US3801319A - Imaging method utilizing chemical reactivities of photoexcited states of aromatic hydroxy compounds - Google Patents

Imaging method utilizing chemical reactivities of photoexcited states of aromatic hydroxy compounds Download PDF

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Publication number
US3801319A
US3801319A US00265053A US3801319DA US3801319A US 3801319 A US3801319 A US 3801319A US 00265053 A US00265053 A US 00265053A US 3801319D A US3801319D A US 3801319DA US 3801319 A US3801319 A US 3801319A
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United States
Prior art keywords
solution
aromatic
hydroxy
process according
compound
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Expired - Lifetime
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US00265053A
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English (en)
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F Saeva
D Sargent
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Xerox Corp
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Xerox Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/725—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing inorganic compounds

Definitions

  • ABSTRACT An imaging process employing the excited state reactivities of aromatic hydroxy materials to produce a visible image.
  • This invention relates, in general, to a novel imaging process which utilizes the increased chemical reactivity of hydroxy aromatic compounds when they are subjected to photoexcitation and, more specifically, this invention relates to a novel imaging process in which hydroxy aromatic compounds are photoexcited in the presence of an inorganic or organic nitrite.
  • a substrate is coated with a composition comprising two components, a diazonium compound which is sensitive to light, and the other component is an azo coupler.
  • the substrate is exposed to ultraviolet rays through the master.
  • the rays destroy or otherwise inactivate the print forming components in all areas of coated material which are not protected by the lines of design of the original.
  • the problem of diazotype materials is that they are notoriously difficult to store for long periods prior to use.
  • the phenomenon known as pre-coupling invariably occurs even in the absence of a developing agent such as, ammonia, etc.
  • the diazonium compound and the azo dye coupling component react slowly to form an azo dye, it is less useful for subsequent copying purposes.
  • diazo-type materials have almost invariably given images of poor light fastness.
  • Another object of this invention is to provide a simple, convenient imaging system.
  • Still another object of this invention is to provide photoprinting materials which have good storage stability prior to use.
  • a still further object of this invention is to accomplish the above objects through the utilization of the enhanced chemical activity of photoexcited aromatic compounds in the presence of inorganic or organic ni- Other objects will be apparent to those skilled in the photoprinting art from the following description of the invention.
  • the present invention comprises the discovery that an hydroxy aromatic compound in the presence of inorganic or aliphatic nitrites and in the absence of acid can be made to undergo a photoinduced coupling reaction when light is absorbed to produce a colored reaction product in an imaging configuration.
  • nitrous acid ordinarily required in the conventional method of producing a coupling reaction is now being generated via the photoexcitation of a hydroxy aromatic compound.
  • the photoexcited aromatic specie has an increased acidity causing the formation of nitrous acid from nitrites as required for the coupling reaction.
  • Photoprinting materials employing the process of this invention have several advantages over previously utilized materials.
  • the materials utilizing the process of this invention are quite stable in dark storage prior to use.
  • diazo-type materials a chemically energetic specie, the diazonium compound,'is always present in the copying material as made.
  • no chemically energetic specie is present until the material is exposed," i.e., until the components are subjected to photoexcitation.
  • very light fastness images can be obtained.
  • no obnoxious developing agents such as, ammonia, is required in the processing of the materials of this invention.
  • the process of this invention may be utilized to prepare, negative print-out materials.
  • the process of this invention may be compared to the blue printing process. But, in contrast to blue printing materials, no cyanide-containing light sensitive materials need be employed.
  • the process of this invention provides means of producing images of an almost unlimited range of colors. It shares with blue printing the possible incorporation of very simple fixing methods, such as washing the photoprinting material with water.
  • Photoprinting materials utilizing the process of this invention require no complex or expensive machines for their exposure, development or fixing. This is in marked contrast to certain currently used photoprinting and copying methods. No equipment employing high voltages, powdered toners, developing fluids, fusing stations, etc., is required.
  • the process of this invention yields well defined images. No thermal transfer steps are required. Thermal transfer almost invariably causes loss of definition and blurry images.
  • the process of this invention utilizes relatively low cost materials. No silver salts or other expensive components are required.
  • the process according to this invention comprises forming a mixture of a hydroxy aromatic compound, e.g., 2-naphthol, inorganic or aliphatic nitrite, e.g., sodium nitrite, and optionally a polymeric matrix such as, polyvinyl pyrrolidone, dissolved in aqueous alcohol solvent to form a colorless solution.
  • a hydroxy aromatic compound e.g., 2-naphthol
  • inorganic or aliphatic nitrite e.g., sodium nitrite
  • a polymeric matrix such as, polyvinyl pyrrolidone
