EP0356898B1 - Matériaux photographiques aux halogénures d'argent contenant des arylhydrazides - Google Patents

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

Info

Publication number
EP0356898B1
EP0356898B1 EP89115534A EP89115534A EP0356898B1 EP 0356898 B1 EP0356898 B1 EP 0356898B1 EP 89115534 A EP89115534 A EP 89115534A EP 89115534 A EP89115534 A EP 89115534A EP 0356898 B1 EP0356898 B1 EP 0356898B1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
alkyl
substituted
radical
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89115534A
Other languages
German (de)
English (en)
Other versions
EP0356898A3 (fr
EP0356898A2 (fr
Inventor
Reinhold Dr. Rüger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont de Nemours Deutschland GmbH
EIDP Inc
Original Assignee
DuPont de Nemours Deutschland GmbH
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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
Publication of EP0356898A2 publication Critical patent/EP0356898A2/fr
Publication of EP0356898A3 publication Critical patent/EP0356898A3/fr
Application granted granted Critical
Publication of EP0356898B1 publication Critical patent/EP0356898B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 exploit effects, for example, in which the development of a grain initiates the development of neighboring grains, even if these have not been exposed sufficiently to be developable 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 inadequate. Therefore, the developer solutions are not sufficiently stable for problem-free work.
  • their high sulfite content they are particularly sensitive to atmospheric oxygen.
  • the development characteristic is changed 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 is split off in the alkaline developer medium 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 specify 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 that are suitable for the production of such materials and can be produced with little effort and good yield.
  • 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 residues with 1 to 20 carbon atoms, residues containing thiourea and other thiocarbonyl groups, alkoxy and aryloxy residues, aliphatic and aromatic acyloxy residues, urethane groups, alkyl and arylsulfonyl, alkyl and arylsulfonamido residues and residues containing nitrogenous nitrogen or sulfur Heterocycles with 5 to 10 members, such as imidazole, thiazole, benzothiazole, benzimidazole.
  • the substituents mentioned can be bonded to the aryl radical independently of one another or else, mutually substituting, can be linked to form a chain which replaces a hydrogen atom of the aryl radical.
  • 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.
  • the substituents on the phenyl group may be the same as those mentioned above for the aryl group Ar.
  • the radical X + can be represented by quaternary ammonium radicals which are bonded to G via a straight-chain or optionally branched hydrocarbon chain having 1 to 4 carbon atoms, which may also contain an oxygen atom bonded to ether, or by heterocyclic radicals containing 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 excluded.
  • radicals are trialkylammoniummethyl, 2-trialkylammoniumethyl, pyridinium-1-ylmethyl, 1-alkylpyridinium-2-yl, 1-alkylpyridinium-3-yl, 1-alkylpyridinium-4-yl, hydroxyethyldimethylammoniummethyl, 4-sulfoethylpyrididium , 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, 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 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.
  • 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 aryl hydrazides according to the invention are preferably incorporated into 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.
  • the 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, for example the binder content and the binder composition, the halide composition and the grain size the emulsion, the degree of chemical ripening of the emulsion and the type and amount of stabilization.
  • the person skilled in the art can easily match the quantity precisely with the parameters mentioned.
  • 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 -2 mol / mol Ag is preferred.
  • Developer solutions which preferably contain dihydroxybenzenes such as hydroquinone as developer substance are used to process the materials according to the invention.
  • they can contain other developer substances, such as 1-phenylpyrazolidinone or N-methyl-p-aminophenol, which also have a superadditive effect as well as 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 of the invention can be developed to 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 reproduction technology, in particular the production of raster images from halftone images in a conventional or electronic manner, the reproduction of line images and photo masks for printed circuits or other products of photo production as well as the production of printing originals by means of photo typesetting technology.
  • the aryl hydrazides according to the invention can preferably be used with light-sensitive silver halides.
  • 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 polyethylacrylate dispersion and conventional coating aids added.
  • the emulsion contained 80 g of gelatin per mole of silver halide.
  • 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 connection pH 10.8 pH 11.6 pH 12.3 No. No Quantity*) 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 as a white crystalline solid by reacting equimolar amounts of ethyl bromoacetate with dimethyl- (2-hydroxymethyl) amine in acetone at room temperature and is used after isolation and drying without further purification.
  • 0.05 mol (11.4 g) of benzyloxyphenylhydrazine hydrochloride are suspended in 50 ml of dry methanol, and 9.1 ml of a 5.5 M sodium methoxide solution in methanol are added.
  • 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.
  • the precipitated yellow solid is filtered off and washed first with tetrahydrofuran, then with water.
  • the filtrate of the reaction mixture is evaporated down and placed in the cold again, product still falling, which is isolated and combined with the first Fraction is united.
  • the product is recrystallized from methanol.
  • 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 antifoggants, 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. 30 S. The evaluation was carried out analogously to Example 5.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Pyridine Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (5)

