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 present invention relates to photographic elements and particularly to photographic elements having surface roughening agents in their topcoats. Displacement of silver halide grains by matting agents is prevented and image quality improved.
• Matting agents are commonly applied to the top layer in photographic elements for a number of purposes.
• the matting agents can improve the ability of the surface to accept writing, adjust the coefficient of friction for mechanical handling of the element, reduce Newton's rings formation during printing and enlarging, and create air pockets to facilitate drawdown of layers against the element in a vacuum system.
• the movement of the matting particles into emulsion layers forces the silver halide grains out of small areas. As there is no silver halide in these areas, no optical density can be provided upon exposure and develop­ment. It is the absence of silver halide grains and the absence of developable optical density that show up as the starry night effect.
• U.S. Patent No. 4,172,731 attempts to solve the starry night problem by using pigmented polymeric particles as the matting agent.
• the pigments are to be of the same color as the image to be formed in the adjacent emulsion layer. These agents merely mask the effect and do not change the undesirable distribution of silver halide in the adjacent layer.
• U.S. Patent No. 4,232,117 does not address the problem of the starry night effect but uses both a matting agent of 1 to 5 microns and colloidal silica of 7 to 120 microns for antiadhesive properties.
• U.S. Patent No. 3,411,907 combines two different types of matting agents, a soft and a hard matting agent, at least 90% by weight of said hard particle matting agents having a diameter of at least about 1 micron and at least 40% by weight of said soft matting agents having a diameter in excess of 4 microns.
• U.S. Patent No. 4,343,873 discloses the use of a light-scattering topcoat layer containing both light-­scattering particles having dimensions between 0.32 and 1.9 microns and matting agent particles having average diameters between 2 and 5 microns.
• the light-scattering particles are present in a concentration of from 0.7 to 10 g/m2 in the coating and must be dissolved from the element during development.
• Radiation sensitive photographic elements are provided with an improved matte layer construction which provides a short contact vacuum drawdown time, acceptable starry night effect levels, good surface friction proper­ties, and acceptable haze.
• Two different size non-­developmentally dissolvable particle components in critical weight proportions are used. The larger particles provide the matte finish and the smaller particles buoy the larger particles in the topcoat layer, reducing the starry night effect.
• Radiation sensitive silver halide photographic elements are provided with an improved surface roughening or matte composition on their outer face.
• the outer face is a surface of the photographic element over a silver halide emulsion layer, usually the surface furthest from the back­ing layer.
• the photographic element may be a black-and-­white photographic element or a color photographic element and may be sensitive to any actinic portion of the electro­magnetic spectrum such as the ultraviolet, visible or infrared regions.
• the surface roughening topcoat comprises a hydro­philic colloidal binder containing two sets of particles having different size distributions and concentrations.
• One of the sets of particles is a matting agent having average particle diameters of greater than 1.0 micron and less than 10 micron in a coating weight of greater than 0.015 g/m2 and less than 0.15 g/m2.
• the other set of particles comprises a buoying agent having an average particle size of between 0.20 and 0.75 microns in a coating weight of between 0.2 and 0.7 g/m2 or 1.0 g/m2. Both particles must be non-­dissolvable during development to provide the final charac­teristics to the product.
• the buoying particles may even be separately included in the emulsion layer. Their size will not create starry night effects in the image, but they still offer some support against penetration by the larger parti­cles into the emulsion layer.
• the particles may be selected from the same or different materials, may be hard or soft, colored or color­less (preferred), and organic or inorganic. They should be light insensitive in that they should not be silver halide particles which are developable to form a visual image.
• the particles may not be soluble during the development process. If the smaller particles were soluble, the large particles could "fall” during development and force their way into lower layers during drying and rethinning of the topcoat layer during drying.
