US3847608A - Photodecorating sheet material with matched colored designs - Google Patents

Photodecorating sheet material with matched colored designs Download PDF

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Publication number
US3847608A
US3847608A US00278778A US27877872A US3847608A US 3847608 A US3847608 A US 3847608A US 00278778 A US00278778 A US 00278778A US 27877872 A US27877872 A US 27877872A US 3847608 A US3847608 A US 3847608A
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United States
Prior art keywords
sheet material
pieces
design
activating light
light
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US00278778A
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English (en)
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R Dessauer
J Ellefson
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EIDP Inc
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EI Du Pont de Nemours and Co
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US00278778A priority Critical patent/US3847608A/en
Priority to IT27354/73A priority patent/IT991479B/it
Priority to FR7328833A priority patent/FR2195942A5/fr
Priority to GB3738173A priority patent/GB1444756A/en
Priority to JP48088568A priority patent/JPS4952065A/ja
Priority to DE19732340226 priority patent/DE2340226A1/de
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Publication of US3847608A publication Critical patent/US3847608A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor

Definitions

  • US. Pat. No. 3,445,234 describes the use of photosensitive materials for image formation on various substrates including fabrics,,paper, plastic and polymeric films, glass, wood and metals.
  • US. Pat. No. 3,658,543 discloses the use of aerosol dispensed photosensitive materials for the decoration of metal, wood, cloth, pa-
  • Another object of this invention is to simplify the laying out and cutting of pieces of sheet material so as to reduce the skill and the time required.
  • a further object of this invention is to permit. rapid accessibility to popular fashion patterns by photographically placing matched recurrent designs on pieces of sheet material befitting their harmonious asing colored designs to such articles.
  • this invention is to an improvement in a process for decorating, with a colored design, material to be used in preparing an article from a multiplicity of pieces, by laying out on sheet material shapes of the pieces to be used in assembling the article and cutting out the pieces, the improvement comprising a. coating thematerial with a photosensitive composition capable of generating color subsequent to exposure to activating light;
  • This invention is also directed to a method for producing an assembled article of manufacture wherein contained pieces of sheet material bear a matched design, which method includes the steps above plus one or more steps of assembling the pieces into the article of manufacture.
  • This invention is also directed to articles of manufacture bearing a design matched from one component piece to another, or among a multiplicity of pieces, upon which matched designs have been placed by the above described process.
  • suitable systems are the well known diazo systems which require moist ammonia development; dry diazo systems; fast print-out dye imaging systems of Horizons, Incorporated based on the light sensitivity of halocarbons; leuco dye systems; and bleachout systems.
  • These and other non-silver systems suitable for use in this invention can be found in Jaromir Kosars book Light-Sensitive Systems, John Wiley & Sons, Inc. 1965, Chapters 6 and 8.
  • photosensitive processes such as the 3M Dry Silver process may be used.
  • Another suitable system employs the light sensitive solutions containing organic haloform compounds and a dye described in U.S. Pat. Nos. 3,305,361; 3,366,480; and 3,434,835.
  • Typical is the. heatdevelopable, heat-fixable photographic system developed by S. D. Warren Company, described in U.S. Pat. Nos. 3,394,391-; 3,410,687; and 3,413,121.
  • Particularly preferred as photosensitive coatings are the lightsensitive leuco dye compositions containing a photooxidant component as described in U.S. Pat. Nos. 3,445,234; 3,585,038; and 3,598,592.
  • Expedients that have been suggested for thedeactivation of imaging systems in the unexposed areas, thereby fixing the image include I. removing one or more of the imaging components, as by volatization; see U.S. Pat. No. 3,042,516 and U.S. Pat. No. 3,413,121;
  • compositions Normally for photodecoration use, such compositions contain one or more imaging components in a polymeric binder which can contain a plasticizer and which serves to thicken or adhere the composition to a sheet material.
  • the binder can also serve as a matrix so that the mixture can be cast, extruded or otherwise formed into an imageable coating.
  • Binder or matrix amounts vary from about 0.5 part to about 200 parts, preferably 3 to 15 parts, by weight per part of combined weight of the imaging component or components.
