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
  • G03C1/30—Hardeners

Definitions

• ABSTRACT Foreign Application Priority Data
• a hexahydro-l,3,5-triazine 52 us. c1. ..96/lll, 260/117, 106/125 carrying a! least two N-vinylcarbonyl or y 511 Im. 01. ..G03c 1/30 sulphonyl groups.
• mucochloric or mucubromic acid is 581 Field 61 Search ..96/1 11; 260/117; 106/125 described
• the hardening of e gelatin layer is rapid without loss of permeability to processing solutions and with no after-hardening occurring.
• the present invention relates to an improved method of hardening photographic gelatin layers and silverhalide emulsion layers containing gelatin as binder.
• aldehydes such as formaldehydes, dialdehydes, diketones such as divinylketone, halogen substituted aldehyde acids such as mucochloric and mucobromic acid, hexahydro-s-triazines carrying vinylcarbonyl, halogenoacetyl and/or acyl groups such as l,3,S-triacryloylhexahydro-l,3,5triazine, 1,3- diacryloyl-S -acetyl-hexahydrol ,3 ,S-triazine, 1,3 ,5 trichloroacetyl-hexahydro-l,3,5-triazine, compounds carrying one or more vinylsulphonyl groups such as divinyl sulphone, 1,3,5-trivinylsulphonyl benzen
• Formaldehyde as well as mucochloric acid show a poor compatibility with photographic color emulsions in that the excess of hardener that has not or not yet reacted with the gelatin shows a strong interaction with the color developer and/or the color forming couplers, particular with the 2-pyrazolin-5-one magenta-forming couplers and the benzoylacetanilide yellow-forming color couplers resulting in a reduction of the color density and the formation of undesirable color fog.
• the organic compounds carrying one or more vinylcarbonyl or vinylsulphonyl groups often give rise to the formation of fog, a loss in sensitivity and flattening of gradation probably owing to their reducing effect on the silver halide and to their rather slow hardening action the maximum hardening being reached only months after coating, so that the sensitometric characteristics of photographic silver halide materials comprising said compounds as hardening agents, vary upon storing which is most undesirable.
• halogen substituted aldehyde acids such as mucochloric acid and mucobromic acid
• hydrogenated diazines and triazines such as piperazine, hexahydropyrimidine, hexahydropyridazine and hexahydro-l,3,5-triazine carrying at least two N-vinylsulphonyl or N-vinylcarbonyl substitutents including such hydrogenated diazines and triazines carryingv further substituents.
• perhydrodiazine and perhydrotriazine derivatives suitable for use in accordance with the invention with halogenated aldehyde acids as well as methods for the preparation of said derivatives can be found in German Pat. Nos. 872,153 and 1,090,427.
• l,3,5-triacryloyl-hexahydrotriazine and 1,3 ,5-trivinyl-sulphonyl-hexahydrotriazine are preferred.
• the hardening agents applied in accordance with the invention are used in a ratio of halogenated aldehyde acid to perhydro diazine or triazine derivative comprised between 5:l-0.5:l, preferably between 3:1-1 :1.
• the total amount of hardening agents used in the photographic gelatin layers may vary within wide limits dependent upon the degree of hardness desired.
• the said amount of hardening agents is generally comprised between about 0.5 and about 3 percent based on the dry weight of the gelatin.
• the compounds are incorporated into the photographic gelatin layers e.g. a gelatino silver halide emulsion layer from a solution in a suitable solvent such as methanol, ethanol, ethylene glycol monomethyl ether, etc. which does not adversely effect the sensitive photographic emulsion; the hardeners are incorporated into the gelatin layers preferably prior to coating.
• photographic gelatin layers there is not only meant photographic gelatino silver halide emulsion layers but all kinds of gelatin layers that are used in the composition of a photographic material such as backing or anti-halation layers, protective coatings, filter layers, etc.
• the combination of hardeners of use according to the present invention has no detrimental effect on the sensitometric characteristics of the photographic lightsensitive material. Moreover, there is no interaction between the hardening agents and other addenda such as color couplers, sensitizers, stabilizers, etc.
• the combination of hardeners according to the present invention is of particular value for the hardening of photographic multilayer color materials wherein the color forming couplers are present in a diffusion fast form in the emulsion layers of said material or in gelatin layers in water-permeable relationship with said emulsion layers.
• EXAMPLE 1 A silver bromoiodide gelatin emulsion comprising g of gelatin per kg is adjusted to pH 6.2 and then di- 1 determined as compared with materials that have been stored under deep-freeze conditions (C).
• the values of AS are log It values and a value of AS 0.30 means that the sensitivity has decreased with 50 percent.
• the material hardened according to the present invention showed better resistance to moisture than the material hardened with mucochloric acid alone.
• the material After exposure and processing, the material is free from fog and shows, as compared with unhardened material, practically no loss in gradation and speed.
• the hardened material further shows an excellent stability on storing in that the photographic properties remain unchanged.
• EXAMPLE 3 A series of identical photographic multilayer color materials are prepared which materials comprise a support, a red-sensitized silver halide emulsion layer containing a cyan color former, a green-sensitized emulsion layer containing a magenta color former, a yellow filter layer and a blue-sensitive silver halide emulsion layer containing a yellow color former.
• the emulsion layers and yellow filter layers of these 7 materials are hardened by means of the hardeners listed in the table below (the amounts are given in percentages by weight relative to the amount of dry gelatin).
• the materials are subjected to an accelerated storing test by keeping them for 4 weeks at 35C and 80 percent of relative humidity.
• the variations in sensitivity (AS), gradation (A7), and maximum density (AD) are EXAMPLE 4 Photographic multilayer color materials as described in Example 3 are stored for 6 months at 20C whereupon the variations in sensitivity (A S) and gradation (A7) are determined as compared with materials that have been stored under deep-freeze conditions (15 C).
• Hardener A S A 7 blue green red blue green red 1%ofA 0.l0 0.17 0.l7 -O.-l2 0.090.l0 0.25 of A 0.04 0.09 -0.07 0.03 0.0-H).01 0.50 of B From the foregoing examples 3 and 4 it is clearly apparent that the multicolor material hardened with the combination of hardening agents according to the present invention shows improved storage stability over the multicolor material hardened with triacrylformal alone.
• a photographic silver halide emulsion element comprising a gelatin layer including therein as hardening agents a hexahydro-l,3,5-triazine carrying at least two N-vinylcarbonyl or N-vinylsulphonyl groups and a member selected from the group consisting of mucochloric acid and mucobromic acid, the ratio of the said mucobromic or mucochloric acid to said hexahydro-l ,3,5-triazine being from about 5:l0.5:l.
• gelatin layer includes the silver halide emulsion.
• gelatin layer is in water-permeable relation to the silver halide emulsion.
• the photographic element according to claim 1 including a color forming coupler compound in the silver halide emulsion.
• hexahydro-1,3,5-triazine is a member selected from the group consisting of 1,3,5-trivinylsulphonyl-hexahydro-l ,3 ,S-triazin'e and 1,3 ,5- triacryloyl-hexahydro-l ,3 ,S-triazine.

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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)
• Compositions Of Macromolecular Compounds (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Lubricants (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=9879247

Family Applications (1)

Country Status (4)

Cited By (2)

Families Citing this family (1)

• 1969
  • 1969-02-24 GB GB981169A patent/GB1290335A/en not_active Expired
• 1970
  • 1970-02-16 US US00011789A patent/US3721564A/en not_active Expired - Lifetime
  • 1970-02-21 DE DE19702008113 patent/DE2008113A1/de active Pending
  • 1970-02-23 BE BE746343D patent/BE746343A/nl unknown

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