ice water and 100 ml of diethyl ether.
• the ether layer was removed after the addition of a small amount of sodium chloride to the aqueous phase to aid phase separation.
• the ether layer was dried over anhydrous magnesium sulfate.
• the ether was removed under reduced pressure, leaving 12.7 g (87 percent) of a white crystalUne powder.
• the material was shown to be 1 -hydroxy cyclohexyl 4-(2- carboxyethyl)carbonylphenyl ketone by nuclear magnetic resonance analysis.
• a 250-ml, three-necked, round-bottomed reaction flask containing a magnetic stirring bar and fitted with a thermometer, condenser, and pressure-equaUzing addition funnel equipped with a nitrogen inlet tube was charged with 10 g (9.8 mmoie) of ⁇ - cyclodextrin (American Maize-Products Company, Hammond, Indiana), 31.6 g (98 mmoles) of 1-hydroxycyclohexyl 4-(2- chloroformylethyl)carbonylphenyl ketone, and 100 ml of N,N- dimethylformamide while being continuously flushed with nitrogen.
• the reaction mixture was heated to 50°C and 0.5 ml of triethylamine added.
• reaction mixture was maintained at 50°C for an hour and allowed to cool to ambient temperature. In this preparation, no attempt was made to isolate the product, a ⁇ -cyclodextrin to which an ultraviolet radiation transorber had been covalently coupled (refened to hereinafter for convenience as ⁇ -cyclodextrin-transorber).
• Lamp A was a 222-nanometer excimer lamp assembly organized in banks of four cyUndrical lamps having a length of about 30 cm.
• the lamps were cooled by circulating water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50°C.
• the power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m 2 ).
• Lamp B was a 500-watt Hanovia medium pressure mercury lamp (Hanovia Lamp Co., Newark, New Jersey). The distance from Lamp B to the sample being inadiated was about 15 cm.
• a few drops of an N,N-dimethylformamide solution of the ⁇ -cyclodextrin- transorber Colorant A inclusion complex were placed on a TLC plate and in a small polyethylene weighing pan. Both samples were exposed to Lamp A and were decolorized (mutated to a colorless state) in 15-20 seconds. Similar results were obtained with Lamp B in 30 seconds.
• a first control sample consisting of a solution of Colorant A and ⁇ -cyclodextrin in N,N-dimethylfo ⁇ namide was not decolorized by Lamp A.
• a second control sample consisting of Colorant A and 1-hydroxycyclohexyl phenyl ketone in N,N- cUmethylformamide was decolorized by Lamp A within 60 seconds. On standing, however, the color began to reappear within an hour.
• Example 2 Because of the possibiUty in the preparation of the colored composition described in the following examples for the acylated transorber acid chloride to at least partially occupy the cavity of the cyclodextrin, to the partial or complete exclusion of colorant, a modified preparative procedure was carried out.
• this example describes the preparation of a ⁇ -cyclodextrin molecular includant having (1) a colorant at least partially included within the cavity of the cyclodextrin and associated therewith by means of hydrogen bonds and/or van der Waals forces, and (2) an ultraviolet radiation transorber covalently bonded to the cyclodextrin substantially outside of the cavity of the cyclodextrin.
• Example 3 This example describes a method of preparing an ultraviolet radiation transorber, 2-[p-(2- methyllactoyl)phenoxy]ethyl 1 ,3-dioxo-2-isoindoUneacetate, designated phthaloylglycine-2959.
• phthaloylglycine-2959 had the following physical parameters:
• This example describes a method of dehydrating the phthaloylglycine-2959 produced in Example 3.
• the resulting reaction product had the following physical parameters:
• This example describes the Nohr-MacDonald eUmination reaction used to dehydrate the phthaloylglycine-2959 produced in Example 3.
• the resulting reaction product had the following physical parameters:
• Mass spectrum m/e: 393 M +, 352, 326, 232, 160.
• This example describes a method of producing a ⁇ - cyclodextrin having dehydrated phthaloylglycine-2959 groups from Example 4 or 5 covalently bonded thereto.
• the ⁇ -cyclodextrin molecule has several primary alcohols and secondary alcohols with which the phthaloylglycine-2959 can react.
• the above representative reaction only shows a single phthaloylglycine-2959 molecule for illustrative pu ⁇ oses.
