EP0618491A1 - Method for generation of negative images having ultrahigh contrast - Google Patents
Method for generation of negative images having ultrahigh contrast Download PDFInfo
- Publication number
- EP0618491A1 EP0618491A1 EP94104901A EP94104901A EP0618491A1 EP 0618491 A1 EP0618491 A1 EP 0618491A1 EP 94104901 A EP94104901 A EP 94104901A EP 94104901 A EP94104901 A EP 94104901A EP 0618491 A1 EP0618491 A1 EP 0618491A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- developer
- group
- compounds
- compound
- onium compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000004010 onium ions Chemical class 0.000 claims abstract description 13
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 3
- -1 silver halide Chemical class 0.000 claims description 30
- 239000000839 emulsion Substances 0.000 claims description 26
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- 229910052709 silver Inorganic materials 0.000 claims description 24
- 239000004332 silver Substances 0.000 claims description 24
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 7
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000001565 benzotriazoles Chemical class 0.000 claims description 3
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical class C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000006294 amino alkylene group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 238000011161 development Methods 0.000 abstract description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 11
- 150000002429 hydrazines Chemical class 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
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- YYTBLBFAVFXULY-UHFFFAOYSA-N 2-[1-[2-(diethylamino)ethyl]-1h-imidazol-1-ium-2-yl]-n,n-diethylethanamine;chloride Chemical compound [Cl-].CCN(CC)CCC=1NC=C[N+]=1CCN(CC)CC YYTBLBFAVFXULY-UHFFFAOYSA-N 0.000 description 4
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- 239000002202 Polyethylene glycol Substances 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
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- 229920001223 polyethylene glycol Polymers 0.000 description 3
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- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 3
- HOWGOXCXIUWXSG-UHFFFAOYSA-N 1-(diethylamino)propane-1,1-diol Chemical compound CCN(CC)C(O)(O)CC HOWGOXCXIUWXSG-UHFFFAOYSA-N 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 2
- HOISBTKPPVRFDS-UHFFFAOYSA-M 1-decyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCCCCCCC[N+]=1C=CN(C)C=1 HOISBTKPPVRFDS-UHFFFAOYSA-M 0.000 description 2
- PNXWPUCNFMVBBK-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+]1=CC=CC=C1 PNXWPUCNFMVBBK-UHFFFAOYSA-M 0.000 description 2
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 2
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- XUEDGYZCOWRRAP-UHFFFAOYSA-N 4-phenyl-3-sulfanyl-2h-tetrazole Chemical compound SN1NN=CN1C1=CC=CC=C1 XUEDGYZCOWRRAP-UHFFFAOYSA-N 0.000 description 2
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- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052741 iridium Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VLLXDIQVPMMHCN-UHFFFAOYSA-N n-(2h-benzotriazol-5-yl)benzamide Chemical compound C1=CC2=NNN=C2C=C1NC(=O)C1=CC=CC=C1 VLLXDIQVPMMHCN-UHFFFAOYSA-N 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 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 class [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical group [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—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
- G03C1/295—Development accelerators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
Definitions
- the invention relates to a method for producing negative images with ultra-partial contrast using photosensitive recording materials with silver halide emulsions and means for carrying out the method
- photosensitive recording materials with silver halide emulsions
- silver halide materials are used, which are developed in special processes for ultra-partial contrast, ie for a maximum gradient of the blackening curve of more than 10.
- the lith process with low-sulfite formaldehyde-containing hydroquinone developers and the development with hydroquinone and a superadditive auxiliary developer in the presence of hydrazine compounds or at a relatively high pH in the presence of development inhibitors such as tetrazole compounds are known.
- EP-00 32 456-B1 claims a process in which a recording material is processed in the presence of a hydrazine compound with a hydroquinone-3-pyrazolidinone developer which contains a contrast-increasing amount of an amino compound.
- EP-04 73 342-A1 describes a photographic silver halide material that can be developed in a developer with a pH ⁇ 11 to ultra-partial contrast.
- the light sensitive coating of this material contains a hydrazine compound of a certain formula as well an amino or a quaternary onium compound and is adjusted to a pH of at least 5.9.
- the known developers generally have a pH above 11. They are therefore not sufficiently stable in practice and have a highly corrosive effect on the components of the development machines.
- the invention has for its object to provide a method for generating negative images with ultra-partial contrast, which can be carried out with a stable, odorless and non-corrosive developer in a short processing time.
- This object is achieved by a method for producing photographic negative images with ultra-partial contrast, a light-sensitive material which has at least one layer with a silver halide emulsion being developed in the presence of an onium compound, and which is characterized in that the molecule of the onium compound is at least one has a quaternary nitrogen atom and at least one tertiary amine function.
- the quaternary nitrogen atom can be incorporated, for example, in a quaternary ammonium or iminium group in acyclic or cyclic structure or in a heterocyclic aromatic group.
- the tertiary amine function is formed by a further nitrogen atom with three substituents, two of which can also form a ring. The third of these substituents bridges the quaternary nitrogen atom.
- Several quaternary nitrogen atoms and tertiary amine functions can also be combined in one molecule.
- the imidazolium, thiazolium or pyridinium groups can be condensed with further aliphatic or aromatic ring systems, for example to form quinolinium, benzimidazolium or benzthiazolium groups. They can also carry further substituents, for example with alkyl groups or with functional groups such as hydroxyl, mercapto, ester and acid amide groups. In the case of N-imidazolium, such a further substituent, preferably alkyl or further substituted alkyl, is necessary on the other nitrogen atom to stabilize the quaternary structure and that positive charge is not located on one of the nitrogen atoms.
- the bridges X, Y and A are preferably represented by chains in which the total number of carbon and possibly the oxygen, nitrogen and sulfur atoms is 2 to 16, wherein in the above-mentioned special case Y can also be a simple bond.
- the alkyl groups of the radicals R1, R2, R3, R4 preferably have 1 to 4 carbon atoms in a straight or branched chain. You can also form pairs in rings, insofar as this is spatially possible, for example R1 with R2 and R3 with R4. If Q+ or Q1+ is represented by quaternary ammonium or iminium, R1 or R3 can also form a ring with a residue on the nitrogen.
- Examples of groups with quaternary ammonium are -N+R5R6R7 (IA) where R5, R6 and R7 are each alkyl, alkenyl or alkynyl having 1 to 10 carbon atoms, R5 is such a group having 1 to 20 carbon atoms or aralkyl and R6 and R7 can also form a ring having 4 to 8 carbon atoms, -N+R8R9-AN+R10R11- (III-A) where R8 and R10 have the same meaning as R5, R9 and R11 have the same meaning as R6 and A have the meaning given for formula (III), R8 with R10 and R9 with R11 can each be linked to form a chain with 2 to 10 carbon atoms be.
- An example of a cyclic cationic group according to formula (III) or (III-A) is double quaternized 1,4-diazabicyclo (2.2.2) octane.
- R12, R13 and R14 have the same meaning as R5, R1 and R2 have the same meaning as in formula (II) and two of these groups can form a ring with 4 to 8 carbon or nitrogen atoms.
- the anions can be represented by inorganic or organic anions usually used in the production of organic salts in the number necessary for charge balancing, for example by chloride, bromide, sulfate, nitrate, perchlorate, acetate, trifluoroacetate, o-toluenesulfonate (o-tosylate).
- onium compounds of the formulas (I), (II) and (III) which are suitable according to the invention are:
- the bridge X or Y links the tertiary amine nitrogen with the quaternary nitrogen of group Q+.
- Such compounds can be produced particularly easily from readily accessible starting substances; for example by reacting the corresponding tertiary amines with ⁇ -haloalkylamines in the presence of alkalis or by reacting glycidyltrimethylammonium chloride with secondary amines, dialkylaminoalkylamines, diamino alcohols or mercaptans.
- Other suitable methods are known to the person skilled in the art (see, for example, Houben-Weyl, Methods of Organic Chemistry, Volume XI / 2, page 591 ff., Stuttgart 1958).
- the compounds according to the invention need not be isolated for use in the production of developers or recording materials if, as in the examples below, there are virtually no side reactions and the presence of the only by-product alkali halide can be tolerated. This makes the method according to the invention particularly simple and economical.
- the residue is taken up in 100 ml of isopropanol, mixed with 9 g (0.1 mol) of imidazole sodium and stirred at 50 ° C. for 6 hours. Now 17.2 g of 2-diethylaminoethyl chloride hydrochloride and a solution of 4 g of sodium hydroxide in 20 ml of water are added and stirring is continued for 3 hours. The reaction mixture is evaporated in vacuo. The oily residue is extracted with 50 ml of tetrahydrofuran and then dissolved in 290 ml of ethanol. After filtering out precipitated salt, a 20 percent is obtained. Solution of the product that is used without further cleaning.
- onium compounds of the general formula (I) those are particularly preferred in which Q Vietnamese is not represented by pyridinium or N'-alkyl-N-imidazolium and X by alkylene in the same molecule.
- the bridges X, Y and / or A consist of polyoxyalkylene chains of 3 to 20 oxyalkylene units each having 2 to 4 carbon atoms.
- the number n of oxyalkylene units is to be understood as the number average.
- Polyoxyethylene chains are particularly preferred.
- Such compounds are particularly suitable for incorporation in emulsion or auxiliary layers, since they are diffusion-inhibited and compatible with anionic coating aids.
- the recording material is preferably developed in the presence of a hydrazine compound.
- this hydrazine compound can either be incorporated into one or more layers of the recording material or added to the developer solution.
- the developer solutions used according to the invention preferably contain a dihydroxybenzene developer substance, for example hydroquinone, pyrocatechol, methylhydroquinone or chlorohydroquinone, and an antioxidant, preferably an alkali sulfite in a concentration of more than 0.3 mol per liter. Solutions with a pH of 9 to a maximum of 11 are particularly preferred. Such developer solutions are also stable in use and produce largely fog-free images.
- a dihydroxybenzene developer substance for example hydroquinone, pyrocatechol, methylhydroquinone or chlorohydroquinone
- an antioxidant preferably an alkali sulfite in a concentration of more than 0.3 mol per liter. Solutions with a pH of 9 to a maximum of 11 are particularly preferred.
- Such developer solutions are also stable in use and produce largely fog-free images.
- the developer solutions preferably contain known super-additive auxiliary developer substances, for example N-methyl-p-aminophenol or 1-phenylpyrazolidinone-3 or derivatives of these compounds.
