US3174861A - Photographic elements containing bischloroacylamido hardening agents - Google Patents
Photographic elements containing bischloroacylamido hardening agents Download PDFInfo
- Publication number
- US3174861A US3174861A US123654A US12365461A US3174861A US 3174861 A US3174861 A US 3174861A US 123654 A US123654 A US 123654A US 12365461 A US12365461 A US 12365461A US 3174861 A US3174861 A US 3174861A
- Authority
- US
- United States
- Prior art keywords
- hardening
- gelatin
- layers
- grams
- emulsion
- 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
- 239000000839 emulsion Substances 0.000 claims description 46
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- 108010010803 Gelatin Proteins 0.000 claims description 39
- 229920000159 gelatin Polymers 0.000 claims description 39
- 239000008273 gelatin Substances 0.000 claims description 39
- 235000019322 gelatine Nutrition 0.000 claims description 39
- 235000011852 gelatine desserts Nutrition 0.000 claims description 39
- -1 SILVER HALIDE Chemical class 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- 239000010410 layer Substances 0.000 description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000975 dye Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229960005141 piperazine Drugs 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- NZYHFRXQFJJPPF-UHFFFAOYSA-N 2-chloro-n'-(2-chloroacetyl)-n,n'-dimethylacetohydrazide Chemical compound ClCC(=O)N(C)N(C)C(=O)CCl NZYHFRXQFJJPPF-UHFFFAOYSA-N 0.000 description 2
- MQTABKLQUXUUQA-UHFFFAOYSA-N 2-chloro-n-[2-[(2-chloroacetyl)-methylamino]ethyl]-n-methylacetamide Chemical compound ClCC(=O)N(C)CCN(C)C(=O)CCl MQTABKLQUXUUQA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GRDLKEBELMXBIA-UHFFFAOYSA-N 2,2-dichloro-n-methylideneacetamide Chemical compound ClC(Cl)C(=O)N=C GRDLKEBELMXBIA-UHFFFAOYSA-N 0.000 description 1
- QYHXZQGNMLVJPX-UHFFFAOYSA-N 2-chloro-1-[4-(2-chloroacetyl)piperazin-1-yl]ethanone Chemical compound ClCC(=O)N1CCN(C(=O)CCl)CC1 QYHXZQGNMLVJPX-UHFFFAOYSA-N 0.000 description 1
- XKMYELXNRJUWPB-UHFFFAOYSA-N 2-chloro-n'-(2-chloroacetyl)acetohydrazide Chemical compound ClCC(=O)NNC(=O)CCl XKMYELXNRJUWPB-UHFFFAOYSA-N 0.000 description 1
- BQUBHNCENTUVMP-UHFFFAOYSA-N 2-chloro-n-[2-[(2-chloroacetyl)amino]ethyl]acetamide Chemical compound ClCC(=O)NCCNC(=O)CCl BQUBHNCENTUVMP-UHFFFAOYSA-N 0.000 description 1
- DNMKJPPCIKKTNT-UHFFFAOYSA-N 2-chloro-n-[4-[(2-chloroacetyl)amino]butyl]acetamide Chemical compound ClCC(=O)NCCCCNC(=O)CCl DNMKJPPCIKKTNT-UHFFFAOYSA-N 0.000 description 1
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 description 1
- ZYKBEIDPRRYKKQ-UHFFFAOYSA-N 4-[4-(diethylamino)-2-methylphenyl]imino-1-oxo-n-phenylnaphthalene-2-carboxamide Chemical compound CC1=CC(N(CC)CC)=CC=C1N=C1C2=CC=CC=C2C(=O)C(C(=O)NC=2C=CC=CC=2)=C1 ZYKBEIDPRRYKKQ-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101710204837 Envelope small membrane protein Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 101710088839 Replication initiation protein Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 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
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- UDAPHSWRVGGHLH-UHFFFAOYSA-N benzene-1,2-diamine;benzene-1,4-diamine Chemical compound NC1=CC=C(N)C=C1.NC1=CC=CC=C1N UDAPHSWRVGGHLH-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- IOVGROKTTNBUGK-SJCJKPOMSA-N ritodrine Chemical compound N([C@@H](C)[C@H](O)C=1C=CC(O)=CC=1)CCC1=CC=C(O)C=C1 IOVGROKTTNBUGK-SJCJKPOMSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
- 150000003754 zirconium Chemical class 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
- G03C1/005—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
- G03C1/30—Hardeners
Definitions
- This invention relates to the hardening of photographic layers, particularly of silver halide emulsion layers which contain as a colloidal carrier material a protein derivative, particularly gelatin.