• Example 7 This example describes a method of associating a colorant and an ultraviolet radiation transorber with a molecular includant. More particularly, this example describes a method of associating the colorant crystal violet with the molecular includant ⁇ — cyclodextrin covalently bonded to the ultraviolet radiation transorber dehydrated phthaloylglycine-2959 of Example 6. The following was placed in a 100 ml beaker: 4.0 g ⁇ - cyclodextrin having a dehydrated phthaloylglycine-2959 group; and 50 ml of water. The water was heated to 70 e C at which point the solution became clear.
• Example 8 This example describes a method of producing the ultraviolet radiation transorber 4(4-hydroxyphenyl) butan-2-one- 2959 (chloro substituted).
• the resulting reaction product had the following physical parameters:
• the ultraviolet radiation transorber produced in this example, 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted), may be associated with ⁇ -cyclodextrin and a colorant such as crystal violet, using the methods described above wherein 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted) would be substituted for the dehydrated phthaloylglycine-2959.
• the mercury discharge Ught is a source of high intensity, broad spectrum Ught that is used in accelerated fading analyses.
• Table 2 shows the results of the fade time with the various solutions. Fade time is defined as the time until the dye became colorless to the naked eye.
• Dehydroxy 2959 20 parts by weight of the hydroxy and the dehydroxy 2959 were admixed separately to one part by weight of Victoria Pure Blue BO in acetonitrile.
• the dye solutions were cwerefully uniformly spread on steel plates to a thickness of approximately 0J mm.
• the plates were then immediately exposed to a mercury discharge Ught at a distance of 30 cm from the Ught.
• the mercury discharge Ught is a source of high intensity, broad spectrum Ught that is used in accelerated fading analyses.
• Table 3 shows the results of the fade time with the various solutions. Fade time is defined as the time until the dye became colorless to the naked eye.
• This example demonstrates the capabiUty of dehydrated phthaloylglycine-2959 bound to ⁇ -cyclodextrin to stabiUze dyes against light.
• the Victoria Pure Blue BO associated with the radiation transorber as discussed in the examples above, was tested to determine its capabihty to stabiUze the associated dye against Ught emitted from a mercury discharge Ught.
• the Victoria Pure Blue BO alone and Victoria Pure Blue BO admixed with ⁇ -cyclodextrin were tested as controls.
• the compositions tested were as follows:
• the protocol for testing the stabiUzing quaUties of the three compositions is as follows: the dye solutions were carefully, uniformly spread on steel plates to a thickness of approximately 0.1 mm. The plates were then immediately exposed to a medium pressure 1200 watt high intensity quartz arc mercury discharge lamp (Conrad-Hanovia, Inc., Newark, New Jersey) at a distance of 30 cm from the lamp.
• a medium pressure 1200 watt high intensity quartz arc mercury discharge lamp Conrad-Hanovia, Inc., Newark, New Jersey
• composition number 3 the Victoria Pure Blue BO included in cyclodextrin with the radiation transorber covalently attached to the ⁇ - cyclodextrin was capable of stabiUzing the dye under the mercury discharge Ught.
• thermometer and magnetic stiner was placed 30.0g (0.076 mol) of the dehydrated phthaloylglycine-2959, 70 ml methanol and 20J ml hydrogen peroxide (30% solution).
• the reaction mixture was stirred and cooled in a water/ice bath to maintain a temperature in the range 15°-20° C. 5.8 ml of a 6 N
• reaction mixture was cooled in a ice bath and 0.5 ml diisopropyl ethyl amine was added. Hydrogen sulfide was bubbled into the flask and a positive pressure maintained for 3 hours. During the last hour, the reaction mixture was allowed to warm to room temperature.
• reaction mixture was flushed with argon for 15 minutes and then poured into 70 ml of water to which was then added 100 ml acetone. A white precipitate occurred and was filtered to yield 20.2 g (84.1%) of a white powder which was used without further purification.
• a 250 ml round bottomed flask fitted with a magnetic stirrer and placed in an ice bath was placed 12.7 (0.031 mol), 80 ml of anhydrous DMF (Aldrich Chemical Co., Milwaukee, Wisconsin) and 15.0 g (0.010 mol) thiol CD.
