CONDUCTIVE COATING COMPOSITION AND COMPOSITE BASES AND ELEMENTS CONTAINING SAME

Abstract: An aqueous coating composition comprises (a) a hydrophilic binder; (b) an ester of cellulose having at least 8 acyl groups per C24 cellulose unit wherein at least a majority of the acyl groups are derived from an aliphatic polycarboxylic acid having from 3 to 6 carbon atoms; or a salt of the ester; and optionally (c) a hardening agent in an amount sufficient to render the composition water-insoluble after coating and drying of the composition. The cellulose used in preparing the ester is preferably a deacetylated cellulose acetate prepared by reacting cellulose acetate with an alkali metal alkoxide dissolved in the corresponding alcohol, e.g. sodium methoxide in methanol. The coating composition is useful for forming water-insoluble, conductive and highly-adherent layers in composite bases or elements, and particularly in photographic elements having hydrophobic supports. The conductive layers can be used, for example, as conductive subbing layers or conductive pelloid layers. Salts of cellulose esters that are derived from cellulose prepared as described above, have a lower solution viscosity, and therefore have improved coatability. They are also more conductive than similar salts prepared from cellulose made by deacetylating cellulose acetate with aqueous ammonia.

Description: CQ DπCTIVE COATING COMPOSITION AND COMPOSITE BASES AND ELEMENTS CONTAINING SAME Technical Field This invention relates to cellulose derivatives useful for forming conductive layers on supports. More specifically, this invention relates to coating compositions useful for providing water-insoluble, conductive, and highly-adherent layers on composite bases or elements. In particular, such compositions are useful for providing conductive subbing layers for adhering hydrophilic layers (e.g. photographic emulsion layers) to hydrophobic supports (e.g. polyester films). It also relates to composite bases and elements containing one or more layers formed from such coating compositions. Background Art Hydrophobic substrates, such as polyester, cellulose triacetate, polyamide or polystyrene film bases and resin-coated paper supports, are well known commercial materials which possess a number of advantages for many uses. In the photographic industry, for example, such substrates are used as supports for various radiation—sensitive elements. However, the use of such hydrophobic materials in the photographic and other arts has been hampered to some extent because of the difficulty of suitably adhering various other layers to them, particularly when such other layers are hydrophilic in nature. In order to improve adhesion of various layers to hydrophobic supports, it is known to apply one or more intermediate layers to the supports before other layers are applied; see for example, in U.S. Patent No. 4,123,278 (issued October 31, 1978 to -3- supports. In particular, it has been difficult for workers in the photographic art to find coating compositions which, when coated and dried, will prevent or reduce electrostatic charge buildup. It has also been difficult to find coating compositions for use in forming conductive layers which readily adhere to hydrophobic supports. U.S. 4,459,352 describes a coating composition which when applied to a support and dried, overcomes aforementioned problems of coating compositions previously known in the art. More particularly, the coating composition of U.S. 4,459,352 can be used to provide a conductive layer which reduces or eliminates electrostatic charge build up which often occurs during manufacturing operations. Further, this subbing layer exhibits excellent adhesion to both hydrophobic support materials and subsequently coating hydrophilic layers. The coating compositions of U.S. 4,459,352 are also useful for providing water—insoluble and conductive pelloid layers on hydrophobic support materials. Pelloid layers ar also known as anti-curl layers. Thus, in one embodiment, U.S. 4,459,352 provides an aqueous coating composition, which is capable of forming a water-insoluble conductive and highly-adherent layer on a support, said layer comprises (a) a hydrophilic binder; (b) an ester of cellulose having at least 8 acyl groups per C 2 cellulose unit wherein at least a majority of the acyl groups are derived from an aliphatic polycarboxylic acid having from 3 to 6 carbon atoms; or a salt of that ester; and optionally (c) a hardening agent in an amount sufficient to render the layer water-insoluble after coating and drying of the coating composition. -4- The instant invention provides an improvement of the invention described in U.S. 4,459,352. More particularly, it has been demonstrated that the way the ester of cellulose is formed has a profound effect on the suitability of the ester (or derivative thereof) for providing conductive, adherent layers. More specifically, it has been found that salts with improved conductivity can be made by (a) de-esterifying a cellulose ester, e.g. deacetylating cellulose acetate, (b) reacting the cellulose thereby obtained with an aliphatic polycarboxylic acid, and (c) thereafter forming a salt by reaction of the cellulose-polycarboxylic acid derivative with a base. Research Disclosure. (December 19781 No. 176 discloses that cellulose acetate film or membranes can be saponified or deacetylated with aqueous alkaline solutions or methanolic sodium ethylate solution . British 389.876 discloses that cellulose ester materials, e.g. yarns, threads and fabrics, can be saponified with ammonia gas at 100-150'C. so that by-product, e.g. acetamide, is produced and removed in the gaseous current as it is formed. If desired, the process can be conducted in the presence of materials which swell the cellulose ester, e.g. methyl or ethyl alcohol. British 433.785 relates to the treatment of cellulose esters to make them more soluble in acetone. The process disclosed comprises treating the esters with an alcohol such as ethanol which swells but does not dissolve the ester, in the presence of a small amount of an esterifying catalyst e.g. phosphoric acid, or sulfuric acid. U.S. 2.270.326 discloses preparing a reactive form of cellulose with sodium in anhydrous ammonia. -5- U.S. 3.950.87? discloses that cellulose triacetate can be deacetylated with minimal molecular weight degradation using sodium ethoxide in methanol under a nitrogen atmosphere. U.S. 4.543.221 discloses formation of cellulose ester gelled semipermeable hollow fibers by deacetylation in aqueous alkali solution. U.S. 4.764.605 discloses deacetylating an acetyl derivative of a saccharide with an aqueous metal hydroxide/aqueous hydrogen peroxide/organic solvent to selectively hydrolyze specific acetate bonds. Manlev. J. of Polvmer Science: Part A Vol. 1, pp. 1893-1899 (1963), discloses that when cellulose triacetate crystals are hydrolyzed