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
• • 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
  • G03C1/33—Spot-preventing agents

Definitions

• R is phenyl or substituted phenyl, alkyl, sub- 'stituted alkyl or alkenyl; p is 0 or 1; m is 0, 1 or 2; and
• n 1 or 2; the sum of m and n being at most 3; or
• R is alkyl, a hydrogen atom, an alkali metal or the atoms necessary to complete an ammonium salt group
• D is the atoms needed to complete a 5 or 6 membered carbocyclic ring; and taken separately, R is hydrogen and R is hydroxy, or taken together R with R represents an oxo-group or (I? o HN HOCHF' HOCH:
• sensitometric characteristics such as covering power, improved density loss on drying, stabilizing and the like, can be improved and attained by the addition of certain additives to light-sensitive composi tions, such as to layers and emulsions containing silver halide. It is also known that the physical properties often suffer after the introduction of such addenda.
• the various sensitometric properties such as maximum optical density after the steps of exposure, processing and drying, depend only in part upon the amount of free silver which results from the development process. They also depend upon the manner in which the silver is laid down in preparation of the photographic element during manufacture and particularly upon the stresses to which it is subjected during drying and high temperature processing.
• Photographic silver halide emulsions possessing increased covering power are of considerable interest and are particularly desirable since their use results in an increase in gamma and very often an increase in speed while the silver content is maintained at the same level. While covering power, and therefore silver density, can be thus increased, it is also essential that reduction in toughness of the photographic layer in the wet states be avoided. For example, it is generally the practice to employ hardening agents whose action on the hardenable colloid, which they effect, results in an increase in resistivity to elevated temperatures by chemical cross-linking.
• cross-linking agents are sometimes desirable in order to provide resistance to abrasion, to provide higher resistance to the elevated environmental temperatures of solutions and air drying chambers and to maintain the dimensional stability and integrity of the various coatings containing those colloids. These characteristics are particularly needed during processing photographic elements under modern, high temperature mechanical processing conditions. Nonetheless, while these colloid containing layers can be hardened by the simple expedient of increasing the concentration of the hardening agent used, such practice invariably causes a reduction in sensitometry such as the density of the image recorded from the light-sensitive emulsion.
• polymeric addenda such as for example, polyacrylamide, poly[N-(Z-hydroxyethyl)acrylamide], poly(vinyl pyrrolidone), poly(N-acrylylmorpholine) and the like, are added, frequently jointly with other additives such as polymeric latexes, even the beneficial effect of the covering power addenda is often lost or appreciably diminished because the emulsion layer and other layers are softened.
• polymeric latex it will be understood that we mean a colloidal dispersion of a substantially insoluble polymer in an essentially aqueous system.
• hydrophilic colloid-containing compositions which could effectively, economically and conveniently utilize the advantages of relative flexibility, toughness, rigidity, lack of dimensional change and the like possessed by elements having combined therein, the tempering agents such as the simple organic polyol toughener compounds disclosed.
• the unexpected advantages would be derived from the combination of substances which produce physical and sensitometric stability such as density on drying of colloid-containing systems While still providing significant tempering of the colloids contained in various of the coated layers such as emulsions.
• R is phenyl, substituted phenyl such as o-methoxyphenyl, 2,4-dichlorophenyl, p-tolyl, p-bromophenyl, 2,4-xylyl, p-acetylphenyl, p-biphenylyl and the like; alkyl of up to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl and the like; substituted alkyl such as hydroxymethyl, methoxymethyl, hydroxyethyl, 3-chloropropyl, benzyl, and the like; or alkenyl such as vinyl, allyl, butadienyl, and the like; p is or 1; m is O, 1 or 2; and n is 1 or 2; the sum of m and n being at most 3; or
• R is an alkyl gorup of from 1 to 8 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, octyl and the like; a hydrogen atom, an alkali metal such as sodium, potassium and the like or the atoms necessary to complete an ammonium salt group, especially the organic ammonium salt group (III) R: Ra
• D is the atoms needed to complete a 5 or 6 membered carbocyclic ring such as a cyclopentane or cyclohexane ring for example; optionally having a 6-membered alicyclic or aromatic ring fused thereto such as a benzocycloheptane, benzocyclo hexane, perhydronaphthalene, or a perhydroindan fused ring group; taken separately R is hydrogen and R is hydroxy, or taken together R represents an oxo-group or HOCII U HOCHz onion CHzOH A number of compounds within the above formulae exhibit especially good properties and are particularly effective tempering addends.