• the precipitate was then dried in a convention oven at 80°C for 2 hours to yield a blue powder 27.9 g (58.1%).
• the resultant white powder was then run through a sephadex column (Aldrich Chemical Co., Milwaukee, Wisconsin) using n-butanol, ethanol, and water (5:4:3 by volume) as eluant to yield a white powder.
• the yield was 10.9%.
• the degree of substitution of the white powder was determined by 13 C NMR spectroscopy (DMF-d6) by comparing the ratio of hydroxysubstituted carbons versus tosylated carbons, both at the 6 position.
• the degree of substitution was calculated by integrating the NMR peak for the 6-position tosylated carbon, integrating the NMR peak for the 6-position hydroxy-substituted carbon, and dividing the former by the latter.
• the integrations yielded 23.6 and 4J, respectively, and a degree of substitution of 5.9.
• the average degree of substitution in this example is about 6.
• the tosylated cyclodextrin with the dehydroxy phthaloylglycine 2959 attached was prepared according to the following reaction:
• the aqueous layer was then treated with 500 ml of acetone and the precipitate filtered and washed with acetone.
• the product was then run on a sephadex column using n-butanol, ethanol, and water (5:4:3 by volume) to yield a white powder. The yield was 16.7 g.
• the degree of substitution of the functionaUzed molecular includant was determined as described above. In this case, the presence of the derivatized ultraviolet radiation transorber shifts the NMR peak of the 6-position carbon atom to 63. L The degree of substitution was calculated by integrating the NMR peak for the
• 6- ⁇ osition substituted carbon integrating the NMR peak for the 6- position hydroxy-substituted carbon, and dividing the former by the latter.
• the integrations yielded 67.4 and 11.7, respectively, and a degree of substitution of 5.7.
• the average degree of substitution in this example is about 6.
• the reaction above shows the degree of substitution to be "n". Although n represents the value of substitution on a single cyclodextrin, and therefore, can be from 0 to 24, it is to be understood that the average degree of substitution is about 6.
• Example 16 The procedure of Example 15 was repeated, except that the amounts of ⁇ -cyclodextrin and p-toluenesulfonic acid (Aldrich) were 6.0 g and 5.0 g, respectively. In this case, the degree of substitution of the cyclodextrin was found to be about 3.
• Example 17 The procedure of Example 15 was repeated, except that the amounts of ⁇ -cyclodextrin and p-toluenesulfonic acid (Aldrich) were 6.0 g and 5.0 g, respectively. In this case, the degree of substitution of the cyclodextrin was found to be about 3.
• Example 17 The procedure of Example 15 was repeated, except that the amounts of ⁇ -cyclodextrin and p-toluenesulfonic acid (Aldrich) were 6.0 g and 5.0 g, respectively. In this case, the degree of substitution of the cyclodextrin was found to be about 3.
• Example 15 The procedure of Example 15 was repeated, except that the derivatized molecular includant of Example 16 was employed in place of that from Example 15.
• the average degree of substitution of the functionaUzed molecular includant was found to be about 3.
• This example describes the preparation of a colored composition which includes a mutable colorant and the functionalized molecular includant from Example 15.
• Example 15 In a 250-ml Erlenmeyer flask containing a magnetic stirring bar was placed 20.0 g (5.4 mmoles) of the functionaUzed molecular includant obtained in Example 15 and 100 g of water. The water was heated to 80°C, at which temperature a clear solution was obtained. To the solution was added slowly, with stining, 3J g (6.0 mmoles) of Victoria Pure Blue BO (Aldrich). A precipitate formed which was removed from the hot solution by filtration.
• the precipitate was washed with 50 ml of water and dried to give 19J g (84 percent) of a blue powder, a colored composition consisting of a mutable colorant, Victoria Pure Blue B0, and a molecular includant having covalently coupled to it an average of about six ultraviolet radiation transorber molecules per molecular includant molecule.
• Example 18 The procedure of Example 18 was repeated, except that the functionaUzed molecular includant from Example 17 was employed in place of that from Example 15.
• This example describes mutation or decolorization rates for the compositions of Examples 7 (wherein the ⁇ -cyclodextrin has dehydrated phthaloyl glycine-2959 from Example 4 covalently bonded thereto), 18 and 19.
