WO1983002506A1

WO1983002506A1 - Electrically conductive compositions and use of same

Info

Publication number: WO1983002506A1
Application number: PCT/US1982/001724
Authority: WO
Inventors: Kodak Compay Eastman; Charles R. Hasenauer; Donald N. Miller
Original assignee: Kodak Compay Eastman
Priority date: 1982-01-08
Filing date: 1982-12-10
Publication date: 1983-07-21
Also published as: US4415626A; AU551966B2; DE3277471D1; JPS59500021A; AU1106883A; CA1181939A; EP0098281B1; EP0098281A1

Abstract

An electrically conductive composition that is particularly useful for reducing the propensity of image-forming elements to accumulate static electrical charge. The composition comprises an aqueous dispersion of a combination of (a) a non-gelatino, polymeric film-forming binder (b) a hardening agent for the binder; (c) particles of matting agent that are substantially transparent and have a diameter in the range of from 1 to 50 micrometers and a specific gravity substantially the same as that of water; (d) a conductivity agent that is non-crystallizable and (e) a charge control agent. This composition is especially useful for forming an image-receiving layer in substantially transparent image-receiving elements. Such image-receiving elements are used in making projection-viewable transparencies by an electrographic copy process.

Description

ELECTRICALLY CONDUCTIVE COMPOSITIONS AND USE OF SAME This invention relates to a formulation of chemical compounds that is particularly useful as an antistatic composition. It also relates to an element incorporating such a composition, which element has reduced propensity to accumulate static electrical charge, and to a method of preparing such an element. In a particular aspect, this invention relates to a substantially transparent image-forming element containing at least one electrically conducting layer formed from such a composition.

In manufacturing and using elements in the radiographic, magnetic, electrographic and photographic fields, the generation of static electrical charge is a serious problem. In the case of photographic and magnetic products, serious deleterious effects are evident when accumulated charge discharges, producing either actinic radiation or "noise" which is recorded as a visible image on photosensitive products or as static on magnetic products such as magnetic tape. Static discharge can occur in the course of manufacturing processes (e.g. coating, finishing or packaging) or during customer use (e.g. in cameras, printers, tape recorders and copier/duplicator equipment) .

Accumulation of static electrical charge on elements designed for electrographic use is very troublesome during customer use since it increases the tendency of such elements to stick to each other when stacked together or when being used. Many times, a "multifeed" occurs when two or more elements are drawn into electrographic copier/duplicator equipment where they stick together and cause a blockage or "jam" in the feed rollers. Also, such

O H elements stick at a fuser station, where toned image is fused and "jams" that station to cause equipment shutdow .

Problems of the type described in the preceding paragraph frequently occur during the preparation of pro ection-viewable transparencies by electrographic copying. During this process, an image of fusible toner particles is formed on an image-receiving layer of a transparent element. The particles are then fixed to the element, e.g. by contacting with a heated fusing surface. This process usually occurs inside electrographic copier/duplica or equipment (sometimes simply called copier/duplicator equipment) where the image-receiving element contacts a variety of components (e.g. rollers, plates and belts). hen an element sticks to any of these components or to another element, this disrupts the entire copying process and impedes the movement of and/or causes damage to such element and to other elements.

Incidences of the so-called "multifeed" and "jam" problems have increased sharply with the introduction of higher speed electrographic copier/duplicator equipment. It is known that the propensity for an element, particularly an image-forming element, to accumulate static electrical charge can be reduced by including an electrically conductive antistatic layer in such element. An. example of such an antistatic layer is one formed from an antistatic composition described in U.S. Patent 3,437,484, issued April 8, 1969. Such composition comprises a poly(vinyl alcohol) binder, a hardening agent for the binder, particles of matting agent, such as beads of polyalkyl methacrylate with cross-section diameters of from 0.5 to 15 micrometers (0.5 to 0.15 microns) and a conductivity agent which is an alkali metal halide such as sodium or potassium chloride. In the past, this type of composition has been quite useful in combatting the problem of static accumulation. However, there is a need for an electrically conducting composition that is even more effective in reducing the accumulation of static electrical charge and has the capability of being used in. a wide variety of image-forming elements, including radiation-sensitive elements such as photographic elements and electrographic elements such as the pro ec io -viewable transparencies described hereinbefor .

This invention provides an electrically conductive composition comprising an aqueous dispersion of a combination of:

(a) a non-gelatino, polymeric, film- forming binder,

(b) a hardening agent for the binder,

(c) particles of matting agent that are substantially transparent and have a diameter of 1 to 50 micrometers (1 to 50 microns) and a specific gravity substantially the same as water,

(d) a conductivity agent that is non- crystallizable, and

(e) a charge control agent.

The invention also provides an element comprising a support and at least one electrically conductive layer formed from the composition just described.

In addition, this invention provides a method of making the aforementioned element by forming the aforementioned electrically conductive composition, coating a layer of the composition on at least one side of the support and drying the coated layer. The electrically conducting layers prepared in practicing this invention provide several important advantages, including the advantages that they can be coated from aqueous solution and the fact that they are durable, non-tacky and strongly adherent to underlayers and to the support.

