EP0821268A1 - An emulsion for a photothermographic material, a production process for the photothermographic material and a recording process therefor - Google Patents
An emulsion for a photothermographic material, a production process for the photothermographic material and a recording process therefor Download PDFInfo
- Publication number
- EP0821268A1 EP0821268A1 EP97201899A EP97201899A EP0821268A1 EP 0821268 A1 EP0821268 A1 EP 0821268A1 EP 97201899 A EP97201899 A EP 97201899A EP 97201899 A EP97201899 A EP 97201899A EP 0821268 A1 EP0821268 A1 EP 0821268A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- emulsion
- silver salt
- silver
- substantially light
- polyhalides
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 92
- 239000000839 emulsion Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title description 3
- -1 silver halide Chemical class 0.000 claims abstract description 85
- 229910052709 silver Inorganic materials 0.000 claims abstract description 64
- 239000004332 silver Substances 0.000 claims abstract description 64
- 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 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000012360 testing method Methods 0.000 claims abstract description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims abstract description 10
- 125000005496 phosphonium group Chemical group 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 77
- 239000003638 chemical reducing agent Substances 0.000 claims description 39
- 239000011241 protective layer Substances 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims 1
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 27
- 238000003756 stirring Methods 0.000 description 27
- 239000006185 dispersion Substances 0.000 description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 19
- 238000001035 drying Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 238000011161 development Methods 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 15
- 239000008199 coating composition Substances 0.000 description 14
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 14
- 239000000975 dye Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 13
- 239000004926 polymethyl methacrylate Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 10
- 239000011888 foil Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- NSBNSZAXNUGWDJ-UHFFFAOYSA-O monopyridin-1-ium tribromide Chemical compound Br[Br-]Br.C1=CC=[NH+]C=C1 NSBNSZAXNUGWDJ-UHFFFAOYSA-O 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 235000021357 Behenic acid Nutrition 0.000 description 7
- 229940116226 behenic acid Drugs 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- CWJJAFQCTXFSTA-UHFFFAOYSA-N 4-methylphthalic acid Chemical compound CC1=CC=C(C(O)=O)C(C(O)=O)=C1 CWJJAFQCTXFSTA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 6
- 229910001622 calcium bromide Inorganic materials 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 6
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 150000003378 silver Chemical class 0.000 description 5
- 238000001931 thermography Methods 0.000 description 5
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 3
- DZAUWHJDUNRCTF-UHFFFAOYSA-N 3-(3,4-dihydroxyphenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=C(O)C(O)=C1 DZAUWHJDUNRCTF-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 230000006399 behavior Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- AFINAILKDBCXMX-PBHICJAKSA-N (2s,3r)-2-amino-3-hydroxy-n-(4-octylphenyl)butanamide Chemical compound CCCCCCCCC1=CC=C(NC(=O)[C@@H](N)[C@@H](C)O)C=C1 AFINAILKDBCXMX-PBHICJAKSA-N 0.000 description 2
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Chemical class 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- VFPFQHQNJCMNBZ-UHFFFAOYSA-N ethyl gallate Chemical compound CCOC(=O)C1=CC(O)=C(O)C(O)=C1 VFPFQHQNJCMNBZ-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 2
- 239000000025 natural resin Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
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- 150000004010 onium ions Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
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- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
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- 229940045105 silver iodide Drugs 0.000 description 2
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- 229960002317 succinimide Drugs 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
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- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- IHAWQAMKUMLDIT-UHFFFAOYSA-N 1,1,1,3,3,3-hexabromopropan-2-one Chemical class BrC(Br)(Br)C(=O)C(Br)(Br)Br IHAWQAMKUMLDIT-UHFFFAOYSA-N 0.000 description 1
- HATRZINXSXGGHD-UHFFFAOYSA-N 1,1-dichloroethene;2-methylidenebutanedioic acid;methyl prop-2-enoate Chemical compound ClC(Cl)=C.COC(=O)C=C.OC(=O)CC(=C)C(O)=O HATRZINXSXGGHD-UHFFFAOYSA-N 0.000 description 1
- UXTZUUVTGMDXNG-UHFFFAOYSA-N 1,2-benzoxazine-3,4-dione Chemical compound C1=CC=C2C(=O)C(=O)NOC2=C1 UXTZUUVTGMDXNG-UHFFFAOYSA-N 0.000 description 1
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical class OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
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- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical group C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- UHKAJLSKXBADFT-UHFFFAOYSA-N 1,3-indandione Chemical class C1=CC=C2C(=O)CC(=O)C2=C1 UHKAJLSKXBADFT-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical class C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- NLERVTXJOGYIKC-UHFFFAOYSA-N 1-(3,4-dihydroxyphenyl)butan-1-one Chemical compound CCCC(=O)C1=CC=C(O)C(O)=C1 NLERVTXJOGYIKC-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- KEQTWHPMSVAFDA-UHFFFAOYSA-N 2,3-dihydro-1h-pyrazole Chemical class C1NNC=C1 KEQTWHPMSVAFDA-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical class OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-UHFFFAOYSA-N 0.000 description 1
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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
- G03C1/49836—Additives
- G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
-
- 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
- G03C1/12—Methine and polymethine 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
- G03C1/005—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
- G03C1/12—Methine and polymethine dyes
- G03C1/127—Methine and polymethine dyes the polymethine chain forming part of a carbocyclic ring
-
- 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
- G03C1/49836—Additives
- G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
- G03C1/49854—Dyes or precursors of 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
- G03C5/164—Infra-red processes
Definitions
- the present invention relates to an emulsion for a photothermographic material, a production process for the photothermographic material and a recording process therefor.
- Thermal imaging or thermography is a recording process wherein images are generated by the use of imagewise modulated thermal energy.
- thermography three approaches are known:
- Thermographic materials of type 1 become photothermographic when a photosensitive agent is present which after exposure to UV, visible or IR light is capable of catalyzing or participating in a thermographic process bringing about changes in colour or optical density.
- photothermographic materials are the so called “Dry Silver” photographic materials of the 3M Company, which are reviewed by D.A. Morgan in “Handbook of Imaging Science”, edited by A.R. Diamond, page 43, published by Marcel Dekker in 1991.
- GB 1 342 525 discloses a photosensitive heat-processable material comprising a support and contained in a layer or layers thereof: (a) an oxidation/reduction image-forming system comprising: (b) a light-insensitive reducible metal compound and (c) an organic reducing agent therefor, (d) a photosensitive silver compound capable, on exposure to actinic radiation, of forming centres which catalyse the thermally induced oxidation/reduction reaction of (b) with (c) to form a visible image, and (e) a substantially colourless photographic speed-increasing onium halide.