in an aqueous medium, polycrystalline cellulose is formed. In contrast, use of a non-aqueous medium gives an amorphous cellulose. Wadehra et al, J. of Applied Polvmer Science Vo1 • * 9 • PP- 2627-2630 (1965), discloses amorphous cellulose is obtained by treating cellulose triacetate sheets with 17, sodium methylate in anhydrous methanol. Jeffries, Journal of Applied Polvmer Science 12, pp. 425-445 (1968) discloses the preparation of films and fibers from highly disordered cellulose by regeneration in non-aqueous media. Disordered cellulose produced from cellulose acetate contains about 3-57. ethanol that is very resistant to evacuation. Disordered celluloses also crystallize very rapidly in water. Sisson, Industrial and Engineering Chemistry. Vol. 30. IV.5. pp. 530-537 (1938) teaches that amorphous cellulose is changed to a crystalline cellulose hydrate when the sample is treated with dilute acid or bleached. -6- DISCLOSURE OF INVENTION This invention relates to a novel material for preparing a conductive coating. The novel material is a cellulose ester having free carboxylic groups, or preferably a salt thereof, that is prepared from a cellulose composition produced by a certain method. Specifically, the method comprises removing carboxy groups from a cellulose ester (e.g. deacetylating a cellulose acetate) using an alkali metal alkoxide admixed with an alcohol as the decarboxylating agent. For example, the agent employed may be sodium methoxide in methanol. After preparation of the cellulose starting material in this manner, it is reacted with an aliphatic polycarboxylic acid having from 3 to 6 carbon atoms to prepare an ester of cellulose having at least 8 acyl groups per C.^ cellulose unit. Thereafter, it is preferred that the resultant ester intermediate be transformed into an alkali metal salt, e.g. a potassium salt, by reaction of free carboxyl groups with a base such as lithium, sodium, potassium and ammonium hydroxides and bicarbonates. In accordance with this invention, conductive cellulose materials prepared as described above are incorporated into an aqueous coating composition comprising (i) water, (ii) the conductivity improving agent, and (iii) a hydrophilic binder such as gelatin, and optionally other ingredients such as a hardener, surfactant, coating aid or the like. Such coating compositions are part of this invention. The coating compositions of this invention are useful for providing conductive layers on materials such as silver halide-based photographic elements, e.g. film. Thus, they may be used to provide a conductive coating to a support such as -7- polyester or cellulose acetate, to prepare a composite base having a conductive layer on one or both sides of the support. To prepare such a composite layer, the coating composition of this 5 invention is applied to the support by a suitable coating technique, and dried. The composite base can be used to prepare a composite element comprising a support, and a hydrophylic layer, on at least one side thereof. The 10 hydrophylic layer is adhered to the support with a conductive layer of this invention. This invention provides many benefits and overcomes difficulties and shortcomings in the prior art. For example, the method employed for forming 15 the cellulose starting material provides good control of the molecular weight of the cellulose-containing conductive material. Secondly, compared to the use of aqueous ammonium hydroxide as a decarboxylating agent, the use of a solution of sodium methoxide in _ 0 methanol provides reduced process time and a more reactive cellulose. Since the cellulose is more reactive, it can be reacted with the polycarboxylic acid much faster. This provides lessened cellulose degradation. The solution viscosities of aqueous 25 coating compositions of this invention are excellent, and the improved viscosity of the solutions afford better conductive coats and decrease product waste due to poor coats. Furthermore, the coatings provided by this invention have much improved _ 0 conductivity and therefore provide lower resistivity. The increased conductivity enables less material to be used, thereby improving product production costs. For all the above reasons, the instant -_ invention is readily adaptable by industry, and considered to be a significant advance in the art. -8- BEST MODE FOR CARRYING OUT THE INVENTION The coating composition of this invention is an aqueous-based composition. Typically, water is the only solvent in the composition. However, mixtures of water and water—miscible organic solvents (e.g. alcohols such as methanol and iεopropanol, and ketones such as acetone) can be used as long as water comprises at least 50 percent, by weight, of the mixture. The first essential component of the coating composition of this invention is one or more hydrophilic binders. Typically, such binders are film-forming and water-soluble. They are either commercially available or readily prepared using methods known to workers skilled in the art. Suitable hydrophilic binders include both naturally occurring substances such as proteins and protein derivatives, cellulose derivatives (e.g. cellulose esters and cellulose nitrate), gelatin and gelatin derivatives, polysaccharides, collagen derivatives; and synthetic hydrophilic polymeric materials such as poly(vinyl alcohol), poly(vinyl acetate)s and the like. Other examples of useful hydrophilic binders known in the art are described, for example, in Research Disclosure, publication 17643, December, 1978, p. 26, paragraph IX (published by Industrial Opportunities, Ltd., Homewell, Havant Hampshire P09 1EF United Kingdom). A binder particularly useful in the practice of this invention is gelatin. The second essential component of the coating compositions of this invention is one or more of certain esters of cellulose, or water-soluble salts of such esters. These esters or salts have at least 8 acyl groups per C 2 cellulose unit wherein at least a majority of the acyl groups are derived from an aliphatic polycarboxylic acid having from 3 -9- to 6 carbon atoms. The esters useful in the practice of this invention can be represented by the following formula of a C 2 cellulose unit: wherein each of R I -R I Λ s independently hydrogen or an acyl group. The term "acyl group" is used in this specification and in the following claims to refer to an organic radical derived from an organic acid by removal of the hydroxyl group (i.e. R,C0— wherein R, is a hydrocarbon moiety). At least 8, and preferably, at least 10 of R- I -R TΛ are acyl groups. Of those acyl groups, at least a majority (i.e. greater than 50 percent), preferably, at least about two-thirds, and most preferably, all of them are derived from one or more suitable aliphatic polycarboxylic acids, which are described in detail hereinbelow. Useful polycarboxylic acids (or acid halides or anhydride equivalents) for