- stabilizers from the groups of benzotriazoles and mercaptotetrazoles are also preferred.
- stabilizers are 1-phenyl-5-mercaptotetrazole, 1- (1-naphthyl) -5-mercaptotetrazole, 1-cyclohexyl-5-mercaptotetrazole, 1- (4-chlorophenyl) -5-mercaptotetrazole, 1- (3-Capramidophenyl) -5-mercaptotetrazole, benztriazole, 5-chlorobenztriazole, 5-bromobenzotriazole, 5-nitrobenzetriazole, 5-benzoylaminobenzotriazole, 1-hydroxymethylbenztriazole, 6-cyanobenzotriazole.
- the light-sensitive silver halides of the recording materials used according to the invention consist of silver chloride, silver bromide, silver chlorobromide, silver bromoiodide or silver chlorobromoiodide. They can be monodisperse or polydisperse, but have a uniform composition, but also have grains with a core-shell structure, and also mixtures of grains of different composition and grain size distribution. They are made using a hydrophilic colloidal binder, preferably gelatin.
- the silver halide grains can be spherical, polyhedral or tabular in shape. Methods for producing suitable light-sensitive silver halide emulsions are known to the person skilled in the art and are summarized, for example, in Research Disclosure 178 043, chapters I and II.
- Preferred for the recording materials used according to the invention are silver halide emulsions which are produced by controlled double jet entry, have a cubic grain shape and whose chloride content is less than 50 mole percent.
- the grain size of the silver halide grains in the emulsions depends on the required sensitivity and can, for example, correspond to the cubic grains with an edge length of 0.1 to 0.7 ⁇ m. A preferred range is between 0.15 and 0.30 ⁇ m.
- Precious metal salts, especially salts of rhodium or iridium, can be present in the usual amounts in the emulsion preparation in order to improve the photographic properties.
- the emulsions are preferably chemically sensitized. Suitable processes are the sulfur, the reduction and precious metal sensitization, which can also be used in combination. For the latter, for example, gold or iridium compounds can be used.
- the emulsions can be spectrally sensitized with conventional sensitizing dyes.
- the emulsions can also contain conventional antifoggants.
- Substituted benzotriazole, 5-nitroindazole and mercury chloride are preferred. These agents can be added at any time during the preparation of the emulsion or can be contained in an auxiliary layer of the photographic material.
- an iodide can be added to the emulsion in an amount of about 1 mmol per mole of silver before or after chemical ripening.
- the emulsions can also contain known polymer dispersions which, for example, improve the dimensional stability of the photographic material. These are generally latices of hydrophobic polymers in an aqueous matrix. Examples of suitable polymer dispersions are mentioned in Research Disclosure 176 043, Chapter IX B (December 1978).
- the photosensitive layers of the photographic materials can be hardened by a known means.
- This hardening agent can be added to the emulsion or introduced via an auxiliary layer, for example an outer protective layer.
- a preferred curing agent is hydroxydichlorotriazine.
- the photographic material can contain other additives which are known and customary for the production of certain properties. Such agents are listed, for example, in Research Disclosure 176 043 in chapters V (brightener), XI (coating aids), XII (plasticizers and lubricants) and XVI (matting agents).
- the gelatin content of the emulsions is generally between 50 and 200 g per mole of silver; the range between 70 and 150 g per mole of silver is preferred.
- the method according to the invention also leads to ultra-gradation if the onium compounds are only contained in the recording material.
- the contrast-increasing amino compounds according to the prior art in particular the alkanolamines, must be added to the developer.
- the required concentration of the compounds used according to the invention is considerably lower than the practically usual concentrations of the alkanolamines according to the prior art.
- the compounds are also non-volatile and readily water-soluble. This has favorable consequences for the economic efficiency as well as for the health protection of the employees and for the disposal.
- the invention can be used to produce negative images with ultra-partial contrast, in particular in the reproduction in the prepress for black and white and multi-color printing.
- Samples of the recording material thus obtained were exposed through a wedge template with a continuous density profile and through a combination of such a wedge with a contact grid.
- the processing was carried out in a roll developing machine with the developers described below at 36 ° C and 28 s development time as well as with a commercially available fixing bath.
- the developers had the following composition: water 500 g, Sodium bisulfite 42 g, Ethylenediaminetetraacetic acid, trisodium salt 3.7 g, Hydroquinone 25 g, N-methyl-p-aminophenol hemisulfate 2.75 g, Potassium bromide 1 g, Benzotriazole 0.5 g, 1-phenyl-2-mercaptotetrazole 0.04 g, Mercaptobenzthiazole 0.04 g, Potassium hydroxide (50 percent solution) 47 ml, Potassium carbonate (50% solution) 28.5 ml, Additives according to table 1 in g, Water to 1000 ml, pH adjusted to 10.9 at 25 ° C.
- the emulsion was applied together with a protective gelatin layer to a polyethylene terephthalate support.
- the application weights of these layers per m2 corresponded to 3.5 g of silver or 0.8 g of gelatin.
- the gelatin protective layer still contained 0.4 g per m2 of a dispersion of a styrene-acrylate copolymer, 2,4-dichloro-6-hydroxytriazine as hardening agent and the additives listed in Table 3 below (in g / m2).
- Table 4 show that the contrast is increased even when processing in the absence of hydrazine compounds by using the compound II-1 according to the invention.
- Table 4 attempt Movie Developer after Dmin Dmax S G1 G2 30th H Trial 10 0.04 5.2 1.00 1.7 5.1 31 H Trial 17 0.04 5.5 1.15 1.7 6.3 32 P Trial 10 0.05 6.4 1.00 1.9 12.5 33 P Trial 17 0.05 6.3 1.20 2.5 13.9
- a cubic silver chlorobromide emulsion (80 mole percent chloride) was prepared by pAg-controlled two-jet inlet.
- the edge length of the grains was 0.21 ⁇ m.
- the emulsion was adjusted to a total gelatin content of 55 g per mol of silver and chemically ripened with thiosulfate and gold salt in the presence of potassium toluene thiosulfonate.
- Example 1 Samples of the recording materials thus obtained were exposed and developed as described in Example 1.
- the developer had the following composition: water 500 g Sodium bisulfite 50 g Potassium hydroxide 27 g Ethylenediaminetetraacetic acid, trisodium salt 3.7 g Hydroquinone 25 g Potassium bromide 4 g Benzotriazole 0.3 g Phenyl mercaptotetrazole 0.05 g 4-hydroxymethyl-4-methyl-1-phenylpyrazolidone 1 g Boric acid 3 g Sodium hydroxide 24 g Diethylene glycol 40 g water to 1 l, pH adjusted to 10.5 at 25 ° C.
- Table 5 show that the gradation by the substances according to the invention is increased unexpectedly even at a relatively high gradation of the gold-ripened chloride-rich starting emulsion and in the absence of known contrast-increasing amino compounds at low pH. They work against this known development accelerators only moderately on gradation and sensitivity.
- Table 5 attempt Compound / amount (mg / m2) Dmin Dmax S G 34 ---- 0.04 6.0 1.00 9.2 35 V1 / 40 0.04 6.0 1.09 13 36 V2 / 40 0.04 6.2 1.05 12th 37 II-10/20 0.04 6.0 1.19 > 25 38 I-25/40 0.04 6.2 1.13 > 25 39 I-5/40 0.04 6.0 1.11 > 25
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- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Erzeugung von Negativbildern mit ultrasteilem Kontrast unter Verwendung von lichtempfindlichen Aufzeichnungsmaterialien mit Silberhalogenidemulsionen sowie Mittel zur Durchführung des Verfahrens
Bei der photomechanischen Reproduktion müssen häufig Halbtonbilder in Rasterpunktbilder umgewandelt werden. Hierzu verwendet man Silberhalogenidmaterialien, die man in besonderen Verfahren zu ultrasteilem Kontrast, d. h. zu einer maximalen Steigung der Schwärzungskurve von mehr als 10, entwickelt. Bekannt sind beispielsweise das Lithverfahren mit sulfitarmen, formaldehydhaltigen Hydrochinonentwicklern sowie die Entwicklung mit Hydrochinon und einem superadditiv wirkenden Hilfsentwickler in Gegenwart von Hydrazinverbindungen oder bei relativ hohem pH in Gegenwart von Entwicklungshemmern wie Tetrazolverbindungen.The invention relates to a method for producing negative images with ultra-partial contrast using photosensitive recording materials with silver halide emulsions and means for carrying out the method
In photomechanical reproduction, halftone images often have to be converted into halftone dot images. For this purpose, silver halide materials are used, which are developed in special processes for ultra-partial contrast, ie for a maximum gradient of the blackening curve of more than 10. For example, the lith process with low-sulfite formaldehyde-containing hydroquinone developers and the development with hydroquinone and a superadditive auxiliary developer in the presence of hydrazine compounds or at a relatively high pH in the presence of development inhibitors such as tetrazole compounds are known.
Bei diesen Verfahren werden häufig gewisse Aminoverbindungen zur weiteren Steigerung des Kontrastes angewendet. So wird in der EP-00 32 456-B1 ein Verfahren beansprucht, bei dem man ein Aufzeichnungsmaterial in Gegenwart einer Hydrazinverbindung mit einem Hydrochinon-3-Pyrazolidinon-Entwickler verarbeitet, der eine kontraststeigernde Menge einer Aminoverbindung enthält.In these processes, certain amino compounds are often used to further increase the contrast. For example, EP-00 32 456-B1 claims a process in which a recording material is processed in the presence of a hydrazine compound with a hydroquinone-3-pyrazolidinone developer which contains a contrast-increasing amount of an amino compound.
In der EP-04 73 342-A1 ist ein photographisches Silberhalogenidmaterial beschrieben, das in einem Entwickler mit einem pH < 11 zu ultrasteilem Kontrast entwickelt werden kann. Die lichtempfindliche Beschichtung dieses Material enthält eine Hydrazinverbindung einer bestimmten Formel sowie eine Amino- oder eine quaternäre Oniumverbindung und ist auf einen pH von mindestens 5,9 eingestellt.EP-04 73 342-A1 describes a photographic silver halide material that can be developed in a developer with a pH <11 to ultra-partial contrast. The light sensitive coating of this material contains a hydrazine compound of a certain formula as well an amino or a quaternary onium compound and is adjusted to a pH of at least 5.9.