Consequently, they do not contaminate equipment employed in manufacturing image-forming elements such as radiation-sensitive elements nor processing baths or equipment used in processing such elements. Such layers also offer significant advantages in other image-forming elements such as those used in preparing pro ectio -viewable transparencies. Thus, image-forming elements containing such layers that are used to prepare projection-viewable - transparencies by electrographic copying are significantly less susceptable than comparable prior art elements to "multifeed" and "jam" problems. Furthermore, the resulting transparencies do not stick together upon exiting copier/duplicator equipment and, therefore, can be easily stacked and packaged. In addition, the surface of such an electrically conducting layer is of sufficiently high quality that it can be used as the image-receiver in forming a projection-viewable transparency by electrographic copying.

The composition of this invention is an aqueous dispersion in which water is usually the only liquid dispersant. However, mixtures of water and water-miscible organic solvents (e.g. alcohols, such as methanol and isopropanol and ketones such as

OMPI acetone) can be used. Water generally comprises at least 50 percent, by weight, of the composition and certain of the components are totally or partially solubilized therein. Typically, some components are dissolved by or solubilized in the water, while others (e.g. the matting agent) are dispersed therein.

The film-forming binder used in the composition can be any non-gelatino, polymeric binder. Such binders are known and, unlike gelatin, they can be applied to a substrate according to this invention to form a non-tacky film. Typical binders are described in detail in Research Disclosure, publication 17643, paragraph IX, (published December, 1978 by Industrial Opportunities, Ltd., Homewell, Havant Hampshire P09 1EF, United Kingdom) and include both natural and synthetic, colloidal and resinous materials. They can be used alone or in combination with one another. Preferably, the binder is a non-proteinaceous, synthetic polymeric binder such as poly(vinyl alcohol) or a derivative thereof, poly(vinyl acetate), carboxy methylcellulose or carboxymethyl hydroxyethylcellulose.

The hardening agent used in the composition of this invention insures that the particular binder used is non-tacky in film form. Suitable hardening agents are well known in the art and are commercially available or easily prepared. They can be used alone or in combination with one another and can be in free or blocked form. Examples of useful hardening agents are Werner chromium complex compounds, chromium halides and sulfates, epoxy-containing compounds, haloethylsulfonyls, bis(vinylsulfonyls) , and zirconium nitrate. Others are described in Research

Disclosure , publication 17643 , paragraph X. When

OMPI poly(vinyl alcohol) is used as the binder, a preferred hardening agent is methacrylatochromic chloride which is commercially available as VOLAN TM from E. I. DuPont, Wilmington, Delaware, U.S.A. The composition of this invention includes particles of a substantially transparent matting agent. Such particles improve the surface lubricity of the electrically conducting layers formed from the compositions. The particles are "substantially transparent" in that they permit essentially all

(greater than about 90 percent) light incident on the particles to pass through the particles. Although the size of the particles of the matting agent can vary widely, such particles are preferably of substantially uniform size. The particles usually have a curvilinear surface and preferably are substantially spherical beads. These particles have a diameter in the range of from 1 to 50, preferably from 2 to 25, and more preferably from 8 to 12, ^" micrometers (μm) . Where the particles are not spherical, this diameter refers to the dimension of the major axis.

The particles of matting agent exhibit little or no swelling (i.e. less than about 20%, preferably less than about 10% swell) in the aqueous medium in which they are dispersed. The particles also have a specific gravity substantially the same as that of water (i.e. about 1) and are sometimes referred to as "neutral bouyancy" particles. Such particles do not settle in the aqueous medium of the composition which facilitates uniform dispersion of matting agent throughout the aqueous medium and correspondingly, throughout a coated layer. The particles of matting agent described herein can be composed of a wide variety of organic polymers, including both natural and synthetic polymers. The polymers can be addition polymers (e.g. polystyrenes or polyacrylates, etc.) or condensation polymers (e.g. polyesters, polycarbonates, polyamides or silicone polymers). Preferably, the matting agent particles are composed of addition polymers (i.e. homopolymers and 0 copolymers) prepared from one or more ethylenically unsaturated polymerizable monomers. Particles of one polymer or a mixture of particles of several polymers can be used.

The polymers of which the particles are c composed can be prepared by any of a variety of polymerization methods. Typical addition polymerization methods include: solution polymerization (followed by appropriate precipitation procedure, if necessary); suspension polymerization _Q . (sometimes called "bead" polymerization) ; emulsion polymerization; dispersion polymerization; and precipitation polymerization. Condensation polymers can be prepared by conventional condensation polymerization processes (e.g. bulk and hot melt polymerization) .

Particularly useful polymers which form the particles of matting agent described herein are addition polymers prepared from at least one of the following ethylenically unsaturated polymerizable monomers: a. Up to 100, preferably up to 99, weight percent of an amino-free styrene, including derivatives and equivalents thereof, such as a monomer having the formula Cffir - CR' ^!-@r^! wherein each of R and R , which can be the same or different, is a non-interfering substituent such as hydrogen, halo (e.g. fluoro, chloro or bromo) or substituted or unsubstituted, amino-free alkyl or aryl having from 1 to 10 carbon atoms (e.g. methyl, ethyl, t-butyl, phenyl or methylphenyl) ; and R is a non-interfering substituent such as hydrogen, halo (e.g. fluoro, chloro or bromo), or a substituted or unsubstituted, amino-free aliphatic or aromatic group having from 1 to 10 carbon atoms, e.g. alkyl, alkoxy, aryl, or aryloxy. Typical of such styrene monomers are styrene, vinyltoluene and t-butylstyrene. b. Up to 25, preferably ip to 20, weight percent of an acrylic acid ester, including derivatives and equivalents thereof, such as an acrylic acid ester having the formula

