US3764329A - Heat activated dry silver - Google Patents
Heat activated dry silver Download PDFInfo
- Publication number
- US3764329A US3764329A US00218579A US3764329DA US3764329A US 3764329 A US3764329 A US 3764329A US 00218579 A US00218579 A US 00218579A US 3764329D A US3764329D A US 3764329DA US 3764329 A US3764329 A US 3764329A
- Authority
- US
- United States
- Prior art keywords
- light
- silver
- sheet
- image
- heating
- 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
Links
- 229910052709 silver Inorganic materials 0.000 title abstract description 15
- 239000004332 silver Substances 0.000 title abstract description 15
- 239000000463 material Substances 0.000 abstract description 24
- 238000010438 heat treatment Methods 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052794 bromium Chemical group 0.000 abstract description 5
- 239000000460 chlorine Substances 0.000 abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 239000000344 soap Substances 0.000 abstract description 3
- 150000002366 halogen compounds Chemical class 0.000 abstract description 2
- 238000003384 imaging method Methods 0.000 abstract description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 17
- 229940124024 weight reducing agent Drugs 0.000 description 11
- -1 silver halide Chemical class 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 5
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 5
- CQJNLNKTOGXYCH-UHFFFAOYSA-N 2-bromophthalazin-1-one Chemical compound C1=CC=C2C(=O)N(Br)N=CC2=C1 CQJNLNKTOGXYCH-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HGRZLIGHKHRTRE-UHFFFAOYSA-N 1,2,3,4-tetrabromobutane Chemical compound BrCC(Br)C(Br)CBr HGRZLIGHKHRTRE-UHFFFAOYSA-N 0.000 description 2
- KSBRTGXRNZVPAT-UHFFFAOYSA-N 2-chlorophthalazin-1-one Chemical compound C1=CC=C2C(=O)N(Cl)N=CC2=C1 KSBRTGXRNZVPAT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 206010034960 Photophobia Diseases 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 208000013469 light sensitivity Diseases 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- OTVPURYEWXIAKH-UHFFFAOYSA-N n,n-dibromobenzenesulfonamide Chemical compound BrN(Br)S(=O)(=O)C1=CC=CC=C1 OTVPURYEWXIAKH-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- VBTQNRFWXBXZQR-UHFFFAOYSA-N n-bromoacetamide Chemical compound CC(=O)NBr VBTQNRFWXBXZQR-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 1
- HHBCEKAWSILOOP-UHFFFAOYSA-N 1,3-dibromo-1,3,5-triazinane-2,4,6-trione Chemical compound BrN1C(=O)NC(=O)N(Br)C1=O HHBCEKAWSILOOP-UHFFFAOYSA-N 0.000 description 1
- HGYMQZVPTMKXGI-UHFFFAOYSA-N 1-(2-hydroxynaphthalen-1-yl)sulfanylnaphthalen-2-ol Chemical compound C1=CC=C2C(SC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 HGYMQZVPTMKXGI-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- PHXLONCQBNATSL-UHFFFAOYSA-N 2-[[2-hydroxy-5-methyl-3-(1-methylcyclohexyl)phenyl]methyl]-4-methyl-6-(1-methylcyclohexyl)phenol Chemical compound OC=1C(C2(C)CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1(C)CCCCC1 PHXLONCQBNATSL-UHFFFAOYSA-N 0.000 description 1
- MARXMDRWROUXMD-UHFFFAOYSA-N 2-bromoisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(Br)C(=O)C2=C1 MARXMDRWROUXMD-UHFFFAOYSA-N 0.000 description 1
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical compound CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- CIFFBTOJCKSRJY-UHFFFAOYSA-N 3α,4,7,7α-tetrahydro-1h-isoindole-1,3(2h)-dione Chemical compound C1C=CCC2C(=O)NC(=O)C21 CIFFBTOJCKSRJY-UHFFFAOYSA-N 0.000 description 1
- MQVDCVRWVSDQNN-UHFFFAOYSA-N 4-methyl-2-(1-methylcyclohexyl)phenol Chemical compound CC1=CC=C(O)C(C2(C)CCCCC2)=C1 MQVDCVRWVSDQNN-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241001147416 Ursus maritimus Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- DVNYDODOESWBJY-UHFFFAOYSA-N n-bromo-n-methylbenzenesulfonamide Chemical compound CN(Br)S(=O)(=O)C1=CC=CC=C1 DVNYDODOESWBJY-UHFFFAOYSA-N 0.000 description 1
- FWLGGSWAIHNLLW-UHFFFAOYSA-N n-bromo-n-phenylacetamide Chemical compound CC(=O)N(Br)C1=CC=CC=C1 FWLGGSWAIHNLLW-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment 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
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000033458 reproduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/49818—Silver halides
-
- 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
Definitions
- Light-stable sheet materials which darken only under relatively severe heating and are rendered light-sensitive and rapidly heat-developable by moderate heating contain an imaging composition containing an organic silver soap and a hindered phenol reducing agent together with a small amount of a reducible halogen compound having the essential structure -CONX or -SO NX wherein X is chlorine or bromine.
