EP0792319A1

EP0792319A1 - Water-based transparent image recording sheet for plain paper copiers

Info

Publication number: EP0792319A1
Application number: EP95937553A
Authority: EP
Inventors: Prabhakara S. Rao; Manisha Sarkar; John J. Stofko, Jr.; Michael G. Vale; Jamshid Azizi; Subodh K. Kulkarni; Virtudes R. Lund; Ying-Yuh Lu
Original assignee: Minnesota Mining and Manufacturing Co
Current assignee: 3M Co
Priority date: 1994-11-18
Filing date: 1995-10-10
Publication date: 1997-09-03
Also published as: WO1996016120A1; JPH10510062A

Abstract

A transparent image receptor for use in a copying application comprising a transparent polymeric substrate, having coated on at least one major surface thereof, a toner receptive layer comprising: a) from 55 to 95 parts of a transparent film forming imageable polymer; b) from 5 to 10 parts of at least one lubricating agent selected from the group consisting of mono-substituted poly(oxyethylenes) and poly-substituted poly(oxyethylene), wherein said mono-substituted poly(oxyethylene) is represented by general formula (I), wherein n is an integer ranging from 5 to 200; and R is an alkylether, said alkyl group can be straight chained or branched, having from 6 to 25 carbon atoms; and poly-substituted poly(oxyethylenes) is represented by formula (II), wherein X and Y are integers, and X ranges from 50 to 500, and Y ranges from 1 to 4; and R1, R2, and R3 are alkyl groups, straight chained or branched, R1 having from 10 to 15 carbons, and R2 having from 10 to 24, and R3 having from 5 to 40 carbons; c) from 1 to 15 parts of at least one polymeric particle; and d) from 0 to 20 parts of an antistatic agent selected from the group consisting of cationic agents, anionic agents, and mixtures thereof.

Description

WATER-BASED TRANSPARENT IMAGE RECORDING SHEET FOR PLAIN PAPER COPIERS

Background of the Invention

Field of the Invention This invention relates to transparent image recording materials suitable for use in xerographic and electrographic copying devices. Specifically, it relates to coatings for transparencies having specific physical properties for use in overhead projectors.

Description of Related Art

Many different types of transparent image receptive sheets or receptors are known in the art. Typically, these are thin transparent oriented polymeric films formed from organic resins such as polyesters, and overcoated on at least one surface with an image receptive layer. They can be used as receptors for a variety of printing and imaging methods, e.g., thermal transfer printing, ink-jet printing and xerographic or electrographic copying, to produce transparencies suitable for use with commercially available overhead projectors.

In the formation and development of xerographic images, a toner composition comprised of resin particles and pigment particles is generally applied to a latent image generated on a photoconductive member. Thereafter, the image is transferred to the receptor and affixed there by the application of heat, pressure, or a combination thereof.

U.S. Patent No. 5,104,721 discloses a medium for electrophotographic printing or copying where the polymeric coating has a Tukon hardness of about 0.5 to 5.0 and a glass transition temperature of about 5° to 45°C. The coating comprises at least one pigment which provides a coefficient of static friction of from 0.20 to 0.80 and a coefficient of dynamic friction of from 0.10 to 0.40. The medium is disclosed to provide improved image quality and toner adhesion, and to be particularly useful in laser electrophotography. The polymer employed in the coating can contain thermosetting or thermoplastic resins, and preferably aqueous acrylic emulsions such as Rhoplex™ resins from Rohm and Haas.

U.S. Patent No. 5,104,731 discloses a dry toner imaging film media having good toner affinity, anti-static properties, and good feedability. The media comprise a suitable polymeric substrate with an antistatic matrix layer coated thereon which has blocking resistance at 78°C after 30 minutes and a surface resistivity of from about 1 x 10⁸ to about 1 x 10¹⁴ ohms per square cm at 20°C and 50% relative humidity. The matrix contains one or more thermoplastic polymers having a T_g of 5°C to 75°C, and at least one crosslinked polymer which is resistant to hot roll fuser embossing, at least one of the polymers being electrically conductive.

U.S. Patent No. 4,480,003 discloses a transparency film with an image receiving layer, comprising a thermoplastic, transparent polymethyl methacrylate polymer containing dispersed silica particles coated on a first major surface of the polymeric film. On the second major surface of the film base is coated, preferably atop a primer, a layer of non-migratory electrically conductive material, preferably a polymer derived from the reaction of pyridine and 2 amino- pyridine with partially chloromethylated polystyrene. A protective overcoating is also preferred. It is disclosed that the sheet can be fed smoothly from a stack and produces clear background areas. U.S. Patent 4,869,955 discloses an element comprising a polyethylene terephthalate support, at least one subbing layer coated thereon and a toner receptive layer comprising a mixture of an acrylate binder, a polymeric antistatic agent having carboxylic acid groups, a crosslinking agent. butylmethacrylate modified polymethacrylate beads and submicron polyethylene beads.