CHR¹ = CH - C00R⁴ wherein R¹ is as defined previously and R is a hydrocarbon having from 1 to 10 carbon atoms, such as aryl (e.g. phenyl), alkyl (e.g. methyl, ethyl, t-butyl), alkaryl (e.g. benzyl, 2-ethylenephenyl) and aralkyl (e.g. xylyl) . c. Up to 100, preferably up to 75, weight percent of a methacrylic acid ester including derivatives and equivalents thereof, such as a methacrylic acid ester having the formula CH₃

CHR¹ =^■ C - C00R⁴ wherein R and R are as defined hereinbefore. d. Up to 30, preferably up to 25, weight percent of a carboxylic acid containing one or more

CMPI ethylenically unsaturated polymerizable groups, such as methacrylic acid, acrylic acid, crotonic acid and itaconic acid. e. Up to 75, preferably up to 50, weight percent of a nitrile containing one or more ethylenically unsaturated polymerizable groups, such as acrylonitrile, methacrylonitrile, and equivalents. f. Up to 20, preferably up to 15, weight percent of amino-substituted styrene monomer, including styrene monomers having N-alkyl substituted a ino substituents on the phenyl ring of the styrene monomers, such amino-substituted styrene monomers typically having the formula

wherein each of n and p, which can be the same or different, is 0 or 1, R 1, 2 and R3 are as

5 defined hereinbefore, R is alkylene having from 1 to 6 carbon atoms (e.g. methylene, ethylene or isopropylene) , and Am is a primary, secondary, or tertiary amino group. Typical amine-substituted styrene monomers are N,N-dimethyl-N-vinylbenzylamine and styrenes containing N-alkyl substituted amino substituents, such as N-methylaminoethylstyrene and N,N-dimethylaminoethylstyrene. g. Up to 20, preferably up to 10, weight percent of a monomer containing a crosslinkable group, including

(1) ethylenically unsaturated polymerizable monomers which can be crosslinked by conventional gelatin hardening agents, or example, aldehyde, haloethylsulfonyl, and bis(vinylsulfonyl) hardening agents. (2) ethylenically unsaturated polymerizable monomers which can be crosslinked by diamines, such monomers containing a conventional gelatin hardening group, for example, aldehyde group-containing monomers, haloethylsulfonyl group-containing monomers and vinylsulfonyl group-containing monomers, h. Up to 20, preferably up to 15, weight percent of a tertiary aminoalkyl acrylate or methacrylate and equivalents thereof, such as dimethylaminoethyl acrylate and diethylaminoethyl methacrylate. i. Up to 100, preferably up to 75, weight percent of a polymerizable, N-heterocyclic vinyl monomer and equivalents thereof, such as 4-vinyl- pyridine and 2-vinylpyridine. j. Up to 20, preferably up to 15, weight percent of an acrylamide or methacrylamide and equivalents thereof, including monomers having the formula

0 CHR¹ = CR⁶C - Am wherein R and Am are as defined hereinbefore and R is hydrogen or methyl. Typical monomers are N,N-dialkyl-acrylamide (e.g. N,N-diisopropyl- acrylamide) or N,N-dialkylmethacrylamide (e.g. N,N-dimethylmeth-acrylamide) . k. Up to 20, preferably up to 5 weight percent, of a crosslinkable monomer containing at least two ethylenically unsaturated polymerizable groups, such as divinylbenzene, N,N-methylenebis- (acrylamide) , ethylene diacrylate, ethylene di ethacrylate and equivalents thereof.

A partial listing of useful polymers includes: poly(styrene-co-methacrylic acid) [98:2]; ρoly(vinyl toluene-co-p-t-butylstyrene-co-methyl- acrylic acid) [61:37:2]; poly(vinyl toluene-co-p- t-butylstyrene-co-methacrylic acid-co-divinylbenzene) [60:37:2:1]; poly(methyl methacrylate); and poly- (styrene-co-acrylonitrile) . The numbers in the brackets following each of the polymer names represent the weight ratio of monomers from which the polymers are prepared. Further examples of useful polymers are described in U.S. Patent 4,258,001, issued March 24, 1981. Individual matting agent particles are comprised of at least 75, and preferably at least 90 weight percent, of the addition or condensation polymers described herein. The remainder can be composed of addenda such as pigments and fillers, provided the requisite transparency is maintained.

Preferably, the particles are composed entirely, i.e. 100 weight percent, of the aforementioned polymers. Still another component of the composition of this invention is a conductivity agent that is non-crystallizable. Such agents are highly electrically conductive. Typical agents are organic non-polymeric or polymeric (including oligomeric) compounds. Such conductivity agents can be used singly or in combination. The conductivity agent is noncrystallizable and, therefore, it does not form crystals on the surface of the electrically conducting layer coated from the compositions- The formation of such crystals results in "haze" (a cloudy appearance) which is particularly detrimental in those situations where a transparent product is desired, e.g. in a projection-viewable transparency. Typical conductivity agents useful in practicing this invention are ionic polymers or resins. Such polymers are sometimes called "polyelectrolytes." Such ionic polymers can be anionic or cationic, have charged moieties in the backbone of the polymer chain or in pendant groups and be free acids or salts of acids. They can be addition or condensation polymers prepared by conventional techniques such as those described previously with regard to the matting agent.

