EP0262504A2 - Préparation de matériaux photographiques multicouches - Google Patents

Préparation de matériaux photographiques multicouches Download PDF

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Publication number
EP0262504A2
EP0262504A2 EP87113451A EP87113451A EP0262504A2 EP 0262504 A2 EP0262504 A2 EP 0262504A2 EP 87113451 A EP87113451 A EP 87113451A EP 87113451 A EP87113451 A EP 87113451A EP 0262504 A2 EP0262504 A2 EP 0262504A2
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EP
European Patent Office
Prior art keywords
layer
layers
gelatin
color
emulsion
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
Application number
EP87113451A
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German (de)
English (en)
Other versions
EP0262504B1 (fr
EP0262504A3 (en
Inventor
Dipl.-Ing. Lalvani
Diethart Dr. Lademann
Hans Dr. Buschmann
Heinz Dr. Reif
Walther Dr. Cohnen
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.)
Agfa Gevaert AG
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Agfa Gevaert AG
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Publication date
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Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0262504A2 publication Critical patent/EP0262504A2/fr
Publication of EP0262504A3 publication Critical patent/EP0262504A3/de
Application granted granted Critical
Publication of EP0262504B1 publication Critical patent/EP0262504B1/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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives

Definitions

  • the invention relates to the production of a multilayer photographic material with an intermediate layer which contains certain polymer particles.
  • photographic recording materials which consist of several layers can often not be produced in one operation, but that the layers are applied to the support material in at least two operations. You can apply single layers as well as layers of layers from several layers in one step.
  • the top layer of each layer package applied in one operation usually contains a hydrophilic binder, for example gelatin, a wetting agent and, if appropriate, alkali, a plasticizer, dyes and colloidal silver.
  • the photographic materials are dried and wound up before they are provided with the next shift or the next shift package.
  • the rolled-up semi-finished products tend to stick to one another and thus cause stains on the recording material.
  • matting agents in intermediate layers with acid-treated gelatin, which are top layers during the manufacture, organic or inorganic materials with a particle size of about 0.2 to 5 ⁇ m being insoluble in water. Since there are differences in the refractive index between these particles and the gelatin, there is increased light scattering on this particle, which leads to increased granularity (DE-A-2 526 970).
  • the invention is therefore based on the object of developing intermediate layers in which the top layer of a first coating step is avoided when all layers are applied in at least two coating steps, and also the static layer Friction is reduced.
  • the other properties important in film technology, in particular the sensitometric properties, should not be adversely affected.
  • a process has now been found for producing a multilayer photographic material, in which the layers are applied in at least two work steps and the material is dried and wound up between the work steps, in which the aforementioned disadvantages are avoided, which is characterized in that the top layer of the first step contains alkali-soluble polymer particles with an average particle diameter of 0.2 to 5.0 ⁇ m.
  • the particle diameter is preferably 0.5 to 3.0 ⁇ m.
  • compositions are selected so that the particles are insoluble in water at pH below 5 and soluble in water at pH above 7.
  • the layer containing the alkali-soluble polymer particles can also contain conventional additives such as hydrophilic binders, for example gelatin, preferably alkaline-ashed gelatin, wetting agents, preferably surface-active organic fluorine compounds, formalin scavengers, plasticizers, colloidal silver and dyes.
  • hydrophilic binders for example gelatin, preferably alkaline-ashed gelatin, wetting agents, preferably surface-active organic fluorine compounds, formalin scavengers, plasticizers, colloidal silver and dyes.
  • the polymer particles are usually applied in an amount of 20 to 200 mg / m2 of photographic material, in particular 50 to 120 mg / m2 of photographic material. They are added to the corresponding casting solution as an aqueous dispersion.
  • the addition of the polymer particles mentioned avoids the adhesive spots, a reduction in the static coefficients of friction and a reduction in the exposures caused by static discharges, the photographic properties of the multilayer photographic material, in particular grain size and sharpness, not being influenced.
  • the method according to the invention can be used for the production of all multilayer photographic materials, in which the layers are applied in at least two work steps, for example for the production of negative and reversal films and photo paper, but in particular for color negative film and color reversal film. If the layers are applied in more than two work steps, the measure according to the invention can be used several times.
  • the photographic materials produced according to the invention can be exposed in the manner customary for them and processed using the processes customary for this.
  • the alkali-soluble matting agents to be used according to the invention are dissolved out of the photographic material by the alkaline developers, so that it thereafter light scatter from these particles can no longer occur due to different refractive indices of polymer and gelatin. Surprisingly, no pores remain in the material, which in turn could cause negative effects.
  • Photographic, in particular color photographic, recording materials to which the method of the present invention can advantageously be applied are preferably multilayer materials which have a plurality of silver halide emulsion layers or emulsion layer units with different spectral sensitivity.
  • Emulsion layer units are understood to mean laminates of 2 or more silver halide emulsion layers of the same spectral sensitivity.
  • Layers of the same spectral sensitivity do not necessarily have to be arranged adjacent to one another, but can also be separated from one another by other layers, in particular also by layers of different spectral sensitivity.
  • the binder in these layers is usually a protein-like binder with free carboxyl groups and free amino groups, preferably gelatin.
  • the layer binder can contain up to 50% by weight of non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives.
  • non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives.
  • the light-sensitive silver halide emulsion layers or emulsion layer units is at least one coloring compound, usually assigned a color coupler, which is able to react with color developer oxidation products to form a non-diffusing dye.
