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

• This invention relates to an improved method of coating upon a support several superimposed distinct layers comprising hardenable organic hydrophilic colloid and a vinylsulfonyl alkyl hardener.
• the improvement comprises adding the vinylsulfonyl alkyl hardener to less than all the layers of the hardenable organic hydrophilic colloid to uniformly harden all the hardenable organic hydrophilic colloid in all the layers.
• This invention relates to a method of coating multilayer, photographic materials.
• it relates to processes for coating multilayer, multicolor coupler forming photographic elements whose layers comprise hydrophilic colloids hardenable by vinylsulfonyl hardeners.
• it relates to improved coating methods whereby superimposed multiple layers of a photographic silver halide element are all substantially hardened by differentially combining a hardener in certain of said layers.
• One such example in a multiple layered photographic element such as film or paper and the like, is the treatment of the various hydrophilic colloid layers coated over the support.
• These layers while providing a variety of functions are usually superimposed by a variety of coating methods whereby the individuality and identity of each layer is maintained While still insuring a rapid rate of coating.
• a simple photographic film consists of numerous such coatings such as a light sensitive emulsion layer, with an abrasion-protecting overcoat, a thin subcoat in order to promote adhesion and still other specific coatings.
• the need for distinct layer arrangement becomes more apparent. For example, the red, blue and green-sensitive emulsion layers and their color filtering coatings cannot be permitted to diffuse into each other.
• pre-hardener solutions and other preparatory steps were required before coating.
• inorganic and organic compounds are known in the art to be effective in hardening hydrophilic-colloids and include such hardeners as the aldehydes, blocked aldehydes, ketones, aziridines, carbodiimides and the like.
• the vinylsulfonyl hardeners found particularly eifective in the present invention are effective in hardening proteins such as natural polymers like gelatin and also synthetic carboxy-containing polymers as disclosed in Belgian Pat. 723,806 issued to Burness Jan. 15, 1969.
• high speed multiple layer coatings as more fully described heretofore, present unique problems of handling, premature and unwanted hardening of non-uniform degree, poor sensitometry and numerous other problems which have not heretofore been solved.
• m is 1 to 4 and Z is oxygen or nitrogen and R is lower alkyl or hydrogen.
• a particularly suitable bis-vinylsulfonylalkyl compound is bis(vinylsulfonylmethyl)ether having the formula:
• the grains of the silver halide layer are surface sensitized, converted halide, silver halide grains in which the halide comprises at least 50 mole percent bromide.
• a silver halide-containing layer is one of at least four of the superimposed distinct layers comprising the layer arrangement, and all of said layers are substantially hardened by combining during coating onto the support bearing said arrangement, a bis(vinylsulfonyl)alkyl hardener.
• Another embodiment of this invention relates to coating onto a support such as a resin coated paper support, a multilayer arrangement of at least four superimposed distinct layers comprising hardenable organic hydrophilic colloids and a vinyl sulfonyl alkyl hardener, the improvement comprising utilizing a simultaneous coating procedure, in which the hardener is combined in less than all of the layer coating melts or reservoirs just prior to coating.
• a resincoated paper support bears a multilayer arrangement comprising distinct superimposed silver halide-containing layers useful in multicolor image formation.
• these layers are sensitive respectively to blue, green and red, said layers containing color-forming dye couplers capable of forming, respectively, yellow, magenta, and cyan dyes upon color development.
• the red-sensitive layer which contains the cyan forming color coupler, is, in one embodiment, the outermost light sensitive layer and the hardening compound is initially combined in a gelatin-containing interlayer coating melt between the blue-sensitive and green-sensitive layers, and between the green-sensitive and red-sensitive layers respectively, said hardening compound being present in a concentration from about 0.5% to about 3% based on the total weight of the gelatin in all the layers to be hardened.
• This embodiment includes the improvement whereby substantial hardening of the gelatin layers is achieved by combining in less than all of said layers the vinylsulfonyl alkyl hardeners described herein.
• the multilayer arrangement comprises distinct superimposed silver halide graincontaining layers sensitive, respectively, to blue, green and red, the layers containing color-forming dye couplers capable of forming, respectively, yellow, magenta and cyan dyes upon color development.
