EP0618491B1 - Procédé de préparation d'images negatives à contraste très élevé - Google Patents

Procédé de préparation d'images negatives à contraste très élevé Download PDF

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Publication number
EP0618491B1
EP0618491B1 EP94104901A EP94104901A EP0618491B1 EP 0618491 B1 EP0618491 B1 EP 0618491B1 EP 94104901 A EP94104901 A EP 94104901A EP 94104901 A EP94104901 A EP 94104901A EP 0618491 B1 EP0618491 B1 EP 0618491B1
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Prior art keywords
developer
compound
group
groups
onium compound
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German (de)
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EP0618491A1 (fr
Inventor
Reinhold Dr. Rüger
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DuPont de Nemours Deutschland GmbH
EIDP Inc
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DuPont de Nemours Deutschland GmbH
EI Du Pont de Nemours and Co
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    • 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 process for the production of negative images with ultrasite contrast using photosensitive recording materials with silver halide emulsions and means for carrying out the method
  • halftone images In photomechanical reproduction, halftone images often need to be converted to halftone dot images.
  • silver halide materials which are obtained in special processes to ultrasmaschinem contrast, d. H. to a maximum slope of the blackening curve of more than 10, developed.
  • the lithiation process using sulphite-containing, 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 containing a contrast-increasing amount of an amino compound.
  • EP-04 73 342-A1 a silver halide photographic material is described which can be developed in a developer with a pH ⁇ 11 to ultrasite contrast.
  • the photosensitive coating of this material contains a hydrazine compound of a particular formula as well an amino or a quaternary onium compound and is adjusted to a pH of at least 5.9.
  • Cationic surfactants and quaternary ammonium group dyes have long been known as development accelerators (L.F.A. Mason, Photographic Processing Chemistry, London and New York, 1966, page 41f.). US 41 35 931 describes the use of certain pyridinium compounds to accelerate lith development. In these known applications, however, there is no increase in the contrast.
  • developers containing a contrast-enhancing amount of an amino compound are not free from disadvantages.
  • the required concentration of the amino compound is considerable and often near the solubility limit. Due to the increase in temperature or small changes in concentration due to water evaporation during use, the solubility limit can be easily exceeded and the amino compound separates out. This may lead to uneven development and contamination of the recording materials and the developing machine. Because of their steam volatility, the precipitated amino compounds can also get to remote locations on the processor and cause undesirable impurities and corrosion.
  • the known developers generally have a pH above 11. Therefore, they are not sufficiently stable in practice and have a strong corrosive effect on the components of the developing machines.
  • the invention has as its object to provide a method for producing negative images with ultrasite contrast, which can be carried out with a short processing time with a stable, odorless and non-corrosive developer.
  • a photosensitive recording material comprising at least one layer having a silver halide emulsion is developed in the presence of an onium compound and characterized in that the molecule of the onium compound is at least one having a quaternary nitrogen atom and at least one tertiary amine function.
  • the quaternary nitrogen atom may 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 another nitrogen atom with three substituents, two of which can form a ring. The third of these substituents forms a bridge to the quaternary nitrogen atom. It is also possible in each case for several quaternary nitrogen atoms and tertiary amine functions to be combined in one molecule.
