US2915392A - Processes for producing photographic images and elements therefor - Google Patents

Processes for producing photographic images and elements therefor Download PDF

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Publication number
US2915392A
US2915392A US502737A US50273755A US2915392A US 2915392 A US2915392 A US 2915392A US 502737 A US502737 A US 502737A US 50273755 A US50273755 A US 50273755A US 2915392 A US2915392 A US 2915392A
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Prior art keywords
phthalocyanine
solution
acid
minutes
paper
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US502737A
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English (en)
Inventor
Pedersen Charles John
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to BE547020D priority Critical patent/BE547020A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US502737A priority patent/US2915392A/en
Priority to GB10498/56A priority patent/GB792438A/en
Priority to DEP16074A priority patent/DE1026170B/de
Priority to FR1149560D priority patent/FR1149560A/fr
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Publication of US2915392A publication Critical patent/US2915392A/en
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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
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G03C1/732—Leuco dyes

Definitions

  • i'T hisinvention relates to photography and more particularly to a process for producing photographicimages 1n the form of phthalocyanine pigments.
  • the invention also relates to photographic elements, e.g., -filr"ns, foils, plates or papers having at least one light-sensitive Stratum :comprising a solvent-soluble phthalocyanine intermediate complex.
  • An object of this invention is to provide a new process for producing photographic images in the form of an insoluble phthalocyanine pigment.
  • a more specific object is to provide a new process for producing photographic images in the form of an insoluble metal phthalo-
  • Another object is to provide such a ject is to provide new photographic elements which can be readily processed to yield insoluble phthalocyanine :pigment images. Still other objects will be apparent from ithe'following description of the invention.
  • photosensitive elements can be prepared by applying on the surface of a suitable support, e.g., a self-supporting film, foil, plate, paper or cloth,'or a laminated sheet made of one or more of such materials, an organic solvent solution of a solvent-soluble phthalocyanine intermediate complex (hereinafter "sometimes referred to as a'leuco-phthalocyanine) and a .light-activatable reducing carboxylic acid or salttaken .R and Rf, as indicated above, may be the same or different and generally should not contain more than 14 carbon atoms.
  • a suitable support e.g., a self-supporting film, foil, plate, paper or cloth,'or a laminated sheet made of one or more of such materials
  • an organic solvent solution of a solvent-soluble phthalocyanine intermediate complex hereinafter "sometimes referred to as a'leuco-phthalocyanine)
  • a .light-activatable reducing carboxylic acid or salttaken .R and Rf
  • C(OEDGOOQ RI! examples include glycolic, glyceric, lactic, 'u-hydroxyisobutyric, tartaric, citric, mandelic, benzylic, atrolactic, gluconic, saccharic, mannonic, rn'ucic and tal'omucic acids and their "sodium'and potassium and ammonium salts. -Mixtur'es of any two or more of such salts or acids can be used.
  • the surface of the support can be provided with a layer of a'wa'tenpermeable colloid, e.g., gelatin, polyvinyl alcohol, apdlyvinyl acetal, etc.
  • a'wa'tenpermeable colloid e.g., gelatin, polyvinyl alcohol, apdlyvinyl acetal, etc.
  • Such a layer will absorb or imbibe the solution of the complex and the reducing acid ice or sa'lt and, upon processing the-element, will serve as a carrier for the resulting photographic image.
  • the solvent solution of solvent-soluble phthalocyanine intermediate complex and the reducing acid or salt can be admixed with an aqueous solution or dispersion of a water-permeable colloid and the resulting dispersion 'coated on the surface of a support to form a photosensitive layer, which is dried.
  • the photosensitive element is exposed through 'a suitable continuous tone, halftone, or line negative to a source of actinic light and treated (a) with a solvent for the leuco-phthalocyanine or (b) with a solution of a strong acid containing water whereby a positive image in the form of a metal phthalocyanine pigment is produced.
  • the image-bearing element is then washed with water and dried.
  • solvent-soluble phthalocyanine intermediate complex which has been defined as a precursor, is believed to consist of 1.5 molecules of phthalocyanine, the half molecule being perpendicular in special relationship to the planar structure of the basic phthalocyanine molecule.
  • This complex or precursor has the empirical formula Q(C H.,N NH in which each of the six C H N vgroups represents one phthalonitrile unit, four of which are joined to Q which is two hydrogen atoms -or a central bivalent metal taken from the group consisting of Ca, Ni and Cu, the two extra phthalonitrile units and the extra NH group representing the precursor wing or divalent radical (C H N NH, said com- .plex being further characterized by yielding a metalfree, or a nickel or copper phthalocyanine, repectivel-y,