  • the most probable mechanism of the reaction is that nitrous acid reacts with the ground state hydroxy aromatic compound as opposed to the excited species providing the colored nitroso derivative. This is based on the fact that the concentration of the excited state species is very much smaller than that of the ground state hydroxy aromatic material and that the probabilities of molecular collision are enhanced for the ground state material.
  • a metallic salt capable of reacting with the nitrosated naphthol such as a ferrous salt
  • a darker colored image e.g., blue-green
  • Any suitable metallic salt may be used. Typical examples are the metal salts of copper, iron, cobalt and zirconium.
  • Any suitable hydroxy aromatic compound may be employed. Typical examples are hydroxy substituted: benzene, naphthalene, anthracene, phenanthracene, naphthacene, biphenyl, durene, acenaphthene, pyrene, chrysene, fluorene, fluoranthene and indene. Furthermore, the hydroxy aromatic compounds may carry other substituents such as, alkyl groups, halo, nitro, cyano, alkoxy, thio, carboxylic or sulfonic acids and salts thereof, esters and aldehydes.
  • an amino hydroxy aromatic compound has been found to undergo diazotization and self-coupling after being exposed imagewise to give a colored image.
  • 8-amino-l-naphthol-3,6-disulfonic acid disodium salt is mixed in an aqueous solution of sodium nitrite which is coated onto paper, air dried and then exposed imagewise with a suitable light source; nitrous acid is again produced in the system causing a diazotization and self-coupling reaction which results in the formation of a colored image.
  • Any suitable hydroxy aromatic compound also containing a primary amino function may be employed.
  • Typical examples of the amino substituted aromatic hydroxy compounds such as, benzene, naphthalene, anthracene, phenanthracene, naphthacene, biphenyl, durene, acenaphthene, pyrene, chrysene, fluorene, fluroanthene, and indene.
  • the amino aromatic hydroxy compound may be further substituted with derivatives such as, alkyl groups, halo, nitro, cyano, alkoxy, thio, acids, esters and aldehydes.
  • coating aids may be added to the coating solutions.
  • polymer thickening or sizing materials such as, polyvinyl pyrrolidone, polyvinyl alcohol, gelatin, crosslinking agents such as, starch anthranilate, modified starch, etc., or the like may be advantageously employed in order to obtain rapid print out, scuff resistant, optically attractive coatings.
  • colloidal materials such as, fillers or pigments, may be added. Among these are finely divided silica, titanium dioxide, clays and the like.
  • Any suitable substrate may be used. Typical examples of substrates may consist of paper, either coated or uncoated; plastic sheeting, either transparent or opaque; metallic sheets, foils, laminates, etc.
  • the coating process employed may include roller coating, knife coating, nib coating, dip coating, spraying, brushing, etc.
  • the active materials are usually coated from solution or suspension in a liquid rather than from the dry powdered state, it is usually necessary to dry the photoprint material so prepared prior to cutting and packaging. It is possible, of course, to apply the requisite combination of materials as dry particulate materials to suitable substrates.
  • the substrate is exposed to light in a negative working system and in the areas where light strikes coloration is effected.
  • Light causes the hydroxy aromatic compound in its excited state to produce nitrous acid from an inorganic or aliphatic nitrite which causes the coupling reaction to occur.
  • the wavelength of light usable in this invention must be absorbed by the hydroxy aromatic compound.
  • Sodium nitrite (1.0 gm) is then dis solved in 1.0 cc of water.
  • the two solutions are then mixed in the dark and applied to a sheet of plain white paper with a brush.
  • the water solvent is allowed to evaporate at room temperature by passing dry air over the coated sheets.
  • the dried paper, positioned 1 inch from an ultraviolet (100 watt) light source is then exposed in an imagewise fashion for 30 seconds and the blue image fixed by washing away any unreacted sodium nitrite with water.
  • EXAMPLE IV Equal molar quantities of 2-naphthol and isoamyl nitrite (0.001 mole) are dissolved in a 50/50 ethanolwater mixture (5 cc) along with 2.0 gm of polyvinylpyrrolidone being careful not to expose the solution to ultraviolet irradiation. The solution is applied to a sheet.
  • the solvent allowed to dry and the coating exposed to ultraviolet irradiation in an imagewise fashion for 30 seconds using a 100 watt (3,000A) light source. Fixing of the yellow image is accomplished by at least one of the reactants by sublimation.
  • Starch anthranilate (1) is prepared by heating potato starch (6.0 gm), sodium carbonate (0.012 gm) and isatoic anhydride (0.012 gm) in 9 ml of water for 4 hours at C. Plain white paper is then coated with the starch (l) and the water solvent allowed to evaporate. The coated paper is then treated with a water solution of 2-naphthol-6-sulfonic acid sodium salt and sodium nitrite (0.1 gm of each in 5 cc of water) under red light conditions. The water is allowed to dry before being contact exposed to ultraviolet light in an imagewise fashion watt ultraviolet light source [3,000A]) for 60 seconds. The resulting orange image is fixed by washing away unreacted naphthol and nitrite salts.
  • An imaging process which comprises exposing in an imagewise manner a composition comprising an aromatic hydroxy compound and an inorganic or aliphatic nitrite salt in aqueous solution to light of a suitable wavelength corresponding to the ultraviolet absorption pattern of the hydroxy aromatic compound, said process being further described in that the composition is droxy compound is substituted with an amino radical.
  • An imaging process employing the excited state reactivities of an aromatic hydroxy material comprising the following steps:
  • a process for producing a colored image comprising:
  • a forming a solution by dissolving a hydroxy aromatic compound, a material selected from the group consisting of an inorganic or aliphatic nitrite or mixtures thereof, and a resinous polymer in a solvent, said solution being characterized in that it contains no ingredient which produces acid in the absence of light of a suitable wavelength corresponding to the ultraviolet absorption spectrum of the aromatic hydroxy compound;

