Patent Publication Number: US-5834174-A

Title: Photographic elements containing highly crosslinked matting agent

Description:
CROSS REFERENCE TO RELATED APPLICATION 
     Reference is made to and priority claimed from U.S. Provisional application Ser. No. 60/006,067, filed 24 Oct. 1995, PHOTOGRAPHIC CONTAINING HIGHLY CROSSLINKED MATTING AGENT. 
     This is a continuation of application Ser. No. 08/667,274, filed Jun. 20, 1996, now abandoned. 
    
    
     FIELD OF THE INVENTION 
     This invention relates to silver halide photographic light-sensitive elements containing a matting agent. 
     BACKGROUND OF THE INVENTION 
     It is conventional to incorporate finely powdered grains or matting agents into the protective layer of a photographic element to increase the surface roughness to achieve the following: (1) reduce self-adhering of the material, (2) reduce sticking of the material to manufacturing and processing devices, (3) improve the antistatic properties of the material, and (4) improve the vacuum release of the material in contact exposure to prevent Newton&#39;s ring. The matting agents are commonly very small particles of organic or inorganic materials, such as silicone dioxide, magnesium oxide, titanium dioxide, calcium carbonate, poly(methyl methacrylate), poly(vinyltoluene), poly(methyl methacrylate-co-methacrylic acid), and so on. 
     This &#34;matting&#34; of the surface layer suffers, however, from various disadvantages. For example, matte beads tend to dust during manufacturing processes such as high speed finishing operations. The &#34;dusted&#34; matte beads gradually build-up on finishing equipment and become redeposited on the film surface as dirt. The dusted matte beads can also cause film surface scratches and processing defects, thus resulting in product waste. In automatic film changers the dusted matte beads build-up in suction cup or driven roll areas causing film transportation difficulties. 
     PROBLEMS TO BE SOLVED BY THE INVENTION 
     Matte bead dusting is a different problem in photographic film processing solutions than that encountered in film manufacturing and transport processes. In processing solutions, the film emulsion layer experiences cycles of swelling and contraction. Matte particles are forced out of the photographic element if they have a weak interaction with the layer in which they are coated. In other words, wet adhesion of matte particles is critical for preventing matte dusting and scum in processing solutions. However, in film manufacturing and transport processes, the film emulsion layer does not experience such swelling and contraction, and matte bead dusting occurs through different mechanisms. For example, matte particles can be crushed under pressure or shaved away from the film surface under mechanical shear. 
     SUMMARY OF THE INVENTION 
     Therefore, a foremost object of the present invention is to provide a silver halide photographic material which exhibits excellent resistance to matte dusting during film manufacturing and transport processes. 
     In accordance with the present invention, a photographic element comprises a support, at least one hydrophilic light-sensitive layer, and a light-insensitive layer containing a binder and solid, nonporous polymer matte particles having the formula: 
     
         (A).sub.x (B).sub.y                                        (I) 
    