  • Binders containing special agents or fillers can be used in order to improve such properties as abrasion resistance or surface gloss of the final article in which the pieces of photodecorated sheet material are incorporated. Binders of this sort are currently in use in the leather industry. They are broadly classified as urethane clears and vinyl clears and are suitable for use as the binder component in photosensitive compositions suitable for this invention providing the binder ingredients do not interfere with image-forming or fixing.
  • Suitable commercially available leather binders or top finishes are General Tire and Rubber Co.s CV 270, CV 940 and CVX 3040; United Finish Co.s U-6366 Urethane Clear and KC-l0-925 Vinyl Clear; Fleming-Joffe Ltd.s U-5573 and 8925 CAB 10 percent SC; United Finish Co.s Permalon KC-10-662 Vinyl Clear, Permuthane U-5900 Clear Urethane, Permuthane U-5057 Clear Urethane, and Permuthane U-4849 Clear Urethane; and Du Pont Co.s 56060 Laminating Adhesive, 46960 Adhesive and C-1924-2 Non-yellowing Urethane.
  • imaging systems which permit convenient fixation of the colored design in situ, i.e., without chemical aftertreatment of the photogenerated image.
  • a deactivating agent is generated in situ by photochemical or thermal means.
  • Such systems can, with the use of a latent image, be stabilized or fixed, prior to color development, and can also be fixed simultaneously with photoactivation.
  • a preferred system of this type is disclosed in U.S. Pat. No. 3,390,996 wherein the composition has a suitable dual response to light. It consists essentially of (1) an organic color-generator, (2) a photo-oxidant, and (3) a redox couple which consists of (a) a reductant component capable of undergoing a photo-initiated redox reaction with the oxidant component, and (b) an oxidant component which, when photo-activated, undergoes with the reductant component a photoinitiated redox reaction which produces a reducing agent.
  • the organic color-generator and the photo-oxidant react to form a visible image in a design corresponding to the pattern of light.
  • the unexposed areas remain uncolored or have a light color characteristic of the unexposed coating.
  • the unexposed areas of the coating are colorstabilized or fixed by exposure to light of a second wavelength, normally in the visible range, which causes the redox couple to produce a reducing agent which reacts with the photo-oxidant, thereby blocking further reaction of the photo-oxidant with the color-generator.
  • a reductant portion of the redox couple which is l0-l00 percent triethanolamine tripropionate or triethanolamine triacetate (with the latter more pre ferred) and 90-0 percent 3,3',3"-nitrotripropionic acid, trimethyl ester.
  • Binders with cellulose acetate butyrate the preferred binder.
  • Plasticizers with alkyl arenesulfonamides preferably present and a mixture of N-ethyl-ptoluenesulfonamide and o-phenylphenol condensed with ethylene oxide, a particularly preferred mixture.
  • leucodye types suitable for the generation of a variety of colors according to this invention are described in US. Pat. Nos. 3,395,018, 3,390,997 and 3,445,234. Mixtures of leuco dyes may be used herein.
  • a system is used that is photo-imageable and heat-fixable in situ.
  • a preferred system of this type is described in US. Pat. No. 3,390,995 in which a composition capable of forming color by light activation similar to those in the aforementioned photo-fixable systems contains, instead of photosensitive redox couple, an organic compound capable of forming a reducing agent by heat.
  • the practice of this invention requires making up a coating formulation to be applied to the sheet material.
  • solvents for the photo-imaging components, binders, plasticizers and such other components as are present are volatile at ordinary pressures.
  • Suitable solvents are amides such as N,Ndimethylformamide and N,N- dimethylacetamide; alcohols such as methanol, ethanol, l-propanol, 2-propanol, butanol and ethylene glycol; esters such as methyl acetate and ethyl acetate; aromatics such as benzene, o-dichlorobenzene and toluene; ketones such as acetone, methyl ethyl ketone and 3-pentanone; aliphatic halocarbons such as methylene 6 chloride, chloroform, l,l,2-trichloroethane, l,l,2,2- tetrachloroethane and l,l,2-trichloroethylene; miscellaneous solvents such as dimethylsulfoxide, pyridine, tetrahydrofuran, dioxane, dicyanocyclobutane and lmethyl-2-oxo-hex
  • compositions so produced are dry to the touch and stable on storage at room temperature. Moisture of the air is absorbed by many of the compositions, particularly those comprising an acid salt of an aminotriarylmethane or cellulosic substrates, and serves as a suitable solvent.
  • a suitable solvent system for cellulose acetate butyrate polymers useful as a coating solvent consist of:
  • Other useful multicomponent solvent systems include ternary mixtures consisting of -90 percent of a methanol/2-propanol mixture (lO/l ratio) and 10-20 percent acetone; or 42.5 percent acetone, 18.5 percent ethyl acetate and 39 percent toluene; and a 6- component system containing 15 percent acetone, 17.7 percent ethyl acetate, 15.2 percent ethanol, 4.9 percent butanol, 23 percent toluene and 24.3 percent hexane.
  • ternary mixtures consisting of -90 percent of a methanol/2-propanol mixture (lO/l ratio) and 10-20 percent acetone; or 42.5 percent acetone, 18.5 percent ethyl acetate and 39 percent toluene; and a 6- component system containing 15 percent acetone, 17.7 percent ethyl acetate, 15.2 percent ethanol, 4.9 percent butanol, 23 percent toluene and 24.3 percent
