EP0031959B1 - Method for hardening photographic gelatin layers - Google Patents
Method for hardening photographic gelatin layers Download PDFInfo
- Publication number
- EP0031959B1 EP0031959B1 EP80108218A EP80108218A EP0031959B1 EP 0031959 B1 EP0031959 B1 EP 0031959B1 EP 80108218 A EP80108218 A EP 80108218A EP 80108218 A EP80108218 A EP 80108218A EP 0031959 B1 EP0031959 B1 EP 0031959B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gelatin
- layer
- compound
- crosslinking agent
- hardening
- 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
Links
- 229920000159 gelatin Polymers 0.000 title claims description 45
- 235000019322 gelatine Nutrition 0.000 title claims description 45
- 108010010803 Gelatin Proteins 0.000 title claims description 40
- 239000008273 gelatin Substances 0.000 title claims description 40
- 235000011852 gelatine desserts Nutrition 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- -1 sulphonyl ethyl Chemical group 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000001828 Gelatine Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims 2
- 239000012062 aqueous buffer Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 63
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- 239000003795 chemical substances by application Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 238000001723 curing Methods 0.000 description 14
- 229910052709 silver Inorganic materials 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 239000004332 silver Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 9
- 239000004971 Cross linker Substances 0.000 description 8
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- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000872 buffer Substances 0.000 description 6
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical group C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
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- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
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- 229910052700 potassium Inorganic materials 0.000 description 4
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
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- 239000000654 additive Substances 0.000 description 3
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- 230000035945 sensitivity Effects 0.000 description 3
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- 239000000080 wetting agent Substances 0.000 description 3
- 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 0 C****S(C(C1)C(*CCOC)C=CC1S(CC*CCCO*C)(=O)=O)(=O)=O Chemical compound C****S(C(C1)C(*CCOC)C=CC1S(CC*CCCO*C)(=O)=O)(=O)=O 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
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- 239000006172 buffering agent Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
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- 235000010334 sodium propionate Nutrition 0.000 description 2
- 229960003212 sodium propionate Drugs 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Images
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
- the invention relates to a method for hardening photographic gelatin or photographic layers containing such gelatin.
- metal salts such as chromium, aluminum or zirconium salts, aldehydes and halogen-containing aldehyde compounds, in particular formaldehyde, dialdehydes and mucochloric acid, 1,2- and 1,4-diketones such as cyclohexanedione-1,2 and quinones and chlorides of 2-basic organic Acids, the anhydrides of tetracarboxylic acids, compounds with several reactive vinyl groups such as vinyl sulfones, acrylamides, compounds with at least two easily cleavable, heterocyclic 3-membered rings such as ethylene oxide and ethylene imine, polyfunctional methanesulfonic acid esters and bis-a-chloroacylamido compounds.
- metal salts such as chromium, aluminum or zirconium salts, aldehydes and halogen-containing aldehyde compounds, in particular formaldehyde, dialdehydes and mucochloric acid, 1,2- and
- high molecular weight curing agents such as. B. polyacrolein or its derivatives or copolymers and alginic acid derivatives known, which are used specifically as layer-limited curing agents.
- the use of the compounds mentioned for photographic purposes is associated with a number of serious disadvantages. Some of these compounds are photographically active and are therefore unsuitable for hardening photographic materials, others influence the physical properties, such as e.g. B. the fragility of the gelatin layers so disadvantageous that they can not be used. Others cause discoloration or a change in pH during the curing reaction. In addition, it is particularly important for the hardening of photographic layers that the hardening reaches its maximum as soon as possible after drying, so that the permeability of the material to be hardened to the developer solution does not change continuously, as in the case of mucochloric acid or formaldehyde, for example .
- crosslinking agents for gelatin also have skin-damaging effects, such as B. the ethyleneimine compounds, so that their application is not appropriate for physiological reasons.
- hardening agents for photographic gelatin layers are compounds with two or more acrylic acid amido groups in the molecule, N, N ', N "-trisacryloylhydrotriazine or methylenebisacrylamide.
- the hardening of the compounds after some time is good, but the compounds are sparingly soluble in water, which can lead to irregularities in the hardening within the layer.
- DE-C-1 100942 aromatic vinyl sulfone compounds and DE-A-1 147733 nitrogen or oxygen as heteroatoms containing heterocyclic vinyl sulfone compounds are known.
- DE-C-1 808 685 and DE-A-2 348 194 describe bis-vinylsulfonylalkyl compounds as curing agents.
- the known vinyl sulfone compounds have proven to be disadvantageous as curing agents in several respects. They are either not sufficiently water-soluble and require special measures to enable them to be used in photographic gelatin layers, or they adversely affect the drying behavior of the layers. It has been found to be particularly disadvantageous that these compounds increase the viscosity of the casting solution in such a way that the casting is considerably disturbed.
- the invention has for its object to develop a hardening process for photographic, gelatin-containing layers by which disturbances during the casting process can be prevented, which are caused by increased viscosity of the casting solutions by premature crosslinking of the gelatin, and by which neither the photographic properties, in particular color photographic materials Adversely affected, difficulties will arise during the later processing of the materials in photographic baths.
- the invention is based on a method for hardening a photographic material consisting of a layer support and at least one gelatin-containing layer applied thereon with a compound reacting with the amino groups of the gelatin as a crosslinking agent, and is characterized in that the casting compound of the gelatin-containing layer (s) or a compound containing 2 to 6 sulfonylethyl sulfate groups in the form of their salts and incorporated in the gelatin-containing layer (s) as a crosslinking agent and that the effectiveness of the compound as a crosslinking agent is adjusted by adjusting a pH of 6 , 5 to 9 in the casting compound or from 6.5 to 11 in the gelatin-containing layer.
- Salts of volatile inorganic or organic acids are particularly suitable for adjusting the pH, in particular, for. B. carbonic acid, acetic acid, propionic acid with non-volatile cations of alkaline earth metal or zinc ions.
- the pH can also be adjusted using buffer mixtures. Suitable mixtures are primary potassium phosphate / secondary sodium phosphate with which pH levels up to 8 can be obtained, hydrochloric acid / sodium borate whose effect extends to pH 9, further sodium borate / sodium hydroxide solution or glycol / sodium hydroxide solution, effective up to pH 11 or 13.
- the compound is concentrated in ice water and the pH is adjusted to 5 by adding aqueous sodium bicarbonate solution. The aqueous solution is evaporated to dryness in vacuo. The product is triturated with acetone and suction filtered. Yield: 22 g. According to NMR measurement, the compound contains no vinyl sulfone groups.
- hydroxyethyl sulfone compounds required for the reaction can be described in a known manner, as described in Ullmann vol. 14, p. 620, in Houben-Weyl, vol. IX, p. 247, or in DT-C-965 902, e.g. B. over the corresponding haloalkanes by reaction with Hydroxialkylmercaptanen and oxidation of the sulfides formed to the Hydroxiethylsulfonen with H 2 0 2 .
- the crosslinking agents used according to the invention can be added to the casting solution either some time before the coating or immediately before the coating by metering devices.
- the compounds can also be added to a coating solution which is applied as a curing coating after the finished photographic material has been prepared.
- the finished layer structure can also be drawn through a solution of the crosslinking agent and thereby receives the necessary amount of crosslinking agent.
- the crosslinkers of the invention bring about the intermediate layers in the overall structure.
- the crosslinkers are generally used in the process of the invention in an amount of 0.01 to 15% by weight and preferably 0.1 to 10% by weight, based on the dry weight of the gelatin in the coating solution.
- the time of addition to the coating solution is not critical, but silver halide emulsions will expediently be added to the hardener after chemical ripening.
- the salts of volatile acids with non-volatile cations mentioned in the first place can be incorporated together with the crosslinking agent or separately into the casting compounds or layers.
- the buffer mixtures cannot be used together with the crosslinker. These are added to the casting compounds containing the crosslinker only shortly before the layers are poured or during the casting. Even if the crosslinker is to be incorporated into a finished layered structure by means of an overlay bath, it is expedient to bathe the buffer mixture only when the diffusion of the crosslinker into the layered structure and its uniform connection in the layers of the structure to be hardened has been completed. It is of course also possible to incorporate the buffer mixture into the casting compound and then to introduce the crosslinking agent into the casting compound or the layer in one of the ways described.
- photographic layers are to be understood very generally as layers which are used in the context of photographic materials, for example light-sensitive silver halide emulsion layers, protective layers, filter layers, antihalo layers, backing layers or very generally photographic auxiliary layers.