Useful conductivity agents are well known and include cationic polymers, such as the vinyl- benzyl quaternary ammonium polymers described in U.S. Patent 4,070,189, issued January 24, 1978; quaternary ammonium polymers described in U.K. Patent 1,549,032, published July 25, 1979 and U.S. Patents 3,708 289, issued January 2, 1973, 3,775,126, issued November 27, 1973 and 4,222,901, issued September 16, 1980; and anionic polymers such as alkali metal and ammonium salts of poly(acrylic acid), poly(meth¬ acrylic acids), poly(styrene sulfonic acids), poly(vinyl phosphates) and free acids thereof; salts of a carboxy ester-lactone of an interpolymer of an α-β-dicarboxylic acid (or anhydride) and a vinyl ester of a carboxylic acid, as described in U.S. Patent 3,206,312, issued September 14, 1965, the anionic polymers described in U.S. Patent 3,033,679, issued May 8, 1962 and in U.K. Patent 1,549,032 and U.S. Patent 3,708,289 mentioned previously. All of these polymers are readily available commercially or can be readily prepared by known techniques. The anionic conductivity agents are preferred for use in this invention. Of these, polymeric carboxylic acids and their metal and ammonium salts, such as poly(acrylic acid) and poly(methacrylic acid), their substituted equivalents and their alkali and ammonium salts are particularly useful. Examples of the polymeric carboxylic acids and salts thereof are sodium polyacrylate, potassium polyacrylate, potassium poly(α-chloroacrylate), poly(acrylic acid) and ammonium polymethacrylate.

Sodium polymethacrylate is a preferred conductivity

TM agent and is commercially available as TAMOL 850 from Rohm Se Haas, Philadelphia, Pennsylvania, U.S.A. The composition of this invention also comprises at least one charge control agent. This agent is capable of being incorporated into or coated onto a surface to adjust the triboelectric charging characteristics thereof. Such agents are well known and are described in detail in U.S. Patents 3,501,653, issued March 17, 1970 and 3,850,642, issued November 26, 1974. They are materials of known triboelectric charging propensity which can be determined by any one of a number of suitable techniques known in the prior art. One such technique is the so-called "impact electrification" method and apparatus for carrying out this method, as described in the aforementioned U.S. Patents 3,501,653 and 3,850,642. A detailed description of an instrument suitable for measuring impact electrification is set forth in U.S. Patent 3,501,653. The instrument and the measured values obtained in the use thereof are defined and explained in detail therein. Stated simply, the theory of the instrument described in U.S. Patent 3,501,653 is that if accurate comparative values for impact electrification of a variety of surfaces are to be determined, a given reference surface must be impacted by a second (reference) surface and separated, all in a controlled and repeatable manner. The electrical charge generated by the impact an separation is accurately measured and recorded. The values obtained are conveniently expressed in microcoulombs per square meter. θ Charge control agents are distinguished from conductivity agents in that the latter are materials which, due to their hygroscopy or ionic nature, tend to conduct away or bleed off static charges generated by contact between two surfaces- This minimizes 5 static charge accumulation. In contrast, charge control agents minimize, maximize or adjust to a prescribed level, the propensity of a given surface to generate static electrical charges when contacted with another usually dissimilar surface. 0 - Th charge control agents used in the practice of this invention provide a reduction in triboelectric charging. Typical useful charge control agents include those described in the aforementioned U.S. Patent 3,850,642, and the 5 fluorinated surface active agents (sometimes called surfactants) described in U.S. Patents 3,754,924, issued August 28, 1973 and 3,884,699, issued May 20, 1975. The fluorinated surfactants of U.S. Patent 3,754,924 are particularly useful, including those having the formula R-. - A - X wherein Rp is a partly or wholly fluorinated hydrocarbon chain comprising at least three fluorine atoms. A is a chemical bond or a bivalent hydrocarbon group having from 1 to 30 carbon atoms, such as an aliphatic (e.g. alkylene or cycloalkylene) , aromatic (e.g. arylene) or mixed aliphatic-aromatic group (e.g. aralkylene or alkarylene) including bivalent groups interrupted by - heteroatoms (e.g. oxygen and sulfur), carbonyloxy

U " 7 7

(-CO-) and amide groups (-CNR - and -S0 NR wherein R 7 is hydrogen or alkyl of 1 to 3 carbon atoms). X is a hydrophilic group, such as (1) a hydrophilic nonionic polyoxyalkylene group like a o polyoxye hylene of the formula (-CI^CH^O) R wherein R is hydrogen or alkyl (branched or linear) of 1 to 5 carbon atoms and n is an integer of from 5 to 20, which polyoxyalkylene can be inter¬ rupted by one or more isopropyleneoxy groups; (2) a hydrophilic betaine such as R⁹ R⁹

-N⁺-Alk-C00^" or -N⁺-Alk-S0,- wherein Alk is R^■ R• alkylene (branched or linear) of from 1 to 5 carbon

Q atoms and R is alkyl (branched or linear) of from 1 to 5 carbon atoms; or (3) an anionic group such as -S0₃M, -0S0₃M, -C00M, -0P0₃M, -0P0₃M ¹⁰ or -PO-₃MR wherein M is hydrogen, an alkali metal ion (e.g. sodium or potassium), an ammonium ion (having hydrogen or alkyl groups) or an organic ammonium ion, such as diethanolammonium, morpholinium or pyridinium, and R is alkyl (branched or linear) of from 1 to 5 carbon atoms or R_..