     where A is a monofunctional ethylenically unsaturated monomer, B is a polyfunctional ethylenically unsaturated monomer, x is about 0 to 55 mole %, and y is about 45 to 100 mole %. 
     The matte particles in accordance with this invention are included in any light insensitive layer of the photographic element, but preferably are included in the top-most layer of a light-sensitive silver halide photographic element, in a separate layer over the top surface of the photographic element, or in a layer in close proximity to the top-most layer so that the matte particles protrude above the surface of the top-most or outer-most layer. The matte particles have a mean size of from 0.3 to 10 μm, preferably from 0.5 to 8 μm, and most preferably from 1 to 6 μm. 
     ADVANTAGEOUS EFFECT OF THE INVENTION 
     Photographic elements in accordance with this invention demonstrate reduced dusting characteristics in transport and finishing operations. 
     DESCRIPTION OF PREFERRED EMBODIMENTS 
     Photographic elements according to this invention can differ widely in structure and composition. For example, they can vary greatly in regard to the type of the support, the number and composition of the imaging forming layers, and the kinds of auxiliary layers that are included in the elements. In particular, the photographic elements can be still films, motion picture films, x-ray films, graphic arts films, paper prints or microfiche. They can be black-and-white elements, color elements adapted for use in a negative-positive process, or color elements adapted for use in a reversal process. Typical supports include cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film, poly(ethylene naphthalate) film, polycarbonate film, glass, metal, paper, polymer-coated paper, and the like. 
     In accordance with the present invention, the matte particles have a composition given by formula I, in which A is a monofunctional ethylenically unsaturated monomer, B is a polyfunctional ethylenically unsaturated monomer, x is from 0 to 55 mole %, preferably from 10 to 45 mole %, and most preferably from 15 to 35 mole %. y is from 45 to 100 mole %, preferably from 55 to 90 mole %, and most preferably from 65 to 85 mole %. The matting agent is preferably incorporated into the surface protective layer of a light sensitive material. However, as indicated above, the matting agent can be incorporated into any light insensitive layer in the light sensitive element. By surface protective layer is meant either the emulsion side surface protective layer, or the backing side surface protective layer, or both. However, it is particularly preferable to incorporate the matting agent in the outermost surface protective layer on either side. The matting agent of the present invention is employed at a coating weight coverage of 0.001 to 0.3 g/m 2 , preferably from 0.002 to 0.2 g/m 2 , and most preferably from 0.003 to 0.15 g/m 2 . 
     Suitable ethylenically unsaturated monomers which can be used as component A of the present invention may include, for example, the following monomers and their mixtures: acrylic monomers, such as acrylic acid, or methacrylic acid, and their alkyl esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, n-octyl acrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, nonyl acrylate, benzyl methacrylate; the hydroxyalkyl esters of the same acids, such as, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate; the nitriles and amides of the same acids, such as, acrylonitrile, methacrylonitrile, acrylamide and methacrylamide; vinyl compounds, such as, vinyl acetate, vinyl propionate, vinylidene chloride, vinyl chloride, and vinyl aromatic compounds such as styrene, t-butyl styrene, ethylvinylbenzene, vinyl toluene; dialkyl esters, such as, dialkyl maleates, dialkyl itaconates, dialkyl methylene-malonates and the like. Preferably, monomer A is styrene, vinyl toluene, ethylvinylbenzene, or methyl methacrylate. Most preferably monomer A is ethylvinylbenzene. 
     Suitable ethylenically unsaturated monomers which can be used as component B of the present invention are monomers which are polyfunctional with respect to the polymerization reaction, and may include, for example, the following monomers and their mixtures: esters of unsaturated monohydric alcohols with unsaturated monocarboxylic acids, such as allyl methacrylate, allyl acrylate, butenyl acrylate, undecenyl acrylate, undecenyl methacrylate, vinyl acrylate, and vinyl methacrylate; dienes such as butadiene and isoprene; esters of saturated glycols or diols with unsaturated monocarboxylic acids, such as, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol tetraacrylate, trimethylol propane trimethacrylate and polyfunctuional aromatic compounds such as divinylbenzene and the like. Preferably, monomer B includes ethylene glycol dimethacrylate, ethylene glycol diacrylate, 1,4-butanediol dimethylacrylate or divinylbenzene. Most preferably, monomer B is divinylbenzene. 
     As to divinylbenzene, although available as pure monomer for laboratory use, it is most commonly sold commercially as a mixture of divinylbenzene and ethylvinylbenzene, available, for instance, from Dow Chemical Company as DVB-55 (typical assay 55.8% divinylbenzene and 43.0% ethylvinylbenzene) or DVB-HP (typical assay 80.5% divinylbenzene and 18.3% ethylvinylbenzene). 
     The matte particles for use in accordance with this invention can be made by various well-known techniques in the art, such as, for example, crushing, grinding or pulverizing of polymer down to the desired size, emulsion polymerization, dispersion polymerization, suspension polymerization, solvent evaporation from polymer solution dispersed as droplets, and the like (see, for example, Arshady, R. in &#34;Colloid &amp; Polymer Science&#34;, 1992, No 270, pages 717-732; G. Odian in &#34;Principles of Polymerization&#34;, 2nd Ed. Wiley (1981); and W. P. Sorenson and T. W. Campbell in &#34;Preparation Method of Polymer Chemistry&#34;, 2nd Ed, Wiley (1968)). A preferred method of preparing matte particles in accordance with this invention is by a limited coalescence technique where polyaddition polymerizable monomer or monomers are added to an aqueous medium containing a particulate suspending agent to form a discontinuous (oil droplet) phase in a continuous (water) phase. The mixture is subjected to shearing forces, by agitation, homogenization and the like to reduce the size of the droplets. After shearing is stopped an equilibrium is reached with respect to the size of the droplets as a result of the stabilizing action of the particulate suspending agent in coating the surface of the droplets and then polymerization is completed to form an aqueous suspension of polymer particles. This process is described in U.S. Pat. Nos. 2,932,629; 5,279,934; and 5,378,577; incorporated herein by reference. 