• the blue sensitive layer contains yellow-forming color coupler and is the outermost light senstive layer.
• the hardening compound is combined in a concentration range of about 0.5 to about 3% based on the total hardenable colloid, such as the gelatin contained in the layers.
• the vinylsulfonyl alkyl hardener is bis(vinylsulfonylmethyl)ether and is differentially combined from the coating melt of (1) a gelatin containing interlayer, (2) a cyan-forming color couplercontaining layer, (3) a gelatin-containing interlayer between a magenta dye-forming color coupler-containing layer and a Carey-Lea silver-containing layer and (4) a cyan and yellow dye-forming color coupler-containing layer, said layers representing less than all of the arranged multiple layers, which are finally substantially uniformly hardned by said hardener.
• the vinylsulfonyl alkyl hardeners used in the practice of this invention are prepared by means well known in the art such as more fully described in Belgian Pat. 723,806 issued Jan. 15, 1969 to Burness et al. Once obtained, the vinylsulfonyl alkyl hardeners are conveniently added to the coating solutions from various aqueous or organic solvent solutions. A variety of methods of blending the sulfonyl-containing solution to the coating mixtures can be employed, such as, for example, blending immediately prior to coating with constant or intermittent stirring.
• a variety of coating techniques can be employed in preparing and coating the multilayer elements which are improved by the present invention.
• a variety of supports can be employed over which the superimposed layers are coated.
• these relatively flexible supports include such supports as cellulose nitrate film, cellulose ester, polyester, poly(vinylacetal), polycarbonates, and various related films including a great variety of resinous materials, as well as more rigid supports such as glass, cardboard, metal and the like.
• a desirable flexible support is comprised of paper easily acetylated, partly or totally, or baryta-coated and/or a-olefin polymer coated.
• a preferred polymer film comprises an a-olefin-containing from 2 to carbon atoms and includes for example the poly-ethylene, polypropylene, ethylenebutene copolymers and the like.
• paper supports the surfaces of which have been overcoated with an a-olefin polymer, especially an a-olefin such as polyethylene, can be further treated to improve their properties such as by electron bombarding prior to coating or in-line electron bombarding during the coating operation as more fully described in British Pat. 1,043,703 of Kemp issued Sept. 21, 1966.
• These particular processes tend to improve the adhesion of hydrophilic colloid layers, especially gelatin layers, coated on the support.
• the vinylsulfonylalkyl hardeners used herein are effective in a broad range of concentrations, such as from about 0.25% to about 6.0% by weight of hardenable 6 material. They are particularly effective at concentrations from about 0.5% to about 3.0% by weight based on hardenable material.
• the term differential as used to describe combining or adding of said class of hardeners is an unequal distribution to other than each and every layer at the outset of the coating operation.
• the hardener can be added to said layers both symmetrically and asymmetrically so long as less than all layers or their coating solutions initially contain said hardener.
• Examplary of one preferred embodiment is the layer arrangement comprised of the following complex layers set forth in their respective superimposed coating patterns as follows:
• Second layer arrangement (a) a slow, red-sensitive silver halide emulsion layer containing a phenolic or naphtholic cyan dye-forming coupler,
• multilayer arrangement is used to describe a highly complex system and configuration of superimposed coatings whose placement and position as to each other is critical for producing the desired results.
• Said layers are distinct in that they re tain their individual character and layer integrity.
• uniform it will be understood to mean the same relative degree of hardness or resistivity to melting of the hardenable colloids in the varying layers regardless of the difference in layer thickness, addenda content or total colloid content in any of said layers.
• gelatin interlayer containing from about 0.5 to about 3.0 bis(vinylsulfonylmethyl or ethyl)ether by total weight of gelatin in all six layers, is added just prior to coating,
• a resin coated support especially a polyethylene treated paper support, electron-bombarded preferably not more than about 24 hours prior to coating time.
• a polyethylene treated paper support bears the following superimposed configuration with unexpected substantially uniform hardening:
• gelatin interlayer containing from about 0.50% to about 3.0% bis(vinylsulfonyhnethyl or ethyl)ether by total weight of gelatin in all six layers added just prior to coating,
• an ultraviolet light absorbing gelatin interlayer containing from about 0.50% to about 3.0% bis(vinylsulfonylmethyl or ethyl)ether by total weight of gelatin contained in all six layers added just prior to coating,
• any series of combinations at various times is believed within the eifective scope and contemplationot this invention.