- the curing method according to the invention is excellently suitable
- layers which are based on non-sensitized emulsions, X-ray emulsions and other spectrally sensitized emulsions there may be mentioned, for example, layers which are based on non-sensitized emulsions, X-ray emulsions and other spectrally sensitized emulsions.
- the hardening process of the invention has proven itself for hardening the gelatin layers used for the various black and white and color photographic processes, such as negative, positive and diffusion transfer processes or printing processes.
- the process according to the invention has proven to be particularly advantageous for the hardening of photographic layer dressings which are intended for carrying out color photographic processes, e.g. B. those that contain emulsion layers with color couplers or emulsion layers that are intended for treatment with solutions containing color couplers.
- the effect of the compounds used in the manner according to the invention is not impaired by the usual photographic additives.
- the hardeners are also indifferent to photographically active substances, such as water-soluble and emulsified water-insoluble color components, stabilizers, sensitizers and the like. Furthermore, they have no adverse effect on the light-sensitive silver halide emulsion.
- the emulsion layers can contain any known silver halides as light-sensitive components, such as silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide, silver chlorobiodobromide and the like.
- the emulsions can be chemically sensitized by precious metal compounds, e.g. B. by compounds of ruthenium, rhodium, palladium, iridium, platinum, gold and the like, such as ammonium chloropalladate, potassium chloroplatinate, potassium chloropalladate, or potassium chloroaurate. They may contain further specific sensitizing agents such as sulfur compounds, Z i n n (11) salts, polyamines or polyalkylene oxide.
- the emulsions be optically sensitized with cyanine dyes, merocyanine dyes and mixed cyanine dyes.
- the emulsions can be a wide variety of couplers, e.g. B. colorless couplers, colored couplers, stabilizers such as mercury compounds, triazole compounds, azainden compounds, benzothiazolium compounds or zinc compounds, wetting agents such as dihydroxyalkanes, the film-forming properties improving agents, for. B.
- couplers e.g. B. colorless couplers, colored couplers, stabilizers such as mercury compounds, triazole compounds, azainden compounds, benzothiazolium compounds or zinc compounds, wetting agents such as dihydroxyalkanes, the film-forming properties improving agents, for. B.
- the couplers such as. B. purple couplers of the 5-pyrazolone type, cyan couplers of the naphthol or phenol type and yellow couplers of the closed ketomethylene type, so-called 2-valent and 4-valent couplers, which are derived from the above-mentioned couplers, and so-called masking couplers with an arylazo group contain the active site, no color changes occur in the photographic materials.
- the crosslinking agents of the invention are particularly distinguished from the known vinylsulfonyl-type hardeners in that they in no case increase the viscosity of the casting solutions by premature crosslinking in solution.
- This disadvantageous behavior can be found in known vinyl sulfonate hardeners, especially in compounds with more than 2 reactive vinyl sulfonyl groups.
- the casting solutions can only be kept for a short time and a considerable technical effort is required to overcome the resulting difficulties.
- the viscosities at 40 ° C were measured every hour.
- the mixtures were digested at 40 ° C. for a long time (approx. 5 hours).
- the behavior of the samples was examined at pH 6, 6.5, 7 and 7.5.
- the pH values were adjusted using a buffer mixture of primary potassium phosphate and secondary sodium phosphate (6, 6.5) and sodium carbonate (7, 7.5).
- the material was stored under various climatic conditions and then tested for crosslinking by determining the layer melting point, the wet scratch resistance and the swelling factor.
- a good cross-linking results from a high layer melting point, a high wet scratch strength and a low swelling factor.
- test specimen is developed as a black sheet in a conventional color development process and weighed after the final bath after the excess water has been stripped off. The sample is then dried and weighed again. The difference from the area of the test object to 1 m 2 converts the water absorption per m 2 .
- the swelling is measured gravimetrically after treatment of a test strip in distilled water at 22 ° C. for 10 minutes. It is denoted by the swelling factor:
- a metal tip of a defined size is passed over the wet layer and loaded with increasing weight.
- the wet scratch resistance is indicated by the weight at which the tip leaves a visible scratch mark on the layer; a high weight corresponds to a high wet scratch resistance.
- the table shows that the entire layer structure is hardened by the diffusing hardening system.
- the hardening starts with the addition of sodium bicarbonate, sodium formate, sodium acetate or sodium propionate and reaches a certain hardening end point more quickly. It turns out that the hardening is higher if the hardening system is poured over, i.e. H. after the production of the layer package.
- the curing system of the invention is inert to the emulsion and color couplers in this application.
- the hardening effect is also accelerated in gelatin-containing black and white photographic materials by adding buffering substances.
- buffering substances 5 g of compound 1 were used per 100 g of gelatin. 4 moles of sodium carbonate per mole of curing agent were added to the casting solutions. A mixture without the addition of the buffer substance served as a comparison.
- the casting solutions contained 35 g of silver halide. The hardening properties were tested after storage of the material under 4 different climatic conditions.
- the melting point increases to over 100 ° C. within a few days when buffer substances are added to the layer.
- the photographic materials hardened in this way are therefore suitable for processing at 38-50 ° C after a short storage period.
- the photographic properties such as fog, sensitivity and gradation are not changed.
- Samples of a photographic paper emulsion which contained 80 g of gelatin and 35 g of halogen silver per liter and each 3% by weight of a crosslinking agent according to the invention were poured onto polyethylene-coated paper substrates which had been provided with an adhesive layer.
- the usual pouring aids such as wetting agents, stabilizers and opt.
- Sensitizers were previously added to the emulsion samples. The layer melting points were determined directly after drying.
- the layer melting points were determined after passing through a 22 ° C. photographic developer bath for black and white materials.
- the melting points are raised after a development time of 1.5 minutes from 35 to well over 100 ° C, proof of the spontaneously triggered hardening due to the high pH of the developer solution.
- the example demonstrates the uncertainty of a curing process not carried out in accordance with the invention, which is due to the latency of the effectiveness of the crosslinking agents.
- the developer solution had the following composition:
Description
Die Erfindung betrifft ein Verfahren zur Härtung photographischer Gelatine bzw. photographischer Schichten, die solche Gelatine enthalten.The invention relates to a method for hardening photographic gelatin or photographic layers containing such gelatin.
Als Härtungsmittel für Proteine und im besonderen für Gelatine sind bereits zahlreiche Substanzen beschrieben worden. Hierzu gehören beispielsweise Metallsalze wie Chrom-, Aluminium- oder Zirkonsalze, Aldehyde und halogenhaltige Aldehydverbindungen, insbesondere Formaldehyd, Dialdehyde und Mucochlorsäure, 1,2- und 1,4-Diketone wie Cyclohexandion-1,2 und Chinone sowie Chloride von 2-basischen organischen Säuren, die Anhydride von Tetracarbonsäuren, Verbindungen mit mehreren reaktionsfähigen Vinylgruppen wie Vinylsulfone, Acrylamide, Verbindungen mit mindestens zwei leichtspaltbaren, heterocyclischen 3-gliedrigen Ringen wie Ethylenoxid und Ethylenimin, mehrfunktionelle Methansulfonsäureester und Bis-a-chloracylamidoverbindungen.Numerous substances have already been described as hardening agents for proteins and in particular for gelatin. These include, for example, metal salts such as chromium, aluminum or zirconium salts, aldehydes and halogen-containing aldehyde compounds, in particular formaldehyde, dialdehydes and mucochloric acid, 1,2- and 1,4-diketones such as cyclohexanedione-1,2 and quinones and chlorides of 2-basic organic Acids, the anhydrides of tetracarboxylic acids, compounds with several reactive vinyl groups such as vinyl sulfones, acrylamides, compounds with at least two easily cleavable, heterocyclic 3-membered rings such as ethylene oxide and ethylene imine, polyfunctional methanesulfonic acid esters and bis-a-chloroacylamido compounds.
In neuerer Zeit wurden hochmolekulare Härtungsmittel, wie z. B. Polyacrolein bzw. seine Derivate oder Mischpolymerisate sowie Alginsäurederivate bekannt, die speziell als schichtbegrenzte Härtungsmittel Verwendung finden.In recent times, high molecular weight curing agents such as. B. polyacrolein or its derivatives or copolymers and alginic acid derivatives known, which are used specifically as layer-limited curing agents.