     While not being bound by any particular theory or mechanism, it is believed that matte dusting is effected by the mechanical strength of the polymeric particles by either physical deformation of the particle&#39;s surface in contact with the hydrophilic colloid or by breakage of the particle itself. Solid matte polymer particles with greater than 45 mole % crosslinking in accordance with this invention have improved mechanical properties with regard to deformation or breakage under physical forces encountered during modern transport and finishing operations. Porous particles are known to be easily broken and are therefore not suitable. It is, therefore, most preferred that the matte particles have a surface area less than 50 m 2  /g. 
     The matte particle surface may include reactive functional groups which form covalent bonds with binders by intermolecular crosslinking or by reaction with a crosslinking agent (i.e. a hardener). Suitable reactive functional groups include: hydroxyl, carboxyl, carbodiimide, epoxide, aziridine, vinyl sulfone, sulfinic acid, active methylene, amino, amide, allyl, and the like. There is no particular restriction on the amount of reactive groups present, but their concentrations are preferably in the range of from 0.5 to 10 weight %. The particle surface may be surrounded with a layer of colloidal inorganic particles as described in U.S. Pat. No. 5,288,598, or a layer of colloidal polymer latex particles which have affinity with suitable binder as described in U.S. Pat. No. 5,279,934, or a layer of gelatin as described in U.S. Pat. No. 4,855,219. 
     Processing removable mattes may be used in the practice of the invention to further enhance the resistance of the photographic element to ferrotyping and blocking. Such processing removable mattes include particles of, for example, copolymers of alkyl (meth)acrylates and methacrylic acid, or acrylic acid, or itaconic acid, copolymers of alkyl (meth)acrylates and maleic monoesters or monoamides, copolymers of styrene or vinyl toluene and (α,β-unsaturated mono- or di-carboxylic acids, or dicarboxylic monoesters or monoamides, graft copolymers containing maleic anhydride or methacrylic acid, and dicarboxylic acid mono-ester of a cellulose derivative, such as phthalate and hexahydro phthalate of methyl cellulose, hydroxyethyl cellulose, or hydroxypropylomethyl cellulose. Such processing soluble mattes are described in further detail in U.S. Pat. Nos. 2,992,101; 3,767,448; 4,094,848; 4,447,525; and 4,524,131; which are incorporated herein by reference. 
     Any suitable binder may be used in the light-insensitive layer in practice of the present invention, including hydrophilic colloids such as gelatin as well as hydrophobic polymer resin binders. While the actual amount of binder coated in order to achieve desirable surface physical properties will vary depending on the size and amount of the matte particles, the binder is preferably coated at less than about 3 g/m 2  to provide surface roughness and greater than about 0.1 g/m 2  to provide effective adhesion of the matte particles to the surface of the element. 
     Useful resin binders include polyurethanes (e.g. Neorez R960 sold by ICI), cellulose acetates (e.g. cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate), poly(methyl methacrylate), polyesters (e.g. Vitel R sold by Goodyear Tire &amp; Rubber Co.), polyamides (e.g. Unirez sold by Union Camp, Vesamide sold by General Electric Co.), polycarbonates (e.g. Makrolon sold by Bayer Co., Lexan sold by General Electric Co.), polyvinyl acetate, coalesced layer as set forth in U.S. Pat. No. 5,366,855 and U.S. application Ser. No. 08/221,432 filed Mar. 31, 1994, and the like. 
     Any suitable hydrophilic binder can be used in practice of the present invention. Gelatin is the most preferred hydrophilic binder. Other hydrophilic binders include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives (e.g. cellulose esters), polysaccharides, casein, and the like, and synthetic water permeable colloids such as poly(vinyl lactams), acrylamide polymers, poly(vinyl alcohol) and its derivatives, hydrolyzed polyvinyl acetates, polymers of alkyl and sulfoalkyl acrylates and methacrylates, polyamides, polyvinyl pyridine, acrylic acid polymers, maleic anhydride copolymers, polyalkylene oxide, methacrylamide copolymers, polyvinyl oxazolidinones, maleic acid copolymers, vinyl amine copolymers, methacrylic acid copolymers, acryloyloxyalkyl sulfonic acid copolymers, vinyl imidazole copolymers, vinyl sulfide copolymers, homopolymer or copolymers containing styrene sulfonic acid, and the like. For crosslinkable binder such as gelatin, the binder is preferably cross-linked so as to provide a high degree of cohesion and adhesion. Crosslinking agents or hardeners which may effectively be used in the coating compositions of the present invention include aldehydes, epoxy compounds, polyfunctional aziridines, vinyl sulfones, methoxyalkyl melamines, triazines, polyisocyanates, dioxane derivatives such as dihydroxydioxane, carbodiimides, chrome alum, zirconium sulfate, and the like. 