Kationische Netzmittel und Farbstoffe mit quaternären Ammoniumgruppen sind seit langem als Entwicklungsbeschleuniger bekannt (L. F. A. Mason, Photographic Processing Chemistry, London and New York, 1966, Seite 41 f.). Die US 41 35 931 beschreibt die Verwendung bestimmter Pyridiniumverbindungen zur Beschleunigung der Lithentwicklung. Bei diesen bekannten Anwendungen tritt aber keine Steigerung des Kontrasts auf.Cationic wetting agents and dyes with quaternary ammonium groups have long been known as development accelerators (L.F.A. Mason, Photographic Processing Chemistry, London and New York, 1966, page 41 f.). US 41 35 931 describes the use of certain pyridinium compounds to accelerate lith development. However, there is no increase in contrast in these known applications.
Entwickler, die eine kontraststeigernde Menge einer Aminoverbindung enthalten, sind nicht frei von Nachteilen. Die erforderliche Konzentration der Aminoverbindung ist beträchtlich und liegt häufig in der Nähe der Löslichkeitsgrenze. Infolge der Temperaturerhöhung oder von geringen Konzentrationsänderungen durch Wasserverdunstung während des Gebrauchs kann die Löslichkeitsgrenze leicht überschritten werden und die Aminoverbindung scheidet sich aus. Dies kann zu ungleichmäßiger Entwicklung und zur Verunreinigung der Aufzeichnungsmaterialien und der Entwicklungsmaschine führen. Wegen ihrer Wasserdampfflüchtigkeit können die ausgeschiedenen Aminoverbindungen auch an entfernte Stellen der Entwicklungsmaschine gelangen und unerwünschte Verunreinigungen sowie Korrosion hervorrufen.Developers containing a contrast-increasing amount of an amino compound are not free from disadvantages. The required concentration of the amino compound is considerable and is often close to the solubility limit. As a result of the temperature increase or slight changes in concentration due to water evaporation during use, the solubility limit can easily be exceeded and the amino compound is eliminated. This can lead to uneven development and contamination of the recording materials and the developing machine. Because of their volatility in water vapor, the amino compounds which have been eliminated can also reach remote locations on the developing machine and cause undesirable impurities and corrosion.
Bei der Verwendung von Entwicklern, welche bekannte Aminoverbindungen enthalten, tritt ein auch sehr unangenehmer Geruch auf, der auf die hohe erforderliche Konzentration und die Flüchtigkeit dieser Verbindungen zurückzuführen ist.When using developers containing known amino compounds, there is also a very unpleasant smell which is due to the high concentration required and the volatility of these compounds.
Da die Aminoverbindungen nur begrenzt löslich sind ist es schwierig, die als wirtschaftliche Handelsform üblichen Entwicklerkonzentrate zu formulieren. Nach der EP-A-02 03 521 können zwar Salze gewisser Sulfo- oder Carbonsäuren als Lösungsvermittler eingesetzt werden. Die übrigen angesprochenen Probleme werden jedoch durch solche Zusätze nicht beeinflußt.Since the amino compounds are only soluble to a limited extent, it is difficult to formulate the developer concentrates which are customary as an economical commercial form. According to EP-A-02 03 521, salts of certain sulfonic or carboxylic acids can be used as solubilizers. However, the other problems raised are not affected by such additives.
Die bekannten Entwickler haben in der Regel einen pH über 11. Daher sind sie für die Praxis nicht hinreichend stabil und wirken stark korrosiv auf die Bauteile der Entwicklungsmaschinen.The known developers generally have a pH above 11. They are therefore not sufficiently stable in practice and have a highly corrosive effect on the components of the development machines.
Die Erfindung stellt sich die Aufgabe, ein Verfahren zum Erzeugen von Negativbildern mit ultrasteilem Kontrast anzugeben, welches bei kurzer Verarbeitungszeit mit einem stabilen, geruchfreien und nicht korrosiven Entwickler durchgeführt werden kann.The invention has for its object to provide a method for generating negative images with ultra-partial contrast, which can be carried out with a stable, odorless and non-corrosive developer in a short processing time.
Diese Aufgabe wird gelöst durch ein Verfahren zum Erzeugen von photographischen Negativbildern mit ultrasteilem Kontrast, wobei ein lichtempfindliches Aufzeichnungsmaterial, das mindestens eine Schicht mit einer Silberhalogenidemulsion aufweist, in Gegenwart einer Oniumverbindung entwickelt wird, und das dadurch gekennzeichnet ist, daß das Molekül der Oniumverbindung mindestens ein quaternäres Stickstoffatom und mindestens eine tertiäre Aminfunktion aufweist.This object is achieved by a method for producing photographic negative images with ultra-partial contrast, a light-sensitive material which has at least one layer with a silver halide emulsion being developed in the presence of an onium compound, and which is characterized in that the molecule of the onium compound is at least one has a quaternary nitrogen atom and at least one tertiary amine function.
Das quaternäre Stickstoffatom kann dabei zum Beispiel in eine quaternäre Ammonium- oder Iminiumgruppe in acyclischer oder cyclischer Struktur oder in eine heterocyclische aromatische Gruppe eingebunden sein. Die tertiäre Aminfunktion wird durch ein weiteres Stickstoffatom mit drei Substituenten gebildet, von denen auch zwei einen Ring bilden können. Der dritte dieser Substituenten bildet eine Brücke zum quaternären Stickstoffatom. Es können auch jeweils mehrere quaternäre Stickstoffatome und tertiäre Aminfunktionen in einem Molekül vereinigt sein.The quaternary nitrogen atom can be incorporated, for example, in a quaternary ammonium or iminium group in acyclic or cyclic structure or in a heterocyclic aromatic group. The tertiary amine function is formed by a further nitrogen atom with three substituents, two of which can also form a ring. The third of these substituents bridges the quaternary nitrogen atom. Several quaternary nitrogen atoms and tertiary amine functions can also be combined in one molecule.
Insbesondere können die erfindungsgemäßen Oniumverbindungen aus einem Kation der allgemeinen Formeln (I), (II) oder (III)
Q⁺ - X - NR₁R₂ (I)
R₁R₂N - X - Q⁺ - Y - NR₃R₄ (II)
R₁R₂N - X - Q⁺ - A - Q₁⁺ - Y - NR₃R₄ (III)
und den zum Ladungsausgleich notwendigen Anionen bestehen. In diesen Formeln bedeuten
- Q⁺, Q₁⁺
- je eine unter Einschluß von X und ggf. Y und A gebildete quaternäre Ammonium- oder Iminiumgruppe oder eine ggf. weiter substituierte N-Imidazolium-, N-Thiazolium- oder N-Pyridiniumgruppe, gleich oder verschieden,
- X, Y, A
- je eine Alkylen-, Hydroxyalkylen-, Alkylenoxyalkylen-, Alkylenthioalkylen-, Alkylenaminoalkylen- oder Hydroxyalkylenoxyalkylengruppe oder eine Polyoxyalkylenkette, gleich oder verschieden, Y auch eine einfache Bindung oder eine Oxyalkylen-, Thioalkylen-, oder Aminoalkylengruppe, falls diese an ein Kohlenstoffatom einer Imidazolium-, Thiazolium- oder Pyridiniumgruppe bindet,
- R₁, R₂, R₃, R₄
- je eine Alkyl-, Alkoxy-, Alkylaryl- oder Phenylgruppe, ggf. substituiert, gleich oder verschieden, wobei jeweils R₁ und R₂ sowie R₃ und R₄ auch einen Ring bilden können.
Q⁺ - X - NR₁R₂ (I)
R₁R₂N - X - Q⁺ - Y - NR₃R₄ (II)
R₁R₂N - X - Q⁺ - A - Q₁⁺ - Y - NR₃R₄ (III)
and the anions necessary to balance the charge. Mean in these formulas
- Q⁺, Q₁⁺
- a quaternary ammonium or iminium group formed with inclusion of X and optionally Y and A or an optionally further substituted N-imidazolium, N-thiazolium or N-pyridinium group, identical or different,
- X, Y, A
- each an alkylene, hydroxyalkylene, alkyleneoxyalkylene, alkylene thioalkylene, alkylene aminoalkylene or hydroxyalkyleneoxyalkylene group or a polyoxyalkylene chain, the same or different, Y also a simple bond or an oxyalkylene, thioalkylene or aminoalkylene group, if this is attached to a carbon atom of an imidazolium , Thiazolium or pyridinium group binds,
- R₁, R₂, R₃, R₄
- each an alkyl, alkoxy, alkylaryl or phenyl group, optionally substituted, the same or different, where each R₁ and R₂ and R₃ and R₄ can also form a ring.
Die Imidazolium-, Thiazolium- oder Pyridiniumgruppen können mit weiteren aliphatischen oder aromatischen Ringsystemen kondensiert sein, beispielsweise zu Chinolinium-, Benzimidazolium- oder Benzthiazoliumgruppen. Sie können auch weitere Substituenten tragen, beispielsweise mit Alkylgruppen oder mit funktionellen Gruppen wie Hydroxyl-, Mercapto-, Ester- und Säureamidgruppen. Im Fall des N-Imidazoliums ist ein solcher weiterer Substituent, vorzugsweise Alkyl oder weiter substituiertes Alkyl, am anderen Stickstoffatom zur Stabilisierung der quaternären Struktur notwendig und die positive Ladung ist nicht an einem der Stickstoffatome lokalisiert.The imidazolium, thiazolium or pyridinium groups can be condensed with further aliphatic or aromatic ring systems, for example to form quinolinium, benzimidazolium or benzthiazolium groups. They can also carry further substituents, for example with alkyl groups or with functional groups such as hydroxyl, mercapto, ester and acid amide groups. In the case of N-imidazolium, such a further substituent, preferably alkyl or further substituted alkyl, is necessary on the other nitrogen atom to stabilize the quaternary structure and that positive charge is not located on one of the nitrogen atoms.
Die Brücken X, Y und A werden bevorzugt durch Ketten dargestellt, in denen die Gesamtzahl der Kohlenstoff- und ggf. der Sauerstoff-, Stickstoff- und Schwefelatome 2 bis 16 beträgt, wobei im oben genannten besonderen Fall Y auch eine einfache Bindung sein kann.The bridges X, Y and A are preferably represented by chains in which the total number of carbon and possibly the oxygen, nitrogen and sulfur atoms is 2 to 16, wherein in the above-mentioned special case Y can also be a simple bond.
