US3871886A - Photochromic copying method - Google Patents

Photochromic copying method Download PDF

Info

Publication number
US3871886A
US3871886A US372405A US37240573A US3871886A US 3871886 A US3871886 A US 3871886A US 372405 A US372405 A US 372405A US 37240573 A US37240573 A US 37240573A US 3871886 A US3871886 A US 3871886A
Authority
US
United States
Prior art keywords
compound
formula
spiropyran
ketone
photochromic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US372405A
Other languages
English (en)
Inventor
Jean Jules Achille Robillard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ricoh Co Ltd
Original Assignee
Ricoh Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR7223184A external-priority patent/FR2191157A1/fr
Priority claimed from FR7224945A external-priority patent/FR2192323A1/fr
Application filed by Ricoh Co Ltd filed Critical Ricoh Co Ltd
Application granted granted Critical
Publication of US3871886A publication Critical patent/US3871886A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
    • 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

Definitions

  • ABSTRACT A stable image can be obtained by the copying 30
  • Foreign Application p i Data method which comprises: applymg 1mage-wise ultravi- June 27 197.) France 72 23184 olet rays havmga wavelength A, corresponding to the Jul France 721M945 absorption wavelength range of a spiropyrancomy pound to a photochromic copying material comprising 21 us. c1.
  • the present invention provides novel methods of reproduction to produce stable, lasting images, wherein a photochromic copying material containing at least one spiropyran of indoline or benzothiazoline as the photochromic compound is employed, and the image area (which assumes a chromic form) and the nonimage area (which assumes an achromic form) are respectively made to be irreversible, that is they are fixed.
  • the present invention provides methods of reproduction which include the steps of applying image-wise ultraviolet rays having the wavelength A 1 corresponding to the absorption wavelength range of a spiropyran compound to a photochromic copying material comprising a support coated with a photosensitive layer containing the spiropyran compound, an aromatic or a cyclic ketone and a doped semi conductive metal oxide; and subsequently applying ultraviolet rays having the wavelength A 2 capable of decomposing said ketone either in the presence of an alcohol in the case of aromatic ketones or in the absence of alcohol in the case of the cyclic ketones to the whole surface of said copying material.
  • these steps may be reversible.
  • spiropyran achromatic form
  • merocyanine chromatic form
  • Spiropyrans of indolines or benzothiaiolines which are useful in the present invention includes those represented by the following general formulas:
  • R represents alkyl groups having l-3 carbon atoms or phenyl;
  • R represents H, alkyl groups having l-3 carbon atoms, alkoxy groups having l-3 carbon atoms or halogen atoms;
  • R represents H, halogen atoms or nitro group;
  • R represents alkyl groups having l-6 carbon atoms, benzyl group or phenyl methyl group;
  • R represents alkyl groups having l-3 carbon atoms, naphthyl group, phenyl group, cyclohexyl group, methoxyphenyl group, hydroxyphenyl group, halogen-substituted phenyl groups or a thiophenyl group;
  • R represents H, OH or SCH and R representss OH or alkoxy groups having l -3 carbon atoms.
  • R H, and R OCH 13 a compound of general formula (ll) wherein R R CH and R R OH;
  • the molecule of a spiropyran (closed ring form) has a molecular structure in which two surfaces meeting at right angles with each other have conjugated portions, which are linked by saturated carbon atoms.
  • this molecule is adsorbed on the surface of an adsorbent, the bond with the adsorbent is effected through a single or several benzene rings within the molecule.
  • the second section of the molecule of the spiropyran becomes freely rotatable centering around carbon atoms linking both planes. This section then becomes parallel to the surface of the adsorbent. As a result it bonds to the adsorbent.
  • This bond resists reclosing of the ring so that the chromatic .form of spiropyran (i.e., merocyanine) is fixed.
  • the substituents R -R or R -R is aromatic, the strength of the molecular bond to the adsorbent is augmented and the stability of the openedring form is increased.
  • any of a variety of semi-conductive adsorbents may be utilized for the purpose of stabilizing the chromatic merocyanine.
  • Doped metal oxides are especially useful.
  • the following materials are illustrative of metal oxides as well as the doping agent applicable thereto which may be employed in the present invention.
  • the doped metal oxides for use in the present invention can be prepared, for instance, by the following procedure.
  • the metal oxide powder is dipped in a solution of a doping metallic salt, whereby doping is effected. Subsequent to this operation the material is heat treated to diffuse the metal ions adsorbed onto the surface of the particle of said substance into the core of the particle.
  • the thus processed powder is next subjected to mechanical stirring for about one-half hour in a large volume of solution, filtered, and then introduced into a furnace as a thin layer of powder and heated at a temperature of 300-500C for several hours.
  • the temperature of the furnace and the time of treatment vary with the properties of the pigment as well as the rate of diffusion of the metal ions adsorbed to the surface of the pigment particle toward the core thereof.
  • the amount of a metal adsorbed to the surface of a particle having a grain size of 10 1.1. within a l percent solution is to the extent of 10* 10 metal atoms per crystal latticeatom of the pigment.
  • the powder is separated from the solution by filtration and is washed several times with a small quantity of distilled water.
  • the powder is filtered again, and then is placed in the boat of furnace in the form of a thin layer for further thermal diffusion. This diffusion is performed twicefirst, at the temperature of T for the period of :1 hours, and next at the temperature of T for the period of hours.
  • the temperature of the furnace is slowly restored to room temperature.
  • the resulting aggregated powder in the form of solid lumps is crushed, and then re-crushed into small spheroids by several hours treatment in a grinder so that the resulting particles may pass a 44 11, mesh sieve.