• Typical of the complex coated elements prepared by the processes of the present invention is a photographic multilayer element which comprises a bis(vinylsulfonyl)alkyl hardened hydrophilic colloid containing in superimposed fashion coated over a flexible support: (1) a first silver halide emulsion sensitive to one region of the visible spectrum and contiguous thereto, a non-diffusible ketomethylene open-chain yellow dye-forming coupler which reacts with oxidized primary aromatic amine color developing agent forming a yellow dye, and (2) a second silver halide emulsion sensitive to another region of the visible spectrum and contiguous thereto a non-diffusible 5pyrazolone coupler which reacts with oxidized primary aromatic amine color developing agent forming a magenta dye.
• the photographic element contains still another silver halide emulsion coated thereover sensitive to a third region of the visibe spectrum and contiguous thereto a non-diffusible phenolic or naphtholic coupler which reacts with oxidized primary aromatic amine color developing agents to form a cyan dye.
• a non-diffusible phenolic or naphtholic coupler which reacts with oxidized primary aromatic amine color developing agents to form a cyan dye.
• Other arrangements of the light sensitive layers are also known, e.g., the emulsion layers can be double-coated as described in British Pat. 923,045, issued to Agfa on Apr. 10, 1963.
• a particularly useful modification of the present invention comprises the process of coating and hardening multilayer, multicolor, coupler-containing, photographic printing element, designed to produce reflection color prints.
• Said element comprising a resin coated paper support, especially an electron-bombarded polyethylene treated paper support.
• This element is successively coated with a blue-sensitive silver halide emulsion containing a ketomethylene open-chain yellow dye-forming coupler, a gelatin containing interlayer, a green sensitive silver halide emulsion containing a magenta dye-forming coupler, an ultraviolet absorbing gelatin containing interlayer, a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler and a gelatin-containing overcoat as described in U.S. Pat. 2,956,879 issued Oct. 18, 1960 to Van Campen.
• Still other arrangements of the sensitive layers are also included in the present invention and the element likewise can have other interlayers for specialized purposes such as antihalation, overcoat, subbing layers and
• the various photographic elements such as printing materials coated by the process of this invention and processed after exposure are particularly acceptable when developed in an aqueous alkaline solution in the presence of a primary aromatic amine color developing agent, followed by silver halide solvent and an oxidizing agent for silver.
• a water wash can be used sometimes immediately after the development, followed by washing and drying or washing and then stabilization with a bath before drying.
• Vinylsulfonylalkyl hardened multilayer, multicolor-coupler forming photographic film elements coated by the process of this invention can likewise be processed in a color reversal process such as the Eastman Kodak ME4 process without a pro-hardener solution or in a color negative process such as the Kodak C-22 process.
• hydrophilic colloids useful in the emulsions, photographic elements and various layers prepared by the processes of the present invention can be employed alone or in combination.
• Suitable hydrophilic materials include both naturally-occurring substances such as proteins, for example, gelatin, modified gelatin and gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances, such as water soluble polvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like.
• the described photographic emulsion layers and other layers of a photographic element employed in the practice of this invention can also contain, alone or in combination with hydrophilic, water permeable colloids.
• Still other synthetic polymeric compounds such as dispersed vinyl compounds such as in latex form and particularly those which increase the dimensional stability of the photographic materials.
• Suitable synthetic polymers include those described, for example, in Nottorf U.S. Pat. 3,142,568 issued July 28, 1964; White U.S. Pat. 3,193,- 386 issued July 6, 1965; Houck et al. U.S. Pat. 3,065,674 issued Nov. 6, 1962; Houck et al. U.S. Pat. 3,220,844 issued Nov. 30, 1965; Ream et al. U.S. Pat.
• the various hydrophilic colloid layers of the above described photographic elements, coated by the process of this invention, can contain hardening agents, such as, aziridine hardeners, isoxazolium salt hardeners, and epoxide compounds in addition to the vinylsulfonyl al'kyl hardeners described herein.