  • the metalphthalocyanine molecule generally consists of 4 phthalonitrile units joined together to a central bivalent metal atom
  • the metal phthalocyanine precursors embrace in their structure a molecule of a metal phthalocyanine plus two extra phthalonitrile units and an extra N'H group.
  • the complexes in question have a structure like that given in col. 2, lines 2 to 18 of Barnhart et a1.
  • U .8. Patent 2,772,284. This type of complex and processes of preparing various complexes are described in Barnhart and Skiles US. application Ser. No. 252,401
  • solvent-soluble phthalocyanine intermediate "complexes are obtained by reacting, in an alcoholic solvent, a phthalonitrile, ammonia and an anhydrou'ssalt of a metal of the group consisting of copper and 'nickel, 'said complexes being characterized by yielding upon reduction a metal phthalocyanine, a phthalo- 'nitrile and ammonia.
  • MPc designates the phthalocyanine compound of the group consisting of metal phthalocyanines and Co, Ni, Cr, Fe, Mg and Na.
  • MPc O-COR wherein MPc designates the molecule of a phthalocyanine compound of the group consisting of metal-phthalocyanines and metal-free phthalocyanines, while COR designates the acyl radical of an organic carboxylic acid having a total of not less than 2 and not more than 7 carbon atoms.
  • leuco-phthalocyanines solvent-soluble phthalocyanine intermediate complexes described above, for convenience, have been referred to as leuco-phthalocyanines, by analogy to the term employed in the vat dye field, it being remembered, however, that whereas a leuco vat compound is a reduction product of the dye, the leuco-phthalocyanines are in a sense a higher oxidation stage than the corresponding phthalocyanines, inasmuch as they yield the latter upon treatment with reducing agents.
  • leuco-phthalocyanines are essentially colorless as compared with the insoluble parent phthalocyanines (which have an intense reddish-blue to greenish-blue color).
  • the leuco-phthalocyanines are barely colored (producing in solution a yellow-brown, or reddish-brown or violet color) and they have no tinctorial value.
  • the leuco-phthalocyanines are readily soluble in common organic solvents, e.g., methanol, ethanol, chloroform, acetone, 2-ethoxy ethanol, ethylene glycol monomethyl, monoethyl or monobutyl ether, benzene, toluene and xylenes. They are insoluble in water.
  • the weak reducing action of the reducing acid or salt is augmented by the ultraviolet light to permit reduction of the leucophthalocyanine (precursor or propigment).
  • the reducing acid or salt is used in molecular excess. Good results can be obtained with 1 to 10 mols of the reducing acid or salt per mol of leuco-phthalocyanine.
  • the photosensitive solutions and photosensitive elements Prior to use, the photosensitive solutions and photosensitive elements should be kept under conditions of darkness and during use should not be exposed to any significant amount of actinic light.
  • the usual darkroom safelights can be used to prevent undesirable exposure.
  • the period of exposure will, of course, depend upon H the intensity of the light source, the particular leucophthalocyanine and the particular reducing agent. In general, a period of 0.1 to 10 minutes is required to give an image of satisfactory intensity.
  • Removal of the leuco-phthalocyanine from the unexposed areas and underexposed portions of the original photosensitive layer can be accomplished by the use of any solvent for the leuco-phthalocyanine.
  • acids are used in the bath for removing the unexposed areas, a variety of aqueous acid solutions can be used. Suitable such acids include hydrochloric, hydrofluoric, fluosilicic, sulfuric, organic sulfonic, phosphoric, partial esters of Example 1
  • Four solutions, A, B, C and D were prepared as follows:
  • a Whatman No. 1 filter paper was dipped in solution A and hung up to dry for 5 minutes. It was then dipped in solution B and dried for 15 minutes. Both treatments, A and B, were performed in a dark room at room temperature.
  • the dull yellow colored paper thus prepared was exposed to direct sunlight for 6 minutes under a contrasty photographic negative placed under a piece of window glass. The dull yellow hue changed to green on exposure to sunlight.
  • the exposed paper was immersed in solution C for 1 to 5 minutes, until the yellow colored portion disappeared.
  • the acid decomposed the unreacted propigment, leaving the blue copper phthalocyanine positive print on the paper.
  • the blue positive print was washed in solution D, then in water and dried.
  • Example 2 Solution E-l was prepared by dissolving 1 gram of the metal-free phthalocyanine precursor (or leuco calcium phthalocyanine) as obtained in Example 2 of Brooks U.S. Patent No. 2,681,348 in grams acetone.
  • Solution E-Z was prepared by dissolving 2.5 grams oxalic acid dihydrate in 300 cc. methanol.
  • Example 3 Solution F was prepared by dissolving 0.05 gram of nickel phthalocyanine propigment, as obtained from NiPc and tertiary butyl hypochlorite according to Example 3 of Pedersen US. Patent 2,662,895, and 0.05 gram of oxalic acid in 5 cc. methanol.
  • a sheet of filter paper was dipped in solution F and, after drying in the air for 5 minutes, was dipped in solution E-2 and then dried in the air for 15 minutes. The paper was then covered lamp located 11 inches from the paper.
