US3716366A - Bis-pyridinium salt and a phenyl boranate as photosensitive combination - Google Patents

Bis-pyridinium salt and a phenyl boranate as photosensitive combination Download PDF

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Publication number
US3716366A
US3716366A US00111764A US3716366DA US3716366A US 3716366 A US3716366 A US 3716366A US 00111764 A US00111764 A US 00111764A US 3716366D A US3716366D A US 3716366DA US 3716366 A US3716366 A US 3716366A
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Prior art keywords
bis
layer
light
phenyl
compounds
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US00111764A
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English (en)
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O Riester
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/735—Organo-metallic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/163—Radiation-chromic compound

Definitions

  • the invention relates to light-sensitive materials which contain, as light-sensitive substances, bispyridiniumcompounds which are converted into dark colored substances by the action of light.
  • These reactions include. e.g. the formation of monomethine dyes by the photolysis of trihaiome'thyl compounds in UV light in the presence of aromatic or heterocyclic, compounds which by virtue .of their constitution haveCH ring-members which are highly reactive in condensation or diazo coupling reactions.
  • these layers are either initially light-sensitive or the reactive components for the photochemical reactionmust be added'before exposure.
  • the systems previously known are only of limited utility because their sensitivityto light is generally too A certain improvement has beenprovided by the .light-sensitive materials described in 'French Pat.
  • Another object of the invention lies in the production of photographic recording materials in which the image produced on exposure can be extinguished either spontaneously or by additional measures so that the material can be used again.
  • R represents (I) an aliphatic group containing up to 18 carbon atoms, preferably up to five carbon atoms, which may be saturated or'unsaturated and may contain further substituents, e.g., phenyl,
  • - halogen such as fluorine, chlorine or bromine
  • hydroxyl which may be esterified, in particular with short chain aliphatic carboxylic acids containing up' to six carbon atoms, carboxyl, esterified carboxyl in which short chain aliphatic alcohols are particularly suitable for the ester component,v 20 acyl, especially acyl radicals derived from short chain aliphatic carboxylic acids, sulfonamide in v which the amide group may be substituted with al- .kyl, aryl, especially phenyl, acyl which is .ad-
  • a cycloalkyl group e.g., cyclopentyl or cyclohexyl
  • an aryl group in-particular a radical of the phenyl or naphthylseries which may be substituted in the same way as the aliphatic radical mentioned under R' represents fan aryl group such as phenyl or naphthyljini particular aradical of the phenyl series; these rings may also be interconnected and this radical may carry other substituents, e.g.', al-
  • kyl preferablycontaining up to five carbon atoms, halogen such as chlorine or bromine, hydroxyl, falkoxy, carboxyl, esterified carboxyl, nitro," riitrile, carbamoyl, sulfonic acid, sulfonaniideor sulfonic 40 I acid ester groups;
  • R" represents a nitrile or R" groupi
  • the nature of'th'e anion or cation is not critical. It will depend mainly on the method ofpreparation used for the above components. Suitable anions are,'e.g., ha-
  • lide ions especiallychloride or bromide, sulfate ions
  • Suitable cations are protons or-cations of the alkali metals, depending on the-pH of thesolution of the components or the pH of the layer. Cations of the alkaline earth metals or ammonium. ions which may carry organic substituents may, of course, also be .used.
  • the only essential condition for the light sensitivity of the material ac'cordingto the invention is the simultaneous presence of bis-pyridiniurn ions and phenyl boranate ions.
  • the bis-pyridinium compounds and phenyl boranates need not be present in stoichiometric quantities in the light-sensitive material. It is sufficient if one of the components is present in an amount of about to 90 percent by weight based on the total weight of the components.
  • the mixture of compounds preferably contains about 40 to 60 percent by weight of one of the compounds.
  • Suitable for this purpose are gelatine, cellulose, cellulose esters, cellulose ethers, polycarbonates, especially those based on bis-phenylol alkanes, polyesters, especially those based on polyethylene terephthalate, polyamides, polyurethanes and various film-forming polymers or copolymers of olefinically unsaturated monomers such as vinyl chloride, vinyl acetate, styrene, olefinically unsaturated carboxylic acids, their esters or other derivatives such as maleic acid anhydride, acrylic acid or methacrylic acid and their derivatives, as well as polyethylene or polyvinylidene chloride, e.g., in the form of their aqueous dispersions.
  • olefinically unsaturated monomers such as vinyl chloride, vinyl acetate, styrene, olefinically unsaturated carboxylic acids, their esters or other derivatives such as maleic acid anhydride, acrylic acid or me
  • the bispyridinium compounds may also be contained in a separate layer and the boron compounds may be contained in a second layer which is in contact with the first.
  • layer supports e.g., paper, glass or natural or synthetic materials such as cellulose esters, especially cellulose acetate or cellulose acetobutyrates, polyesters, especially those based on polyethylene terephthalate, polycarbonates, particularly those derived from bis-phenylol alkanes,