Die Alkylgruppen der Reste R₁, R₂, R₃, R₄ weisen bevorzugt 1 bis 4 Kohlenstoffatome in gerader oder verzweigter Kette auf. Sie können auch paarweise Ringe bilden, soweit dies räumlich möglich ist, also beispielsweise R₁ mit R₂ und R₃ mit R₄. Wenn Q⁺ bzw. Q₁⁺ durch quaternäres Ammonium oder Iminium dargestellt wird, können R₁ oder R₃ auch mit einem Rest am Stickstoff einen Ring bilden.The alkyl groups of the radicals R₁, R₂, R₃, R₄ preferably have 1 to 4 carbon atoms in a straight or branched chain. You can also form pairs in rings, insofar as this is spatially possible, for example R₁ with R₂ and R₃ with R₄. If Q⁺ or Q₁⁺ is represented by quaternary ammonium or iminium, R₁ or R₃ can also form a ring with a residue on the nitrogen.
Beispiele für Gruppen mit quaternärem Ammonium sind
-N⁺R₅R₆R₇ (I-A)
wobei R₅, R₆ und R₇ jeweils Alkyl, Alkenyl oder Alkinyl mit 1 bis 10 Kohlenstoffatomen, R₅ eine solche Gruppe mit 1 bis 20 Kohlenstoffatomen oder Aralkyl bedeuten und R₆ und R₇ auch einen Ring mit 4 bis 8 Kohlenstoffatomen bilden können,
-N⁺R₈R₉-A-N⁺R₁₀R₁₁- (III-A)
wobei R₈ und R₁₀ die gleiche Bedeutung wie R₅, R₉ und R₁₁ die gleiche Bedeutung wie R₆ und A die für Formel (III) genannte Bedeutung haben, dabei können auch R₈ mit R₁₀ sowie R₉ mit R₁₁ jeweils zu einer Kette mit 2 bis 10 Kohlenstoffatomen verbunden sein. Ein Beispiel für eine cyclisch aufgebaute kationische Gruppe nach Formel (III) bzw. (III-A) ist zweifach quaterniertes 1,4-Diazabicyclo(2.2.2)-octan.Examples of groups with quaternary ammonium are
-N⁺R₅R₆R₇ (IA)
where R₅, R₆ and R₇ are each alkyl, alkenyl or alkynyl having 1 to 10 carbon atoms, R₅ is such a group having 1 to 20 carbon atoms or aralkyl and R₆ and R₇ can also form a ring having 4 to 8 carbon atoms,
-N⁺R₈R₉-AN⁺R₁₀R₁₁- (III-A)
where R₈ and R₁₀ have the same meaning as R₅, R₉ and R₁₁ have the same meaning as R₆ and A have the meaning given for formula (III), R₈ with R₁₀ and R₉ with R₁₁ can each be linked to form a chain with 2 to 10 carbon atoms be. An example of a cyclic cationic group according to formula (III) or (III-A) is double quaternized 1,4-diazabicyclo (2.2.2) octane.
Eine quaternäre Iminiumgruppe kann beispielsweise in der Form
-N⁺R₁₂=CR₁₃-R₁₄ (I-B)
oder
-N⁺R₁₂=CR₁₃-NR₁R₂ (II-B)
vorliegen. Dabei haben R₁₂, R₁₃ und R₁₄ die gleiche Bedeutung wie R₅, R₁ und R₂ die gleiche Bedeutung wie in Formel (II) und je zwei dieser Gruppen können einen Ring mit 4 bis 8 Kohlenstoff- bzw. Stickstoffatomen bilden.For example, a quaternary iminium group can be in the form
-N⁺R₁₂ = CR₁₃-R₁₄ (IB)
or
-N⁺R₁₂ = CR₁₃-NR₁R₂ (II-B)
available. R₁₂, R₁₃ and R₁₄ have the same meaning as R₅, R₁ and R₂ have the same meaning as in formula (II) and two of these groups can form a ring with 4 to 8 carbon or nitrogen atoms.
Die Anionen können durch bei der Herstellung organischer Salze üblicherweise verwendete anorganische oder organische Anionen in der zum Ladungsausgleich notwendigen Anzahl dargestellt werden, beispielsweise durch Chlorid, Bromid, Sulfat, Nitrat, Perchlorat, Acetat, Trifluoracetat, o-Toluolsulfonat (o-Tosylat).The anions can be represented by inorganic or organic anions usually used in the production of organic salts in the number necessary for charge balancing, for example by chloride, bromide, sulfate, nitrate, perchlorate, acetate, trifluoroacetate, o-toluenesulfonate (o-tosylate).
Beispiele für erfindungsgemäß geeignete Oniumverbindungen nach den Formeln (I), (II) und (III) sind:
Die Brücke X bzw. Y verknüpft den tertiären Aminstickstoff mit dem quaternären Stickstoff der Gruppe Q⁺. Solche Verbindungen lassen sich besonders einfach aus leicht zugänglichen Ausgangssubstanzen herstellen; beispielsweise durch Umsetzung der entsprechenden tertiären Amine mit ω-Halogenalkylaminen in Gegenwart von Alkalien oder durch Umsetzung von Glycidyltrimethylammoniumchlorid mit sekundären Aminen, Dialkylaminoalkylaminen, Diaminoalkoholen oder -mercaptanen. Weitere geeignete Methoden sind dem Fachmann bekannt (siehe z. B. Houben-Weyl, Methoden der organischen Chemie, Band XI/2, Seite 591 ff., Stuttgart 1958).Examples of onium compounds of the formulas (I), (II) and (III) which are suitable according to the invention are:
The bridge X or Y links the tertiary amine nitrogen with the quaternary nitrogen of group Q⁺. Such compounds can be produced particularly easily from readily accessible starting substances; for example by reacting the corresponding tertiary amines with ω-haloalkylamines in the presence of alkalis or by reacting glycidyltrimethylammonium chloride with secondary amines, dialkylaminoalkylamines, diamino alcohols or mercaptans. Other suitable methods are known to the person skilled in the art (see, for example, Houben-Weyl, Methods of Organic Chemistry, Volume XI / 2, page 591 ff., Stuttgart 1958).
Die erfindungsgemäßen Verbindungen brauchen für die Verwendung bei der Herstellung von Entwicklern oder Aufzeichnungsmaterialien nicht isoliert zu werden, wenn, wie in den folgenden Beispielen, so gut wie keine Nebenreaktionen auftreten und die Anwesenheit des einzigen Nebenprodukts Alkalihalogenid toleriert werden kann. Dadurch wird das erfindungsgemäße Verfahren besonders einfach und wirtschaftlich.The compounds according to the invention need not be isolated for use in the production of developers or recording materials if, as in the examples below, there are virtually no side reactions and the presence of the only by-product alkali halide can be tolerated. This makes the method according to the invention particularly simple and economical.
In einem 100 ml-Erlenmeyerkolben werden 17,2 g (0,1 mol) 2-Chlorethyl-diethylaminhydrochlorid, 3,4 g (0,05 mol) Imidazol und 30 ml Wasser vorgelegt. Bei Raumtemperatur werden unter Rühren 6 g (0,15 mol) Natriumhydroxid Zugesetzt. Unter spontaner Erwärmung bildet sich eine zweite Phase. Nach weiterem Rühren über 2 Stunden ist eine homogene farblose Lösung entstanden, die mit Wasser auf 75,6 g aufgefüllt wird. Man erhält so eine zwanzigprozentige Lösung der Verbindung II-1.17.2 g (0.1 mol) of 2-chloroethyl-diethylamine hydrochloride, 3.4 g (0.05 mol) of imidazole and 30 ml of water are placed in a 100 ml Erlenmeyer flask. At room temperature, 6 g (0.15 mol) of sodium hydroxide are added with stirring. A spontaneous warming forms a second phase. After further stirring for 2 hours, a homogeneous colorless solution is formed, which is made up to 75.6 g with water. A 20 percent solution of compound II-1 is thus obtained.
55 g (0,1 mol) Polyethylenglykol(550)monomethylether werden in 250 ml Tetrahydrofuran gelöst und mit 11,2 g (0,11 mol) Triethylamin versetzt. In die mit Eis gekühlte Mischung werden unter Stickstoff 12,6 g (0,11 mol) Methansulfonylchlorid tropfenweise eingerührt. Hierbei bildet sich das Methansulfonat des Polyethylenglykolmethylethers. Bei Zimmertemperatur wird 24 Stunden weitergerührt und danach 2 Stunden am Rückfluß gekocht. Nach dem Abkühlen wird das ausgefallene Triethylammoniumchlorid abfiltriert und das Lösungsmittel nebst dem überschüssigen bin im Vakuum auf dem Wasserbad verdampft. Der Rückstand wird mit 100 ml Isopropanol aufgenommen, mit 9 g (0,1 mol) Imidazol-Natrium versetzt und bei 50 °C 6 Stunden gerührt. Nun werden 17,2 g 2-Diethylaminoethylchloridhydrochlorid und eine Lösung von 4 g Natriumhydroxid in 20 ml Wasser Zugegeben und 3 Stunden weitergerührt. Die Reaktionsmischung wird im Vakuum eingedampft. Der ölige Rückstand wird mit 50 ml Tetrahydrofuran extrahiert und danach in 290 ml Ethanol gelöst. Nach Abfiltrieren von ausgefallenem Salz erhält man eine 20proz. Lösung des Produkts, die ohne weitere Reinigung verwendet wird.55 g (0.1 mol) of polyethylene glycol (550) monomethyl ether are dissolved in 250 ml of tetrahydrofuran and mixed with 11.2 g (0.11 mol) of triethylamine. 12.6 g (0.11 mol) of methanesulfonyl chloride are stirred dropwise into the mixture, which is cooled with ice, under nitrogen. This forms the methanesulfonate of the polyethylene glycol methyl ether. At room temperature, stirring is continued for 24 hours and then refluxed for 2 hours. After cooling, the precipitated triethylammonium chloride is filtered off and the solvent, together with the excess, is evaporated in vacuo on a water bath. The residue is taken up in 100 ml of isopropanol, mixed with 9 g (0.1 mol) of imidazole sodium and stirred at 50 ° C. for 6 hours. Now 17.2 g of 2-diethylaminoethyl chloride hydrochloride and a solution of 4 g of sodium hydroxide in 20 ml of water are added and stirring is continued for 3 hours. The reaction mixture is evaporated in vacuo. The oily residue is extracted with 50 ml of tetrahydrofuran and then dissolved in 290 ml of ethanol. After filtering out precipitated salt, a 20 percent is obtained. Solution of the product that is used without further cleaning.