Of the fluorinated surfactants, the anionic compounds are preferred, including those wherein R„ is a partly or wholly fluorinated alkyl of from 1 to 12 carbon atoms (e.g. methylene, isopropylene, hexylene or dodecylene) A is a chemical bond and X is an anionic group, especially a εulfonate. One particularly useful charge control agent has the formula CF₃ CF₂)_?S0₃ ^" N C₂H₅)₄ ⁺ and is commercially available under the name FLUORTENSIDE FT 248™ from Mobay Chemical Company, Pittsburgh, Pennsylvania, U.S.A. The charge control agents useful in this invention are readily available commercially, or they can be prepared by known techniques.

The components of the composition of this invention can be mixed together in any suitable fashion in which coagulation or agglomeration is avoided. Generally, the individual components are added to the aqueous medium under ambient conditions one at a time with sufficient agitation to disperse or solubilize them. The components are added in small amounts so as to keep the resulting composition relatively dilute. In general, the percent solids of the composition is in the range of from 0.1 to 20, but it can be outside of this range. Preferably, it is from 0.5 to 2.5 percent solids, and most preferably from 1.5 to 2. One convenient method of preparing the composition is to first mix the binder and matting agent; disperse these components in water with suitable agitation; and add, in order, the charge control agent, the hardening agent and the conductivity agent, all with good agitation.

The amounts of the described components of the composition of this invention can vary widely. However, typical and preferred amounts are as follows, each based on total composition solids (i.e. dry weight) :

^«£ )RE-

OM?I - (a) The non-gelatino, polymeric binder is present in an amount sufficient to provide a continuous film when the composition is applied to a substrate. The other components of the composition are substantially homogeneously (i.e. uniformly) distributed within this film. Typically, the binder comprises from 5 to 80, preferably, from 50 to 70, weight percent.

(b) The hardening agent is present in an amount sufficient to render the binder non-tacky.

Typically, it comprises from 0.5 to 8, and preferably from 1 to 2, weight percent.

(c) The matting agent is present in an amount such that the layer formed from the composition has the desired surface lubricity and transparency. Typically, the matting agent comprises from 2 to 30, preferably from 15 to 25, weight percent.

(d) The conductivity agent is present in an amount effective to provide a layer from the composition that is sufficiently conductive. In practice, the layer surface generally has a surface resistivity of from 1x10 7 to 1x1012 ohms per square, preferably from 1x10 to 1x10 ohms per square and more preferably from 5x10 to 5x10 ohms per square, all measured at 21°C and 50% R.H.

The resistivity, in ohms per square, is the electrical resistance of a square of a thin film of material measured in the plane of the material between opposite sides of the square. The value is substantially independent of square size. Typically, the conductivity agent comprises from 2 to 20, and preferably from 8 to 12, weight percent.

(e) The charge control agent is present in an amount sufficient to provide the desired triboelectric charging in a layer of the composition. In practice, such charging is less than +15 microcoulombs per square meter, and preferably less than +5 microcoulombs per square meter. Typically, the charge control agent comprises from 0.01 to 0.3, preferably from 0.08 to 0.15, weight percent.

The amount of each component of the composition of this invention can also be character- ized by specifying the dry weight coverage of such component in a layer formed from the composition. Typically, such a layer has an average thickness in the range of from 0.05 to 5 micrometers, and preferably from 0.1 to 1 micrometer, depending upon the particular characteristics of the element. At such thicknesses, the matting agent particles normally protrude beyond the surface of the coated layer, although it is not necessary that they do so in all uses. In typical layers the binder is present " in a coverage of from 5 to 1600, and preferably from 50 to 1400, milligrams per square meter; the hardening agent is present in a coverage of from 0.5 to 160, and preferably from 1 to 40, milligrams per square meter; the matting agent is present in a coverage of from 2 to 600, and preferably from 15 to 500, milligrams per square meter; the conductivity agent is present in a coverage of from 2 to 400, and preferably from 8 to 240, milligrams per square meter; and the charge control agent is present in a coverage of from 0.01 to 6, and preferably from 0.08 to 3, milligrams per square meter.

In addition to the essential components described hereinbefore, the composition of this invention can also contain one or more various other addenda common to antistatic compositions, provided such addenda do not adversely affect the desired properties discussed previously herein. Such addenda include, for example, wetting aids, surface active agents, lubricants, colorants, inorganic matting agents, defoamers, biocides and thickeners.

The compositions of this invention can be used with any element where there is need to provide electrical conductivity and to reduce the propensity of such element to accumulate static electrical charge. Generally, such elements are multilayer elements, particularly image-forming elements such as photographic elements (both positive and negative working), including photothermographic, thermographic, radiographic, and diffusion or image transfer film units. Examples of such photographic elements include photographic papers, aerial films, micrographic films, graphic arts films and integral or two-sheet diffusion or image transfer products, including those sometimes called "peel apart" products, and those described in U.S. Patent 4,296,195, issued October 20, 1982 and 4,297,432, issued October 27, 1981. The characteristics and components of such products are well-known in the art. Another class of image-forming elements are the electrographic elements. Such elements include electrostatographic, electrophotographic and xero¬ graphic elements. The art describing such products is too voluminous to list, however, some references describing such elements, including image-forming materials such as photographic silver halide emulsions and photoconductors, and layers are

Research Disclosure, publications 10938, May, 1973; 15161, November, 1976; 17029, June, 1978 and 17643, December, 1978.

