US3642479A - Photographic element and process - Google Patents
Photographic element and process Download PDFInfo
- Publication number
- US3642479A US3642479A US15867A US3642479DA US3642479A US 3642479 A US3642479 A US 3642479A US 15867 A US15867 A US 15867A US 3642479D A US3642479D A US 3642479DA US 3642479 A US3642479 A US 3642479A
- Authority
- US
- United States
- Prior art keywords
- radical
- pyran
- photographic
- phenyl
- image
- 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
- 238000000034 method Methods 0.000 title claims description 15
- 230000008569 process Effects 0.000 title claims description 13
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- WIFWCSTVYGGLAE-UHFFFAOYSA-N 4ah-benzo[f]chromene Chemical compound C1=CC=C2C3=CC=COC3C=CC2=C1 WIFWCSTVYGGLAE-UHFFFAOYSA-N 0.000 claims abstract 5
- -1 halocarbon compound Chemical class 0.000 claims description 66
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 13
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 11
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 claims description 10
- 150000000531 4H-pyrans Chemical class 0.000 claims description 9
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical group [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 150000003254 radicals Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 3
- BALWMOXNCOBPOZ-UHFFFAOYSA-N ethyl 2-cyano-2-(2-phenyl-4H-chromen-4-yl)acetate Chemical compound O1C2=CC=CC=C2C(C(C#N)C(=O)OCC)C=C1C1=CC=CC=C1 BALWMOXNCOBPOZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 11
- 150000004880 oxines Chemical class 0.000 description 10
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 150000005840 aryl radicals Chemical class 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000000051 modifying effect Effects 0.000 description 4
- 239000000025 natural resin Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229950000688 phenothiazine Drugs 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 description 2
- MRUWJENAYHTDQG-UHFFFAOYSA-N 4H-pyran Chemical class C1C=COC=C1 MRUWJENAYHTDQG-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 206010034960 Photophobia Diseases 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 208000013469 light sensitivity Diseases 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- POJPQMDDRCILHJ-UHFFFAOYSA-N 1,1,1,2,2,2-hexabromoethane Chemical compound BrC(Br)(Br)C(Br)(Br)Br POJPQMDDRCILHJ-UHFFFAOYSA-N 0.000 description 1
- OGVPXEPSTZMAFF-UHFFFAOYSA-N 1,1,1,2,2-pentabromoethane Chemical compound BrC(Br)C(Br)(Br)Br OGVPXEPSTZMAFF-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- QQLPPRIZUPEKMV-ZHACJKMWSA-N 2-[(e)-2-phenylethenyl]-1h-benzimidazole Chemical compound N=1C2=CC=CC=C2NC=1/C=C/C1=CC=CC=C1 QQLPPRIZUPEKMV-ZHACJKMWSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- JZIBVTUXIVIFGC-UHFFFAOYSA-N 2H-pyrrole Chemical compound C1C=CC=N1 JZIBVTUXIVIFGC-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- 235000007173 Abies balsamea Nutrition 0.000 description 1
- 239000004857 Balsam Substances 0.000 description 1
- 244000018716 Impatiens biflora Species 0.000 description 1
- 241001246312 Otis Species 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 150000004891 diazines Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical class O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- DCNUQRBLZWSGAV-UHFFFAOYSA-N n,n-diphenylformamide Chemical compound C=1C=CC=CC=1N(C=O)C1=CC=CC=C1 DCNUQRBLZWSGAV-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 125000003367 polycyclic group Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000010944 pre-mature reactiony Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- MVDRXYIEGOGRAI-UHFFFAOYSA-N tribromomethylbenzene Chemical compound BrC(Br)(Br)C1=CC=CC=C1 MVDRXYIEGOGRAI-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/60—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/163—Radiation-chromic compound
Definitions
- an object of this invention is to provide novel photographic elements.
- Another object of this invention is to provide new photographic elements useful in preparing printout images.
- Still another object of the present invention is to provide novel photographic elements including, as the image-forming components, at least one halocarbon and at least one 4H- pyran derivative.
- An additional object of this invention is to provide a new photographic process for producing printout images.
- the objects of this invention are accomplished both with photographic elements wherein a support is coated with a layer including a light-sensitive halocarbon and a 4H-pyran derivative and with a photographic process for the preparation of printout images including. imagewise exposing an element such as described above to actinic rays.
- 4H-pyran derivatives useful in the photographic elements of this invention include those having at least one aromatic substituent on the pyran ring. Especially desirable are those substituted at the 2-position and at the 4-position, with at least one of these substituents being an aromatic radical which itself can be still additionally substituted. Additionally the pyran nucleus is desirably fused to an aromatic nucleus to form, for example, a benzopyran or a [2, l -b]naphthopyran.
- each of R and R represent either a hydrogen atom, an alkyl radical or an aryl radical and at least one of R or R is an aryl radical
- R and R when taken together, represent the atoms necessary to complete an aromatic ring system.
- alkyl radical refers to straight and branched chain alkyl radicals having from one to about four carbon atoms like methyl, ethyl, 2-methoxyethyl, propyl, isopropyl, n-butyl, or the like, etc.
- the alkyl radical can be additionally substituted, e.g., ethoxycarbonylcyanomethyl, ethoxycarbonylbenzoylmethyl, nitromethyl, etc.
- Alkoxy radical refers to alkoxy radicals having from one to about four carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc., and preferably methoxy or ethoxy.
- aryl radical designates aromatic substituted or unsubstituted aryl radicals having from six to 10 carbon atoms in the nucleus, and including such aryl radicals as phenyl, naphthyl, p-tolyl, p-ethoxyphenyl, p-dimethylaminophenyl and the like.
- aromatic ring system refers to a mono or poly cyclic, carbocyclic aromatic nucleus like benzene, naphthalene, anthracene, phenanthrene, etc., which is completed by the atoms represented by R and R taken together and is fused to the parent pyran ring between the adjacent carbon atoms substituted by R and R.