• the particles may be selected from amongst inorganic particles such as barium sulfate, silica, calcium, carbonate, baria, titania, calcium sulfate, barium carbonate, and the like, or organic particles such as cellulose esters, cellulose ethers, acrylic or methacrylic resins (such as polymers or copolymers or methylmethacryl­ate, acrylic acid, methacrylic acid, n-butylmethacrylate, etc.), polyvinyl resins, polymers and copolymers of ethylenically unsaturated resins such as styrene, butadiene, and the like, polycarbonates, etc.
• inorganic particles such as barium sulfate, silica, calcium, carbonate, baria, titania, calcium sulfate, barium carbonate, and the like
• organic particles such as cellulose esters, cellulose ethers, acrylic or methacrylic resins (such as polymers or copo
• the size range of the particles and their coating weights are critical to the practice of the present inven­tion. If the small particle sizes are less than 0.20 microns or if their coating weight is less than 0.2 g/m2, there will be no buoying effect. If the size of the small particles exceeds an average of 0.75 microns, the particles will contribute to the starry night effect. If the coating weight of small particles exceeds 0.7 g/m2, increased haze will be produced in the photographic element. The propor­tions and size of the larger particles are important in providing the matte finish and minimizing the starry night effect.
• any of the various types of photographic silver halide emulsions may be used in the practice of the present invention.
• Silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chlorobromide and mixtures thereof may be used for example. Any configuration of grains, cubic orthorhombic, hexagonal, epitaxial, lamellar, tabular or mixtures thereof may be used.
• These emulsions are prepared by any of the well-known procedures, e.g., single or double jet emulsions as described by Wietz et al., U.S. Patent 2,222,264, Illingsworth, U.S. Patent 3,320,069, McBride, U.S. Patent 3,271,157 and U.S. Patents 4,425,425 and 4,425,426.
• the silver halide emulsions of this invention can be unwashed or washed to remove soluble salts.
• the soluble salts can be removed by chill-setting and leaching or the emulsion can be coagulation washed e.g., by the procedures described in Hewitson et al., U.S. Patent 2,618,556; Yutzy et al., U.S. Patent 2,614,928; Yackel, U.S. Patent 2,565,418; Hart et al., U.S. Patent 3,241,969; and Waller et al., U.S. Patent 2,489,341.
• Photographic emulsions 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 chemical sensitization procedures are described in Shepard, U.S. Patent 1,623,499; Waller, U.S. Patent 2,399,083; McVeigh, U.S. Patent 3,297,447; and Dunn, U.S. Patent 3,297,446.
• the silver halide emulsions of 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. Patent 2,886,437; Chechak, U.S. Patent 3,046,134; Carroll et al., U.S. Patent 2,944,900; and Goffe, U.S. Patent 3,294,540.
• speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper, U.S. Patent 2,886,437; Chechak, U.S. Patent 3,046,134; Carroll et al., U.S. Patent 2,944,900; and Goffe, U.S. Patent 3,294,540.
• Silver halide emulsions can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
• Suitable antifoggants and stabilizers which can be used alone or in combination, include the thiazolium salts described in Staud, U.S. Patent 2,131,038 and Allen U.S. Patent 2,694,716; the azaindenes described in Piper, U.S. Patent 2,886,437 and Heimbach, U.S. Patent 2,444,605; the mercury salts described in Allen, U.S. Patent 2,728,663; the urazoles described in Anderson, U.S. Patent 3,287,135; the sulfocatechols described in Kennard, U.S.
• Patent 3,235,652 the oximes described in Carrol et al., British Patent 623,448; nitron; nitroindazoles; the polyvalent metal salts described in Jones, U.S. Patent 2,839,405; the thiuronium salts described in Herz, U.S. Patent 3,220,839; and the palladium, platinum and gold salts described in Trivelli, U.S. Patent 2,566,263 and Damschroder, U.S. Patent 2,597,915.
• Silver halide can be dispersed in colloids that 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 sulfones, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides e.g., dialdehyde starch, oxyguargum, etc.
• various organic or inorganic hardeners such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid deriva­tives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds, epoxy compounds, aziridines,
• Photographic emulsions can contain various col­loids alone or in combination as vehicles or binding agents.
• Suitable hydrophilic materials include both naturally-­occurring substances such as proteins, for example, gelatin, gelatin derivatives (e.g., phthalated gelatin), cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds, e.g., poly(vinylpyrrolidone) acrylamide polymers or other synthetic polymeric compounds such as dispersed vinyl compounds in latex form, and par­ticularly those which increase the dimensional stability of the photographic materials.