- US-P 3,957,517 discloses a dry method for the stabization of a print-out silver halide photographic material wherein the silver halide is the image-forming substance, which comprises (1) imagewise exposure of a silver halide photographic emulsion material to form a print-out image, wherein said silver halide photographic emulsion material consists essentially of silver halide grains at least 50mol% of which consists of silver bromide and 0.1 to 33 mol%, based on the silver halide, of an onium compound having an iodide ion or an anion containing iodine, said onium compound being a member selected from the group consisting of compounds of the formulae: wherein A is N, P, As or Sb, B is O, S, SO, Se or Sn, and each of R 1 to R 9 is an alkyl group having less than 8 carbon atoms, or an aryl group having less than 16 carbon atoms, or of said R 1 to R 9 two groups can be connected
- a dry image forming material capable of forming an image by preliminary heating, imagewise exposure to light, and heat development thereof, said material comprising (a) a non-photosensitive organic silver salt oxidizing agent, (b) a reducing agent for a silver ion and (c) at least one halogen molecule selected from the group consisting of a bromine molecule, an iodine molecule, iodine chlorides, iodine bromide and bromine chloride and optionally further comprising at least one halogen ion source in addition to said at least one halogen molecule.
- the halogen ion source and the halogen molecule may be added separately, or a compound or compounds capable of forming a halogen ion source and a halogen molecule by reaction at the preparation of the image forming material may be used, for example triphenylphosphite nonaiodide.
- US-P 5,028,523 discloses a photothermographic emulsion comprising silver halide, light-insensitive silver oxidizing compound, reducing agent for silver ion, and a binder, said emulsion also comprising a hydrobromic salt of a nitrogen-containing heterocyclic ring compound associated with a pair of bromine atoms.
- hydrobromic salt of a nitrogen-containing heterocyclic ring compound associated with a pair of bromine atoms used in the invention example of US-P 5,028,523, pyridinium hydrobromide perbromide exhibits a high reactivity with silver behenate to form photosensitive silver bromide which, as is mentioned above, is undesirable as regards control over the gradation of the image as expressed by the dependence of optical density upon exposure to actinic light.
- an emulsion comprising a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association with the substantially light-insensitive organic silver salt and a binder, characterized in that the emulsion further comprises a polyhalide compound selected from the group consisting of quaternary ammonium polyhalides, quaternary phosphonium polyhalides and ternary sulphonium polyhalides, which satisfies a test specified in the description, or a product of a reaction between the polyhalide compound and a reducing species present in the emulsion.
- a polyhalide compound selected from the group consisting of quaternary ammonium polyhalides, quaternary phosphonium polyhalides and ternary sulphonium polyhalides, which satisfies a test specified in the description, or a product of a reaction between the polyhalide compound and a reducing species present in the emulsion.
- a process for producing a photothermographic recording material capable of image formation without preliminary heating prior to exposure, comprising the step of producing a photo-addressable thermally developable element by coating an emulsion, as referred to above, on a support thereby forming an emulsion layer.
- a photothermographic recording material capable of image formation without preliminary heating prior to exposure, comprising a photo-addressable thermally developable element comprising a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association with the substantially light-insensitive organic silver salt, an organic reducing agent in thermal working relationship with the substantially light-insensitive organic silver salt and a binder, characterized in that the photo-addressable thermally developable element further comprises a polyhalide compound selected from the group consisting of quaternary ammonium polyhalides, quaternary phosphonium polyhalides and ternary sulphonium polyhalides, which satisfies a test specified in the description.
- a photothermographic recording process comprising the steps of:
- an emulsion comprising a polyhalide compound selected from the group consisting of quaternary ammonium polyhalides, quaternary phosphonium polyhalides and ternary sulphonium polyhalides, which satisfies a test given below, or a product of a reaction between the polyhalide compound and a reducing species present in the emulsion.
- optical density of less than 0.3 indicates that little photosensitive silver halide is formed due to reaction between the compound being evaluated and silver behenate.
- hydrobromic salts of nitrogen-containing heterocyclic ring compounds associated with a pair of bromine atoms did not satisfy this test, optical densities ⁇ 1.2 being observed, which indicates the formation of a considerable quantity of photosensitive silver halide due to reaction between such compounds and silver behenate.
- the polyhalide compound is selected from the group of polyhalide compounds consisting of tetramethylammonium chloride perbromide, trimethylphenylammonium bromide perbromide and tetramethylammonium bromide perbromide.
- the quaternary ammonium, quaternary phosphonium and ternary sulphonium polyhalides, used according to the present invention may be added as solids or solutions or may be formed in the dispersion of particles of the substantially light-insensitive silver salt by metathesis between a salt with polyhalide anions and onium salts with anions other than polyhalide.
- Preferred polyhalide anions used according to the present invention, consist of chlorine, bromine and iodine atoms.
- the quaternary ammonium, quaternary phosphonium and ternary sulphonium polyhalides, used according to the present invention may be polymeric or non-polymeric.
- Suitable non-polymeric onium salts for use according to the present invention are the quaternary ammonium polyhalides (QAP's):
- the quaternary ammonium, quaternary phosphonium and ternary sulphonium polyhalides, used according to the present invention are preferably present in quantities of between 0.1 and 5.0mol% with respect to the quantity of substantially light-insensitive organic silver salt of organic, with quantities between 0.4 and 2.4mol% being particularly preferred.
- the photo-addressable thermally developable element comprises a substantially light-insensitive silver salt of a fatty acid, photosensitive silver halide in catalytic association therewith and an organic reducing agent in thermal working relationship with the substantially light-insensitive silver salt of a fatty acid and a binder.
- the element may comprise a layer system with the silver halide in catalytic association with the substantially light-insensitive organic silver salt ingredients, spectral sensitizer optionally together with a supersensitizer in intimate sensitizing association with the silver halide particles and the other ingredients active in the thermal development process or pre- or post-development stabilization of the element being in the same layer or in other layers with the proviso that the organic reducing agent and the toning agent, if present, are in thermal working relationship with the substantially light-insensitive organic silver salt i.e. during the thermal development process the reducing agent and the toning agent, If present, are able to diffuse to the substantially light-insensitive silver salt of a fatty acid.
- Preferred substantially light-insensitive organic silver salts used according to the present invention are silver salts of aliphatic carboxylic acids known as fatty acids, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salts are also called "silver soaps"; silver dodecyl sulphonate described in US-P 4,504,575; and silver di-(2-ethylhexyl)-sulfosuccinate described in EP-A 227 141.
- Modified aliphatic carboxylic acids with thioether group as described e.g.
- the photosensitive silver halide used in the present invention may be employed in a range of 0.75 to 25 mol percent and, preferably, from 2 to 20 mol percent of substantially light-insensitive organic silver salt.
- the silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide etc.
- the silver halide may be in any form which is photosensitive including, but not limited to, cubic, orthorhombic, tabular, tetrahedral, octagonal etc. and may have epitaxial growth of crystals thereon.