- Especially advantageous pyran derivatives as described herein include those wherein R represents either a hydrogen atom, a methyl radical, an N,N-dimethylaminophenyl radical or a p-methylphenylthio radical and R represents a phenyl radical including substituted phenyl radicals like p-ethox yphenyl, N,N-dimethylaminophenyl and the like.
- Preferred 4l-l-pyran derivatives useful in the photographic elements of this invention include TABLEl Compound l l-(p-N,N-dimethylaminophenyh-l H-3-(pethoxyphenyhnaphthol2,I-h]pyran, 2 l-(p-N,N-dimethylaminophcnyl)-lH-3- phenylnaphthol2,l-b]pyran, 3 4-(p-N,N-dimethylaminophenyl)-2-phenyl-4H-lbenzol blpyran 4 2-(p-N,N-dimethylaminophenyl)-4H-benzo[blpyran 5 lH-3-(p-N,N-dimethylaminophcnyl)naphlhol2,l-hlpyran, 6 2- hcnyl-4H-bcnzo[blpyran. 7 l-(p-mlylthio)-1
- halocarbon or polyhalocarbon compound is at least one halocarbon or polyhalocarbon compound.
- the pyran derivatives and halocarbon compounds are generally combined herein in weight ratios of from about 3:1 to about 1:5 respectively, and preferably in substantially equal amounts by weight.
- Useful halocarbon compounds include, for example, a-halocarbonyl compounds like 01,01,04- tribromoaceto-phenone, poly(vinyl halides) such as poly(vinyl bromide) as well as perhalides and the like.
- Especially desirable halocarbon compounds are those known to be decomposed by exposure to actinic rays (i.e., ultraviolet and blue light) and which are not acidic.
- Preferred halocarbon compounds of this type include polyhalocarbons having three halogen atoms chemically bonded to a terminal carbon atom, ie, those having the formula R -C-(X) wherein X represents a halogen atom and R represents either a halogen atom, an alkyl radical, a haloalkyl radical, an aryl radical or an aroyl radical.
- exemplary polyhalogens include such compounds as polyhaloalkanes like iodoform, carbon tetrabromide, pentabromoethane, hexabromoethane, hexachloroethane and tribromophenylmethane. Bromo and iodo compounds are especially preferred clue to their inherently greater light sensitivity as compared to that of the corresponding chloro compounds.
- Polyhalocarbons, such as iodoform such as iodoform
- the photographic elements of this invention can contain additional addenda, e.g., sensitizers or addenda to enhance storage stability or either image quality or raw stock or image stability.
- additional addenda e.g., sensitizers or addenda to enhance storage stability or either image quality or raw stock or image stability.
- certain nitrogen containing compounds promote the photographic speed and resultant image density at any given exposure level.
- These materials are well known in the photographic art and include such compounds as 5dimethylaminocoumarin, 6-diethylamino-4- methylcoumarin, carbazole, diphenylformamide, 4- dimethylaminobenzaldehyde, phenothiazine and the like.
- materials which inhibit premature reaction in the sensitive layers are useful inclusions.
- such compounds which can be included singly or in combination and admixture, function to buffer the imageforming components against a pH change, i.e., to an acidic pH, which would promote a premature printout reaction.
- Desirable stabilizing materials include nitrogen-containing heterocycles like benzimidazole, Z-methylbenzimidazole, 2- styrylbenzimidazole as well as related nitrogen containing compounds such as azoles like isoazole, triazole, benzotriazole, etc., azine compounds like pyrimidine, pyrazine, benzopyrimidine and other diazines or triazine compounds such as l,2,4-triazine, 1,2,3-triazine, l,3,5-triazine, etc.
- image stabilizers are compounds which enhance the resistance of a resultant photographic image against deterioration from subsequent exposure to heat, light or the like energies which can cause fading or discoloration of the image.
- exemplary such stabilizers include thiazine compounds like phenothiazine and oxines such as alkoxyboroxines.
- the image-forming components and additional stabilizing or other modifying addenda are dispersed in a hydrophobic film-forming resin binder to promote the formation of a coated layer.
- Desirable resinous matrix vehicles include those which have a softening point sufficiently high to resist tackiness at the temperature ranges, i.e., up to about l50 C., useful for intensifying or stabilizing photographic images produced on elements of this invention.
- the pH of the resin binder should not be such that it either promotes or unduly inhibits, i.e., more than do the described stabilizers, the image-forming reaction.
- Exemplary matrix vehicles, having the noted characteristics can be selected from a wide variety of materials, including natural resins, modified natural resins and synthetic resins.
- Exemplary useful natural resins are balsam resins, colophony and shellac.
- Exemplary suitable modified natural resins are colophony-modified phenol resins and other resins listed below with a large proportion of colophony.
- Suitable synthetic resins include the extensive variety ofsynthetic resins, for example, polymers, such as vinyl polymers including a polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl acetals, polyvinyl ether and polyacrylic and polymethacrylic esters; polystyrene and substituted polystyrenes or polycondensates, e.g., polyesters, such as phthalate resin, terephthalic and isophthalic polyesters, maleinate resin and colophony-mixed esters of higher alcohols; phenol-formaldehyde resins, including colophony-modified phenol-formaldehyde condensates, aldehyde
- the image-forming components and such supplemental addenda compounds as are desired are generally dissolved or dispersed in a solution of matrix vehicle to prepare a coating composition which can then be applied to a support material by solvent coating techniques.
- the halocarbon and pyran derivative are generally present in stoichiometric amounts or with an excess of pyran derivative.
- Modifying addenda if included, can be present in widely varying amounts and the chosen amount will depend on both the selection and quantities of image-forming components as well as the modifying effect desired. Conventionally they are included in an amount of from about 1 to about 35 percent by weight of the image-forming ingredients.
- the image-forming compositions including stabilizers or other modifying addenda are generally incorporated into a coating formulation in an amount of from about 5 to about 50 parts by weight per parts by weight of matrix vehicle.
- the composite coating formulation contains from about 5 to about 20 weight percent solid for ease of coating, although wider variations can be used if desired for particular situations.