  • Table 1 below shows a variety of solutions applicable to various pigments, the temperature for heat treatment and the time thereof.
  • Table ll shows the properties of the starting oxides.
  • Table l Pigment Crystal form Solution of Concentration T t T t doping agent '7 "C hr. C hr Ti(). ,Rl.l6 rutilc Cu 50, 1 I00 I 420 4 'l'i(). RL futile Cc(SO. NiCl 0.92-0.78 I00 I 400 4 'li() RL rutile Cc(SO ),Ni(l 0.92-0.78 200 l 380 4 TiO AT 1 miutase LaCl, NlCl l -0.78 200 l 350 6 v TiO AT 4 anatusc Cu(SO.,) CuSO,.
  • sensitizers useful in the present invention include keton'es such as those already known as sensitizers for use in photochromism of spiropyran.
  • a -propio1actone Photochromic copying materials according to the present invention may be prepared by applying a photosensitive liquid comprising a spiropyran compound, a semi-conductor doped with a metal, and a sensitizer selected from the group of aromatic ketones and cyclic ketones onto a support by coating or impregnation.
  • a photosensitive liquid comprising a spiropyran compound, a semi-conductor doped with a metal, and a sensitizer selected from the group of aromatic ketones and cyclic ketones
  • Suitable binders include for example, acrylic, methacrylic, alkyl, silicone and styrene resins.
  • the thickness of the layer is normally from about 1 to 50 microns.
  • the amount of the sensitizer for use in the present invention is from about lO' *-O.5 parts by weight thereof per 1 part by weight of the spiropyran compound employed.
  • the amount of doped semiconductor will be at least sufficient to adsorb the selected spiropyran compound.
  • rays of light having the wavelength A, corresponding to the absorption wavelength range of spiropyran are first applied image-wise onto a photochromic material prepared as above. Through this process, the portion of said photochromic material exposed to light becomes irreversively colored.
  • fixation of the non-image area is performed through the process comprising coating an alcohol such as isopropyl alcohol on the whole surface of the photochromic material and applying rays of light having the wavelength capable of decomposing the aromatic ketone to said material coated with alcohol in the case of employing an aromatic ketone as the sensitizer, or through the process of just applying rays of light having the wavelength A capable of decomposing the cyclic ketone to the photochromic material intact in the case of employing a cyclic ketone as the sensitizer.
  • the absorption wavelength A, of spiropyran varies with the kind thereof, and it is in the range of about 2800-4500A.
  • the wavelength A for use in decomposing ketones also varies with the kind thereof, and it is in the range of 2800-6000A. Accordingly, in the ease of employing a cyclic ketone as the sensitizer, it is necessary to employ a spiropyran having an absorption wavelength A, falling within the range of wavelengths not decomposing said cyclic ketone. The above operations may be reversed.
  • the selective sensitization operated in the process of the invention permits the obtaining of an increase of the sensitivity of the photochromic composition, that is to say an increase in the quantum yield of this composition.
  • M is the concentration of spiropyran
  • 1 is the quantum yield of the photochromic reaction
  • r is the time of exposure to wavelength M
  • m is the concentration of sensitizer
  • 1 is the quantum yield of the photochromic reaction of destruction of the sen sitizer and t the time of exposure to A
  • Example 1 A composition according to the present invention was prepared by thoroughly mixing the following components.
  • Example 2 A composition according to the present invention was prepared by thoroughly mixing the following components.
  • Example 3 A composition according to the present invention 5 was prepared by thoroughly mixing the following components.
  • Example 4 A composition according to the present invention was prepared by thoroughly mixing the following components.
  • a copying method selected from the group consisting of:
  • said copying material comprising a support and a photosensitive layer comprising (a) a spiropyran, (b) an aromatic or a cyclic ketone and (c) a semiconductive metal oxidevdoped with at least one metal;
  • said wavelength A corresponding to the absorption wavelength of the spiropyran compound;
  • said spiropyran compound having the general formula:
  • R and R are alkyl containing 1 to 3 carbon atoms, R is alkyl containing 1 to 3 carbon atoms or phenyl,
  • R is hydrogen, alkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 3 carbon atoms or halogen,
  • R is hydrogen, halogen or nitro
  • R is alkyl containing 1 to .6 carbon atoms, or
  • R is alkyl containing 1 to 3 carbon atoms, naphthyl, phenyl, cyclohexyl, methoxyphenyl, hydroxyphenyl, halogen substituted phenyl or thiophenyl,
  • R is hydrogen, hydroxyl, or thiomethyl
  • R is hydroxyl or alkoxy containing 1 to 3 carbon atoms
  • said-ketone being selected from the group consisting of benzophenone, biphenyl-o-acetophenone, triketoindane, xanthotoxine and B-propiolactone;
  • said doped metal oxide being selected from the group consisting of TiO /TiO doped with Cu;
  • a second method which is the reverse of said first method whereby the first exposure is to light of wavelength A and the second exposure is to light of wavelength A,.
  • a photochromic copying material comprising a support and a photosensitive layer comprising (a) a spiropyran, (b) an aromatic or a cyclic ketone and (c) a semiconductive metal oxide doped with at least one metal;
  • said wavelength A corresponding to the absorption wavelength of the spiropyran compound;
  • said spiropyran compound having the general formula:
  • R is alkyl containing 1 to 3 carbon atoms or phenyl
  • R is hydrogen, alkyl containing l to 3 carbon atoms, alkoxy containing 1 to 3 carbon atoms or halogen
  • R is hydrogen, halogen, or nitro, R is alkyl containing l to 6 carbon atoms, or benzyl, R is alkyl containing 1 to 3 carbon atoms, naphthyl, phenyl, cyclohexyl, methoxyphenyl, hydroxyphenyl, halogen substituted phenyl or thiophenyl, R is hydrogen, hydroxyl, or thiomethyl, and 0 R is hydroxyl or alkoxy containing 1 to 3 carbon 5 atoms; said ketone being selected from the group consisting of benzophenone, biphenyl-S-acetophenone, triketoindane, xanthotoxine and B-propiolactone; said doped metal oxide being selected from the group consisting of TiO /TiO doped with Cu; Ti0 doped with Ce/Ni, La/Ni or Ce/Cu; ZrO doped with Ce/Ni, ZrO doped with La/Cu; and Zn