• hardening agents such as, aziridine hardeners, isoxazolium salt hardeners, and epoxide compounds in addition to the vinylsulfonyl al'kyl hardeners described herein.
• the silver halide emulsions used with this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
• converted-halide silver halide grains employed herein is well known to those skilled in the art. This term relates to silver halide grains, prepared in a variety of ways, such as by first forming an emulsion or dispersion of silver salt grains consisting at least in part of a silver salt more soluble in water than silver bromide, and then converting at least a portion of said salt grains to silver bromide or bromoiodide salts as more fully described in U.S. Pat. 2,592,250 of Davey et al. issued Apr. 8, 1952.
• the emulsions can be prepared by any of the well-known procedures, and can include various emulsion types such as single jet, double jet, Lippmann, ammoniacal, thiocyanate or thioether ripened emulsions and those described in Nietz et al. U.S. Pat. 2,222,264 issued Nov. 19, 1940; Illingsworth U.S. Pat. 3,320,069 issued May 16, 1967; and McBride U.S. Pat. 3,271,157 issued Sept. 6, 1966.
• Surface image emulsions can be used as well as internal image emulsions such as those described in Davey et al. U.S. Pat. 2,592,250 issued May 8, 1952; Porter et al. U.S. Pat.
• the emulsions can be regular grain emulsions such as the type described in Klein and Moisar, J. Phot. Sci., vol. 12, No. 5, September/October 1964, pp. 242-251.
• the silver halide emulsions used with this invention can be unwashed or washed to remove soluble salts.
• the soluble salts are removed by chill-setting and leaching or the emulsion is coagulation Washed, e.g. by the procedures described in Hewitson et al. U.S. Pat. 2,618,556 issued Nov. 18, 1952; Yackel U.S. Pat. 2,565,418 issued Aug. 21, 1951; Hart et al. U.S. Pat. 3,241,969 issued Mar. 22, 1966; and Waller et al. UJS- Pat. 2,489,341 issued Nov. 29, 1949.
• the emulsions used with this invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these. Suitable procedures are described in Sheppard et al. U.S. Pat. 1,623,499 issued Apr. 5, 1927; Waller et al. U.S. Pat. 2,399,083 issued Apr. 23, 1946; McVeigh U.S.
• the silver halide emulsions used in the practice of this invention can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
• Suitable antifoggants and stabilizers each used alone or in combination include thiazolium salts described in Brooker et al. U.S. Pat. 2,131,038 issued Sept. 27, 1938 and Allen et al. U.S. Pat. 2,694,716 issued Nov. 16, 1954; the azaindenes described in Piper U.S. Pat. 2,886,437 issued May 12, 1959; and Heimbach et al. US. Pat. 2,444,605 issued July '6, 1948; the mercury salts as described in Allen et al. U.S. Pat. 2,728,663 issued Dec.
• the photographic layers employed in the practice of this invention can contain plasticizers and lubricants such as polyalcohols, e.g. glycerin and diols of the type described in Milton et al. U.S. Pat. 2,960,404 issued Nov. 15, 1960; fatty acids or esters such as those described in Robijns U.S. Pat. 2,588,765 issued Apr. 11, 1952 and Duane U.S. Pat. 3,121,060 issued Feb. 11, 1964; and silicone resins such as those described in Du Pont British Pat. 955,061 issued Apr. 15, 1964.
• plasticizers and lubricants such as polyalcohols, e.g. glycerin and diols of the type described in Milton et al. U.S. Pat. 2,960,404 issued Nov. 15, 1960; fatty acids or esters such as those described in Robijns U.S. Pat. 2,588,765 issued Apr. 11, 1952 and Duane U.S. Pat. 3,121,060 issued Feb.
• the photographic layers employed in the practice of this invention can contain surfactants such as saponin; anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. 2,600,831 issued June 17, 1952; amphoteric compounds such as those described in Ben-Ezra U.S. Pat. 3,133,816 issued May 19, 1964: and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British 1,022,878 issued Mar. 16, 1966.
• Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the light sensitive silver halide emulsion of the multilayer photographic elements of the invention.
• additional spectral sensitization can be obtained by treating the emulsion with a solution of a sensitizing dye in an organic solvent or the dye can be added in the form of a dispersion as described in Owens et al. British Pat. 1,154,781 issued June 11, 1969.