• hydroxyalkylaminoakane polyols having Formula I are 2-(2-hydroxyethylamino) -2-hydroxymethyl)-1,3-propanediol or 2[bis(2 hydroxyethyl)amino] 2-(hydroxymethyl)-1,3-
• preferred compounds are those wherein D forms a 6- membered ring optionally having a ring fused thereto such as 2,2,6,6-tetramethylolcyclohexanol,
• 2,2,5,5-tetramethylolcyclopentanol and 1,1,3,3-tetramethylol-2-decalone also those having the structural formulae of IV or V namely, 2,2 dimethylolindanone or 4,4-dimethylol-2- oxazolidone.
• These compounds can be used without significant adverse sensitometric effects in any effective concentration such as for example from about 5 percent to about 50 percent based upon the weight of the organic colloid in the layer.
• tempering it will be understood to mean imparting to a hydrophilic colloid by an addend or agent, a high degree of rigidity or structural toughness resembling well-known hardening characteristics achieved heretofore by chemical cross-linking agents.
• the tempering agents disclosed herein unexpectedly provide a high degree of toughness to those colloids Without adversely affecting the sensitometric characteristics as chemical cross-linking agents sometimes do.
• While the compounds, disclosed herein to achieve the desirable and unexpected properties set forth, are generally classified as simple organic polyols, they include various cyclic compounds and they are distinguished from those poly-hydroxy type compounds such as glycerol or glycol whose previous disclosed use in photographic gelatin emulsions has been as plasticizers. 'Plasticizing or softening is virtually the opposite of the action of the polyols used in the practice of this invention since the former is a softening and the latter, rigidizing or tempering.
• mushiness as applied to colloid-layers herein, it will be understood to mean the physical property of softness as determined in the numerical values recorded by a weighted stylus drawn across said layers.
• R is phenyl, substituted phenyl such as o-methoxyphenyl, 2,4-dichlorophenyl, p'tolyl, p-bromophenyl, 2, 4-xylyl, p-acetylphenyl, p-biphenylyl and the like; alkyl of up to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl and the like; substituted alkyl such as hydroxymethyl, methoxymethyl, hydroxyethyl, 3- chloropropyl, benzyl, and the like; or alkenyl such as vinyl, allyl, butadienyl, and the like; p is or 1; m is 0, 1 or 2; and n is 1 or 2; the sum of
• R is an alkyl group of from 1 to 8 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, octyl and the like; a hydrogen atom, an alkali metal such as sodium, potassium and the like or the atoms necessary to complete an ammonium salt group, especially the organic ammonium salt group I (HO CHz)aCNHa- (III) R2 R3 (HO CHzh-C C(CHZOHM wherein D is the atoms needed to complete a 5 or 6 membered carbocyclic ring such as a cyclopentane or cyclohexane ring for example; optionally having a 6-membered alicyclic or aromatic ring fused thereto such as a benzocycloheptane, benzocyclo hexane, perhydronaphthalene, or a perhydroindon fused ring group; taken separately R is hydrogen and R is hydroxy, or taken
• silver salts like the halides, such as silver chloride, silver bromide, silver chlorobromide and the like.
• These silver halide-containing emulsions can contain a binding agent such as all-gelatin and gelatin derivatives, all-nongelatin, and mixtures thereof such as gelatin and a soluble extender polymer system or gelatin and latex polymer, or various combinations of gelatin, latex and soluble polymers, as set forth herein.
