WO1981001757A1 - Color imaging system - Google Patents
Color imaging system Download PDFInfo
- Publication number
- WO1981001757A1 WO1981001757A1 PCT/US1980/001506 US8001506W WO8101757A1 WO 1981001757 A1 WO1981001757 A1 WO 1981001757A1 US 8001506 W US8001506 W US 8001506W WO 8101757 A1 WO8101757 A1 WO 8101757A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dye
- nitrate
- imageable layer
- present
- binder
- Prior art date
Links
- 238000003384 imaging method Methods 0.000 title abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 30
- 150000002823 nitrates Chemical class 0.000 claims abstract description 27
- -1 silver halide Chemical class 0.000 claims abstract description 11
- 239000000975 dye Substances 0.000 claims description 106
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 41
- 150000003839 salts Chemical class 0.000 claims description 24
- 230000003287 optical effect Effects 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001228 spectrum Methods 0.000 claims description 5
- WZKXBGJNNCGHIC-UHFFFAOYSA-N Leucomalachite green Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=CC=C1 WZKXBGJNNCGHIC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
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- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical class C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
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- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 claims description 2
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- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 claims description 2
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- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims 1
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 28
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- 238000011161 development Methods 0.000 description 15
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 14
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
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- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
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- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- XLABPPWWFVQMBZ-UHFFFAOYSA-O pyridin-1-ium;nitrate Chemical compound [O-][N+]([O-])=O.C1=CC=[NH+]C=C1 XLABPPWWFVQMBZ-UHFFFAOYSA-O 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
-
- 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
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
Definitions
- a layer comprising 1) an oxidizing ion and 2) leuco dye or bleachable dye in a binder is useful as either an imaging layer or as a heat-bleachable antihalation layer.
- the antihalation layer is particularly useful in photothermographic systems where the development temperature acts to oxidize the leuco dye or bleach the dye.
- the present invention may be practiced in any polymeric binder system having the necessary active ingredients therein.
- These ingredients comprise leuco dyes or bleachable dyes and a non-dye-reactive nitrate salt.
- the active agents may also include any material which supplies hydrogen ion, such as an acidic material, and in particular an acid.
- a binder material containing these ingredients can be colorized or decolorized locally by heating portions of the binder layer or generally decolorized by heating the entire layer. The presence of an acidic material accelerates the decolorization phenomenum.
- the three required components are the dye (leuco or bleachable), the nitrate salt, and the polymeric binder.
- the Binder Any polymeric binder may be used in the practice of the present invention.
- the pH of the resin has been found to affect only the speed of the discolorizing effect. If the speed is not important, any resin may be used.
- Such resins as polyvinyl acetals, polyesters, polyvinyl resins, polyvinyl pyrolidone, polyesters, polycarbonates, polyamides, polyvinyl butyral, polyacrylates, cellulose esters, copolymers and blends of these classes of resins, and others have been used with particular success.
- Natural polymeric materials such as gelatin and gum arabic may also be used. Where the proportions and activities of dyes and nitrate ion require a particular developing time and temperature, the resin should be able to withstand those conditions.
- the polymer not decompose or lose its structural integrity at 200°F (93°C) for 30 seconds, and more preferred that it not decompose or lose its structural integrity at 260°F (127°C) for 30 seconds and most preferred that it withstand 290°F (144°C) for 60 seconds.
- Nitrate Salt Nitrate salts are themselves well known. They may be supplied as various compounds forms, but are preferably provided as a metal salt, and most preferably provided as a hydrated metal salt.
- oxidizing ions which are ordinarily good oxidizing ions such as nitrite, chlorate, iodate, perchlorate, periodate, and persulfate do not provide comparable results.
- the composition are satisfactory.
- metal salts, acid salts, mixtures of acids and salts, and other means of supplying the ion are useful.
- nitrates of zinc, cadmium, potassium, calcium, zirconyl, nickel, aluminum, chromium, iron, copper, magnesium, lead, and cobalt, ammonium nitrate, and cerous ammonium nitrate have been used.
- the nitrate salt component of the present invention must be present in a form within the imaging layer so that HNO 3 , NO, NO 2 , or N 2 O 4 will be provided within the layer when it is heated to a temperature no greater than 200°C for 60 seconds and preferably no greater than 160°C for 60 or most preferably 30 seconds. This may be accomplished with many different types of salts, both organic and inorganic, and in variously different types of constructions.