OIΛH The elements prepared with the compositions of this invention comprise a support and one or more layers thereon. Typical supports include polymeric films, wood fiber or cellulosic substrates (e.g. paper), metallic sheets and foil, glass, and ceramic substances. Typical cellulosic supports are paper supports having a baryta or polymeric (e.g. polyolefinic) coating thereon.

A substantially transparent support is used for projection-viewable transparencies. In the case of a projection-viewable transparency, the support is usually a transparent polymeric film. Useful polymeric films 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 poly(ethylene terephthalate) film.

A detailed description of useful supports and methods of making them is provided in Research Disclosure, publication 17643, paragraph XVII, cited previously herein and the references mentioned therein.

The composition of this invention can be coated on one or both sides of the support, but preferably, both sides, to form electrically conductive layers. The composition can be coated directly on the support or it can be coated over another layer on the support. It can be applied 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 and curtain coating. The resulting layers can be dried by any suitable technique. Descriptions of useful coating and drying techniques are given in Research Disclosure, publication 17643, paragraphic XV, cited hereinbefore and the references mentioned therein. The resistivity of the resulting electrically conductive layer can be measured by any suitable technique. One such technique is described is 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 February 28, 1975. U.S. Patent 3,525,621, issued August 25, 1970, also discusses measurement of surface resistivities of coated layers. As previously indicated herein, triboelectric charging characteristics can be measured by the "impact electrification" method described in U.S. Patents

3,501,653 and 3,850,642, cited hereinbefore. In this method, the propensity of a given surface to generate static electrical charge is measured relative to another standard surface, such as polyurethane or stainless steel.

The elements prepared according to this invention can comprise other layers in addition to the electrically conducting layer or layers. Such layers include electrically conducting layers prepared from compositions not of this invention, as well as subbing, antihalation, adhesive and protective layers. Preferably, the elements contain one or more subbing layers between the support and the electrically conductive layers. Suitable subbing materials include those described in U.K. Patent 1,463,727, published February 9, 1977, and U.S. Patents 2,627,088, issued February 3, 1953, 2,943,937, issued July 5, 1960, 3,271,345, issued September 6, 1966, 3,437,484, issued April 8, 1969, 3,501,301, issued March 17, 1970, and 3,919,156, issued November 11, 1975. Particularly useful subbing materials are those prepared from vinylidene chloride copolymers, including poly(vinylidene choride-co-methyl acrylate-co-itaconic acid) and poly- (acrylonitrile-co-vinylidene chloride-co-acrylic acid) .

A preferred image-forming element prepared according to this invention is a substantially transparent image-receiving element. Such elements and the supports used therein permit essentially all (greater than 90 percent) light incidents thereon to pass through. A typical element of this type forms an image by receiving such image during the course of, for example, an electrographic copying process.

Such an element comprises a substantially transparent polymeric support having on each side thereof a non-tacky, electrically conductive layer with a surface resistivity of from about 1x10 to 12 1x10 ohms per square when measured at 21°C and

50% R.H. Each electrically conductive layer comprises (a) a film-forming binder; (b) a hardening agent for the binder; (c) particles of substantially transparent matting agent having a diameter in the range of from 2 to 25 micrometers; (d) a conductivity agent that is noncrystallizable; and (e) a charge control agent in an amount sufficient to reduce

OV •/A \ZI_- triboelectric charging of each electrically conductive layer to less than +15 microcoulombs per square meter. Preferably, the element has a subbing layer between the support and each image-receiving layer. Since the element has an electrically conducting layer on each side of the support, either side can be used to receive an image. Typically, the electrically conducting layer on one side is used to receive an image while the electrically conducting layer on the other side functions as an antistatic layer.

An example of a particularly useful transparent image-receiving element prepared according to this invention has a substantially transparent polymeric support (e.g. a poly(ethylene terephthalate) film) . On each surface of the support, outwardly, is a subbing layer and a non-tacky, electrically conductive layer with a surface resistivity of from 5x10 to 5x10 ohms per square when measured at 21°C and 50% R.H. Each electrically conductive layer comprises (a) poly(vinyl alcohol); (b) methacrylatochromic chloride; (c) particles of a substantially transparent matting agent having diameter in the range of from 8 to 12 micrometers and comprising an addition polymer prepared from at least one ethylenically unsaturated polymerizable monomer; (d) an alkali metal salt of a polymeric carboxylic acid; and (e) an ammonium salt of a fluorinated alkyl sulfonic acid in an amount sufficient to reduce triboelectric charging of the layer to less than +5 microcoulombs per square meter. As previously indicated herein, the substantially transparent image-receiving elements of this invention can be used in an electrographic copy process to prepare a projection-viewable transparency. Such electrographic copy processes are known in the art, as described, for example, in U.S. Patents 3,549,360, issued December 22, 1970, 3,854,942, issued December 17, 1974, and 4,259,422, issued March 31, 1981. Such an electrographic copy process is also known as "xerographic reproduction" or "electrostatic copying."

The electrographic copy process typically employs an electrophotographic element comprising a support bearing a coating of a normally insulating material. The electrical resistance of the insulating material, moreover, varies with the amount of incident actinic radiation it receives during imagewise exposure. The element is first given a uniform surface charge, generally in the dark. It is then exposed to a pattern of actinic radiation which reduces the potential of the surface charge in accordance with the relative energy contained in various parts of the radiation pattern. The differential surface charge (sometimes known as an electrostatic latent image) remaining on the element is then transferred to the image-receiving layer of the substantially transparent image-receiving element of this invention.