- Coating can be accomplished by a wide variety of techniques including flow coating, doctor blade coating, whirl coating, extrusion hopper coating, etc.
- the support material onto which the light-sensitive layer is applied is widely variable and includes such supports as cellulosic materials like cellulose acetate, cellulose acetate butyrate, etc., as well as polystyrenes, polycarbonates, polyvinyl compounds like polyvinylacetals, polyesters such as poly(ethylene terephthalate), poly-a-olefins like polyethylene, polypropylene and other poly-a-olefins conventionally having from two to 10 carbon atoms, and including metals like zinc and aluminum and paper including polyethylene and polypropylene coated papers.
- the resultant element can be imagewise exposed to actinic rays to prepare visible printout images.
- heating like that previously described can be employed to intensity or stabilize the lightinduced photographic image. Stabilization, as noted above, is accomplished by exhausting unreacted halocarbon from the layer. lntensification results from the heat promoted action of an image intensifier like those described herein. Desirably, heating is within a range of from about 100 to about C., but wider variations in temperature can be used if desired.
- EXAMPLE 1 A solution of 0.15 g. ofcompound l,from Table I, 0.15 g. of 6-diethylamino-4-methylcoumarin, 0.3 g. of carbon tetrabromide, and 0.03 g. of 2-methylbenzimidazole in 4 ml. of dichloroethane is added to ll ml. of a 10 percent solution of poly(vinyl butyral) dichloroethane and methanol (51]). The resulting solution is doctor blade coated on a paper support at a wet thickness of0.004 inch and allowed to dry.
- the resultant element is then exposed through a negative transparency in an Ozamatic Printer, manufactured by the Ozalid Corp., at a linear transport speed of 8 ft./min. to obtain a dark green, positive image on a white background.
- the Ozamatic printer uses a 1,200 watt high-pressure mercury arc lamp as an exposure source. Heat treatment for 10 seconds at 150 C. increases the image density, and stabilizes the print against further light reaction.
- EXAMPLE 2 A solution of0.l5 g. of compound 3, from Table l, 0.15 g. of 6-diethylamino-4-methylcoumarin, 0.35 g. of carbon tetrabromide, and 0.03 g. of 2-methylbenzimidazole in 4 ml. of dichloroethane is added to 11 ml. of a poly(vinyl butyral) solution as in Example 1. The resulting solution is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is then exposed and heated as in Example 1 to obtain an intensified, stable dark blue image on a light blue background.
- EXAMPLE 3 To 4 ml. of a percent solution of a styrene-butylmethacrylate copolymer in dichloroethane is added a solution of 25 mg. of compound 1 from Table l, 25 mg. of carbon tetrabromide, 2.5 mg. of 2-methyl-benzimidazole, and 10 mg. of 6-diethylamino-4-methylcoumarin in 1 ml. dichloroethane. This solution is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is exposed as in Example 1, but at a linear speed of 5 ft./min. Heat treatment at 150 C. for 10 seconds gives an intensified dark green, positive image on a white background.
- EXAMPLE 4 A solution of 25 mg. of compound 7 from Table l, 5 mg. of Z-methylbenzimidazole, 25 mg. of carbon tetrabromide, and 10 mg. of 6-diethylamino-4-methyl-coumarin in 1 ml. dichloroethane is added to 4 ml. of a 10 percent solution of a styrene-butyl-methacrylate copolymer in dichloroethane. The solution is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is exposed and heated as in Example 3 to give an orangebrown image on a light tan background.
- EXAMPLE 5 A coating composition as in Example 4 but employing 25 mg. of compound 9 from Table l as the color-forming agent is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is then exposed and heated as in Example 3 to give a dark tan, positive image on a pale yellow background.
- EXAMPLE 6 A coating composition identical to that in Example 4, except employing 25 mg. of compound 3 from Table l as the color-forming agent, in lieu of compound 7, is coated at a wet thickness of 0.004 inch on a paper support and allowed to dry. The resultant element is then exposed and heated as in Example 3, to provide an intensified blue image on a white background.
- EXAMPLE 7 A coating composition as in Example 3, except employing 25 mg. of compound 10 from Table I as the color-forming agent is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. When exposed and heated as in Example 3, the resultant element gives an intensified, stable greenish-yellow image on a white background.
- EXAMPLE 8 A solution of 25 mg. of compound 1 1 from Table l, 5 mg. of 2-methylbenzimidazole, 25 mg. of carbon tetrabromide, and 10 mg. of phenothiazine in 1 ml. dichloroethane is added to 4 ml. ofa l0 percent solution of poly(vinyl butyral) in a mixture of dichloroethane and methanol (5:1). This solution is doctor blade coated at a wet thickness of 0.004 inch on a paper support and allowed to dry. The resultant element is exposed and heated as in Example 3 to provide an intensified, stable yellow-orange image on a light yellow background.
- a photographic element for the production of printout images comprising a support having coated thereon a layer comprising a light-sensitive halocarbon compound that is decomposed on exposure to actinic rays and a 4H-pyran derivative that is a benzopyran or a naphthopyran having at least one aryl group substituted on the pyran ring, said pyran and said halocarbon compound being combined in a weight ratio of from 3:1 to
- each of R and R represent a member selected from the group consisting of a hydrogen atom, an alkyl radical and an aryl radical and at least one of R and R is an aryl radical,
- each of R and R when taken alone, represents a hydrogen atom
- R and R when taken together, represent the atoms necessary to complete an aromatic ring system.
- R represents a radical selected from the group consisting of a hydrogen atom, a methyl radical, an N,N-dimethylaminophenyl radical, and a p-methylphenylthio radical and R represents a phenyl radical.
- methyl radical represented by R is selected from the group consisting of a l-ethoxycarbonyl-l-cyanomethyl radical, a lethoxycarbonyl-l-benzoylmethyl radical and a nitromethyl radical and the phenyl radical represented by R is selected from the group consisting of a phenyl radical, a p-ethoxyphenyl radical and a p-dimethylaminophenyl radical.