- Photographic materials are treated with photographic processing solutions which have different pH values and diiferent temperatures. It is, therefore, extremely important to use photographic products with colloidal layers which when compared with pure gelatin are more resistant to water, swell less and have a higher melting point. For this reason, the gelatin layers must be hardened without depriving them of their water permeability.
- a large number of publications have recommended whole series of compounds and classes of compounds as hardening agents.
- Metal salts such as chromium, aluminum or Zirconium salts; aldehydes and halogen containing aldehydes such as formaldehyde, dialdehydes (glyoxal) and mucochloric acid; 1,2 and 1,4-diketones such as cyclohexanedione-l,2; quinone; chlorides of di basic organic acids; dianhydrides of tetracarboxylic acids; compounds with several reactive vinyl group such as vinylsulfone or acrylamide; compounds with at least two easily splitable heterocyclic rings such as ethylene oxide and ethyleneamine; and polyfunctional esters of methanesulfonic acid.
- Metal salts such as chromium, aluminum or Zirconium salts
- aldehydes and halogen containing aldehydes such as formaldehyde, dialdehydes (glyoxal) and mucochloric acid
- 1,2 and 1,4-diketones such as cyclo
- the hardening agents increase the viscosity of the coating solution to an alarming degree.
- Other hardening agents suffer from the disadvantage that they become active only after prolonged storage. In this manner, these hardening agents change the sensitometric characteristics of the layer in an uncontrollable manner. One refers to this effect as after-hardening.
- R R R and R which may be alike or different represent hydrogen or lower alkyl groups such as methyl, ethyl, or propyl; n is a positive integer ranging from 1 to 7; X and X together represent the carbon atoms necessary to complete a fully hydrogenated 5 or 6 membered heterocyclic nucleus such as a piperazine or pyrazolidine; and Y and Y together represent the atoms necessary to complete an aromatic nucleus of the benzene series which may be further substituted by a suitable group such as a carboXy group to increase the water solubility of the hardening agent.
- hardening agents can be readily prepared by reacting in an aqueous alkaline solution, an aliphatic, aromatic or heterocyclic diamine with the chloride of an ot-chlorocarboxylic acid.
- the separation and purification of the reaction products does not offer any difiiculties because the compounds precipitate from the solution and need only to be purified by recrystallizing the precipitate.
- diamines which can be used in the reaction are the following:
- l-iexamethylenediamine 1,2-phenylenediamine 1,4-phenylenediamine Pip erazine Pyrazolidine
- chlorides of a-chlorocarboxylic acids which can be used in the preparation of the novel hardening agents are: a-chloracetyl chloride, oc-ChlOlOPIOPiOIlYl chloride and ct-chlorobutyryl chloride.
- a great advantage of the hardeners of this invention resides in the feature that they will not react with any color formers which are present in multilayer color materials. Consequently, they can also be used in multilayer materials having incorporated in the emulsions color formers which are fast to diffusion.
- the compounds do not only harden the layers but improve the adhesion of the several over-coated layers in multilayer materials.
- the danger of separation of the layers in the wet state during the processing and drying is, therefore, reduced.