preparing the -10- described esters include both aliphatic saturated and aliphatic unsaturated polycarboxylic acids having at least two carboxyl groups. Preferably, aliphatic saturated acids having only two carboxyl groups (i.e. dicarboxylic acids) are used. Examples of useful polycarboxylic acids include phthalic acid, terephthalic acid, trimellitic acid, malonic acid, succinic acid, glutaric acid, fumaric acid, glutaconic acid, 2-methylsuccinic acid, adipic acid, 1,2,3-propanetricarboxylic acid, and the like. Preferred acids include dicarboxylic acids having from 3 to 6 carbon atoms, such as succinic acid, malonic acid, and glutaric acid. A particularly useful polycarboxylic acid is succinic acid. Mixtures of the described esters or salts thereof can be used in the coating compositions of this invention, if desired. Preferably, one or more salts of such esters are used. Such salts include the ammonium or alkali metal (e.g. lithium, sodium, potassium, etc.) salts. The sodium and potassium salts are particularly useful. The improved conductive coatings of this invention can be used in two general ways. First, they can be used to reduce or prevent electrostatic charge build up during manufacture of the composite element, e.g. photographic film. When used for this purpose, it is not necessary to render the conductive layer of this invention water insoluble. In other words, useful coatings of this invention can be made by merely drying the conductive layer deposited on the support, after coating the support with an aqueous coating composition of the invention. When used in this manner, the coating compositions need not contain a hardener. The second general way of using the coating compositions is to provide protection against electrostatic build up during and -11- after manufacture of the composite element. When used in this manner, the conductivity layers of this invention are rendered water insoluble by use of a hardener. Rendering our coating compositions water insoluble with a hardener can be accomplished in either of two ways: (1) by including a suitable hardening agent in the aqueous coating composition itself in an amount sufficient to render the composition water-insoluble after coating and drying of the composition; or (2) by incorporating a suitable diffusible hardening agent which is capable of rendering the composition water-insoluble at any appropriate place in the composite base or element. For example, a diffusible hardening agent can be incorporated in a hydrophilic coating composition which is coated "in association with" the coated conductive layer. As used in this specification "in association with" refers both to layers which are contiguous and to layers, which have intervening layers there-between through which the diffusible hardening agent can diffuse to reach the conductive layer. Preferably, when a diffusible hardening agent is used in the practice of this invention, it is incorporated in a layer contiguous to the conductive layer so that diffusion of the hardening agent is expedited. In a preferred embodiment of this invention, the hardening agent is included in the aqueous coating composition with the cellulose ester or salt thereof. The hardening agent can also be used to harden the hydrophilic binder in the composition, if necessary, as when gelatin is used as the binder. Useful hardening agents, both diffusible and nondiffusible are well within the skill of an ordinary worker in the photographic art. Many of -12- them are commercially available. Others can be readily prepared. They can be used alone or in mixtures, and in a free or blocked form. Useful hardeners include Werner chromium complex compounds, chromium halides and sulfates, aldehydes, epoxy-containing compounds, haloethylsulfonyls, bis(-vinylsulfonyl)s, zirconium nitrate and others described, for example, in Research Disclosure. December, 1989, 308119, paragraph 10, pages 1004-1005. Preferred hardeners for use in this invention include diepoxides, such as butanediol diglycidyl ether. The proportions of the components making up the coating compositions of this invention can be varied widely to meet the requirements of conductivity, adhesion and water-insolubility for a given use. Typically, the hydrophilic binder in the aqueous coating composition is present in an amount in the range of from about 20 to about 50, and preferably from about 35 to about 50, percent based on total dry composition weight. Further, the ester of cellulose or salt thereof is generally present in an amount in the range of from about 50 to about 80, percent based on total dry composition weight. The hardening agent is typically present in the aqueous coating compositions in an amount in the range of from about 10 to about 30, and preferably from about 15 to about 20, percent based on total dry composition weight. When a diffusible hardening agent is incorporated in another location in the composite base element, additional amounts may be needed so that a sufficient amount diffuses to the coating conductive layer to render it water—insoluble. The coating compositions of this invention can include additional nonessential ingredients in amounts which are typically used in the art. For -13- example, they can contain matting agents (e.g. silica, starch, titanium dioxide, polymeric beads, zinc oxide and calcium carbonate), coating aids (e.g. alcohols and surfactants), biocides, wetting aids, dyes, defoamers, thickeners, colorants, and other addenda commonly employed in such compositions. Typically the percentage solids in the aqueous coating compositions of this invention is in the range of from about 0.5 to about 15 percent based on total wet composition weight depending upon the use of the coating composition. For example, if it is used to provide a conductive subbing layer, the percent solids typically ranges from about 0.5 to about 2.5 percent. If the use intended is as pelloid or backing layer, the percent solids typically ranges from about 5 to about 15 percent. The coating compositions of this invention can be applied to a suitable support material to form a conductive layer in the preparation of a composite base or composite element. Typical support materials include subbed or unsubbed polymeric films, wood fiber or cellulosic substances (e.g. paper), metallic sheets and foil, glass and ceramic substances. Typical of useful cellulosic supports are paper supports having a baryta or resin (e.g. polyolefinic) coating thereon. Preferably, the support is a hydrophobic material, such as a resin-coated paper or a polymeric film. By "hydrophobic" is meant that the supports have a high or strong tendency to repel water. This hydrophobicity can be conveniently determined by measuring the receding water contact angle, Θ R , established between a droplet of distilled water and the surface of the support. Methods for determining Θ R are well