Die Synthese von erfindungsgemäßen Verbindungen mit Polyoxyalkylenketten, bei denen Q+ eine quaternäre Ammoniumgruppe oder eine Pyridiniumgruppe ist, kann beispielsweise durch Umsetzung des entsprechenden mono- oder bifunktionellen Polyoxyalkylenmethansulfonats mit einer tertiären Amino- oder einer Pyridinverbindung erfolgen.Compounds according to the invention with polyoxyalkylene chains in which Q + is a quaternary ammonium group or a pyridinium group can be synthesized, for example, by reacting the corresponding mono- or bifunctional polyoxyalkylene methanesulfonate with a tertiary amino or a pyridine compound.
Von den Oniumverbindungen der allgemeinen Formel (I) werden besonders bevorzugt solche, bei denen nicht im gleichen Molekül Q⁺ durch Pyridinium oder N'-Alkyl-N-imidazolium und X durch Alkylen dargestellt werden.Of the onium compounds of the general formula (I), those are particularly preferred in which Q nicht is not represented by pyridinium or N'-alkyl-N-imidazolium and X by alkylene in the same molecule.
Besonders bevorzugt werden Verbindungen der Formel (I), (II) und (III) verwendet, bei denen die Gruppen X, Y und/oder A durch Alkylenoxyalkylen oder durch Hydroxyalkylen mit insgesamt 2 bis 12 Kohlenstoff- und Sauerstoffatomen in der Kette realisiert ist. Der Einbau solcher Gruppen in das Molekül bietet - neben der Auswahl der Gruppe Q und der Substituenten R₁, R₂, R₃, R₄ - eine zusätzliche Möglichkeit, je nach den übrigen gewünschten Verfahrensparametern, beispielsweise Konzentration und pH der Entwicklerlösung, Art der Entwicklersubstanz und der Hydrazinverbindung, Entwicklungstemperatur und -zeit, durch geeignete Festlegung der Anzahl der Hydroxyl- bzw. Ethersauerstoffatome eine Verbindung mit optimaler Balance Zwischen hoher Löslichkeit und hoher kontraststeigernder Wirksamkeit auszuwählen. Hierzu kann der Fachmann bekannte Lehren aus dem Gebiet der oberflächenaktiven Substanzen heranziehen.Compounds of the formulas (I), (II) and (III) in which the groups X, Y and / or A are realized by alkyleneoxyalkylene or by hydroxyalkylene having a total of 2 to 12 carbon and oxygen atoms in the chain are particularly preferably used. The incorporation of such groups in the molecule offers - in addition to the selection of the group Q and the substituents R₁, R₂, R₃, R₄ - an additional possibility, depending on the other desired process parameters, for example concentration and pH of the developer solution, type of developer substance and the hydrazine compound , Development temperature and time, by appropriately determining the number of hydroxyl or ether oxygen atoms to select a compound with an optimal balance between high solubility and high contrast-increasing effectiveness. For this purpose, those skilled in the art can use lessons learned from the field of surface-active substances.
Bei einer anderen bevorzugten Ausführungsform bestehen die Brücken X, Y und/oder A aus Polyoxyalkylenketten aus 3 bis 20 Oxyalkyleneinheiten mit je 2 bis 4 Kohlenstoffatomen. Die Anzahl n der Oxyalkyleneinheiten ist dabei als Zahlenmittelwert zu verstehen. Besonders bevorzugt sind Polyoxyethylenketten. Solche Verbindungen eignen sich insbesondere zum Inkorporieren in Emulsions- oder Hilfsschichten, da sie diffusionsgehemmt und mit anionischen Beschichtungshilfsmitteln verträglich sind.In another preferred embodiment, the bridges X, Y and / or A consist of polyoxyalkylene chains of 3 to 20 oxyalkylene units each having 2 to 4 carbon atoms. The number n of oxyalkylene units is to be understood as the number average. Polyoxyethylene chains are particularly preferred. Such compounds are particularly suitable for incorporation in emulsion or auxiliary layers, since they are diffusion-inhibited and compatible with anionic coating aids.
Beim erfindungsgemäßen Verfahren wird das Aufzeichnungsmaterial bevorzugt in Gegenwart einer Hydrazinverbindung entwickelt. Diese Hydrazinverbindung kann in an sich bekannter Weise entweder in eine oder mehrere Schichten des Aufzeichnungsmaterials inkorporiert oder der Entwicklerlösung zugesetzt werden. Geeignete Verbindungen und Anwendungsverfahren sind beispielsweise beschrieben in Research Disclosure 235 010 (November 1983), DE-27 25 743-A1, EP-00 32 456-B, EP-01 26 000-A2, EP-01 38 200-A2, EP-02 03 521-A2, EP-02 17 310-A2, EP-02 53 665-A2, EP-03 24 391-A2, EP-03 24 426-A2, EP-03 26 443-A2, EP-03 56 898-A2, EP-04 73 342-A1, EP-05 01 546-A1.In the method according to the invention, the recording material is preferably developed in the presence of a hydrazine compound. In a manner known per se, this hydrazine compound can either be incorporated into one or more layers of the recording material or added to the developer solution. Suitable compounds and application methods are described, for example, in Research Disclosure 235 010 (November 1983), DE-27 25 743-A1, EP-00 32 456-B, EP-01 26 000-A2, EP-01 38 200-A2, EP -02 03 521-A2, EP-02 17 310-A2, EP-02 53 665-A2, EP-03 24 391-A2, EP-03 24 426-A2, EP-03 26 443-A2, EP-03 56 898-A2, EP-04 73 342-A1, EP-05 01 546-A1.
Beispiele geeigneter Hydrazinverbindungen sind
Die erfindungsgemäß verwendeten Entwicklerlösungen enthalten bevorzugt eine Dihydroxybenzol-Entwicklersubstanz, beispielsweise Hydrochinon, Brenzkatechin, Methylhydrochinon oder Chlorhydrochinon, und ein Oxydationsschutzmittel, bevorzugt ein Alkalisulfit in einer Konzentration von mehr als 0,3 mol je Liter. Besonders bevorzugt werden Lösungen mit pH-Werten von 9 bis höchstens 11. Solche Entwicklerlösungen sind auch im Gebrauch gut haltbar und ergeben weitgehend schleierfreie Bilder.Examples of suitable hydrazine compounds are
The developer solutions used according to the invention preferably contain a dihydroxybenzene developer substance, for example hydroquinone, pyrocatechol, methylhydroquinone or chlorohydroquinone, and an antioxidant, preferably an alkali sulfite in a concentration of more than 0.3 mol per liter. Solutions with a pH of 9 to a maximum of 11 are particularly preferred. Such developer solutions are also stable in use and produce largely fog-free images.
Bevorzugt enthalten die Entwicklerlösungen bekannte superadditiv wirkende Hilfsentwicklersubstanzen, beispielsweise N-Methyl-p-aminophenol oder 1-Phenylpyrazolidinon-3 oder Derivate dieser Verbindungen.The developer solutions preferably contain known super-additive auxiliary developer substances, for example N-methyl-p-aminophenol or 1-phenylpyrazolidinone-3 or derivatives of these compounds.
Ebenfalls bevorzugt sind Entwickler, die Stabilisatoren aus den Gruppen der Benztriazole und Mercaptotetrazole enthalten. Solche Stabilisatoren sind beispielsweise 1-Phenyl-5-mercaptotetrazol, 1-(1-Naphthyl)-5-mercaptotetrazol, 1-Cyclohexyl-5-mercaptotetrazol, 1-(4-Chlorphenyl)-5-mercaptotetrazol, 1-(3-Capramidophenyl)-5-mercaptotetrazol, Benztriazol, 5-Chlorbenztriazol, 5-Brombenztriazol, 5-Nitrobenztriazol, 5-Benzoylaminobenztriazol, 1-Hydroxymethylbenztriazol, 6-Cyanobenztriazol.Developers containing stabilizers from the groups of benzotriazoles and mercaptotetrazoles are also preferred. Examples of such stabilizers are 1-phenyl-5-mercaptotetrazole, 1- (1-naphthyl) -5-mercaptotetrazole, 1-cyclohexyl-5-mercaptotetrazole, 1- (4-chlorophenyl) -5-mercaptotetrazole, 1- (3-Capramidophenyl) -5-mercaptotetrazole, benztriazole, 5-chlorobenztriazole, 5-bromobenzotriazole, 5-nitrobenzetriazole, 5-benzoylaminobenzotriazole, 1-hydroxymethylbenztriazole, 6-cyanobenzotriazole.
Die lichtempfindlichen Silberhalogenide der erfindungsgemäß verwendeten Aufzeichnungsmaterialien bestehen aus Silberchlorid, Silberbromid, Silberchlorobromid, Silberbromoiodid oder Silberchlorobromoiodid. Sie können monodispers oder polydispers sein, eine einheitliche Zusammensetzung haben aber auch Körner mit Kern-Schale-Aufbau aufweisen, sowie auch Gemische von Körnern verschiedener Zusammensetzung und Korngrößenverteilung sein. Sie werden unter Verwendung eines hydrophilen kolloidalen Bindemittels, bevorzugt Gelatine, hergestellt. Die Silberhalogenidkörner können sphärische, polyedrische oder tafelförmige Gestalt haben. Methoden zur Herstellung geeigneter lichtempfindlicher Silberhalogenidemulsionen sind dem Fachmann bekannt und beispielsweise in der Research Disclosure 178 043, Kapitel I und II zusammengefaßt.The light-sensitive silver halides of the recording materials used according to the invention consist of silver chloride, silver bromide, silver chlorobromide, silver bromoiodide or silver chlorobromoiodide. They can be monodisperse or polydisperse, but have a uniform composition, but also have grains with a core-shell structure, and also mixtures of grains of different composition and grain size distribution. They are made using a hydrophilic colloidal binder, preferably gelatin. The silver halide grains can be spherical, polyhedral or tabular in shape. Methods for producing suitable light-sensitive silver halide emulsions are known to the person skilled in the art and are summarized, for example, in Research Disclosure 178 043, chapters I and II.