• a polymeric covering power addendum is employed in a photographic silver halide emulsion and said emulsion is toughened by the addition of the tempering compounds set forth above without adverse loss of sensitometry diminution of covering power or softening.
• Another embodiment comprises substantially dried layers derived from a combination of a gelatin sol and a latex resulting from the polymerization of a substantially water insoluble alkyl ester of an ethylenically unsaturated acid.
• the polyols useful in this invention which conform to structure I can be prepared by the addition of the appropriate acid chloride to tris (hydroxymethyl)methylarnine or by the action of tris (hydroxymethyl)methylamine on an alkyl or substituted alkyl halide.
• Compounds of structure II are prepared by the direct esterification of the acid with the corresponding alcohol.
• Compounds of structure IH and IV are prepared by the reaction of formaldehyde with the carbocyclic ketone in the presence of a base such as calcium oxide.
• Compounds having the structure of formula IV are prepared by the action of phenyl chloroformate on tris(hydroxymethyl)methylamine.
• the silver halide emulsions used with this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
• the emulsions can be coarse or fine grain and can be prepared by any of the well-known procedures, e.g. single jet emulsions, double jet emulsions, such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as 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.
• Negative type emulsions can be used or direct positive emulsions such as those described in Leermakers U.S. Pat. 2,184,013 issued Dec. 19, 1939; Kendall et al. U.S. Pat. 2,541,472 issued Feb. 13, 1951; Berriman U.S. Pat. 3,367,778 issued Feb. 6, 1968; Schouwenaars British Pat. 723,019 issued Feb. 2, 1955; Illingsworth 'et al. French Pat. 1,520,821 issued Mar. 4, 1968; Ives U.S. Pat. 2,563,785 issued Aug. 7, 1951; Knott et al. U.S. Pat. 2,456,953 issued Dec. 21, 1948, and Land 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 chillsetting and leaching or the emulsion can be coagulation washed, e.g. by the procedures described in Hewitson et al. U.S. Pat. 2,618,556 issued Nov. 18, 1952; Yutzy et al. U.S. Pat. 2,614,928 issued Oct. 21, 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 a1.
• U.S. 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.
• 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. Pat. 3,297,447 issued Jan. 10, 1967; and Dunn U.S. Pat. 3,297,446 issued Jan. 10, 1967.
• the silver halide emulsions used with this invention can contain speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper U.S. Pat. 2,886,437 issued May 12, 1959; Dann et al. U.S. Pat. 3,046,134 issued July 24, 1962; Carroll et al. U.S. Pat. 2,944,900 issued July 12, 1960; and Gotfe U.S. Pat. 3,294,540 issued Dec. 27, 1966.
• speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper U.S. Pat. 2,886,437 issued May 12, 1959; Dann et al. U.S. Pat. 3,046,134 issued July 24, 1962; Carroll et al. U.S. Pat. 2,944,900 issued July 12, 1960; and Gotfe U.S. Pat. 3,294,540 issued Dec. 27, 1966.
• 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. U.S. Pat. 2,444,605 issued July 6, 1948; the mercury salts as described in Allen et a1.
• the photographic elements of this invention can contain incorporated developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylenediamines. Combinations of developing agents can be employed in the practice of the invention.
• the developing agents can be in a silver halide emulsion and/or in another suitable location in the photographic element.
• the developing agents can be added from suitable solvents or in the form of dispersions as described in Yackel U.S. Pat. 2,592,368
• the photographic and other hardenable layers used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguar gum and the like.
• various organic or inorganic hardeners such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active
• the photographic emulsions and elements described in the practice of this invention can contain various colloids alone or in combination as vehicles, binding agents and various layers.
• Suitable hydrophilic materials include both naturally-occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like.
• the described photographic emulsion layers and other layers of a photographic element empolyed in the practice of this invention can also contain alone or in combination with hydrophilic, water permeable colloids, 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. 3,062,674 issued Nov. 6, 1962; Houck et al. US. Pat. 3,220,844 issued Nov. 30, 1965; Ream et al. U.S. Pat.