known. A suitable method is the Sessile drop method described in Physical Chemistr y -14- of Surfaces, by A. W. Adamson (published by Interεcience Publishing Corp., 1967, pp. 352-375). Although it can be lower, typically, the Θ R for supports used in the practice of this invention, as determined by the Sessile drop method, is greater than about 75 # , and preferably greater than about 90° Typically useful polymeric film supports include cellulose nitrate; cellulose esters (e.g. cellulose triacetate); polystyrene; polyamides; polymers prepared from vinyl chloride; polyolefins (e.g. polyethylene); polycarbonates; polyacrylates; polysulfones; polyamides and polyesters of dibasic aromatic carboxylic acids with divalent alcohols. A particularly useful polymeric support is a poly(ethylene terephthalate) film. A more detailed description of useful supports and methods of making same is provided in Research Disclosure, publication 308,119, paragraph XVII, cited previously herein and the references mentioned therein. The aqueous coating composition of this invention can be applied to one or both sides of the support, but preferably to both sides, to form an electrically conductive layer. The composition can be applied or located on the supports by any of a number of suitable procedures, including immersion or dip coating, roller coating, reverse roll coating, air knife coating, doctor blade coating, gravure coating, spray coating, extrusion coating, bead coating, stretch-flow coating, skim-pan air knife coating, and curtain coating. The composition can be applied alone or as one of several layers applied with multilayer coating techniques. Applied layers can be dried by any suitable evaporation technique. Descriptions of coating and drying techniques are given in Research Disclosure, publication 308,119, -15- paragraph XV, cited hereinabove and the references mentioned therein. The thickness of the coated conductive layer will depend upon the particular requirements of the composite base or element involved and is well within the skill of an ordinary worker in the photographic coating art. The conductive layer can be formed with one or more coating passes to obtain desired coverages. Drying of the coated layer(s) can be carried out over a wide range of temperatures as is known in the art. The coated and dried conductive layer typically has a surface resistivity of less than about 10 ohms per square, and preferably from 8 9 about 10 to about 10 ohms per square, all measured at 21"C. and 507. relative humidity. This resistivity can be measured by any suitable technique. One such technique is described in ASTM Standard C59.3, designation D257-75 entitled "Standard Methods of Test for D-C Resistance or Conductance of Insulating Materials, " pp. 66-85, published Feb. 29, 1975. U.S. Pat. No. 3,525,621 (issued Aug. 25, 1970 to Miller) also discusses measurement of surface resistivities of coated layers. The composite bases of this invention can be used for any number of products which require a substrate having one or more conductive layers thereon. One such use is for preparing composite elements which additionally carry one or more additional layers which may not adhere adequately to hydrophobic supports. Typically, such additional layers are hydrophilic in nature. By "hydrophilic" is meant that the layers have a strong tendency to attract water. As with the hydrophobic supports described hereinabove, the hydrophilicity of such layers can be determined by measuring the Θ R by the Sessile drop method. -1 - Typical hydrophilic layers contained in the composite elements include subbing layers, antihalation layers, antistatic layers, matting layers, reflective layers, timing layers, neutralizing layers, protective layers and the like as are commonly used in the photographic art. Such hydrophilic layers would also include hydrophilic image—forming and image—bearing layers useful in the printing, electrographic (e.g. electrophotographic), photographic and other imaging arts. The hydrophilic layers typically contain one or more hydrophilic binders (referred to in this specification and in the claims as "second hydrophilic binder") which can be the same or different from what is described in the element claims as the "first" hydrophilic binders used in the aqueous coating compositions of this invention. Preferably, the first and second hydrophilic binders are the same. For example, preferably both are gelatin. I n one embodiment of this invention, the composite elements are useful as image-forming elements which typically comprise one or more image-forming layers containing components capable of providing an image under certain conditions, e.g. in repsonse to electromagnetic radiation, heat, electricity or chemical treatment. Typical image-forming compounds are described, for example, in Research Disclosure, publications 10938 (May, 1973); 15162 (November, 1976); 17029 (June, 1978); and 17643 (December, 1978). In another embodiment of this invention, the composite elements are useful as image-receiving elements which comprise one or more image-receiving layers containing components capable of "receiving" an image. Such elements can be used as receivers in. for example, integral image transfer film units or -17- two-sheet instant film products, including those sometimes called "peel apart" products and those described in U.S. Patent Nos. 4,296,195 (issued October 20, 1981 to Bishop et al) and 4,297,432 (issued October 27, 1981 to Bowman et al). They can also be photoconductive elements designed to receive toned images. In a preferred embodiment of this invention, a radiation-sensitive element comprises a suitable support (e.g. a resin-coated paper or polyester film). To this support, one or more radiation-sensitive layers are adhered with a conductive subbing layer composed of the hydrophilic binder, cellulose ester (or salt thereof) and hardener described herein. Preferably, the hardening agent is provided in the aqueous coating compositions which is applied and dried, but if diffusible, it can be incorporated in another appropriate place in the element if desired. Such radiation-sensitive elements include elements intended for use in both black-and-white and color photography, such as photothermographic, photographic, thermographic and radiographic elements, diffusion or image transfer film units and the like. Examples of photographic elements include photographic papers, aerial films, micrographic films and graphic arts films. The characteristics, components and methods of making such elements are known in the art. One reference summarizing much of the art is Research Disclosure. Publication 368,119 cited previously hereinabove. In another preferred embodiment of this invention, the aqueous coating composition of this invention is coated on a suitable support and dried to be used as a conductive pelloid layer. This pelloid