- This invention relates to the visible recording of lightirnages, and in particular to normally light-insensitive coatings and coated sheet materials which are rendered lightsensitive and heatdevelopable by brief preliminary heating.
- the invention makes possible the preparation, storage, and handling under normal lighting conditions of compositions, coatings and sheet materials which in the last-named form may be made light-sensitive by mere heating.
- the sheet materials of the invention have particular utility in the preparation of add-on copies, such for example as microfilm, microfiche cards, or other recordmaintaining media. Portions of the total film or card area may be provided with desired indicia by selective activation, image exposure, and development, and without affecting adjacent areas which then may subsequently be similarly imaged for up-dating or adding further data to the record.
- the sheet thus serves as an easily up-dated permanent record from which copies for immediate or temporary inspection may be made at any time.
- U.S. Pat. No. 3,457,075 describes a dry silver sheet material which is light-sensitive and heat-developable. It contains photosensitive silver halide, an organic silver salt, and a reducing agent. Exposure to a light-image generates from the silver halide component a catalyst which accelerates the image-forming reaction between the other two components to make possible the subsequent heat development of the visible image.
- the photosensitive silver halide is formed by reaction of a source of halide ions with a small proportion of the organic silver salt. The reaction must therefore be carried out, and the products thereafter maintained, in the absence of light.
- halogen-containing compounds are not reactive with the silver salt and accordingly may be introduced with the image-forming components prior to spreading and without protection from exposure to light.
- the composition is applied in liqiud form in a volatile liquid vehicle which is then permitted to evaporate at less than activation temperature, and the resulting dry layer or coated sheet or film is stable to light.
- Moderate heating above an activation temperature of about C. then causes reduction of the halogen-containing compound, with formation of a halogen source material which reacts with the silver salt to form photosensitive silver halide.
- Reduction of the halogen-containing compound is achieved at least in part by reaction with the reducing agent of the imageforming composition and may be exclusively by such means although the presence of small amounts of other reducing agents for the halogen-containing compound is not precluded.
- Silver salts of long chain fatty acids such for example as silver stearate or silver behenate, have been found particularly useful in the sheet materials of the invention.
- Silver behenate prepared by precipitation with silver nitrate solution from solutions of the sodium soap of commercial behenic acid and if desired, with co-precipitation of minor proportions of the fatty acid, is presently pre ferred.
- Other organic silver salts useful in the practice of this invention have been mentioned in the aboveidentified Pat. No. 3,457,075.
- the reducingagents for silver ion must not be so reactive with the organic silver salt as to cause any significant optical change during the heat activation step.
- Water-insoluble ortho-alkylor -aryl-substituted hindered phenols are found to meet the requirements and to yield sheet materials capable of producing dense black images with substantially no background darkening. Typical examples include 2,6-ditertiarybutyl-4-methylphenol,
- the amounts of organic silver salt and of hindered phenolic reducing agent must be sufficient to enable the formation of the desired dense black image and in the interests of economy of materials the amount of silver salt will ordinarily be little if any greater than such amount.
- concentration of organic silver salt may be as low as about 50 to 200 mgm. of silver per sq. m. of the coating.