• the dye is either added to the emulsion as a final step or at some earlier stage.
• Sensitizing dyes useful in sensitizing such emulsions are described, for example, in Brooker et al. U.S. Pat. 2,526,632 issued Oct. 24, 1950; Sprague U.S. Pat. 2,503,- 776 issued Apr. 11, 1950; Brooker et a1, U.S. Pat. 2,493,- 748 issued Jan. 10, 1950; and Taber et a1.
• U.S. Pat. 3,384,486 issued May 21, 1968.
• Spectral sensitizers which can be used include the cyanines, merocyanines, complex (tri or tetranuclear) merocyanines, complex (tri or tetranuclear) cyanines, holopolar cyanines, styryls, hemicy- 11 anines (e.g. enamine hemicyanines), oxonols and hemioxonols.
• Dyes of the cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles.
• Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfu alkyl, carboxyalkyl, aminoalkyl and enamine groups and can be fused to carbocyclicor heterocyciic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, c'yano, or alloxy groups.
• the dyes can be symmetrical or unsymmetrical and can contain, alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain.
• the merocyanine dyes can contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile.
• acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkyamino groups, or heterocyclic nuclei. Combinations of these dyes can be used, if desired.
• supersensitizing addenda which do not absorb visible light
• addenda for example, ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acids as described in McFall et al. U.S. Pat. 2,933,390 issued Apr. 19, 1960 and Jones et a1.
• U.S. Pat. 2,937,089 issued May 17, 11960.
• the various layers, including the photographic layers, employed in the practice of this invention can contain light absorbing materials and filter dyes such as those described in Sawdey US. Pat. 3,253,921 issued May 31, 1966; Gaspar U.S. Pat. 2,274,782 issued Mar. 3, 1942; Silberstein et al. US. Pat. 2,527,583 issued Oct. 31, 1950 and Van Campen US. Pat. 2,956,879 issued Oct. 18, 1960.
• the dyes can be mordanted, for example, as described in Milton et al. US. Pat. 3,282,699 issued Nov. 1, 1966.
• any non-diirusible ketomethylene open-chain yellow dye-forming coupler that reacts with primary aromatic amine color developing agents to form a yellow dye is advantageously used in our photographic materials.
• These couplers include all of the well-known non-difiusing openchain ketomethylene yellow dye-forming couplers including those that have a coupling-01f group substituted on the active carbon atom.
• R represents an alkyl group (substituted or not), an aromatic group (substituted or not), a heterocyclic group (substituted or not), etc.
• -R' represents a group such as an alkyl group, a carbamyl group, an amino group, an amide group (e.g. amido, a benzamido group, an allo amido group, etc.)
• Y represents a coupling-oft group such as the thiocyano group, an acyloxy group, an aryloxy group, an alkoxy group, an alkylthio group, an arythio group, the chlorine atom, the fluorine atom, the sulfo group, etc.
• the R and/or R groups are advantageously substituted with any of the well-known substituent groups used in color-forming couplers including ballasting groups to render the couplers non-dilfusible in hydrophilic colloid layers, and solubilizing groups.
• magenta dye-forming couplers examples include the following:
• R represents hydrogen, an alkyl group, an aryl group, a heterocyclic group, an amino group (e.g. amino, alkylamio, arylarnino, heterocyclic amino, etc.), a substituted canbonamido group (e.g. an alkylcarbonamido group, an arylcarbonamido group, and a heterocycliccarbonamido group), a substituted sulfonamido group (e.g.
• R R and R each represent any of the groups represented by R and in addition the chlorine atom, an alkoxy group, etc.; R R R and R are advantageously further substituted by any of the ballasting groups well known in the art;
• Y represents the groups previously defined for Y but does not represent an aryloxy group;
• Y represents the groups previously defined for Y and also includes a cyclic imido group (e.g. a maleimidc group, a succinimido group, a 1,2-dicanboxylimido group, a phthalimido group, etc.)
• cyan-forming couplers examples include the following:
• the couplers used in the practice of this invention are advantageously dispersed in the hydrophilic colloid by any of the techniques well known in the art.