layer could provide both antistatic and -18- anti—curl characteristics to the resulting composite base or element. It is located on the side of the support opposite to that side on which any image-forming or image-receiving layers are applied. Such conductive pelloid layers also typically contain a matting agent, such as silica. Between the pelloid layer and the support can be one or more intervening layers if desired. The radiation-sensitive layers useful in the practice of this invention can contain any suitable radiation-sensitive material. Preferably, they are photographic emulsion layers which contain one or more of the conventional photographic silver halides. Such materials include, for example, silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, and mixtures thereof. Typically, these emulsion layers also contain one or more hydrophilic binders. Illustrative examples of such binders are proteins such as gelatin, protein derivatives, cellulose derivatives, polysaccharides such as starch, sugars such as dextran, plant gums, and synthetic polymers such a polyvinyl alcohol, polyacrylamide and polyvinylpyrrolidone. Conventional addenda such as antifoggants, stabilizers, sensitizers, development modifiers, developing agents, hardeners, plasticizers, coating aids, etc. can also be included in the radiation-sensitive layers. In addition to the conductive and radiation-sensitive layers described hereinabove, the elements of this invention can include other appropriate subbing, pelloid, protective, adhesive, filter, reflective, opacifying, antistatic, intermediate and other layers commonly incorporated in radiation-sensitive products. -19- The hydrophilic (e.g. radiation-sensitive) layers, and other optional layers, in the elements of this invention can be applied to a support or composite base in any suitable manner, including those well known techniques described hereinabove for applying the aqueous coating compositions of this invention. The hydrophilic layers can be bonded directly to the support with the described conductive layer or if desired, there can be one or more intervening layers either between the support and the conductive layer, or between the conductive layer and the hydrophilic layer. Preferably, the hydrophilic layer is bonded directly to the support with the conductive layer. In an embodiment of this invention, a photographic element comprises a polyester support having on at least one side thereof, one or more photosensitive silver halide emulsion layers. These emulsion layers are adhered to the support with a conductive and highly-adherent subbing layer formed from an aqueous coating composition comprising: gelatin; potassium cellulose succinate; and butanediol diglycidyl ether hardener in an amount sufficient to render said potassium cellulose succinate water-insoluble after coating and drying of the coating composition. Better results are obtained if the molecular weight of the cellulose ester in the coating composition is controlled, at least to some extent. Generally speaking, the preferred molecular weight range of the conductive material is dependent to at least some extent on the coating technique employed to prepare the conductive coating of this invention, and the particular apparatus employed when carrying out the selected technique. -20- Thus, for example, when using a skim pan-air knife coating technique, it has been found that good results are obtained if the coating composition is prepared, using the technique described herein, from a cellulose having a degree of polymerization of from about 75 to about 130, i.e. a weight average molecular weight of from about 12,150 to about 21,060. Such a cellulose can be obtained, for example, by decarboxylating a cellulose ester of a monocarboxylic acid, e.g. a lower fatty acid having 2—6 carbon atoms. Preferably, the cellulose fatty acid ester is cellulose acetate having 2 or 3 acetyl units per C 6 cellulose unit. More preferably, there is on average, about 2.5 acetyl groups per each C 6 cellulose unit. For a cellulose acetate having a degree of polymerization of 75-200 (i.e. from 75 to 200 C 6 H 10 05 units) the weight average molecular weight of such a material is from about 20,000 to about 50,000. Above, it was mentioned that coating can be made from coating compositions of this invention using a skim pan-air knife coating system. Skim pan—air knife coating is accomplished by transporting a web to be coated under a roller, and raising a pan of coating solution up to the level at which the solution is just touching the support for application. A coating solution feed system (usually gravity activated) maintains a constant coating solution level in the pan. The amount of coating solution applied in this manner is controlled by the viscosity and percent solids of the coating solution. Coverage can also be varied by increasing or decreasing the air pressure on the air knife which blows excess coating solution off the support and back into the pan. An air knife is an air manifold. -21- The cellulose used as a starting material (to prepare the conductive agent of this invention) is prepared by decarboxylating a cellulose ester of a fatty acid, such as described above, in a non-aqueous medium. Preferred non-aqueous media are lower alkanols c n B 2n+l 0H ' wherein n * s fro 1 t0 about 3. Preferred alcohols are methanol and ethanol. These alcohols are used as the deacylating agent, and an excess is employed to provide a non-aqueous 10 reaction medium which facilitates the contacting of reactants and catalyst. The decarboxylating agent used to prepare cellulose from its fatty acid ester is employed in the presence of a catalyst, e.g. an alkali metal ^5 alkoxide, preferably a sodium or potassium alkoxide of an alcohol described above. Sodium alkoxides are preferred. It is preferred that the alkoxide be derived from the alcohol that is used as a reaction medium. Thus 20 highly preferred decarboxylation agents are sodium methoxide/methanol mixtures, and sodium ethoxide/ethanol mixtures. The concentration of the alkoxide is not critical; however, up to a point, the concentration of alkoxide will have an effect on the „_ reaction rate. Preferred concentrations are in the range of from about 0.05 to about 0.5 weight percent. It is important to be sure of the purity of the sodium methoxide. If it is exposed to air it will pick up water and carbon dioxide, yielding „ n sodium hydroxide, sodium carbonate and bicarbonate. The carbonates are inactive. While the sodium hydroxide will deacetylate cellulose acetate, it is not a catalyst since it is consumed in the reaction, forming sodium acetate. Impure material can be used __ as long as the required amount of methoxide is present. -22- When such decarboxylating agents are employed, it is preferred that they be employed at a temperature in the range of from about 50 • to about 80 # C; more