- Somewhat larger molar amounts of the hindered phenolic reducing agent may be present, particularly where the same reducing agent is required to react with the halogen-containing compound.
- the amount of the last-named compound will be sufiicient to bring about the conversion of from at least about one to not more than about ten or twelve percent of the silver salt to silver halide, depending on the particular sensitometric characteristics desired; conversion of about three to about eight percent is usually preferred.
- Compounds which have been found particularly useful as sources of halide ion for use in the practice of this invention include N bromophthalimide, N bromosuccinimide, N-bromoacetamide, N-bromoacetanilide, N-bromo- 1 (2H) hthalazinone, N,N dibromobenzenesulfonamide, N-bromo-N-methylbenzene-sulfonamide, 1,3 dibromo-4,4-dimethylhydantoin, potassium salt of dibromoisocyanuric acid, trichloroisocyanuric acid.
- N-chloro counterparts of many of these compounds have likewise been shown to be useful but less desirable both in their reaction characteristics and in the photographic sensitivity of the resulting sheet.
- Presently available N-iodo counterparts are too reactive to provide a light-stable sheet.
- Compounds are preferred which are free of aliphatic unsaturation and of amino or mercapto groups or of other groups the presence of which might be expected to result in uncontrollable light-sensitivity, or spontaneous decomposition, or excessive color, or other deleterious influence.
- the coatings of the invention will usually contain a film-forming binder, a toner for the silver image, and a photosensitizing dye, and may contain additional components such as wetting agents, antifoam agents, pigments, fillers, etc. Coatings of such compositions may be made on a temporary support and removed therefrom in dry thin film form, but will ordinarily be applied to paper or film substrates which form a part of the final sheet product. The substrate may be primed or subbed for improved bonding or to prevent excessive penetration or for other purposes, and the coating may be further protected with additional surface layers desired. Transparent coatings on transparent film backings or supports are particularly desirable in permitting subsequent copying of data from the imaged sheet by methods involving light projection or contact printing onto a photosensitive receptor.
- the sheet material prepared as above described is stable to light and may be left for many days exposed to ordinary room light conditions. When thus exposed and then briefly heated at image development temperature, no visible change occurs in the coating. On subsequent exposure to a light-image followed by further heating, the sheet will be found to undergo extensive darkening at the light-struck areas. Accordingly, it is possible to first activate the sheet by controlled heating in absence of light, and thereafter to expose to a light-image and then develop the image by further controlled heating.
- Proportions are by weight unless otherwise indicated.
- a portion of the sheet is heated for ten seconds at 134 C. without visible change. When then exposed to a lightimage from a photo flash lamp and again heated, a visible record is obtained, the light-exposed areas becoming black in appearance. Another portion is first heated for 8-10 seconds at 90-l00 0., exposed to the light image, and heat developed for 10 seconds at 134 C. to provide an equally distinct visible record.
- EXAMPLE 2 Silver behenate suspension, gm 100 Methylethyl ketone, ml. 77 Polyvinyl butyral, gm 2 N-bromo-phthalazinone, gm. 0.2 Tetrabromobutane, gm. 1.6 Polyvinyl butyral, gm. 18 Solution of sensitizing dye, ml. 20 Solution of mercuric acetate, ml. 4.0
- the silver behenate suspension contains 12 parts of the salt in 88 parts of a 2:1 mixture of methylethyl ketone and toluene. It is homogenized and is gelatinous and nonsettling.
- the dye solution contains 0.13 gram of dye per liter of methylethyl ketone.
- the dye is the blue sensitizer dye identified as 1-carboxymethyl-3-(N-methylbenzothiazolylindy1)-4-thia-2-thiohydantoin.
- the mercuric acetate solution contains 5% of the salt, dissolved in methanol.
- the silver salt suspension, solvent and two grams of binder are mixed together until the binder is dissolved.
- the remaining components are added in the order indicated with continuous and intermediate mixing.
- the mixture is coated on polyester film from a 4 mil (0.1 mm.) orifice and dried at C.
- a second coating is next applied, at an orifice of 2.5 mils (0.064 mm.), and promptly dried at room tempera-
- the coated sheets are stable toward light for at least several months under normal room conditions. When first activated by brief heating they are light-sensitive and when then exposed to a light-image and again heated are found to yield high contrast sharp negative reproductions, the light-struck areas becoming a dense black.