     Gelatin can be used together with other water dispersible polymers as binders in the practice of the present invention. The water dispersible polymers can be incorporated into either light sensitive or light-insensitive layers. Suitable water dispersible polymers include both synthetic and natural water dispersible polymers. Synthetic water dispersible polymers may contain a nonionic group, an anionic group, or a nonionic group and an anionic group in the molecular structure. The nonionic group may be, for example, an ether group, an ethylene oxide group, an amide group, or a hydroxyl group. The anionic group may be, for example, a sulfonic acid group or the salt thereof, a carboxylic acid group or the salt thereof, or a phosphoric acid group or the salt thereof. The natural water soluble polymer may include a nonionic group, an anionic group, or a nonionic group and an anionic group in the molecular structure. Preferably, the natural water dispersible polymer is a glucose polymer or a derivative thereof, more preferably, starch, glycogen, cellulose, or dextran, and most preferably, dextran or a derivative thereof. The water dispersible polymers may be incorporated into the photographic materials of the present invention in an amount of preferably at least 1%, preferably from 5 to 50%, and most preferably from 10 to 30% based on the amount of the whole coated amount of gelatin on the side having a layer containing the matte particle of the present invention. 
     Water dispersible polymers useful for the present invention include vinyl polymer latex particles prepared by such as emulsion polymerization process, water-borne polyurethane dispersions, water-borne epoxy dispersions, water-borne polyester dispersions, and the like. The mean size of the dispersed particles is within the range of from 0.01 to 0.5 μm, preferably from 0.02 to 0.2 μm. 
     The photographic element of the present invention can contain at least one electrically conductive layer, which can be either surface protective layer or a sub layer. The surface resistivity of at least one side of the support is preferably less than 1×10 12  Ω/square, more preferably less than 1×10 11  Ω/square at 25° C. and 20% relative humidity. To lower the surface resistivity, a preferred method is to incorporate at least one type of electrically conductive material in the electrically conductive layer. Such materials include both conductive metal oxides and conductive polymers or oligomeric compounds. Such materials have been described in detail in, for example, U.S. Pat. Nos. 4,203,769; 4,237,194; 4,272,616; 4,394,441; 4,418,141; 4,495,276; 4,542,095; 4,582,781; 4,610,955; 4,916,011; and 5,340,676. 
     Any lubricant can be used in the outermost layer of the present invention. Typical lubricants include (1) silicone based materials disclosed, for example, in U.S. Pat. Nos. 3,489,567; 3,080,317; 3,042,522; 4,004,927; and 4,047,958; and in British Patent Nos. 955,061 and 1,143,118; (2) higher fatty acids and derivatives, higher alcohols and derivatives, metal salts of higher fatty acids, higher fatty acid esters, higher fatty acid amides, polyhydric alcohol esters of higher fatty acids, etc disclosed in U.S. Pat. Nos. 2,454,043; 2,732,305; 2,976,148; 3,206,311; 3,933,516; 2,588,765; 3,121,060; 3,502,473; 3,042,222; and 4,427,964; in British Patent Nos. 1,263,722; 1,198,387; 1,430,997; 1,466,304; 1,320,757; 1,320,565 and 1,320,756; and in German Patent Nos. 1,284,295 and 1,284,294; (3) liquid paraffin and paraffin or wax like materials such as carnauba wax, natural and synthetic waxes, petroleum waxes, mineral waxes and the like; (4) perfluoro- or fluoro- or fluorochloro-containing materials, which include poly(tetrafluoroethlyene), poly(trifluorochloroethylene), poly(vinylidene fluoride), poly(trifluorochloroethylene-co-vinyl chloride), poly(meth)acrylates or poly(meth)acrylamides containing perfluoroalkyl side groups, and the like. Lubricants useful in the present invention are described in further detail in Research Disclosure No.308, published December 1989, page 1006. 
     The light-insensitive layer useful in the practice of the invention may optionally contain surface active agents, antistatic agents, charge control agents, ultraviolet absorbing agents, thickeners, silver halide particles, colloidal inorganic particles, magnetic recording particles, and various other additives. When silver halide particles are included they are there for purposes other than image formation, such as, to control gloss and haze. 
     The matte-containing layer useful in the practice of the invention can be applied by any of a number of well-known techniques, such as dip coating, rod coating, blade coating, air knife coating, gravure coating and reverse roll coating, extrusion coating, slide coating, curtain coating, and the like. After coating, the protective layer is generally dried by simple evaporation, which may be accelerated by known techniques such as convection heating. Known coating and drying methods are described in further detail in Research Disclosure No. 308, Published December 1989, pages 1007 to 1008. 
     The present invention is also directed to a single-use camera having incorporated therein a photographic element as described above. Single-use cameras are known in the art under various names: film with lens, photosensitive material package unit, box camera and photographic film package. Other names are also used, but regardless of the name, each shares a number of common characteristics. Each is essentially a photographic product (camera) provided with an exposure function and preloaded with a photographic material. The photographic product comprises an inner camera shell loaded with the photographic material, a lens opening and lens, and an outer wrapping(s) of some sort. The photographic material is exposed in a similar manner as any photographic materials are exposed in cameras, and then the product is sent to the developer who removes the photographic material and develops it. Return of the product to the consumer does not normally occur. 
     Single-use cameras and their methods of manufacture and use are described in U.S. Pat. Nos. 4,801,957; 4,901,097; 4,866,459; 4,849,325; 4,751,536; 4,827,298; European Patent Applications 0 460 400; 0 533 785; 0 537 908; and 0 578 225; all of which are incorporated herein by reference. 
    