- the most convenient way of providing such thermal oxidant providing nitrate salts is to provide a hydrated nitrate salt such as aluminum nitrate nonahydrate (Al(NO 3 ) 2 .9H 2 O).
- This salt when heated in a binder, will generate HNO 3 , NO, NO 2 and/or N 2 O 4 in various amounts.
- the binder should not be at such a high pH that the liberated nitric acid would be profely neutralized as this would adversely affect the oxidizing capability of the system. It is not essential that a completely acidic or neutral pH environment be provided, but pH levels above 8.5 may in many cases completely prevent oxidation. It is therefore desired that the nitrate salt containing layer have an acidic environment such as a pH less than 7.5, preferably equal to or less than 7.0, and more preferably equal to or less than 6.5.
- non-hydrated salts in layers having a pH less than 7.5, and preferably in an acidic environment are also capable of providing HNO 3 , NO, NO 2 , and/or N 2 O 4 in sufficient quantities to provide the oxidizing capability necessary for practice of the present invention.
- Ammonium nitrate for example, does not enable good oxidation in the present invention in a layer having a pH of 8.0 or higher, but when a moderate strength organic acid such as phthalic acid is added to lower the pH to below 7.0, a quite acceptable imaging system is provided.
- organic salts in non-alkaline environments are also quite useful in the practice of the present invention.
- nitrated quaternary ammonium salts such as guanadinium nitrate work quite well in acid environments, but will not provide any useful image at alkaline pH levels of 8.0 or higher.
- the alkaline environment causes any oxidizing agent (e.g., HNO 3 , NO, NO 2 and/or N 2 O 4 ) which is liberated from the nitrate salt to be preferentially reacted with hydroxy ions or other neutralizing moieties so as to prevent oxidation of the dyes.
- any oxidizing agent e.g., HNO 3 , NO, NO 2 and/or N 2 O 4
- One other consideration should be given in the selection of the nitrate salt and that is the choice of a salt in which the cation is non-reactive with the dye.
- Non-reactive salts are defined in the practice of the present invention as those salts the cations of which do not spontaneously oxidize the dyes that they are associated with at room temperature. This may be readily determined in a number of fashions.
- the dye and a non-nitrate (preferably halide) salt of the cation may be codissolved in a solution. If the salt oxidizes the dye spontaneously (within two minutes) at room temperature, it is a reactive salt.
- Such salts as silver nitrate, in which the cation is itself a strong oxidizing agent, is a reactive salt. Cerric nitrate is also reactive, while hydrated cerrous nitrate is not.
- Preferred salts are the hydrated metal salts such as nickel nitrate hexahydrate, magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, ferric nitrate nonahydrate, cupric nitrate trihydrate, zinc nitrate hexahydrate, cadmium nitrate tetrahydrate, bismuth nitrate pentahydrate, thorium nitrate tetrahydrate, cobalt nitrate hexahydrate, gadolinium or lanthanum nitrate nonahydrate, mixtures of these hydrated nitrates and the like.
- Nonhydrated or organic nitrates may be admixed therewith.
- Organic nitrates are also quite useful in the practice of the present invention. These nitrates are usually in the form of quaternary nitrogen containing compounds such as guanadinium nitrate, pyridinium nitrate, and the like. Nitrated dyes will also be useful, but again, they must be used in an environment which will not neutralize any liberated HNO 3 , NO, NO 2 , and/or N 2 O 4 .
- nitrate ion per mole of dye It is preferred to have at least 0.10 moles of nitrate ion per mole of dye. It is more preferred to have at least 0.30 or 0.50 moles of ion per mole of dye. Even amounts of from 1.0 to 100 moles of nitrate ion per mole of dye have been found useful. With dyes having relatively higher oxidation potentials, more nitrate is desirable.
- leuco dyes as defined herein
- dyes are useful in the present invention. With some constructions it may be desirable to select dyes which have an oxidation potential of less than or equal to +1.0.
- the dyes may be selected from any class of dyes.