preferably from about 65 to about 78.5'C. Reflux temperatures are conveniently used. It is preferred that the decarboxylation reaction be conducted for a time of from about 2 to about 10 hours, more preferably from about 3 to about 6 hours. Although not critical, it is preferred that the decarboxylation reaction be conducted while agitating the reaction mixture, for example, by stirring. Cellulose prepared in this manner can be dried, and stored as a dry powder. When the cellulose is dried, it is preferred that the drying temperature not exceed about 40 *C for a substantial period of time; otherwise there may be a decrease in reactivity. Drying is preferably conducted under reduced pressures to decrease the amount of time to reach a desired volatileε content. For example, a pressure of 25mm Hg can be used. Such a pressure and a drying temperature of 40*C has been used to prepare a cellulose having a volatileε content of less than Vk in 24 hours. Cellulose prepared in the above manner is preferentially used soon after preparation. If stored in a cold room (2*C), it should be used within 90 days. Cellulose prepared in the manner described above can be reacted with a polycarboxylic acid (or acid halide or anhydride equivalent) according to the skill in the art. Preferably, the process is conducted in the presence of a solvent for the polycarboxylic acid or equivalent, e.g. a liquid fatty acid such as glacial acetic acid, and an esterification catalyst such as an alkali metal salt of an acid, e.g. potassium acetate. -23- The esterification reaction is preferably conducted under conditions in which reaction of more than one carboxyl group in the polycarboxylic acid or equivalent is kept low, so as to retard the formation of product having an elevated viscosity. Thus, the reaction is conducted under such conditions of time and temperature as to maximize the formation of an ester product having one carboxy function of the polycarboxylic acid reacted with cellulose, and minimize the formation of product in which more than one carboxy group, per molecule of polycarboxylic acid, is esterfied with cellulose. When the reaction is conducted in this way, good viscosity control is realized, and the product has improved conductivity. It has been found that good results are obtained in the reaction of succinic acid and cellulose if the reaction of the process is conducted at 65 # -85*C for from 1 to 24 hours. Analogous times and temperatures can be used when other Polycarboxylic acid (or equivalent) reactants are substituted for succinic acid. In a preferred embodiment, the cellulose ester of polycarboxylic acid, prepared as described above, is not used per e to form a coating composition of this invention. Instead, such esters are converted into salts, preferably sodium or potassium salts, or mixtures thereof. Salts are conveniently prepared by reacting the ester intermediate with the amount of metal hydroxide or bicarbonate calculated to react with the carboxylic acid functions not bonded to cellulose ("εtoichiometric amount"). The reaction is preferably conducted while stirring or otherwise agitating the reactants to promote good mixing. It is not critical to use the εtoichiometric amount of salt forming reactant, but convenient to do so. -24- If less than the stoichiometric amount is used, then the product will have lessened conductivity, if more than stoichiometric is used, product isolation is complicated and there may be a deleterious effect on composites formed therefrom. Preparative Example 1 Deacylation of Cellulose Using Sodium Methoxide in Methanol, In a 5 liter 3 neck flask equipped with εtirrer and reflux condenser, were placed 500 grams of cellulose acetate, 1500 grams of methanol and 30 grams of a 25% solution of sodium methoxide in methanol. The flask is heated in a 72*C constant temperature bath and the contents refluxed with vigorous stirring for 4 hours. After 4 hours, the contents are cooled, filtered, washed with 2 x 200 grams of methanol and dried for 16 hours at 40 β C under vacuum. Analysiε εhowε less than 27, of the acetyl groups remaining. The ester of polycarboxylic acid can be prepared in general accordance with the procedure discussed above and illustrated by the Comparative Example. However, there are decided advantages obtained in using the cellulose prepared by reacting cellulose acetate with an alcohol, such as methanol, in the presence of a catalyst such as sodium methoxide. For example, using the latter method and a reflux temperature of 64 β C (methanol) the deacetylation reaction can be conducted in about 4 hours. This is in contrast to the approximately 48 hours required to react aqueous ammonia with cellulose acetate at 25 β C. Furthermore, the product obtained from Na0CH 3 /CH 3 0H is in acceptable form -25- after only one methanol rinse, whereas the product obtained rom aqueouε ammonia iε rinεed three times with water and three times with glacial acetic acid. That product is stored while wet with acetic acid, while an alcohol/alkoxide product can be stored dry. In the following Examples and Tables, "DACA" is used to mean ".deacetylated cellulose Acetate". Likewise "DACA-1" is used to εignify a DACA made by conducting the deacetylation with aqueouε ammonia hydroxide. Furthermore, "DACA-2" is used to signify a deacylated cellulose acetate made by conducting the deacylation with methanol in the presence of sodium methoxide. Example 2 Preparation of a eacetvlated Cellulose Acetate: To a stirred and heated reactor equipped with a reflux condenser, add 5 parts by weight methanol. Add 1.66 parts Eastman grade CA398-3 cellulose acetate (number average molecular weight is 27,000). Add 0.1 part sodium methoxide. Heat to about 65*C and reflux for 4 hours. Cool to 20'C. Isolate the slurry of cellulose on a buchner funnel or filtering centrifuge. Rinse the filter cake with 2.2 parts of fresh methanol. Dry at 40*C under vacuum. The yield is 1 part DACA-2 by weight. Volatiles are less than 37.. Residual acetyl content is leεε than 37. by weight. Inherent viεcosity in iron sodium tartrate solution is between 0.9 and 1.2 dL/g (measured at 0.57. weight per volume). Example 3 Preparation of Trihvdrogen Cellulose Trisuccinate (BCS): To a dry, heated and stirred reactor, add 4.3 parts by weight glacial acetic acid. Add 0.97 parts -26- εuccinic anhydride. Add 0.35 parts DACA-2 prepared as in Example 2. Add 0.54 parts potaεsium acetate. Heat the slurry to 85'C and hold for 8 hours. During the first 30 minutes the viscosity will increase sharply, but within 45 minutes the substitution will have proceeded far enough that the HCS will begin to dissolve in the acetic acid and viscoεity will diminiεh. To the still hot reactor after 8 hours, add 1.23 parts demineralized water and then cool reactor to 20*C. Precipitate the polymer dope in 44 parts cold water containing 0.027 partε sodium hypochlorite