Image transfer is generally carried out by contacting the insulating surface of the exposed electrophotographic element with the surface of the image-receiving layer. An electric field is established between these surfaces and the electrostatic charge is transferred to the image-receiving layer where it is trapped. The transferred latent image is then made visible by contacting the surface of the image-receiving layer with fusible toner particles. Such toner, whether contained in an insulating liquid or on a dry carrier, can be deposited on the image-receiving element either in the areas where there is an electrostatic charge or in the areas where the charge is absent. The toned image comprising particles of fusible, typically resinous, material is fixed to the image-receiving layer of the image-receiving element by the application of heat (conductive, convective or radiation source). Typically, the toned layer is brought into contact with a heated fuser surface, such as a heated fuser roller, where heat is applied to soften the toner particles, thereby fusing the image to the image-receiving element.

The temperature of the fuser surface can vary widely depending on such factors as the type of toner used and the duration of contact between the image-receiving element and the heated surface. In general, the temperature is in the range of from 160° to 210°C, and preferably from 170° to 190°C. Typical fuser surfaces are described in Product Licensing Index, Vol. 99, publication 9944, July, 1972, pp. 72-73; and Research Disclosure, publication 16730, March, 1978, pp. 76-77 (both published by Industrial Opportunities, Ltd., Ho ewell, Havant Hampshire P09 1EF, United Kingdom). The heated surface can be coated with a suitable release liquid to inhibit transfer of toner particles onto the roll during fusing as described, for example, in U.S. Patent 4,259,422, issued March 31, 1981. Fusible toner particles that are suitable for forming visible toned image can comprise a variety of known, mostly resinous, materials including natural and synthetic resins. Examples of useful toner materials are given in U.S. Patent 4,259,422 mentioned previously.

The following examples are included to further illustrate the invention. Example 1 in this example, a transparent image-forming element, specifically an image-receiving element, was prepared according to this invention. For comparison, two comparable elements (Controls A and B) containing electrically conducting antistatic layers of the type disclosed in U.S. Patent 3,437,484 were also prepared.

The element of this invention was prepared by coating an electrically conducting composition

2 (dry weight coverage of 0.25 g/m ) on both sides of a poly(ethylene terephthalate) support (subbed on both surfaces with a copolymer of acrylonitrile, vinylidene chloride and acrylic acid). The coated layers were then dried. For convenience, one side of the element was designated the "front-si e" and the other side the "back-side." The composition comprised the following components:

c^*-_? VΠ- parts per hundred poly(vinyl alcohol) binder 1.25 ethacrylatochromic chloride hardening agent 0.031 ρoly(vinyltoluene-co-p-tertiary- butylstyrene-co- ethacrylic acid) [61:37:2 weight ratio] matting agent particles (diameter 8-12 micrometers) 0.4 sodium polymethacrylate conductivity agent 0.2

CF₃(CF₂)₇S0₃ ^" (C₂H₅)₄ + charge control agent 0.002 water 98.117

Controls A and B each comprised a poly¬ ethylene terephthalate) support subbed on both surfaces with a copolymer of acrylonitrile, vinylidene chloride and acrylic acid. An antistatic layer was coated on one side

(the "back-side") of the subbed support for each of Controls A and B. The antistatic layers comprised poly(vinyl alcohol) binder, zirconium nitrate hardening agent for the binder, potassium chloride conductivity agent and particles of polymethyl metacrylate matting agent, (an antistatic composition as described in U.S. Patent 3,437,484, issued April 8, 1967).

The other side (the "front-side") of the subbed support of Control A was coated with an image-receiving layer formed from the electrically conducting composition described previously in this Example except that gelatin was used in place of poly(vinyl alcohol) as the binder, formaldehyde was used as the hardening agent and sodium nitrate was used as the conductivity agent.

C' FI VIPO Control B was coated on its "front-side" with an image-receiving layer formed from the electrically conducting composition described previously in this Example except that sodium nitrate was used in place of sodium polymethacrylate as the conductivity agent.

The surface resistivities for the surfaces of the conducting layers on the "front-side" of several samples of elements prepared according to this invention (Example 1) and Controls A and B were determined at several different concentrations of conductivity agent. The average resistivities at each of the concentrations of conductivity agent are set forth in the following Table. Resistivity was measured according to ASTM standard C59.3 described hereinbefore.

_-7 __l TABLE

Concentration of

Conductivity Agent

(Percent of Coating Surface Resistivity

Compositionj , wet (21°C, 50% R.H.) weight) [Log (ohms/sq.)]

0 Example 1 13.8 Control B 13.8 Control A 14.8

0.1 Example 1 12.0 Control B 12.6 Control A 13.8

0.2 Example 1 10.8 Control B 11.6 Control A 13.1

0.3 Example 1 9.9 Control B 11.1 Control A 12.5

0.4 Example 1 9.3 Control B 10.8 Control A 12.0

0.5 Example 1 8.9 Control B 10,.5 Control A 11.6

0.6 Example 1 8.7 Control B 10.4 Control A 11.2

0.7 Example 1 8.6 Control B 10.4 Control A 10.9

The data presented in the Table shows that at each concentration level, the composition of this invention provided significantly improved conductivity in comparison to the comparable prior art compositions of Controls A and B. Furthermore, as the concentration of sodium nitrate (a crystallizable conductivity agent) was increased in Control B to improve surface resistivity, the haze of the conducting layer increased. In contrast, the conducting layer prepared according to this invention (Example 1) exhibited no haze at any concentration of conductivity agent reported. This lack of haze is particularly advantageous when elements are used in the preparation of projection-viewable trans¬ parencies. Similar surface resistivities are obtained with image-forming elements that are coated on one side of a resin-coated paper photographic support with an electrically conducting antistatic layer as in Example 1 and Controls A and B and on the other side with a green-sensitive, high-speed, high contrast, gelatino-silver bro oiodide black-and- white photographic emulsion of the type used in pho otyp -setting. Example 2 This example illustrates that there is a significant reduction in "multifeeds" and "jams" in copier/duplicator equipment using transparent image-receiving elements prepared according to this invention in comparison to comparable elements prepared according to the prior art.