Die Verwendung der genannten Verbindungen für photographische Zwecke ist jedoch mit einer Reihe schwerwiegender Nachteile verbunden. Einige dieser Verbindungen sind photographisch aktiv und sind deshalb zur Härtung photographischer Materialien ungeeignet, andere beeinflussen die physikalischen Eigenschaften, wie z. B. die Brüchigkeit der Gelatineschichten so nachteilig, daß sie nicht verwendet werden können. Andere wiederum verursachen Verfärbungen oder eine Änderung des pH-Wertes während der Härtungsreaktion. Darüber hinaus ist es für die Härtung photographischer Schichten besonders wichtig, daß die Härtung möglischst kurze Zeit nach dem Auftrocknen ihr Maximum erreicht, damit nicht, wie beispielsweise im Falle der Mucochlorsäure oder des Formaldehyds, sich die Durchlässigkeit des zu härtenden Materials für die Entwicklerlösung fortlaufend ändert.However, the use of the compounds mentioned for photographic purposes is associated with a number of serious disadvantages. Some of these compounds are photographically active and are therefore unsuitable for hardening photographic materials, others influence the physical properties, such as e.g. B. the fragility of the gelatin layers so disadvantageous that they can not be used. Others cause discoloration or a change in pH during the curing reaction. In addition, it is particularly important for the hardening of photographic layers that the hardening reaches its maximum as soon as possible after drying, so that the permeability of the material to be hardened to the developer solution does not change continuously, as in the case of mucochloric acid or formaldehyde, for example .
In gewissen Fällen haben Vernetzungsmittel für Gelatine auch hautschädigende Wirkung, wie z. B. die Ethyleniminverbindungen, so daß ihre Anwendung schon aus physiologischen Gründen nicht angebracht ist.In certain cases, crosslinking agents for gelatin also have skin-damaging effects, such as B. the ethyleneimine compounds, so that their application is not appropriate for physiological reasons.
Es ist weiter bekannt, Trichlortriazin, Hydroxydichlortriazin und Dichloraminotriazine als Härtungsmittel zu verwenden. Nachteilig sind hierbei der verhältnismäßig hohe Dampfdruck, Abspaltung von Salzsäure während der Härtung und die physiologische Wirkung dieser Verbindungen, Wasserlösliche Derivate, die Carboxyl- und Sulfonsäuregruppen enthalten und die durch Umsetzung von Cyanurchlorid mit einem Mol Aminoalkyl- oder Diaminoarylsulfonsäure oder Carbonsäure erhalten werden, zeigen diese Nachteile nicht und sind deshalb in neuerer Zeit als Härtungsmittel vorgeschlagen worden. Ihre praktische Verwendbarkeit ist jedoch begrenzt, da sie sich infolge ihrer guten Löslichkeit beim Stehen in wäßrigen Lösungen zersetzen und dadurch ihre Wirksamkeit schnell einbüßen.It is also known to use trichlorotriazine, hydroxydichlorotriazine and dichloraminotriazine as curing agents. Disadvantages here are the relatively high vapor pressure, the elimination of hydrochloric acid during the curing and the physiological action of these compounds, water-soluble derivatives which contain carboxyl and sulfonic acid groups and which are obtained by reacting cyanuric chloride with one mole of aminoalkyl or diaminoarylsulfonic acid or carboxylic acid, these show Disadvantages do not and have therefore recently been proposed as hardening agents. However, their practical usability is limited because, due to their good solubility, they decompose when standing in aqueous solutions and therefore quickly lose their effectiveness.
Es ist schließlich bei einem Härtungsmittel für photographische, gelatinehaltige Schichten sowohl aus Herstellungs- als auch aus Verarbeitungsgründen von größter Bedeutung, daß auch das Einsetzen der Vernetzungsreaktion in gewissen Grenzen bestimmbar ist, beispielsweise durch Wahl der Trocknungstemperatur oder durch Wahl des pH-Wertes.Finally, it is of the utmost importance for a hardening agent for photographic, gelatin-containing layers, both for production and processing reasons, that the onset of the crosslinking reaction can be determined within certain limits, for example by choosing the drying temperature or by choosing the pH.
Als Härtungsmittel für photographische Gelatineschichten bekannt sind auch Verbindungen mit zwei oder mehreren Acrylsäureamidogruppen im Molekül, N,N',N"-Trisacryloylhydrotriazin oder Methylenbisacrylamid.Also known as hardening agents for photographic gelatin layers are compounds with two or more acrylic acid amido groups in the molecule, N, N ', N "-trisacryloylhydrotriazine or methylenebisacrylamide.
Die Härtung der Verbindungen nach einiger Zeit ist zwar gut, jedoch sind die Verbindungen in Wasser schwer löslich, was innerhalb der Schicht zu Ungleichmäßigkeiten in der Härtung führen kann.The hardening of the compounds after some time is good, but the compounds are sparingly soluble in water, which can lead to irregularities in the hardening within the layer.
Besondere Probleme ergeben sich bei der in zunehmendem Maße gebrauchten Schnellverarbeitung photographischer, insbesondere farbphotographischer Materialien, die gesteigerte Anforderungen an die mechanischen Eigenschaften und das Quellverhalten der Materialien stellt. Dazu kommen die Schwierigkeiten, die sich aus der Notwendigkeit, immer dünnere photographische Schichten herzustellen, ergeben. Man hat versucht, solche Probleme durch Anwendung verschiedenartiger Härtungsmittel zu lösen. Die bekannten Härtungsmittel haben dabei aber entweder neue Schwierigkeiten verursacht oder sich einfach als ungeeignet erwiesen.Particular problems arise with the increasingly rapid processing of photographic, especially color photographic, materials, which places increased demands on the mechanical properties and the swelling behavior of the materials. In addition, there are the difficulties that arise from the need to produce ever thinner photographic layers. Attempts have been made to solve such problems by using various hardening agents. However, the known hardening agents either caused new difficulties or simply proved unsuitable.
Dazu zählen die zahlreichen bekannten Vinylsulfongruppen enthaltenden Härtungsmittel, von denen Divinylsulfon (DE-C-872 153) zu den am längsten bekannten gehört. Einer Anwendung des Divinylsulfons steht seine Toxizität entgegen.These include the numerous known curing agents containing vinyl sulfone groups, of which divinyl sulfone (DE-C-872 153) is one of the longest known. The use of divinyl sulfone prevents its toxicity.
Weiter sind durch die DE-C-1 100942 aromatische Vinylsulfonverbindungen und durch die DE-A-1 147733 Stickstoff oder Sauerstoff als Heteroatome enthaltende heterocyclische Vinylsulfonverbindungen bekannt geworden. Schließlich beschreibt die DE-C-1 808 685 und die DE-A-2 348 194 Bis-vinylsulfonylalkylverbindungen als Härtungsmittel.Furthermore, DE-C-1 100942 aromatic vinyl sulfone compounds and DE-A-1 147733 nitrogen or oxygen as heteroatoms containing heterocyclic vinyl sulfone compounds are known. Finally, DE-C-1 808 685 and DE-A-2 348 194 describe bis-vinylsulfonylalkyl compounds as curing agents.
Die bekannten Vinylsulfonverbindungen haben sich als Härtungsmittel in mehrfacher Hinsicht als nachteilhaft erwiesen. Sie sind entweder nicht hinreichend wasserlöslich und machen besondere Maßnahmen erforderlich, um ihre Anwendung in photographischen Gelatineschichten zu ermöglichen, oder sie beeinflussen das Trocknungsverhalten der Schichten in nachteiliger Weise. Besonders nachteilig hat sich erwiesen, daß diese Verbindungen die Viskosität der Gießlösung so erhöhen, daß der Beguss erheblich gestört wird.The known vinyl sulfone compounds have proven to be disadvantageous as curing agents in several respects. They are either not sufficiently water-soluble and require special measures to enable them to be used in photographic gelatin layers, or they adversely affect the drying behavior of the layers. It has been found to be particularly disadvantageous that these compounds increase the viscosity of the casting solution in such a way that the casting is considerably disturbed.
Der Erfindung liegt die Aufgabe zugrunde, ein Härtungsverfahren für photographische, gelatinehaltige Schichten zu entwickeln, durch das sich Störungen während des Gießprozesses verhindern lassen, die durch Viskositätserhöhungen der Gießlösungen durch vorzeitiges Vernetzen der Gelatine verursacht werden, und durch das weder die photographischen Eigenschaften insbesondere farbphotographischer Materialien nachteilig beeinflußt werden noch bei der späteren Verarbeitung der Materialien in photographischen Bädern Schwierigkeiten entstehen.The invention has for its object to develop a hardening process for photographic, gelatin-containing layers by which disturbances during the casting process can be prevented, which are caused by increased viscosity of the casting solutions by premature crosslinking of the gelatin, and by which neither the photographic properties, in particular color photographic materials Adversely affected, difficulties will arise during the later processing of the materials in photographic baths.