• the photographic elements used with this invention can contain antistatic or conducting layers, such layers can comprise soluble salts, e.g. chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk U.S. Pat. 2,861,056 issued Nov. 18, 1958 and Sterman et al., U.S. Pat. 3,206,312 issued Sept. 14, 1965 or insoluble inorganic salts such as those described in Trevoy U.S. Pat. 3,428,451 issued Feb. 18, 1969.
• soluble salts e.g. chlorides, nitrates, etc.
• evaporated metal layers ionic polymers such as those described in Minsk U.S. Pat. 2,861,056 issued Nov. 18, 1958 and Sterman et al., U.S. Pat. 3,206,312 issued Sept. 14, 1965 or insoluble inorganic salts such as those described in Trevoy U.S. Pat. 3,428,451 issued Feb. 18, 1969.
• Typical supports include cellulose nitrate film, cellulose ester film, poly(vinyl acetal) fihn, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like.
• a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/ or an alphaolefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
• 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. 1, 1966; 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. 1, 1966; 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. 3,121,0
• the photographic layers employed in the practice of this invention can contain surfactants such as saponin; anionic compounds such as the alkyl aryl sulfouates 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 Pat. 1,022,878 issued Mar. 16, 1966.
• surfactants such as saponin
• anionic compounds such as the alkyl aryl sulfouates 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
• water soluble adducts of glycidol and an alkyl phenol such as those described
• the photographic elements employed in the practice of this invention can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Pat. 2,992,101 issued July 11, 1961 and Lynn U.S. Pat. 2,701,245, issued Feb. 1, 1955.
• matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Pat. 2,992,101 issued July 11, 1961 and Lynn U.S. Pat. 2,701,245, issued Feb. 1, 1955.
• the photographic elements used in this invention can contain brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents.
• Brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents.
• Water soluble brightening agents can be used such as those described in Alberz et al., German Pat. 972,067 and McFall et al. U.S.
• 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 al. U.S. Pat. 2,493,748 issued Jan. 10, 1950; and Taber et al. 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 (trior tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines (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, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups and can be fused to carboxylic or heterocyclic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano, or alkoxy 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, rhodaniones, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile.
• acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups, or heterocycic nuclei. Combinations of these dyes can be used, if desired.
• supersensitizing addenda which do not absorb visible light
• addenda which do not absorb visible light
• ascorbic acid derivatives for instance, 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 al. U.S. Pat. 2,937,089 issued May 17, 1960.
• 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 U.S. Pat. 3,253,921 issued May 31, 1966; Gaspar U.S. Pat. 2,274,782 issued Mar. 3, 1942; Silberstein et al. U.S. Pat. 2,527,583 issued Oct. 31, 1950, and VanCampen U.S. Pat. 2,956,879 issued Oct. 18, 1960.
• the dyes can be mordanted, for example, as described in Milton et al. U.S. Pat. 3,282,699 issued Nov. 1, 1966.
• the sensitizing dyes and other addenda used in the practice of this invention can be added from water solutions or suitable organic solvent solutions can be used.
• the compounds can be added using various procedures including those described in Collins et al. U.S. Pat. 2,912,- 343 issued Nov. 10, 1959; McCrossen et al., U.S. Pat. 3,342,605 issued Sept. 19, 1967; Audran U.S. Pat. 2,996,- 287 issued Aug. 15, 1961 and Johnson et al., U.S. Pat. 3,425,835 issued Feb. 14, 1969.
• photographic layers used in the practice of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Beguin U.S. Pat. 2,681,294 issued June 15, 1954. If
• two or more layers may be coated simultaneously by the procedures described in Russell U.S. Pat. 2,761,791 issued Sept. 4, 1956 and Wynn British Pat. 837,095.
• This invention also can be used for silver halide layers coated by vacuum evaporation as described in British Pat. 968,- 453 and LuValle et al. U.S. Pat. 3,219,451 issued Nov. 23, 1965.