  • the color couplers are expediently non-diffusing and accommodated in the light-sensitive layer itself or in close proximity to it.
  • the color couplers assigned to the two or more partial layers of an emulsion layer unit do not necessarily have to be identical. They are only intended to give the same color in color development, usually a color that is complementary to the color of the light to which the photosensitive silver halide emulsion layers are sensitive.
  • the red-sensitive silver halide emulsion layers are consequently assigned at least one non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthol type.
  • a coupler of the phenol or ⁇ -naphthol type usually a coupler of the phenol or ⁇ -naphthol type.
  • Particularly noteworthy are, for example, cyan couplers as described in US-A 2,474,293, US-A 2,367,531, US-A-2,895,826, US-A 3,772,002, EP-AO 028 099, EP-AO 112 514.
  • the green-sensitive silver halide emulsion layers contain at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used. Cyanoacetyl compounds, oxazolones and pyrazoloazoles are also suitable as magenta couplers. Of particular note are, for example, purple couplers as described in US-A-2,600,788, US-A-4,383,027, DE-A-1,547,803, DE-A 1,810,464, DE-A 24 08 665, DE-A- 32 26 163.
  • the blue-sensitive silver halide emulsion layers contain at least one non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
  • Yellow couplers as described in US-A-3 408 194, US-A-3 933 501, DE-A-23 29 587, DE-A-24 56 976, are particularly noteworthy.
  • Color couplers of these types are known in large numbers and are described in a large number of patents. Examples include the publications “Color Coupler” by W. Pelz, “Messages from the Research Laboratories of AGFA, Leverkusen / Kunststoff", Volume III (1961) p. 111, and by K. Venkataraman in “The Chemistry of Synthetic Dyes” , Vol. 4., 341 to 387, Academic Press (1971).
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. As is known, the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling.
  • the 2-equivalent couplers include both those that are practically colorless and those that have an intense intrinsic color that the Color coupling disappears or is replaced by the color of the image dye generated (mask coupler).
  • the known white couplers are also to be counted among the 2-equivalent couplers, but they essentially result in colorless products on reaction with color developer oxidation products.
  • the 2-equivalent couplers are also those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and which either directly or after one or more further groups have been cleaved from the primarily cleaved residue (eg DE-A-27 03 145, DE-A 28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.
  • Suitable DIR couplers are described, for example, in GB-A-953 454, DE-A-1 800 420, DE-A 20 15 867, DE-A-24 14 006, DE-A-28 42 063, DE-A- 34 27 235.
  • Suitable DAR or FAR couplers are described, for example, in DE-A-32 09 110, EP-A-O 089 834, EP-A-0 117 511, EP-A-O 118 087.
  • DIR, DAR or FAR couplers Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, are also such DIR, DAR or FAR couplers are suitable which, when coupled, result in essentially colorless products, as described, for example, in DE-A 1 547 640.
  • the cleavable residue can also be a ballast residue, so that when reacting with color developer oxidation products coupling products e.g. Dyes can be obtained which are diffusible or at least have a weak or restricted mobility, as described, for example, in US Pat. No. 4,420,556.
  • High molecular weight color couplers are described for example in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A- 33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
  • the high molecular weight color couplers are generally produced by polymerizing ethylenically unsaturated monomeric color couplers . However, they can also be obtained by polyaddition or polycondensation.
  • the layers can contain further additives, for example hardening agents, antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
  • the layers can also contain compounds absorbing UV light.
  • Carboxyl group-activating curing agents are preferably used, in particular those of the general formula wherein R1 and R2 are an alkyl group having 1 to 8 carbon atoms or an aryl or aralkyl group optionally substituted with an alkyl group with 1 or 2 carbon atoms or with a halogen atom, or together to complete an optionally with an alkyl group with 1 or 2 carbon atoms or with a halogen atom substituted heterocyclic ring required atoms, R3 is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms and n is 0 or 2.
  • a color photographic recording material for reverse color development was produced by the on a transparent layer of cellulose triacetate following layers were applied in the order given, namely layers 1 and 2, layers 3 to 6, layers 7 to 10, layers 11 to 14 together and then layer 15.
  • the quantities given relate to 1 m2.
  • the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • Intermediate layer 0.4 g gelatin 0.1 g hydroxypropylmethyl cellulose hexahydrophthalate (alkali-soluble) with an average particle diameter of 2.0 ⁇ m.
  • the described partial layer structures (layers 1-6) were tested for sliding properties and surface resistance.
  • UV absorber layer 1.5 g gelatin 0.8 g of compound UV-1
  • the breaking strength, granularity and sharpness of the finished layers were measured.
  • the stain load was assessed visually and given in percent load.
  • the parallel breaking strength was characterized by the parameters breaking diameter [mm] and breaking strength [N].
  • breaking diameter is the inner diameter of the loop
  • breaking force is the force with which the two jaws act on the loop at the moment when the loop breaks along the perforation line.
  • Granularity RMS granularity described in SPSE Handbook of Photografic science and Engineering 1973, p. 935, measuring aperture 48 ⁇ m.
  • M-1 coupler 7 from US-A-2,000,788 Y-1 coupler 16 from US-A-3,933,501 WM-1 commercially available aqueous dispersion of an anionic modified polyurethane
  • a color photographic recording material for the color negative development was produced by applying a transparent layer of cellulose triac did the following layers were applied in the order listed; namely layers 1 and 2, layers 3 to 5, layers 6 to 9, layers 10 to 13 together and finally layer 14 were applied.
  • the quantities given relate to 1 m2.
  • the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • (2nd green-sensitized layer) green-sensitized silver bromide iodide emulsion from 1.5 g AgNO3 (mixture of 70% by weight of an emulsion with 7 mol% of iodide, average particle diameter of 0.8 ⁇ m and narrow particle size distribution and 30% by weight of an emulsion with 10 mol% of iodide, average particle diameter of 0.8 ⁇ m and broad particle size distribution), 1.7 g gelatin and 0.2 g coupler M2, emulsified with 0.2 g tricresyl phosphate
  • UV absorber layer 1.5 g gelatin and 0.8 g of compound UV-1

