EP0356898A2 - Matériaux photographiques aux halogénures d'argent contenant des arylhydrazides - Google Patents

Matériaux photographiques aux halogénures d'argent contenant des arylhydrazides Download PDF

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Publication number
EP0356898A2
EP0356898A2 EP89115534A EP89115534A EP0356898A2 EP 0356898 A2 EP0356898 A2 EP 0356898A2 EP 89115534 A EP89115534 A EP 89115534A EP 89115534 A EP89115534 A EP 89115534A EP 0356898 A2 EP0356898 A2 EP 0356898A2
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EP
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Prior art keywords
carbon atoms
group
alkyl
substituted
radical
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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EP89115534A
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German (de)
English (en)
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EP0356898A3 (fr
EP0356898B1 (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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Priority claimed from DE19883829078 external-priority patent/DE3829078A1/de
Application filed by DuPont de Nemours Deutschland GmbH, EI Du Pont de Nemours and Co filed Critical DuPont de Nemours Deutschland GmbH
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Publication of EP0356898A3 publication Critical patent/EP0356898A3/fr
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Publication of EP0356898B1 publication Critical patent/EP0356898B1/fr
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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
    • G03C1/061—Hydrazine compounds

Definitions

  • the invention relates to silver halide photographic materials for forming ultra-gradation images, preferably for rapid processing, containing certain aryl hydrazides, and to new aryl hydrazides for use in such photographic materials.
  • Photographic silver halide systems with ultra-gradation are used, for example, in reproduction technology for generating rasterized images from halftone recordings, for photo typesetting technology, as well as for line recordings and photo masks.
  • the term "ultra-part” is intended to mean that the gradation is higher than can be expected if one assumes that each individual emulsion grain is exposed and developed independently of its neighbors.
  • Such systems take advantage of effects in which the development of a grain initiates the development of neighboring grains, even if these have not been exposed sufficiently to be able to be developed on their own (“contagious development").
  • So-called lith systems have been known for a long time. These consist of films in which most of the silver halide is present as chloride and associated developers, which are characterized by a relatively high pH value, a low sulfite content and the lack of super-additive developer substances. Accordingly, the photosensitivity of the films and their development speed are relatively limited, and it requires considerable effort to keep the activity of the developers constant over a long period of time.
  • a disadvantage of the systems with hydrazine compounds is that the development has to be carried out at relatively high pH values.
  • the relevant documents describe developer pH values in the range from about 9 to 12.5, but in practice only values above 11.5 are used because otherwise a satisfactory development speed is not achieved and the image quality is insufficient. Therefore, the developer solutions are not sufficiently stable for problem-free work.
  • their high sulfite content they are particularly sensitive to atmospheric oxygen. Also, inevitable small fluctuations in the pH during operation change the development characteristic so much that it is difficult to obtain uniform results over a long period of time.
  • EP 02 53 665-41 proposes photographic materials which contain hydrazine compounds in which the activating group in the alkaline developer medium is split off to form an annular structure. These materials can be developed with a satisfactory result even at pH 11. As a result, the disadvantages described above are alleviated; however, there is still a need for further improvement. In addition, the aryl hydrazides used there can only be prepared via multistage syntheses or with moderate yields.
  • the object of the invention is therefore to provide photographic silver halide materials with hydrazine compounds which can be developed comparatively quickly to ultra-gradation at relatively low pH values. Another task is to provide materials of this type, in which the result of the development depends only slightly on the pH of the developer. Another object is to provide new hydrazine compounds which are suitable for the production of such materials and can be prepared with little effort and good yield.
  • Ar is a substituted phenyl group or another substituted or unsubstituted aryl group
  • X+ is a radical which contains a cationic group
  • R, R1, R2 are hydrogen, alkyl or alkylsulfinyl having 1 to 6 carbon atoms, A ⁇ an anion.
  • the Ar radical can also be represented by another, substituted or unsubstituted aryl radical, for example a naphthyl, an anthryl or a phenanthryl radical.
  • the substituents on the aromatic ring system of the radical Ar preferably contain those groups which are used according to the prior art in order to impart certain properties to the hydrazine compound, such as, for example, a certain diffusibility (ballast groups) or a certain adsorption behavior on the silver halide (adsorption-promoting groups).
  • substituents are unbranched, branched or cyclic alkyl, alkenyl or alkynyl, preferably having 1 to 20 carbon atoms, which in turn can also be further substituted by one of the radicals mentioned in this paragraph, halogen atoms, cyano, carboxyl, amino, substituted or unsubstituted aryl radicals with 6 to 14 carbon atoms, alkylamino and acylamino radicals with 1 to 20 carbon atoms, thiourea radicals and other thiocarbonyl radicals containing radicals, alkoxy and aryloxy radicals, aliphatic and aromatic acyloxy radicals, urethane groups, alkyl and arylsulfonyl, alkyl and arylsulfonamido radicals and also sulfur-containing nitrogen radicals and sulfur-containing nitrogen radicals Heterocycles with 5 to 10 members, such as imidazole, thiazole, benzothiazole, benzimide,