• This invention can be used with elements designed for color photography, for example, elements containing color-forming couplers such as those described in Frohlich et al. U.S. Pat. 2,376,679 issued May 22, 1945; Jelley et al., U.S. Pat. 2,322,027 issued June 15, 1943; Fierke et al., U.S. Pat. 2,801,171 issued July 30, 1957; Godowsky U.S. Pat. 2,698,794 issued Jan. 4, 1955; Barr et al., U.S. Pat. 3,227,554 issued Jan. 4, 1966; and Graham et al. U.S. Pat. 3,046,129 issued July 24, 1962; or elements to be developed in solutions containing color-forming couplers such as those described in Mannes et al. U.S. Pat. 2,252,-
• Photographic elements prepared according to this invention can be processed by various methods including processing in alkaline solutions containing conventional developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, hydroxylamines, hydrazines, reductones and the like; web processing such as described in Tregillus et al. U.S. Pat. 3,179,517 issued Apr. 20, 1965; stabilization processing as described in Russell et al. Stabilization Processing of Films and Papers, PSA Journal, vol. 16B, August 1950; monobath processing as described in Levy Combined Development and Fixation of Photographic Images with Monobaths, Phot. Sci. and Eng, vol. 2, No.
• conventional developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, hydroxylamines, hydrazines, reductones and the like
• web processing such as
• the photographic elements of this invention can be processed in hardening developers such as those described in Allen et al., U.S. Pat. 3,232,761 issued Feb. 1, 1966; in roller transport processors such as those described in Russell et al., U.S. Pat. 3,025,779 issued Mar. 20, 1962; or by surface application processing as described in Example 3 of Kitze U.S. Pat. 3,418,132 issued Dec. 24, 1968.
• the silver halide emulsions used with this invention can be used for making lithographic printing plates such as by the colloid transfer of undeveloped and unhardened areas of an exposed and developed emulsion to a suitable support as described in Clark et al. U.S. Pat. 2,763,553 issued Sept. 18, 1956; to provide a relief image as described in Woodward U.S. Pat. 3,402,045 issued Sept. 17, 1968 or Spencer U.S. Pat. 3,053,658 issued Sept. 11, 1962; to prepare a relief printing plate as described in Baxter et al. U.S. Pat. 3,271,150 issued Sept. 6, 1966.
• This invention can be used with elements designed for colloid transfer processes such as described in Yutzy et al. U.S. Pat. 2,716,059 issued Aug. 23, 1953; silver salt diifusion transfer processes such as described in Rott U.S. Pat. 2,352,014 issued June 20, 1944; Land U.S. Pat. 2,543,- 181 issued Feb. 27, 1951; Yacket et al. U.S. Pat. 3,020,155 issued Feb. 6, 1962; and Land U.S. Pat. 2,861,885 issued Nov. 25, 1958; color image transfer processes such as described in Rogers U.S. Pats. 3,087,817 issued Apr.
• This invention may be used in elements designed for recording print out images as described in Fallesen U.S. Pat. 2,369,449 issued Feb. 13, 1945 or Bacon et a1.
• This invention can be used in elements designed for physical development such as those described in Agfa British Pat. 920,277 and Gilman et al. British Pat. 1,131,238.
• Hydrophilic colloid materials which can be used in the practice of the invention include various waterperrneable binder vehicles which materials can be suspended in colloidal dispersions.
• Hydrophilic colloids suitable as binder vehicles and layers include proteinaceous compounds such as, for example, gelatin, colloidal albumin and other hydrophilic colloids such as, for example, polyvinyl compounds, cellulose derivatives, acrylamide polymers, etc., though gelatin materials are preferred.
• the high molecular weight materials for binder vehicles and layers which are generally considered soluble in aqueous solutions and do not form small discrete particles when mixed with an aqueous gelatin emulsion, as can be determined upon observation of a photomicrograph, can be considered hydrophilic colloids for purposes of this invention.