• approximately 10 mg of the composition was placed on a steel plate (Q-Panel Company, Cleveland, Ohio).
• acetonitrile Bill & Jackson, Muskegon, Michigan
• the assembly consisted of a bank of four cylindrical lamps having a length of about 30 cm.
• the lamps were cooled by circulating water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50°C.
• the power density at the lamp's outer surface typically was in the range of from about 4 to about 20 joules per square meter (J/m 2 ). However, such range in reaUty merely reflects the capabiUties of cunent excimer lamp power suppUes; in the future, higher power densities may be practical.
• the distance from the lamp to the sample being inadiated was 4.5 cm.
• the time for each film to become colorless to the eye was measured. The results are summarize ⁇ in Table 6.
• This example describes the preparation of a complex consisting of a mutable colorant and the derivatized molecular includant of Example 15.
• Example 18 The procedure of Example 18 was repeated, except that the functionaUzed molecular includant of Example 15 was replaced with 10 g (4.8 mmoles) of the derivatized molecular includant of Example 15 and the amount of Victoria Pure Blue BO was reduced to 2.5 g (4.8 mmoles).
• the yield of washed soUd was 10.8 g (86 percent) of a mutable colorant associated with the ⁇ -cyclodextrin having an average of six tosyl groups per molecule of molecular includant.
• Example 22 This example describes the preparation of a colored composition which includes a mutable colorant and a functionaUzed molecular includant.
• Example 15 The procedure of preparing a functionaUzed molecular includant of Example 15 was repeated, except that the tosylated ⁇ -cyclodextrin was replaced with 10 g (3.8 mmoles) of the complex obtained in Example 21 and the amount of the derivatized ultraviolet radiation transorber prepared in Example
• This example further demonstrates the abihty of the present invention to stabilize colorants against Ught.
• the two compounds containing Victoria Pure Blue BO as an includant in the cyclodextrin cavity were tested for Ught fastness under a medium pressure mercury discharge lamp. 100 mg of each compound was dissolved in 20 ml of acetonitrile and was uniformly spread on steel plates to a thickness of approximately 0J mm. The plates were then immediately exposed to a medium pressure 1200 watt high intensity quartz arc mercury discharge lamp (Conrad-
• This example describes the preparation of films consisting of colorant, ultraviolet radiation transorber, and thermoplastic polymer.
• the colorant and ultraviolet radiation transorber were ground separately in a mortar.
• the desired amounts of the ground components were weighed and placed in an aluminum pan, along with a weighed amount of a thermoplastic polymer.
• the pan was placed on a hot plate set at 150°C and the mixture in the pan was stined until molten.
• a few drops of the molten mixture were poured onto a steel plate and spread into a thin film by means of a glass microscope sUde.
• Each steel plate was 3 x 5 inches (7.6 cm x 12.7 cm) and was obtained from Q-Panel Company, Cleveland, Ohio.
• the film on the steel plate was estimated to have a thickness of the order of 10-20 micrometers.
• UVRT ultraviolet radiation transorber
• Irgacure® 500 Irgacure® 500
• UVRT B Irgacure® 651
• UVRT C Irgacure® 907
• the polymer was one of the following: an epichlorohydrin-bisphenol A epoxy resin ("Polymer A”), Epon® 1004F (Shell Oil Company, Houston, Texas); a poly(ethylene glycol) having a weight-average molecular weight of about 8,000 (“Polymer B”), Carbowax 8000 (Aldrich Chemical Company); and a polyethylene glycol) having a weight-average molecular weight of about 4,600 (“Polymer C”), Carbowax 4600 (Aldrich Chemical Company).
• a control film was prepared which consisted only of colorant and polymer. The compositions of the films are summarized in Table 8.
• UVRT Ultraviolet Radiation Transorber
• each film was exposed to ultraviolet radiation.
• the steel plate having the film sample on its surface was placed on a moving conveyor belt having a variable speed control.
• Three different ultraviolet radiation sources, or lamps, were used.
• Lamp A was a 222- nanometer excimer lamp and Lamp B was a 308-nanometer excimer lamp, as already described.
• Lamp C was a fusion lamp system having a "D" bulb (Fusion Systems Corporation, Rockville, Maryland).