  • the substituents mentioned can be bonded to the aryl radical independently of one another or else, mutually substituted, can be connected to form a chain which replaces a hydrogen atom of the aryl radical. Substituents which have the Increasing the electron density of the aromatic ring system through mesomeric or inductive effects.
  • the rest X+ contains a group with a permanent positive charge, such as are present in onium compounds such as ammonium, phosphonium, oxonium compounds.
  • the anion A ⁇ can be a halide anion, for example a chloride, bromide or iodide ion, but also a complex inorganic ion such as sulfate or perchlorate or a common organic anion such as toluenesulfonate or trichloroacetate.
  • Anions of strong acids are preferred. If the hydrazine compound is substituted on a residue with an anionic group, the anion may be omitted because of the formation of an inner salt.
  • substituted phenyl groups Ph are preferred because of their easier accessibility. Accordingly, the preferred aryl hydrazides correspond to the formula: Ph - NR - NR1 - G - X+ A ⁇ (Ia).
  • Ph is a substituted phenyl group
  • X+ is a radical which contains a cationic group
  • R, R1, R2 are hydrogen, alkyl or alkylsulfinyl having 1 to 6 carbon atoms, A ⁇ an anion.
  • the substituents on the phenyl group may be the same as those mentioned above for the aryl group Ar.
  • radicals X+ which contain a cationic group
  • the corresponding arylhydrazides are represented by the formula Ph - NR - NR1 - G - Y+ A ⁇ (Ic) reproduced.
  • Ph is a substituted phenyl group
  • Y+ is a radical which contains a cationic group with at least one quaternized nitrogen atom
  • R, R1 is hydrogen, alkyl or alkylsulfinyl having 1 to 6 carbon atoms, A ⁇ an anion.
  • the rest Y+ can by quaternary ammonium radicals, which are straight-chain or optionally branched Hydrocarbon chain with 1 to 4 carbon atoms, which can also contain an ether atom-bonded oxygen atom, are bonded to G or are also represented by heterocyclic radicals with quaternary nitrogen. In the latter case, the binding of the quaternary nitrogen to G is achieved both by carbon atoms of the heterocyclic ring system and by side chain carbon or oxygen atoms. A direct binding of the quaternary nitrogen to G is impossible.
  • radicals are trialkylammoniummethyl, 2-trialkylammoniumethyl, pyridinium-1-ylmethyl, 1-alkylpyridinium-2-yl, 1-alkylpyridinium-3-yl, 1-alkylpyridinium-4-yl, hydroxyethyldimethylammoniummethyl, 4-sulfoethylpyrididinium , n-dodecyldimethylammoniummethyl, 2-methylthiazolinium-3-ylmethyl, N-ethylpyridinium-3-oxymethyl.
  • arylhydrazides according to the invention can be prepared in a simple manner by various processes, for example from equimolar amounts of arylhydrazine, the corresponding carboxylic acid and dicyclohexylcarbodiimide (cf.Methods of Organic Chemistry (Houben-Weyl), 4th edition, volume X / 2, page 355 ).
  • Another way of incorporating the aryl radical into the hydrazide is via quinone monoacyl hydrazones or quinonoximmonoacyl hydrazones (see Houben-Weyl, same volume, page 233).
  • a third possibility is the hydrazinolysis of carboxylic acid esters (Houben-Weyl, same volume, page 360 f.). Further synthesis possibilities are known to the person skilled in the art.
  • a particularly preferred embodiment of the invention are photographic silver halide materials which contain compounds of the general formula (II).
  • the light-sensitive silver halides of the materials 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. 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 material 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 emulsions depends on the required sensitivity and can be between 0.1 and 0.7 ⁇ m Edge length, the preferred range is between 0.15 and 0.30 ⁇ m edge length.
  • Precious metal salts in particular 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 methods are sulfur, reduction and noble metal sensitization, which can also be used in combination. For the latter, for example, iridium compounds can be used.
  • the emulsions can be spectrally sensitized with conventional sensitizing dyes.
  • the emulsions can also contain conventional antifoggants.
  • Optionally 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 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 aryl hydrazides according to the invention are preferably incorporated in the emulsion, but can also be contained in an auxiliary layer in contact with the emulsion layer.
  • a solution of the aryl hydrazide is added to one of the casting solutions.
  • the addition to the emulsion is preferably carried out after chemical ripening, but can also take place at another time.
  • a suitable solvent for the aryl hydrazides according to the invention is, for example, ethanol.
  • concentration of the compounds in the film can be varied over a wide range and depends not only on the effectiveness of the compound but also on the dependencies of the infectious development known to the person skilled in the art on the further composition of the film, e.g.
  • the concentration of the compounds can be in the range between 10 ⁇ 5 mol / mol Ag to 5x10 ⁇ 2 mol / mol Ag, the range between 5x10 ⁇ 4 and 10 ⁇ 23 mol / mol Ag is preferred.
  • Developer solutions which preferably contain dihydroxybenzenes such as hydroquinone as developer substance are used for processing the materials according to the invention. In addition, they can contain other, also super-additive developer substances such as 1-phenylpyrazolidinone or N-methyl-p- aminophenol and known antifoggants.
  • the sulfite content is preferably above 0.15 mol / l.
  • the development is preferably carried out in the presence of further contrast-increasing agents, such as, for example, alkanolamines or secondary aliphatic or aromatic alcohols.
  • the developer temperature is between 15 and 50 ° C., preferably between 30 and 45 ° C.
  • the developer solution has a pH between 9 and 12.5, the range between 10 and 11.5 being preferred.
  • the development time can be 10 to 500 s.