Landscapes

  • 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)
US372405A 1972-06-27 1973-06-21 Photochromic copying method Expired - Lifetime US3871886A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7223184A FR2191157A1 (en) 1972-06-27 1972-06-27 Photochromatic recording material - contg indoline or benzothiazoline-spiropyrans ketones and doped oxides
FR7224945A FR2192323A1 (en) 1972-07-10 1972-07-10 Photochromatic recording material - contg indoline or benzothiazoline-spiropyrans ketones and doped oxides

Publications (1)

Publication Number Publication Date
US3871886A true US3871886A (en) 1975-03-18

Family

ID=26217184

Family Applications (1)

Application Number Title Priority Date Filing Date
US372405A Expired - Lifetime US3871886A (en) 1972-06-27 1973-06-21 Photochromic copying method

Country Status (3)

Country Link
US (1) US3871886A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS5544935B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2319439C3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4029506A (en) * 1974-10-21 1977-06-14 E. I. Du Pont De Nemours And Company Universal product code marking composition containing a photosensitive dye former, a pigment and a binder and the use thereof
US4052218A (en) * 1974-05-24 1977-10-04 Laboratoires De Physicochimie Appliquee I S S E C Novel spiro-heterocyclic compounds, their preparation, and use thereof in a thermographic recording material
US4207102A (en) * 1974-10-21 1980-06-10 E. I. Du Pont De Nemours And Company Marking transfer sheets and process
US4232108A (en) * 1979-05-01 1980-11-04 E. I. Du Pont De Nemours And Company Marking transfer sheets
US4725527A (en) * 1984-12-30 1988-02-16 Richard L. Scully Photosensitive compositions for direct positive color photography
US20060222972A1 (en) * 2005-03-30 2006-10-05 Xerox Corporation Dual-layer protected transient document