  • the imidazolium, thiazolium or pyridinium groups may be condensed with other aliphatic or aromatic ring systems, for example quinolinium, benzimidazolium or benzthiazolium groups. They may also bear 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 another substituent, preferably alkyl or further substituted alkyl, is necessary on the other nitrogen atom to stabilize the quaternary structure, and the positive charge is not localized at one of the nitrogen atoms.
  • the bridges X, Y and A are preferably represented by chains in which the total number of carbon and optionally the oxygen, nitrogen and sulfur atoms is 2 to 16, wherein in the special case mentioned above Y can also be a simple bond.
  • the alkyl groups of the radicals R 1 , R 2 , R 3 , R 4 preferably have 1 to 4 carbon atoms in a straight or branched chain. You can also form pairs of rings, as far as this is possible spatially, so for example R 1 with R 2 and R 3 with R 4 .
  • Q + or Q 1 + is represented by quaternary ammonium or iminium, R 1 or R 3 can also form a ring with a residue on the nitrogen.
  • Examples of quaternary ammonium groups are -N + R 5 R 6 R 7 (IA) wherein R 5 , R 6 and R 7 are each alkyl, alkenyl or alkynyl of 1 to 10 carbon atoms, R 5 is such a group of 1 to 20 carbon atoms or aralkyl and R 6 and R 7 can also form a ring of 4 to 8 carbon atoms .
  • R 8 and R 10 have the same meaning as R 5
  • R 9 and R 11 have the same meaning as R 6 and A have the meaning given for formula (III)
  • R 8 with R 10 and R 9 with R 11 each connected to a chain of 2 to 10 carbon atoms.
  • An example of a cyclic cationic group according to formula (III) or (III-A) is di-quaternized 1,4-diazabicyclo (2.2.2) octane.
  • R 12 , R 13 and R 14 have the same meaning as R 5
  • R 1 and R 2 have the same meaning as in formula (II) and any two of these groups may form a ring having 4 to 8 carbon or nitrogen atoms.
  • the anions may be represented by inorganic or organic anions commonly used in the preparation 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 according to the formulas (I), (II) and (III) are: (CH 3 ) 3 N ⁇ -CH 2 -CHOH-CH 2 -N (C 2 H 5 ) 2 Cl - (I-18) (CH 3 ) 3 N ⁇ -CH 2 -CHOH-CH 2 -NH-C 2 H 4 -N (C 2 H 5 ) 2 Cl - (I-19) (CH 3 ) 3 N ⁇ -CH 2 -CHOH-CH 2 -NH-C 3 H 6 -N (C 4 H 9 ) 2 Cl - (I-20) (CH 3 ) 3 N ⁇ -CH 2 -CHOH-CH 2 -OC 2 H 4 -N (C 4 H 9 ) 2 Cl - (I-22) (CH 3 ) 3 N ⁇ -CH 2 -CHOH-CH 2 -S-C 2 H 4 -N (C 2 H 5 ) 2 Cl - (I-23) (CH 3 ) 3 N
  • the bridge X or Y links the tertiary amine nitrogen with the quaternary nitrogen of the group Q + .
  • Such compounds are particularly easy to produce from readily available starting materials; for example, by reacting the corresponding tertiary amines with ⁇ -haloalkylamines in the presence of alkalis or by reacting glycidyltrimethylammonium chloride with secondary amines, dialkylaminoalkylamines, diaminoalcohols or mercaptans. Further 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 et seq., Stuttgart 1958).
  • the compounds of this invention need not be isolated for use in the preparation of developers or recording materials if, as in the following examples, there are virtually no side reactions and the presence of the sole by-product alkali metal halide can be tolerated. As a result, the inventive method is particularly simple and economical.
  • onium compounds of the general formula (I) are particularly preferably those which are not shown in which the same molecule Q + by pyridinium or N'-alkyl-N-imidazolium, and X by alkylene.
  • 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 a number average.
  • Particularly preferred are polyoxyethylene chains.
  • 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 in one or more layers of the recording material or added to the developer solution in a manner known per se. Suitable compounds and methods of use 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.
  • the developer solutions used according to the invention preferably comprise a dihydroxybenzene developing agent, for example hydroquinone, pyrocatechol, methylhydroquinone or chlorohydroquinone, and an antioxidant, preferably an alkali metal sulphite in a concentration of more than 0.3 mol per liter. Particular preference is given to solutions having a pH of from 9 to at most 11. Such developer solutions are also readily stable in use and give substantially fog-free images.