  • Example 4 Solution G was prepared by dissolving 1 gram of dodecachloroleuco-calcium phthalocyanine. and 0.8 gram of oxalic acid in 100' grams'of acetone. Said leuco compound was prepared from phthalonitrile, ammonia and calcium oxide by the method of Example 1 of Brooks US. Patent 2,681,348, except that 99 parts of 4,5-dichlorophthalonitrile was used instead of the 64 parts of phthalonitrile in the Brooks example.
  • a sheet of filter paper was treated with the leuco phthalocyanine and oxalic acid solution G, dried, dipped into solution E-2 and again dried according to the procedure described in Example 3. After covering a portion of the treated paper it was exposed for 105 minutes under the 275 watt General Electric Reflector Sun sun- The print was l Example 5 and further processed in solutions C and D as in Example 1. The print obtained contained a positive image-which was blue in hue.
  • Example 6 Example 5 was repeated except that solution Iwas replaced by a solution of 2.5 grams of mandelic acid in 100 cc. water. The photo-reduction was even faster than that of Example 5. Similar results were obtained in both of these examples.
  • Example 7 Example 6 was repeated with mandelic acid and benzilic acid as photoreducers. The exposed and developed papers showed clear pictures, although the one prepared with benzilic acid had higher density and contrast than the one prepared with mandelic acid.
  • Example 8 Example 5 was repeated except that solution I was replaced by a solution of 2.5 grams of atrolactinic acid in 100 cc. water. The print obtained was similar to the one produced in Example 5.
  • Example 9 Under conditions of subdued light, a piece of Dacron fabric made from polyethylene terephthalate filament fibers was dipped into a saturated solution of sodium chromate in methanol, removed from the solution and dried. The fiber was then dipped into solution H, then dried and finally it was dipped into solution I of Example 5 and dried. The fiber was then partly covered with ob- 1y white.
  • Example 10 While operating in subdued light, a piece of cotton cloth was dipped into a solution of 1 gram of the copper phthalocyanine precursor of Example 5 dissolved in a mixture of 25 ml. of chloroform and 25 cc. of methanol. After air-drying, the cloth was impregnated with a 1% aqueous solution of ammonium acid oxalate. Excess moisture was pressed out and the cloth was placed between two pieces of glass, the top glass bearing a design drawn with a black crayon. Said assembly was exposed to direct sunlight for 5 minutes. The cloth was then removed, dipped into solution C of Example 1 for one-half minute, rinsed thoroughly in water, neutralized with dilute aqueous ammonia and dried. A blue design of copper phthalocyanine was obtained on the cloth.
  • Example 11 The solutions were prepared as follows:
  • Suitable sources in addition to sunlight include carbon arcs, mercury vapor arcs, fluorescent lamps with special ultraviolet light emitting phosphors, argon glow lamps and photographic flood (incandescent) lamps. These light sources emit light in the range 1800 to 7000 A. and emit an appreciable amount of radiation at wavelengths of 3000 to 4800 A. which are believed to be the most effective wavelengths. They can be used at various distances but generally are used at distances 7 to 20 inches from the surface of the layer to be exposed.
  • An advantage of the invention is that it provides new photosensitive elements whereby permanent colored images can be obtained. Another advantage is that it provides practical processes for producing photographic images in the form of phthalocyanine pigments, which images are exceptionally fast to light.
  • a further advantage. is that the invention is simple and practical and does not wherein M represents a metal of the group consisting of copper, nickel and calcium, and A and B together represent the bivalent grouping said compound being characterized by yielding the copper, nickel and metal-free phthalocyanine, respectively, phthalonitrile and ammonia upon being treated with re- :lucing agents, and (b) such a compound represented by the first formula of clause (a) wherein M represents a divalent atom taken from the group consisting of Cu, Fe, Co, Ni, Cr and two hydrogen atoms, and A and B stand for OCOR groups wherein CORis the acyl radical of an organic carboxylic acid of 2' to 7 carbon atoms, and (2) a reducing compound taken from the group consisting of oxalic
  • a processs which comprises exposing through an image-bearing transparency by means of light containing a substantial amount of radiations of wavelength between 3,000 and 5,000 A.
  • a layer containing (1) an ethanolsoluble phthalocyanine complex having the formula wherein M represents a divalent atom taken from the group consisting of Cu, Fe, Co, Ni, Cr and two hydrogen atoms, X is a halogen taken from the group consisting of chlorine and bromine and OR is an alkoxy radical, and (2) a reducing compound taken from the group consisting of oxalic acid and alpha-hydroxycarboxylic acids and their alkali metal and ammonium salts, removing said complex in the unexposed and underexposed areas of said layer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Photoreceptors In Electrophotography (AREA)
US502737A 1955-04-20 1955-04-20 Processes for producing photographic images and elements therefor Expired - Lifetime US2915392A (en)