To illustrate, a transparent image-receiving element was prepared according to Example 1 and designated Example 2. A typical prior art transparent image-receiving element, designated Control C, was prepared as described in U.S. Patent 4,259,422, issued March 31, 1981.

Control C comprised a poly(ethylene terephthalate) support subbed on both surfaces with a copolymer of acrylonitrite, vinylidene chloride and

GI.ΓFI v <A r V /L w acrylic acid. An antistatic layer, as in Controls A and B, was coated on one side (back-side) of the subbed support. The other side (front-side) of the. subbed support was coated with an image-receiving gelatin layer containing a hardening agent and particles of poly(methyl methacrylate) matting agent, as described in U.S. Patent 4,259,422.

The performance of each of these elements (Example 2 and Control C) in conventional copier/- duplicator equipment was evaluated in the following manner.

Approximately 25 samples of each of the transparent image-receiving elements were placed in the supply box of two separate, but identical, KODAK EKTAPRINT™ copier/duplicators. Twenty-five transparencies were made from each of Example 2 and Control C elements, five from each of 5 different images (some light, some normal, some dark images. The resulting transparencies were evaluated for image - quality and the copy process was evaluated for the frequency of "multifeeds" as well as "jams" at the fuser station. This procedure was performed four times each day for two consecutive days over a period of several months so that hundreds of transparencies were made from both Example 2 and Control C elements. In all transparencies, the image quality was acceptable although it was somewhat improved for the Example 2 transparencies. However, there was a significant reduction in the frequency of "multifeeds" and "jams" for Example 2 transparencies in comparison Control C transparencies. Frequency is the decimal fraction of the total elements tested which resulted in malfunctions. The smaller the fraction, the fewer malfunctions. For Control C elements, the frequencies measured over a period of several months varied from about 0.04 to 0.1. In contrast, the frequency for Example 2 elements was consistently about 0.0067. Stated another way, for Control C transparencies, a malfunction occurred in about 1 out of every 10 to 25 elements run, whereas a malfunction occurred in only about 1 out of every 150 Example 2 transparencies. Additionally, upon exiting the copier/- duplicator, Control C transparencies had considerable static and tended to stick together. They could not be easily and neatly stacked upon exiting the copier/- duplicator. In contrast, Example 2 transparencies had little static and showed little, if any, tendency to stick together upon exiting the copier/- duplicator. These elements could be easily stacked.

Claims

Claims:

1. An electrically conductive composition particularly useful as an antistatic composition for reducing the propensity for an image-forming element to accumulate static electrical charge, characterized in that the composition comprises an aqueous dispersion of a combination of:

(a) a non-gelatino, polymeric, film-forming binder, (b) a hardening agent for the binder,

(c) particles of matting agent that are substantially transparent and have a diameter of 1 to 50 micrometers and a specific gravity substantially the same as water, (d) a conductivity agent that is non-crystallizable, and

(e) a charge control agent.

2. The composition of Claim 1, character¬ ized in that the binder is poly(vinyl alcohol), poly- (vinyl acetate) , carboxymethyl cellulose or carboxy¬ methyl hydroxyethylcellulose.

3. The composition of either of Claims 1 or

2, characterized in that the conductivity agent is an anionic polymer and the charge control agent is an anionic fluorinated surface active agent.

4. The composition of any of Claims 1, 2 or

3, characterized in that the binder is poly(vinyl alcohol) , the conductivity agent is a polymeric carboxylic acid or alkali metal or ammonium salt thereof, and the charge control agent is a fluorinated alkyl sulfonate.

5. An element comprising a support and at least one electrically conductive layer, characterized in that the layer is formed from a composition of any of claims 1, 2, 3 or 4.

6. The element of Claim 5, characterized in that the electrically conductive layer is coated on each side of the support.

7. The element of either of Claims 5 or 6, characterized in that the support is substantially transparent.

8. The element of any of Claims 5, 6 or 7 characterized in that the electrically conductive layer has a resistivity of from 1x10 7 to 1x1012 ohms per square when measured at 21°C and 50 % R.H. , and the charge control agent is present in an amount sufficient- to reduce triboelectric charging of the electrically conductive layer to less than +15 microcoulombs per square meter.

9. The element of any of Claims 5, 6, 7 or 8, characterized in that the support is polyethylene terephthalate, the binder is poly(vinyl alcohol), the - conductivity agent is a polymeric carboxylic acid or alkali metal or ammonium salt thereof and the charge control agent is a fluorinated alkyl sulfonate.

10. A method for making an element comprising a support and at least one electrically conductive layer, which method comprises forming an electrically conductive composition, coating a layer of the composition on at least one side of the support and drying the coated layer, characterized in that the electrically conductive composition is a composition of any of Claims 1, 2, 3, or 4.