Die Erfindung geht aus von einem Verfahren zur Härtung eines aus einem Schichtträger und mindestens einer darauf angebrachten gelatinehaltigen Schicht bestehenden, photographischen Materials mit einer mit den Aminogruppen der Gelatine reagierenden Verbindung als Vernetzer, und ist dadurch gekennzeichnet, daß der Begußmasse der gelatinehaltigen Schicht(en) oder der (den) auf dem Schichtträger angebrachten, gelatinehaltigen Schicht(en) als Vernetzer eine Verbindung einverleibt wird, die 2 bis 6 Sulfonylethylsulfat-Gruppen in Form ihrer Salze enthält und daß die Wirksamkeit der Verbindung als Vernetzer durch Einstellung eines pH-Wertes von 6,5 bis 9 in der Begußmasse oder von 6,5 bis 11 in der gelatinehaltigen Schicht ausgelöst wird.The invention is based on a method for hardening a photographic material consisting of a layer support and at least one gelatin-containing layer applied thereon with a compound reacting with the amino groups of the gelatin as a crosslinking agent, and is characterized in that the casting compound of the gelatin-containing layer (s) or a compound containing 2 to 6 sulfonylethyl sulfate groups in the form of their salts and incorporated in the gelatin-containing layer (s) as a crosslinking agent and that the effectiveness of the compound as a crosslinking agent is adjusted by adjusting a pH of 6 , 5 to 9 in the casting compound or from 6.5 to 11 in the gelatin-containing layer.
Die erfindungsgemäß als Vernetzer verwendeten Verbindungen entsprechen der allgemeinen Formel
- Z = ein n-wertiger aliphatischer, gesättigter oder olefinisch ungesättigter geradkettiger oder verzweigter, gegebenenfalls substituierter, Kohlenwasserstoffrest mit 1 bis 9 Kohlenstoffatomen, der Oxygruppen enthalten kann, ein n-wertiger, gegebenenfalls substituierter 6-gliedriger cycloaliphatischer, aromatischer oder heterocyclischer Rest, wie z. B. ein von Cyclohexan, Benzol, Piperazin oder Hexohydrotriazin abgeleiteter Rest, oder die Gruppe NaS03-O--C=, H
- Y = eine einfache Bindung, eine verzweigte oder unverzweigte Alkylengruppe mit 1 bis 4 Kohlenstoffatomen, die Oxy- oder Carbonyl- und/oder Iminogruppen enthalten kann,
- n = eine ganze Zahl von 2 bis 6,
- Me = im Alkalimetallatom, wie Natrium oder Kalium.
- Z = an n-valent aliphatic, saturated or olefinically unsaturated straight-chain or branched, optionally substituted, hydrocarbon radical with 1 to 9 carbon atoms, which may contain oxy groups, an n-valent, optionally substituted 6-membered cycloaliphatic, aromatic or heterocyclic radical, such as e.g. . B. a radical derived from cyclohexane, benzene, piperazine or hexohydrotriazine, or the group NaS0 3 -O - C =, H
- Y = a single bond, a branched or unbranched alkylene group with 1 to 4 carbon atoms, which may contain oxy or carbonyl and / or imino groups,
- n = an integer from 2 to 6,
- Me = in the alkali metal atom, such as sodium or potassium.
Für die Einstellung des pH-Wertes eignen sich ganz allgemein Salze von flüchtigen anorganischen oder organischen Säuren, insbesondere, z. B. Kohlensäure, Essigsäure, Propionsäure mit nichtflüchtigen Kationen von Erdalkali- Alkalimentallen oder Zinkionen.Salts of volatile inorganic or organic acids are particularly suitable for adjusting the pH, in particular, for. B. carbonic acid, acetic acid, propionic acid with non-volatile cations of alkaline earth metal or zinc ions.
Der pH-Wert kann auch mit Hilfe von Puffergemischen eingestellt werden. Als geeignete Gemische seien genannt primäres Kaliumphosphat/sekundäres Natriumphosphat womit pH-Stufen bis zu 8 erhalten werden können, Salzsäure/Natriumborat dessen Wirkung bis pH 9 reicht, weiter Natriumborat/Natronlauge oder Glykokoll/Natronlauge, wirksam bis pH 11 bzw. 13.The pH can also be adjusted using buffer mixtures. Suitable mixtures are primary potassium phosphate / secondary sodium phosphate with which pH levels up to 8 can be obtained, hydrochloric acid / sodium borate whose effect extends to pH 9, further sodium borate / sodium hydroxide solution or glycol / sodium hydroxide solution, effective up to pH 11 or 13.
Als Beispiele für vernetzende Verbindungen, die für das verfahren der Erfingung geeignet sind, seien genannt :
Das Herstellungsverfahren der vernetzenden Verbindungen wird im folgenden anhand der Herstellung der Verbindungen 1, 4, 18, 15, 17 erläutert. Alle anderen Verbindungen lassen sich dementsprechend herstellen.The production process of the crosslinking compounds is explained below with reference to the preparation of the
10,1 g Tetrakis-hydroxyethylsulfonylmethyl-methan
Die Verbindung wird konzentriert in Eiswasser gelöst und durch Zugabe von wäßriger Natriumbicarbonatlösung stellt man den pH-Wert 5 ein. Die wäßrige Lösung wird im Vakuum zur Trockene eingedampft. Das Produkt wird mit Aceton verrieben und abgesaugt. Ausbeute : 22 g. Die Verbindung enthält nach NMR-Messung keine Vinylsulfongruppen.The compound is concentrated in ice water and the pH is adjusted to 5 by adding aqueous sodium bicarbonate solution. The aqueous solution is evaporated to dryness in vacuo. The product is triturated with acetone and suction filtered. Yield: 22 g. According to NMR measurement, the compound contains no vinyl sulfone groups.
27,6 g der Verbindung
Der Rückstand wird in Eiswasser gelöst und die Mischung mit Natriumbicarbonat Lösung auf pH 5 gestellt. Der unlösliche Anteil wird mit Ether ausgeschüttelt und die wäßrige Lösung mit Bleicherde geklärt. Ausbeute 46 g (als 16 %ige Lösung).The residue is dissolved in ice water and the mixture is adjusted to pH 5 with sodium bicarbonate solution. The insoluble portion is shaken out with ether and the aqueous solution clarified with bleaching earth. Yield 46 g (as a 16% solution).
27,2 g der Verbindung
38,8 g der Verbindung
Die für die Umsetzung notwendigen Hydroxiethylsulfon-Verbindungen können in bekannter Weise, wie in Ullmann Bd. 14, S. 620, in Houben-Weyl, Bd. IX, S. 247, oder in der DT-C-965 902 beschrieben, z. B. über die entsprechenden Halogenalkane durch Umsetzung mit Hydroxialkylmercaptanen und Oxidation der entstandenen Sulfide zu den Hydroxiethylsulfonen mit H202 hergestellt werden.The hydroxyethyl sulfone compounds required for the reaction can be described in a known manner, as described in Ullmann vol. 14, p. 620, in Houben-Weyl, vol. IX, p. 247, or in DT-C-965 902, e.g. B. over the corresponding haloalkanes by reaction with Hydroxialkylmercaptanen and oxidation of the sulfides formed to the Hydroxiethylsulfonen with H 2 0 2 .
Die gemäß der Erfindung verwendeten Vernetzer können der Gießlösung zugesetzt werden entweder einige Zeit vor dem Beguß oder unmittelbar vor dem Beguß durch Dosierungseinrichtungen. Die Verbindungen können auch einer Übergußlösung zugesetzt werden, die nach Herstellung des fertigen photographischen Materials als Härtungsüberguß aufgebracht wird. Der fertiggestellte Schichtaufbau kann auch durch eine Lösung der vernetzer gezogen werden und erhält dadurch die notwendige Menge an Vernetzer zugeführt. Schließlich lassen sich bei Mehrschichtenaufbauten, z. B. bei Colorfilmen und Colorpapier, die Vernetzer der Erfindung über die Zwischenschichten in den Gesamtaufbau einbringen.The crosslinking agents used according to the invention can be added to the casting solution either some time before the coating or immediately before the coating by metering devices. The compounds can also be added to a coating solution which is applied as a curing coating after the finished photographic material has been prepared. The finished layer structure can also be drawn through a solution of the crosslinking agent and thereby receives the necessary amount of crosslinking agent. Finally, with multi-layer structures, e.g. B. in color films and color paper, the crosslinkers of the invention bring about the intermediate layers in the overall structure.