• dispersion can be effected in high-boiling crystalloidal compounds by methods such as described by Jelley and Vittum in US. Pat. 2,322,027 issued June 15, 1943.
• the couplers are advantageously dispersed in low solvent dispersions as described by Fierke in US. Pat. 2,801,171 issued June 30, 1957. Also applicable is dispersion in natural resin-type solvents as described by Martinez in US. Pat.
• Cellulose acetate support The known gelatin hardener, mucochloric! acid, is added as follows to each liquid photographic emulsion prior to its actual coating: layers 1 to 11 each contain mucochloric acid at 0.27% by total weight of gelatin present in each layer; layer 12 contains mucochloric acid at a concentration of 2.15% by total weight of gelatin in the layer. A coated and hardened sample of this is kept for a period of 7 days at a temperature of 120 F. and 50% relative humidity and compared to a check control sample kept for 7 days at 40 F. and 50% relative humidity. Samples of the control and incubated elements are color processed in an Eastman Kodak ME-4 Process which includes a pre-hardener solution and in which the solutions are kept at F.
• the degree of swell of the gelatin layers is used as a measure of relative hardness and is determined for each element during the entire color processing sequence. Table I records these determinations and indicates the difference in degree of swell (A t) between the check control element and the incubated sample after the first developer step and at the end of the processing.
• EXAMPLE 2 In order to provide data recording the degree of hardening, i.e. swelling of gelatin layers, when the vinylsulfonylalkyl hardener is added immediately prior to coating to all layers as conventionally done heretofore, the coating procedure described in Example 1 is repeated. Bis(vinylsulfonylmethyDether is added immediately prior to coating to each layer within each arrangement at a concentration of 2% by total weight of gelatin in each layer. A sample of this multilayer, multicolor coupler containing element is incubated and processed as described in Example 1 with the exception that no pre-hardener solution is employed. Table I contains the swell measurements obtained as described in Example 1.
• EXAMPLE 3 In order to demonstrate one aspect of the present invention, less than all of the hardcnable layers are coated With a preferred hardener.
• Example 1 The coating procedure described in Example 1 is repeated with the exception that a representative hardener of the vinylsulfonylalkyl class, bis(vinylsulfonylmethyl) ether, is blended with the aqueous coating solutions just prior to coating as described in US. Pat. 2,912,343 of Collins et a1.
• FIGURE 2 Layer 6, dried overcoat Gelatin. Layer 5, cyan AgClBr plus gelatin plus cyan dye forming coupler.
• Layer 4 ultraviolet absorben--- Gelatin plus ultraviolet absorber.
• Layer 3 magenta. AgGlBr plus gelatin plus magenta dye forming coupler.
• the several multicolor-coupler forming elements are imagewise exposed and color processed.
• the addition of the bis(vinylsulfonylmethyhether hardening agent is virtually devoid of any adverse sensitomertic effect, such as speed, maximum density or minimum density of the cyan, magenta or yellow layers.
• EXAMPLE 5 The invention is further exemplified by tests conducted on multilayer, multicolor-coupler forming photographic printing papers prepared by coating all layers simultaneously as described in Russel US. Pat. 2,761,791 (supra).
• the support is paper coated with polyethylene on both sides and whose surface is in-line electron bombarded at the time of coating as more fully described in Kemp British Pat. 1,043,703 (supra).
• the graphic structural cross section of these elements is shown in previous FIG.
• Example D in which the hardening agent bis (vinylsulfonylmethyl)ether (VSE) has been added to the liquid photographic material just prior to coating during a simultaneous multilayer coating operation, unexpectedly provides the hardest photographic element as shown by the significant results obtained by the vertical swell testing.
• VSE hardening agent bis (vinylsulfonylmethyl)ether
• EXAMPLE 6 In order to further demonstrate the unexpected and superior results afiorded by the present invention, two elements are prepared. One is like Example 1 herein where the hardener is added to each layer to be hardened at the coating stage and the other element is as described in Example 3 wherein the hardener is preferentially placed in less than all of the layers to be hardened.
