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Publication numberUS3154416 A
Publication typeGrant
Publication dateOct 27, 1964
Filing dateMar 30, 1961
Priority dateMar 30, 1961
Also published asDE1221559B
Publication numberUS 3154416 A, US 3154416A, US-A-3154416, US3154416 A, US3154416A
InventorsGeorge Fidelman J
Original AssigneeHorizons Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photographic process
US 3154416 A
Images(1)
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Description  (OCR text may contain errors)

' Oct. 27, 1964 FIG. I.

J G. FlDELMAN 3,154,416

Pl-IOTOGRAPHIC PROCESS Filed March so, 1961 Blue @Light Green & Light Red & Lighl n lllllllllllllllllll ll IIIWWIIIII ransm lg Blue Absorbs Blue Bleached Absorbs Greeh Bleached (Film Or Paper) EFFECT OF LIGHT OF THE PRIMARY COLORS FIG. 2;

While &

Cyan Dye C Mugenla Dye 8 Yellow Dye A Subslrcle Tronsmils Blue Eighl l Absorb; Re

r reen Absorbs lue Absor s l TransmilsGreen Transmlls Red EFFECT OF PROJECTING WHITE LIGHT THROUGH FILMAFTER EXPOSURE OF FIG. I.

Yellow lnrerlayer Magenta lnlerlayer Film Base FIG. 3.

Yellow lnferlay Cyan Film

Magenta FIG. 4.

INVENTOR J George Fidelman ATTORNEY United States Patent 3,154,416 PHQTQGRAEHEC PRGQESS .l George Fidelnzan, Fort Lauderdale, Fla, assignor to Horizons incorporated, @levelaud, Ohio, a corporation of New Jersey Filed Mar. 30, 1961, Ser. No. 99,413 6 Claims. (Cl. 96-73) This invention relates to a non-silver direct-positive dye-bleach photographic process wherein both full-color transparencies and full-color prints on a white opaque substrate are produced with images which are sharp and distinct, and to the materials from which the color transparencies and color prints are produced.

In patent application Serial No. 50,696 (fled August 19, 1960, jointly by me) which issued as United States lPatent 3,104,973 on September 24, 1963, and in patent application Serial No. 47,849 (filed August 5, 1960, by Sprague, Fichter and Hamilton) which issued as United States Patent 3,102,027 on August 27, 1963, of which I have knowledge, photosystemsare described comprising photolytically sensitive halogen-containing organic compounds and cyanine and merocyanine dyes which bleach out on exposure to light of a suitable wavelength.

in attempting the practice of the invention described in the aforesaid patent applications on a semi-commercial or production basis it was found that in many instances the photosensitivity and color separation obtainable with one batch of film was not reproducibly obtainable with succeeding materials prepared and processed in the identical manner from identical source materials.

The principal object of the present invention is to provide means whereby images which are intense, sharp cutting, and in brilliant colors, with good color separation, yieldin a very high-quality color rendition are reproducibly obtained and which eliminate the loss in sensitivity and color-separation occasionally experienced in directpositive non-silver dye-bleach photographic systems.

One object of this invention is to provide a non-silver direct-positive dye-bleach photographic system capable of producing full color photographic prints.

Still another object of the invention is to provide a relatively simple photosystem wherein full-color direct positive prints are produced solely by the action of the exposing light without any chemical development.

Still another object of the invention is to provide a process wherein the colored image produced may be stabilized and fixed by a simple heat treatment.

A still further object of this invention is to provide a process for producing positive transparencies in full color, either for projection or for color prints when coated on a white opaque substrate.

A still further object of the invention is to provide a simple photosystem for the production of office copy.

These and other objects are achieved by utilizing the present photographic system in any of the several alternative modes of practicing the invention described below and illustrated in the accompanying drawings in which:

FIGURE 1 diagrammatically illustrates the efiect of exposure of a tripack to light of various colors;

FIGURE 2 schematically shows the resulting direct positive obtained after the exposure of FIGURE. 1; and

FIGURES 3 and 4 each show a modified tripack which may be used in place of that shown in FIGURE 1.