Bevorzugt für die erfindungsgemäß verwendeten Aufzeichnungsmaterialien werden Silberhalogenidemulsionen, die durch kontrollierten Doppelstrahleinlauf hergestellt werden, eine kubische Kornform haben und deren Chloridanteil weniger als 50 Molprozent beträgt.Preferred for the recording materials used according to the invention are silver halide emulsions which are produced by controlled double jet entry, have a cubic grain shape and whose chloride content is less than 50 mole percent.
Die Korngröße der Silberhalogenidkörner in den Emulsionen richtet sich nach der erforderlichen Empfindlichkeit und kann beispielsweise der kubischer Körner von 0,1 bis 0,7 µm Kantenlänge entsprechen. Ein bevorzugter Bereich liegt zwischen 0,15 und 0,30 µm. Bei der Emulsionsherstellung können Edelmetallsalze, besonders Salze von Rhodium oder Iridium zur Verbesserung der photographischen Eigenschaften in den üblichen Mengen anwesend sein.The grain size of the silver halide grains in the emulsions depends on the required sensitivity and can, for example, correspond to the cubic grains with an edge length of 0.1 to 0.7 μm. A preferred range is between 0.15 and 0.30 µm. Precious metal salts, especially salts of rhodium or iridium, can be present in the usual amounts in the emulsion preparation in order to improve the photographic properties.
Die Emulsionen werden bevorzugt chemisch sensibilisiert. Geeignete Verfahren sind die Schwefel-, die Reduktions- und die Edelmetallsensibilisierung, die auch in Kombination angewendet werden können. Für letztere können beispielsweise Gold- oder Iridiumverbindungen benutzt werden.The emulsions are preferably chemically sensitized. Suitable processes are the sulfur, the reduction and precious metal sensitization, which can also be used in combination. For the latter, for example, gold or iridium compounds can be used.
Die Emulsionen können mit üblichen Sensibilisierungsfarbstoffen spektral sensibilisiert werden.The emulsions can be spectrally sensitized with conventional sensitizing dyes.
Die Emulsionen können auch übliche Antischleiermittel enthalten. Bevorzugt sind ggf. substituiertes Benztriazol, 5-Nitroindazol und Quecksilberchlorid. Diese Mittel können zu jedem Zeitpunkt bei der Emulsionsherstellung zugesetzt werden oder in einer Hilfsschicht des photographischen Materials enthalten sein. Zur Verbesserung der photographischen Eigenschaften kann der Emulsion vor oder nach der chemischen Reifung ein Jodid in einer Menge von etwa 1 mmol je Mol Silber zugesetzt werden.The emulsions can also contain conventional antifoggants. Substituted benzotriazole, 5-nitroindazole and mercury chloride are preferred. These agents can be added at any time during the preparation of the emulsion or can be contained in an auxiliary layer of the photographic material. To improve the photographic properties, an iodide can be added to the emulsion in an amount of about 1 mmol per mole of silver before or after chemical ripening.
Die Emulsionen können auch bekannte Polymerdispersionen enthalten, durch die beispielsweise die Dimensionsstabilität des photographischen Materials verbessert wird. Es handelt sich dabei in der Regel um Latices hydrophober Polymere in wäßriger Matrix. Beispiele für geeignete Polymerdispersionen sind in der Research Disclosure 176 043, Kapitel IX B (Dezember 1978) genannt.The emulsions can also contain known polymer dispersions which, for example, improve the dimensional stability of the photographic material. These are generally latices of hydrophobic polymers in an aqueous matrix. Examples of suitable polymer dispersions are mentioned in Research Disclosure 176 043, Chapter IX B (December 1978).
Die lichtempfindlichen Schichten der photographischen Materialien können mit einem bekannten Mittel gehärtet sein. Dieses Härtemittel kann der Emulsion zugesetzt oder über eine Hilfsschicht beispielsweise eine äußere Schutzschicht, eingebracht werden. Ein bevorzugtes Härtungsmittel ist Hydroxydichlorotriazin.The photosensitive layers of the photographic materials can be hardened by a known means. This hardening agent can be added to the emulsion or introduced via an auxiliary layer, for example an outer protective layer. A preferred curing agent is hydroxydichlorotriazine.
Das photographische Material kann weitere Zusätze, die für die Erzeugung bestimmter Eigenschaften bekannt und üblich sind, enthalten. Solche Mittel sind zum Beispiel in der Research Disclosure 176 043 in den Kapiteln V (Aufheller), XI (Beschichtungshilfsmittel), XII (Weichmacher und Gleitmittel) und XVI (Mattierungsmittel) aufgeführt.The photographic material can contain other additives which are known and customary for the production of certain properties. Such agents are listed, for example, in Research Disclosure 176 043 in chapters V (brightener), XI (coating aids), XII (plasticizers and lubricants) and XVI (matting agents).
Der Gelatinegehalt der Emulsionen liegt im allgemeinen zwischen 50 und 200 g je Mol Silber; bevorzugt wird der Bereich zwischen 70 und 150 g je Mol Silber.The gelatin content of the emulsions is generally between 50 and 200 g per mole of silver; the range between 70 and 150 g per mole of silver is preferred.
Bei dem erfindungsgemäßen Verfahren ist die Verwendung von Alkanolaminen nach dem Stand der Technik entweder völlig entbehrlich oder ihre Menge kann auf einen geringen Bruchteil vermindert werden. Dadurch arbeitet das Verfahren ohne störende oder schädliche Geruchsbelästigung und die Korrosion durch aus dem Entwickler sich verflüchtigende Aminoverbindungen wird vermieden.In the process according to the invention, the use of alkanolamines according to the prior art is either completely unnecessary or their amount can be reduced to a small fraction. As a result, the process works without annoying or harmful odor nuisance and the corrosion caused by amino compounds evaporating from the developer is avoided.
Das erfindungsgemäße Verfahren führt auch dann zu ultrasteiler Gradation, wenn die Oniumverbindungen nur im Aufzeichnungsmaterial enthalten ist. Dagegen müssen die kontraststeigernden Aminoverbindungen nach dem Stand der Technik, insbesondere die Alkanolamine, notwendig dem Entwickler zugesetzt werden.The method according to the invention also leads to ultra-gradation if the onium compounds are only contained in the recording material. In contrast, the contrast-increasing amino compounds according to the prior art, in particular the alkanolamines, must be added to the developer.
Die erforderliche Konzentration der erfindungsgemäß eingesetzten Verbindungen ist wesentlich geringer als die praktisch üblichen Konzentrationen der Alkanolamine nach dem Stand der Technik. Auch sind die Verbindungen nicht flüchtig und gut wasserlöslich. Dadurch ergeben sich günstige Folgen für die Wirtschaftlichkeit sowie für den Gesundheitsschutz der Beschäftigten und bei der Entsorgung.The required concentration of the compounds used according to the invention is considerably lower than the practically usual concentrations of the alkanolamines according to the prior art. The compounds are also non-volatile and readily water-soluble. This has favorable consequences for the economic efficiency as well as for the health protection of the employees and for the disposal.
Die Erfindung kann zur Erzeugung von Negativbilder mit ultrasteilem Kontrast, insbesondere bei der Reproduktion in der Druckvorstufe für den Schwarz-Weiß- und Mehrfarbdruck, angewendet werden.The invention can be used to produce negative images with ultra-partial contrast, in particular in the reproduction in the prepress for black and white and multi-color printing.
In den Ausführungsbeispielen wurden folgende bekannte Entwicklungsbeschleuniger und kontraststeigernde Mittel als Vergleichssubstanzen verwendet:
- V1 1-Phenethylpicoliniumbromid
- V2 1-Dodecylpyridiniumbromid
- V3 1-Decyl-3-methylimidazoliumbromid
- V4 Tetrabutylammoniumhydroxid
- V5 1-(2-Dimethylaminoethyl)imidazol
- V6 2-Diethylaminoethanol
- V7 Diethylaminopropandiol
Die erfindungsgemäßen Verbindungen wurden stets in Form wäßriger Lösungen mit Gehalten von 20 bis 50 g je 100 ml eingesetzt. Die Mengenangaben beziehen sich jedoch jeweils auf die reine Substanz.The following known development accelerators and contrast-enhancing agents were used as comparison substances in the exemplary embodiments:
- V1 1-phenethylpicolinium bromide
- V2 1-dodecylpyridinium bromide
- V3 1-decyl-3-methylimidazolium bromide
- V4 tetrabutylammonium hydroxide
- V5 1- (2-dimethylaminoethyl) imidazole
- V6 2-diethylaminoethanol
- V7 diethylaminopropanediol
The compounds according to the invention were always used in the form of aqueous solutions with contents of 20 to 50 g per 100 ml. However, the quantities given relate to the pure substance.
Durch pAg-geregelten Zweistrahleinlauf wurde eine kubische Silberbromidemulsion hergestellt, deren Körner eine Kantenlänge von 0,23 µm hatten. Nach der Entfernung der löslichen Salze mittels des Flockungsverfahrens wurde auf einen Gesamtgelatinegehalt von 80 g je mol Silber eingestellt und eine chemische Reifung mit Goldsalz und Thiosulfat durchgeführt. Danach wurden noch ein optischer Sensibilisator für den grünen Bereich, übliche Stabilisatoren und Beschichtungshilfsmittel sowie 0,17 g 1-Pyridiniumacetyl-2-(4-benzyloxyphenyl)hydrazinbromid (Verbindung H-7) je mol Silber zugesetzt. Die Emulsion wurde gemeinsam mit einer Gelatineschutzschicht auf einen Polyethylenterephthalat-Schichtträger aufgetragen. Die Auftragsgewichte dieser Schichten je m² entsprachen 4,5 g Silber bzw. 0,9 g Gelatine.A cubic silver bromide emulsion, the grains of which had an edge length of 0.23 μm, was produced by pAg-regulated two-jet inlet. After the soluble salts had been removed by means of the flocculation process, the total gelatin content was adjusted to 80 g per mol of silver and chemical ripening was carried out using gold salt and thiosulfate. Then an optical sensitizer for the green area, customary stabilizers and coating aids and 0.17 g of 1-pyridiniumacetyl-2- (4-benzyloxyphenyl) hydrazine bromide (compound H-7) were added per mole of silver. The emulsion was applied together with a protective gelatin layer to a polyethylene terephthalate support. The application weights of these layers per m² corresponded to 4.5 g of silver or 0.9 g of gelatin.