- a photographic element for the production of printout images comprising a support having coated thereon a layer comprising a halocarbon selected from the group consisting of carbon tetrabromide and dichloroethane and a 4H- pyran derivative as described in claim 3.
- a photographic element for the production of printout images comprising a support having coated thereon a layer comprising a carbon tetrabromide and a 4H-pyran derivative selected from the group consisting a. l-(p-N,N-dimethylaminophenyl) l H-3-(p-ethoxyphenb. 4-(p-N,N-dimethlaminophenyl)2-phenyl-4H- l -benzo[b] pyran c. lH-3-(p-N,N-dimethylaminophenyl)naphtho[2,l-b]- pyran d. l-(p-tolylthio)-lH-3-(p-ethoxyphenyl)naphtho-[2,l-b]
- pyran e 1-( l-ethoxycarbonyl-lcyanomethyl)- l H-3-(p-ethoxyphenyl)naphtho[2,l-b]pyran f. 4-( l-ethoxycarbonyll -cyanomethyl)-2-phenyl-4H- benzo[b]pyran g. l-( l-ethoxycarbonyl-l-ben2oylmethyl)-lH-3-(p-ethoxyphenyl)naphtho[2,l-b]pyran h.
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Abstract
Photographic elements having a support on which is coated a layer including a light-sensitive halocarbon and a 1,4-pyran derivative like 1-(p-N,N-dimethylaminophenyl)-1H-3-(pethoxyphenyl)naphtho(2,1-b)pyran or 4-(p-N,Ndimethylaminophenyl)-2-phenyl-4H-1-benzo(b)pyran yield printout images in exposed areas on exposure to actinic rays. The resultant printout image can be intensified by heating.
Description
United States Patent Van Allan et al.
[451 Feb. 15, 1972 [54] PHOTOGRAPHIC ELEMENT AND PROCESS [72] Inventors: James A. Van Allan; Dennis E. De Meyer, both of Rochester, N.Y.; Frank D. Allen,
, deceased, late of Rochester, NY.
[73] Assignee: Eastman Kodak Company, Rochester,
[22] Filed: Mar. 2, 1970 211 Appl. No.: 15,867
[52] US. Cl ..96/48 R, 96/90, 96/90 PC [51] Int. Cl. 5/24, G036 1/72 I 58] Field of Search ..96/90, 90 PC, 48
I56] References Cited UNITED STATES PATENTS 3,486,899 l2/l969 Brown ..96/90 3,121,633 2/1964 Sprague et a]. ..96/90 3,532,638 10/1970 Otis ..96/90 PC X Primary Examiner-Norman G. Torchin Assistant ExaminerRichard E. Fichter AttorneyW. H. J. Kline, J. R. Frederick and D. M. De Leo [57] ABSTRACT The resultant printout image can be intensified by heating.
9 Claims, No Drawings PHOTOGRAPHIC ELEMENT AND PROCESS This invention relates to photography and particularly to photographic elements and processes for forming printout images.
It is known that certain halocarbons and polyhalocarbons are light sensitive and yield photographic products which are capable of producing colored materials from such colorless materials as certain dyes, and diarylamines. Examples of this light sensitivity can be found in Mechanisms and Structures In Organic Reaction, Gould, page 744; and in U.S. Pat. Nos. 3,102,810 and 3,121,633; in British Pat. Nos. 916,779 and 719,919. These references are based on the photoreaction of polyhalocarbons with leuco dyes to yield the corresponding colored forms of the dyes.
While polyhalocarbons havingbeen employed separately as light-sensitive addenda for certain photographic processes and elements. They have not been combined with 4H-pyran derivatives to prepare photographic printout elements.
Accordingly, an object of this invention is to provide novel photographic elements. 7
Another object of this invention is to provide new photographic elements useful in preparing printout images.
Still another object of the present invention is to provide novel photographic elements including, as the image-forming components, at least one halocarbon and at least one 4H- pyran derivative.
An additional object of this invention is to provide a new photographic process for producing printout images.
Other objects and advantages of this invention will become increasingly apparent from a reading of the following specification and appended claims.
The objects of this invention are accomplished both with photographic elements wherein a support is coated with a layer including a light-sensitive halocarbon and a 4H-pyran derivative and with a photographic process for the preparation of printout images including. imagewise exposing an element such as described above to actinic rays.
4H-pyran derivatives useful in the photographic elements of this invention include those having at least one aromatic substituent on the pyran ring. Especially desirable are those substituted at the 2-position and at the 4-position, with at least one of these substituents being an aromatic radical which itself can be still additionally substituted. Additionally the pyran nucleus is desirably fused to an aromatic nucleus to form, for example, a benzopyran or a [2, l -b]naphthopyran.
Particularly advantageous pyran derivatives include those having the formula:
wherein a. each of R and R represent either a hydrogen atom, an alkyl radical or an aryl radical and at least one of R or R is an aryl radical, b. each of R and R, when taken alone, represents a hydrogen atom, and
c. R and R, when taken together, represent the atoms necessary to complete an aromatic ring system.
As defined herein, the term alkyl radical refers to straight and branched chain alkyl radicals having from one to about four carbon atoms like methyl, ethyl, 2-methoxyethyl, propyl, isopropyl, n-butyl, or the like, etc. The alkyl radical can be additionally substituted, e.g., ethoxycarbonylcyanomethyl, ethoxycarbonylbenzoylmethyl, nitromethyl, etc. Alkoxy radical refers to alkoxy radicals having from one to about four carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc., and preferably methoxy or ethoxy. The term aryl radical designates aromatic substituted or unsubstituted aryl radicals having from six to 10 carbon atoms in the nucleus, and including such aryl radicals as phenyl, naphthyl, p-tolyl, p-ethoxyphenyl, p-dimethylaminophenyl and the like. Also as used herein, the designation aromatic ring system refers to a mono or poly cyclic, carbocyclic aromatic nucleus like benzene, naphthalene, anthracene, phenanthrene, etc., which is completed by the atoms represented by R and R taken together and is fused to the parent pyran ring between the adjacent carbon atoms substituted by R and R.