  • the layer supports may be transparent or contain pigments such as titanium dioxide, barium sulphate, etc.
  • The'surface'of the layer support may be smooth or profiled.
  • the substances for use according to the invention may, of course, be added directly to the layer support.
  • the light-sensitive compound for use according to the invention may also be applied in self-supporting layers.
  • Layer binders of the type mentioned above are also suitable for this purpose. in principle, it is immaterial which layer binder is used and a suitable layer binder can easily be chosen by simple tests from the wide variety of known natural or synthetic hydrophilic or hydrophobic layer forming substances.
  • Suitable solvents for the compounds for use according to the invention are, e.g., water, short chain aliphatic alcohols such as methanol or ethanol, acetone, dimethyl formamide or the like.
  • the concentration of the light-sensitive substances in the binder may be varied within any limits.
  • the gradation or maximum density can be influenced by'varying the concentration as well as the application.
  • the pH may be varied within the limits at which no significant change takes place in the binder, such as degradation in the case of gelatine.
  • the substances are advantageously used in quantities of l to percent, based on the dry layer.
  • Casting additives e.g., wetting agents or compounds which improve the mechanical properties (e.g., hardness) may be added to the layers.
  • the light-sensitive compounds used in the materials according to the invention yield colored products which are stable for several hours to several days, depending on the nature of the reactants and the structure of the light-sensitive layer.
  • Hydroxyl-substituted V aromatic compounds particularly those of the phenyl or naphthyl series, e.g., hydroquinone, pyrocatechol, naphthols and the like, are suitable for this purpose.
  • heterocyclic compounds which contain nitrogen, e.g., pyrrolidones, especially N-methyl pyrrolidone, or acid amides such as dimethyl formamide.
  • the materials according to the in--- vention are particularly important for processes in which extinction of the image and reuse of the material are required.
  • the photographic images obtained in this way can be fixed by rendering the compounds in the unexposed parts of the layer insensitive to light. This can be achieved, e.g., by means of reagents which react with one of the components to form stable colorless products. Separation of exposed and unexposed parts in the layer can also be achieved by selectively dissolving out one of the components with suitable solvents.
  • the layers according to the invention are generally pale yellow in color.
  • The are sensitive to UV light, including the longer wavelength end of the range, so that in principle they can be exposed with ordinary artificial light. They are particularly suitable for exposure with nitraphot lamps, neon tubes and laser light.
  • the exposure time depends, of course, on the intensity of the source of light, the distance of the layer from the source of light and the sensitivity of the layer. Exposure times of a few seconds to several minutes are generally sufficient.
  • the layers according to the invention can be spectrally sensitized.
  • sensitizers are, e.g., cyanine dyes, xanthylium dyes, acridinium dyes or the like.
  • the sensitizing dyes are added in quantities of about H500 to l/l0,000 of the weight of the phenyl boranate. Sensitized layers are additionally sensitive to the visible range of the spectrum.
  • the thickness of the dry layer is 16 mm. It is exposed imagewise to a nitraphot lamp at a distance of 10 cm for 2 minutes. A deep blue image is obtained on the slightly yellowish layer.
  • EXAMPLE 2 if in the casting solution for the above layer the polyvinyl pyrrolidone is replaced, e.g., by 1 g of hydroquinone dissolved in IQ ml of water, the image obtained after suitable processing is deep blue and persists for much longer, about 2 days. If a protective layer containing 5 percent of gelatine is cast on this light-sensitive layer, the image persists for over a week.
  • Theabove mentioned layer can be spectrally sensitized. If, for example, 0.01 g of 5,6-benzobcnzothiazole purple dissolved in 10 ml of methanol is added to the casting solution, a pale pink layer is obseconds. A deep blue negative image of the original is obtained.
  • a pale yellow layer is obtained.
  • a reddish violet negative image of the original is obtained.
  • the layer is then processed as described in Example 1. A blueish violet negative image of the original is obtained.
  • lf exposure is carried out at elevated. temperature, e.g., between 50 and C the color change is to a distinctly darker color.
  • the exposure time can be reduced to obtain the same color change.
  • the layer is then processed as described in Example 1. A greyish violet image of the original is obtained.
  • EXAMPLE 7 A solution of 0.67 g of compound L1 in 50 ml ofa 5 percent aqueous gelatine solution which contains 1 ml of polyvinyl pyrrolidone and 1.5 ml of a 10 percent aqueous saponin solution is applied to a layer support of cellulose triacetate. When this first layer has partly mm H dried, a solution of 0.75 g of compound ",2 in 50 ml of l percent gelatine solution which contains 1 ml of :l Nai polyvinyl pyrrolidone and 1.5 ml of saponin solution is 5 applied to it. When the layer is completely dry, an almost colorless light-sensitive material is obtained on which a dark blue image is obtained on exposure as 3.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US00111764A 1970-02-19 1971-02-01 Bis-pyridinium salt and a phenyl boranate as photosensitive combination Expired - Lifetime US3716366A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702007524 DE2007524A1 (de) 1970-02-19 1970-02-19 Lichtempfindliche Materialien