Die Vernetzer werden für das Verfahren der Erfindung im allgemeinen in einer Menge von 0,01 bis 15 Gew.-% und vorzugsweise von 0,1 bis 10 Gew.-%, bezogen auf das Trockengewicht der Gelatine in der Beschichtungslösung, angewandt. Der Zeitpunkt der Zugabe zu der Beschichtungslösung ist nicht kritisch, Silberhalogenidemulsionen wird man dem Härter aber zweckmäßigerweise nach der chemischen Reifung zusetzen.The crosslinkers are generally used in the process of the invention in an amount of 0.01 to 15% by weight and preferably 0.1 to 10% by weight, based on the dry weight of the gelatin in the coating solution. The time of addition to the coating solution is not critical, but silver halide emulsions will expediently be added to the hardener after chemical ripening.
Von den zur Einstellung des pH-Wertes verwendeten Mittel werden jeweils maximal in Bezug auf die Anzahl der Sulfatgruppen des Vernetzers molare Mengen eingesetzt.Of the agents used to adjust the pH, a maximum of molar amounts are used in relation to the number of sulfate groups in the crosslinking agent.
Die an erster Stelle genannten Salze flüchtiger Säuren mit nichtflüchtigen Kationen können zusammen mit dem Vernetzer oder getrennt den Begußmassen oder Schichten einverleibt werden. Die Puffergemische dagegen können nicht mit dem Vernetzer zusammen angewandt werden. Diese werden der den Vernetzer enthaltenden Begußmassen erst kurz vor dem Gießen der Schichten oder während des Gegußes zugesetzt. Auch dann, wenn der Vernetzer mittels eines Überschichtungsbades in einem fertiggestellten Schichtverband eingearbeitet werden soll, ist es zweckmäßig, das Puffergemisch erst dann einzubaden, wenn die Diffusion des Vernetzers in den Schichtverband und seine gleichmäßige Verbindung in den zu härtenden Schichten des Verbandes abgeschlossen ist. Es ist natürlich auch möglich, das Puffergemisch der Begußmasse einzuverleiben und danach den Vernetzer in einer der beschriebenen Weisen in die Begußmasse oder die Schicht einzubringen.The salts of volatile acids with non-volatile cations mentioned in the first place can be incorporated together with the crosslinking agent or separately into the casting compounds or layers. The buffer mixtures, on the other hand, cannot be used together with the crosslinker. These are added to the casting compounds containing the crosslinker only shortly before the layers are poured or during the casting. Even if the crosslinker is to be incorporated into a finished layered structure by means of an overlay bath, it is expedient to bathe the buffer mixture only when the diffusion of the crosslinker into the layered structure and its uniform connection in the layers of the structure to be hardened has been completed. It is of course also possible to incorporate the buffer mixture into the casting compound and then to introduce the crosslinking agent into the casting compound or the layer in one of the ways described.
Die Vernetzungsreaktion wird dann, wenn die Einsteuerung eines pH-Wertes von 6,5 bis 11 nicht in erfindungsgemäßer Weise vorgenommen wird, noch nachträglich in Gang gebracht werden, wenn das den Vernetzer enthaltende photographische Material mit alkalischen Entwicklerbädern in Kontakt kommt. Da aber das photographische Material in diesem Falle von seiner Herstellung an bis zu seiner Verarbeitung in einem bezüglich der Härtung nicht erwünschten labilen Zustand verbleibt, hat dieser Vorgang technisch keine Bedeutung.If the control of a pH value of 6.5 to 11 is not carried out in the manner according to the invention, the crosslinking reaction will still be started after the photographic material containing the crosslinking agent comes into contact with alkaline developer baths. However, since the photographic material in this case remains in an unstable state which is undesirable in terms of hardening from its production to its processing, this process has no technical significance.
Unter photographischen Schichten sollen im vorliegenden Zusammenhang ganz allgemein Schichten verstanden werden, die im Rahmen photographischer Materialien Anwendung finden, beispielsweise lichtempfindliche Silberhalogenidemulsionsschichten, Schutzschichten, Filterschichten, Antihaloschichten, Rückschichten oder ganz allgemein photographische Hilfsschichten.In the present context, photographic layers are to be understood very generally as layers which are used in the context of photographic materials, for example light-sensitive silver halide emulsion layers, protective layers, filter layers, antihalo layers, backing layers or very generally photographic auxiliary layers.
Als lichtempfindliche Emulsionsschichten, für die das erfindungsgemäße Härtungsverfahren vorzüglich geeignet ist, seien beispielsweise solche Schichten genannt, denen nicht sensibilisierte Emulsionen, Röntgenemulsionen und andere spektral sensibiliserte Emulsionen zugrunde liegen. Weiter bewährt sich das Härtungsverfahren der Erfindung zur Härtung der für die verschiedenen photographischen Schwarz-Weiß- und Farbverfahren, wie Negativ-, Positiv- und Diffusionsübertragungsverfahren oder Druckverfahren verwendeten Gelatineschichten. Als besonders vorteilhaft hat sich das erfindungsgemäße Verfahren für die Härtung photographischer Schichtverbände erwiesen, die zur Durchführung farbphotographischer Prozesse bestimmt sind, z. B. solcher, die Emulsionsschichten mit Farbkupplern enthalten oder Emulsionsschichten, die zur Behandlung mit Lösungen bestimmt sind, welche Farbkuppler enthalten.As light-sensitive emulsion layers for which the curing method according to the invention is excellently suitable, there may be mentioned, for example, layers which are based on non-sensitized emulsions, X-ray emulsions and other spectrally sensitized emulsions. Furthermore, the hardening process of the invention has proven itself for hardening the gelatin layers used for the various black and white and color photographic processes, such as negative, positive and diffusion transfer processes or printing processes. The process according to the invention has proven to be particularly advantageous for the hardening of photographic layer dressings which are intended for carrying out color photographic processes, e.g. B. those that contain emulsion layers with color couplers or emulsion layers that are intended for treatment with solutions containing color couplers.
Die Wirkung der in erfindungsgemäßer Weise angewandten Verbindungen wird durch die üblichen photographischen Zusätze nicht beeinträchtigt. Ebenso sind die Härtungsmittel indifferent gegenüber photographisch wirksamen Substanzen, wie wasserlösliche und emulgierte wasserunlösliche Farbkomponenten, Stabilisatoren, Sensibilisatoren und dergleichen. Sie üben ferner keinen nachteiligen Einfluß auf die lichtempfindliche Silberhalogenidemulsion aus.The effect of the compounds used in the manner according to the invention is not impaired by the usual photographic additives. The hardeners are also indifferent to photographically active substances, such as water-soluble and emulsified water-insoluble color components, stabilizers, sensitizers and the like. Furthermore, they have no adverse effect on the light-sensitive silver halide emulsion.
Als lichtempfindliche Bestandteile können die Emulsionsschichten beliebige bekannte Silberhalogenide, wie Silberchlorid, Silberjodid, Silberbromid, Silberjodbromid, Silberchlorbromid, Silberchlorjodbromid und dergleichen, enthalten. Die Emulsionen können durch Edelmetallverbindungen chemisch sensibilisiert werden, z. B. durch Verbindungen von Ruthenium, Rhodium, Palladium, Iridium, Platin, Gold und dergleichen, wie Ammoniumchlorpalladat, Kaliumchloroplatinat, Kaliumchloropalladat, oder Kaliumchloroaurat. Sie können ferner spezielle Sensibilisierungsmittel wie Schwefelverbindungen, Zinn(11) salze, Polyamine oder Polyalkylenoxidverbindungen enthalten. Weiterhin können die Emulsionen mit Cyaninfarbstoffen, Merocyaninfarbstoffen und Mischcyaninfarbstoffen optisch sensibilisiert werden.The emulsion layers can contain any known silver halides as light-sensitive components, such as silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide, silver chlorobiodobromide and the like. The emulsions can be chemically sensitized by precious metal compounds, e.g. B. by compounds of ruthenium, rhodium, palladium, iridium, platinum, gold and the like, such as ammonium chloropalladate, potassium chloroplatinate, potassium chloropalladate, or potassium chloroaurate. They may contain further specific sensitizing agents such as sulfur compounds, Z i n n (11) salts, polyamines or polyalkylene oxide. Furthermore, the emulsions be optically sensitized with cyanine dyes, merocyanine dyes and mixed cyanine dyes.