  • a suitable composition is coated upon sheet material either before or after it is cut. Coating is normally done before cutting for convenience. The term cutting" is employed in its broad sense.
  • suitable sheet material are leather; poromerics, plastics, polymeric materials such as vinyl polymers and copolymers, polyolefms, polypropylene,
  • the sheet material must be an inert substrate for the photosensitive materials and preferably should not dissolve the active components but absorb them and retain sufficient solvent to provide a medium for rapid image formation upon irradiation.
  • the solution In applying a solution to leather, fabrics or to the surface of rigid substrates such as glass, wood or metals, the solution can be sprayed, brushed, applied by a roller or an immersion coater, flowed over the surface, picked up by immersion or spread by other means. Complete coverage of the substrate can be attained or a pattern of the light-sensitive composition can be applied to the substrate.
  • concentrations of solution and pick-up by the leather are controlled so as to provide from about 0.01 milligram to about 5.0 milligrams per square inch of substrate of the triarylmethane leuco dye and equivalent amount of the hexaarylbiimidazole.
  • Images of greater and lesser intensity of color can be produced by the application of greater and lesser amounts of the leuco dye to the substrate.
  • typical devices for continuously laying down wet films as nip-fed three-roll reverse-roll coating heads, gravure coaters, trailing blade coaters, knife overroll, 4-roll pan fed and Mayer bar coating heads.
  • the wet thickness is adjusted such that the dry thickness after solvent removal is in the desired range, about 0.05l.5 mils usually.
  • the substrates bearing a solution of the compositions utilized herein can be dried simply at room temperature. They can also be dried under vacuum at room temperature, by forced air solvent evaporation, or at elevated temperatures, as by radiant heating. With the preferred compositions of U.S. Pat. No. 3,390,994 the upper temperature limit is important in combination with exposure time. A short exposure to heat of 90C. may not be detectably harmful, while several hours exposure to this heat may reduce the light sensitivity of the composition.
  • the coated sheet material is normally stored in the dark at room temperature and is periodically tested to determine its retention of photosensitivity. Exposure to a 275 watt sun lamp preferably yields a contrast of at least 0.4 optical density units with less than 20 percent variation for periods from 1 to 10 days.
  • Means to generate matching designs on pieces of the sheet material can include those normally employed to produce patterns of light such as stencils, templates and photographic negatives or positives that are used in contact with a photosensitive surface.
  • Other means can be used at a distance from the photosensitive surface, for example, a photographic system capable of projecting one or more images at a time such as the systems described in U.S. Pat. Nos. 3,212,396; 3,387,532; 3,391,601; 3,401,594 and 3,661,461.
  • the desired designs in the form of modulated patterns of light can be generated from live models by reflection optics, by transmission of light through photographic negatives and the like using enlargement or reduction in size or by a combination of images from different sources.
  • Light modulating means are prepared such that there is generally a means for each piece to be decorated, and each means corresponds exactly to the design to be placed on each shaped piece cut from-the material.
  • a means can be used more than once, however.
  • a particular photographic negative can be reused in contact registration or projection registration with more than one piece of sheet material whenever decorations are to be duplicated or applied as mirror images.
  • a particular negative can be used with different pieces or with the same piece of sheet material provided a portion of its photosensitive surface is protected from exposure to activating light during prior use of the negative, thereby reserving the protected area for subsequent exposure.
  • a negative is larger than pieces to be decorated, selected portions of it can be moved into proper registration with successive pieces to photodecorate each of them with matching designs.
  • a single negative, in fact, bearing a recurrent design is sufficient to decorate many pieces with matching recurrent designs. According to the process of this invention, however, there is always a proper means to place in proper registration with the proper piece of photosensitized sheet material according to a predetermined pattern.
  • Positioning of the modulated pattern of light on the surface of a piece of sheet material coated with a photosensitive composition is normally accomplished by moving either the light modulating means or the piece relative to each other until reaching a desired registration of one upon the other.
  • Projection systems can usually be redirected for example by internal adjustment of optical parts such as mirrors or lenses.