- the silver halide used in the present invention may be employed without modification. However, it may be chemically sensitized with a chemical sensitizing agent such as a compound containing sulphur, selenium, tellurium etc., or a compound containing gold, platinum, palladium, iron, ruthenium, rhodium or iridium etc., a reducing agent such as a tin halide etc., or a combination thereof.
- a chemical sensitizing agent such as a compound containing sulphur, selenium, tellurium etc., or a compound containing gold, platinum, palladium, iron, ruthenium, rhodium or iridium etc.
- a reducing agent such as a tin halide etc.
- a suspension of particles containing a substantially light-insensitive organic silver salt may be obtained by using a process, comprising simultaneous metered addition of a solution or suspension of an organic compound with at least one ionizable hydrogen atom or its salt; and a solution of a silver salt to a liquid, as described in EP-A 754 969.
- the silver halide may be added to the photo-addressable thermally developable element in any fashion which places it in catalytic proximity to the substantially light-insensitive organic silver salt.
- Silver halide and the substantially light-insensitive organic silver salt which are separately formed, i.e. ex-situ or "preformed", in a binder can be mixed prior to use to prepare a coating solution, but it is also effective to blend both of them for a long period of time.
- it is effective to use a process which comprises adding a halogen-containing compound to the organic silver salt to partially convert the substantially light-insensitive organic silver salt to silver halide as disclosed in US-P 3,457,075.
- a particularly preferred mode of preparing the emulsion of organic silver salt and photosensitive silver halide, used according to the present invention is that disclosed in US-P 3,839,049, but other methods such as those described in Research Disclosure, June 1978, item 17029 and US-P 3,700,458 may also be used for producing the emulsion.
- the emulsion further comprises a reducing agent for silver ion.
- Organic reducing agent for photo-addressable thermally developable elements coated from non-aqueous media Organic reducing agent for photo-addressable thermally developable elements coated from non-aqueous media
- Suitable organic reducing agents for the reduction of the substantially light-insensitive organic heavy metal salts in photo-addressable thermally developable coated from non-aqueous media are organic compounds containing at least one active hydrogen atom linked to O, N or C, such as is the case with, mono-, bis-, tris- or tetrakis-phenols; mono- or bis-naphthols; di- or polyhydroxynaphthalenes; di- or polyhydroxybenzenes; hydroxymonoethers such as alkoxynaphthols, e.g. 4-methoxy-1-naphthol described in US-P 3,094,41; pyrazolidin-3-one type reducing agents, e.g.
- PHENIDONE (tradename); pyrazolin-5-ones; indan-1,3-dione derivatives; hydroxytetrone acids; hydroxytetronimides; 3-pyrazolines; pyrazolones; reducing saccharides; aminophenols e.g. METOL (tradename); p-phenylenediamines, hydroxylamine derivatives such as for example described in US-P 4,082,901; reductones e.g. ascorbic acids; hydroxamic acids; hydrazine derivatives; amidoximes; n-hydroxyureas; and the like, see also US-P 3,074,809, 3,080,254, 3,094,417 and 3,887,378.
- Polyphenols such as the bisphenols used in the 3M Dry SilverTM materials, sulfonamide phenols such as used in the Kodak DacomaticTM materials, and naphthols are particularly preferred for photothermographic recording materials with photo-addressable thermally developable elements on the basis of photosensitive silver halide/organic silver salt/reducing agent.
- Organic reducing agent for photo-addressable thermally developable elements coated from aqueous media Organic reducing agent for photo-addressable thermally developable elements coated from aqueous media
- Suitable organic reducing agents for the reduction of the substantially light-insensitive organic heavy metal salts in photo-addressable thermally developable coated from aqueous media are organic compounds containing at least one active hydrogen atom linked to O, N or C.
- Particularly suitable organic reducing agents for the reduction of the substantially light-insensitive organic silver salt in such photo-addressable thermally developable elements are non-sulfo-substituted 6-membered aromatic or heteroaromatic ring compounds with at least three substituents one of which is a hydroxy group at a first carbon atom and a second of which is a hydroxy or amino-group substituted on a second carbon atom one, three or five ring atoms removed in a system of conjugated double bonds from the first carbon atom in the compound, in which (i) the third substituent may be part of an annelated carbocyclic or heterocyclic ring system; (ii) the third substituent or a further substituent is not an aryl- or oxo-
- the ring atoms of the non-sulfo-substituted 6-membered aromatic or heteroaromatic ring compound consist of nitrogen and carbon ring atoms and the non-sulfo-substituted 6-membered aromatic or heteroaromatic ring compound is annelated with an aromatic or heteroaromatic ring system.
- the non-sulfo-substituted 6-membered aromatic or heteroaromatic ring compound is substituted with one or more of the following substituents which may also be substituted: alkyl, alkoxy, carboxy, carboxy ester, thioether, alkyl carboxy, alkyl carboxy ester, aryl, sulfonyl alkyl, sulfonyl aryl, formyl, oxo-alkyl and oxo-aryl.
- Particularly preferred reducing agents are substituted catechols or substitued hydroquinones with 3-(3',4'-dihydroxyphenyl)-propionic acid, 3',4'-dihydroxy-butyrophenone, methyl gallate, ethyl gallate and 1,5-dihydroxy-naphthalene being especially preferred.
- the reducing agent must be present in such a way that it is able to diffuse to the substantially light-insensitive organic silver salt particles so that reduction of the substantially light-insensitive organic silver salt can take place.
- the reducing agent must be present in such a way that it is able to diffuse to said substantially light-insensitive organic heavy metal salt particles so that reduction of said organic heavy metal salt can take place.
- the silver image density depends on the coverage of the above defined reducing agent(s) and organic silver salt(s) and has to be preferably such that, on heating above 80 °C, an optical density of at least 2.5 can be obtained.
- an optical density of at least 2.5 can be obtained.
- at least 0.10 moles of reducing agent per mole of organic heavy metal salt is used.
- auxiliary reducing agents may be used in conjunction with so-called auxiliary reducing agents.
- Auxiliary reducing agents that may be used in conjunction with the above mentioned primary reducing agents are sulfonyl hydrazide reducing agents such as disclosed in US-P 5,464,738, trityl hydrazides and formyl-phenyl-hydrazides such as disclosed in US-P 5,496,695 and organic reducing metal salts, e.g. stannous stearate described in US-P 3,460,946 and 3,547,648.
- the photo-addressable thermally developable element of the photothermographic recording material may contain a spectral sensitizer, optionally together with a supersensitizer, for the silver halide.
- the silver halide may be spectrally sensitized with various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes optionally, particularly in the case of sensitization to infra-red radiation, in the presence of a so-called supersensitizer.
- Useful cyanine dyes include those having a basic nucleus, such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus.
- a basic nucleus such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus.
- Useful merocyanine dyes which are preferred include those having not only the above described basic nuclei but also acid nuclei, such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus.
- acid nuclei such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus.
- imino groups or carboxyl groups are particularly effective.
