EP0589323B1 - Matériau photographique couleur à l'halogénure d'argent - Google Patents

Matériau photographique couleur à l'halogénure d'argent Download PDF

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Publication number
EP0589323B1
EP0589323B1 EP93114677A EP93114677A EP0589323B1 EP 0589323 B1 EP0589323 B1 EP 0589323B1 EP 93114677 A EP93114677 A EP 93114677A EP 93114677 A EP93114677 A EP 93114677A EP 0589323 B1 EP0589323 B1 EP 0589323B1
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EP
European Patent Office
Prior art keywords
silver halide
mmol
mol
colour photographic
material according
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
EP93114677A
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German (de)
English (en)
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EP0589323A1 (fr
Inventor
Otto Dr. Lapp
Jörg Dr. Siegel
Klaus Dr. Wagner
Alfred Dr. Mitschker
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
    • 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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • 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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • G03C2001/0157—Ultrafiltration

Definitions

  • the invention relates to a low-silver color photographic silver halide material improved sensitivity and with faster development kinetics for short-term processing.
  • the photographic sensitivity of a color photographic material is in the mainly due to the silver halide grains, the most important influencing factors Grain size, grain shape and halide composition are. Another one an important criterion is the coverage of the silver halide grains with adsorbent dyes that the grains beyond the inherent sensitivity for sensitize the green and red spectral range. Although mostly that The grain surface is only partially covered with a sensitizer Adding another sensitizer does not increase sensitivity. It occurs rather, often even a decrease in sensitivity.
  • the developmental kinetics of a photographic material largely depend on the Halide composition of the emulsions.
  • Emulsions rich in silver chloride excel e.g. characterized by high developmental kinetics, but can photographic materials due to sensitivity not to relative high proportions of silver bromide and silver iodide can be dispensed with.
  • the Developmental kinetics of a photographic layer also depends on the amount of from the base applied emulsion. The lower the order, the faster develops the layer. On the other hand, there is a reduction in the silver order with a Decrease in gradation and also usually with a decrease in sensitivity connected.
  • the object of the invention was to find materials that are as low as possible Silver halide application have an improved sensitivity without Grain shape, grain size and halide composition change.
  • Another object of the invention was to find a recording material for a short-term development is advantageous.
  • the amount of chloride and bromide that can be washed out is determined as follows:
  • any existing back layers were first removed mechanically down to the cellulose base. Then a 10 cm 2 perforation-free sample was punched out. This sample was washed with 20 ml of deionized water in an airtight Erlenmeyer flask for 3 hours at 25 ° C. on a shaking table. The aqueous extract was then filtered through a chloride-free sterile filter and introduced into an ion chromatograph with an injection volume of 100 ⁇ l.
  • the silver halide deposits of the examined film materials were titrimetrically included determined by the thioacetamide method.
  • the anions that could be washed out were then in mmol of halide per mol of silver halide specified.
  • the invention thus relates to a color photographic silver halide material with a support and coated thereon with at least one blue-sensitive, yellow-coupling silver halide emulsion layer, at least one red-sensitive, blue-green coupling silver halide emulsion layer and at least one green-sensitive, purple-coupling silver halide emulsion layer, characterized in that the total amount of chloridide which can be leached out is less than 25 mmol of bromide and bromide / mol of silver halide, preferably less than 20 mmol / mol of silver halide and the amount of silver halide, measured in g AgNO 3 / m 2 , is less than 10, preferably less than 7.5
  • the silver halide here is the sum of photosensitive and, if appropriate understood non-photosensitive silver halide.
  • the latter is for example especially fine-grained silver halide (micrate emulsion), which does not cause dye formation is used.
  • the spectral color sensitivities used as sensitizers cyanine dyes before all from the classes of oxa, thia and imidacarbo- and dicarbocyanines, their Reduction potential, measured with the Ag / AgCl electrode, between -0.8 and -1.3V, preferably between -0.9 and -1.2V.
  • the amount of each The sensitizer used is in particular between 0.1 and 2 mmol / mol sensitized silver halide, preferably between 0.2 and 1 mmol / mol silver halide, very particularly preferably between 0.4 and 1 mmol / mol therewith sensitized silver halide.
  • Suitable sensitizers are, for example R 1 R 2 R 3 R 4 S-9 Cl Cl (CH 2 ) 3 SO 3 (-) (CH 2 ) 3 SO 3 (-) (CH 3 ) 3 NH (+) S-10 Cl Cl (CH 2 ) 4 SO 3 (-) C 2 H 5 S-11 Cl Cl (CH 2 ) 2 CH (CH 3 ) SO 3 (-) C 2 H 5 S-12 CH 3 Cl (CH 2 ) 3 SO 3 (-) C 2 H 5 S-13 CH 3 CH 3 (CH 2 ) 3 SO 3 (-) (CH 2 ) 3 SO 3 (-) K (+) S-14 CH 3 CH 3 (CH 2 ) 3 SO 3 (-) C 2 H 5 R 1 R 2 R 3 R 4 R 5 R 6 S-18 CN H CN H (CH 2 ) 4 SO 2 N (-) COCH 3 C 2 H 5 S-19 Cl Cl Cl Cl (CH 2 ) 2 CH (CH 3 ) SO 3 (-) C 2 H 5 S-20 CF 3 Cl CF 3 Cl (CH 2 ) 3 SO 3
  • Color photographic materials according to the invention show another surprising one Advantage. They have the same amount of sensitizer and a reduced proportion soluble chloride and bromide a faster development kinetics in Kurzwit processing.
  • the silver halide as a light-sensitive component in the photographic material can be chloride, bromide or iodide or mixtures thereof as halide contain.
  • the halide content of at least one layer can be 0 to 15 mol% from iodide, from 0 to 100 mol% from chloride and from 0 to 100 mol% Bromide exist.
  • silver bromide iodide emulsions in the case of color negative and color reversal paper usually silver chloride bromide emulsions with a high chloride content up to used for pure silver chloride emulsions. It can be mostly compact Act crystals that e.g.
  • the diameter of a grain is defined as the diameter of a circle with a Circle content according to the projected area of the grain.
  • the aspect ratio can range up to 20 and beyond.
  • the silver halide grains can also have a multi-layered grain structure have, in the simplest case with an inner and an outer com area (core / shell), the halide composition and / or other modifications, such as. Doping of the individual grain areas are different.
  • the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be both homodisperse and heterodisperse. Homodisperse Grain size distribution means that 95% of the grains do not exceed ⁇ 30% deviate from the average grain size.
  • the emulsions can next to the Silver halide also contain organic silver salts, e.g. Silberbenztriazolat or Silver behenate.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glaffkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Phtographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikmann et al, Making and Coating Phtographic Emulsion, The Focal Press, London (1966) can be prepared from soluble silver salts and soluble halides.