- Activation may be accomplished by heating above about 90 C., for example for 30 seconds at C., 15 seconds at C., for 5 seconds at C.
- Develop ment may then be accomplished by heating for 20 seconds at 115 C., 10 seconds at 127 C., or 5 seconds at 143 C.
- activation involves heating sufficiently to cause reduction of the organic haloamide and formation of a source of halogen reactive with silver but short of incipient darkening or backgrounding; whereas development involves heating sufliciently to obtain maximum contrast at minimum or permissible backgrounding.
- N,N-dibromobenzene-sulfonamide for the N-bromophthalazinone of the 2,2'-methylenebis-(4-methyl-6-tert.butylphenol) 1,1'-thiobis-(2-naphthol) 2-(4-hydroxy-3,S-di-t-butylphenoxy) 6 (n octlythio)- 1,3,5-triazine.
- the N-bromophthalazinone is made by a process involving dropwise addition of bromine (14.6 gm.) to a cold solution of 1-(2H)-phthalazinone (13.3 gm.) in aqueous methyl alcohol (500 ml., 50% by volume) followed by dropwise addition of sodium hydroxide solution (3.64 gm. in 50 ml. water).
- the yellowish-white precipitate after filtering, washing with methyl alcohol and with n-heptane, and drying in vacuo, melts at about 160 C. with decomposition, and on analysis shows the compositiOn C3H5N2OBI'.
- N-chlorophthalazinone is also eifective. This compound is made by gradually mixing 1-(2H)-phthalazinone gm.) into cold aqueous sodium hyprochlorite solution (100 ml., 5% NaOCl), extracting with dichloromethane, drying, and concentrating under reduced pressure to yield a mass of colorless needles which is washed with n-hexane and dried. The product melts at about 142 C. without decomposition and analyzes as C H N OCl.
- Example 2 The mixture is prepared and coated as described in Example 2. Separate portions are then top-coated with solutions of cellulose acetate, phthalazinone and developer, also as described in Example 2, using as specific developers the following compounds:
- A 2,2-methylenebis(4-ethyl-6-tert-butylphenol)
- B 2,2'-methylenebis-(4-methyl-6-(l-methylcyclohexyl) phenol)
- C 2,4,4 trimethylphentyl-bis(2-hydroxy-3,5-dimethylphenyl)methane.
- Sheets A and B tend to give positive rather than negative images when activated or developed at relatively high temperature or for extended periods of time.
- EXAMPLE 4 This example illustrates the use of smaller amounts of silver salt in sheet materials similar to those of Example 2.
- the first coat composition contains 12% silver salt suspension, gm 75 35 Acetone, m1 77 77 Polyvinyl butyral, gm- 2O 20 N-bromophthalazinone, 0. 2 0. 2 Tetrabromobutane, gm... 1. 6 1. 6 Dye solution, ml 20 20 Mercuric acetate solution, ml 2. 5 2. 5
- the top coat is as described under Example 3(0).
- the resulting sheets are stable under prolonged exposure.
- Sheet A is activated 5 seconds at 127 C., exposed, and developed 10 seconds at 127 C. to produce a negative print with good contrast and high image density.
- Sheet B is activated 5 seconds at 143 C., exposed, and developed 15 seconds at 127 C. and produces a less dense image with some darkening in the unexposed background areas.
- EXAMPLE 5 Transparent polyester film is sub-coated with a 4 mil (0.1 mm.) thickness of a solution containing N-chlorophthalazinone 1 Polyvinyl butyral 10 Dichloromethane 190 and the sheet is dried at C. It is then coated with a applied at 4 mils (0.1 mm.) and again dried at 80 C. A final topcoat of a solution as described under Example 3(C), completes the construction.
- the sheet is stable under prolonged room condition exposure. It is activated in 5 seconds at 132 C. and after flash-lamp exposure to a light-image forms a high density black image at the exposed image areas when developed for 10 seconds at 127 C.