- These classes include but are not limited to 1) methines, 2) indamines, 3) anthraquinones, 4) triarylmethanes, 5) benzylidenes, 6) monoazos, 7) oxazines, 8) azines, 9) thiazines, 10) xanthenes, 11) indigoids, 12) oxonols, 13) cyanines, 14) merocyanines, 15) phenols, 16) naphthols, 17) pyrazolones, and others, of which most are classified by the Colour Index System.
- oxidation potentials is well known to the ordinarily skilled artisan.
- the measurements in the present invention are taken by measuring the voltage and current transferred between a carbon and a platinum electrode through the appropriate solution.
- 0.1 M lithium chloride in anhydrous methanol with 1 to 10 millimoles/liter of the appropriate dye was the standard solution used in the measurements given herein with a saturated calomel electrode.
- Leuco dyes are colorless dyes which when subjected to an oxidation reaction form a colored dye. These leuco dyes are well known in the art (e.g.. The Theory of the Photographic Process, 3rd Ed., Mees and James, pp. 283-4, 390-1, Macmillion Co., N.Y.; and Light-Sensitive Systems, Kosar, pp. 367, 370-380, 406 (1965) Wiley and Sons, Inc., N.Y. ) and U.S. Patent 3,974,147.
- leuco malachite blue leuco malachite blue
- leuco malachite green leuco crystal violet
- 1(2-(1,3,3-trimethylindolyl))-2-(p-morpholinyl ⁇ henyl)ethene Only those leuco dyes which can be converted to colored dyes by oxidation are useful in the practice of the present invention. Acid or base sensitive dyes such as phenolphthalein are not useful in the present invention unless they are also oxidizable to a colored state. Indicator dyes would only form transient images or would be too sensitive to changes in the environment.
- the leuco dye should be present as at least 0.3% by weight of the binder, preferably as at least 1% by weight of the binder, and most preferably as from 2 to 10% or more by weight of the binder.
- the proportions of nitrate salt and leuco dye should be such that on heating the layer at 260°F (127°C) for 30 seconds there is at least an optical density of 0.2 obtained, although with a mechanical viewing of the image or heating to a higher temperature, a lower optical density is useful.
- the relative proportion of nitrate ion to dye may vary. As a general rule, at least 0.1 moles of nitrate ion per mole of dye is desirable in the practice of the present invention. At least 0.3 or 0.5 moles of nitrate per mole of dye is more preferred, and at least 0.7 or 0.9 moles of nitrate per mole of dye is most preferred.
- the binder prior to imaging so that at least 15% of incident radiation (including ultraviolet and infrared) in a 50 nm range would be absorbed through a 0.5 mm layer of binder and dye. Preferably at least 75% of the incident radiation in a 20 nm range would be absorbed. These ranges must of course be chosen within the spectral absorption region of the particular dye, but such absorption in any portion of the spectra is useful. In terms of weight percentages, it would be preferred to have at least 0.30% by weight of dye as compared to the binder. Preferably, at least 0.50% by weight of dye to binder is desired and most preferably there should be at least 1% by weight of dye to binder in the layer up to 10% or more.
- the bleachable dyes which have been specificall shown to work in the present invention include but are not limited to the following:
- R 2 C 2 H 5 ; C 7 H 15 ; (CH 2 ) 5 COOH ; C 8 H 17 ; CH 2 CH 2 ⁇ ; or
- R 3 H ; C 2 H 5 O ; or Cl
- R 4 C 2 H 5 ; or CH 2 CH 2 C 6 H 5 wherein
- R 1 H ; or -CN
- R 5 -C 2 H 5 ; -CH 2 CH-CH 2 or -C 7 H 15
- R 3 -CH 3 ; or -C 2 H 5
- R 1 -C 2 H 5 ; --(CH 2 ) 2 OH ; - ⁇ CH 2 ) 2 COOH ; -CH 2 COOH ; or -(CH 2 ) 3 SO 3
- R 2 -C 2 H 5 ; -(CH 2 ) 2 OH ; -(CH 2 ) 2 COOH ; -CH 2 COOH ; or -CH 3
- R. H ; -CH 3 ; -SCH 3 ; or -C 2 H 5
- R 4 H ; -CH 3 ; -Br ; or -N(C 2 H 5 ) 2
- R 5 H ; -CH 3 ; or -Br
- R 3 H ; Br wherein
- R 1 S ;
- R 1 -CH 3 ; or CH 3 O-
- R 2 -C 2 H 5 ; or -C 7 H 15
- R 3 H ; -OH ; or -NHC 2 H 5
- R 1 H ; -CH 3 ; or -C 2 H 5
- R 2 H ; -C 2 H 5 ; or -CH 2 COOH
- R 1 H ; -N(CH 3 ) 2
- R 2 H ; -Cl
- the bleachable dyes of the present invention are preferably colored, that is, having absorbance in the visible portion of the electromagnetic spectrum (approximately 400 to 700 nm), but may also be colorless, having absorbance only or predominately in the infrared (700 to 1100 nm) or ultraviolet (310 to 400 nm) portions of the electromagnetic spectrum.