• the synthetic polymeric latex materials referred to herein are generally polymeric materials which are relatively insoluble in water compared to water-soluble polymers, but have sufiicient water solubility to form colloidal suspensions of small polymeric micelles.
• Typical latex polymeric materials can be made by rapid copolymerization with vigorous agitation in a liquid carrier, of at least one monomer which would form a hydrophobic homopolymer and at least one monomer which would form a hydrophilic homopolymer. In certain preferred embodiments, from about 1 to about 30%, by weight, of units of monomer containing the water-solubilizing group is present in the copolymer product.
• Copolymers prepared by this method and analogous methods provide discrete micelles of the copolymer which have low viscosities in aqueous suspensions.
• Typical useful copolymers include interpolymers of acrylic esters and sulfoesters as disclosed in Dykstra, U.S. Pat. 3,411,911 issued Nov. 19, 1968, interpolymers of acrylic esters and sulfobetaines as described in Dykstra and Whiteley, U.S. Pat. 3,411,912 issued Nov. 19, 1968, interpolymers of alkyl acrylates and acrylic acids as disclosed in Ream and Fowler, U.S. Pat. 3,287,289 issued Nov.
• Polymeric latex materials can also be made by rapid polymerization with vigorous agitation of hydrophobic polymers when polymerized in the presence of high concentrations of surfactants which contain water-solubilizing groups.
• Generally good latex materials are also disclosed 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. 3,062,674 issued Nov. 6, 1962; and Houck et al., U.S. Pat. 3,220,844 is sued Nov. 30, 1965.
• the latex polymers which can be used according to this invention are acrylic interpolymers, i.e. those interpolymers prepared from polymerizable 12 acrylic monomers containing the characteristic acrylic group
• Such polymers are conveniently prepared by the interpolymerization of an acrylic monomer with at least one dissimilar monomer which can be another acrylic monomer or some other different polymerizable ethylenically unsaturated monomer.
• the acrylic interpolymers employed in the practice of this invention are compatible with gelatin and have a T of less than 20 C. (T can be calculated by differential thermal analysis as disclosed in Techniques and Methods of Polymer Evaluation, vol. 1, Marcel Dekker, Inc., NY. 1966).
• preferred interpolymers which can be used in this invention comprise units of an alkyl acrylate such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylates (e.g. n-butyl or t-butyl acrylates), amyl acrylates, hexyl acrylates and the like.
• Acrylic interpolymers containing units of acrylic acid or a sulfoester acrylate are especially useful in the process.
• Typical polymers of this type are copoly(butyl acrylate-acrylic acid), copoly(methyl acrylate-acrylic acid), copoly(ethyl acrylateacrylic acid), copoly(butyl acrylate-sulfopropyl acrylate) and the like. Additional examples of suitable polymers are disclosed in U.S. Pat. 3,459,790 issued Aug. 5, 1969 to Smith.
• the copolymer comprises up to about 30%, by weight, of acrylic acid or the sulfoester acrylate; especially good results being obtained with latex alkyl acrylate copolymers having up to about 20 percent, by weight, of the acrylate acid or the sulfoester acrylate.
• solubilizing groups such as the acrylic acid groups or the sulfoester groups produce a more soluble solutiontype polymer with respect to water carrier solvents and, therefore, preferably concentrations of about 5 to about 25 percent by weight are utilized to provide the better latex polymers, depending on the molecular weight of the monomer unit. Mixtures of the more soluble solutiontype polymers and the latex polymers can also be used within the scope of this invention to achieve the desired emulsion characteristics.
• the acrylic interpolymer generally comprises at least 10 percent and to about 99 percent, by weight, of the binder vehicle for the emulsion.
• the binder vehicle comprises from about 25 to about percent of the acrylic interpolymer and from about 75 percent to about 25 percent, by weight, gelatin of the total binder.
• the emulsion comprises less than 100 grams of gelatin per mole of silver halide in the emulsion to permit fast drying times of the developed emulsion.