- the hardening agents are added to the photographic coating preparations in the form of a solution in a suitable water-miscible organic solvent such as methanol, ethanol, dioxane, dimethylformarnide and the like prior to coating. Neither the viscosity nor the pH of the coating solutions are altered by this technique.
- the amounts of hardening agents added depend on the desired effect. In general, from 1.0 to 20.0 grams of hardening agents per kilogram of dry colloidal carrier material such as gelatin are sufiicient. One thereby obtains layers with high melting points. The action of the hardening starts only after the drying of the layer.
- the action of the hardening agents can be explained on a hypothetical basis by assuming that the a-chlorine atom is rendered more labile by the proximity of the CO group and is readily split off; so that the remaining part of the hardener molecule reacts with the amino group of one or several gelatin molecules as indicated by the following formula:
- the emulsion layers and intermediate layers which are hardened with our novel hardening agents can be coated on all known supports such as glass, paper, cellulose esters or other film forming synthetic polymers.
- the general composition of the coating solutions used for the preparation of these layers does not need to be changed because the adhesion of these layers is not adversely influenced by the hardening. In some cases, the.
- adhesion is even improved through the use of the novel hardening agents.
- sensitizing procedure or other conventional methods of preparing the emulsions can be retained without change.
- the hardening agents described herein can be combined with previously known hardening agents if special efl ects are desired.
- these dye-forming compounds unite with the oxidation products of the developing agent to form an azornethine or indoaniline dye.
- the emulsion layer may be free from color formers in which case the film is processed with the color formers in the color developers by the selective second exposure and color development method as described in US. Patent 1,897,866, 1,900,870, 1,928,709, and 1,980,941.
- Multicolor film in which each element bears a color yielding layer comprising a hydrophilic film-forming synthetic polymer containing a plurality of hydroxyl groups and having a plurality of color components and, in addition, containing light-sensitive silver salts in described in US. Patents 2,397,864, 2,397,865, 2,397,866, and 2,397,867.
- Example I To 1 kilogram of a silver chlorobromide emulsion which is ready for coating and contains about 65 grams of gelatin, there was added 1.5 grams of bis-chloroacetyl- N,N-di1nethylethylenediamine dissolved in methanol. The addition of this hardening mixture does not increase the viscosity and does not change the pH which is preferably kept between a range of 6.0 to 8.0. The emulsion is coated on baryta paper. After the usual drying and storing for 48 hours at a temperature of 45, it was noted that the layer had a melting point of 100 C. The hardening is not influenced by the pH in a pH range of 6.0 to 8.0 and the photographic properties of the emulsions are not changed.
- the coating solution contains as the hardening agent 1.4 grams of bis-chloroacetyl-N,N'-dimethylethylenediamine dissolved in methanol.
- the coated layer is dried and stored for 48 hours after which time it showed a melting point of C. After completed color processing, the layer showed good adhesion to the support and contained a stain-free yellow dye image.
- the photo graphic properties of this emulsion including color density, speed and contrast were the same as those of an unhardened type emulsion.
- Example III The light-sensitive material prepared in accordance with Example II was overcoated with a red-sensitive silver chloride emulsion which contains per 1 liter of solution:
- the coating solution contained 3 grams of the hardening agent bis-chloroacetyl-ethylenediamine. After coating, drying and storage, the melting point of the layer was determined as being above 90 C. The adhesion of the two color emulsion layers was noticeably improved by our hardening agent when compared with conventional hardening agents.
- Example IV A subbed cellulose acetate film support was coated with 1 kilogram of a gelatin solution which contained approximately 30 grams of gelatin together with an antihalation dye and 1 gram of the compound bis-chloroacetyl-1,2- phenylenediamine-4-carboxylic acid dissolved in ethanol. After drying and storage, the backing layer had a melting point above C. This layer showed no tendancy to swell and had a very high resistance to abrasion in its wet state.
- Example V Example IV was repeated with the exception that the hardening agent used was 1 gram of bis-chloroacetyl-N, N'-dimethylhydrazine.