- Suitable sensitizers of silver halide to infra-red radiation include those disclosed in the EP-A's 465 078, 559 101, 616 014 and 635 756, the JN's 03-080251, 03-163440, 05-019432, 05-072662 and 06-003763 and the US-P's 4,515,888, 4,639,414, 4,713,316, 5,258,282 and 5,441,866.
- Suitable supersensitizers for use with infra-red spectral sensitizers are disclosed in EP-A's 559 228 and 587 338 and in the US-P's 3,877,943 and 4,873,184.
- the film-forming binder for the photo-addressable thermally developable element used according to the present invention may be coatable from a solvent or aqueous dispersion medium.
- the film-forming binder for the photo-addressable thermally developable element used according to the present invention may be coatable from a solvent dispersion medium, used according to the present invention, may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously: e.g.
- polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene or mixtures thereof.
- the film-forming binder for the photo-addressable thermally developable element coatable from an aqueous dispersion medium may be all kinds of transparent or translucent water-dispersible or water soluble natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously for example proteins, such as gelatin and gelatin derivatives (e.g.
- phthaloyl gelatin cellulose derivatives, such as carboxymethylcellulose, polysaccharides, such as dextran, starch ethers etc., galactomannan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, homo-or co-polymerized acrylic or methacrylic acid, latexes of water dispersible polymers, with or without hydrophilic groups, or mixtures thereof.
- Polymers with hydrophilic functionality for forming an aqueous polymer dispersion (latex) are described e.g. in US-P 5,006,451, but serve therein for forming a barrier layer preventing unwanted diffusion of vanadium pentoxide present as an antistatic agent.
- the binder to organic heavy metal salt weight ratio is preferably in the range of 0.2 to 6, and the thickness of the photo-addressable thermally developable element is preferably in the range of 5 to 50 ⁇ m.
- binders or mixtures thereof may be used in conjunction with waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the reaction speed of the redox-reaction at elevated temperature.
- heat solvent in this invention is meant a non-hydrolyzable organic material which is in solid state in the recording layer at temperatures below 50°C but becomes a plasticizer for the recording layer in the heated region and/or liquid solvent for at least one of the redox-reactants, e.g. the reducing agent for the organic heavy metal salt, at a temperature above 60°C.
- the recording layer contains preferably in admixture with said organic heavy metal salts and reducing agents a so-called toning agent known from thermography or photo-thermography.
- Suitable toning agents are succinimide and the phthalimides and phthalazinones within the scope of the general formulae described in US-P 4,082,901. Further reference is made to the toning agents described in US-P 3,074,809, 3,446,648 and 3,844,797.
- Other particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type as described in GB-P 1,439,478, US-P 3,951,660 and US-P 5,599,647.
- the photothermographic recording material of the present invention may contain antihalation or acutance dyes which absorb light which has passed through the photosensitive layer, thereby preventing its reflection.
- Such dyes may be incorporated into the photo-addressable thermally developable element or in any other layer comprising the photothermographic recording material of the present invention.
- the antihalation dye may also be bleached either thermally during the thermal development process, as disclosed in the US-P's 4,033,948, 4,088,497, 4,153,463, 4,196,002, 4,201,590, 4,271,263, 4,283,487, 4,308,379, 4,316,984, 4,336,323, 4,373,020, 4,548,896, 4,594,312, 4,977,070, 5,258,274, 5,314,795 and 5,312,721, or photo-bleached after removable after the thermal development process, as disclosed in the US-P,s 3,984,248, 3,988,154, 3,988,156, 4,111,699 and 4,359,524.
- antihalation layer may be contained in a layer which can be removed subsequent to the exposure process, as disclosed in US-P 4,477,562 and EP-A 491 457.
- Suitable antihalation dyes for use with infra-red light are described in the EP-A's 377 961 and 652 473, the EP-B's 101 646 and 102 781 and the US-P's 4,581,325 and 5,380,635.
- stabilizers and antifoggants may be incorporated into the thermographic and photothermographic materials of the present invention.
- suitable stabilizers and antifoggants and their precursors include the thiazolium salts described in US-P 2,131,038 and 2,694,716; the azaindenes described in US-P 2,886,437 and 2,444,605; the urazoles described in US-P 3,287,135; the sulfocatechols described in US-P 3,235,652; the oximes described in GB-P 623,448; the thiuronium salts described in US-P 3,220,839; the palladium, platinum and gold salts described in US-P 2,566,263 and 2,597,915; the tetrazolylthio-compounds described in US-P 3,700,457; the mesoionic 1,2,4-triazol
- the photo-addressable thermally developable element may contain other additives such as free fatty acids, surface-active agents, antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H, silicone oil, e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY), ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, silica, colloidal silica, fine polymeric particles [e.g. of poly(methylmethacrylate)] and/or optical brightening agents.
- antistatic agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
- silicone oil e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY)
- the support for the photothermographic recording material used according to the present invention may be transparent, translucent or opaque, e.g. having a white light reflecting aspect and is preferably a thin flexible carrier made e.g. from paper, polyethylene coated paper or transparent resin film, e.g. made of a cellulose ester, e.g. cellulose triacetate, corona and flame treated polypropylene, polystyrene, polymethacrylic acid ester, polycarbonate or polyester, e.g. polyethylene terephthalate or polyethylene naphthalate as disclosed in GB 1,293,676, GB 1,441,304 and GB 1,454,956.
- a paper base substrate is present which may contain white reflecting pigments, optionally also applied in an interlayer between the recording material and said paper base substrate.
- the support may be in sheet, ribbon or web form and subbed if need be to improve the adherence to the thereon coated thermosensitive recording layer.
- the support may be made of an opacified resin composition, e.g. polyethylene terephthalate opacified by means of pigments and/or micro-voids and/or coated with an opaque pigment-binder layer, and may be called synthetic paper, or paperlike film; information about such supports can be found in EP's 194 106 and 234 563 and US-P's 3,944,699, 4,187,113, 4,780,402 and 5,059,579. Should a transparent base be used, said base may be colourless or coloured, e.g. having a blue colour.
- One or more backing layers may be provided to control physical properties such as curl or static.
- the photo-addressable thermally developable element is provided with a protective layer to avoid local deformation of the photo-addressable thermally developable element, to improve its resistance against abrasion and to prevent its direct contact with components of the apparatus used for thermal development.
- This protective layer may have the same composition as an anti-sticking coating or slipping layer which is applied in thermal dye transfer materials at the rear side of the dye donor material or protective layers used in materials for direct thermal recording.
- the protective layer preferably comprises a binder, which may be solvent soluble (hydrophobic), solvent dispersible, water soluble (hydrophilic) or water dispersible.
- a binder which may be solvent soluble (hydrophobic), solvent dispersible, water soluble (hydrophilic) or water dispersible.
- hydrophobic binders polycarbonates as described in EP-A 614 769 are particularly preferred.