• Suitable synthetic polymers include those described, for example, in U.S.
• Emulsions in accordance with this invention can be used in photographic elements which contain antistatic or conducting layers, such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Patents 2,861,056 and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Patent 3,428,451.
• antistatic or conducting layers such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Patents 2,861,056 and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Patent 3,428,451.
• Photographic emulsions can be coated on a wide variety of supports.
• Typical supports include polyester film, subbed polyester film, poly(ethylene terephthalate) film, cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polycarbonate film and related 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 alpha-olefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
• Emulsions of the invention can contain plasti­cizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Patent 2,960,404; fatty acids or esters such as those described in Robins, U.S. Patent 2,588,765 and Duane, U.S. Patent 3,121,060; and silicone resins such as those described in DuPont British Patent 955,061.
• polyalcohols e.g., glycerin and diols of the type described in Milton, U.S. Patent 2,960,404
• fatty acids or esters such as those described in Robins, U.S. Patent 2,588,765 and Duane, U.S. Patent 3,121,060
• silicone resins such as those described in DuPont British Patent 955,061.
• the emulsions as described herein can contain surfactants such as saponin, anionic compounds such as the alkylarylsulfonates described in Baldsiefen, U.S. Patent 2,600,831 fluorinated surfactants, and amphoteric compounds such as those described in Ben-Ezra, U.S. Patent 3,133,816.
• surfactants such as saponin
• anionic compounds such as the alkylarylsulfonates described in Baldsiefen, U.S. Patent 2,600,831 fluorinated surfactants
• amphoteric compounds such as those described in Ben-Ezra, U.S. Patent 3,133,816.
• Photographic elements as described herein 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. Patent 2,992,101 and Lynn, U.S. Patent 2,701,245.
• matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Patent 2,992,101 and Lynn, U.S. Patent 2,701,245.
• Emulsions of the invention can be utilized in photographic elements which contain brightening agents including stilbene, triazine, oxazole and coumarin brightening agents.
• Brightening agents including stilbene, triazine, oxazole and coumarin brightening agents.
• Water soluble brightening agents can be used such as those described in Albers et al., German Patent 972,067 and McFall et al., U.S. Patent 2,933,390 or disper­sions of brighteners can be used such as those described in Jansen, German Patent 1,150,274 and Oetiker et al., U.S. Patent 3,406,070.
• Photographic elements containing emulsion layers according to the present invention can be used in photo­graphic elements which contain light absorbing materials and filter dyes such as those described in Sawdey, U.S. Patent 3,253,921; Gaspar, U.S. Patent 2,274,782; Carroll et al., U.S. Patent 2,527,583 and Van Campen, U.S. Patent 2,956,879.
• the dyes can be mordanted, for example, as described in Milton and Jones, U.S. Patent 3,282,699.
• Contrast enhancing additives such as hydrazines, rhodium, iridium and combinations thereof are also useful.
• Photographic emulsions 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. Patent 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell, U.S. Patent 2,761,791 and Wynn British Patent 837,095.
• the couplers may be present either directly bound by a hydrophilic colloid or carried in a high temperature boiling organic solvent which is then dispersed within a hydrophilic colloid.
• the colloid may be partially hardened or fully hardened by any of the variously known photographic hardeners.
• Such hardeners are free aldehydes (U.S. Patent 3,232,764), aldehyde releasing compounds (U.S. Patent 2,870,013 and 3,819,608), s-triazines and diazines (U.S. Patent 3,325,287 and 3,992,366), aziridines (U.S. Patent 3,271,175), vinylsulfones (U.S. Patent 3,490,911), carbodiimides, and the like may be used.
• the silver halide photographic elements can be used to form dye images therein through the selective formation of dyes.
• the photographic elements described above for forming silver images can be used to form dye images by employing developers containing dye image formers, such as color couplers, as illustrated by U.K. Patent No. 478,984; Yager et al., U.S. Patent No. 3,113,864; Vittum et al., U.S. Patent Nos. 3,002,836, 2,271,238 and 2,362,598.
• the developer contains a color-­developing agent (e.g., a primary aromatic amine which in its oxidized form is capable of reacting with the coupler (coupling) to form the image dye.