As described in the above noted applications, a direct positive full color print may be obtained byutilization of an integral tripack of three sensitive layers. comprises a sensitive coating containing a dye of the proper color mixed with a suitableactivating agent and dispersed in a convenient film-former. Any of the layers may also include extraneous materials added for specific purposes, e.g. to alter the speed of the system. When Each layer 3, l 54,4 l h Patented Get. 27, 1964 "ice the sensitive coating is exposed image-wise to light of the Wavelength absorbed by the dye, the dye is bleached in the area struck by the light, with the result that a directpositive image remains in the layer. By proper selection of the dyes an accurate color rendition is obtained by a subtractive process.

For example, a green sensitive layer may be obtained with the process, using a magenta dye, which is, of course, green absorbing, transmitting blue and red freely. When such a film is exposed in a camera, for example, to light reflected from colored objects, the action of green light on this layer is to bleach the magenta dye. It is not, of course, aifected by blue or red light; light of these wavelengths is not absorbed by the sensitive material. What is obtained in this layer, therefore, is a minus-green record which corresponds, for example, with the magenta printer in conventional color printing processes.

Similarly, a blue-sensitive layer, comprising a yellow dye, is bleached on exposure to blue light, giving a minusblue record which corresponds to the yellow printer in conventional printing processes.

Finally, a red-sensitive layer, containing a cyan dye, is bleached by red light, giving a minus-red image corresponding to the cyan printer in color printing processes.

When these three sensitive layers are superimposed in an integral tripack it will be seen that, since all three of the dyes transmit freely in the areas in which they do not absorb, light of a particular color will aifect only a single layer. The result of the subtractive reflection of light from a white, opaque substrate on such developed layers is the reflection of light of the same color as that originally exposing the material.

This may be further illustrated by reference to FIG- URE 1.

The three-layer integral tripack, depicted in FIGURE 1 consists of three light-sensitive layers superimposed, one on top of the other. The coating nearest the substrate is a blue-sensitive yellow dye labelled A, the coating on top of this is a green-sensitive magenta dye labelled B, and the topmost coating is a red-sensitive cyan dye labelled C.

The effect of light of the primary colors, blue, green and red, on such a coating is illustrated by the diagram under the areas marked Blue Light, Green Light, and Red Light. Since the red-sensitive layer, C, and the green-sensitive layer, B, transmit blue light freely, no efiect is obtained with blue light until layer A is reached; whereupon the yellow dye is bleached in this area. Therefore, in the area of the film struck by blue light, there remain the cyan layer and the magenta layer. After fixing, which may be accomplished by short heating, if such a developed film is viewed under White light,

the cyan layer will absorb red light; the magenta layer will absorb green light; while both the cyan layer and magenta layer will transmit blue freely, as shown in Fl URE 2.

In this way, the result is reflection or transmission of only blue in the area which was originally struck by blue light; in other words, a direct positive is obtained. Similarly, when green light strikes the three-layer coating, the cyan dye will transmit the green freely while the magenta dye will absorb the green light and be bleached. Since the cyan dye and the yellow dye are still intact and the former will absorb red while the latter will absorb blue, the net reflection or transmission from the bleached layer will be green; again, a direct positive. Finally, in the area struck by red light, the cyan dye will absorb this radiation and be bleached. The greenand blue-sensitive layers will be unaffected. The magenta dye will absorb the green light, the yellow dye will absorb the blue light, and the net reflection from the combined three layers will be red.

As indicated above, the three-layer integral tripack depicted in FIGURE 1 comprises three light-sensitive layers superimposed on one another on a suitable base material. To insure that the sensitivity of the tripack is not diminished or even entirely lost by undesirable reactions, which may occur when materials from more than one layer of the tripack are permitted to intermingle even to a limited extent, I have devised modes of preparation of the tripack which preserve the photosensitivity and which yield images with good color separation.

In one embodiment of the invention intermingling of the dye-bleach materials of the tripack shown in FIGURE 1 is avoided by selecting solvents, vehicles and carriers so that successive layers are formulated from materials which do not dissolve or penetrate into the solid substrate to which they are applied. In a second embodiment shown in FIGURES 3 and 4 intermingling of the dye-bleach materials is avoided by interposing a barrier layer between successive photosensitive layers.

The following is a typical coating procedure for the preparation of a color-sensitized film and is intended to be illustrative of a generally applicable procedure:

(1) A film of a suitable substrate, eg a mil sheet of clear or white cellulose acetate film, is flooded on one side for three seconds with a cyan dye solution; the excess solution is then poured off.

(2) The coated film is dried for about one minute in a stream of air at 50 C., e.g. by suspending the wet coated film in a suitable drying oven.