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US00265053A 1972-06-21 1972-06-21 Imaging method utilizing chemical reactivities of photoexcited states of aromatic hydroxy compounds Expired - Lifetime US3801319A (en)

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US26505372A 1972-06-21 1972-06-21

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US3801319A true US3801319A (en) 1974-04-02

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US (1) US3801319A (enrdf_load_stackoverflow)
JP (1) JPS4944734A (enrdf_load_stackoverflow)
CA (1) CA1000549A (enrdf_load_stackoverflow)
GB (1) GB1429501A (enrdf_load_stackoverflow)
NL (1) NL7308674A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1981001757A1 (en) * 1979-12-07 1981-06-25 Minnesota Mining & Mfg Color imaging system
WO1981001756A1 (en) * 1979-12-07 1981-06-25 Minnesota Mining & Mfg Diazonium imaging system
US4336323A (en) * 1979-12-07 1982-06-22 Minnesota Mining And Manufacturing Company Decolorizable imaging system
US4370401A (en) * 1979-12-07 1983-01-25 Minnesota Mining And Manufacturing Company Light sensitive, thermally developable imaging system
US4373020A (en) * 1979-12-07 1983-02-08 Minnesota Mining And Manufacturing Company Decolorizable imaging system

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6027124Y2 (ja) * 1976-09-07 1985-08-16 旭硝子株式会社 浮動構造物
JPS60100409U (ja) * 1983-12-14 1985-07-09 積水化成品工業株式会社 浮桟橋
JPH0322993U (enrdf_load_stackoverflow) * 1989-07-11 1991-03-11
JPH04185591A (ja) * 1990-11-20 1992-07-02 Fudo Constr Co Ltd 浮体連結構造
JPH04333704A (ja) * 1991-05-10 1992-11-20 Sajima Mariina Kk 浮桟橋の連結構造

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1981001757A1 (en) * 1979-12-07 1981-06-25 Minnesota Mining & Mfg Color imaging system
WO1981001756A1 (en) * 1979-12-07 1981-06-25 Minnesota Mining & Mfg Diazonium imaging system
US4336323A (en) * 1979-12-07 1982-06-22 Minnesota Mining And Manufacturing Company Decolorizable imaging system
US4370401A (en) * 1979-12-07 1983-01-25 Minnesota Mining And Manufacturing Company Light sensitive, thermally developable imaging system
US4373020A (en) * 1979-12-07 1983-02-08 Minnesota Mining And Manufacturing Company Decolorizable imaging system

Also Published As

Publication number Publication date
NL7308674A (enrdf_load_stackoverflow) 1973-10-25
GB1429501A (en) 1976-03-24
CA1000549A (en) 1976-11-30
JPS4944734A (enrdf_load_stackoverflow) 1974-04-27

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