• a color-­developing agent e.g., a primary aromatic amine which in its oxidized form is capable of reacting with the coupler (coupling) to form the image dye.
• instant self-­developing diffusion transfer film can be used as well as photothermographic color film or paper using silver halide in catalytic proximity to reducable silver sources and leuco dyes.
• the dye-forming couplers can be incorporated in the photographic elements, as illustrated by Schneider et al. Die Chemie , Vol. 57, 1944, p. 133, Mannes et al. U.S. Patent No. 2,304,940, Martinez U.S. Patent No. 2,269,158, Jelley et al. U.S. Patent No. 2,322,027, Frolich et al. U.S. Patent No. 2,376,679, Fierke et al. U.S. Patent No. 2,801,171, Smith U.S. Patent No. 3,748,141, Tong U.S. Patent No. 2,772,163, Thirtle et al. U.S. Patent No.
• the dye-forming couplers are commonly chosen to form subtractive primary (i.e., yellow, magenta and cyan) image dyes and are non-diffusible, colorless couplers, such as two and four equivalent couplers of the open chain ketomethylene, pyrazolone, pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, phenol and naphthol type hydro­phobically ballasted for incorporation in high-boiling organic (coupler) solvents.
• Such couplers are illustrated by Salminen et al. U.S. Patent Nos.
• Dye-forming couplers of differ­ing reaction rates in single or separate layers can be employed to achieve desired effects for specific photo­graphic applications.
• the dye-forming couplers upon coupling can release photographically useful fragments, such as development inhibitors or accelerators, bleach accelerators, developing agents, silver halide solvents, toners, hardeners, fogging agents, antifoggants, competing couplers, chemical or spectral sensitizers and desensitizers.
• Development inhibitor-releasing (DIR) couplers are illustrated by Whitmore et al. U.S. Patent No. 3,148,062; Barr et al. U.S. Patent No. 3,227,554; Barr U.S. Patent No. 3,733,201; Sawdey U.S. Patent No. 3,617,291; Groet et al. U.S. Patent No.
• Dye-forming couplers and non-dye-forming com­pounds which upon coupling release a variety of photo­graphically useful groups are described by Lau U.S. Patent No. 4,248,962.
• DIR compounds which do not form dye upon reaction with oxidized color-developing agents can be employed, as illustrated by Fujiwhara et al. German OLS 2,529,350 and U.S. Patent Nos. 3,928,041, 3,958,993 and 3,961,959; Odenwalder et al. German OLS No. 2,448,063; Tanaka et al. German OLS No. 2,610,546; Kikuchi et al. U.S. Patent No. 4,049,455 and Credner et al.
• the photographic elements can incorporate colored dye-forming couplers, such as those employed to form integral masks for negative color images, as illustrated by Hanson U.S. Patent No. 2,449,966; Glass et al. U.S. Patent No. 2,521,908; Gledhill et al. U.S. Patent No. 3,034,892; Loria U.S. Patent No. 3,476,563; Lestina U.S. Patent No. 3,519,429; Friedman U.S. Patent No. 2,543,691; Puschel et al. U.S. Patent No. 3,028,238; Menzel et al. U.S. Patent No. 3,061,432 and Greenhalgh U.K. Patent No.
• the photographic elements can include image dye stabilizers.
• image dye stabilizers are illustrated by U.K. Patent No. 1,326,889; Lestina et al. U.S. Patent Nos. 3,432,300 and 3,698,909; Stern et al. U.S. Patent No. 3,574,627; Brannock et al. U.S. Patent No. 3,573,050; Arai et al. U.S. Patent No. 3,764,337 and Smith et al. U.S. Patent No. 4,042,394.
• photographic addenda such as coating aids, antistatic agents, acutance dyes, antihalation dyes and layers, antifoggants, latent image stabilizers, antikinking agents, and the like may also be present.
• a photographic emulsion comprising 0.15 micron cubic chlorobromide grains (64/36, Cl/Br) in a gelatin binder were coated on primed and subbed polyethylenetere­phthalate base at a silver coating weight of 4.0 g/m2.
• Five different gelatin topcoats were applied to samples of this coated emulsion to evaluate the effects of particle sizes and coating weights on starry night, haze and drawdown time. The film was exposed and conventionally developed and sensitometry readings on those three parameters were taken. The results are shown in Table 1. 2.35 micron silica was used as the large particles (LP) and 0.5 micron polymethyl­methacrylate was used as the small particles (SP).
• the values for starry night are interpretable as meaning that 6 is unacceptable, 5 is poor, 4 is marginally accept­able, 3 is very good and 2 is excellent. Haze values up to a maximum of 15 are acceptable.

Landscapes

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

Applications Claiming Priority (2)

Publications (2)

Family

ID=21815379

Family Applications (1)

Country Status (2)

Cited By (1)

Families Citing this family (2)

Citations (6)

• 1988
  • 1988-02-12 EP EP88301203A patent/EP0282171A3/de not_active Withdrawn
  • 1988-03-08 JP JP5473188A patent/JPS63236027A/ja active Pending

Patent Citations (6)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events