• the excimer lamps were organized in banks of four cyUndrical lamps having a length of about 30 cm, with the lamps being oriented normal to the direction of motion of the belt.
• the lamps were cooled by circulating water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50°C.
• the power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m 2 ).
• UV radiation Transorber UV radiation Transorber
• Example 25 This Example demonstrates that the 222 nanometer excimer lamps illustrated in Figure 4 produce uniform intensity readings on a surface of a substrate 5.5 centimeters from the lamps, at the numbered locations, in an amount sufficient to mutate the colorant in the compositions of the present invention which are present on the surface of the substrate.
• the lamp 10 comprises a lamp housing 15 with four excimer lamp bulbs 20 positioned in parallel, the excimer lamp bulbs 20 are approximately 30 cm in length.
• the lamps are cooled by circulating water through a centrally located or inner tube (not shown) and, as a consequence, the lamps are operated at a relatively low temperature, i.e., about 50 * C.
• the power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m 2 ).
• Table 10 summarizes the intensity readings which were obtained by a meter located on the surface of the substrate.
• the readings numbered 1, 4, 7, and 10 were located approximately 7.0 centimeters from the left end of the column as shown in Figure 4.
• the readings numbered 3, 6, 9, and 12 were located approximately 5.5 centimeters from the right end of the column as shown in Figure 4.
• the readings numbered 2, 5, 8, and 11 were centrally located approximately 17.5 centimeters from each end of the column as shown in Figure 4.
• the excimer lamp 10 comprises a lamp housing 15 with four excimer lamp bulbs 20 positioned in parallel, the excimer lamp bulbs 20 are approximately 30 cm in length.
• the lamps are cooled by circulating water through a centrally located or inner tube (not shown) and, as a consequence, the lamps are operated at a relatively low temperature, i.e., about 50°C.
• the power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m 2 ).
• Table 11 summarizes the intensity readings which were obtained by a meter located on the surface of the substrate.
• the readings numbered 1, 4, and 7 were located approximately 7.0 centimeters from the left end of the columns as shown in Figure 5.
• the readings numbered 3, 6, and 9 were located approximately 5.5 centimeters from the right end of the columns as shown in Figure 5.
• the readings numbered 2, 5, 8 were centrally located approximately 17.5 centimeters from each end of the columns as shown in Figure 5.
• the excimer lamp 10 comprises a lamp housing 15 with four excimer lamp bulbs 20 positioned in parallel, the excimer lamp bulbs 20 are approximately 30 cm in length.
• the lamps are cooled by circulating water through a centrally located or inner tube (not shown) and, as a consequence, the lamps are operated at a relatively low temperature, i.e., about 50°C.
• the power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter (J/m 2 ).
• Table 12 summarizes the intensity readings which were obtained by a meter located on the surface of the substrate at position 1 as shown in Figure 6. Position 1 was centrally located approximately 17 centimeters from each end of the column as shown in Figure 6.
• This example describes a method of making the following wavelength-selective sensitizer:
• the wavelength-selective sensitizer is synthesized as summarized below: + H 3 C- ?C— (T NaOH/EtOH/H 2 0
• the resulting reaction product had the following physical parameters: Mass. Spec, m/e (m+) 252, 207, 179, 157, 105, 77, 51.
• This example describes a method of making the following wavelength-selective sensitizer, namely 4- [4' -carboxy phenyl]-3- buten-2-one:
• the wavelength-selective sensitizer is synthesized as summarized below:
• Example 28 The method of Example 28 was followed except that acetone (Fisher, Optima Grade) was added first, and then the carboxybenzaldehyde was added. More particularly, 32.2 (0.21 mole) of carboxybenzaldehyde was reacted with 12.2 g (0.21 mole) of acetone in the sodium hydroxide/ethanol/water mixture described in Example 28. Dilute HCl was added to bring the reaction mixture to neutral pH, yielding 37J g (91%) of a pale yellow powder which was used without further purification in the following examples.