Die Emulsionen können schließlich die verschiedensten Kuppler, z. B. farblose Kuppler, farbige Kuppler, Stabilisatoren, wie Quecksilberverbindungen, Triazolverbindungen, Azaindenverbindungen, Benzothiazoliumverbindungen oder Zinkverbindungen, Netzmittel, wie Dihydroxyalkane, die Filmbildungseigenschaften verbessernde Mittel, z. B. die bei der Emulsionspolymerisation von Alkylacrylat-oder Alkylmethacrylat/Acrylsäure- oder Methacrylsäure erhaltenen, in Wasser dispergierten, teilchenförmigen Hochpolymeren, Styrol/Maleinsäure-Mischpolymere oder Styrol/Maleinsäureanhydridhalbalkylester-Mischpolymere, Beschichtungshilfsmittel, wie Polyethylenglykollaurylether, sowie die verschiedensten sonstigen photographischen Zusätze, enthalten.Finally, the emulsions can be a wide variety of couplers, e.g. B. colorless couplers, colored couplers, stabilizers such as mercury compounds, triazole compounds, azainden compounds, benzothiazolium compounds or zinc compounds, wetting agents such as dihydroxyalkanes, the film-forming properties improving agents, for. B. obtained in the emulsion polymerization of alkyl acrylate or alkyl methacrylate / acrylic acid or methacrylic acid, dispersed in water, particulate high polymers, styrene / maleic acid copolymers or styrene / maleic anhydride half-alkyl ester copolymers, coating aids such as polyethylene glycol lauryl ether, and various other additives, contain various other photographic additives .
Bemerkenswert ist, daß die Vernetzer der Erfindung, wenn sie in farbphotographischen Materialien angewendet werden, die Kuppler, wie z. B. Purpurkuppler vom 5-Pyrazolontyp, Blaugrünkuppler vom Naphthol- oder Phenol-typ und Gelbkuppler vom geschlossenen Ketomethylen-Typ, sogenannte 2- wertige und 4-wertige Kuppler, die von den obengenannten Kupplern abgeleitet sind, und sogenannte maskierende Kuppler mit einer Arylazogruppe an der aktiven Stelle enthalten, keine Farbveränderungen in den photographischen Materialien auftreten.It is noteworthy that the crosslinkers of the invention, when used in color photographic materials, the couplers, such as. B. purple couplers of the 5-pyrazolone type, cyan couplers of the naphthol or phenol type and yellow couplers of the closed ketomethylene type, so-called 2-valent and 4-valent couplers, which are derived from the above-mentioned couplers, and so-called masking couplers with an arylazo group contain the active site, no color changes occur in the photographic materials.
Die Vernetzer der Erfindung zeichnen sich den bekannten Härtern vom Vinylsulfonyl-Typ gegenüber besonders dadurch aus, daß sie in keinem Falle die Viskosität der Gießlösungen durch vorzeitige Vernetzung in Lösung erhöhen. Dieses nachteilige Verhalten findet man bei bekannten Vinylsulfonat-Härtern, besonders bei Verbindungen mit mehr als 2 reaktiven Vinylsulfonyl-Gruppen. Die Gießlösungen sind nur kurze Zeit haltbar und es ist ein erheblicher technischer Aufwand erforderlich, um die sich daraus ergebenden Schwierigkeiten zu überwinden.The crosslinking agents of the invention are particularly distinguished from the known vinylsulfonyl-type hardeners in that they in no case increase the viscosity of the casting solutions by premature crosslinking in solution. This disadvantageous behavior can be found in known vinyl sulfonate hardeners, especially in compounds with more than 2 reactive vinyl sulfonyl groups. The casting solutions can only be kept for a short time and a considerable technical effort is required to overcome the resulting difficulties.
Es wurde die Zunahme der Viskosität 10 %iger wäßriger Gelatinelösungen in Abhängigkeit von Zeit und pH-Wert unter der Wirkung von zwei nicht erfindungsgemäßen Härtungsmitteln und einer erfindungsgemäßen Verbindung verglichen. Zu 10%igen wäßrigen Gelatinelösungen wurden jeweils 1 Gew.-% Härtungsmittel, bezogen auf Gelatine, gegeben.The increase in the viscosity of 10% aqueous gelatin solutions as a function of time and pH was compared under the action of two curing agents not according to the invention and one compound according to the invention. 1% by weight hardening agent, based on gelatin, was added to 10% aqueous gelatin solutions.
Für den Vergleich wurden folgende Verbindungen verwendet :
- VV1
- C(CH2-SOZ-CH=CH2)4
- VV2
- (CH2=CH―SO2―CH2)3≡C―CH2―SO2CH2―CH2―NH―CH2―CH2―SO3⊖Na⊕
erfindungsgemäße Verbindung 1
- VV1
- C (CH 2 -SO Z -CH = CH 2 ) 4
- VV2
- (CH 2 = CH ― SO 2 ―CH 2 ) 3 ≡C ― CH 2 ―SO 2 CH 2 ―CH 2 ―NH ― CH 2 ―CH 2 ―SO 3 ⊖Na⊕
-
Compound 1 according to the invention
Die Viskositäten bei 40 °C wurden stündlich gemessen. Die Mischungen wurden bei 40 °C längere Zeit (ca. 5 Stunden) digeriert. Das Verhalten der Proben wurde bei den pH-Werten 6, 6,5, 7 und 7,5 untersucht. Die pH-Werte wurden mittels eines Puffergemisches aus primärem Kaliumphosphat und sekundärem Natriumphosphat (6, 6,5) und Natriumcarbonat (7, 7,5) eingestellt.The viscosities at 40 ° C were measured every hour. The mixtures were digested at 40 ° C. for a long time (approx. 5 hours). The behavior of the samples was examined at
Die Ergebnisse sind in Figur 1 dargestellt. Die gestrichelt gezeichneten Kurven 1 bis 4 gelten für die erfindungsgemäße Verbindung 1 und für die pH-Werte 6 (Kurve 1), 6,5 (Kurve 2), 7 (Kurve 3) und 7,5 (Kurve 4). Die ausgezogenen Kurven 5 (pH 6) und 6 (pH 6,5) gelten für die Vergleichsverbindung VV1, die Kurven 7 und 8 für die Vergleichsverbindung VV2. Die Vergleichsverbindung VV1 vernetzt die Gelatine entsprechend Kurve 6 bei einem pH von 6,5 nach 4 Studen. Vergleichsverbindung VV2 bewirkt bei pH 6 eine Vernetzung in ebenfalls etwa 4 Stunden (Kurve 7) und bei pH 6,5 (Kurve 8) schon nach 2 Stunden.The results are shown in Figure 1.
Die Ergebnisse zeigen deutlich, daß bei den nichterfindungsgemäßen Verbindungen innerhalb von wenigen Stunden ein starker Viskositätsanstieg erfolgt, während die erfindungsgemäße Verbindung bei beiden pH-Werten keine Erhöhung der Viskosität zeigt. 10 %ige Gelatine-Gießlösungen können also mit den Vergleichsverbindungen VV1 und VV2 nicht digeriert werden, und man erhält während des Begußes Unregelmäßigkeiten auf der begossenen Unterlage, die auf die Erhöhung der Viskosität zurückzuführen sind.The results clearly show that the viscosity of the compounds not according to the invention increases sharply within a few hours, while the compound according to the invention shows no increase in viscosity at both pH values. 10% gelatin casting solutions cannot therefore be digested with the comparative compounds VV1 and VV2, and irregularities are obtained on the coated base during the pouring, which are due to the increase in viscosity.
Zu 100 ml einer gießförmigen photographischen Silberbromid-Gelatine-Emulsion, die 10Gew.-% Gelatine enthielt, wurden bei pH 6,2 jeweils 1 g und 5 g der erfindungsgemäßen Verbindungen, bezogen auf 100 g Gelatine, in Form einer wäßrigen bicarbonatalkalischen Lösung zugeben (jeweils 1,2 und 5 g Natriumbicarbonat). Die Mischung wurde gut gerührt und mit einer üblichen Gießmaschine auf eine präparierte Cellulosetriacetatunterlage gegossen und getrocknet.1 g and 5 g of the compounds according to the invention, based on 100 g of gelatin, in the form of an aqueous bicarbonate-alkaline solution were added at pH 6.2 to 100 ml of a cast photographic silver bromide gelatin emulsion which contained 10% by weight gelatin. 1.2 and 5 g sodium bicarbonate, respectively). The mixture was stirred well and poured onto a prepared cellulose triacetate base with a conventional casting machine and dried.