and 0.11 parts of 36% hydrochloric acid. Using decantation washes, the HCS is washed 5 times with 44 parts of demineralized water in each wash. The HCS is isolated on a buchner funnel or filtering centrifuge and dried at 40'C under vacuum. The theoretical yield is one part HCS at 3 out of a poεεible 3 succinyl substitutions on each glucose repeating unit. Volatiles are less than 2%. Residual succinic acid is lesε than 1% by weight. Succinyl subεtitution iε at least 57.7% by weight (2.16 moles out of a possible 3) and is typically 637. (2.7 moles out of 3). Inherent viscoεity in IN sodium acetate in acetic acid is 0.7 to 1.0 dL/g (0.5% weight per volume). When a cellulose having an appreciably higher molecular weight, e.g. about 30,000 is employed, one preferably uses a reaction vessel with high torque stirring sufficient to agitate the viscous reaction mixture containg the cellulose. Example 4 Preparation of Tripotassium Cellulose Trisuccinate To a stirred and cooled tank, add 5.9 parts by weight of demineralized water. Add 1 part dry HCS. Over 2 hours, meter 13.4 parts of a 2.7% by -27- weight potassium hydroxide solution in water into the HCS slurry. Keep the HCS temperature below 30*C. The major portion of dissolution and reaction to KCS will have occurred by the end of the potassium hydroxide addition. Stir the solution overnight to complete the reaction. Adjust the pΞ to between 6.6 and 7.2 with potassium hydroxide. Filter the solution through a 50 micron filter. Solids will be between 5.5% and 6.5% by weight. The solution viscosity at 25'C and 5.5% solidε iε between 5 and 25 centipoise. Comparative Example eacetvlation of Cellulose Acetate Using Ammonium Hydroxide and Subsequent Preparation of HCS and KCS A mixture is prepared using lOOg of cellulose acetate having a degree of polymerization of 75-130, and a number average molecular weight of 20,000 to 35,000; 500g of H 2 0, and 500g of concentrated aqueous ammonia. The mixture is allowed to stand for 48 hours and then washed three times with 2000 g of H 2 0 and then dewatered three times using 500 g of glacial acetic acid. The deacetylated celluloεe acetate iε at a concentration of about 26% in acetic acid. Deacetylated product (164g) prepared as above, is introduced with 175g of succinic anhydride, 583.5g of glacial acetic acid and 65g of potasεium acetate catalyεt into a 2000 ml, 3-neck flask equipped with a stirrer, reflux condenser and a thermometer. The resultant mixture (28.6% solids) is reacted for 20 hours at 92% C. The εuccinic acid half ester of cellulose product thereby produced is recovered by precipitation in water. The product is then water washed and dried at 65*C. -28- The succinic acid ester product prepared as above is converted into a potassium salt as follows: 10.5g of the cellulose succinate is εlurried in 63g of H-O and εtirred rapidly. While εtirring 136.5g of 0.5 N KOH iε added slowly. Following the general procedure given above, a sample of potasεium cellulose εuccinate was prepared using as a starting material a cellulose acetate having a degree of polymerization of 100 and a weight average molecular weight of 27,000. The sample was used as the comparison material in the testε reported below. Differences in HCS and KCS when using the preferred (nonaqyeous) PACA-2 instead of the (aqueous) PACA-1; In the HCS reaction, the use of DACA-2 made by a non-aqueous route allows a 48% reduction in the amount of succinic anhydride required. A 7*C (92*C to 85*C) reduction in reaction temperature and a 12 hour (20 "to 8) reduction in reaction time is realized. The reaction masε iε easily stirred throughout the reaction compared to the extremely difficult to stir reaction with DACA-1. Aqueouε prepared DACA-1 will not react to completion uεing the HCS recipe deεcribed in Example 3. The final HCS from DACA-2 has a lower inherent viscoεity compared to HCS from aqueouε DACA, and it iε completely εoluble in 80 β C water which HCS from aqueouε DACA iε not. The color of the HCS iε significantly improved. When εtarting with DACA-2, the dissolution of the KCS is faster and much more complete with an easy filtration of the final solution. The final KCS solution viεcosity is about 20 centipoise compared to about 70 centipoiεe for KCS made from aqueouε DACA. -29- Comparative Results Three batches of KCS made from DACA-2 were obtained. Using the DACA-1 procedure, (see Comparative Example) two batches of KCS were made. The percent solids and viscoεity of each batch were measured. Using each batch of KCS in a statistically designed experiment, KCS/gel formulations were made at varying ratios and coated at different coverages with wire wound rodε on ESTAR polyester film support and dried at 260*F. Randomized coatings were made with the center point formula coated four times . The surface resistivity of each coating was meaεured at 50% RH. Results and Discussion Table 1 liεtε the % solids and viscosities of the five batches of KCS that were investigated. The data show that one batch (Batch 2) has a lower % solidε (5.2 vε 6) and, hence, has the lowest viεc ' oεity. The data alεo εhow that the KCS made from DACA-2 have lower viεcosities than the KCS made from DACA-1 which iε advantageous in coating from a skim pan-air knife hopper. The lower reactivity of the DACA-1 requires a longer esterification time, hence, the more possibility for transesterification and higher solution viscosity. Table 2 listε the surface resistivities of the coatings of the five batches of KCS at 50% RH in ohms/sq. x 10 exp 10. Excellent reproducibility of the resistivity values is seen in the center point formula (1:1 KCS/gel). The data also show the higher the KCS/gel ratio or the higher total coverage the lower the surface resistivity. The key point in the resiεtivity data iε the 1 to 1.5 decade increase in conductivity of the KCS/gel coatings made from the DACA-2 εyntheεiε verεuε the DACA-1 εynthesis. -30- The lower viscosity and increased conductivity of KCS made by the DACA-2 εyntheεis allows reduction of the KCS/gel ratio from 4/1 to 1/1, thereby reducing the cost of a subbing layer while maintaining excellent coatability and a surface resiεtivity well within the εpecificationε of 10 exp 8 to 10 exp 10 ohms/sq. at 50% RH. ______!____! KCS Solutions made from PACA 2 PACA 1 PACA 1 Batch; 1 1 1 Δ B_ % Solids 6.2 5.2 5.9 6.1 6.2 Viscoεity cpε 22.6 12.1 17.4 76.6 33.3 31 α> t ft ft ft t ft ft f t t t O Ή •• •• — . »M ' © o o o © © © © r-ι σ^ © © © ». m iΛ IΛ 4-> ' Λ in iΛ lΛ O O O O N N O O O O N N ^ K rt r-l »-l © © ι-< «-< ι-l »- «-l τ-l »-l »-t ,-l f-l »-4 © -32- The invention haε been described and illustrated above with particular reference to preferred embodiments. A skilled practitioner, familiar with Applicants' detailed deεcription can make many εubstitutions or modificationε without departing from the scope and spirit of the appended claims which appear below.