- Suitable hydrophilic binders are, for example, gelatin, polyvinylalcohol, cellulose derivatives or other polysaccharides, hydroxyethylcellulose, hydroxypropylcellulose etc., with hardenable binders being preferred and polyvinylalcohol being particularly preferred.
- a protective layer used according to the present invention may be crosslinked.
- Crosslinking can be achieved by using crosslinking agents such as described in WO 95/12495 for protective layers, e.g. tetra-alkoxysilanes, polyisocyanates, zirconates, titanates, melamine resins etc., with tetraalkoxysilanes such as tetramethylorthosilicate and tetraethylorthosilicate being preferred.
- a protective layer used according to the present invention may comprise in addition at least one solid lubricant having a melting point below 150°C and at least one liquid lubricant in a binder, wherein at least one of the lubricants is a phosphoric acid derivative, further dissolved lubricating material and/or particulate material, e.g. talc particles, optionally protruding from the outermost layer.
- suitable lubricating materials are surface active agents, liquid lubricants, solid lubricants which do not melt during thermal development of the recording material, solid lubricants which melt (thermomeltable) during thermal development of the recording material or mixtures thereof.
- the lubricant may be applied with or without a polymeric binder.
- Such protective layers may also comprise particulate material, e.g. talc particles, optionally protruding from the protective outermost layer as described in WO 94/11198.
- Other additives can also be incorporated in the protective layer e.g. colloidal particles such as colloidal silica.
- an antistatic layer is applied to the outermost layer not comprising at least one solid lubricant having a melting point below 150°C and at least one liquid lubricant in a binder, wherein at least one of said lubricants is a phosphoric acid derivative.
- Suitable antistatic layers therefor are described in EP-A's 444 326, 534 006 and 644 456, US-P's 5,364,752 and 5,472,832 and DOS 4125758.
- the emulsion layer is overcoated with a layer comprising a polymer and said emulsion layer and/or said overcoat layer further comprise(s) an organic reducing agent in thermal working relationship with the substantially light-insensitive organic silver salt.
- any layer of the recording material of the present invention may proceed by any coating technique e.g. such as described in Modern Coating and Drying Technology, edited by Edward D. Cohen and Edgar B. Gutoff, (1992) VCH Publishers Inc. 220 East 23rd Street, Suite 909 New York, NY 10010, U.S.A.
- Photothermographic materials used according to the present invention, may be exposed with radiation of wavelength between an X-ray wavelength and a 5 microns wavelength with the image either being obtained by pixel-wise exposure with a finely focussed light source, such as a CRT light source; a UV, visible or IR wavelength laser, such as a He/Ne-laser or an IR-laser diode, e.g. emitting at 780nm, 830nm or 850nm; or a light emitting diode, for example one emitting at 659nm; or by direct exposure to the object itself or an image therefrom with appropriate illumination e.g. with UV, visible or IR light.
- a finely focussed light source such as a CRT light source
- a UV, visible or IR wavelength laser such as a He/Ne-laser or an IR-laser diode, e.g. emitting at 780nm, 830nm or 850nm
- any sort of heat source can be used that enables the recording materials to be uniformly heated to the development temperature in a time acceptable for the application concerned e.g. contact heating, radiative heating, microwave heating etc.
- a photothermographic recording process is further provided, according to the present invention, wherein subsequent to imagewise exposure no further heating is required to stabilize the image.
- the photothermographic recording materials of the present invention can be used for both the production of transparencies and reflection type prints.
- the support will be transparent or opaque, e.g. having a white light reflecting aspect.
- a paper base substrate is present which may contain white reflecting pigments, optionally also applied in an interlayer between the recording material and said paper base substrate. Should a transparent base be used, said base may be colourless or coloured, e.g. has a blue colour.
- PET polyethyleneterephthalate
- subbing layer consisting of a terpolymer latex of vinylidene chloride-methyl acrylate-itaconic acid (88/10/2) in admixture with colloidal silica (surface area 100m 2 /g).
- colloidal silica surface area 100m 2 /g.
- the antihalation/antistatic layers of the photothermographic recording materials of INVENTION EXAMPLE 1 and COMPARATIVE EXAMPLE 1 were prepared by first adsorbing antihalation dye D01 onto the polymethyl methacrylate particles of LATEX01 by adding 55mg of D01 dissolved in ethyl acetate/g polymethyl methacrylate and then evaporating off the ethyl acetate.
- An silver halide emulsion consisting of 3.11% by weight of silver halide particles consisting of 97mol% silver bromide and 3mol% silver iodide with an weight average particle size of 50nm, 0.47% by weight of GEL as dispersing agent in deionized water was prepared using conventional silver halide preparation techniques such as described, for example, in T.H. James, "The Theory of the Photographic Process", Fourth Edition, Macmillan Publishing Co. Inc., New York (1977), Chapter 3, pages 88-104.
- the silver behenate/silver halide emulsion was prepared by adding a solution of 6.8kg of behenic acid in 67L of 2-propanol at 65°C to a 400L vessel heated to maintain the temperature of the contents at 65°C, converting 96% of the behenic acid to sodium behenate by adding with stirring 76.8L of 0.25M sodium hydroxide in deionised water, then adding with stirring 10.5kg of the above-described silver halide emulsion at 40°C and finally adding with stirring 48L of a 0.4M solution of silver nitrate in deionized water. Upon completion of the addition of silver nitrate the contents of the vessel were allowed to cool and the precipitate filtered off, washed, slurried with water, filtered again and finally dried at 40°C for 72 hours.
- Coating compositions for the emulsion layers of the photothermographic recording materials of INVENTION EXAMPLE 1 and COMPARATIVE EXAMPLE 1 were prepared by adding the following solutions or liquids to 40.86g of the above-mentioned silver behenate/silver halide emulsion in the following sequence with stirring: 6.87g of 2-butanone, 0.95g of a 9% solution of QAP 03 or 2.34g of a 0.77% solution of tetramethylammonium bromide in methanol followed by 2 hours stirring, 0.2g of a 11% solution of calcium bromide in methanol and 1.39 of 2-butanone followed by 30 minutes stirring, a solution consisting of 0.21g of LOWINOXTM 22IB46, 0.5g of TMPS and 9.24g of 2-butanone followed by 15 minutes stirring, 1.8g of a 0.11% solution of SENSI in methanol followed by 30 minutes stirring and finally 4.35g of ButvarTM B76 followed by 45 minutes stirring.
- a coating composition for the emulsion layer of the photothermographic recording material of COMPARATIVE EXAMPLE 1 was prepared as for that for the emulsion layer of the photothermographic recording material of INVENTION EXAMPLE 1 except that QAP01 was omitted from the coating composition.