• the emulsion comprises less than 75 grams of gelatin per mole of silver halide.
• the above-mentioned copolymers contain units of a third monomer.
• the synthetic polymers comprise units of 1) alkyl acrylates, (2) acrylic acid or sulfoester acrylates and (3) an acrylic monomer unit having active methylene groups in side chains such as in malonic ester groups, acetoacetic ester groups, cyanoacetic ester groups or 1,3-diketone groups such as disclosed in Smith U.S. Pat. 3,488,708 issued Jan. 6, 1970.
• Typical polymers of this class include copoly(ethyl acrylate-acrylic acid 2 acetoacetoxy ethyl methacrylate), copoly(butyl acrylate-sodium acryloxy propane sulfonate 2 aceto-acetoxyethyl methacrylate), copoly- (methyl acrylate-sodium acryl-oyloxypropane sulfonate- 2-acetoacetoxycthyl methacrylate), copoly(butyl acrylateacrylic acid 2 cyanoacetoxyethyl methacrylate) and the like and mixtures thereof.
• results obtained from the following examples indicate that known covering power addenda such as polyacrylamide and poly(vinyl B hydroxyethylcarbamylmethylearbamate), produce a marked softening or mushiness in photographic elements processed in both an automatic processor and the other known methods. These addenda also produce increased vertical swelling of the emulsion in water and a concomitant increase in mushiness of the gelatin layer. In contrast thereto, the polyol addenda useful in this invention in the same concentrations produce less mushiness and a significant increase in toughness and resistivity to deterioration of the physical integrity of the element. When these polyols are used in combination with the covering power addenda, substantial rigidity and toughness is noted by the decrease in percent vertical swell.
• covering power addenda such as polyacrylamide and poly(vinyl B hydroxyethylcarbamylmethylearbamate)
• EXAMPLE I In the example of the following tables, polyol tempering compounds are added and coated by known methods in the concentrations shown to a medium speed photographic silver bromoiodide emulsion.
• the coatings of these examples are made on polyester (polyethylene terephthalate) support at 450 mg. silver/ft. and 1248 mg. gel/ft. for the medium speed silver bromoiodide emulsion.
• the films are exposed to an Eastman IB sensitometer, developed in Kodak DK-SO Developer for 5 minutes, fixed, washed and dried.
• the higher values recorded for mushiness indicate an increase in wet jelly strength and a reduced mushiness.
• the lower values recorded in percent vertical swell likewise indicate a general firming up and resistance to mushiness of the emulsion layer when the polyol compounds are added.
• mucochloric acid based on the weight of gelatin.
• Example 1 these films are exposed to an Eastman 1B sensitometer, developed in Kodak DK-SO developer for 5 minutes, fixed, washed and dried. Similar good results are obtained when a high speed roller transport system is employed using the X-OMAT processor (a trademark of the Eastman Kodak Company for its high speed roller transport type processor).
• the developer solutions contain glutaraldehyde, a chemical crosslinking type hardener as described more fully in Belgian Pat. 700,301 of Barnes et a1 issued Aug. 31, 1967.
• pmpnnnriinl 30 N own-All coatings contain mucochlon'c acid at 0.235% based on the weight oigelatinin the emulsion layer plus a gelatin overcoat containing 0.34% mucochloric acid based on the weight of gelatin.
• the tougheners in accordance with our invention have shown themselves to be useful in color photography such as in photographic emulsions in which color couplers have been incorporated.
• the use of these polyols results in layer toughness with little adverse sensitometric effects used in levels producing satisfactory tempering in contrast with some of the crosslinking types of gelatin hardeners. No adverse effects upon dye hue or stability of the emulsion has been observed.
• these tempering agents have been used with good effect:
• Layer 6Gelatin layer Layer 5Red-sensitive silver chlorobromide gelatin consisting of 90 mole percent bromide and a phenolic cyan 1
• the polyols in accordance with our invention can be used in all six of the layers of the product or they can be used in the emulsion compositions with other hardeners being used in the gelatin layers if desired.