    
     The invention will be further illustrated by the following examples. 
     EXAMPLES 
     Matte Particles Used in the Example Coatings 
     Matte particles used in the example coatings are listed in Table 1 together with their chemical composition and mean particle size. 
     
                       TABLE 1                                                     
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Matte      Matte Composition                                              
                           Size (μm)                                   
______________________________________                                    
M-1        Polystyrene     6                                              
M-2        Poly(methyl methacrylate)                                      
                           3.6                                            
M-3.sup.a  Poly(chloromethyl styrene-                                     
                           3.8                                            
           co-divinyl benzene) (97/3)                                     
M-4.sup.b  Poly(methyl methacrylate)                                      
                           3.4                                            
M5.sup.c   Poly(divinylbenzene-co-                                        
                           3.9                                            
           ethylvinylbenzene) (80/20)                                     
M6.sup.d   Poly(divinylbenzene-co                                         
                           3.0                                            
           ethylvinylbenzene) (80/20)                                     
M7.sup.d   Poly(styrene-co-                                               
                           2.8                                            
           ethylvinylbenzene-co-                                          
           divinylbenzene) (20/35/45)                                     
M8.sup.d   Polystyrene     2.7                                            
______________________________________                                    
 .sup.a Matte contains functional groups reactive with gelatin according t
 U.S. Pat. No. 4,855,219 and is colloidal silica covered according to U.S.
 Pat. No. 5,378,577                                                       
 .sup.b Matte is treated with caustic according to U.S. Pat. No. 5,206,127
 .sup.c Matte is colloidal silica covered according to U.S. Pat. No.      
 5,378,577                                                                
 .sup.d Mattes are coated with a layer of gelatin as described in U.S. Pat
 No. 4,855,219.                                                           
 