  • the silver halide is preferably precipitated in the presence of the binder, e.g. the gelatin and can be in the acidic, neutral or alkaline pH range be carried out, preferably silver halide complexing agent additionally be used.
  • the latter include e.g. Ammonia, thioether, imidazole, Ammonium thiocynate or excess halide.
  • the merger of the water-soluble silver salts and the halides are optionally carried out in succession the single-jet or at the same time according to the double-jet process or any Combination of both methods.
  • the dosage is preferred with increasing Inflow rates, being the "critical" feed rate at which just about none New germs arise, should not be exceeded.
  • the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method in which a certain pAg value is constant is held or a defined pAg profile is traversed during the precipitation.
  • the preferred precipitation in the case of excess halide is also the so-called inverse Precipitation possible with excess of silver ions.
  • the silver halide crystals also through physical ripening (Ostwald ripening), in the present grow from excess halide and / or silver halide complexing agent.
  • the growth of the emulsion grains can even predominantly through Oswald ripening take place, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter becomes.
  • the silver halide grains can also salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe to be available.
  • metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe to be available.
  • the precipitation can also be carried out in the presence of sensitizing dyes.
  • Complexing agents and / or dyes can be used at any time render ineffective, e.g. by changing the pH or by an oxidative Treatment.
  • the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flaking and washing, by ultrafiltration or by ion exchange. According to the removal of the salts is carried out so that the below the upper limits of the chloride and bromide concentration will.
  • the silver halide emulsion generally undergoes chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and Sensitizer concentration - until the sensitivity and Subject to optimum veils.
  • the procedure is e.g. with H. frieser "Die Fundamentals of the Phtographic Processes with Silver Halides "Page 675-734, Academic publishing company (1968).
  • the chemical sensitization with the addition of compounds of Sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (e.g. gold, platinum, palladium, iridium) continue to occur can thiocyanate compounds, surface-active compounds, such as thioethers, heterocyclic nitrogen compounds (e.g. imidazoles, azaindenes) or also spectral sensitizers (described e.g. by F. Hamer "The Cyanine Dyes and Related Compounds ", 1964, or Ullmann's encyclopedia or technical chemistry, 4th edition, vol. 18, p. 431 ff. And Research Disclosure 17643 (Dec. 1978), Chapter III) be added.
  • thiocyanate compounds e.g. gold, platinum, palladium, iridium
  • surface-active compounds such as thioethers
  • heterocyclic nitrogen compounds e.g. imidazoles, azaindenes
  • a reduction sensitization can with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, Amonioborane, Silane, Formamidinsulfinklare) by hydrogen, by low pAg (e.g. less than 5) and / or high pH (e.g. above 8).
  • reducing agents titanium-II salts, amines, hydrazine derivatives, Amonioborane, Silane, Formamidinsulfinklare
  • the photographic emulsions can be used to prevent fog or to stabilize the photographic function during production, storage or photographic processing.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Furthermore, salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzosulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
  • metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzosulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
  • Heterocycles containing mercapto groups for example mercaptobenzthiazoles, seacaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • mercaptobenzthiazoles seacaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
  • water-solubilizing group for example a carboxyl group or sulfo group.
  • the stabilizers can the silver halide emulsions before, during or after their maturation are added. Of course you can also do the connections other photographic layers associated with a halogen silver layer clog.
  • Preferred stabilizers come from the compound classes of the azaindenes, Imidazoles, triazoles, tetrazoles, thiazoles and their mercapto compounds and are used in amounts of 0.2-2 mmol per mol of silver halide.
  • the photographic emulsion layers or other hydrophilic colloid layers of the Photosensitive material produced according to the invention can be surface-active Contain agents for various purposes, such as coating aids, to prevent the electrical charging, to improve the sliding properties, to emulsify the Dispersion, to prevent adhesion and to improve the photographic Characteristics (e.g. acceleration of development, high contrast, sensitization etc.).
  • surface-active compounds e.g. Saponin
  • surfactants Use: non-ionic surfactants, e.g. Alkylene oxide compounds, glycerol compounds or Glycidol compounds, cationic surfactants, e.g.
  • alkylamines quaternary Ammonium salts, pyridine compounds and other heterocyclic compounds, Containing sulfonium compounds or phosphonium compounds, anionic surfactants an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters an amino alcohol.
  • anionic surfactants an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric acid ester or phosphoric acid ester group
  • ampholytic surfactants e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters an amino alcohol.
  • a color photographic recording material was produced by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application. All silver halide emulsions per 100 g of AgNO 3 were stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • Em 1 is manufactured according to EP-A-152822
  • Em 4 is manufactured according to EP-A-6543.
  • Em 2 and Em4 are produced in that (a) initially a germ precipitation with 2 to 20 mol% AgI at 30 to 50 ° C and pBr 1.2 to 2.3 formed by double entry, (b) in the growth phase silver ions as well as bromide and iodide in a ratio added, which lies within the AgBrI mixture gap, and (c) at least Another silver halide layer is noticed, the iodide content below 20 mol% is.
  • Example 1 was repeated, but the emulsions were treated empirically to such an extent before the stabilization that the amount of chloride and bromide which could be washed out fell below the value of 20 mmol / mol of silver halide. A different method was used for each color package to demonstrate the performance of the different methods. In addition to the individual results of the layer packs, the content of chloride and bromide that can be washed out of the finished material was determined (Table 1). Leachable chloride + bromide (mmol / mol AgX) Example 1 Ex. 2 method Layers 3 and 4 (cyan package) 32 15 Layers 6 and 7 (purple package) 32 15 Layers 10 and 11 (yellow package) 30th 20th Total material 32 16
  • Example 2 The materials of Examples 1 and 2 were subjected to short-term developments (60, 90, 125 s) in the CN process AP 70 / C 41 at 38 ° C and sensitivity (0.2 via fog) and fog were determined (Table 2). The measured values for sensitivity and fog were set to 100 for the comparative example at 90 ss development time.
  • Example 3 All castings of Example 3 were developed in the CN process AP 70 / C 41 195 s at 38 ° C and then bleached, fixed, washed and dried in the usual way. The measured values for sensitivity and fog are entered in Table 3.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (7)