- the images where colorless dyes are used must then be viewed through a filter, by an ultraviolet sensitive apparatus, or by some enhancement technique.
- bleachable dye present in the layers of this invention so that an optical density of at least 0.1 in the visible portions of the spectrum is obtained or at least 5% of incident colorless light (including ultraviolet or infrared) is absorbed. It is preferred that an optical density of at least .0.5 or 0.8 be obtained and most preferably that there be sufficient dye so that an optical density of at least 1.0 be obtained in the layer.
- colorless dyes e.g., ultraviolet and infrared absorbing dyes
- the proportions of nitrate ion and dye should be such that on heating the layer at 260°F (127°C) for 30 seconds there is at least a 20% reduction in optical density, although with a mechanical viewing of the image, a lower reduction in optical density is useful.
- the relative proportion of nitrate ion to dye may vary. As a general rule, at least 0.1 moles of nitrate ion per mole of dye is desirable in the practice of the present invention. At least 0.3 or 0.5 moles of nitrate per mole of dye is more preferred, and at least 0.7 or 0.9 moles of nitrate per mole of dye is most preferred.
- decolorizable layers of the present invention are used as antihalation layers, particularly with thermally developable imaging materials, more than a 20% reduction in optical density is usually desirable. At least 50% or 60% is preferred and at least 90% or 95% reduction in optical density is most preferred. These reductions can be measured at the development temperatures for the imaging materials, e.g., 127°C for 30 seconds or 155°C for 45 seconds.
- the acids optionally useful in the present invention are acids as generally known to the skilled chemist.
- Organic acids are preferred, but inorganic acids (generally in relatively smaller concentrations) are also useful.
- Organic acids having carboxylic groups are more preferred.
- the acid may be present in a ratio of from 0 . to 10 times the amount of the nitrate ion. More preferably it is present .in amounts from 0.2 to 2.0 times the amount of nitrate ion.
- temperatures should, of course, not be used during manufacture which would completely oxidize decolorize the layer.
- Some colorization or decolorization is tolerable, with the initial dye concentrations chosen so as to allow for anticipated color changes. It is preferred, however, that little or no dye be formed or decolorized during forming or coating so that more standardized layers can be formed.
- the coating or forming temperature can be varied.
- the drying temperature could be 280°F (138°C) and it would not be desirable for the layer to lose 20% of its optical density at the drying temperature in less than 4-5 minutes, although it would be tolerable by correspondingly increasing the amount of dye.
- the preferred limitation of at least 20% reduction in optical density or absorbance of colorless light at 127°C for 30 seconds is based on the assumption of a development temperature of 127°C. For an anticipated higher or lower development temperature, the 20% reduction in optical density or absorbance should occur at that development temperature within a reasonable period of time.
- a reasonable development temperature range is between 180°F (82°C) and 380°F (193°C) and a reasonable dwell time is between 5 seconds and 5 minutes, preferably at between 220°F (105°C) and 350°F (167°C) and for 10 to 180 seconds, with the longer times most likely associated with the lower development temperatures. Therefore, all of the absorbance characteristics are applicable to the generally useful development range of 82°C to 193°C.
- Photothermographic imaging materials are well known in the art in various and sundry forms. Silver reduction systems (e.g., as disclosed in U.S. Patent. No. 3,457,075 and 3,849,049), thermal diazonium salt systems (e.g., as described in U.S.
- Patent No, 3,754,916), and others are examples of these systems.
- Typical constructions of these photothermographic systems will comprise one or two layers which constitute a photothermographic imaging system coated over a base.