  • By similar positioning of a second modulated pattern of light that bears a matched relationship to the first-mentioned pattern upon the surface of a second piece of sheet material there can be produced matched designs on each of the two pieces.
  • the third, fourth and other pieces, when part of the system to be assembled, are handled in the same way.
  • Matching of recurrent designs on different pieces can, however, become a matter of artistry, when a particular element of a recurrent design on one piece is to be placed in a novel but harmonious relationship to an element or elements of a recurrent design on another piece of sheet material in the finished article of manufacture.
  • a repeated continuous tone image of a person may be harmoniously associated with repeated background or logo information on an adjacent piece of sheet material.
  • Other types of matching can be devised by those skilled in the designing arts.
  • Film negatives to be used in contact with pieces of sheet material are preferred means for generating matching designs. They are readily obtained by photographing the various parts of a three-dimensional mock-up model of the finished article of manufacture desired, either in its assembled form or as disassembled pieces.
  • model pieces need not be photographed directly if molds are required for postdecorative finishing operations on each piece.
  • embossing may be needed to provide smooth or grained leather finish, stitching detail, pinking, perforations, overlap or folded or bound edges on a pair of shoes.
  • the prepared molds for embossing can be individually photographed to obtain full-size negatives which show just the contour shapes of the various pieces of each shoe size.
  • these negatives are hand-painted to form simple matching designs using ordinary touch-up paints for film negatives.
  • the unpainted negatives can also be overlayed with a second negative bearing an overall recurrent design.
  • the two negatives together in proper registration can comprise the means to generate sought after matching designs of color by the process of this invention.
  • Laying out the desired contour shapes of the pieces on the sheet material normally proceeds after working up a three-dimensional model of each size required.
  • the model or pattern is disassembled into a multiplicity of pieces of the same or different shapes and areas and the contour shape of each piece of each size is laid out on a substrate in a close packing arrangement with minimum waste of substrate surface, usually first on paper ratherthan on the final sheet material.
  • the contour shapes are placed as close to one another as practicable. This normally results in adjacent contours touching or nearly touching each other.
  • Pieces can be positioned and oriented relative to each other to take advantage of similarities in negative and positive curvatures of different pieces. They can be laid out transversely, in the sheet direction, or on a bias to save space, fitting small pieces between big pieces wherever possible. Pieces of different sizes can be intermingled. This results in minimum waste determined primarily by the contours or shapes of the collective component parts that are desired.
  • Cutting dies can be prepared according to the layout for cutting the pieces for each size.
  • the coated sheet material is die-cut as laid out on paper with minimum waste. Multiple breadths or thicknesses of sheet material can be cut together where practicable to save time or effort. Where the thickness of material permits, other means of cutting, even scissors, can be used.
  • photodecoration is achieved by placing the cut pieces in registration with the corresponding selected means of generating matching patterns. Registration can be carried out either before or after the cut pieces are assembled into a finished article of manufacture.
  • Means for generating matched designs such as photographic negatives can be prepared that are sufficiently flexible to assume the same proportional curvature as the pieces to be decorated after such pieces are assembled into a three-dimensional article. Normally, however, pieces are photodecorated singly or in groups while flat, prior to final assembly.
  • a preferred procedure is to place each cut piece in turn in registration with the proper film negative and expose through the negative with activating light of a suitable wave-length for sufficient time to develop the desired color. Color stabilization is normally carried out as soon as possible.
  • Such further coatings can also contain coloring agents, such as pigments or soluble dyes, to impart additional overall color and modify the color already generated during photodecoration, thereby producing novel two-color or multi-color designs. Additional images and colorful embellishments to the basic matched design can also be added by recoating with the same or different photosensitive compositions and re-exposing to activating light through suitable light-modulating means to produce novel color and design effects.
  • coloring agents such as pigments or soluble dyes
  • the term with minimum waste means ar ranging the piece shapes to be cut out as close to one another as practicable.