• Both elements are coated and dried at high speeds of the coated web in drying chambers where hot air is forced under pressure through numerous nozzle-outlets. At webcoating speeds of about ft./rninute both elements appear to dry satisfactorily while the multiple layers of each still remain intact on the support. However, as the web-speed increases up to about 200 ft./minute and more, the prior art coating like Example 1 is blown off its support under the same degree of force of hot air suitable at slower web speeds. In contrast thereto, all layers of the coated element hardened by the process of the present invention remained intact at 200 ft./ minute showing that all such layers were unexpectedly sufiiciently hardened by selective layer hardening addition, that they exhibited uniform and vastly superior hardening.
• n 1r [CH CHS 02 CH mlrz where m is 1 to 4 and Z is oxygen or an amine nitrogen, R is lower alkyl or hydrogen, and n is at least 2 the improvement comprising adding said vinylsulfonyl alkyl hardener to at least one, but less than all layers of said hydrophilic colloid, whereby said vinylsulfonyl alkyl hardener substantially uniformly hardens all hardenable organic hydrophilic colloid in said layers.
• hardenable hydrophilic colloid layers which comprise distinct superimposed photographic silver halide containing layers sensitive respectively to blue, green and red, and gelatin-containing interlayers between said blue-sensitive and green-sensitive layers and said green-sensitive and red-sensitive layers, respectively, said layers containing color-forming dye couplers capable of forming, respectively, yellow, magenta, and cyan dyes upon color development, the red-sensitive layer, containing cyan-forming color coupler, being the outermost light sensitive layer and a vinyl sulfonyl alkyl hardener which has the structural formula:
• a support hardenable hydrophilic colloid layers which comprise distinct superimposed photographic silver halide containing layers, sensitive respectively to blue, green and red, said layers containing color-forming dye couplers capable of forming, respectively, yellow, magenta and cyan dyes upon color development, the blue sensitive layer, containing yellowforming color coupler, being the outermost light-sensitive layer and a vinylsulfonyl alkyl hardener which has the structural formula:
• n is at least 2 the improvement comprising adding said vinylsulfonyl alkyl hardener to at least one, but less than all layers of said hydrophilic colloid, whereby said vinylsulfonyl alkyl hardener substantially uniformly hardens all hardenable organic hydrophilic colloid in said layers.
• a method of coating onto a polyethylene coated support hardenable hydrophilic colloid layers which comprise distinct superimposed surface-sensitized convertedhalide photographic silver halide grain containing layers sensitive resepectively to blue, green and red, and gelatin-containing interlayers between said blue-sensitive layers and said green-sensitive and red-sensitive layers respectively, said layers containing color-forming dye couplers capable of forming, respectively, yellow, magenta and cyan dyes upon color development, the red-sensitive layer, containing cyan-forming color coupler, being the outermost light sensitive layer and a vinylsulfonyl alkyl hardener which has the structural formula:
• A is or -O-, R being an alkyl of l to 4 carbon atoms
• X is an acid anion
• Z is a polyvalent radical of n second red-sensitive photographic silver halide and cyan dye coupler containing layer located on said first red-sensitive layer
• n is an m eger in t e range 0 om i i l t i layer t I i c L .1
• a ir gear in in er ayer con aimng areyea 51 ver a located on said second green-sensitive layer and ⁇ CHFCHsOlH mhz a first blue-sensitive photographic silver halide and where m is 1 to 4 and Z is oxygen or an amine nitro- 15 zg gz i gg gfigfi zi ggg layer located on Sald R3 is lower alkyl or hydrogen and n is at least a second blue-sensitive photographic silver halide and the improvement in which said vinylsulfonyl alkyl g g g gi gggg i igi layer located on sald 5:35:: i giig gfiggg fgg ggg?figg g bis(vinylsulfonyl methyl-or-ethyl) ether hardener, to ab 3; t 313% based on the total weight of the improvement comprising adding said bis(vmylhardenable hydrophilic colloid, where

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• 1970
  • 1970-04-29 US US33046A patent/US3687707A/en not_active Expired - Lifetime
• 1971
  • 1971-03-09 CA CA107244A patent/CA925753A/en not_active Expired
  • 1971-04-28 BR BR2524/71A patent/BR7102524D0/pt unknown
  • 1971-04-29 FR FR7115306A patent/FR2090921A5/fr not_active Expired
  • 1971-04-29 GB GB1217871A patent/GB1322662A/en not_active Expired

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