• acetone Fisher, Optima Grade
• This example describes a method of covalently bonding the
• Example 29 The method of Example 29 was followed except that 5.0 g of the 4-[4'-carboxy phenyl]-3-buten-2-one was used. More particularly, 5.0 g (0.026 mole) of the 4-[4'-carboxy phenyl]-3- buten-2-one produced in Example 30 was reacted with 3.3 g (0.026 mole) of oxalyl chloride in anyhydrous DMF at about O'C. Next, approximately 7.1 g (0.005 mole) hydroxyethyl substituted cyclodextrin was added to the mixture (5:1 ratio) under the conditions described in Example 30 and was further processed as described therein, to produce 10.8 g of white powder. The NMR of the product showed both the aromatic protons of the 4-[4'- carboxy phenyl]-3-buten-2-one produced in Example 30 and the glucose protons of the cyclodextrin.
• Example 32 This example describes a method of covalently bonding the compound produced in Example 28 to a photoreactor, namely DARCUR 2959, as is summarized below:
• Example 30 To determine whether the 4-[4'-carboxy phenyl]-3-buten-2- one produced in Example 30 has the capabitity to stabiUze colorants, the following experiment was conducted. Test films were made up containing 90% carbowax 4600 and 10% of a 1 part Victoria Pure Blue BO (Aldrich) to 19 parts 4-[4' -carboxy phenyl]-3-buten-2-one. The mixture was melted on a hot plate, stined, then drawn down on metal plates (at approximately 60°C), using a #3 drawdown bar. A similar sample was made with only 1% Victoria Pure Blue BO in 99% carbowax.
• Victoria Pure Blue BO Aldrich
• the plates were exposed to a 1200 Watt Mercury medium pressure lamp for one hour, the lamp being about 2 feet from the plates. After one hour, the Victoria Pure Blue BO plate was essentially colorless, while the plate having the mixture of
• Example 34 A further experiment to determine the colorant stabiUzing capabiUty of the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 is as follows. The experiment used in Example 33 was repeated except that no carbowax was used. Instead, the materials were dissolved in acetonitrile and a film formed, allowed to dry, and then exposed to the 1200 Watt lamp. Again, after one hour, the dye (Victoria Pure Blue BO) was essentially colorless while the mixture containing the 4- [4 '-carboxy phenyl]- 3-buten-2-one was unchanged in color.
• Example 35 A further experiment to determine the colorant stabiUzing capabiUty of the 4-[4'-carboxy phenyl]-3-buten-2-one produced in Example 30 is as follows. The experiment used in Example 33 was repeated except that no carbowax was used. Instead, the materials were dissolved in acetonitrile and a film formed, allowed to dry, and then exposed to
• Example 34 A further experiment to determine the colorant stabiUzing capabiUty of the compounds produced in Examples 28, 29, 30 (4- [4'-carboxy phenyl]-3-buten-2-one), and 31 (4-[4' -carboxy phenyl]-3-buten-2-one/cyclodextrin) was as follows. The experiment used in Example 34 was repeated for all four compounds, separately. More particularly, five metal plates were prepared using the acetonitrile slurry method of Example 34, with the compositions as follows:
• compositions (2) through (5) contained one part Victoria Pure Blue BO per 20 parts of the compounds produced in the above examples. More particularly, 0J g of Victoria Pure Blue BO was mixed with approximately 2.0 g of one of the compounds produced in the above examples, in 10 ml of acetonitrile. The mixtures were drawn down using a #8 bar and allowed to air dry in a ventilation hood. All of the plates were simultaneously exposed to the 1200 Watt mercury lamp for one hour. Each plate was half covered with aluminum foil during exposure to the lamp to maintain a reference point with respect to fading of the colorant. After one hour under the lamp, mixture (1) had gone colorless, while mixtures (2) through (5) all remained unchanged.
• Example 36 Example 36
• Example 29 Another experiment to determine the colorant stabiUzing capabiUty of the compound produced in Example 29 was as follows. Briefly described, the compound of Example 29 was used with color inks removed from the color cartridges of a
• the ink was re ⁇ installed into the cartridges, which were installed into the ink jet printer, and color test pages were generated.
• the fortieth color test page was used in the present study. More particularly, the four cartridges were of BJI-201, and the four inks (cyan, magenta, black, and yellow) were prepared as follows:
• the cartridges were then refilled with the conesponding ink solutions (1) through (4) above. Forty pages were run off, and the fortieth page was exposed to a 1200 Watt medium pressure mercury lamp with a control sheet for nine hours.
• the control sheet is the fortieth color test page run off using the ink compositions that were in the original ink cartridges.