- Coated sheet materials are prepared in accordance with the formulas and procedures given in Example 2 except that in the second coat formulations another material is substituted for half of the phthalazinone content.
- the operating and image characteristics are substantially the same as those obtained with the earlier formulation.
- the substituents are:
- Light-stable sheet material which can be rendered photosensitive by heating, characterized by including a stratum containing an organic silver salt and an organic haloamide compound which is non-reactive with the silver salt and which has the essential structure -CONX-- or 4O NX- wherein X is chlorine or bromine, the amount of said haloamide compound being suificient to supply from about one to about 12 moles of said X component for each moles of said silver salt.
- Light-stable sheet material of claim 1 wherein is included a water-insoluble ortho-substituted hindered phenol reducing agent for silver ion.
- Light-stable sheet material of claim 2 wherein the amount of said haloamide compound is sufficient to supply from about three to about eight moles of said X component for each 100 moles of said silver salt.
- Light-stable sheet material of claim 2 wherein said silver salt and said haloamide are contained in one layer and said reducing agent in an adjacent layer of said stratum.
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US21857972A | 1972-01-17 | 1972-01-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3764329A true US3764329A (en) | 1973-10-09 |
Family
ID=22815652
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00218579A Expired - Lifetime US3764329A (en) | 1972-01-17 | 1972-01-17 | Heat activated dry silver |
Country Status (15)
Country | Link |
---|---|
US (1) | US3764329A (fr) |
JP (1) | JPS532687B2 (fr) |
AR (1) | AR193314A1 (fr) |
AU (1) | AU451588B2 (fr) |
BE (1) | BE794090A (fr) |
BR (1) | BR7300354D0 (fr) |
CA (1) | CA994150A (fr) |
CH (1) | CH577695A5 (fr) |
DE (1) | DE2302462C3 (fr) |
FR (1) | FR2168370B1 (fr) |
GB (1) | GB1423033A (fr) |
IT (1) | IT976908B (fr) |
NL (1) | NL7300171A (fr) |
SE (1) | SE383930B (fr) |
ZA (1) | ZA727395B (fr) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3816132A (en) * | 1972-03-27 | 1974-06-11 | Oriental Photo Ind Co Ltd | Heat-developable light-sensitive materials |
US3892569A (en) * | 1972-12-04 | 1975-07-01 | Gen Film Dev Corp | Photosensitive sheets comprising organic dyes and sensitizers |
DE2657080A1 (de) * | 1975-12-16 | 1977-06-30 | Asahi Chemical Ind | Trocken-bildaufzeichnungsmaterial |
US4069759A (en) * | 1974-07-27 | 1978-01-24 | Canon Kabushiki Kaisha | Light and heat formation of conductive image printing plate |
US4173482A (en) * | 1977-03-16 | 1979-11-06 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material containing an organic silver salt oxidizing agent, a reducing agent and a halogen molecule |
US4188226A (en) * | 1977-07-18 | 1980-02-12 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material containing diarylhalomethane |
DE2931920A1 (de) * | 1978-08-11 | 1980-02-21 | Asahi Chemical Ind | Bilderzeugungsverfahren und vorrichtung hierfuer |
US4237215A (en) * | 1974-02-19 | 1980-12-02 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive material |
US4268626A (en) * | 1978-08-28 | 1981-05-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material |
US4327176A (en) * | 1979-11-09 | 1982-04-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material |
US4332889A (en) * | 1980-05-23 | 1982-06-01 | Asahi Kasei Kogyo Kabushiki Kaisha | Post-activation type dry image forming material |
US4347310A (en) * | 1977-10-14 | 1982-08-31 | Asahi Kasei Kogyo Kabushiki Kaisha | Heat developable silver image forming materials |