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US3716366A true US3716366A (en) 1973-02-13

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US (1) US3716366A (enrdf_load_stackoverflow)
BE (1) BE762918A (enrdf_load_stackoverflow)
CA (1) CA973418A (enrdf_load_stackoverflow)
CH (1) CH553425A (enrdf_load_stackoverflow)
DE (1) DE2007524A1 (enrdf_load_stackoverflow)
FR (1) FR2078870A5 (enrdf_load_stackoverflow)
GB (1) GB1293111A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4307182A (en) * 1980-05-23 1981-12-22 Minnesota Mining And Manufacturing Company Imaging systems with tetra(aliphatic) borate salts
US4343891A (en) * 1980-05-23 1982-08-10 Minnesota Mining And Manufacturing Company Fixing of tetra (hydrocarbyl) borate salt imaging systems
US4447521A (en) * 1982-10-25 1984-05-08 Minnesota Mining And Manufacturing Company Fixing of tetra(hydrocarbyl)borate salt imaging systems
US4772541A (en) * 1985-11-20 1988-09-20 The Mead Corporation Photohardenable compositions containing a dye borate complex and photosensitive materials employing the same
US4804613A (en) * 1983-10-14 1989-02-14 Canon Kabushiki Kaisha Optical recording medium and optical recording process using such medium
US5260180A (en) * 1992-09-02 1993-11-09 Minnesota Mining And Manufacturing Company Photothermographic imaging media employing silver salts of tetrahydrocarbyl borate anions
US20050053864A1 (en) * 2003-09-05 2005-03-10 Rolf Dessauer Phthalocyanine precursors in infrared sensitive compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3121012A (en) * 1960-02-08 1964-02-11 Miehle Goss Dexter Inc Light sensitive triphenylmethane leucocyanide compositions
US3300314A (en) * 1963-02-01 1967-01-24 Eastman Kodak Co Nonsilver, light-sensitive photographic elements
US3597212A (en) * 1968-10-30 1971-08-03 Eastman Kodak Co Photosensitive elements and process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3121012A (en) * 1960-02-08 1964-02-11 Miehle Goss Dexter Inc Light sensitive triphenylmethane leucocyanide compositions
US3300314A (en) * 1963-02-01 1967-01-24 Eastman Kodak Co Nonsilver, light-sensitive photographic elements
US3597212A (en) * 1968-10-30 1971-08-03 Eastman Kodak Co Photosensitive elements and process

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4307182A (en) * 1980-05-23 1981-12-22 Minnesota Mining And Manufacturing Company Imaging systems with tetra(aliphatic) borate salts
US4343891A (en) * 1980-05-23 1982-08-10 Minnesota Mining And Manufacturing Company Fixing of tetra (hydrocarbyl) borate salt imaging systems
US4447521A (en) * 1982-10-25 1984-05-08 Minnesota Mining And Manufacturing Company Fixing of tetra(hydrocarbyl)borate salt imaging systems
US4804613A (en) * 1983-10-14 1989-02-14 Canon Kabushiki Kaisha Optical recording medium and optical recording process using such medium
US4772541A (en) * 1985-11-20 1988-09-20 The Mead Corporation Photohardenable compositions containing a dye borate complex and photosensitive materials employing the same
US4865942A (en) * 1985-11-20 1989-09-12 The Mead Corporation Photohardenable compositions containing a dye-borate complex and photosensitive materials employing the same
US5260180A (en) * 1992-09-02 1993-11-09 Minnesota Mining And Manufacturing Company Photothermographic imaging media employing silver salts of tetrahydrocarbyl borate anions
US20050053864A1 (en) * 2003-09-05 2005-03-10 Rolf Dessauer Phthalocyanine precursors in infrared sensitive compositions

Also Published As

Publication number Publication date
DE2007524A1 (de) 1971-08-26
CA973418A (en) 1975-08-26
BE762918A (enrdf_load_stackoverflow) 1971-08-16
CH553425A (de) 1974-08-30
FR2078870A5 (enrdf_load_stackoverflow) 1971-11-05
GB1293111A (en) 1972-10-18

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