  1. Matériau de photographie couleur aux halogénures d'argent comportant un support et, appliquées sur ce support, au moins une couche d'émulsion d'halogénure d'argent sensible au rouge avec un coupleur de cyan, au moins une couche d'halogénure d'argent sensible au vert avec un coupleur de magenta et au moins une couche d'émulsion d'halogénure d'argent sensible au bleu avec un coupleur de jaune, caractérisé en ce que la quantité totale de bromure et de chlorure extractibles à l'eau est inférieure à 25 mmol/mol d'halogénure d'argent, de préférence inférieure à 20 mmol/mol d'halogénure d'argent, et la quantité appliquée d'halogénure d'argent, mesurée en g d'AgNO3/m2, est inférieure à 10, de préférence inférieure à 7,5.
  2. Matériau de photographie couleur aux halogénures d'argent selon la revendication 1, caractérisé en ce que l'on utilise comme sensibilisateurs spectraux des colorants de type cyanine dont le potentiel de réduction, mesuré avec l'électrode Ag/AgCl, est compris entre -0,8 et -1,3 V, de préférence entre -0,9 et -1,2 V.
  3. Matériau de photographie couleur aux halogénures d'argent selon la revendication 1, caractérisé en ce que la quantité de sensibilisateurs spectraux utilisés est de 0,1 à 2 mmol/mol, de préférence de 0,2 à 1 mmol/mol d'halogénure d'argent.
  4. Matériau de photographie couleur aux halogénures d'argent selon la revendication 1, caractérisé en ce que la quantité totale réduite de chlorure et de bromure extractibles à l'eau est obtenue par ultrafiltration ou échange d'ions des solutions de coulée ou de préférence des émulsions.
  5. Matériau de photographie couleur aux halogénures d'argent selon la revendication 1, caractérisé en ce qu'il contient, par mole d'halogénure d'argent, 0,2 à 2 mmol, de préférence 0,4 à 1 mmol de stabilisants des classes de composés des azaindènes, des imidazoles, des triazoles, des tétrazoles, des thiazoles et des composés mercapto correspondants.
  6. Matériau de photographie couleur aux halogénures d'argent selon la revendication 1, caractérisé en ce que le pH de la solution de coulée est supérieur à 6,5, de préférence supérieur à 7,5.
  7. Matériau de photographie couleur aux halogénures d'argent selon la revendication 1, caractérisé en ce que, dans au moins une couche d'émulsion d'halogénure d'argent, sont introduites des émulsions à cristaux d'halogénure d'argent en plaquettes ayant un rapport d'aplatissement supérieur à 5, de préférence supérieur à 7.
EP93114677A 1992-09-24 1993-09-13 Matériau photographique couleur à l'halogénure d'argent Expired - Lifetime EP0589323B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4231770 1992-09-24
DE4231770A DE4231770A1 (de) 1992-09-24 1992-09-24 Farbfotografisches Silberhalogenidmaterial