  • a dihydroxybenzene developing agent for example hydroquinone, pyrocatechol, methylhydroquinone or chlorohydroquinone
  • an antioxidant preferably an alkali metal sulphite in a concentration of more than 0.3 mol per liter.
  • Such developer solutions are also readily stable in use and give substantially fog-free images.
  • the developer solutions preferably comprise known superadditive auxiliary developer substances, for example N-methyl-p-aminophenol or 1-phenylpyrazolidinone-3 or derivatives of these compounds.
  • stabilizers from the groups of the benzotriazoles and mercaptotetrazoles.
  • Such stabilizers are, for example, 1-phenyl-5-mercaptotetrazole, 1- (1-naphthyl) -5-mercaptotetrazole, 1-cyclohexyl-5-mercaptotetrazole, 1- (4-chlorophenyl) 5-mercaptotetrazole, 1- (3-capramidophenyl) -5-mercaptotetrazole, benzotriazole, 5-chlorobenzotriazole, 5-bromobenzotriazole, 5-nitrobenzotriazole, 5-benzoylaminobenzotriazole, 1-hydroxymethylbenzotriazole, 6-cyanobenzotriazole.
  • the photosensitive silver halides of the recording materials used in the present invention are silver chloride, silver bromide, silver chlorobromide, silver bromoiodide or silver chlorobromoiodide. They may be monodisperse or polydisperse, but have a uniform composition and have grains with core-shell structure, as well as mixtures of grains of different composition and particle size distribution. They are prepared using a hydrophilic colloidal binder, preferably gelatin.
  • the silver halide grains may be spherical, polyhedral or tabular in shape. Methods for preparing suitable photosensitive silver halide emulsions are known to those skilled in the art and are summarized, for example, in Research Disclosure 178,043, Chapters I and II.
  • silver halide emulsions prepared by controlled double jet injection have a cubic grain shape and their 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 may, for example, correspond to cubic grains of 0.1 to 0.7 ⁇ m edge length. A preferred range is between 0.15 and 0.30 ⁇ m.
  • noble metal salts especially salts of rhodium or iridium, may be present in conventional amounts to enhance photographic properties.
  • the emulsions are preferably chemically sensitized. Suitable methods are the sulfur, the reduction and the 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 may also contain conventional antifoggants. Preference is given to substituted or unsubstituted benzotriazole, 5-nitroindazole and mercuric chloride. These agents may be added at any time in the emulsion preparation or contained in an auxiliary layer of the photographic material. To improve the photographic properties, an iodide may be added to the emulsion before or after chemical ripening in an amount of about 1 mmol per mole of silver.
  • the emulsions may 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 may be cured by a known means.
  • This hardener may be added to the emulsion or may be introduced via an auxiliary layer, for example an outer protective layer.
  • a preferred curing agent is hydroxydichlorotriazine.
  • the photographic material may contain other additives which are known and customary for the production of certain properties.
  • 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 is preferably between 70 and 150 g per mole of silver.
  • alkanolamines according to the prior art are either completely dispensable or their amount can be reduced to a small fraction.
  • the process works without disturbing or harmful odor nuisance and the corrosion is avoided by evaporating from the developer amino compounds.
  • the method of the invention results in ultra-division gradation even when the onium compounds are contained only in the recording material.
  • the contrast-enhancing amino compounds according to the prior art in particular the alkanolamines, must necessarily be added to the developer.
  • the required concentration of the compounds used according to the invention is substantially lower than the practically usual concentrations of the alkanolamines according to the prior art. Also, the compounds are non-volatile and readily soluble in water. This results in favorable consequences for the profitability as well as for the health protection of the employees and for the disposal.