Proben des so erhaltenen Aufzeichnungsmaterials wurden durch eine Keilvorlage mit kontinuierlichem Dichteverlauf und durch eine Kombination aus einem solchen Keil mit einem Kontaktraster belichtet. Die Verarbeitung erfolgte in einer Rollenentwicklungsmaschine mit den unten beschrieben Entwicklern bei 36 °C und 28 s Entwicklungszeit sowie mit einem handelsüblichen Fixierbad.Samples of the recording material thus obtained were exposed through a wedge template with a continuous density profile and through a combination of such a wedge with a contact grid. The processing was carried out in a roll developing machine with the developers described below at 36 ° C and 28 s development time as well as with a commercially available fixing bath.
An den verarbeiteten Proben wurden folgende Daten gemessen:
- Maximaldichte Dmax,
- Empfindlichkeit S als Kehrwert der für den Rastertonwert 50 % erforderlichen Belichtung, bezogen auf die Probe 1 als Vergleich,
- Gradation G als mittlere Steigung der am Verlaufskeil aufgenommenen Schwärzungskurve zwischen den optischen Dichten 2,0 und 4,0.
- Maximum density Dmax,
- Sensitivity S as the reciprocal of the exposure required for the halftone value 50%, based on sample 1 as a comparison,
- Gradation G as the average slope of the blackening curve recorded on the gradient wedge between the optical densities 2.0 and 4.0.
Die Entwickler hatten folgende Zusammensetzung:
Wasser zu 1000 ml, pH eingestellt auf 10,9 bei 25 °C.
Water to 1000 ml, pH adjusted to 10.9 at 25 ° C.
Die Versuchsergebnisse sind in Tabelle 1 zusammengestellt. Man sieht, daß in Gegenwart der bekannten Entwicklungsbeschleuniger V1 und V2 keine befriedigenden Dichte- und Gradationswerte erreicht werden. Die Aminoverbindung V6 wirkt zwar in hoher Menge ausreichend kontraststeigernd, dies ist jedoch mit lästigem und schädlichem Geruch verbunden. Daß die Verbindung von quaternärem Stickstoff und Aminofunktion in einem Molekül tatsächlich wesentlich für die erfindungsgemäße Wirkung ist, zeigt der Vergleich der Versuche 4 und 5 einerseits mit 8 und 9 andererseits.
Proben des in Beispiel 1 verwendeten Aufzeichnungsmaterials wurden wie dort beschrieben belichtet, entwickelt und ausgewertet, wobei Entwickler der nachstehend angegebenen Zusammensetzung verwendet wurden:
Wasser zu 1000 ml, pH bei 25 °C eingestellt nach Tabelle 2.Water at 1000 ml, pH adjusted at 25 ° C according to Table 2.
Die Ergebnisse sind in Tabelle 2 zusammengestellt.
Durch pAg-geregelten Zweistrahleinlauf wurde eine kubische Silberbromidemulsion hergestellt, deren Körner eine Kantenlänge von 0,20 µm hatten. Nach der Entfernung der löslichen Salze mittels des Flockungsverfahrens wurde auf einen Gesamtgelatinegehalt von 80 g je mol Silber eingestellt und eine chemische Reifung mit Goldsalz und 0,3 mmol Thiosulfat je mol Silber durchgeführt. Danach wurden noch 5 mmol Kaliumiodid, ein optischer Sensibilisator für den grünen Bereich, übliche Stabilisatoren und Beschichtungshilfsmittel sowie 1 mmol 1-Pyridiniumacetyl-2-(4-benzyloxyphenyl)hydrazinbromid (Verbindung H-7) je mol Silber zugesetzt. Die Emulsion wurde gemeinsam mit einer Gelatineschutzschicht auf einen Polyethylenterephthalat-Schichtträger aufgetragen. Die Auftragsgewichte dieser Schichten je m² entsprachen 3,5 g Silber bzw. 0,8 g Gelatine. In der Gelatineschutzschicht waren noch 0,4 g je m² einer Dispersion eines Styrol-Acrylat-Copolymeren, 2,4-Dichloro-6-hydroxytriazin als Härtungsmittel sowie die in der folgenden Tabelle 3 aufgeführten Zusätze (in g/m²) enthalten.A cubic silver bromide emulsion, the grains of which had an edge length of 0.20 μm, was produced by pAg-regulated two-jet inlet. After the soluble salts had been removed by means of the flocculation process, the total gelatin content was adjusted to 80 g per mol of silver and chemical ripening was carried out using gold salt and 0.3 mmol of thiosulfate per mol of silver. Then 5 mmol of potassium iodide, an optical sensitizer for the green area, customary stabilizers and coating aids and 1 mmol of 1-pyridiniumacetyl-2- (4-benzyloxyphenyl) hydrazine bromide (compound H-7) were added per mol of silver. The emulsion was applied together with a protective gelatin layer to a polyethylene terephthalate support. The application weights of these layers per m² corresponded to 3.5 g of silver or 0.8 g of gelatin. The gelatin protective layer still contained 0.4 g per m² of a dispersion of a styrene-acrylate copolymer, 2,4-dichloro-6-hydroxytriazine as hardening agent and the additives listed in Table 3 below (in g / m²).
Proben der so erhaltenen Aufzeichnungsmaterialien wurden wie in Beispiel 1 beschrieben belichtet, verarbeitet und ausgewertet, wobei die in Versuch 13 bzw. 14 des Beispiels 2 angegebenen Entwickler Verwendung fanden.Samples of the recording materials thus obtained were exposed, processed and evaluated as described in Example 1, the developers given in Experiments 13 and 14 of Example 2 being used.
Die Ergebnisse sind in Tabelle 3 aufgeführt. Dabei ist die Empfindlichkeit S auf den Versuch 18 bezogen.
Diese Ergebnisse zeigen, daß man nur dann einen ultrasteilen Kontrast erzielt, wenn die erfindungsgemäßen Verbindungen wenigstens im Aufzeichnungsmaterial oder im Entwickler vorhanden sind.These results show that an ultra-fine contrast can only be achieved if the compounds according to the invention are present at least in the recording material or in the developer.
Proben eines handelsüblichen Hellraum-Kopierfilms (Film H; Typ BLE der Du Pont de Nemours (Deutschland) GmbH) und eines Photosatzfilms (Film P; Typ CHI des gleichen Herstellers) wurden durch einen Verlaufskeil belichtet und unter Verwendung der Entwickler aus den Versuchen 10 und 17 des Beispiels 2 verarbeitet. Die Entwicklungszeit betrug 28 s, die Temperatur 36 °C. An den verarbeiteten Proben wurden die Minimal- und die Maximaldichte Dmin und Dmax, die Empfindlichkeit S als Kehrwert der für die Dichte 3,5 erforderlichen Belichtung, jeweils bezogen auf die mit dem Entwickler nach Versuch 10 entwickelte Probe, die Gradation G1 zwischen den Dichtewerten 0,1 und 0,4 sowie die Gradation G2 zwischen den Dichten 0,4 und 3,5 bestimmt.Samples of a commercially available bright space copying film (film H; type BLE from Du Pont de Nemours (Deutschland) GmbH) and a photosetting film (film P; type CHI from the same manufacturer) were exposed through a gradient wedge and using the developers from experiments 10 and 17 of Example 2 processed. The development time was 28 s, the temperature 36 ° C. The minimum and maximum densities Dmin and Dmax, the sensitivity S as the reciprocal of the exposure required for the density 3.5, based in each case on the sample developed with the developer according to test 10, the gradation G1 between the density values 0 were obtained on the processed samples , 1 and 0.4 and the gradation G2 between the densities 0.4 and 3.5 are determined.
Die in Tabelle 4 aufgeführten Ergebnisse zeigen, daß auch bei Verarbeitung in Abwesenheit von Hydrazinverbindungen durch Verwendung der erfindungsgemäßen Verbindung II-1 der Kontrast erhöht wird.
Durch pAg-geregelten Zweistrahleinlauf wurde eine kubische Silberchlorobromidemulsion (80 Molprozent Chlorid) hergestellt. Die Kantenlänge der Körner betrug 0,21 µm. Nach Entfernung der löslichen Salze mittels des Flockverfahrens wurde die Emulsion auf einen Gesamtgelatinegehalt von 55 g je mol Silber eingestellt und mit Thiosulfat und Goldsalz in Gegenwart von Kaliumtoluolthiosulfonat chemisch gereift. Danach wurden Kaliumjodid (1,6 mmol je mol Silber), Benztriazol und Hydroxymethyltetraazainden als organische Stabilisatoren, eine Dispersion von Polyethylen, ein Sensibilisator für den grünen Spektralbereich, übliche Beschichtungshilfsmittel, 0,1 mmol je mol Silber der Verbindung H-7 und 0,15 mmol Dichlorohydroxytriazin je Gramm Gelatine zugesetzt. Die Emulsion wurde gleichzeitig mit einer Schutzschichtlösung auf einen Polyethylenterephthalat-Schichtträger aufgetragen. Die Schutzschichtlösung enthielt Gelatine, Mattierungsmittel, Beschichtungshilfsmittel und die Zusätze nach Tabelle 5 in Wasser. Das Auftragsgewicht der Emulsion entsprach 4,2 g Silber je m², das der Schutzschicht 0,9 g Gelatine je m².A cubic silver chlorobromide emulsion (80 mole percent chloride) was prepared by pAg-controlled two-jet inlet. The edge length of the grains was 0.21 µm. After removal of the soluble salts by means of the flocking process, the emulsion was adjusted to a total gelatin content of 55 g per mol of silver and chemically ripened with thiosulfate and gold salt in the presence of potassium toluene thiosulfonate. After that, potassium iodide (1.6 mmol per mol of silver), benzotriazole and hydroxymethyltetraazaindene became common as organic stabilizers, a dispersion of polyethylene, and a sensitizer for the green spectral range Coating aids, 0.1 mmol per mol of silver compound H-7 and 0.15 mmol dichlorohydroxytriazine per gram of gelatin were added. The emulsion was applied simultaneously to a protective layer solution on a polyethylene terephthalate support. The protective layer solution contained gelatin, matting agents, coating aids and the additives according to Table 5 in water. The application weight of the emulsion corresponded to 4.2 g of silver per m², that of the protective layer 0.9 g of gelatin per m².