• Example 29 The results of this experiment were as follows. After three hours under the 1200 Watt lamp, the control was 40 to 50% bleached, while the inks containing the compound produced in Example 29 were unchanged. After nine hours, the control was 50 to 60% bleached while the inks containing the compound of Example 29 were only about 10 to 20 % bleached. Accordingly, the compound produced in Example 29 is capable of stabiUzing the dyes found in standard ink jet inks.
• test sheet The forty-eighth sheet (test sheet) was generated using the ink solutions (1) through (4) of Example 36 each containing about 10% of the compound of Example 29, and was then exposed to a
• Example 29 works well as a dye stabilizer to visible and ultraviolet radiation.
• This example describes a method of preparing the following wavelength-selective sensitizer:
• the wavelength-selective sensitizer is synthesized as summarized below:
• the reaction product has the following physical parameters: Mass. Spectrum m/e: 268 (m+), 245, 218, 193, 179, 151, 125, 73.
• reaction product has the following physical parameters: Mass. Spectrum m/e: 501, 484, 234, 193, 179, 125.
• This example describes a method of preparing the following wavelength-selective sensitizer:
• the wavelength-selective sensitizer is synthesized as summarized below:
• Example 38 Into a 250 ml round bottom flask fitted with a Dean and Stark adaptor is placed 10.0 g (0.037 mole) of the product produced in Example 38 (reaction A), 7.1 g (0.037 mole) of the wavelength-selective sensitizer produced in Example 30, 100 ml of dry benzene (Aldrich) and 0.3 g of p-toluene sulfonic acid (Aldrich). The reaction mixture is heated at reflux for eight hours. The solvent is then removed under reduced pressure to yield a Ught yellow solid. The solid is pumped under vacuum to yield 15.2 g (93%) of product.
• reaction A Into a 250 ml round bottom flask fitted with a Dean and Stark adaptor is placed 10.0 g (0.037 mole) of the product produced in Example 38 (reaction A), 7.1 g (0.037 mole) of the wavelength-selective sensitizer produced in Example 30, 100 ml of dry benzene (Al
• This example describes a method of covalently bonding the compound produced in Example 38 to cyclodextrin as is summarized below:
• Example 38 is treated with oxalyl chloride to produce the acid chloride of the compound produced in Example 38. (See Example 29)
• oxalyl chloride to produce the acid chloride of the compound produced in Example 38.
• Example 39 describes a method of covalently bonding the compound produced in Example 39 to cyclodextrin as is summarized below:
• Example 39 is treated with oxalyl chloride to form the acid chloride derivative of the compound produced in Example 39.
• oxalyl chloride Into a 250 ml round bottom flask fitted with a magnetic stir bar is placed 20.0 g (0.015 mole) of hydroxyethyl- substituted alpha- cyclodextrin (American Maize Company, Hammond, Indiana), 21.0 g (0.03 mole) of the acid chloride form of the wavelength- selective sensitizer produced in Example 39, 100 ml of dry dimethylsulfoxide (Aldrich), and 3 drops of triethylamine. The reaction mixture is stined for eight hours and then poured into 300 ml of acetone. The resultant white precipitate is filtered, and pumped under vacuum to yield 22J g of product.
• EXAMPLE 42 See Example 29
• Into a 250 ml round bottom flask fitted with a magnetic stir bar is placed 20.0 g (0.015 mole) of
• this example determines the colorant stabiUzing capabiUty of the compounds produced in Examples 29,
• Examples 29, 40 and 41 are used with color inks removed from the ink cartridges (5020036-Black and 5020036-Color) removed from an Epson Stylus Color Printer (Model EscP2) and from the ink removed from the ink cartridges (HP51640Y-yellow,
• HP51640C-cyan, HP51640M-magenta, and HP51640A-black) removed from an Hewlett-Packard Desk Jet Color Printer (Model 1200C). More particularly, the above ink cartridges are drilled and 5 ml of the ink therein is removed by syringe. Next, an amount of the compound from Examples 29, 40 or 41 is added to the inks from the above cartridges. More particularly, the compounds are measured in moles so that the number of molecules of each compound would be the same. The admixture is mixed for ten minutes, and then placed back into the ink cartridge from which it came, and the hole covered by tape.

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