- the support base is transparent, the heatbleachable layer of the present invention may be coated either between the imaging layers and the base or on the backside of the base. If coated between the base and the imaging layer, .it is desirable to minimize competing reactions. This can be done, for example, by selecting polymers and solvent systems for the various layers which will not promote migration between the layers.
- the heat-bleachable layer must be between the imaging layers and the base. This would, of course, also be true if there were more than one imaging layer. All of this will be more thoroughly understood by consideration of the following examples: Examples 1-13 A three component system of the present invention was evaluated by using nickel nitrate hexahydrate, phthalic acid and a merocyanine dye of the formula
- the dye was provided as a solution of 0.8 g dye/100 ml of a solvent comprising 50/50 volume proportions of methanol and N-methylpyrollidone. Three different concentrations of each ingredient were used. These ingredients were added to 2.5 g methanol and 12.5 g of a 10% by weight solids solution of polyvinylbutyral (as a binder) and methanol. The solutions were coated at 0.076 mm thickness on a polyester backing then dried for 3 minutes at 70°C. Maximum optical density (D max ) readings were taken. The coated sheets were then heated at 127°C for 30 seconds and the final maximum optical density (D f ) measured. The difference between D max and D f is the change in optical density ( ⁇ D) . The concentrations of materials and results appear in Table I.
- Example 14 bleached from medium blue to pale yellow, 15 became a lighter purple, and 16 became a light yellow. This shows that in the absence of an acid environment, greater concentrations of nitrate are desirable for more complete bleaching.
- Examples 17-24 show the wide variety of acids which can be used in the construction and indicates that the acid functionality is not dependent upon the structure of the acid. All constructions were identical to those of Examples 14-16 except that 5.5 ml of dye and 0.05 g of nickel nitrate hexahydrate were used. The sheets were heated at 127°C for 30 seconds in an inert fluorocarbon bath. All sheets were initially a medium blue.
- Example 25 This example demonstrates the use of the heat decolorizable layer as an antihalation backing for a photothermographic film.
- a solution was prepared by dissolving 8 g of magnesium nitrate hexahydrate and 12 g of phthalic acid in 75 g of methanol. This was broken down into aliquots of 3 g of solution, to which were added 4 ml of dye solution containing 0.15 g of malachite green and 0.05 g of crystal violet in 10 ml of a 50/50 volume solution of methanol and N-methylpyrolidone.
- Crystal violet has an oxidation potential greater than +1.0 and has the structure:
- Acid malachite green also used in the practice of the present invention, has the same structure except that one of the dimethylamine groups has been replaced by a hydrogen atom.
- a photothermographic film with the antihalation backing was exposed at the same time as the sample without the backing to artificial daylight through a continuous step wedge. Both examples were then developed at 127oC for 30 seconds.
- the antihalation backing bleached to a pale yellow.
- the effect of the antihalation layer was obvious to the untrained eye. Image flare was significantly reduced.
- Example 26 The antihalation backing of the previous example was coated on transparent polyester film and dried at 70°C.
- the colored film was thermographically exposed imagewise in a thermographic copier ("Secretary" Copier by 3M).
- the film bleached in an area corresponding to the image on the original.
- This demonstrates the use of the films as an image producing element which, for example, could be used as a transparency for overhead projector.
- the imaging materials have excellent shelf life. They may set for months at ambient conditions and in room light without any deterioration in properties, to the degree that the dyes themselves are light stable. They are inexpensive to make and have a broad range of utility.
- Examples 27-39 Examples 1-13 were repeated for each of the following nitrate salts: Aluminum nitrate, nonahydrate, cobalt nitrate hexahydrate, zirconyl nitrate, eerie ammonium nitrate, barium nitrate, cupric nitrate trihydrate, silver nitrate, chromium nitrate nonahydrate, thorium nitrate tetrahydrate, bismuth nitrate pentahydrate, ferric nitrate nonahydrate, sodium nitrate and potassium nitrate. These systems also showed decolorizing effects.
- the multivalent salts tended to be significantly better than the monovalent salts, except that silver nitrate performed as well as many of the multivalent salts because of the oxidizing ability of the silver ion.
- the imaging layers of the present invention may contain various materials in combination with the essential ingredients of the present invention.