- a protective layer coating composition for the photothermographic recording materials of INVENTION EXAMPLE 1 and COMPARATIVE EXAMPLE 1 was prepared by dissolving 4.08g of CAB and 0.16g of PMMA in 56.06g of 2-butanone and 5.2g of methanol and adding the following solutions or liquids with stirring in the following sequence: 0.5g of phthalazine, 0.2g of 4-methylphthalic acid, 0.1g of tetrachlorophthalic acid, 0.2g of tetrachlorophthalic acid anhydride and a solution consisting of 2.55g of LOWINOXTM 22IB46 and 5.95g of 2-butanone.
- the emulsion layers of INVENTION EXAMPLE 1 and COMPARATIVE EXAMPLE 1 were then doctor blade-coated at a blade setting of 100 ⁇ m with a protective layer composition to a wet layer thickness of 80 ⁇ m, which after drying for 8 minutes at 80°C on an aluminium plate in a drying cupboard produced a layer with the following composition: PMMA 0.16g/m 2 CAB 4.08g/m 2 Phthalazine 0.50g/m 2 4-methylphthalic acid 0.20g/m 2 tetrachlorophthalic acid anhydride 0.20g/m 2 tetrachlorophthalic acid 0.10g/m 2 LOWINOXTM 22IB46 2.55g/m 2
- the photothermographic recording materials of INVENTION EXAMPLE 1 and COMPARATIVE EXAMPLE 1 were exposed to a 849nm single mode diode laser beam from SPECTRA DIODE LABS with a nominal power of 100mW of which 61mW actually reaches the recording material focussed to give a spot diameter (1/e 2 ) of 28 ⁇ m, scanned at speed of 50m/s with a pitch of 14 ⁇ m through a wedge filter with optical density varying between 4.2 and 0 in optical density steps of 0.20.
- pyridinium hydrobromide perbromide as disclosed in US-P 5,028,523, has a very strong reactivity with silver behenate to form photosensitive silver bromide. Therefore the pyridinium hydrobromide perbromide present is only partly available for stabilization. Furthermore, the additional silver halide formed may have a particle size which considerably differs from that of the photosensitive silver halide already present, which may have an undesirable influence on the gradation of the image of a photothermographic material.
- QAP01, QAP02 and QAP03 of the present invention exhibit a low reactivity with silver behenate to form photosensitive silver halide and therefore will be completely available for stabilization. Furthermore, since little photosensitive silver halide is formed, little or no influence on the gradation of the image of a photothermographic material will be observed.
- the 245.0g of the silver behenate/ silver behenate powder prepared as described for INVENTION EXAMPLE 1 containing 9mol% silver halide and 4mol% behenic acid with respect to silver behenate were then dispersed in a solution of 122.5g of ButvarTM B76 in 1L of 2-butanone using convention dispersion techniques yielding a dispersion with 31.4% by weight of solids.
- a coating composition for the emulsion layer of the photothermographic recording material of INVENTION EXAMPLE 5 was prepared by adding the following solutions or liquids to 53.6g of the above-mentioned silver behenate/silver halide emulsion in the following sequence with stirring: 8.2g of 2-butanone, 1.5g of a 9% solution of QAP01 in methanol followed by 2 hours stirring, 0.2g of a 11% solution of calcium bromide in methanol followed by 30 minutes stirring, 1g of 2-butanone, 1.8g of a 0.1% solution of SENSI in methanol followed by 30 minutes stirring, 2g of methanol, 2.4g of LOWINOXTM 22IB46 followed by 15 minutes stirring and 0.5g of TMPS followed by 15 minutes stirring.
- a coating composition for the emulsion layer of the photothermographic recording material of COMPARATIVE EXAMPLE 3 was prepared as for that for the emulsion layer of the photothermographic recording material of INVENTION EXAMPLE 5 except that the solution of QAP01 was omitted from the coating composition and substituted with 1.5g of methanol.
- a protective layer coating composition for the photothermographic recording materials of INVENTION EXAMPLE 5 and COMPARATIVE EXAMPLE 3 was prepared by dissolving 4.08g of CAB and 0.16g of PMMA in 44.9g of 2-butanone and 4.16g of methanol and adding the following solutions or liquids with stirring in the following sequence: 0.5g of phthalazine, 0.2g of 4-methylphthalic acid and 0.2g of tetrachlorophthalic acid anhydride.
- the emulsion layers of INVENTION EXAMPLE 5 and COMPARATIVE EXAMPLE 3 were then doctor blade-coated at a blade setting of 100 ⁇ m with a protective layer composition to a wet layer thickness of 57 ⁇ m, which after drying for 8 minutes at 80°C on an aluminium plate in a drying cupboard produced a layer with the following composition: PMMA 0.16g/m 2 CAB 4.08g/m 2 Phthalazine 0.50g/m 2 4-methylphthalic acid 0.20g/m 2 tetrachlorophthalic acid anhydride 0.20g/m 2
- the photothermographic recording materials of INVENTION EXAMPLE 5 and COMPARATIVE EXAMPLE 3 were exposed to an EG&G lamp through a L775-filter and a wedge filter with optical densities varying between 0 and 3.0 in steps of 0.15 for 30s.
- Thermal processing was carried out for 10s with the side of the support coated with the silver behenate/silver halide and the protective layer in contact with a drum heated to a temperature of 118°C.
- the optical densities of the resulting wedge images were evaluated with a MACBETHTM TD904 densitometer with a blue filter to produce a sensitometric curve for the photothermographic materials.
- the D max - and D min -values obtained are summarized in table 3 below.
- the 245.0g of the silver behenate/ silver behenate powder prepared as described in INVENTION EXAMPLE 1 containing 9mol% silver halide and 4mol% behenic acid with respect to silver behenate were then dispersed in a solution of 122.5g of ButvarTM B76 in 1L of 2-butanone using convention dispersion techniques yielding a 31.3% by weight dispersion.
- An emulsion layer coating composition for the photothermographic recording material of INVENTION EXAMPLE 6 was prepared by adding the following solutions or liquids to 40.9g of the above-mentioned silver behenate/silver halide emulsion in the following sequence with stirring: 12.2g of 2-butanone, 0.43g of a 9% solution of QAP01 in methanol followed by a 2 hours stirring, 0.2g of a 11% solution of calcium bromide in methanol, 1.3g of 2-butanone followed by 30 minutes stirring, 0.7g of a 30% solution of LOWINOXTM 22IB46 in 2-butanone, 9.25g of a 5.4% solution of TMPS in 2-butanone followed by 15 minutes stirring, 1.8g of a 0.1% solution of SENSI in 2-butanone followed by 30 minutes stirring and finally 4.35g of ButvarTM B76.
- a protective layer coating composition for the photothermographic recording material of INVENTION EXAMPLE 6 was prepared by dissolving 4.16g of CAB and 0.16g of PMMA in 36.3g of 2-butanone and 4.16g of methanol and adding the following solutions or liquids with stirring in the following sequence: 0.5g of phthalazine, 0.2g of 4-methylphthalic acid, 0.1g of tetrachlorophthalic acid, 0.2g of tetrachlorophthalic acid anhydride and 8.5g of a 30% solution of LOWINOXTM 22IB46 in 2-butanone.