  1. Matériaux photographiques aux halogénures d'argent contenant des arylhydrazides destinés à la création d'images ultracontrastées, caractérisés en ce qu'ils contiennent des arylhydrazides répondant à la formule générale (I);

            Ar - NR - NR1 - G - X+ A-     (I)

    dans laquelle,
    Ar   désigne un groupe phényle substitué ou un autre groupe aryle substitué ou non substitué,
    G   désigne le groupe CO, SO, SO2, PO2, PO3, ou C=NR2,
    X+   désigne un reste contenant un groupe cationique renfermant au moins un atome d'azote quaternisé,
    R, R1, R2,   désignent un atome d'hydrogène, un radical alkyle ou alkylsulfinyle renfermant de 1 à 6 atomes de carbone ;
    A-   désigne un anion.
  2. Matériaux photographiques aux halogénures d'argent selon la revendication 1, caractérisés en ce qu'ils contiennent des arylhydrazides de formule (Ia),

            Ph - NR - NR1 - G - X+ A-     (Ia)

    dans laquelle :
    Ph   désigne un groupe phényle substitué,
    G   désigne un groupe CO, SO, SO2, PO2,PO3 ou C=NR2,
    X+   désigne un reste contenant un groupe cationique renfermant au moins un atome d'azote quaternisé,
    R, R1, R2,   désignent un atome d'hydrogène, un radical alkyle ou alkylsulfinyle renfermant de 1 à 6 atomes de carbone,
    A-   désigne un anion.
  3. Matériaux photographiques aux halogénures d'argent selon la revendication 1 ou 2, caractérisés en ce qu'ils contiennent des arylhydrazides de formule (Ib)

            Ph- NR - NR1 - CO - X+ A-     (Ib)

    dans laquelle :
    Ph   désigne un groupe phényle substitué,
    X+   désigne un reste contenant un groupe cationique renfermant au moins un atome d'azote quaternisé,
    R, R1,   désignent un atome d'hydrogène, un radical alkyle ou alkylsulfinyle renfermant de 1 à 6 atomes de carbone;,
    A-   désigne un anion.
  4. Matériaux photographiques aux halogénures d'argent selon la revendication 1 à 3, caractérisés en ce qu'ils contiennent des arylhydrazides de formule (II),
    Figure imgb0054
     dans laquelle :
    R1 à R5   désignent des restes qui peuvent être identiques ou différents, au moins l'un d'entre eux cependant ne représentant pas un atome d'hydrogène, et qui peuvent être représentés par un atome d'hydrogène, un radical alkyle, hydroxyalkyle, un atome d'halogène, un radical haloalkyle, alkoxy, alkylamino, acylamino ou cycloalkyle aliphatique renfermant chacun de 1 à 20 atomes de carbone, aryle, aryloxy ou acylamino aromatique renfermant chacun de 6 à 10 atomes de carbone, aralkyle ou aralkoxy dont la chaîne alkyle renferme de 1 à 3 atomes de carbone ou un reste acylamino aliphatique renfermant de 1 à 4 atomes de carbone substitué par un seul reste phénoxy substitué par un seul ou le cas échéant par un ou plusieurs restes alkyle renfermant de 1 à 10 atomes de carbone,
    Q+   désigne un radical trialkylammonium, ou pyridinium-1-yle ou N-alkylpyridinium-m-yle, avec m = 2, 3, ou 4, ou thiazolinium-3-yle ou N-alkylthiazolinium-m-yle, avec m = 2, 4, ou 5 ,
    les cycles hétérocycliques pouvant être substitués par d'autres restes alkyles, et tous les groupes alkyles d'un reste Q+ étant identiques ou différents et/ou pouvant être substitués par des groupes hydroxyle ou des groupes acides sulfoniques, chaque groupe alkyle contenant au maximum 12 atomes de carbone, mais cependant, dans le cas d'un trialkylammonium, deux d'entre eux pouvant former avec l'azote quaternaire un cycle de 3 à 12 éléments,
    B   désigne un pont constitué de 1 à 3 groupes méthylène pouvant chacun être substitués par le radical méthyle ou éthyle, ou bien, lorsque Q+ représente un radical N-alkylpyridimium-m-yle ou N-alkylthiazolinium-m-yle, B peut aussi être constitué d'un seul atome d'oxygène ou d'une liaison simple.
    A-   désigne un anion qui disparaît lorsque Q+ contient un groupe sulfonique.
  5. Arylhydrazides de formule (II)
    Figure imgb0055
     dans laquelle :
    R1 à R5   désignent des restes qui peuvent être identiques ou différents, au moins l'un d'entre eux cependant ne représentant pas un atome d'hydrogène, et qui peuvent être représentés par un atome d'hydrogène, un radical alkyle, hydroxyalkyle, un atome d'halogène, un radical haloalkyle, alkoxy, alkylamino, acylamino ou cycloalkyle aliphatique renfermant chacun de 1 à 20 atomes de carbone, aryle, aryloxy ou acylamino aromatique renfermant chacun de 6 à 10 atomes de carbone, aralkyle ou aralkoxy renfermant de 1 à 3 atomes de carbone dans la chaîne alkyle ou un reste acylamino aliphatique renfermant de 1 à 4 atomes de carbone substitué par un seul reste phénoxy substitué par un seul ou le cas échéant par un ou plusieurs restes alkyle renfermant de 1 à 10 atomes de carbone,
    Q+   désigne un radical trialkylammonium, ou pyridinium-1-yle ou N-alkylpyridinium-m-yle, avec m = 2, 3, ou 4, ou thiazolinium-3-yle ou N-alkylthiazolinium-m-yle, avec m = 2, 4, ou 5 ,
    les cycles hétérocycliques pouvant être substitués par d'autres restes alkyles, et tous les groupes alkyles d'un reste Q+ étant identiques ou différents et/ou pouvant être substitués par des groupes hydroxyle ou des groupes acides sulfoniques, chaque groupe alkyle contenant au maximum 12 atomes de carbone, mais cependant, dans le cas d'un trialkylammonium, deux d'entre eux pouvant former avec l'azote quaternaire un cycle de 3 à 12 éléments,
    B   désigne un pont constitué de 1 à 3 groupes méthylène pouvant chacun être substitués par le radical méthyle ou éthyle, ou bien, lorsque Q+ représente un radical N-alkylpyridinium-m-yle ou N-alkylthiazolinium-m-yle, B peut aussi être constitué d'un seul atome d'oxygène ou d'une liaison simple.
    A-   désigne un anion qui disparaît lorsque Q+ contient un groupe sulfonique.
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