Publications (2)

Publication Number Publication Date
EP0589323A1 EP0589323A1 (fr) 1994-03-30
EP0589323B1 true EP0589323B1 (fr) 1998-04-01

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EP93114677A Expired - Lifetime EP0589323B1 (fr) 1992-09-24 1993-09-13 Matériau photographique couleur à l'halogénure d'argent

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EP (1) EP0589323B1 (fr)
JP (1) JPH06208204A (fr)
DE (2) DE4231770A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3738834A (en) * 1971-04-22 1973-06-12 Addressograph Multigraph Method of preparing silver halide emulsions and image processes usingsame
US4036643A (en) * 1973-06-11 1977-07-19 Gaf Corporation Diffusion transfer color process using lactone or sultone ring containing lipophilic non-diffusing color formers which yield diffusing dyes
DE3539845A1 (de) * 1985-11-09 1987-05-14 Agfa Gevaert Ag Verfahren und vorrichtung zur herstellung fotografischer silberhalogenidemulsionen
JP2579689B2 (ja) * 1989-11-06 1997-02-05 富士写真フイルム株式会社 ハロゲン化銀写真乳剤

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EP0589323A1 (fr) 1994-03-30
DE4231770A1 (de) 1994-03-31
JPH06208204A (ja) 1994-07-26
DE59308335D1 (de) 1998-05-07

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