- the backing layer obtained therefrom shows very little swelling and a high abrasion resist ance in the wet state.
- a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a bis-chloroacylamido hardening agent selected from the group of compounds having the following general formulae:
- R1OHC o-N-c'n cn-N o o-cn-Ri I 1 -Yr 01 wherein R R R and R are members selected from the group consisting of a hydrogen atom and lower alkyl groups, n represents a positive integer ranging from 1 to 7; X and X represent the carbon atoms necessary to complete a hydrogenated heterocyclic nucleus; and Y and Y represent the carbon atoms necessary to complete an aromatic nucleus of the benzene series.
- a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a compound having the following formula:
- a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a compound having the following formula:
- a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a compound having the following formula:
- a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amine developing agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent selected from the group of compounds having the following general formulae:
- R R R and R are members selected from the group consisting of a hydrogen atom and lower alkyl groups, n represents a positive integer ranging from 1 to 7; X and X represent the carbon atoms necessary to complete a hydrogenated heterocyclic nucleus; and Y and Y represent the carbon atoms necessary to complete an aromatic nucleus of the benzene series.
- a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amino developing agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent of the following formula:
- a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amino agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent of the following formula:
- a photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amino development agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent of the following formula:
- a photo-sensitive element comprising a support and coated thereon a gelatin silver halide emulsion layer and a gelatin layer, at least one of these gelatin layers containing a hardening amount of a bis-chloroacylamido hardening agent selected from the group of compounds having the following general formulae:
- R R R and R are members selected from the group consisting of a hydrogen atom and lower alkyl groups, n represents a positive integer ranging from 1 to 7; X and X represent the carbon atoms necessary to complete a hydrogenated heterocyclic nucleus; and Y and Y represent the carbon atoms necessary to complete an aromatic nucleus of the benzene series.
- a photo-sensitive element comprising a support carrying a gelatin silver halide emulsion and a gelatin layer coated thereon, at least one of these gelatin layers containing a hardening amount of a compound having the following formula:
- a photo-sensitive element comprising a support carrying a gelatin silver halide emulsion and a gelatin layer coated thereon, at least one of these gelatin layers containing a hardening amount of a compound having the following formula:
- a photo-sensitive element comprising a support References fired by the Examiner carrying a gelatin silver halide emulsion and a gelatin UNITED STATES PATENTS layer coated thereon, at least one of these gelatin layers r containing a hardening amount of a compound having the 3/61 Levme 11 FOREIGN PATENTS following formula: 5
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEA35144A DE1130283B (de) | 1960-07-16 | 1960-07-16 | Verfahren zum Haerten photographischer Schichten |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3174861A true US3174861A (en) | 1965-03-23 |
Family
ID=6928864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US123654A Expired - Lifetime US3174861A (en) | 1960-07-16 | 1961-07-13 | Photographic elements containing bischloroacylamido hardening agents |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3174861A (en(2012)) |
| BE (1) | BE606194A (en(2012)) |
| DE (1) | DE1130283B (en(2012)) |
| GB (1) | GB932978A (en(2012)) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3881933A (en) * | 1971-05-18 | 1975-05-06 | Fuji Photo Film Co Ltd | Light-sensitive material undergoing little change of latent image formed therein |