- lubricants e.g., ascorbic acid, hindered phenols, phenidone, etc. in amounts that would not prevent oxidation of the dyes when heated
- surfactants e.g., ascorbic acid, hindered phenols, phenidone, etc. in amounts that would not prevent oxidation of the dyes when heated
- surfactants e.g., antistatic agents, mild oxidizing agents in addition to the nitrate, and brighteners may be used without adversely affecting practice of the invention.
- the imaging layers of the present invention must allow reactive association of the active ingredients in order to enable imaging. That is, the individual ingredients may not be separated by impenetrable barriers within the layer, as with dispersed immiscible phases.
- the active ingredients are homogeneously mixed (e.g., a molecular mixture of ingredients) within the layer. They may be individually maintained in heat softenable binders which are dispersed or mixed within the layer and which soften upon heating to allow migration of ingredients, but this would require a longer development time.
- light sensitive or radiation sensitive components such as silver halide, photolabile halogen compounds, diazonium salts, or photooxidant compounds are not essential for the practice of the present invention.
- the preferred construction of the present invention is not light sensitive. That is, if the element were exposed to light in an imagewise manner prior to thermal development of the entire sheet, there would be no dramatic differential image formed. As almost all dyes fade or bleach with prolonged exposure to light, light insensitivity for the element must be defined as stated above, with the exposure being less than that capable of photobleaching the dye itself.
- a coating composition comprising 2.0 grams phthalic acid, 0.3 grams crystal violet, 12.3 grams acetone, 15.4 grams N-methylpyrrolidone, 150 grams of 30% by weight solutions of polyvinylidine chloride in tetrahydrofuran (5%) and methylethylketone (65%) and 0.17 grams of quanidine and nitric acid in equal molar proportions was coated at 75 microns wet thickness on polyester base and dried for three minutes at 75°C. Imagewise heating for forty seconds at 290°F (143°C) provided an image with a D min of 0.17 and a D max of -0.86.
- Example 41 Each and every one of the dye structures listed above with Roman numerals was found to thermally imaging by bleaching in one of the following systems.
- the first system tried was 3 ml of a dye solution formed by dissolving 0.1 g dye in 10 ml of a N-methylpyrolidone/methanol (50/50 volume). To this was added 0.05 g of Ni(NO 3 ) 2 .6H 2 O and 0.05 g of phthalic. acid in 2.5 g methanol. This was then combined with 12.5 g of a resin solution comprising 10% by weight cellulose acetate, 10% methylisobutyl ketone, and 80% acetone.
- Example 42 A coating solution was prepared by dissolving 8g of magnesium nitrate hexahydrate and 12g of phthalic acid in 75g of methanol.
- Example 43-46 Example 42 was repeated except that the magnesium salt was replaced with equimolar (based on nitrate ion) proportions of aluminum nitrate nonahydrate, nickel nitrate hexahydrate, chromium nitrate nonaydrate, and potassium nitrate (the last with 0.5g of glycerol added to the first solution).
- the nickel, aluminum, and chromium salts showed similar results with D max values in excess of 0.9.
- the potassium salt produced a much weaker, but visible image.
- Example 47-49 Example 42 was repeated except that the leuco malachite green was replaced by equal molar amounts of leuco crystal violet, 1(2-(1,3,3-trimethylindolyl))-2- (p-mor ⁇ holinylphenyl)ethene, and the leuco dye
- Example 42 Upon development as in Example 42, violet, red and pale blue images were respectively formed in each of the colorizable systems.
- the imaging layers of the present invention may contain various materials in combination with the essential ingredients of the present invention.
- lubricants e.g., ascorbic acid, hindered phenols, phenidone, etc. in amounts that would not prevent oxidation of the dyes when heated
- surfactants e.g., ascorbic acid, hindered phenols, phenidone, etc. in amounts that would not prevent oxidation of the dyes when heated
- surfactants e.g., antistatic agents, mild oxidizing agents in addition to the nitrate, and brighteners may be used without adversely affecting practice of the invention.
- the imaging layers of the present invention must allow reactive association of the active ingredients in order to enable imaging. That is, the individual ingredients may not be separated by impenetrable barriers within the layer, as with dispersed immiscible phases.
- the active ingredients are homogeneously mixed (e.g., a molecular mixture of ingredients) within the layer. They may be individually maintained in heat softenable binders which are dispersed or nixed within the layer and which soften upon heating to allow migration of ingredients, but this would require a longer development time.