  • Fixation, washing and drying of the materials according to the invention can be carried out according to known and established methods.
  • the photographic silver halide materials according to the invention can be developed into ultra-gradation and excellent dot quality even at relatively low pH values and short development times. They show little fog and little tendency to form the black spots known to the person skilled in the art as "pepper" in unexposed or little exposed areas.
  • the influence of the developer pH on the development speed and the sensitivity is small, especially in the range around pH 11, so that slight pH fluctuations which are unavoidable during operation do not have any noticeable effect on the photographic result.
  • the aryl hydrazides according to the invention are more effective than nucleating agents compared to the hydrazine compounds known from the prior art, in particular compared to the formyl hydrazides with a comparable chemical structure. They can therefore be used in smaller quantities. They can be easily produced from easily accessible starting materials.
  • the field of application of the materials according to the invention is the reproduction technology, in particular the production of raster images from halftone images in the conventional or also electronic way, the reproduction of line images and photo masks for printed circuits or other products of photo production, as well as the production of printing templates by means of the photo typesetting technology.
  • the aryl hydrazides according to the invention can preferably be used with light-sensitive silver halides.
  • arylhydrazide-containing silver halide photographic materials Although the invention is directed to arylhydrazide-containing silver halide photographic materials, a method in which arylhydrazides are also contained in the developing solution should not be excluded.
  • the extract was cooled to -18 ° C and filtered off after 16 h.
  • the mother liquor of the reaction mixture was concentrated to half, left to stand at ⁇ 18 ° C. for 2 days, the bottom body was filtered off and combined with the first fraction. Yield 8 g (58%).
  • a silver iodobromide emulsion (2 mole percent iodide) with cubic grains with an average edge length of 0.25 ⁇ m was produced by pAg-controlled double jet enema.
  • the emulsion was washed and chemically sensitized in the presence of 0.11 mmol sodium thiosulfate per mole of silver halide. Thereafter, her usual amounts of benzotriazole and 5-nitroindazole were used as an antifoggant Sensitizing dye for the green spectral range, a polyethyl acrylate dispersion and conventional coating aids added.
  • the emulsion contained 80 g of gelatin per mole of silver halide.
  • Table 1 Sample No. connection Dmin Dmax S gamma PQ No. Quantity 1) 1 II-1 1.25 0.04 4.6 9.1 > 25 8th 2nd II-1 2.5 0.04 4.7 10.2 > 25 8th 3rd II-5 2.5 0.04 4.5 8.0 18th 8th 4th II-5 5.0 0.05 4.6 8.5 22 8th 5 II-2 0.6 0.06 4.6 10.5 > 25 9 6 II-2 1.2 0.06 4.5 11.2 > 25 9 7 II-3 2.0 0.06 4.6 9.0 25th 9 8th II-3 4.0 0.06 4.6 9.6 25th 9 9 II-7 2.5 0.04 4.4 7.6 14 7 10th II-7 5.0 0.05 4.4 8.0 16 8th 11 II-4 1.25 0.05 4.6 9.6 > 25 10th 12 II-4 2.5 0.05 4.5 10.6 > 25 10th 13 II-8 1.25 0.05 4.7 8.4 18th 10th 14 II-8 2.5 0.05 0.05 4.5 10.6 > 25 10th 13 II-8 1.25 0.05 4.7 8.4 18th 10th 14 II-8 2.5 0.05 0.05 4.5 10.6 >
  • Example 5 The test and evaluation described in Example 5 was repeated with some film samples. However, the pH of the developer was changed by adding sulfuric acid or potassium hydroxide. The development took 40 s at 38 ° C. Table 2 Sample No. connection pH 10.8 pH 11.6 pH 12.3 No Amount*) S gamma S gamma S gamma 2nd II-1 2.5 9.4 23 10.8 25th **) 16 A 8th 3.0 4.6 10.6 25th **) 22 D 10th 2.8 3.6 3.4 3.6 9.0 18th *) Amount in mmol of compound per mole of silver halide. **) Cannot be evaluated due to heavy concealment.
  • Carboethoxymethyldimethyl- (2-hydroxyethyl) ammonium bromide is obtained by reacting equimolar amounts of ethyl bromoacetate with dimethyl- (2-hydroxymethyl) amine in acetone at room temperature as a white crystalline solid and, after isolation and drying, is used without further purification.
  • Carbomethoxymethylpyridinium bromide is prepared by reacting methyl bromoacetate with dry pyridine in acetone at room temperature. During the reaction, the product falls as a crystalline white solid and can be used without further purification.
  • II-4 was prepared according to the procedure given for compound II-1. Batch size: 0.05 mol, yield 7.5 g, approx. 45%, yellowish needles from methanol, mp 237 ° C.
  • a silver bromide emulsion with cubic grains with an average edge length of 0.25 ⁇ m was produced by pAg-controlled double jet inlet.
  • the emulsion was washed and sensitized in the presence of 0.16 mmol sodium thiosulfate per mole of silver halide. Thereafter, her usual amounts of benzotriazole and 5-nitroindazole as an antifoggant, a sensitizing dye for the green spectral range, 2.3x10 ⁇ 3 mol of potassium iodide per mol of silver, an acrylate polymer dispersion and conventional coating aids were added.
  • the emulsion contained 80 g of gelatin per mole of silver.
  • Example 5 The same parts of the base emulsion were mixed with solutions of the compounds listed in Table 4 in ethanol. Experimental films were then produced from the emulsions as described in Example 5. Samples of these films were then exposed as described in Example 5. The films were then developed in a processor (Dürr Graphica) with Kodak ultratecc developer, the pH of which had previously been adjusted to 10.8 by adding sulfuric acid, at 38 ° C. for 30 minutes. The evaluation was carried out analogously to Example 5.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Pyridine Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP89115534A 1988-08-27 1989-08-23 Matériaux photographiques aux halogénures d'argent contenant des arylhydrazides Expired - Lifetime EP0356898B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19883829078 DE3829078A1 (de) 1988-08-27 1988-08-27 Arylhydrazide enthaltende photographische silberhalogenidmaterialien
DE3829078 1988-08-27
DE3921134 1989-06-28
DE3921134 1989-06-28