| US3977881A (en) * | 1974-01-31 | 1976-08-31 | Ciba-Geigy Ag | Acylurea compounds |
| US4039520A (en) * | 1973-03-12 | 1977-08-02 | Konishiroku Photo Industry Co., Ltd. | Gelatin hardening process |
| US5378591A (en) * | 1990-07-04 | 1995-01-03 | Eastman Kodak Company | Reversal color photographic material |
| US8105349B2 (en) | 2004-04-16 | 2012-01-31 | Cook Medical Technologies Llc | Removable vena cava filter having primary struts for enhanced retrieval and delivery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL106968C (en(2012)) | 1960-08-06 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB787400A (en) * | 1956-04-13 | 1957-12-04 | Bayer Ag | New condensation products of haloacetamides |
| US2976152A (en) * | 1958-12-19 | 1961-03-21 | Gen Aniline & Film Corp | Photographic gelatin layers containing triazine hardeners |
-
0
- BE BE606194D patent/BE606194A/xx unknown
-
1960
- 1960-07-16 DE DEA35144A patent/DE1130283B/de active Pending
-
1961
- 1961-07-13 US US123654A patent/US3174861A/en not_active Expired - Lifetime
- 1961-07-14 GB GB25649/61A patent/GB932978A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB787400A (en) * | 1956-04-13 | 1957-12-04 | Bayer Ag | New condensation products of haloacetamides |
| US2976152A (en) * | 1958-12-19 | 1961-03-21 | Gen Aniline & Film Corp | Photographic gelatin layers containing triazine hardeners |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3881933A (en) * | 1971-05-18 | 1975-05-06 | Fuji Photo Film Co Ltd | Light-sensitive material undergoing little change of latent image formed therein |
| US4039520A (en) * | 1973-03-12 | 1977-08-02 | Konishiroku Photo Industry Co., Ltd. | Gelatin hardening process |
| US3977881A (en) * | 1974-01-31 | 1976-08-31 | Ciba-Geigy Ag | Acylurea compounds |
| US5378591A (en) * | 1990-07-04 | 1995-01-03 | Eastman Kodak Company | Reversal color photographic material |
| US8105349B2 (en) | 2004-04-16 | 2012-01-31 | Cook Medical Technologies Llc | Removable vena cava filter having primary struts for enhanced retrieval and delivery |
Also Published As
| Publication number | Publication date |
|---|---|
| BE606194A (en(2012)) | |
| DE1130283B (de) | 1962-05-24 |
| GB932978A (en) | 1963-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3642908A (en) | Vinyl and ether containing sulfones | |
| US2983611A (en) | Gelatin compositions containing hardeners | |
| US3220839A (en) | Photographic emulsions containing isothiourea derivatives | |
| US3689274A (en) | Process of hardening photographic gelatin layers with a sulfonyl ester or a sulfonamide | |
| US3137578A (en) | Photographic emulsions containing 2-heterocyclic benzimidazole antifoggants | |
| US3547638A (en) | N,n-disubstituted amino-methylthiocarboxylic acids and use thereof as antifoggants in photographic emulsions | |
| US2950197A (en) | Hardening of gelatin | |
| US3232764A (en) | Gelatin compositions adapted for the preparation of hardened coatings | |
| US3923517A (en) | Method for rapidly forming photographic images | |
| US3174861A (en) | Photographic elements containing bischloroacylamido hardening agents | |
| US3765901A (en) | Spectral sensitization of light-sensitive silver halide emulsions | |
| US2444607A (en) | Stabilizers for photographic emulsions | |
| US3791830A (en) | Silver halide photographic element containing a reaction product of a heterocyclic mercaptan and a chloroformic acid ester as antifog agent | |
| US4039520A (en) | Gelatin hardening process | |
| US3255013A (en) | Increasing the sensitivity of photographic emulsions | |
| JPS61189530A (ja) | 感光性の安定化された写真記録材料 | |
| US3026201A (en) | Antifoggants and stabilizers for photographic silver halide emulsions | |
| US3671255A (en) | Silver halide emulsion fog inhibited with quaternary ammonium,triazole and tetrazaindene compounds | |
| US3543292A (en) | Photographic gelatin hardened with bis isoxazole compounds and their quaternary salts | |
| US3981857A (en) | Gelatin hardening process | |
| US4281059A (en) | Photographic material | |
| US3910794A (en) | Imidazole couplers for two component diazotype systems | |
| US2295008A (en) | Photographic color forming compound | |
| US2606833A (en) | Photographic film with antihalation layer | |
| US2976152A (en) | Photographic gelatin layers containing triazine hardeners |