Especially advantageous pyran derivatives as described herein include those wherein R represents either a hydrogen atom, a methyl radical, an N,N-dimethylaminophenyl radical or a p-methylphenylthio radical and R represents a phenyl radical including substituted phenyl radicals like p-ethox yphenyl, N,N-dimethylaminophenyl and the like. Still other especially desirable pyran compounds include those wherein R and R when taken together, represent a 1,4-buta-1,3- dienylene radical (i.e., CH=CH-CH:CH) with R and R thereby completing a benzene nucleus.
Preferred 4l-l-pyran derivatives useful in the photographic elements of this invention include TABLEl Compound l l-(p-N,N-dimethylaminophenyh-l H-3-(pethoxyphenyhnaphthol2,I-h]pyran, 2 l-(p-N,N-dimethylaminophcnyl)-lH-3- phenylnaphthol2,l-b]pyran, 3 4-(p-N,N-dimethylaminophenyl)-2-phenyl-4H-lbenzol blpyran 4 2-(p-N,N-dimethylaminophenyl)-4H-benzo[blpyran 5 lH-3-(p-N,N-dimethylaminophcnyl)naphlhol2,l-hlpyran, 6 2- hcnyl-4H-bcnzo[blpyran. 7 l-(p-mlylthio)-1H-3-(p-cthnxyphenyl)naphtho-l2,1-
blpyran. 8 2-ethoxyphenyl-4-(p-tolyllhio)-4H-benzn|blpyran, 9 l( l-ethoxycarbonyl-l-cyanomethyl)-l H-3-(pethoxyphenyUnaphlhol 2,l-b]pyran, l0 4-( l-ethoxycarbonyl-l-eyanomethyl)-2-phcnyl-4H- benzolhlpyran, ll l(l-cthoxycarbonyl-1-benzoylmcthyl)1H-3-(pethoxyphenyUnaplhoIZ. l -blpyran. and 12 l-nitromethyl-lH-3-(p-N.N-
dimethylaminophcnyl)naphthol-hlpyran.
Also included in the present photographic elements, in
combination with at least one pyran derivative like those mentioned hereinabove is at least one halocarbon or polyhalocarbon compound. The pyran derivatives and halocarbon compounds are generally combined herein in weight ratios of from about 3:1 to about 1:5 respectively, and preferably in substantially equal amounts by weight. Useful halocarbon compounds include, for example, a-halocarbonyl compounds like 01,01,04- tribromoaceto-phenone, poly(vinyl halides) such as poly(vinyl bromide) as well as perhalides and the like. Especially desirable halocarbon compounds are those known to be decomposed by exposure to actinic rays (i.e., ultraviolet and blue light) and which are not acidic. Preferred halocarbon compounds of this type include polyhalocarbons having three halogen atoms chemically bonded to a terminal carbon atom, ie, those having the formula R -C-(X) wherein X represents a halogen atom and R represents either a halogen atom, an alkyl radical, a haloalkyl radical, an aryl radical or an aroyl radical. Exemplary polyhalogens include such compounds as polyhaloalkanes like iodoform, carbon tetrabromide, pentabromoethane, hexabromoethane, hexachloroethane and tribromophenylmethane. Bromo and iodo compounds are especially preferred clue to their inherently greater light sensitivity as compared to that of the corresponding chloro compounds. Polyhalocarbons, such as iodoform,
which can be inactivated or diffused from a coated layer on heat treatment are also preferred since they permit convenient stabilization of the photographic image by the application of heat.
In addition to pyran derivatives and halocarbon compounds, the photographic elements of this invention can contain additional addenda, e.g., sensitizers or addenda to enhance storage stability or either image quality or raw stock or image stability. As an example, certain nitrogen containing compounds promote the photographic speed and resultant image density at any given exposure level. These materials are well known in the photographic art and include such compounds as 5dimethylaminocoumarin, 6-diethylamino-4- methylcoumarin, carbazole, diphenylformamide, 4- dimethylaminobenzaldehyde, phenothiazine and the like.
As well as sensitizing addenda, materials which inhibit premature reaction in the sensitive layers are useful inclusions. Presumably, such compounds, which can be included singly or in combination and admixture, function to buffer the imageforming components against a pH change, i.e., to an acidic pH, which would promote a premature printout reaction. Desirable stabilizing materials include nitrogen-containing heterocycles like benzimidazole, Z-methylbenzimidazole, 2- styrylbenzimidazole as well as related nitrogen containing compounds such as azoles like isoazole, triazole, benzotriazole, etc., azine compounds like pyrimidine, pyrazine, benzopyrimidine and other diazines or triazine compounds such as l,2,4-triazine, 1,2,3-triazine, l,3,5-triazine, etc.
Other useful addenda materials include image stabilizers, they being compounds which enhance the resistance of a resultant photographic image against deterioration from subsequent exposure to heat, light or the like energies which can cause fading or discoloration of the image. Exemplary such stabilizers include thiazine compounds like phenothiazine and oxines such as alkoxyboroxines.
Generally, the image-forming components and additional stabilizing or other modifying addenda are dispersed in a hydrophobic film-forming resin binder to promote the formation of a coated layer. Desirable resinous matrix vehicles include those which have a softening point sufficiently high to resist tackiness at the temperature ranges, i.e., up to about l50 C., useful for intensifying or stabilizing photographic images produced on elements of this invention. Additionally, the pH of the resin binder should not be such that it either promotes or unduly inhibits, i.e., more than do the described stabilizers, the image-forming reaction. Exemplary matrix vehicles, having the noted characteristics, can be selected from a wide variety of materials, including natural resins, modified natural resins and synthetic resins. Exemplary useful natural resins are balsam resins, colophony and shellac. Exemplary suitable modified natural resins are colophony-modified phenol resins and other resins listed below with a large proportion of colophony. Suitable synthetic resins include the extensive variety ofsynthetic resins, for example, polymers, such as vinyl polymers including a polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl acetals, polyvinyl ether and polyacrylic and polymethacrylic esters; polystyrene and substituted polystyrenes or polycondensates, e.g., polyesters, such as phthalate resin, terephthalic and isophthalic polyesters, maleinate resin and colophony-mixed esters of higher alcohols; phenol-formaldehyde resins, including colophony-modified phenol-formaldehyde condensates, aldehyde resins, ketone resins, polyamides and polyadducts, e.g., polyurethanes. Moreover, high-melting polyolefins, such as various polyethylenes, polypropylenes, polyisobutylenes and chlorinated rubber are suitable. Additional useful resinous binder materials are known to those skilled in the polymer arts.