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EP0356898A2 true EP0356898A2 (fr) 1990-03-07
EP0356898A3 EP0356898A3 (fr) 1991-08-07
EP0356898B1 EP0356898B1 (fr) 1996-11-27

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US (3) US4937160A (fr)
EP (1) EP0356898B1 (fr)
JP (1) JPH0650373B2 (fr)
DE (1) DE58909752D1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0398355A2 (fr) * 1989-05-19 1990-11-22 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent
WO1993011456A1 (fr) * 1991-12-02 1993-06-10 E.I. Du Pont De Nemours And Company Systemes revelateurs ameliores pour films contenant de l'hydrazine
EP0618486A2 (fr) * 1993-03-31 1994-10-05 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent
EP0628861A1 (fr) * 1993-06-09 1994-12-14 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent
US5407792A (en) * 1993-04-10 1995-04-18 E. I. Du Pont De Nemours And Company Photosensitive silver halide recording material with reduced pressure sensitivity
EP0693708A1 (fr) * 1994-07-21 1996-01-24 Minnesota Mining And Manufacturing Company Elément photographique à l'halogénure d'argent et procédé de formation d'images à haut contraste
EP0694808A1 (fr) 1994-07-29 1996-01-31 Dainippon Ink And Chemicals, Inc. Procédé de formation d'images négatives à très haut contraste et matériau photographique à l'halogénure d'argent et développateur utilisé pour celui-ci
US6218070B1 (en) 1993-03-30 2001-04-17 Agfa-Gevaert, N.V. Process to make ultrahigh contrast images