Claims: -33- Claimε : 1. An aqueous coating composition which is capable of forming a conductive and highly-adherent layer on a support, said coating composition comprising: (a) a hydrophilic binder; (b) an ester of cellulose having at least 8 acyl groups per C 24 cellulose unit wherein at least a majority of said acyl groups are derived from an aliphatic polycarboxylic acid having from 3 to 6 carbon atoms; or a salt of said ester, said cellulose characterized by having been derived, prior to preparation of said ester, by deacylation of cellulose triacetate with an alkali metal alkoxide in an alcohol, said alkoxide and said alcohol having from one to three carbon atoms. 2. The composition of Claim 1 wherein said alcohol is methanol and said alkoxide is sodium or potassium methoxide. 3. The composition of Claim 1 wherein said alkoxide is sodium ethoxide, and said alcohol is ethanol. 4. The coating composition of Claim 1 wherein said ester salt is an alkali metal ester εalt. 5. The coating composition of Claim 4 wherein said eεter salt is a potassium εalt. 6. The coating composition of Claim 1 wherein at least about two-thirds of said acyl groups are derived from said aliphatic polycarboxylic acid. -34- 7. The coating composition of Claim 1 having at least 10 acyl groups per C^ cellulose unit. 8. The coating composition of Claim 1 wherein said polycarboxylic acid is a dicarboxylic acid. 9. A composite base comprising a support having on at least one side thereof, a conductive and highly-adherent layer compoεed of: (a) a hydrophilic binder; (b) an eεter of celluloεe having at leaεt 8 acyl groups per Z^ cellulose unit wherein at leaεt a majority of said acyl groups are derived from an aliphatic polycarboxylic acid having from 3 to 6 carbon atoms; or a salt of εaid ester, said cellulose characterized by having been derived, prior to preparation of said ester, by deacylation of cellulose triacetate with an alkali metal alkoxide in an alcohol, said alkoxide and said alcohol having from one to three carbon atoms. 10. The composite base of Claim 9 having a hydrophobic εupport. 11. A composite element comprising a support and on at least one side thereof, a hydrophilic layer, εaid hydrophilic layer being adhered to εaid εupport with a conductive and hi hly-adherent subbing layer composed of: (a) a first hydrophilic binder; and (b) an eεter of cellulose having at least 8 acyl groups per C 2 A cellulose unit wherein at least a majority of said acyl groups are derived from an aliphatic polycarboxylic acid -35- having from 3 to 6 carbon atoms; or a salt of said ester, said cellulose characterized by having been derived, prior to preparation of said ester, by deacylation of cellulose triacetate with an alkali metal alkoxide in an alcohol, said alkoxide and said alcohol having from one to three carbon atoms. 12. A photographic element comprising a polyester support and, on at least one side thereof, a photosensitive silver halide emulsion layer, said emulsion layer adhered to said support with a conductive and highly-adherent subbing layer formed from an aqueous coating composition comprising: (a) gelatin; (b) potassium cellulose succinate containing at least 10 succinyl groups per C 2 ^ cellulose unit, said cellulose characterized by having been derived, prior to preparation of said eεter, by deacylation of cellulose triacetate with an alkali metal alkoxide in an alcohol, said alkoxide and said alcohol having from one to three carbon atoms. 13. A photographic element comprising a support and, on at least one side thereof, a photosensitive silver halide emulsion layer which iε adhered to said support by a conductive subbing layer, said subbing layer comprising: (a) a hydrophilic binder, (b) a water-soluble salt of a cellulose ester, said cellulose ester having at least 8 acyl groups per C 2 celluloεe unit wherein at leaεt a majority of εaid acyl groupε are derived from an aliphatic polycarboxylic acid -36- having from 3 to 6 carbon atoms, εaid celluloεe characterized by having been derived, prior to preparation of said eεter, by deacylation of cellulose triacetate with an alkali metal alkoxide in an alcohol, said alkoxide and said alcohol having from one to three carbon atoms. 14. A photographic element comprising a polyester support and, on at least one side thereof, a photoεenεitive εilver halide emulεion layer which is adhered to said support by a conductive subbing layer, εaid subbing layer comprising: (a) a hydrophilic binder, (b) a water-soluble salt of a celluloεe ευccinate, said celluloεe succinate containing at least 10 succinyl groups per C 2 celluloεe unit, said cellulose characterized by having been derived, prior to preparation of εaid eεter, by deacylation of cellulose triacetate with an alkali metal alkoxide in an alcohol, εaid alkoxide and εaid alcohol having from one to three carbon atomε. 15. A photographic element comprising a poly(ethylene terephthalate) support and, on at least one side thereof, a photosensitive silver halide gelatin emulεion layer which iε adhered to εaid εupport by a conductive subbing layer, said subbing layer comprising: (a) gelatin, (b) a water-soluble salt of a cellulose succinate, said cellulose succinate containing at least 10 succinyl groups per C 24 celluloεe unit, said cellulose -37- characterized by having been derived, prior to preparation of said ester, by deacylation of cellulose triacetate with an alkali metal alkoxide in an alcohol, said alkoxide and 5 said alcohol having from one to three carbon atoms. 10 15 20 25 30 35

Inventors: HANNON CHARLES W, JONES RAYMOND T, HANNON, CHARLES, W., JONES, RAYMOND, T.
Applicants: EASTMAN KODAK CO, EASTMAN KODAK COMPANY
Application year: 1991
Main classification: C09D101
IPC codes: C08B3, C09D101, G03C1