(3) Next, a barrier layer is formed on the cyan layer by coating a plastic layer onto the cyan layer from a suitable coating solution.

(4) The plastic layer is dried by baking for two. minutes at 50 C., as in Step 2.

(5) Then a magenta dye solution is coated on top of the plastic layer after drying.

(6) A barrier layer is applied to the magenta layer by coating a plastic layer onto the magenta layer from a suitable coating solution.

(7) The plastic layer is dried by baking as before.

(8) A yellow dye solution is then coated on the second plastic barrier layer.

(9) The coated film is dried in a stream of air at 50 C. for about one minute.

In the preferred method outlined above all three photosensitive layers are located on one side of the film, this being a necessity on white opaque substrates. 7 When a transparent base is utilized, it is equally feasible to put cyan and yellow on one side and magenta on the other, or cyan and magenta on one side and yellow on the other, using a suitable plastic interlayer between each pair of adjacent dye layers.

The essential and necessary compositional limitation which must be observed is that, in laying down any layer, care must be exercised that the liquid coating formulation be free from any material which acts as a solvent for the dye in the layer on which the liquid is being deposited.

As in the aforesaid applications, in the bleachout-dye layer the essential constituents are (1) an organic halogen-containing compound such as those represented by the general formula RC-X wherein R is a monovalent radical selected from the group consisting of hydrogen, chlorine, bromine, iodine, alkyl, substituted alkyl, aryl and substituted aryl, and each X is selected from the group consisting of Cl, Br and I; and (2) a dye which bleachs when exposed to light of a suitable wavelength in the presence of the compound (1).

Although I do not wish to be bound by any specific theory, it is possible that a complex may be formed between the halogen-containing compound and the bleachout dye which may require less energy to raise it to an excited state to permit the desired photolytic reaction to take place than when such complexes do not form.

The dyes of the present invention (when a suitable organic halogen compound is present) are bleached when 4 exposed to light, giving as described above a direct positive image. Furthermore, the bleachout process of this invention requires no solvent extraction for fixation to render the dye image permanent; a short heating period only is needed to destroy any sensitivity remaining in the system after exposure to visible light.

Organic halogen-containing compounds which are suitable in the photographic systems of this invention include carbon tetrabrornide, pentabromoethane, carbon tetrachloride, carbon tetraioclide, iodoform, bromoform, chloroform, hexachlorethane, bromotrichloromethane, benzotribromide, and similarly polyhalogenated hydrocarbon compounds in which at least three halogen atoms are attached to a single carbon atom.

The bleachout dyes useful in the photosystems of this invention are polymethine dyes such as the cyanines, carbocyanines, merocyanines, styryl dyes and their higher vinylene homologs.

Other plastic supports may be used in place of the 10 mil cellulose acetate, which is preferred. For example plastic coated paper, Mylar (a polyester), polyvinylchloride and a variety of other plastics could be used, provided the bleachout dye solution is suitably formulated.

Example 1 The coating procedure for producing a color-sensitized film was as follows:

A sheet of lO-mil clear cellulose acetate film was flooded on one side for three seconds with a solution of 37 mg. of the cyan dye, l',3-diethylthia-4'-carbocyanine iodide, and 10 mg. of carbon tetrabromide in 7 cc. of a mixture of equal parts by volume of methanol, acetone and dimethylformamide, then excess solution was poured off. The dyed wet film was dried for one minute in a stream of air at 50 C.

Next, a plastic interlayer solution, consisting of a 10% solution of ethylcellulose (Hercules Type N, 4.5 c.p.s.) in toluene was poured over the first coating and, after 3 seconds contact, the excess solution was poured off and the coated strip was dried (baked) for two minutes in a stream of air at 50 C.

Then a solution of 12 mg. of the magenta dye, 3-ethyl- 5- 1-ethyl-2 1H) -pyridylidene) -ethylidene] rhodanine, and 0.3 g. carbon tetrabromide in 7 cc. of toluene was coated on the plastic interlayer deposited as related above, excess solution being poured 01f after contact of 3 seconds.

Finally, on the reverse (and uncoated) side of the film, a solution of 15 mg. of the yellow dye, 5-[3-ethyl- 2(3H) benzoxazolylidene) ethylidene] 3 phenyl-2- phenylimino-4-thiazolidone, and one gram of CBr in 7 cc. of a mixture of equal parts by volume of methanol, acetone and dimethylformamide, was coated, the excess being poured off, and the film being dried for a third time in a stream of air at 50 C. for one minute.