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Application Number Priority Date Filing Date Title
BE547020D BE547020A (enrdf_load_html_response) 1955-04-20
US502737A US2915392A (en) 1955-04-20 1955-04-20 Processes for producing photographic images and elements therefor
GB10498/56A GB792438A (en) 1955-04-20 1956-04-05 Improvements in and relating to photosensitive elements and processes of preparing photographic images
DEP16074A DE1026170B (de) 1955-04-20 1956-04-16 Verfahren zur Herstellung von Farbstoffbildern und lichtempfindliches Material zur Durchfuehrung des Verfahrens
FR1149560D FR1149560A (fr) 1955-04-20 1956-04-19 Perfectionnements aux éléments photosensibles et procédés de préparation d'images photographiques

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3096340A (en) * 1959-10-15 1963-07-02 Basf Ag New phthalocyanine dyes
US3265500A (en) * 1963-03-19 1966-08-09 Modern Engraving And Machine C Making accurately registrable printing and embossing rolls
US3482972A (en) * 1967-12-28 1969-12-09 Polaroid Corp Substituted phthalocyanine dye developers and their use in multicolor diffusion transfer processes
US3957514A (en) * 1974-09-26 1976-05-18 Eastman Kodak Company Photographic element containing a photoreducible salt of an aryl hydroxy-carboxy anion and a tetrazolium cation and the use thereof
US4046569A (en) * 1975-04-14 1977-09-06 Eastman Kodak Company Physical development of pd(ii) photosensitive complexes with a leucophthalocyanine dye and a reducing agent therefor
US4788128A (en) * 1984-03-30 1988-11-29 Imperial Chemical Industries Plc Transfer printing medium with thermal transfer dye and infra-red radiation phthalocyanine absorber
US20050053864A1 (en) * 2003-09-05 2005-03-10 Rolf Dessauer Phthalocyanine precursors in infrared sensitive compositions
US11141483B2 (en) 2015-08-18 2021-10-12 Rakuten Medical, Inc. Methods for manufacturing phthalocyanine dye conjugates and stable conjugates
US11364297B2 (en) 2010-07-09 2022-06-21 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Photosensitizing antibody-fluorophore conjugates
US11781955B2 (en) 2014-08-08 2023-10-10 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Photo-controlled removal of targets in vitro and in vivo
US12383620B2 (en) 2018-06-01 2025-08-12 Rakuten Medical, Inc. Phthalocyanine dye conjugate compositions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3140948A (en) * 1961-10-18 1964-07-14 Horizons Inc Photography