Das Material wurde unter verschiedenen Klimabedingungen gelagert und anschließend auf Vernetzung durch Bestimmung des Schichtschmelzpunktes, der Naßkratzfestigkeit und des Quellfaktors geprüft. Eine gute Vernetzung gibt sich durch einen hohen Schichtschmelzpunkt, eine hohe Naßkratzfestigkeit und einen niedrigen Quellfaktor zu erkennen.The material was stored under various climatic conditions and then tested for crosslinking by determining the layer melting point, the wet scratch resistance and the swelling factor. A good cross-linking results from a high layer melting point, a high wet scratch strength and a low swelling factor.
Die Ergebnisse sind in der weiter unter folgenden Tabelle zusammengestellt. Für die einzelnen Bestimmungen wurden die nachstehend beschriebenen Methoden benutzt.The results are summarized in the table below. The methods described below were used for the individual determinations.
Die Vernetzung des photographischen Materials wird mit Hilfe des Schmelzpunktes der Schichten bestimmt, der sich wie folgt ermitteln läßt :
- Der auf eine Unterlage vergossene Schichtverband wird zur Hälfte in Wasser getaucht, das kontinuierlich bis 100 °C erwärmt wird. Die Temperatur, bei der die Schicht von der Unterlage abläuft (Schlierenbildung), wird als Schmelzpunkt bzw. Abschmelzpunkt bezeichnet. Nach diesem Meßverfahren zeigen ungehärtete Proteinschichten in keinem Falle eine Schmelzpunkterhöhung. Der Abschmelzpunkt liegt unter diesen Bedingungen bei 30
bis 35 °C.
- Half of the layered compound cast on a base is immersed in water, which is continuously heated to 100 ° C. The temperature at which the layer runs off the substrate (streak formation) is referred to as the melting point or melting point. According to this measuring method, uncured protein layers never show an increase in melting point. The melting point is 30 to 35 ° C under these conditions.
Zur Bestimmung der Wasseraufnahme wird der Prüfling in einem herkömmlichen FarbentwicklungsprozeB als Schwarzblatt entwickelt und nach dem Schlußbad nach Abstreifen des überschüssigen Wassers gewogen. Dann wird die Probe getrocknet und erneut gewogen. Die Differenz ergibt von der Fläche des Prüflings auf 1 m2 umgerechnet die Wasseraufnahme pro m2.To determine the water absorption, the test specimen is developed as a black sheet in a conventional color development process and weighed after the final bath after the excess water has been stripped off. The sample is then dried and weighed again. The difference from the area of the test object to 1 m 2 converts the water absorption per m 2 .
Die Quellung wird nach 10 Minuten Behandlung eines Probestreifens in destilliertem Wasser bei 22 °C gravimetrisch gemessen. Sie wird durch den Quellfaktor bezeichnet:
Zur Bestimmung der Naßkratzfestigkeit wird eine Metallspitze definierter Größe über die nasse Schicht geführt und mit zunehmendem Gewicht belastet. Die Naßkratzfestigkeit wird durch das Gewicht angegeben, bei dem die Spitze eine sichtbare Kratzspur auf der Schicht hinterläßt ; ein hohes Gewicht entspricht einer hohen Naßkratzfestigkeit.
Aus der Tabelle 1 ist zu ersehen, daß man kochfeste (Schmelzpunkt > 100 °C) Schichten bereits bei Zusatz von 3-5 g Härter pro 100 g Gelatine erhält. Nach Lagerung bei 36 °C und 80 % rel. Luftfeuchtigkeit nimmt die Härtung in gemäßigter Form zu und man erhält keine Überhärtung. Die Gießlösungen können 1 Stunde ohne Viskositätserhöhungen stehen gelassen werden, ein Zeichen für die gewünschte geringe Vernetzung der Gelatine in der Lösung. Die Schichten zeigten gegenüber der ungehärteten Schicht nach der Entwicklung und Fixierung keine gravierenden Unterschiede. Empfindlichkeit, Schleierwerte und die y-Werte veränderten sich nicht. Die Härtungsmittel verhielten sich gegenüber der Halogensilberemulsion auch nach längerer Lagerung der Schichten inert.It can be seen from Table 1 that boil-proof (melting point> 100 ° C.) layers are obtained with the addition of 3-5 g hardener per 100 g gelatin. After storage at 36 ° C and 80% rel. Humidity increases the hardening in a moderate form and no over-hardening is obtained. The casting solutions can be left for 1 hour without increasing the viscosity, a sign of the desired low level of crosslinking of the gelatin in the solution. The layers showed no serious differences compared to the uncured layer after development and fixation. Sensitivity, fog values and the y values did not change. The hardeners remained inert towards the halogen silver emulsion even after the layers had been stored for a long time.
Ein Farbaufsichtsmaterial wurde hergestellt, indem auf eine mit Polyethylen kaschierte und mit einer Haftschicht versehene Papierunterlage nacheinander folgende Schichten aufgetragen wurden, wobei die Emulsionsschichten die üblichen Zusätze an Netzmittel, Stabilisatoren usw. aber kein Härtungsmittel enthielten.
- 1. Als Unterguß eine 4 µm dicke blauempfindliche Silberbromidemulsionsschicht, die
pro kg Emulsion 25,4 g Silber (88 % AgBr, 12 % AgCI), 80 g Gelatine und 34 g der Gelbkomponente
- 2.
als Zwischenschicht eine 1 µm dicke Gelatineschicht, - 3. als Mittelguß eine 4 µm dicke grünempfindliche Silberchloridbromidemulsionsschicht, die pro kg Emulsion 22 g Silber (77 % AgCI, 23 % AgBr), 80 g Gelatine und 13 g der Purpurkomponente
- 4. eine 1 µm dicke
Zwischenschicht wie unter 2. angegeben, - 5. als Oberguß eine 4 µm dicke rotempfindliche Silberchloridbromidemulsionsschicht, die pro kg Emulsion 23 g Silber (80 % AgCl, 20 % AgBr), 80
g Gelatine und 15,6 g der Blaugrünkomponente
- 6. eine 1 µm dicke Schutzschicht aus Gelatine.
- 1. As a base, a 4 µm thick blue-sensitive silver bromide emulsion layer containing 25.4 g of silver (88% AgBr, 12% AgCI), 80 g of gelatin and 34 g of the yellow component per kg of emulsion
- 2. a 1 µm thick gelatin layer as an intermediate layer,
- 3. as a center casting, a 4 μm thick green-sensitive silver chloride bromide emulsion layer containing 22 g of silver (77% AgCl, 23% AgBr), 80 g of gelatin and 13 g of the purple component per kg of emulsion
- 4. a 1 µm thick intermediate layer as indicated under 2.,
- 5. as a upper-4 microns thick red-sensitive Silberchloridbromidemulsionsschicht that per k g of emulsion 23 g of silver (80% AgCl,
AgBr 20%), 80 g of gelatin and 15.6 g of the cyan component - 6. a 1 µm thick protective layer made of gelatin.
Auf das getrocknete Schichtpaket wurden wäßrige Lösungen von 1/200 Mol pro 100 ml der Verbindung 1, die jeweils pro 100 ml Lösung 1/50 Mol Natriumbicarbonat, Natriumformiat, Natriumacetat und Natriumpropionat enthielten, gegossen und der Schichtverband danach getrocknet. Die Schichten wurden auf Vernetzung nach 1,2 und 3 Tagen Lagerung bei 22 °C unter Feuchtigkeitsausschluß und nach Klimalagerung untersucht.Aqueous solutions of 1/200 mol per 100 ml of
Die Ergebnisse zeigt die folgende Tabelle.The results are shown in the following table.
Aus der Tabelle ist ersichtlich, daß der gesamte Schichtverband durch das eindiffundierende Härtungssystem gehärtet wird. Im Gegensatz zur Vergleichsprobe, bei der keine puffernde Substanz zugesetzt wurde, beginnt die Härtung bei Zusatz von Natriumbicarbonat, Natriumformiat, Natriumacetat oder Natriumpropionat eher und erreicht schneller einen bestimmten Härtungsendpunkt. Es zeigt sich, daß die Härtung höher ist, wenn man das Härtungssystem durch Überguß, d. h. nach der Herstellung des Schichtpaketes, einbringt.The table shows that the entire layer structure is hardened by the diffusing hardening system. In contrast to the comparative sample, in which no buffering substance was added, the hardening starts with the addition of sodium bicarbonate, sodium formate, sodium acetate or sodium propionate and reaches a certain hardening end point more quickly. It turns out that the hardening is higher if the hardening system is poured over, i.e. H. after the production of the layer package.