To prepare a composite photographic element of this invention, the image-forming components and such supplemental addenda compounds as are desired are generally dissolved or dispersed in a solution of matrix vehicle to prepare a coating composition which can then be applied to a support material by solvent coating techniques. In a coating formulation, the halocarbon and pyran derivative are generally present in stoichiometric amounts or with an excess of pyran derivative. Modifying addenda, if included, can be present in widely varying amounts and the chosen amount will depend on both the selection and quantities of image-forming components as well as the modifying effect desired. Conventionally they are included in an amount of from about 1 to about 35 percent by weight of the image-forming ingredients. The image-forming compositions, including stabilizers or other modifying addenda are generally incorporated into a coating formulation in an amount of from about 5 to about 50 parts by weight per parts by weight of matrix vehicle. Advantageously, the composite coating formulation contains from about 5 to about 20 weight percent solid for ease of coating, although wider variations can be used if desired for particular situations.
Coating can be accomplished by a wide variety of techniques including flow coating, doctor blade coating, whirl coating, extrusion hopper coating, etc. The support material onto which the light-sensitive layer is applied is widely variable and includes such supports as cellulosic materials like cellulose acetate, cellulose acetate butyrate, etc., as well as polystyrenes, polycarbonates, polyvinyl compounds like polyvinylacetals, polyesters such as poly(ethylene terephthalate), poly-a-olefins like polyethylene, polypropylene and other poly-a-olefins conventionally having from two to 10 carbon atoms, and including metals like zinc and aluminum and paper including polyethylene and polypropylene coated papers.
Subsequent to coating and drying to form a composite photographic element of this invention, the resultant element can be imagewise exposed to actinic rays to prepare visible printout images. After exposure, heating like that previously described can be employed to intensity or stabilize the lightinduced photographic image. Stabilization, as noted above, is accomplished by exhausting unreacted halocarbon from the layer. lntensification results from the heat promoted action of an image intensifier like those described herein. Desirably, heating is within a range of from about 100 to about C., but wider variations in temperature can be used if desired.
The following examples are included for a further understanding of the invention.
EXAMPLE 1 A solution of 0.15 g. ofcompound l,from Table I, 0.15 g. of 6-diethylamino-4-methylcoumarin, 0.3 g. of carbon tetrabromide, and 0.03 g. of 2-methylbenzimidazole in 4 ml. of dichloroethane is added to ll ml. of a 10 percent solution of poly(vinyl butyral) dichloroethane and methanol (51]). The resulting solution is doctor blade coated on a paper support at a wet thickness of0.004 inch and allowed to dry. The resultant element is then exposed through a negative transparency in an Ozamatic Printer, manufactured by the Ozalid Corp., at a linear transport speed of 8 ft./min. to obtain a dark green, positive image on a white background. The Ozamatic printer uses a 1,200 watt high-pressure mercury arc lamp as an exposure source. Heat treatment for 10 seconds at 150 C. increases the image density, and stabilizes the print against further light reaction.
EXAMPLE 2 A solution of0.l5 g. of compound 3, from Table l, 0.15 g. of 6-diethylamino-4-methylcoumarin, 0.35 g. of carbon tetrabromide, and 0.03 g. of 2-methylbenzimidazole in 4 ml. of dichloroethane is added to 11 ml. of a poly(vinyl butyral) solution as in Example 1. The resulting solution is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is then exposed and heated as in Example 1 to obtain an intensified, stable dark blue image on a light blue background.
EXAMPLE 3 To 4 ml. of a percent solution of a styrene-butylmethacrylate copolymer in dichloroethane is added a solution of 25 mg. of compound 1 from Table l, 25 mg. of carbon tetrabromide, 2.5 mg. of 2-methyl-benzimidazole, and 10 mg. of 6-diethylamino-4-methylcoumarin in 1 ml. dichloroethane. This solution is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is exposed as in Example 1, but at a linear speed of 5 ft./min. Heat treatment at 150 C. for 10 seconds gives an intensified dark green, positive image on a white background.
EXAMPLE 4 A solution of 25 mg. of compound 7 from Table l, 5 mg. of Z-methylbenzimidazole, 25 mg. of carbon tetrabromide, and 10 mg. of 6-diethylamino-4-methyl-coumarin in 1 ml. dichloroethane is added to 4 ml. of a 10 percent solution of a styrene-butyl-methacrylate copolymer in dichloroethane. The solution is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is exposed and heated as in Example 3 to give an orangebrown image on a light tan background.
EXAMPLE 5 A coating composition as in Example 4 but employing 25 mg. of compound 9 from Table l as the color-forming agent is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is then exposed and heated as in Example 3 to give a dark tan, positive image on a pale yellow background.
EXAMPLE 6 A coating composition identical to that in Example 4, except employing 25 mg. of compound 3 from Table l as the color-forming agent, in lieu of compound 7, is coated at a wet thickness of 0.004 inch on a paper support and allowed to dry. The resultant element is then exposed and heated as in Example 3, to provide an intensified blue image on a white background.
EXAMPLE 7 A coating composition as in Example 3, except employing 25 mg. of compound 10 from Table I as the color-forming agent is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. When exposed and heated as in Example 3, the resultant element gives an intensified, stable greenish-yellow image on a white background.