- the emulsion layer was then doctor blade-coated at a blade setting of 100 ⁇ m with the protective layer coating composition to a wet layer thickness of 57 ⁇ m, which after drying for 8 minutes at 80°C on an aluminium plate in a drying cupboard produced a layer with the following composition: CAB 4.08g/m 2 PMMA 0.16g/m 2 Phthalazine 0.50g/m 2 4-methylphthalic acid 0.20g/m 2 tetrachlorophthalic acid 0.10g/m 2 tetrachlorophthalic acid anhydride 0.20g/m 2 LOWINOXTM 22IB46 2.55g/m 2
- the photothermographic recording material of INVENTION EXAMPLE 6 was image-wise exposed, thermally processed and the images evaluated as described for INVENTION EXAMPLE 1 to yield a D max -value of 3.54 and a D min -value of 0.10.
- the photothermographic recording materials of INVENTION EXAMPLES 7 to 10 and COMPARATIVE EXAMPLE 4 were produced as described for INVENTION EXAMPLE 6 except that in the materials of INVENTION EXAMPLES 7, 8 and 9 the QAP01 concentrations used in the emulsion layer were 4.09mmol/mol silver behenate, 16.36mmol/mol silver behenate and 24.54mmol/mol silver behenate respectively, in the materials of INVENTION EXAMPLE 10 16.0mmol/mol silver behenate of QAP02 was substituted for QAP01 in the emulsion layer and in the material of COMPARATIVE EXAMPLE 4 QAP01 was omitted from the emulsion layer.
Abstract
Description
- QAP01
- = tetramethylammonium chloride perbromide
- QAP02
- = trimethylphenylammonium bromide perbromide
- QAP03
- = tetramethylammonium bromide perbromide
- KELZAN™ S:
- a xanthan gum from MERCK & CO., Kelco Division, USA, which according to Technical Bulletin DB-19 is a polysaccharide containing mannose, glucose and glucuronic repeating units as a mixed potassium, sodium and calcium salt;
- PT-dispersion:
- a dispersion of poly(3,4-ethylenedioxy-thiophene)/polystyrene sulphonic acid produced by the polymerization of 3,4-ethylenedioxy-thiophene in the presence of polystyrene sulphonic acid and ferric sulphate as described in US-P 5,354,613;
- ULTRAVON™ W:
- an aryl sulfonate from CIBA-GEIGY;
- PERAPRET™ PE40:
- a 40% aqueous dispersion of polyethylene wax from BASF;
- KIESELSOL™ 100F:
- a 36% aqueous dispersion of colloidal silica from BAYER;
- MAT01:
- 20% aqueous dispersion of particles of methylmethacrylate(98% by weight)-stearylmethacrylate(2% by weight)-copolymeric beads with an average particle size of 5.9µm produced as described in US-P 4,861,812;
- LATEX01:
- a 12% by weight dispersion of polymethyl methacrylate with an average particle size of 88.8nm prepared as described in US-P 5,354,613;
- D01:
- in the photo-addressable thermally developable element:
- GEL:
- phthaloylgelatin, type 16875 from ROUSSELOT;
- PHP:
- pyridinium hydrobromide perbromide;
- Butvar™ B76:
- polyvinylbutyral from MONSANTO;
- SENSI:
- LOWINOX™ 22IB46:
- 2-propyl-bis(2-hydroxy-3,5-dimethylphenyl)methane from CHEM. WERKE LOWI;
- TMPS:
- tribromomethyl benzenesulfinate;
and in the protective layer: - CAB:
- cellulose acetate butyrate, CAB-171-15S from EASTMAN;
- PMMA:
- polymethylmethacrylate, Acryloid™ K120N from ROHM & HAAS;
- LOWINOX™ 22IB46:
- 2-propyl-bis(2-hydroxy-3,5-dimethylphenyl)methane from CHEM. WERKE LOWI.
KELZAN™ S: | 7.5mg/m2 |
Dried PT-dispersion: | 15 mg/m2 |
ULTRAVON™ W: | 21 mg/m2 |
polyethylene wax (from PERAPRET™ PE40): | 10 mg/m2 |
colloidal silica (from KIESELSOL™ 100F): | 20 mg/m2 |
5.9µm beads of methylmethacrylate-stearyl-methacrylate copolymer (from MAT01): | 6 mg/m2 |
polymethylmethacrylate (from LATEX01): | 200 mg/m2 |
Antihalation dye D01: | 11 mg/m2 |
INVENTION EXAMPLE 1 | COMPARATIVE EXAMPLE 1 | |
Butvar™ B76 | 8.70g/m2 | 8.70g/m2 |
GEL | 0.045g/m2 | 0.045g/m2 |
AgBr0.97I0.03 | 0.301g/m2 | 0.301g/m2 |
silver behenate | 7.929g/m2 | 7.929g/m2 |
QAP03 | 0.0855g/m2 (15.2mmol/mol silver behenate) | - |
(CH3)4NBr | - | 0.0181g/m2 (6.54mmol/mol silver behenate) |
calcium bromide | 0.022g/m2 | 0.022g/m2 |
LOWINOX™ 22IB46 | 0.210g/m2 | 0.210g/m2 |
SENSI | 0.002g/m2 | 0.002g/m2 |
TMPS | 0.500g/m2 | 0.500g/m2 |
PMMA | 0.16g/m2 |
CAB | 4.08g/m2 |
Phthalazine | 0.50g/m2 |
4-methylphthalic acid | 0.20g/m2 |
tetrachlorophthalic acid anhydride | 0.20g/m2 |
tetrachlorophthalic acid | 0.10g/m2 |
LOWINOX™ 22IB46 | 2.55g/m2 |
Comparative example number | Antifoggant present | Antifoggant concentration mmol/mol silver behenate | image characteristics | |
Dmax | Dmin | |||
1 | (CH3)4NBr | 6.54 | 3.20 | 2.60 |
Invention example number | ||||
1 | QAP03 | 15.20 | 2.97 | 0.13 |
Invention Example number | Onium polyhalide | Test result | |
Compound(s) used | mol% vs. AgBeh | ||
2 | QAP01 | 8 | passed |
3 | QAP02 | 8 | passed |
4 | QAP03 | 8 | passed |
Comparative Example number | |||
2 | PHP | 8 | failed |
INVENTION EXAMPLE 5 | COMPARATIVE EXAMPLE 3 | |
Butvar™ B76 | 8.70g/m2 | 8.70g/m2 |
GEL | 0.045g/m2 | 0.045g/m2 |
AgBr0.97I0.03 | 0.301g/m2 | 0.301g/m2 |
silver behenate | 7.929g/m2 | 7.929g/m2 |
behenic acid | 0.316g/m2 | 0.316g/m2 |
QAP01 | 0.138g/m2 (29mmol/mol silver behenate) | - |
calcium bromide | 0.022g/m2 | 0.022g/m2 |
LOWINOX™ 22IB46 | 2.400g/m2 | 2.400g/m2 |
SENSI | 0.002g/m2 | 0.002g/m2 |
TMPS | 0.500g/m2 | 0.500g/m2 |
PMMA | 0.16g/m2 |
CAB | 4.08g/m2 |
Phthalazine | 0.50g/m2 |
4-methylphthalic acid | 0.20g/m2 |
tetrachlorophthalic acid anhydride | 0.20g/m2 |
Comparative example number | Antifoggant present | Antifoggant concentration mmol/mol silver behenate | image characteristics | |
Dmax | Dmin | |||
2 | - | - | 3.5 | 3.0 |
Invention example number | ||||
4 | QAP01 | 29 | 3.1 | 0.17 |
Butvar™ B76 | 8.49g/m2 |
GEL | 0.044g/m2 |
AgBr0.97I0.03 | 0.295g/m2 |
silver behenate | 7.733g/m2 |
behenic acid | 0.308g/m2 |
QAP01 | 0.038g/m2 (8.18mmol/mol silver behenate) |
calcium bromide | 0.021/m2 |
LOWINOX™ 22IB46 | 0.205/m2 |
SENSI | 0.002g/m2 |
TMPS | 0.488g/m2 |
CAB | 4.08g/m2 |
PMMA | 0.16g/m2 |
Phthalazine | 0.50g/m2 |
4-methylphthalic acid | 0.20g/m2 |
tetrachlorophthalic acid | 0.10g/m2 |
tetrachlorophthalic acid anhydride | 0.20g/m2 |