Nach der farbphotographischen Verarbeitung in den üblichen Verarbeitungsbädern wurden Schichten mit vergleichbaren photographischen Werten, wie Empfindlichkeit, Schleier, Gradation erhalten. Das Härtungssystem der Erfindung verhält sich in dieser Anwendungsform gegenüber der Emulsion und den Farbkupplern inert. ,After color photographic processing in the usual processing baths, layers with comparable photographic values such as sensitivity, fog, gradation were obtained. The curing system of the invention is inert to the emulsion and color couplers in this application. ,
Die Härtungswirkung wird auch in gelatinehaltigen photographischen Schwarz- Weiß- Materialien durch Zusatz von puffernden Substanzen beschleunigt. Es wurde jeweils 5 g Verbindung 1 auf 100 g Gelatine eingesetzt. Zu den Gießlösungen wurde jeweils 4 Mol Natriumcarbonat pro Mol Härtungsmittel zugegeben. Als Vergleich diente eine Mischung ohne Zusatz der Puffersubstanz. Die Gießlösungen enthielten 35 g Silberhalogenid. Die Härtungseigenschaften wurden nach Lagerung des Materials unter 4 verschiedenen Klimabedingungen geprüft.
Die Ergebnisse sind in der folgenden Tabelle wiedergegeben.The results are shown in the table below.
Aus der Tabelle ist zu ersehen, daß sich der Schmelzpunkt bei Zusatz von Puffersubstanzen zur Schicht innerhalb weniger Tage auf über 100 °C erhöht. Die so gehärteten photographischen Materialien sind daher schon nach kurzer Lagerzeit für eine Verarbeitung bei 38-50 °C geeignet. Die photographischen Eigenschaften wie Schleier, Empfindlichkeit und Gradation werden nicht verändert.From the table it can be seen that the melting point increases to over 100 ° C. within a few days when buffer substances are added to the layer. The photographic materials hardened in this way are therefore suitable for processing at 38-50 ° C after a short storage period. The photographic properties such as fog, sensitivity and gradation are not changed.
Auf polyethylenkaschierte Papierunterlagen, die mit einer Haftschicht versehen waren, wurden Proben einer photographischen Papieremulsion die 80 g Gelatine und 35 g Halogensilber pro Liter und jeweils 3 Gew.-% eines erfindungsgemäßen Vernetzers enthielten, gegossen. Die üblichen Gießhilfsmittel wie Netzmittel, Stabilisatoren und opt. Sensibilisatoren wurden den Emulsionsproben vorher zugesetzt. Die Schichtschmelzpunkte wurden direkt nach der Trocknung bestimmt.Samples of a photographic paper emulsion which contained 80 g of gelatin and 35 g of halogen silver per liter and each 3% by weight of a crosslinking agent according to the invention were poured onto polyethylene-coated paper substrates which had been provided with an adhesive layer. The usual pouring aids such as wetting agents, stabilizers and opt. Sensitizers were previously added to the emulsion samples. The layer melting points were determined directly after drying.
Nach einer Lagerzeit des photographischen Materials von 24 Stunden wurden die Schichtschmelzpunkte nach Durchlaufen eines 22 °C warmen photographischen Entwicklerbades für Schwarzweiß-Materialien bestimmt.After the photographic material had been stored for 24 hours, the layer melting points were determined after passing through a 22 ° C. photographic developer bath for black and white materials.
Wie aus der folgenden Tabelle ersichtlich, werden die Schmelzpunkte nach einer Entwicklungszeit von 1,5 Minuten von 35 auf weit über 100 °C erhöht, ein Beweis für die spontan ausgelöste Härtung durch den hohen pH-Wert der Entwicklerlösung. Das Beispiel demonstriert die Unsicherheit eines nicht in erfindungsgemäßer Weise geführten Härtungsverfahrens, die durch die Latenz der Wirksamkeit der Vernetzungsmittel bedingt ist.As can be seen from the following table, the melting points are raised after a development time of 1.5 minutes from 35 to well over 100 ° C, proof of the spontaneously triggered hardening due to the high pH of the developer solution. The example demonstrates the uncertainty of a curing process not carried out in accordance with the invention, which is due to the latency of the effectiveness of the crosslinking agents.
Die Entwicklerlösung hatte die folgende Zusammensetzung :
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3000407 | 1980-01-08 | ||
| DE19803000407 DE3000407A1 (en) | 1980-01-08 | 1980-01-08 | METHOD FOR CURING PHOTOGRAPHIC GELATINS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0031959A1 EP0031959A1 (en) | 1981-07-15 |
| EP0031959B1 true EP0031959B1 (en) | 1983-03-30 |
Family
ID=6091644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80108218A Expired EP0031959B1 (en) | 1980-01-08 | 1980-12-27 | Method for hardening photographic gelatin layers |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4338394A (en) |
| EP (1) | EP0031959B1 (en) |
| JP (1) | JPS56104328A (en) |
| CA (1) | CA1155701A (en) |
| DE (2) | DE3000407A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3224983A1 (en) * | 1982-07-03 | 1984-01-05 | Agfa-Gevaert Ag, 5090 Leverkusen | METHOD FOR CURING PHOTOGRAPHIC GELATINS WITH VINYL SULPHONES CONTAINING SULFONYL ETHYL SULFATE GROUPS |
| JPH0612408B2 (en) * | 1986-05-09 | 1994-02-16 | 富士写真フイルム株式会社 | How to harden gelatin |
| DE3708541A1 (en) * | 1987-03-17 | 1988-10-13 | Agfa Gevaert Ag | HARDENER FOR PROTEINS, A HARDENED BINDER LAYER AND A PHOTOGRAPHIC RECORDING MATERIAL CONTAINING SUCH A LAYER |
| US5399480A (en) * | 1993-09-14 | 1995-03-21 | Eastman Kodak Company | Attachment of gelatin-grafted polymer particles to pre-precipitated silver halide grains |
| US5411856A (en) * | 1994-01-10 | 1995-05-02 | Eastman Kodak Company | Carbamyl-substituted bis(vinylsulfonyl) methane hardeners |
| EP4183862A1 (en) | 2021-11-17 | 2023-05-24 | Agfa Nv | Biomaterial for producing hydrogen |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3853940A (en) * | 1962-01-08 | 1974-12-10 | Stevens & Co Inc J P | Inner salts of alkyl alkoxyalkyl hydroxyalkyl sulfonium sulfates |
| US3392023A (en) * | 1964-03-02 | 1968-07-09 | Eastman Kodak Co | Gelatin-silver halide emulsion containing a salt of tris (beta-sulfatoethyl)-sulfonium inner salt |
| US3834902A (en) * | 1972-09-29 | 1974-09-10 | Eastman Kodak Co | Photographic material containing a mesylate compound as hardener and antifoggant |
| JPS532459B2 (en) * | 1974-04-01 | 1978-01-28 | ||
| US4142897A (en) * | 1975-08-09 | 1979-03-06 | Konishiroku Photo Industry Co., Ltd. | Gelatino silver halide photographic material hardened with a reaction product of a vinylsulfonyl compound and a water soluble compound |
| JPS5236007A (en) * | 1975-09-17 | 1977-03-19 | Sony Corp | Reel control device |
-
1980
- 1980-01-08 DE DE19803000407 patent/DE3000407A1/en not_active Withdrawn
- 1980-12-27 DE DE8080108218T patent/DE3062556D1/en not_active Expired
- 1980-12-27 EP EP80108218A patent/EP0031959B1/en not_active Expired
- 1980-12-29 US US06/220,756 patent/US4338394A/en not_active Expired - Fee Related
-
1981
- 1981-01-06 JP JP19781A patent/JPS56104328A/en active Pending
- 1981-01-06 CA CA000367953A patent/CA1155701A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0031959A1 (en) | 1981-07-15 |
| CA1155701A (en) | 1983-10-25 |
| DE3000407A1 (en) | 1981-07-09 |
| DE3062556D1 (en) | 1983-05-05 |
| US4338394A (en) | 1982-07-06 |
| JPS56104328A (en) | 1981-08-20 |
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