  • the process of this invention normally results in contiguous contours, adjacent and touching, that are positioned and oriented relative to each other to take advantage of similarities in negative and positive curvatures.
  • the process of this invention also results in reduced material loss because no designs need be present on the sheet material at the time it is cut.
  • the process of this invention also avoids the necessity of having to space or orient related pieces according to a predetermined pattern. For example, left and right shoe uppers need not be spaced a repeat length apart and oriented in the direction of the belly lines of a reptile pattern.
  • minimum waste implies freedom to lay out pieces transversely or at any inclination to the sheet direction, and frequently results in uninterrupted cutting lines from piece-to-piece. Defects in the sheet material may interfere, such things as hard and soft spots in leather, fat wrinkles, evenholes, but the minimum waste is primarily determined by contours or shapes of the collective component parts that are desired.
  • matched means designs which bear spatial relationship to each other by virtue of their positions or locations on individual pieces of sheet material. If the two pieces have identical contours or have contours that are mirror images, matched designs are observed to be in the same or mirror-opposite positions on each piece. If the two pieces are related by function so as to be adjacent in a finished article rather than by symmetry of use, the two pieces are placed in the same relative positions that they will assume in the finished article. Their designs are matched if a design feature such as the repeat length of a recurring design on either piece is continued onto the adjacent piece. Not knowing their intended function in a finished article merely calls for more elaborate testing of two given test pieces.
  • a photosensitive coating composition is prepared from the following ingredients:
  • each piece used in the models is then transferred and laid out with minimum waste of space on paper, ignoring the surface decoration already applied to each piece by the pattern maker. cutting dies are prepared for each piece in each size.
  • the coated sheet material is tested satisfactorily for photosensitivity and is then die-cut according to the layout on paper. The pieces are then ready for embossing.
  • the desired recurrent designs are hand-painted on the film negatives using high density touch-up paints.
  • the decoration applied by the pattern maker to the model is used as a guide to achieve matching of the designs on the negatives of those pieces that are to be ad- 12 jacent or located symmetrically on the right and left shoes of each size.
  • the cut pieces are then photodecorated by placing the selected film negative in proper registration with the coated surface of a selected piece, and exposing through the negative with blue fluorescent ultraviolet light for 15 seconds.
  • the deep blue design thus produced on each photodecorated piece is photofixed by exposure to an intense Xenon visible light source for one to two minutes.
  • Decoration is completed by embossing the shoe pieces with heat between pressure plates in a Compo-Fit Model D machine.
  • the shoes are fabricated and finished by applying an overall clear top finish to impart gloss and scuff resistance.
  • An ultraviolet screening agent is incorporated into the top finish to stabilize the color of the recurrent design for the life of the shoe.
  • the process of this invention can be advantageously employed in a variety of applications. It is suitable as stated above for use with a variety of substrates and can be employed to impart for example an advertising logo for uniforms, or for a continuous tone photographic design. Particularly suitable uses are the application of matched designs such as that of a reptile skin, to leather, vinyl or poromeric substrate for use in manufacturing shoes and gloves, and for the application of designs, such as wood grain characteristics, to wood or metal.
  • a process of claim 1 wherein the sheet material is wood, leather, vinyl or a poromeric material.
  • a process of claim 12 wherein the photosensitive composition is one which generates color directly on exposure to activating light.
  • a process of claim 12 wherein the fixing process is chemical fixation.
  • a process of claim 12 wherein the fixing process is heat fixation.
  • a process of claim 12 wherein the sheet material is wood, leather, vinyl or a poromeric material.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
US00278778A 1972-08-08 1972-08-08 Photodecorating sheet material with matched colored designs Expired - Lifetime US3847608A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US00278778A US3847608A (en) 1972-08-08 1972-08-08 Photodecorating sheet material with matched colored designs
IT27354/73A IT991479B (it) 1972-08-08 1973-07-31 Processo di fotodecorazione
FR7328833A FR2195942A5 (OSRAM) 1972-08-08 1973-08-07
GB3738173A GB1444756A (en) 1972-08-08 1973-08-07 Process for photodecoration of sheet material
JP48088568A JPS4952065A (OSRAM) 1972-08-08 1973-08-08
DE19732340226 DE2340226A1 (de) 1972-08-08 1973-08-08 Photodekorierungsverfahren