Proben der so erhaltenen Aufzeichnungsmaterialien wurden wie in Beispiel 1 beschrieben belichtet und entwickelt. Der Entwickler hatte folgende Zusammensetzung:
Die in Tabelle 5 aufgeführten Ergebnisse zeigen, daß die Gradation durch die erfindungsgemäßen Substanzen auch bei relativer hoher Gradation der goldgereiften chloridreichen Ausgangsemulsion und in Abwesenheit bekannter kontrasterhöhender Aminoverbindungen bei niedrigem pH in unerwarteter Weise gesteigert wird. Dagegen wirken die bekannten Entwicklungsbeschleuniger nur mäßig auf Gradation und Empfindlichkeit.
Claims (10)
dadurch gekennzeichnet, daß
das Molekül der Oniumverbindung mindestens ein quaternäres Stickstoffatom und mindestens eine tertiäre Aminfunktion aufweist.A method for producing photographic negative images with ultra-high contrast, wherein a light-sensitive material which has at least one layer with a silver halide emulsion is developed in the presence of an onium compound,
characterized in that
the molecule of the onium compound has at least one quaternary nitrogen atom and at least one tertiary amine function.
dadurch gekennzeichnet, daß
die Oniumverbindung aus einem Kation der allgemeinen Formeln (I), (II) oder (III)
Q⁺ - X - NR₁R₂ (I)
R₁R₂N - X - Q⁺ - Y - NR₃R₄ (II)
R₁R₂N - X - Q⁺ - A - Q₁⁺ - Y - NR₃R₄ (III),
worin bedeuten
characterized in that
the onium compound from a cation of the general formulas (I), (II) or (III)
Q⁺ - X - NR₁R₂ (I)
R₁R₂N - X - Q⁺ - Y - NR₃R₄ (II)
R₁R₂N - X - Q⁺ - A - Q₁⁺ - Y - NR₃R₄ (III),
in what mean
dadurch gekennzeichnet, daß
das Aufzeichnungsmaterial in Gegenwart einer Hydrazinverbindung entwickelt wird.The method of claim 1 or 2,
characterized in that
the recording material is developed in the presence of a hydrazine compound.
dadurch gekennzeichnet, daß
die Gruppen X, Y und/oder A durch Ketten mit insgesamt 2 bis 16 Kohlenstoff-, Sauerstoff-, Stickstoff- oder Schwefelatomen dargestellt werden.Method according to claim 2 or 3,
characterized in that
the groups X, Y and / or A are represented by chains with a total of 2 to 16 carbon, oxygen, nitrogen or sulfur atoms.
dadurch gekennzeichnet, daß
die Gruppen X, Y und/oder A Alkylenoxyalkylen oder Hydroxyalkylen mit insgesamt 2 bis 12 Kohlenstoff- und Sauerstoffatomen in der Kette oder Polyoxyalkylenketten aus 3 bis 20 Oxyalkyleneinheiten mit je 2 bis 4 Kohlenstoffatomen sind.Method according to one of claims 2 to 4,
characterized in that
the groups X, Y and / or A are alkyleneoxyalkylene or hydroxyalkylene with a total of 2 to 12 carbon and oxygen atoms in the chain or polyoxyalkylene chains of 3 to 20 oxyalkylene units with 2 to 4 carbon atoms each.
dadurch gekennzeichnet, daß
die Oniumverbindung im Entwickler enthalten ist.Method according to one of claims 1 to 5,
characterized in that
the onium compound is contained in the developer.
dadurch gekennzeichnet, daß
die Oniumverbindung in mindestens einer Emulsionsschicht oder in einer mit dieser in reaktiver Beziehung stehenden anderen Schicht enthalten ist.Method according to one of claims 1 to 5,
characterized in that
the onium compound is contained in at least one emulsion layer or in another layer which is reactive with it.
dadurch gekennzeichnet, daß
der Entwickler eine Dihydroxybenzol-Entwicklersubtanz und mindestens 0,3 mol/l Sulfit enthält.Method according to one of claims 1 to 7,
characterized in that
the developer contains a dihydroxybenzene developer substance and at least 0.3 mol / l sulfite.
dadurch gekennzeichnet, daß
der Entwickler einen pH zwischen 9 und 11 hat.A method according to claim 8,
characterized in that
the developer has a pH between 9 and 11.
dadurch gekennzeichnet, daß
der Entwickler Stabilisatoren aus den Gruppen der Benztriazole und Mercaptotetrazole enthält.Method according to one of claims 8 or 9,
characterized in that
the developer contains stabilizers from the groups of benzotriazoles and mercaptotetrazoles.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4310327 | 1993-03-30 | ||
| DE4310327A DE4310327A1 (en) | 1993-03-30 | 1993-03-30 | Method of producing negative images with ultra-contrast contrast |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0618491A1 true EP0618491A1 (en) | 1994-10-05 |
| EP0618491B1 EP0618491B1 (en) | 1997-08-27 |
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ID=6484237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94104901A Expired - Lifetime EP0618491B1 (en) | 1993-03-30 | 1994-03-28 | Method for generation of negative images having ultrahigh contrast |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6218070B1 (en) |
| EP (1) | EP0618491B1 (en) |
| JP (1) | JP2736223B2 (en) |
| DE (2) | DE4310327A1 (en) |
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| EP0740194A1 (en) * | 1995-04-28 | 1996-10-30 | Du Pont De Nemours (Deutschland) Gmbh | Silver halide containing material for making negative images having ultrahigh contrast |
| US5789144A (en) * | 1996-04-19 | 1998-08-04 | Eastman Kodak Company | Method for developing a photographic product with incorporated developer |
| WO2015058047A3 (en) * | 2013-10-18 | 2015-06-18 | President And Fellows Of Harvard College | Fluorination of organic compounds |
| US9150516B2 (en) | 2011-04-12 | 2015-10-06 | President And Fellows Of Harvard College | Fluorination of organic compounds |
| US9273083B2 (en) | 2012-09-26 | 2016-03-01 | President And Fellows Of Harvard College | Nickel fluorinating complexes and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19510614A1 (en) * | 1995-03-23 | 1996-09-26 | Du Pont Deutschland | Silver halide recording material for producing negative images with ultra-contrast contrast |
| MA34873B1 (en) | 2010-10-21 | 2014-02-01 | Reforcetech Ltd | Reinforcing bar and method of manufacturing |
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| US4937160A (en) | 1988-08-27 | 1990-06-26 | E. I. Du Pont De Nemours And Company | Photographic silver halide elements containing aryl hydrazides |
| US5236807A (en) * | 1989-03-24 | 1993-08-17 | Fuji Photo Film Co., Ltd. | Image formation method and silver halide photographic material therefor |
| EP0439142B1 (en) * | 1990-01-24 | 1998-04-01 | Fuji Photo Film Co., Ltd. | Composition for color-development and method for processing using same |
| US5190847A (en) | 1990-02-26 | 1993-03-02 | E. I. Du Pont De Nemours And Company | Photographic silver halide materials containing aryl hydrazides |
| US5229248A (en) | 1990-08-16 | 1993-07-20 | Konica Corporation | Silver halide photographic light sensitive material |
| US5284733A (en) * | 1990-10-03 | 1994-02-08 | Dainippon Ink And Chemicals, Inc. | High-contrast image forming process |
| EP0501546A1 (en) | 1991-02-26 | 1992-09-02 | Agfa-Gevaert N.V. | High contrast developer containing an aprotic solvent |
| US5372911A (en) * | 1991-06-13 | 1994-12-13 | Dainippon Ink And Chemicals, Inc. | Process of forming super high-contrast negative images and silver halide photographic material and developer being used therefor |
| US5279919A (en) * | 1991-07-30 | 1994-01-18 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| JP2709765B2 (en) * | 1991-09-02 | 1998-02-04 | 富士写真フイルム株式会社 | Image forming method |
| JP2787630B2 (en) * | 1992-02-06 | 1998-08-20 | 富士写真フイルム株式会社 | Silver halide photosensitive material |
| US5316889A (en) * | 1992-03-31 | 1994-05-31 | Fuji Photo Film Co., Ltd. | Silver halide photographic material and photographic image forming method using the same |
| DE69321884T2 (en) * | 1992-06-29 | 1999-05-12 | Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa | Silver halide photographic material |
| JP2775560B2 (en) * | 1992-11-12 | 1998-07-16 | 富士写真フイルム株式会社 | Silver halide photographic material |
-
1993
- 1993-03-30 DE DE4310327A patent/DE4310327A1/en not_active Withdrawn
-
1994
- 1994-03-10 US US08/209,174 patent/US6218070B1/en not_active Expired - Fee Related
- 1994-03-28 DE DE59403824T patent/DE59403824D1/en not_active Expired - Fee Related
- 1994-03-28 EP EP94104901A patent/EP0618491B1/en not_active Expired - Lifetime
- 1994-03-29 JP JP6058695A patent/JP2736223B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2648604A (en) * | 1951-12-28 | 1953-08-11 | Gen Aniline & Film Corp | Photographic developer containing a pyridinium salt and process of development |
| EP0034038A1 (en) * | 1980-02-06 | 1981-08-19 | E.I. Du Pont De Nemours And Company | Use of silver halide development accelerators, photographic films and processes for developing lithografic film |
| EP0254195A2 (en) * | 1986-07-23 | 1988-01-27 | Minnesota Mining And Manufacturing Company | Photographic silver halide developer compositions and process for forming photographic silver images |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0740194A1 (en) * | 1995-04-28 | 1996-10-30 | Du Pont De Nemours (Deutschland) Gmbh | Silver halide containing material for making negative images having ultrahigh contrast |
| US5789144A (en) * | 1996-04-19 | 1998-08-04 | Eastman Kodak Company | Method for developing a photographic product with incorporated developer |
| US9150516B2 (en) | 2011-04-12 | 2015-10-06 | President And Fellows Of Harvard College | Fluorination of organic compounds |
| US9273083B2 (en) | 2012-09-26 | 2016-03-01 | President And Fellows Of Harvard College | Nickel fluorinating complexes and uses thereof |
| WO2015058047A3 (en) * | 2013-10-18 | 2015-06-18 | President And Fellows Of Harvard College | Fluorination of organic compounds |
| US10759764B2 (en) | 2013-10-18 | 2020-09-01 | President And Fellows Of Harvard College | Fluorination of organic compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2736223B2 (en) | 1998-04-02 |
| DE59403824D1 (en) | 1997-10-02 |
| EP0618491B1 (en) | 1997-08-27 |
| DE4310327A1 (en) | 1994-10-06 |
| JPH0749552A (en) | 1995-02-21 |
| US6218070B1 (en) | 2001-04-17 |
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