  • the invention can be used to produce ultra-contrast contrast negative images, particularly in pre-press reproduction for black-and-white and multi-color printing.
  • 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 amounts are based on the pure substance.
  • a cubic silver bromide emulsion was prepared by pAg-controlled two-wire feed, the grains having an edge length of 0.23 ⁇ m. After removing the soluble salts by the flocculation method, the total gelatin content of 80 g per mol of silver was adjusted and chemical ripening was performed with gold salt and thiosulfate. Thereafter, a green sensitizer, common stabilizers and coating aids and 0.17 g of 1-pyridinium acetyl-2- (4-benzyloxyphenyl) hydrazine bromide (Compound H-7) per mol of silver were further added. The emulsion was coated on a polyethylene terephthalate support together with a gelatin protective layer. The coating weights of these layers per m 2 corresponded to 4.5 g of silver or 0.9 g of gelatin.
  • Samples of the resulting recording material were exposed through a continuous density wedge pattern and through a combination of such a wedge with a contact grid.
  • the processing was carried out in a roll development machine with the developers described below at 36 ° C and 28 s development time and with a commercially available fixer.
  • 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-aminophenolphemisulfat 2.75 g, potassium 1 g, benzotriazole 0.5 g, 1-Phenyl-2-mercaptotetrazole 0.04 g, mercaptobenzothiazole 0.04 g, Potassium hydroxide (50% solution) 47 ml, Potassium carbonate (50% solution) 28.5 ml, Additives according to table 1 in g, Water to 100 ml, pH adjusted to 10.9 at 25 ° C.
  • a cubic silver bromide emulsion having an edge length of 0.20 ⁇ m was prepared by pAg-controlled two-wire feed. After removal of the soluble salts by the flocculation method, the total gelatin content of 80 g per mol of silver was adjusted and chemical ripening was performed with gold salt and 0.3 mmol of thiosulfate per mol of silver. Thereafter, 5 mmol of potassium iodide, an optical sensitizer for the green range, conventional stabilizers and coating aids and 1 mmol of 1-pyridinium acetyl-2- (4-benzyloxyphenyl) hydrazine bromide (compound H-7) per mole of silver were added.
  • the emulsion was coated on a polyethylene terephthalate support together with a gelatin protective layer.
  • the coating weights of these layers per m 2 corresponded to 3.5 g of silver or 0.8 g of gelatin.
  • In the gelatin protective layer were still 0.4 g per m 2 of a dispersion of a styrene-acrylate copolymer, 2,4-dichloro-6-hydroxytriazine as a curing agent and the additives listed in Table 3 below (in g / m 2 ).
  • Table 4 show that even when processed in the absence of hydrazine compounds by using the compound II-1 of the invention, the contrast is increased.
  • Table 4 attempt Movie Developer after Dmin Dmax S G1 G2 30 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 2-wire run. The edge length of the grains was 0.21 ⁇ m. After removal of the soluble salts by the flocking process, the emulsion was adjusted to a total gelatin content of 55 g per mole of silver and chemically ripened with thiosulfate and gold salt in the presence of potassium toluene thiosulfonate.
  • Example 1 Samples of the resulting recording materials 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 4 g benzotriazole 0.3 g phenylmercaptotetrazole 0.05 g 4-hydroxymethyl-4-methyl-1-phenylpyrazolidon 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 is unexpectedly increased by the substances according to the invention even at relatively high gradation of the gold-ripened chloride-rich starting emulsion and in the absence of known contrast-increasing amino compounds at low pH.
  • the known development accelerators only moderately on gradation and sensitivity.
  • Table 5 attempt Compound / amount (mg / m 2 ) 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 12 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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  • Physics & Mathematics (AREA)
  • 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)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (10)