US4395484A (en) * | 1982-06-25 | 1983-07-26 | Minnesota Mining And Manufacturing Company | Roomlight-stable ultraviolet-response photothermographic imaging material |
US4396712A (en) * | 1980-05-30 | 1983-08-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material |
US4433037A (en) * | 1982-07-15 | 1984-02-21 | Eastman Kodak Company | Heat erasable photographic element and process comprising silver halide |
US4725534A (en) * | 1981-05-13 | 1988-02-16 | Oriental Photo Industrial Co., Ltd. | Process for producing a heat-developable photosensitive material |
US4743948A (en) * | 1985-12-23 | 1988-05-10 | Fuji Photo Film Co., Ltd. | Recording and projecting apparatus |
WO1988005559A1 (fr) * | 1987-01-22 | 1988-07-28 | The Foxboro Company | Procede de configuration d'une reserve |
US4893148A (en) * | 1986-09-04 | 1990-01-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for storing dry silver salt roll film for rotary type microphotography and rotary type microphotography camera system |
US5015553A (en) * | 1985-06-10 | 1991-05-14 | The Foxboro Company | Method of patterning resist |
US5041368A (en) * | 1990-06-07 | 1991-08-20 | Minnesota Mining And Manufacturing Company | Photothermographic elements |
US5254435A (en) * | 1985-06-10 | 1993-10-19 | The Foxboro Company | Method of patterning resist |
US5369000A (en) * | 1993-04-29 | 1994-11-29 | Minnesota Mining And Manufacturing Company | Post-processing stabilizers for photothermographic articles |
US5968714A (en) * | 1996-03-14 | 1999-10-19 | Agfa-Gevaert | Sensitivity-increasing recording process for a photosensitive thermally developable photographic material |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5423813B2 (fr) * | 1972-12-26 | 1979-08-16 | ||
JPS5340484B2 (fr) * | 1973-11-09 | 1978-10-27 | ||
JPS5820418B2 (ja) * | 1977-11-14 | 1983-04-22 | 旭化成株式会社 | 乾式画像形成材料の製造方法 |
EP0730196B1 (fr) * | 1995-03-02 | 2000-10-25 | Agfa-Gevaert N.V. | Matériau d'enregistrement thermosensible à propriétés stabilisatrices de l'image |
DE69610725T2 (de) * | 1995-03-02 | 2001-05-10 | Agfa-Gevaert N.V., Mortsel | Wärmeempfindliches Aufzeichnungsmaterial mit bildstabilisierenden Eigenschaften |
-
0
- BE BE794090D patent/BE794090A/fr not_active IP Right Cessation
-
1972
- 1972-01-17 US US00218579A patent/US3764329A/en not_active Expired - Lifetime
- 1972-10-17 ZA ZA727395*7A patent/ZA727395B/xx unknown
- 1972-12-28 CA CA160,127A patent/CA994150A/en not_active Expired
-
1973
- 1973-01-04 SE SE7300100A patent/SE383930B/xx unknown
- 1973-01-05 NL NL7300171A patent/NL7300171A/xx not_active Application Discontinuation
- 1973-01-16 GB GB231973A patent/GB1423033A/en not_active Expired
- 1973-01-16 JP JP732273A patent/JPS532687B2/ja not_active Expired
- 1973-01-16 FR FR7301381A patent/FR2168370B1/fr not_active Expired
- 1973-01-16 BR BR73354A patent/BR7300354D0/pt unknown
- 1973-01-16 CH CH58973A patent/CH577695A5/xx not_active IP Right Cessation
- 1973-01-16 AR AR246158A patent/AR193314A1/es active
- 1973-01-16 IT IT47715/73A patent/IT976908B/it active
- 1973-01-16 DE DE2302462A patent/DE2302462C3/de not_active Expired
- 1973-04-02 AU AU54014/73A patent/AU451588B2/en not_active Expired
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3816132A (en) * | 1972-03-27 | 1974-06-11 | Oriental Photo Ind Co Ltd | Heat-developable light-sensitive materials |
US3892569A (en) * | 1972-12-04 | 1975-07-01 | Gen Film Dev Corp | Photosensitive sheets comprising organic dyes and sensitizers |
US4237215A (en) * | 1974-02-19 | 1980-12-02 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive material |
US4069759A (en) * | 1974-07-27 | 1978-01-24 | Canon Kabushiki Kaisha | Light and heat formation of conductive image printing plate |