The resulting film was exposed under a multicolored subject using an RFL No. 2 photoflood lamp at a distance of 10 inches as light source. The transparency was accurately duplicated as a direct positive on exposure for 10 minutes.

In place of the ethylcellulose plastic used for the separating layer, other suitable plastics may be substituted,

e.g. methylcellulose, polystyrene, and the like.

Example 2 seconds contact with excess solution, the film was hung up to dry for two minutes in a stream of air at 50 C.

Then a solution of mg. of the yellow dye, 5-[(3- ethyl-2(3H)-benzoxazolylidene)-ethylidene] 3 phenyl Z-phenylimino-4-thiazolidone, and one gram of pentabromoethane in 7 cc. of toluene was applied in a similar manner to the same side of the film, and dried as above.

Next, another layer of ethylcellulose was applied as in the second step above.

Finally, a cold solution of 15 mg. of the magenta dye, 3 ethyl 5 [(l-methyl-Z(lI-l)-pyridylidene) ethylidene]-rhodanine, and 0.2 g. of pentabromoethane in 7 cc. toluene was applied to the same side of the film, dried in a stream of cool air until dry to the touch and then oven-dried as above. The yellow dye was not affected by cold toluene in the short time involved, although it dissolved quite readily in hot toluene, and remained in solution on cooling to room temperature.

In place of the ethylcellulose plastic used for the separating layer, other suitable plastics may be substituted, e.g. methylcellulose, polystyrene, and the like.

Example 3 The following coatings were applied successively to one side of a sheet of l0-mil white-pigmented cellulose acetate, in the order mentioned:

The sheet was first flooded for three seconds with a solution or" 7 mg. of the cyan dye, 1,3-diethylthia-4- carbocyanine iodide, and mg. of carbon tetrabromide in 18 cc. of a mixture of equal parts of acetone, ethanol, and dimethylformamide. The sheet was dried in a stream of air at 50 C. for one minute.

Next, a solution of 8 mg. of the yellow dye, 5-[ (Ii-ethyl- 2(3H) benzoxazolylidene) ethylidene] 3 phenyl-Z- phenylimino-4-thiazolidone, 4 g. of carbon tetrabromide and 5 cc. of a 2% ethyl cellulose in toluene solution in 14 cc. of toluene (heated solution to dissolve dye, then cooled to room temperature) Was coated and similarly dried.

Finally, a solution of 8 mg. of the magenta dye, 3-ethyl 5 [(1-ethyl-2(ll-l) pyridylidene)-ethylidene]- rhodanine, 5 cc. of 2% ethyl cellulose-toluene solution, and 0.3 g. carbon tetrabromide was applied on top of the previous two coatings and dried in a stream of air at room temperature.

The sensitized sheets thus obtained were used to make contact prints, in color, from color transparencies and also to make projection-enlargement copies, in color, of a number or" -min. color-transparency subjects.

In place of the ethylcellulose plastic used for the separating layer, other suitable plastics may be substituted, e.g. methylcellulose, polystyrene, and the like.

The products obtained in each of the above examples had a sharper color separation than those usually obtained in practicing the inventions in the above noted patent applications.

Having now described my invention in accordance with the patent statutes, 1 claim:

1. An article comprising a support member and at least two photosensitive layers supported thereon as follows:

a binder-free first photosensitive layer on said substrate consisting essentially of (1) an organic halogen containing compound selected from the group consisting of alkyl and aralkyl compounds in which at least three halogen atoms are attached to a single carbon atom, said halogens being selected from the group consisting of Cl, Br and I, and (2) a bleachable polymethine dye selected from the group consisting of cyanines, carbocyanines, merocyanines, styryl dyes and their high vinylene homologs;

a photoinsensitive layer of clear plastic coated on said first layer, said plastic having been deposited on said first layer from a solution of said plastic formulated from materials which do not dissolve or pene trate into the first layer when the solution was applied thereto;

and a second photosensitive layer on said photoinsensithe layer, said second photosensitive layer consisting essentially of an organic halogen containing compound selected from the group consisting of alkyl and aralkyl compounds in which at least three halogen atoms are attached to a single carbon atom, said halogens being selected from the group consisting of Cl, Br and l, and a bleachable polymethine dye selected from the group consisting of cyanines, carbocyanines, merocyanines, styryl dyes and their higher vinylene homologs and sensitive to light of Wavelengths different from those to which the dye in said first layer is sensitive, the organic halogen containing compounds in said first and second layers being present in an amount suflicient to accelerate the bleaching out of said dyes when exposed to radiation absorbed by said dyes.