• EXAMPLE VII In a manner similar to that described in the foregoing example, additional photographic examples are prepared by coating onto a polyethylene terephthalate film support a coarse grain silver bromoiodide gelatin emulsion having 6 mole percent iodide and the remainder, bromide. Silver bromoiodide covering is effected at 459 mg. silver per square foot and gelatin coverage at 1037 mg. per square foot.
• the following stable records various swell measurements and demonstrates that the toughening compounds useful in the practice of the present invention appear to differ in their mechanism of action when compared to known crosslinking compounds, the latter exhibiting a swell value of substantially less than 500%.
• EXAMPLE VIII As in Example VI, still other photographic examples are prepared in the same manner as described. Tables VIIIA and VIIIB which follow record the fresh and incubated sensitometric values along with the corresponding mushiness in various processing solutions. The percent swell determined in fresh examples and after incubation, clearly demonstrates the superior properties of the compounds useful in the practice of this invention.
• mueochloric acid based on the weight of gelatm.
• Norm-All coatings contain 0.235% mucochloric acid based on the weight of gelatin in the emulsion layer plus a gelatin overcoat containing 0.34%
• mueochloric acid based on the weight of gelatin.
• R is phenyl or substituted phenyl selected from the group consisting of o-methoxyphenyl, 2,4-dichlorophenyl, p-tolyl, p-bromophenyl, 2,4-xylyl, p-acetylphenyl and p-biphenylyl; alkyl group of from 1 to 8 carbon atoms; substituted alkyl selected from the group consisting of hydroxymethyl, methoxymethyl, hydroxyethyl, 3-chloropropyl and benzyl or alkenyl; p is or 1; m is 0, 1 or 2; and n is l or 2; the sum of m and n being at most 3; or
• R is alkyl group of from 1 to 8 carbon atoms, a hydrogen atom, an alkali metal or the atoms necessary to complete an ammonium salt group;
• the element of claim 1 further comprising colorforming couplers.
• a process for tempering a photographic silver halide element comprising a support, a hydrophilic colloid layer chemically hardened by reaction with a crosslinking agent which process comprises incorporating into said layer or in a layer adjacent thereto a tempering concentration of a compound having the structural formula:
• R is phenyl, or substituted phenyl selected from the group consisting of o-methoxyphenyl, 2,4-dichlorophenyl, p-tolyl, p-bromophenyl, 2,4-xylyl, p-acetylphenyl, p-biphenylyl; substituted alkyl selected from the group consisting of hydroxymethyl, methoxymethyl, hydroxy ethyl, 3-chloropropyl and benzyl; or alkenyl; p is 0 or 1; m is 0, 1 or 2; and n is l or 2; the sum of m and n being at most 3; or
• R is an alkyl group of (from 1 to .8 carbon atoms, a hydrogen atom, an alkali metal or the atoms necessary to complete an ammonium salt group;
• D is the atoms needed to complete a 5 or 6 membered carbocyclic ring; and taken separately R is hydrogen and R is hydroxy, or taken together R and R represents an oxo-group or V) 0 ll noon I onion mono said tempering concentration is in an amount equal to from about 5 to about 50 weight percent of said hydrophilic colloid.
• the element of claim 1 which further comprises a substantially dried latex resulting from the polymerization of a substantially water insoluble alkyl ester of an ethylenically unsaturated acid.

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• 1971
  • 1971-02-04 US US00112768A patent/US3733196A/en not_active Expired - Lifetime
• 1972
  • 1972-01-07 CA CA131,900A patent/CA976412A/en not_active Expired
  • 1972-01-18 FR FR7201514A patent/FR2124237A1/fr not_active Withdrawn
  • 1972-01-20 BE BE778303A patent/BE778303A/xx unknown
  • 1972-02-03 GB GB504472A patent/GB1384464A/en not_active Expired
  • 1972-02-04 DE DE19722205297 patent/DE2205297A1/de active Pending

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