DE2657080A1 (de) * | 1975-12-16 | 1977-06-30 | Asahi Chemical Ind | Trocken-bildaufzeichnungsmaterial |
US4173482A (en) * | 1977-03-16 | 1979-11-06 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material containing an organic silver salt oxidizing agent, a reducing agent and a halogen molecule |
US4188226A (en) * | 1977-07-18 | 1980-02-12 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material containing diarylhalomethane |
US4347310A (en) * | 1977-10-14 | 1982-08-31 | Asahi Kasei Kogyo Kabushiki Kaisha | Heat developable silver image forming materials |
US4335957A (en) * | 1978-08-11 | 1982-06-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Image forming method and apparatus therefor |
DE2931920A1 (de) * | 1978-08-11 | 1980-02-21 | Asahi Chemical Ind | Bilderzeugungsverfahren und vorrichtung hierfuer |
US4287295A (en) * | 1978-08-11 | 1981-09-01 | Asahi Kasei Kogyo Kabushiki Kaisha | Image forming method and apparatus therefor |
US4268626A (en) * | 1978-08-28 | 1981-05-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material |
US4327176A (en) * | 1979-11-09 | 1982-04-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material |
US4332889A (en) * | 1980-05-23 | 1982-06-01 | Asahi Kasei Kogyo Kabushiki Kaisha | Post-activation type dry image forming material |
US4396712A (en) * | 1980-05-30 | 1983-08-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material |
US4725534A (en) * | 1981-05-13 | 1988-02-16 | Oriental Photo Industrial Co., Ltd. | Process for producing a heat-developable photosensitive material |
US4395484A (en) * | 1982-06-25 | 1983-07-26 | Minnesota Mining And Manufacturing Company | Roomlight-stable ultraviolet-response photothermographic imaging material |
US4433037A (en) * | 1982-07-15 | 1984-02-21 | Eastman Kodak Company | Heat erasable photographic element and process comprising silver halide |
US5015553A (en) * | 1985-06-10 | 1991-05-14 | The Foxboro Company | Method of patterning resist |
US5254435A (en) * | 1985-06-10 | 1993-10-19 | The Foxboro Company | Method of patterning resist |
US4743948A (en) * | 1985-12-23 | 1988-05-10 | Fuji Photo Film Co., Ltd. | Recording and projecting apparatus |
US4893148A (en) * | 1986-09-04 | 1990-01-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for storing dry silver salt roll film for rotary type microphotography and rotary type microphotography camera system |
WO1988005559A1 (fr) * | 1987-01-22 | 1988-07-28 | The Foxboro Company | Procede de configuration d'une reserve |
US5041368A (en) * | 1990-06-07 | 1991-08-20 | Minnesota Mining And Manufacturing Company | Photothermographic elements |
US5369000A (en) * | 1993-04-29 | 1994-11-29 | Minnesota Mining And Manufacturing Company | Post-processing stabilizers for photothermographic articles |
US5464737A (en) * | 1993-04-29 | 1995-11-07 | Minnesota Mining And Manufacturing Company | Post-processing stabilizers for photothermographic articles |
US5968714A (en) * | 1996-03-14 | 1999-10-19 | Agfa-Gevaert | Sensitivity-increasing recording process for a photosensitive thermally developable photographic material |
Also Published As
Publication number | Publication date |
---|---|
AU451588B2 (en) | 1974-08-15 |
NL7300171A (fr) | 1973-07-19 |
FR2168370A1 (fr) | 1973-08-31 |
GB1423033A (en) | 1976-01-28 |
FR2168370B1 (fr) | 1977-01-07 |
AR193314A1 (es) | 1973-04-11 |
DE2302462A1 (de) | 1973-07-19 |
DE2302462C3 (de) | 1980-01-17 |
ZA727395B (en) | 1973-06-27 |
BE794090A (fr) | 1973-07-16 |
AU5401473A (en) | 1974-08-15 |
IT976908B (it) | 1974-09-10 |
CA994150A (en) | 1976-08-03 |
SE383930B (sv) | 1976-04-05 |
JPS4880030A (fr) | 1973-10-26 |
CH577695A5 (fr) | 1976-07-15 |
JPS532687B2 (fr) | 1978-01-31 |
BR7300354D0 (pt) | 1973-10-09 |
DE2302462B2 (de) | 1979-05-03 |
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