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Color Television Image Signal Generators (AREA)
- Closed-Circuit Television Systems (AREA)
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE8181900104T DE3070044D1 (en) | 1979-12-07 | 1980-11-10 | Color imaging system |
AT81900104T ATE11460T1 (de) | 1979-12-07 | 1980-11-10 | Farbphotographisches abbildungssystem. |
JP81500296A JPS56501480A (de) | 1979-12-07 | 1980-11-10 | |
BR8008959A BR8008959A (pt) | 1979-12-07 | 1980-11-10 | Sistema formador de imagem em cor |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10119779A | 1979-12-07 | 1979-12-07 | |
US10114479A | 1979-12-07 | 1979-12-07 | |
US101144 | 1993-08-02 |
Publications (1)
Publication Number | Publication Date |
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WO1981001757A1 true WO1981001757A1 (en) | 1981-06-25 |
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ID=26797946
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1980/001506 WO1981001757A1 (en) | 1979-12-07 | 1980-11-10 | Color imaging system |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0041540B1 (de) |
JP (1) | JPS56501480A (de) |
AT (1) | ATE11460T1 (de) |
AU (1) | AU543071B2 (de) |
BR (1) | BR8008959A (de) |
DE (1) | DE3070044D1 (de) |
IT (1) | IT1148239B (de) |
MX (1) | MX157192A (de) |
WO (1) | WO1981001757A1 (de) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0055111A2 (de) * | 1980-12-22 | 1982-06-30 | Minnesota Mining And Manufacturing Company | Wärmeempfindliches Aufzeichnungsmaterial für schwarze Bilder |
EP0159874A2 (de) * | 1984-04-16 | 1985-10-30 | Minnesota Mining And Manufacturing Company | Fleckvermeidung in thermischen Aufzeichnungsmaterialien |
EP0181085A1 (de) * | 1984-10-01 | 1986-05-14 | Minnesota Mining And Manufacturing Company | Stabilisierte, leucophenazine Farbstoffe und ihre Verwendung für Aufzeichnungssysteme |
US4889932A (en) * | 1984-10-01 | 1989-12-26 | Minnesota Mining And Manufacturing Company | Stabilized leuco phenazine dyes and their use in an imaging system |
EP0646628A1 (de) * | 1993-09-27 | 1995-04-05 | Minnesota Mining And Manufacturing Company | Spektralsensibilisierte photographische Silberhalogenidelemente |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4386154A (en) * | 1981-03-26 | 1983-05-31 | Minnesota Mining And Manufacturing Company | Visible light sensitive, thermally developable imaging systems |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2324060A (en) * | 1940-10-09 | 1943-07-13 | Eastman Kodak Co | Photographic copying paper |
US2756144A (en) * | 1951-04-25 | 1956-07-24 | Brown Allen Chemicals Inc | Photochemical multicolor printing of textile and the like |
US2880153A (en) * | 1957-01-28 | 1959-03-31 | American Viscose Corp | Photopolymerization process |
US3300314A (en) * | 1963-02-01 | 1967-01-24 | Eastman Kodak Co | Nonsilver, light-sensitive photographic elements |
US3595657A (en) * | 1968-10-03 | 1971-07-27 | Little Inc A | Non-silver direct positive dye bleachout system using indigoid dyes and colorless activators |
US3595655A (en) * | 1968-10-03 | 1971-07-27 | Little Inc A | Non-silver direct positive dyes bleachout system using polymethine dyes and colorless activators |
US3801319A (en) * | 1972-06-21 | 1974-04-02 | Xerox Corp | Imaging method utilizing chemical reactivities of photoexcited states of aromatic hydroxy compounds |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3460964A (en) * | 1964-11-19 | 1969-08-12 | Eastman Kodak Co | Heat-sensitive recording element and composition |
JPS5143786B2 (de) * | 1972-12-23 | 1976-11-24 | ||
JPS6010781B2 (ja) * | 1977-06-22 | 1985-03-20 | 潤三 下飯坂 | 準静的重液選別方法と装置 |
-
1980