    
     EXAMPLES 1 TO 5 
     Preparation of the Photographic Element 
     A series of photographic elements are prepared as follows: A 178 μm thick polyethylene terephthalate support that contains an adhesion promoting subbing layer comprising a terpolymer latex of acrylonitrile,vinylidene chloride, and acrylic acid and a gelatin subbing layer is coated with the following layers in sequence: an emulsion layer (Table 2), an interlayer (Table 3), and an overcoat layer (Table 4). 
     
                       TABLE 2                                                     
______________________________________                                    
Composition of the emulsion layer                                         
Gelatin               3.12 g/m.sup.2                                      
AgBr particles (1.27 μm in diameter and                                
                      3.91                                                
0.013 m in thickness)                                                     
5-methyl-s-triazole-(2-3-a)-pyrimidine                                    
                      0.043                                               
7-ol Na salt                                                              
3,5-disulfocatechol disodium salt                                         
                      0.018                                               
Maleic acid hydrazide 0.00096                                             
Sorbitol              0.055                                               
Glycerin              0.060                                               
KBr                   0.0007                                              
Resorcinol            0.091                                               
______________________________________                                    
 
    
     
                       TABLE 3                                                     
______________________________________                                    
Composition of the interlayer                                             
Gelatin                0.35 g/m.sup.2                                     
Carboxymethyl casein   0.081                                              
Polyacrylamide         0.054                                              
Resorcinol             0.062                                              
5-methyl-s-triazole-(2-3-a)-pyrimidine                                    
                       0.048                                              
7-ol Na salt                                                              
Poly(acrylamide-co-2-sulfo-1,1-                                           
                       0.012                                              
dimethylethylacrylamide) (20/80) Na salt                                  
5-nitroindazole        0.0038                                             
______________________________________                                    
 
    
     
                       TABLE 4                                                     
______________________________________                                    
Composition of the overcoat layer                                         
Gelatin                0.35 g/m.sup.2                                     
Carboxymethyl casein   0.073                                              
Matte (see Table 5)    0.056                                              
Polyacrylamide         0.054                                              
Ludox AM colloidal silica                                                 
                       0.11                                               
Resorcinol             0.006                                              
Trifluromethane sulfonic acid, lithium salt                               
                       0.038                                              
silicone/polyethylene glycol                                              
                       0.051                                              
Zonyl FSN              0.024                                              
______________________________________                                    
 