Publications (3)

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

Family

ID=25871544

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89115534A Expired - Lifetime EP0356898B1 (fr) 1988-08-27 1989-08-23 Matériaux photographiques aux halogénures d'argent contenant des arylhydrazides

Country Status (4)

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

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2899625B2 (ja) * 1989-05-19 1999-06-02 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
US5190847A (en) * 1990-02-26 1993-03-02 E. I. Du Pont De Nemours And Company Photographic silver halide materials containing aryl hydrazides
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
EP0569580A1 (fr) * 1991-12-02 1993-11-18 E.I. Du Pont De Nemours And Company Systemes revelateurs ameliores pour films contenant de l'hydrazine
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
DE4310327A1 (de) 1993-03-30 1994-10-06 Du Pont Deutschland Verfahren zur Erzeugung von Negativbildern mit ultrasteilem Kontrast
JP3136025B2 (ja) * 1993-03-31 2001-02-19 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
DE4311888A1 (de) * 1993-04-10 1994-10-13 Du Pont Deutschland Lichtempfindliches Silberhalogenid-Aufzeichnungsmaterial mit verminderter Druckempfindlichkeit
DE69326886T2 (de) * 1993-06-09 2000-03-30 Fuji Photo Film Co Ltd Photographisches Silberhalogenidmaterial
US5686222A (en) * 1994-05-24 1997-11-11 Ilford A.G. Dihydrazides
GB9410425D0 (en) * 1994-05-24 1994-07-13 Ilford Ag Novel bishydrazides
US5494776A (en) * 1994-05-24 1996-02-27 Minnesota Mining And Manufacturing Company Hybrid graphic arts films with reduced occurrence of pepper fog
US5415975A (en) 1994-05-24 1995-05-16 Minnesota Mining And Manufacturing Company Contrast-promoting agents in graphic arts media
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
DE69524304T2 (de) 1994-07-29 2002-07-25 Dainippon Ink & Chemicals Verfahren zur Herstellung von Negativbildern mit ultrahohem Kontrast und photographisches Silberhalogenidmaterial und Entwickler dafür
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

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE502879A (fr) * 1950-04-29
US2670348A (en) * 1952-06-10 1954-02-23 Du Pont Girard derivatives of 5-halosalicylaldehydes
DE1199612B (de) * 1964-03-05 1965-08-26 Agfa Ag Verfahren zur Stabilisierung photographischer Halogensilber-Emulsionen
US4031127A (en) * 1975-08-06 1977-06-21 Eastman Kodak Company Acyl hydrazino thiourea derivatives as photographic nucleating agents
GB1579956A (en) * 1976-06-07 1980-11-26 Fuji Photo Film Co Ltd Silver halide photographic image-forming process
JPS62275247A (ja) * 1986-02-28 1987-11-30 Mitsubishi Paper Mills Ltd 画像形成方法
GB8617335D0 (en) * 1986-07-16 1986-08-20 Minnesota Mining & Mfg Photographic light-sensitive systems
JPH0764132B2 (ja) * 1988-06-09 1995-07-12 株式会社日研化学研究所 老化回復処理液