- 1980-11-10 AU AU66445/81A patent/AU543071B2/en not_active Ceased
- 1980-11-10 JP JP81500296A patent/JPS56501480A/ja active Pending
- 1980-11-10 BR BR8008959A patent/BR8008959A/pt not_active IP Right Cessation
- 1980-11-10 AT AT81900104T patent/ATE11460T1/de not_active IP Right Cessation
- 1980-11-10 WO PCT/US1980/001506 patent/WO1981001757A1/en active IP Right Grant
- 1980-11-10 DE DE8181900104T patent/DE3070044D1/de not_active Expired
- 1980-11-10 EP EP81900104A patent/EP0041540B1/de not_active Expired
- 1980-12-05 IT IT50318/80A patent/IT1148239B/it active
- 1980-12-05 MX MX185070A patent/MX157192A/es unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2324060A (en) * | 1940-10-09 | 1943-07-13 | Eastman Kodak Co | Photographic copying paper |
US2756144A (en) * | 1951-04-25 | 1956-07-24 | Brown Allen Chemicals Inc | Photochemical multicolor printing of textile and the like |
US2880153A (en) * | 1957-01-28 | 1959-03-31 | American Viscose Corp | Photopolymerization process |
US3300314A (en) * | 1963-02-01 | 1967-01-24 | Eastman Kodak Co | Nonsilver, light-sensitive photographic elements |
US3595657A (en) * | 1968-10-03 | 1971-07-27 | Little Inc A | Non-silver direct positive dye bleachout system using indigoid dyes and colorless activators |
US3595655A (en) * | 1968-10-03 | 1971-07-27 | Little Inc A | Non-silver direct positive dyes bleachout system using polymethine dyes and colorless activators |
US3801319A (en) * | 1972-06-21 | 1974-04-02 | Xerox Corp | Imaging method utilizing chemical reactivities of photoexcited states of aromatic hydroxy compounds |
Non-Patent Citations (1)
Title |
---|
N, Light-Sensitive Systems, August 1965 (JOHN WILEY & SONS, Inc., New York/London/Sydney) JEROME KOSAR, pages 187 and 193 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0055111A2 (de) * | 1980-12-22 | 1982-06-30 | Minnesota Mining And Manufacturing Company | Wärmeempfindliches Aufzeichnungsmaterial für schwarze Bilder |
EP0055111A3 (en) * | 1980-12-22 | 1983-01-05 | Minnesota Mining And Manufacturing Company | Black image from a thermographic imaging system |
EP0159874A2 (de) * | 1984-04-16 | 1985-10-30 | Minnesota Mining And Manufacturing Company | Fleckvermeidung in thermischen Aufzeichnungsmaterialien |
EP0159874A3 (en) * | 1984-04-16 | 1986-06-04 | Minnesota Mining And Manufacturing Company | Prevention of spotting in thermal imaging compositions |
EP0181085A1 (de) * | 1984-10-01 | 1986-05-14 | Minnesota Mining And Manufacturing Company | Stabilisierte, leucophenazine Farbstoffe und ihre Verwendung für Aufzeichnungssysteme |
US4647525A (en) * | 1984-10-01 | 1987-03-03 | Minnesota Mining And Manufacturing Company | Stabilized leuco phenazine dyes and their use in an imaging system |
US4889932A (en) * | 1984-10-01 | 1989-12-26 | Minnesota Mining And Manufacturing Company | Stabilized leuco phenazine dyes and their use in an imaging system |
EP0646628A1 (de) * | 1993-09-27 | 1995-04-05 | Minnesota Mining And Manufacturing Company | Spektralsensibilisierte photographische Silberhalogenidelemente |
US5422236A (en) * | 1993-09-27 | 1995-06-06 | Minnesota Mining And Manufacturing Company | Spectrally sensitized silver halide photographic elements |
Also Published As
Publication number | Publication date |
---|---|
ATE11460T1 (de) | 1985-02-15 |
EP0041540A1 (de) | 1981-12-16 |
EP0041540B1 (de) | 1985-01-23 |
IT8050318A0 (it) | 1980-12-05 |
EP0041540A4 (de) | 1982-03-29 |
BR8008959A (pt) | 1981-10-20 |
MX157192A (es) | 1988-11-03 |
JPS56501480A (de) | 1981-10-15 |
DE3070044D1 (en) | 1985-03-07 |
AU543071B2 (en) | 1985-03-28 |
IT1148239B (it) | 1986-11-26 |
AU6644581A (en) | 1981-07-06 |
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