2. The article of claim 1 including in addition a second photoinsensitive layer as a film of clear plastic deposited on said second photosensitive layer from a solution formulated of materials which do not dissolve or penetrate into said second photosensitive layer when the solution is applied thereto and a binder-free third photosensitive layer consisting essentially of organic halogen compound selected from the group consisting of alkyl and aralkyl compounds in which at least three halogen atoms are attached to a single carbon atom, said halogens being selected from the group consisting of Cl, Br

and I, and bleachable polymethine dye selected from the group consisting of cyanines, carbocyanines, merocyanines, styryl dyes and their higher vinylene homologs and wherein said dye is sensitive to light of wave-lengths difierent from those to which the dyes in said first and second layers are sensitive.

3. The article of claim 1 including in addition a binder-free third photosensitive layer on the uncoated face of said support member; said third photosensitive layer consisting essentially of organic halogen compound selected from the group consisting of alkyl and aralkyl compounds in which at least three halogen atoms are attached to a single carbon atom, said halogens being selected from the group consisting of Cl, Br and I, and bleachable polymethine dye selected from the group consisting of cyanines, carbocyanines, merocyanines, styryl dyes and their higher vinylene homologs and wherein said dye is sensitive to light of wave-lengths diiierent from those to which the dyes in said first and second layers are sensitive.

4. The article of claim 1 wherein the support is a transparent plastic material.

5. The article of claim 1 wherein the support is a White opaque material.

6. A method of preparing a photosensitive element comprising a support member and at least two photosensitive layers supported thereon comprising: depositing a binder-free first layer on said substrate from a solution containing a bleach-out dye selected from the group consisting of cyanines, carbocyanines, merocyanines, styryl dyes and their higher vinylene homologs and an organic halogen-containing compound selected from the group consisting of alkyl and aralltyl compounds in which at least three halogen atoms are attached to a single carbon atom, said halogens being selected from the group consisting of Cl, Br and I; removing the solvent from said layer by drying; depositing a photoinsensitive layer comprising a film of clear plastic laid down on said dried layer by applying a solution of said plastic formulated from materials which do not dissolve or penetrate said layer to which the clear plastic layer is applied; and depositing a binder-free second photosensitive layer on said photoinsensitive layer from a solution containing a leach-out dye selected from the group consisting of cyanines, carbocyanines, merocyanines, styryl dyes and their higher vinylene homologs and wherein the solvent for said dye being a non-solvent for the dye in the first photosensitive layer, and an organic halogen-containing compound selected from the group consisting of alkyl and aralkyl compounds in which at least three halogen atoms are attached to a sinlge carbon atom, said halogens being selected from the group consisting of Cl, Br and I and removing the solvent from said second photosensitive layer by drying.

References Cited in the file of this patent UNITED STATES PATENTS Szczepanik May 22, Christensen Nov. 25, Rust et a1. Sept. 15, Seymour Dec. 18, Rogers May 9, Haas et al. July 10, Sprague et a1 Sept. 24,