EXAMPLE 8 A solution of 25 mg. of compound 1 1 from Table l, 5 mg. of 2-methylbenzimidazole, 25 mg. of carbon tetrabromide, and 10 mg. of phenothiazine in 1 ml. dichloroethane is added to 4 ml. ofa l0 percent solution of poly(vinyl butyral) in a mixture of dichloroethane and methanol (5:1). This solution is doctor blade coated at a wet thickness of 0.004 inch on a paper support and allowed to dry. The resultant element is exposed and heated as in Example 3 to provide an intensified, stable yellow-orange image on a light yellow background.
The invention has been described in detail with particular reference to preferred embodiments thereof, but, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
We claim:
1. A photographic element for the production of printout images and comprising a support having coated thereon a layer comprising a light-sensitive halocarbon compound that is decomposed on exposure to actinic rays and a 4H-pyran derivative that is a benzopyran or a naphthopyran having at least one aryl group substituted on the pyran ring, said pyran and said halocarbon compound being combined in a weight ratio of from 3:1 to |:5 respectivel 2. A photographic element as (described in claim I wherein the halocarbon compound is selected from the group consisting of halocarbon and polyhalocarbon compounds and wherein the 4H-pyran derivative has the formula:
wherein a. each of R and R represent a member selected from the group consisting of a hydrogen atom, an alkyl radical and an aryl radical and at least one of R and R is an aryl radical,
b. each of R and R when taken alone, represents a hydrogen atom, and
c. R and R when taken together, represent the atoms necessary to complete an aromatic ring system.
3. A photographic element as described in claim 2 wherein R represents a radical selected from the group consisting of a hydrogen atom, a methyl radical, an N,N-dimethylaminophenyl radical, and a p-methylphenylthio radical and R represents a phenyl radical.
4. A photographic element as described in claim 2 wherein R and R when taken together, represent a l,4-but-l,3- dienylene radical.
5. A photographic element as described in claim 3 wherein the methyl radical represented by R is selected from the group consisting of a l-ethoxycarbonyl-l-cyanomethyl radical, a lethoxycarbonyl-l-benzoylmethyl radical and a nitromethyl radical and the phenyl radical represented by R is selected from the group consisting of a phenyl radical, a p-ethoxyphenyl radical and a p-dimethylaminophenyl radical.
6. A photographic element for the production of printout images and comprising a support having coated thereon a layer comprising a halocarbon selected from the group consisting of carbon tetrabromide and dichloroethane and a 4H- pyran derivative as described in claim 3.
7. A photographic element for the production of printout images and comprising a support having coated thereon a layer comprising a carbon tetrabromide and a 4H-pyran derivative selected from the group consisting a. l-(p-N,N-dimethylaminophenyl) l H-3-(p-ethoxyphenb. 4-(p-N,N-dimethlaminophenyl)2-phenyl-4H- l -benzo[b] pyran c. lH-3-(p-N,N-dimethylaminophenyl)naphtho[2,l-b]- pyran d. l-(p-tolylthio)-lH-3-(p-ethoxyphenyl)naphtho-[2,l-b]
pyran e. 1-( l-ethoxycarbonyl-lcyanomethyl)- l H-3-(p-ethoxyphenyl)naphtho[2,l-b]pyran f. 4-( l-ethoxycarbonyll -cyanomethyl)-2-phenyl-4H- benzo[b]pyran g. l-( l-ethoxycarbonyl-l-ben2oylmethyl)-lH-3-(p-ethoxyphenyl)naphtho[2,l-b]pyran h. l-nitromethyl-lH-3-(p-(N,N-dimethylamino)phenyl)- naphtho[ 2, l -b lpyran, said pyran and said carbon tetrabromide being combined in a weight ratio of from 3:1 to 1:5 respectively.
8. A photographic image-forming process for the preparation of printout images on a photographic element as described in claim 1, which process comprises imagewise exposing said element to actinic rays, whereupon a printout image is produced in exposed ares.
9. A photographic image-forming process as described in claim 8 and additionally including heating said exposed element to intensify the printout image.
Claims (8)
- 2. A photographic element as described in claim 1 wherein the halocarbon compound is selected from the group consisting of halocarbon and polyhalocarbon compounds and wherein the 4H-pyran derivative has the formula:
- 3. A photographic element as described in claim 2 wherein R represents a radical selected from the group consisting of a hydrogen atom, a methyl radical, an N,N-dimethylaminophenyl radical, and a p-methylphenylthio radical and R1 represents a phenyl radical.
- 4. A photographic element as described in claim 2 wherein R2 and R3, when taken together, represent a 1,4-but-1,3-dienylene radical.
- 5. A photographic element as described in claim 3 wherein the methyl radical represented by R is selected from the group consisting of a 1-ethoxycarbonyl-1-cyanomethyl radical, a 1-ethoxycarbonyl-1-benzoylmethyl radical and a nitromethyl radical and the phenyl radical represented by R1 is selected from the group consisting of a phenyl radical, a p-ethoxyphenyl radical and a p-dimethylaminophenyl radical.
- 6. A photographic element for the production of printout images and comprising a support having coated thereon a layer comprising a halocarbon selected from the group consisting of carbon tetrabromide and dichloroethane and a 4H-pyran derivative as described in claim 3.
- 7. A photographic element for the production of printout images and comprising a support having coated thereon a layer comprising a carbon tetrabromide and a 4H-pyran derivative selected from the group consisting a. 1-(p-N,N-dimethylaminophenyl)1H-3-(p-ethoxyphenyl)naptho (2, 1-b)pyran b. 4-(p-N,N-dimethlaminophenyl)-2-phenyl-4H-1-benzo(b)pyran c. 1H-3-(p-N,N-dimethylaminophenyl)naphtho(2,1-b)-pyran d. 1-(p-tolylthio)-1H-3-(p-ethoxyphenyl)naphtho-(2,1-b)pyran e. 1-(1-ethoxycarbonyl-1-cyanomethyl)-1H-3-(p-ethoxyphenyl)naphtho(2,1-b)pyran f. 4-(1-ethoxycarbonyl-1-cyanomethyl)-2-phenyl-4H-benzo(b)pyran g. 1-(1-ethoxycarbonyl-1-bEnzoylmethyl)-1H-3-(p-ethoxyphenyl)naphtho(2,1 -b)pyran h. 1-nitromethyl-1H-3-(p-(N,N-dimethylamino)phenyl)-naphtho(2,1-b)pyran, said pyran and said carbon tetrabromide being combined in a weight ratio of from 3:1 to 1:5 respectively.