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US00278778A US3847608A (en) 1972-08-08 1972-08-08 Photodecorating sheet material with matched colored designs

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US3847608A true US3847608A (en) 1974-11-12

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US (1) US3847608A (OSRAM)
JP (1) JPS4952065A (OSRAM)
DE (1) DE2340226A1 (OSRAM)
FR (1) FR2195942A5 (OSRAM)
GB (1) GB1444756A (OSRAM)
IT (1) IT991479B (OSRAM)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050053870A1 (en) * 2003-09-05 2005-03-10 Willard Randall Orson Leuco dye-containing coating compositions
US20060141228A1 (en) * 2004-12-23 2006-06-29 Rearick Brian K Color harmonization coatings for articles of manufacture comprising different substrate materials
US20070269737A1 (en) * 2006-05-16 2007-11-22 Bhatt Jayprakash C Color forming compositions and associated methods
US20100151208A1 (en) * 2008-12-14 2010-06-17 Chien-Feng Lin Sensing Clothing

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5321048A (en) * 1976-08-10 1978-02-27 Nippon Electric Co Constant current density plating device

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2009586A (en) * 1932-06-11 1935-07-30 Kenway Corp Process of screen shading in photoengraving
US2041853A (en) * 1934-10-02 1936-05-26 Mollo Eugene Method of decorating large surfaces by photography
US2084792A (en) * 1933-06-17 1937-06-22 Maria Vincent De Method and means for reproducing and printing wood grains and the like
US2491386A (en) * 1945-03-16 1949-12-13 George Eisler Photographic method of imprinting a design on globes
US2541178A (en) * 1945-08-18 1951-02-13 Gen Aniline & Film Corp Photographic process for dyeing of textile materials
US3445234A (en) * 1962-10-31 1969-05-20 Du Pont Leuco dye/hexaarylbiimidazole imageforming composition
US3698899A (en) * 1969-08-27 1972-10-17 Begy Soc Europ De Bas Sans Cou Method of manufacture of printed articles,in particular printed knitted articles

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2009586A (en) * 1932-06-11 1935-07-30 Kenway Corp Process of screen shading in photoengraving
US2084792A (en) * 1933-06-17 1937-06-22 Maria Vincent De Method and means for reproducing and printing wood grains and the like
US2041853A (en) * 1934-10-02 1936-05-26 Mollo Eugene Method of decorating large surfaces by photography
US2491386A (en) * 1945-03-16 1949-12-13 George Eisler Photographic method of imprinting a design on globes
US2541178A (en) * 1945-08-18 1951-02-13 Gen Aniline & Film Corp Photographic process for dyeing of textile materials
US3445234A (en) * 1962-10-31 1969-05-20 Du Pont Leuco dye/hexaarylbiimidazole imageforming composition
US3698899A (en) * 1969-08-27 1972-10-17 Begy Soc Europ De Bas Sans Cou Method of manufacture of printed articles,in particular printed knitted articles

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050053870A1 (en) * 2003-09-05 2005-03-10 Willard Randall Orson Leuco dye-containing coating compositions
US7462443B2 (en) 2003-09-05 2008-12-09 Hewlett-Packard Development Company, L.P. Leuco dye-containing coating compositions
US20060141228A1 (en) * 2004-12-23 2006-06-29 Rearick Brian K Color harmonization coatings for articles of manufacture comprising different substrate materials
US7906199B2 (en) * 2004-12-23 2011-03-15 Ppg Industries Ohio, Inc. Color harmonization coatings for articles of manufacture comprising different substrate materials
US20070269737A1 (en) * 2006-05-16 2007-11-22 Bhatt Jayprakash C Color forming compositions and associated methods
US8283100B2 (en) 2006-05-16 2012-10-09 Hewlett-Packard Development Company, L.P. Color forming compositions and associated methods
US20100151208A1 (en) * 2008-12-14 2010-06-17 Chien-Feng Lin Sensing Clothing

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JPS4952065A (OSRAM) 1974-05-21
DE2340226A1 (de) 1974-02-21
GB1444756A (en) 1976-08-04
IT991479B (it) 1975-07-30
FR2195942A5 (OSRAM) 1974-03-08

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