    
     All the above layers can optionally contain bis(vinylsulfonyl methyl)ether or chrome alum hardener, or Saponin surfactant, or Olin 10G surfactant, or Tergitol surfactant, or Duponol ME surfactant. 
     Matte Dusting Evaluation 
     After conditioning film samples overnight at 25° C. (70° F.) and 50% RH, they are treated using a Model #1503 Teledyne Taber Abrader equipped with CS-5 wool felt wheels. These mildly abrasive wheels gently dislodge (or break off) matte beads without abrading the surface of the film. Films are run for 100 cycles under a normal load of 185 grams with a single pair of wheels. Two replicates per sample are run. Quantification of film &#34;dusting&#34; is achieved using a Gould Model 200 Micro Topographer equipped with a 2 to 2.5 μm diamond stylus. Vertical and lateral magnifications are 5000 and 50-100 X, respectively. Twenty topographic traces in each of four areas of each sample are done. Measurements are taken in &#34;treated&#34; and &#34;untreated&#34; film regions and the matte dusting results are reported on a percentage of number loss basis. Dusting is rated according to the following scale: 1=less than or equal to 15% of matte beads are lost in the test, 2=greater than 15% and less than or equal to 30% of matte beads are lost in the test, 3=greater than 30% and less than or equal to 50% of matte beads are lost in the test, and 4=greater than 50% of matte beads are lost in the test. 
     The testing results are reported in Table 5. 
     
                       TABLE 5                                                     
______________________________________                                    
              Matte                                                       
                   Matte dusting                                          
______________________________________                                    
Example 1       M-1    4                                                  
(comparison)                                                              
Example 2       M-2    3                                                  
(comparison)                                                              
Example 3       M-3    4                                                  
(comparison)                                                              
Example 4       M-4    3                                                  
(comparison)                                                              
Example 5       M-5    1                                                  
(invention)                                                               
______________________________________                                    
 
    
     The comparative matte M-1 and M-2 dust heavily under normal film finishing and transport processes and are not acceptable. The comparative matte x-3 contains functional groups which are reactive with gelatin according to U.S. Pat. No. 4,855,219. However, it dusts very badly and is not acceptable. The comparative matte M-4 is caustically treated in accordance with the procedure described in U.S. Pat. No. 5,206,127. That treatment does not improve the matte dusting behavior. On the other hand, matte M-5 of the present invention shows very little dust demonstrating superior performance in film finishing and transport processes. 
     EXAMPLES 6 TO 9 
     Preparation of the Photographic Element 
     A series of photographic elements are prepared as in Examples 1 to 5 except the Ag Br particles in Table 2 are 1.95 μm in diameter and the overcoat layer has the composition listed in Table 6. 
     
                       TABLE 6                                                     
______________________________________                                    
Composition of the overcoat layer                                         
Gelatin                0.35 g/m.sup.2                                     
Carboxymethyl casein   0.073                                              
Matte (see Table 7)    0.056                                              
Polyacrylamide         0.054                                              
Ludox AM colloidal silica                                                 
                       0.11                                               
Resorcinol             0.006                                              
Trifluromethane sulfonic acid, lithium salt                               
                       0.038                                              
Dow Corning DC-200 polydimethyl                                           
                       0.007                                              
siloxane                                                                  
Zonyl FSN              0.014                                              
______________________________________                                    
 
    
     The elements can optionally contain bis(vinylsulfonyl) methyl)ether or chrome alum hardener, or saponin surfactant, or Olin 10G surfactant, or Tergitol surfactant, or Duponol ME surfactant. 
     Matte Dusting Evaluation 
     Dusting is determined qualitatively by rubbing the matted surfaces of two pieces of film together and then rubbing the surfaces with black felt and observing whether the felt is contaminated with a white powder, which is dislodged matte. The white contamination is rated slight, moderate, or heavy with slight and moderate being acceptable and heavy being unacceptable. 
     The testing results are reported in Table 7 
     
                       TABLE 7                                                     
______________________________________                                    
             Matte                                                        
                  Black Felt dusting                                      
______________________________________                                    
Example 6      M-2    Heavy                                               
(comparison)                                                              
Example 7      M-8    Heavy                                               
(comparison)                                                              
Example 8      M-7    Moderate                                            
(invention)                                                               
Example 9      M-6    Slight                                              
(Invention)                                                               
______________________________________