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7425406B2 (en) 2004-07-27 2008-09-16 Fujifilm Corporation Lithographic printing plate precursor and lithographic printing method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3317321A (en) * 1962-11-21 1967-05-02 American Cyanamid Co Photochromic compositions comprising doped inorganic metal oxides suspended in polyester binders
US3451816A (en) * 1965-06-16 1969-06-24 American Cyanamid Co Photographic dodging method
US3485764A (en) * 1964-05-22 1969-12-23 American Cyanamid Co Polymeric photochromic compositions stabilized with ultraviolet light absorbers
US3485765A (en) * 1966-07-06 1969-12-23 Eastman Kodak Co Azo modifier containing phototropic compositions
US3486899A (en) * 1965-12-13 1969-12-30 Minnesota Mining & Mfg Imagewise photochromic responsive element and process
US3660086A (en) * 1969-01-17 1972-05-02 Xerox Corp Electrophotographic plate and process employing inorganic photoconductive material with a photochromic sensitizing agent
US3704127A (en) * 1970-08-17 1972-11-28 Du Pont Co-irradiation method for producing positive images utilizing phototropic spiropyran or indenone oxide or dual response photosensitive composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3317321A (en) * 1962-11-21 1967-05-02 American Cyanamid Co Photochromic compositions comprising doped inorganic metal oxides suspended in polyester binders
US3485764A (en) * 1964-05-22 1969-12-23 American Cyanamid Co Polymeric photochromic compositions stabilized with ultraviolet light absorbers
US3451816A (en) * 1965-06-16 1969-06-24 American Cyanamid Co Photographic dodging method
US3486899A (en) * 1965-12-13 1969-12-30 Minnesota Mining & Mfg Imagewise photochromic responsive element and process
US3485765A (en) * 1966-07-06 1969-12-23 Eastman Kodak Co Azo modifier containing phototropic compositions
US3660086A (en) * 1969-01-17 1972-05-02 Xerox Corp Electrophotographic plate and process employing inorganic photoconductive material with a photochromic sensitizing agent
US3704127A (en) * 1970-08-17 1972-11-28 Du Pont Co-irradiation method for producing positive images utilizing phototropic spiropyran or indenone oxide or dual response photosensitive composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052218A (en) * 1974-05-24 1977-10-04 Laboratoires De Physicochimie Appliquee I S S E C Novel spiro-heterocyclic compounds, their preparation, and use thereof in a thermographic recording material
US4029506A (en) * 1974-10-21 1977-06-14 E. I. Du Pont De Nemours And Company Universal product code marking composition containing a photosensitive dye former, a pigment and a binder and the use thereof
US4207102A (en) * 1974-10-21 1980-06-10 E. I. Du Pont De Nemours And Company Marking transfer sheets and process
US4232108A (en) * 1979-05-01 1980-11-04 E. I. Du Pont De Nemours And Company Marking transfer sheets
US4725527A (en) * 1984-12-30 1988-02-16 Richard L. Scully Photosensitive compositions for direct positive color photography
US20060222972A1 (en) * 2005-03-30 2006-10-05 Xerox Corporation Dual-layer protected transient document
US7432027B2 (en) * 2005-03-30 2008-10-07 Xerox Corporation Dual-layer protected transient document

Also Published As

Publication number Publication date
JPS4936332A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1974-04-04
DE2319439C3 (de) 1980-01-10
DE2319439A1 (de) 1974-01-17
DE2319439B2 (de) 1974-08-01
JPS5544935B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1980-11-14

Similar Documents

Publication Publication Date Title
US3595658A (en) Non-silver direct positive dye bleachout system using polymethine dyes and colored activators
US3617288A (en) Propenone sensitizers for the photolysis of organic halogen compounds
US3595655A (en) Non-silver direct positive dyes bleachout system using polymethine dyes and colorless activators
US3892569A (en) Photosensitive sheets comprising organic dyes and sensitizers
DE2329170A1 (de) Photothermographisches aufzeichnungsmaterial
US3525612A (en) Electrophotographic reproduction process employing a light sensitive material and a photoconductive material
US3871886A (en) Photochromic copying method
US3658540A (en) Production of photographic materials with photosensitive compounds other than silver halides
DE2043769A1 (de) Elektrophotographisches Kopier verfahren
US3666464A (en) Dye-sensitized photosensitive materials having improved photographic speed
US2987395A (en) Electrophotographic printing element
US3973966A (en) Photochromic composition containing a diphenyl dibenzochrom-3-ene
JPS61170737A (ja) 光記録媒体
US3510300A (en) Process for making latent dye salt image visible
JPS5837078A (ja) フオトクロミツク感光性組成物
US3635706A (en) Sensitized electrophotographic layers
US3558308A (en) Process for producing photographic images with photosensitive materials and products produced thereby
JPH0668104B2 (ja) フオトクロミツク組成物
US3634333A (en) Process for coating zinc oxide powder with cadmium sulfide
US4394439A (en) Non-silver X-ray recording process
US4010033A (en) Photosensitive layer and method of forming a photographic image therefrom
US3663225A (en) Photographic reflex process
DE2046687A1 (de) Supersensibilisierte, lichtempfindh ehe, photographische Silberhalogenidemul sion
US3690889A (en) Photocolorable vacuum sublimed xanthene dye
US3705037A (en) Photochromic composition containing a bleached-out dye and a reducing agent therefor