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Laminated Bodies (AREA)
EP87113451A 1986-09-27 1987-09-15 Préparation de matériaux photographiques multicouches Expired - Lifetime EP0262504B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3632914 1986-09-27
DE19863632914 DE3632914A1 (de) 1986-09-27 1986-09-27 Herstellung eines mehrschichtigen fotografischen materials

Publications (3)

Publication Number Publication Date
EP0262504A2 true EP0262504A2 (fr) 1988-04-06
EP0262504A3 EP0262504A3 (en) 1990-08-08
EP0262504B1 EP0262504B1 (fr) 1992-09-02

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ID=6310514

Family Applications (1)

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EP87113451A Expired - Lifetime EP0262504B1 (fr) 1986-09-27 1987-09-15 Préparation de matériaux photographiques multicouches

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EP (1) EP0262504B1 (fr)
JP (1) JPS6389847A (fr)
DE (2) DE3632914A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2681163B2 (ja) * 1988-07-07 1997-11-26 コニカ株式会社 ハロゲン化銀カラー写真感光材料
JPH0255350A (ja) * 1988-08-22 1990-02-23 Konica Corp 画像パターン転写に使用するハロゲン化銀写真乾板

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3424893A1 (de) * 1984-07-06 1986-02-06 Agfa-Gevaert Ag, 5090 Leverkusen Photographisches silberhalogenidaufzeichnungsmaterial

Also Published As

Publication number Publication date
DE3632914A1 (de) 1988-03-31
EP0262504B1 (fr) 1992-09-02
EP0262504A3 (en) 1990-08-08
JPS6389847A (ja) 1988-04-20
DE3781490D1 (de) 1992-10-08

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