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Publication number Priority date Publication date Assignee Title
DE59103306D1 (de) * 1990-02-26 1994-12-01 Du Pont Deutschland Arylhydrazide enthaltende photographische Silberhalogenidmaterialien.
JP2694573B2 (ja) * 1990-08-13 1997-12-24 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
US5147756A (en) * 1991-04-11 1992-09-15 E. I. Du Pont De Nemours And Company Stabilized, aqueous hydrazide solutions for photographic elements
US5252426A (en) * 1991-07-29 1993-10-12 E. I. Du Pont De Nemours And Company Mono- and difluoroacetylphenyl hydrazine compounds as silver halide adjuvants
US5279919A (en) * 1991-07-30 1994-01-18 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5384232A (en) * 1991-12-02 1995-01-24 E. I. Du Pont De Nemours And Company Process for rapid access development of silver halide films using pyridinium as development accelerators
JP2847595B2 (ja) * 1992-07-07 1999-01-20 富士写真フイルム株式会社 ハロゲン化銀写真感光材料の処理方法
GB9410425D0 (en) * 1994-05-24 1994-07-13 Ilford Ag Novel bishydrazides
US5686222A (en) * 1994-05-24 1997-11-11 Ilford A.G. Dihydrazides
US5415975A (en) 1994-05-24 1995-05-16 Minnesota Mining And Manufacturing Company Contrast-promoting agents in graphic arts media
US5494776A (en) * 1994-05-24 1996-02-27 Minnesota Mining And Manufacturing Company Hybrid graphic arts films with reduced occurrence of pepper fog
US5858611A (en) * 1994-10-14 1999-01-12 Fuji Photo Film Co., Ltd. Development processing method of silver halide black-and-white photographic material
US5607815A (en) * 1995-02-17 1997-03-04 E. I. Du Pont De Nemours And Company Ultrahigh contrast bright light films with rapid processing
US5702864A (en) * 1996-08-30 1997-12-30 Sun Chemical Corporation Reduced scratch sensitization in nucleated photographic film
EP0848287A1 (fr) 1996-12-11 1998-06-17 Imation Corp. Composition de révélateur pour des matériaux photographiques à l'halogénure d'argent et procédé pour former des images photographiques d'argent
US5939233A (en) * 1997-04-17 1999-08-17 Kodak Polychrome Graphics Llc Nucleating agents for graphic arts films
JP3830060B2 (ja) * 1997-06-09 2006-10-04 富士写真フイルム株式会社 熱現像記録材料

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RESEARCH DISCLOSURE. no. 235, November 1983, HAVANT GB pages 346 - 352; Anonymous: "Development nucleation by hydrazine and hydrazine derivatives" *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0398355A2 (fr) * 1989-05-19 1990-11-22 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent
EP0398355B1 (fr) * 1989-05-19 1996-03-06 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent
WO1993011456A1 (fr) * 1991-12-02 1993-06-10 E.I. Du Pont De Nemours And Company Systemes revelateurs ameliores pour films contenant de l'hydrazine
US6218070B1 (en) 1993-03-30 2001-04-17 Agfa-Gevaert, N.V. Process to make ultrahigh contrast images
EP0618486A2 (fr) * 1993-03-31 1994-10-05 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent
EP0618486A3 (fr) * 1993-03-31 1994-11-23 Fuji Photo Film Co Ltd Matériau photographique à l'halogénure d'argent.
US5468592A (en) * 1993-03-31 1995-11-21 Fuji Photo Film Co. Ltd. Silver halide photographic material
US5407792A (en) * 1993-04-10 1995-04-18 E. I. Du Pont De Nemours And Company Photosensitive silver halide recording material with reduced pressure sensitivity
EP0628861A1 (fr) * 1993-06-09 1994-12-14 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent
EP0693708A1 (fr) * 1994-07-21 1996-01-24 Minnesota Mining And Manufacturing Company Elément photographique à l'halogénure d'argent et procédé de formation d'images à haut contraste
EP0694808A1 (fr) 1994-07-29 1996-01-31 Dainippon Ink And Chemicals, Inc. Procédé de formation d'images négatives à très haut contraste et matériau photographique à l'halogénure d'argent et développateur utilisé pour celui-ci

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Publication number Publication date
US4937160A (en) 1990-06-26
US5130480A (en) 1992-07-14
JPH02120736A (ja) 1990-05-08
EP0356898A3 (fr) 1991-08-07
DE58909752D1 (de) 1997-01-09
JPH0650373B2 (ja) 1994-06-29
EP0356898B1 (fr) 1996-11-27
US5013844A (en) 1991-05-07

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