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US821200 *Aug 16, 1902May 22, 1906Jan SzczepanikProcess for the production of photographs in natural colors.
US1517049 *Sep 6, 1919Nov 25, 1924Herman Christensen JensFilm and method for the production of colored pictures
US2054390 *Aug 29, 1934Sep 15, 1936 Photographic bleachjng-out layers
US2391198 *May 27, 1943Dec 18, 1945Eastman Kodak CoSensitive interlayers in multilayer film
US2983606 *Jul 14, 1958May 9, 1961Polaroid CorpProcesses and products for forming photographic images in color
US3043692 *Dec 17, 1958Jul 10, 1962Polaroid CorpPhotographic products and processes
US3104973 *Aug 5, 1960Sep 24, 1963Horizons IncPhotographic bleaching out of cyanine dyes
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3305361 *Dec 28, 1962Feb 21, 1967Gen ElectricInformation recording
US3485630 *Jan 21, 1966Dec 23, 1969Gen ElectricMethod of etching a metal layer coated with a layer containing a photolytic halogen liberator and a bleachable organic dye
US5616443 *Jun 1, 1995Apr 1, 1997Kimberly-Clark CorporationToner for electrography
US5643356 *Jun 5, 1995Jul 1, 1997Kimberly-Clark CorporationUnsaturated ketone sensitizer bonded to radiation transorber with color, molecular includent and vehicles
US5643701 *Jun 1, 1995Jul 1, 1997Kimberly-Clark CorporationElectrophotgraphic process utilizing mutable colored composition
US5645964 *Jun 5, 1995Jul 8, 1997Kimberly-Clark CorporationStabilizers
US5681380 *Dec 19, 1996Oct 28, 1997Kimberly-Clark Worldwide, Inc.Ink for ink jet printers
US5683843 *Feb 22, 1995Nov 4, 1997Kimberly-Clark CorporationSolid colored composition mutable by ultraviolet radiation
US5685754 *May 19, 1995Nov 11, 1997Kimberly-Clark CorporationMethod of generating a reactive species and polymer coating applications therefor
US5686503 *Jan 22, 1996Nov 11, 1997Kimberly-Clark CorporationPhotoinitiators
US5700850 *Jun 5, 1995Dec 23, 1997Kimberly-Clark WorldwidePhotostability; colorant and radiation absorber
US5709955 *Oct 16, 1996Jan 20, 1998Kimberly-Clark CorporationLamination, photoreactor with wavelength-specific sensitizer bonded to photoinitiator
US5721287 *Jun 5, 1995Feb 24, 1998Kimberly-Clark Worldwide, Inc.Radiating in presence of transorber
US5733693 *Jan 2, 1997Mar 31, 1998Kimberly-Clark Worldwide, Inc.Method for improving the readability of data processing forms
US5739175 *Jun 5, 1995Apr 14, 1998Kimberly-Clark Worldwide, Inc.Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5747550 *Jun 5, 1995May 5, 1998Kimberly-Clark Worldwide, Inc.Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5773182 *Jun 5, 1995Jun 30, 1998Kimberly-Clark Worldwide, Inc.Method of light stabilizing a colorant
US5782963 *Nov 27, 1996Jul 21, 1998Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US5786132 *May 29, 1996Jul 28, 1998Kimberly-Clark CorporationPre-dyes, mutable dye compositions, and methods of developing a color
US5798015 *Jun 5, 1995Aug 25, 1998Kimberly-Clark Worldwide, Inc.Exposing a photoreactor composition to radiation in which the photoreactor composition comprises a wavelength-specific sensitizer associated with a reactive-species generating photoinitiator
US5811199 *Jun 5, 1995Sep 22, 1998Kimberly-Clark Worldwide, Inc.Exposing photoreactor to radiation; photoreactor comprises wavelength specific sensitizer
US5837429 *Jun 5, 1996Nov 17, 1998Kimberly-Clark WorldwideDye covalently bound to radiation transorber that is colorless and will form color when irradiated
US5849411 *Jun 5, 1995Dec 15, 1998Kimberly-Clark Worldwide, Inc.Polymer film, nonwoven web and fibers containing a photoreactor composition
US5855655 *Apr 15, 1997Jan 5, 1999Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US5858586 *May 16, 1997Jan 12, 1999Kimberly-Clark CorporationDigital information recording media and method of using same
US5865471 *Dec 21, 1994Feb 2, 1999Kimberly-Clark Worldwide, Inc.For use with photo-sensing apparatus
US5885337 *Oct 31, 1997Mar 23, 1999Nohr; Ronald SinclairComprising a reducing agent and/or a molecular inclusion compound for inhibiting discoloration when exposed to sunlight or artificial light
US5891229 *Jul 31, 1997Apr 6, 1999Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US5908495 *Sep 24, 1997Jun 1, 1999Nohr; Ronald SinclairColorant; a modified photoreactor; and a liquid vehicle wherein the colorant is rendered light-stable in the mixture