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2193574A (en) * 1936-10-21 1940-03-12 Shell Dev Process for the production of colored images by photography
US2683643A (en) * 1949-08-25 1954-07-13 Bayer Ag Process of dyeing and printing and composition therefor
US2772284A (en) * 1951-10-20 1956-11-27 Du Pont Solvent-soluble, complex, phthalocyanine-yielding compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2193574A (en) * 1936-10-21 1940-03-12 Shell Dev Process for the production of colored images by photography
US2683643A (en) * 1949-08-25 1954-07-13 Bayer Ag Process of dyeing and printing and composition therefor
US2772284A (en) * 1951-10-20 1956-11-27 Du Pont Solvent-soluble, complex, phthalocyanine-yielding compounds

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3096340A (en) * 1959-10-15 1963-07-02 Basf Ag New phthalocyanine dyes
US3265500A (en) * 1963-03-19 1966-08-09 Modern Engraving And Machine C Making accurately registrable printing and embossing rolls
US3482972A (en) * 1967-12-28 1969-12-09 Polaroid Corp Substituted phthalocyanine dye developers and their use in multicolor diffusion transfer processes
US3957514A (en) * 1974-09-26 1976-05-18 Eastman Kodak Company Photographic element containing a photoreducible salt of an aryl hydroxy-carboxy anion and a tetrazolium cation and the use thereof
US4046569A (en) * 1975-04-14 1977-09-06 Eastman Kodak Company Physical development of pd(ii) photosensitive complexes with a leucophthalocyanine dye and a reducing agent therefor
US4788128A (en) * 1984-03-30 1988-11-29 Imperial Chemical Industries Plc Transfer printing medium with thermal transfer dye and infra-red radiation phthalocyanine absorber
US20050053864A1 (en) * 2003-09-05 2005-03-10 Rolf Dessauer Phthalocyanine precursors in infrared sensitive compositions
US11364297B2 (en) 2010-07-09 2022-06-21 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Photosensitizing antibody-fluorophore conjugates
US11364298B2 (en) 2010-07-09 2022-06-21 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Photosensitizing antibody-fluorophore conjugates
US12296013B2 (en) 2010-07-09 2025-05-13 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Photosensitizing antibody-fluorophore conjugates
US11781955B2 (en) 2014-08-08 2023-10-10 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Photo-controlled removal of targets in vitro and in vivo
US11141483B2 (en) 2015-08-18 2021-10-12 Rakuten Medical, Inc. Methods for manufacturing phthalocyanine dye conjugates and stable conjugates
US12383620B2 (en) 2018-06-01 2025-08-12 Rakuten Medical, Inc. Phthalocyanine dye conjugate compositions

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GB792438A (en) 1958-03-26
DE1026170B (de) 1958-03-13
FR1149560A (fr) 1957-12-27
BE547020A (enrdf_load_html_response)

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