LOWINOX™ 22IB46 | 2.55g/m2 |
Comparative example number | Antifoggant present | Antifoggant concentration mmol/mol silver behenate | image characteristics | |
Dmax | Dmin | |||
4 | - | - | 3.44 | 0.9 |
Invention example number | ||||
7 | QAP01 | 4.09 | 3.80 | 0.12 |
6 | QAP01 | 8.18 | 3.54 | 0.10 |
8 | QAP01 | 16.36 | 3.33 | 0.11 |
9 | QAP01 | 24.54 | 3.70 | 0.12 |
10 | QAP02 | 16.0 | 3.30 | 0.13 |
Claims (11)
- An emulsion comprising a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association with said substantially light-insensitive organic silver salt and a binder, characterized in that said emulsion further comprises a polyhalide compound selected from the group consisting of quaternary ammonium polyhalides, quaternary phosphonium polyhalides and ternary sulphonium polyhalides, which satisfies a test specified in the description, or a product of a reaction between said polyhalide compound and a reducing species present in said emulsion.
- Emulsion according to claim 1, wherein said polyhalide compound is selected from the group of polyhalide compounds consisting of tetramethylammonium chloride perbromide, trimethylphenylammonium bromide perbromide and tetramethylammonium bromide perbromide.
- Emulsion according to claim 1 or 2, wherein said polyhalide compound is present in quantities of between 0.1 and 5.0mol% with respect to the quantity of said substantially light-insensitive organic silver salt.
- Emulsion according to any of the preceding claims, wherein said emulsion further comprises a compound having an absorption maximum in the wavelength range 600 to 1100nm.
- Emulsion according to any of the preceding claims, wherein said substantially light-insensitive organic silver salt is a silver salt of an aliphatic carboxylic acid.
- Emulsion according to any of the preceding claims, wherein said emulsion further comprises a reducing agent for silver ion.
- A process for producing a photothermographic recording material, capable of image formation without preliminary heating prior to exposure, comprising the step of producing a photo-addressable thermally developable element by coating an emulsion, according to any of claims 1 to 5, on a support thereby forming an emulsion layer.
- Process according to claim 7, wherein said emulsion layer is overcoated with a layer comprising a polymer and said emulsion layer and/or said overcoat layer further comprise(s) an organic reducing agent in thermal working relationship with said substantially light-insensitive organic silver salt.
- A photothermographic recording material, capable of image formation without preliminary heating prior to exposure, comprising a photo-addressable thermally developable element comprising a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association with said substantially light-insensitive organic silver salt, an organic reducing agent in thermal working relationship with said substantially light-insensitive organic silver salt and a binder, characterized in that said photo-addressable thermally developable element further comprises a polyhalide compound selected from the group consisting of quaternary ammonium polyhalides, guaternary phosphonium polyhalides and ternary sulphonium polyhalides, which satisfies a test specified in the description.
- Photothermographic recording material according to claim 9, wherein said photo-addressable thermally developable element is provided with a protective layer.
- Photothermographic recording process comprising the steps of: (i) image-wise exposing a photothermographic recording material, according to claim 9 or 10 or produced according to claim 7 or 8, to a source of actinic radiation; and (ii) thermally developing the image-wise exposed photothermographic recording material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP97201899A EP0821268B1 (en) | 1996-07-24 | 1997-06-21 | An emulsion for a photothermographic material, a production process for the photothermographic material and a recording process therefor |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96202105 | 1996-07-24 | ||
EP96202105 | 1996-07-24 | ||
EP97201899A EP0821268B1 (en) | 1996-07-24 | 1997-06-21 | An emulsion for a photothermographic material, a production process for the photothermographic material and a recording process therefor |
Publications (2)
Publication Number | Publication Date |
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EP0821268A1 true EP0821268A1 (en) | 1998-01-28 |
EP0821268B1 EP0821268B1 (en) | 2004-04-07 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP97201899A Expired - Lifetime EP0821268B1 (en) | 1996-07-24 | 1997-06-21 | An emulsion for a photothermographic material, a production process for the photothermographic material and a recording process therefor |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6506737B1 (en) * | 2000-04-05 | 2003-01-14 | Ecolab, Inc. | Antimicrobial phosphonium and sulfonium polyhalide compositions |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3957517A (en) * | 1972-12-08 | 1976-05-18 | Fuji Photo Film Co., Ltd. | Dry stabilization of a silver halide photographic material |
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 |
US5028523A (en) * | 1990-06-04 | 1991-07-02 | Minnesota Mining And Manufacturing Company | Photothermographic elements |
-
1997
- 1997-06-21 EP EP97201899A patent/EP0821268B1/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3957517A (en) * | 1972-12-08 | 1976-05-18 | Fuji Photo Film Co., Ltd. | Dry stabilization of a silver halide photographic material |
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 |
US5028523A (en) * | 1990-06-04 | 1991-07-02 | Minnesota Mining And Manufacturing Company | Photothermographic elements |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6506737B1 (en) * | 2000-04-05 | 2003-01-14 | Ecolab, Inc. | Antimicrobial phosphonium and sulfonium polyhalide compositions |
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