US6008268 *Jan 22, 1998Dec 28, 1999Kimberly-Clark Worldwide, Inc.A photoreactor compound comprising a wavelength-specific sensitizer moiety covalently bonded to two reactive species-generating photoinitiator moieties; photopolymerization; photocuring; low-energy lamps
US6017471 *Apr 23, 1997Jan 25, 2000Kimberly-Clark Worldwide, Inc.Colorants and colorant modifiers
US6017661 *Oct 8, 1997Jan 25, 2000Kimberly-Clark CorporationSubstrate surface attached to merchandise and labeled with indicia comprising a mutable colorant, molecular includant and a transorber which irreversibly decolors colorant upon exposure to ultraviolet radiation
US6033465 *Apr 5, 1996Mar 7, 2000Kimberly-Clark Worldwide, Inc.Colorants and colorant modifiers
US6054256 *Dec 3, 1998Apr 25, 2000Kimberly-Clark Worldwide, Inc.Colorimetric analysis; detecting dosage radiation
US6060200 *Feb 3, 1998May 9, 2000Kimberly-Clark Worldwide, Inc.Photo-erasable data processing forms and methods
US6060223 *Dec 3, 1998May 9, 2000Kimberly-Clark Worldwide, Inc.Plastic article for colored printing and method for printing on a colored plastic article
US6063551 *Nov 16, 1998May 16, 2000Kimberly-Clark Worldwide, Inc.A leuco dye associated with a radiation transorber where the radiation transorber comprises a wavelength-selective sensitizer covalently bonded to a reactive species-generating photoreactor; phthaloylglycine; 4-(4-hydroxyphenyl)but-2-one
US6066439 *Dec 3, 1998May 23, 2000Kimberly-Clark Worldwide, Inc.Instrument for photoerasable marking
US6071979 *Dec 26, 1997Jun 6, 2000Kimberly-Clark Worldwide, Inc.To generate photoinitiators for polymerizing unsaturated monomers and curing an unsaturated oligomer/monomer mixture
US6090236 *Dec 31, 1997Jul 18, 2000Kimberly-Clark Worldwide, Inc.Photocuring, articles made by photocuring, and compositions for use in photocuring
US6099628 *Jan 23, 1997Aug 8, 2000Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US6120949 *Dec 3, 1998Sep 19, 2000Kimberly-Clark Worldwide, Inc.A temporary markings comprising a colorant, a mutable colorant and an ultraviolet radiation transorber, when irradiating with ultraviolet radiation, and changing the colorant to colorless
US6127073 *Dec 3, 1998Oct 3, 2000Kimberly-Clark Worldwide, Inc.Method for concealing information and document for securely communicating concealed information
US6168654Apr 6, 1999Jan 2, 2001Kimberly-Clark Worldwide, Inc.Porphine imparts light-stability to the colorant so that the colorant does not fade
US6168655Dec 15, 1998Jan 2, 2001Kimberly-Clark Worldwide, Inc.Phenol derivatives
US6211383Feb 10, 1998Apr 3, 2001Kimberly-Clark Worldwide, Inc.Reacting the compound in a non-aqueous non-polar solvent in the presence of a transition metal salt such that the hydroxy group is dehydrated
US6228157Jul 20, 1999May 8, 2001Ronald S. NohrInk jet ink compositions
US6235095Jun 1, 1999May 22, 2001Ronald Sinclair NohrInk for inkjet printers
US6242057Apr 29, 1998Jun 5, 2001Kimberly-Clark Worldwide, Inc.Photoreactor composition and applications therefor
US6265458Sep 28, 1999Jul 24, 2001Kimberly-Clark Worldwide, Inc.Photoinitiators and applications therefor
US6277897Jun 3, 1999Aug 21, 2001Kimberly-Clark Worldwide, Inc.Photoinitiators and applications therefor
US6294698Apr 16, 1999Sep 25, 2001Kimberly-Clark Worldwide, Inc.Photoinitiators and applications therefor
US6331056Feb 24, 2000Dec 18, 2001Kimberly-Clark Worldwide, Inc.Printing apparatus and applications therefor
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US6368395May 12, 2000Apr 9, 2002Kimberly-Clark Worldwide, Inc.Colorfastness; photostability
US6368396Jan 19, 2000Apr 9, 2002Kimberly-Clark Worldwide, Inc.Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6486227Jun 19, 2001Nov 26, 2002Kimberly-Clark Worldwide, Inc.Zinc-complex photoinitiators and applications therefor
US6503559Jun 3, 1999Jan 7, 2003Kimberly-Clark Worldwide, Inc.Neonanoplasts and microemulsion technology for inks and ink jet printing
US6524379Jan 12, 2001Feb 25, 2003Kimberly-Clark Worldwide, Inc.Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
Classifications
U.S. Classification430/503, 430/559
International ClassificationG03C7/02, G03C1/675
Cooperative ClassificationG03C1/675, G03C7/02
European ClassificationG03C7/02, G03C1/675