  1. Procédé d'obtention d'une image photographique négative à contraste ultra-forte dans lequel un matériau d'enregistrement photosensible, qui comporte au moins une couche d'émulsion à l'halogénure d'argent, est développé en présence d'un composé onium, caractérisé en ce que la molécule du composé onium comprend au moins un atome d'azote quaternaire et au moins une fonction amino-tertiaire.
  2. Procédé selon la revendication 1, caractérisé en ce que le composé onium est obtenu à partir d'un cation de formule générale (I), (II) ou (III)

            Q+ - XNR1R2     (I)



            R1R2N - X Q+ - Y - NR3R4     (II)



            R1R2N - X Q+ - A - Q1 + - Y - NR3R4     (III),

    dans lesquelles
    Q+,Q1 +   identiques ou diffiérents, désignent avec les groupes X et Y ou A auxquels ils sont liés, un groupe ammonium quaternaire ou iminium quaternaire ou un groupe N-imidazolium-, N-thiazolium- ou N-pyridinium, éventuellement substitués,
    X, Y, A   identiques ou différents, désignent chacun un groupe alkylène, hydroxyalkylène, alkyléneoxyalkylène, alkylènethioalkylène, alkylèneaminoalkylène ou hydroxyalkylène-oxyalkylène, ou bien polyoxyalkylène, Y pouvant aussi représenter une liaison simple ou un groupe oxyalkylène, thioalkylène ou aminoalkylène, et en ce cas, se liant à un atome de carbone d'un groupe imidazolium, thiazolium ou pyridinium,
    R1, R2, R3, R4   représentent, indépendamment les uns des autres, des groupes alkyle, alkoxy, alkylaryle ou phényle, éventuellement substitués, identiques ou différents, dans lesquels R1 et R2, ainsi que R3 et R4, peuvent également former un cycle,
    ainsi que les anions nécessaires pour l'équilibre des charges.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le matériau d'enregistrement est développé en présence d'un dérivé d'hydrazine.
  4. Procédé selon la revendication 2 ou 3, caractérisé en ce que les groupes X, Y et/ou A sont constitués de chaînes comprenant en tout 2 a 16 atomes de carbone, d'oxygène, d'azote ou de soufre.
  5. Procédé selon l'une quelconque des revendications 2 à 4, caractérisé en ce que les groupes X, Y, et/ou A sont des alkylènes-oxyalkylènes ou des hydroxyalkylènes dont la chaîne comporte 2 à 12 atomes de carbone et d'oxygène, ou des chaînes polyoxyalkylènes comportant 3 à 20 unités oxyalkylène comprenant, comportant chacune 2 à 4 atomes de carbone.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caraciérisé en ce que le dérivé onium est contenu dans l'agent de développement.
  7. Procédé selon une quelconque des revendications 1 à 5, caractérisé en ce que le dérivé onium est présent dans au moins une couche d'émulsion ou dans une autre couche se trouvant en relation de réaction avec celle-ci.
  8. Procédé selon une quelconque des revendications 1 à 7, caractérisé en ce que le développeur comprend une substance de développement à base de dihydroxybenzole, et au moins 0,3 mole/litre de sulfite.
  9. Procédé selon la revendication 8, caractérisé en ce que le développeur présente un pH compris entre 9 et 11.
  10. Procédé selon une quelconque des revendications 8 ou 9, caractérisé en ce que le développeur comprend des stabilisants choisis dans le groupe des benzotriazoles et mercaptotétrazoles.
EP94104901A 1993-03-30 1994-03-28 Procédé de préparation d'images negatives à contraste très élevé Expired - Lifetime EP0618491B1 (fr)

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Application Number Priority Date Filing Date Title
DE4310327A DE4310327A1 (de) 1993-03-30 1993-03-30 Verfahren zur Erzeugung von Negativbildern mit ultrasteilem Kontrast
DE4310327 1993-03-30

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EP0618491B1 true EP0618491B1 (fr) 1997-08-27

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DE19510614A1 (de) * 1995-03-23 1996-09-26 Du Pont Deutschland Silberhalogenid-Aufzeichnungsmaterial zur Erzeugung von Negativbildern mit ultrasteilem Kontrast
DE19515619A1 (de) * 1995-04-28 1996-10-31 Du Pont Deutschland Silberhalogenid-Aufzeichnungsmaterial zur Erzeugung von Negativbildern mit ultrasteilem Kontrast
FR2747806B1 (fr) * 1996-04-19 1998-07-03 Kodak Pathe Nouveau procede de developpement d'un produit photographique a developpateur incorpore
UA109284C2 (uk) 2010-10-21 2015-08-10 Арматурний стрижень і спосіб його виробництва
EP2697204B1 (fr) 2011-04-12 2017-03-08 President and Fellows of Harvard College Fluoration de composés organiques
WO2014052622A1 (fr) 2012-09-26 2014-04-03 President And Fellows Of Harvard College Complexes de fluoration de nickel et leurs utilisations
US10759764B2 (en) 2013-10-18 2020-09-01 President And Fellows Of Harvard College Fluorination of organic compounds

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JP2736223B2 (ja) 1998-04-02
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US6218070B1 (en) 2001-04-17
EP0618491A1 (fr) 1994-10-05
DE4310327A1 (de) 1994-10-06

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