Also Published As

Publication number Publication date
DE58909752D1 (de) 1997-01-09
US4937160A (en) 1990-06-26
EP0356898A3 (fr) 1991-08-07
US5013844A (en) 1991-05-07
EP0356898A2 (fr) 1990-03-07
JPH0650373B2 (ja) 1994-06-29
US5130480A (en) 1992-07-14
JPH02120736A (ja) 1990-05-08

Similar Documents

Publication Publication Date Title
EP0356898B1 (fr) Matériaux photographiques aux halogénures d'argent contenant des arylhydrazides
DE3041923C2 (fr)
EP0444506B1 (fr) Matériaux photographiques aux halogénures d'argent contenant des arylhydrazides
EP0011051B1 (fr) Matériel d'enregistrement photographique en couleurs, procédé pour sa stabilisation et préparation d'images photographiques en couleurs
DE2362752C2 (de) Einen photographischen Entwicklungsinhibitor abspaltende Verbindung und ihre Verwendung
DE2938535C2 (fr)
DE3144313C2 (fr)
DE2842063A1 (de) Lichtempfindliches farbphotographisches aufzeichnungsmaterial
DE2429892A1 (de) Verfahren zum entwickeln eines lichtempfindlichen photographischen silberhalogenidmaterials
EP0046871B1 (fr) Matériau photographique, procédé pour sa préparation, procédé pour la fabrication d'images photographiques ainsi que triazoles
EP0618491B1 (fr) Procédé de préparation d'images negatives à contraste très élevé
DE3337882A1 (de) Verfahren zum entwickeln von belichteten photographischen silberhalogenidmaterialien
DE3117890A1 (de) Fotografisches, lichtempfindliches silberhalogenidmaterial
DE3438249A1 (de) Photographisches silberhalogenidmaterial
EP0002476B1 (fr) Matériel photographique et bains de traitement photographique contenant un agent de stabilisation ainsi qu'un procédé pour la fabrication d'images photographiques en présence d'un agent de stabilisation
DE3439870C2 (de) Verfahren zur Herstellung eines Bildes
DE3829078C2 (fr)
EP0001415B1 (fr) Procédé photographique d'inversion par voilage chimique, bains de voilage chimique et leur emploi pour obtenir des images photographiques
DE4042595C2 (de) Arylhydrazide
EP0378831A1 (fr) Emulsion photographique à l'halogènure d'argent
EP0023661B1 (fr) Emulsion photographique d'halogénure d'argent contenant un stabilisant, son procédé de fabrication, matériau d'enregistrement photographique et procédé de réalisation d'images photographiques
DE2212550A1 (de) Verwendung von Azotriazolen und Azotetrazolen als Antischleier- und Antispotmittel und selektive Desensibilisatoren in photographischen Halogensilberemulsionen und in photographischen Baedern,sowie diese Verbindungen enthaltendes photographisches Aufzeichnungsmaterial
DE4006032A1 (de) Arylhydrazide enthaltende photographische silberhalogenidmaterialien
EP0740194B1 (fr) Matériau d'enregistrement à l'halogénure d'argent pour la préparation des images négatives ayant un contraste très haut
DE3001498A1 (de) Fotografisches material mit einem stabilisierungsmittel, verfahren zu dessen herstellung, ein entwicklungsverfahren, neue pyrazole, ein verfahren zu deren herstellung sowie zwischenprodukte

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19901210

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE CH DE ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19921223

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: E.I. DU PONT DE NEMOURS AND COMPANY

Owner name: DU PONT DE NEMOURS (DEUTSCHLAND) GMBH

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE ES FR GB IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19961127

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19961127

RHK1 Main classification (correction)

Ipc: G03C 1/10

ET Fr: translation filed
REF Corresponds to:

Ref document number: 58909752

Country of ref document: DE

Date of ref document: 19970109

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19970227

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19970214

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970821

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970831

Ref country code: BE

Effective date: 19970831

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
BERE Be: lapsed

Owner name: E.I. DU PONT DE NEMOURS AND CY

Effective date: 19970831

Owner name: DU PONT DE NEMOURS (DEUTSCHLAND) G.M.B.H.

Effective date: 19970831

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980823

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19980823

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20030619

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20030620

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050429

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050823