- 8. A photographic image-forming process for the preparation of printout images on a photographic element as described in claim 1, which process comprises imagewise exposing said element to actinic rays, whereupon a printout image is produced in exposed ares.
- 9. A photographic image-forming process as described in claim 8 and additionally including heating said exposed element to intensify the printout image.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1586770A | 1970-03-02 | 1970-03-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3642479A true US3642479A (en) | 1972-02-15 |
Family
ID=21774082
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15867A Expired - Lifetime US3642479A (en) | 1970-03-02 | 1970-03-02 | Photographic element and process |
Country Status (5)
Country | Link |
---|---|
US (1) | US3642479A (en) |
BE (1) | BE763286A (en) |
CA (1) | CA969411A (en) |
FR (1) | FR2083941A5 (en) |
GB (1) | GB1334752A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3773508A (en) * | 1970-11-19 | 1973-11-20 | Fuji Photo Film Co Ltd | Imagewise exposing and heating a photosensitive composition containing a spiropyran compound and an organic peroxide |
US3844792A (en) * | 1972-12-07 | 1974-10-29 | American Cyanamid Co | A photosensitive composition containing a photochromic benzoylchromone or dibenzofuran and a strong organic amine base |
US3887808A (en) * | 1972-06-26 | 1975-06-03 | Agfa Gevaert | Thermoimaging process utilizing a photochromic material containing a spiropyran, a polyhalogenated hydrocarbon, a thiol compound and a polyvinylcarbazole |
US3907569A (en) * | 1973-01-31 | 1975-09-23 | Horizons Inc | Ultraviolet holdback of nonsilver photosensitive systems by incorporating therein certain organic additives |
US3973966A (en) * | 1974-05-08 | 1976-08-10 | Xerox Corporation | Photochromic composition containing a diphenyl dibenzochrom-3-ene |
US3980480A (en) * | 1970-09-01 | 1976-09-14 | Urbain Leopold Laridon | Photographic recording and reproduction of information photochromic composition containing polyhalogenated hydrocarbon, spiropyran compound and heterocyclic mercapto compound and the use thereof |
US4010033A (en) * | 1973-08-03 | 1977-03-01 | Agence Nationale De Valorisation De La Recherche (Anvar) | Photosensitive layer and method of forming a photographic image therefrom |
US4827149A (en) * | 1986-10-09 | 1989-05-02 | Sharp Kabushiki Kaisha | Operation halting circuit |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3121633A (en) * | 1962-07-25 | 1964-02-18 | Horizons Inc | Process of making print-out images with cyanine dye bases and styryl dye bases |
US3486899A (en) * | 1965-12-13 | 1969-12-30 | Minnesota Mining & Mfg | Imagewise photochromic responsive element and process |
US3532638A (en) * | 1967-04-28 | 1970-10-06 | Eastman Kodak Co | Phototropic compositions |
-
1970
- 1970-03-02 US US15867A patent/US3642479A/en not_active Expired - Lifetime
-
1971
- 1971-02-08 CA CA104,739A patent/CA969411A/en not_active Expired
- 1971-02-22 BE BE763286A patent/BE763286A/en unknown
- 1971-02-23 FR FR7106042A patent/FR2083941A5/fr not_active Expired
- 1971-04-19 GB GB2282171A patent/GB1334752A/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3121633A (en) * | 1962-07-25 | 1964-02-18 | Horizons Inc | Process of making print-out images with cyanine dye bases and styryl dye bases |
US3486899A (en) * | 1965-12-13 | 1969-12-30 | Minnesota Mining & Mfg | Imagewise photochromic responsive element and process |
US3532638A (en) * | 1967-04-28 | 1970-10-06 | Eastman Kodak Co | Phototropic compositions |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3980480A (en) * | 1970-09-01 | 1976-09-14 | Urbain Leopold Laridon | Photographic recording and reproduction of information photochromic composition containing polyhalogenated hydrocarbon, spiropyran compound and heterocyclic mercapto compound and the use thereof |
US3773508A (en) * | 1970-11-19 | 1973-11-20 | Fuji Photo Film Co Ltd | Imagewise exposing and heating a photosensitive composition containing a spiropyran compound and an organic peroxide |
US3887808A (en) * | 1972-06-26 | 1975-06-03 | Agfa Gevaert | Thermoimaging process utilizing a photochromic material containing a spiropyran, a polyhalogenated hydrocarbon, a thiol compound and a polyvinylcarbazole |
US3844792A (en) * | 1972-12-07 | 1974-10-29 | American Cyanamid Co | A photosensitive composition containing a photochromic benzoylchromone or dibenzofuran and a strong organic amine base |
US3907569A (en) * | 1973-01-31 | 1975-09-23 | Horizons Inc | Ultraviolet holdback of nonsilver photosensitive systems by incorporating therein certain organic additives |
US4010033A (en) * | 1973-08-03 | 1977-03-01 | Agence Nationale De Valorisation De La Recherche (Anvar) | Photosensitive layer and method of forming a photographic image therefrom |
US3973966A (en) * | 1974-05-08 | 1976-08-10 | Xerox Corporation | Photochromic composition containing a diphenyl dibenzochrom-3-ene |
US4827149A (en) * | 1986-10-09 | 1989-05-02 | Sharp Kabushiki Kaisha | Operation halting circuit |
Also Published As
Publication number | Publication date |
---|---|
FR2083941A5 (en) | 1971-12-17 |
BE763286A (en) | 1971-07-16 |
CA969411A (en) | 1975-06-17 |
GB1334752A (en) | 1973-10-24 |
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