U.S. 4,956,225 discloses a transparency where the toner receptive coating comprises blends selected from a group consisting of poly(ethylene oxide) and carboxymethyl cellulose; poly(ethylene oxide), carboxymethyl cellulose and hydroxypropyl cellulose; poly(ethylene oxide) and vinylidene fluoride/hexafluoropropylene copolymer; poly(chloroprene) and poly(alpha-methylstyrene) ; poly(caprolactone) and poly(alpha-methylstyrene) ; poly(vinyl isobutylether) and poly(alpha-methylstyrene) ; poly(caprolactone) and poly(a- methylstyrene) ; chlorinated poly(propylene) and poly(a- methylstyrene) ; chlorinated poly(ethylene) and poly(a- methylstyrene) ; and chlorinated rubber and poly(a- methylstyrene) . Also disclosed are transparencies with two layers.

U.S. Patent No. 5,229,188 discloses a transparent laminate film for full color image-forming comprising two transparent resin layers. The first resin layer is heat- resistant, and the second resin layer must be compatible with a binder resin constituting the toner to be used for color image formation. The second resin layer has a larger elasticity than that of the binder resin of the toner at a fixing temperature of the toner. The second resin can be of the same "kind" i.e., type, e.g., styrene-type or polyester type, as the toner binder, as long as the resins differ in storage elasticity.

U.S. Patent No. 5,254,403 discloses a recording sheet comprising an image receiving layer comprised of a mixture of a latex-forming polymer, a polysaccharide and a polymer containing oxyalkylene monomers. The recording sheets exhibit high optical density, minimum intercolor bleeding, and minimum blocking at humidities of 50% to 80% at temperatures over 50°C. U.S. Patent 4,891,285 discloses an image copy film comprising a transparent or opaque film substrate, a receiving layer on a surface thereof and a toner image layer overcoated thereon. The receiving layer comprises of a terpolymer of vinyl halide, a vinyl ester of a saturated aliphatic carboxylic acid, and a functional group containing an ethylenically-unsaturated termonomer.

U.S. Patent No. 5,212,008 discloses a recording sheet comprising a first coating in contact with a substrate and a second coating in contact with the first coating. The first coating comprises a crosslinking agent selected from a specific group, a catalyst and a polymer selected from another specific group capable of being crosslinked by the crosslinking agent. The second coating comprises a binder and a material selected from quaternary amino compounds.

Such recording sheets are suitable for use in both printing and copying.

U.S. Patent No. 5,289,245 discloses a recording material for use in electrography in which a toner image is formed on the recording material and fixed thereto by the applying of pressure using a fixing rotatable member coated with a releasing agent. The recording material can have a base layer, a first resin layer having greater compatibility with the toner used, and a second resin layer which absorbs releasing agents. The two resin layers may be coated atop the base layer in either order. In another embodiment, the resin layer having greater compatibility with the toner also contains a releasing agent absorbing substance.

U.S. Patent No. 5,266,383 discloses a recording medium comprises a surface layer composed mainly of aluminum oxide particles and a lower layer having ink absorptivity, this lower layer being formed of paper. The aluminum oxide particles have particle sizes of 5 mm or less. This is disclosed to give an image that is high in density, has excellent ink absorptivity and color forming characteristics, with little deterioration due to in-room decoloration.

U.S. Patent No. 5,330,823 discloses a recording sheet comprising a substantially transparent substrate, a binder polymer coated on the substrate, and particles of an antistatic component, said particles being present on at least the surface of the binder polymer coating. This recording sheet is stated to exhibit improved image adhesion. Alternately, a transparent recording sheet is provided wherein both an antistatic component and an anti- slip component are contained in a single coating layer of the sheet.

U.S. Patent No. 5,306,437 discloses lubricants and release agents comprising the copolymers of a-olefins, unsaturated carboxylic acids and unsaturated carboxylic acid esters, and optionally, vinyl aromatic compounds of the styrene type. These lubricants and release agents can be employed in molding compositions.

U.S. Patent No. 5,310,591 discloses a transparent image-recording sheet suitable for use in a plain paper copier, comprising a transparent backing having two major surfaces, said sheet having a machine direction, and a transverse direction, at least one of the major surfaces having coated thereon, a transparent water-based toner- receptive coating comprising from about 65 to about 99.9 parts of an imageable polymer, from about 0.1 to about 15 parts of at least one polymeric particle having a mean particle size ranging from about 1 mm to about 15 mm, and up to about 20 parts of an antistatic agent. The toner- receptive coating is coated onto the transparent backing at a time during manufacture of the backing selected from the group consisting of a) before any orientation of said film, and b) after uniaxial orientation in the machine direction.

U.S. Patent No. 5,310,595 discloses a transparent image-recording sheet suitable for use in a plain paper copier, comprising a transparent backing having two major surfaces, said sheet having a machine direction, and a transverse direction, at least one of the major surfaces having coated thereon, a transparent water-based toner- receptive coating comprising an imageable polymer formed from at least one monomer selected from the group consisting of bicyclic alkyl (meth) acrylates, aliphatic alkyl (meth) acrylates having from about one to about 12 carbon atoms, aromatic (meth)acrylates, and a polar monomer; at least one novel long chain polymeric particle having good antifriction characteristics and optionally, an antistatic agent selected from the group consisting of cationic agents, anionic agents, fluorinated agents, and non-ionic agents. U.S. Patent No. 5,164,436 describes waxy esters of aromatic alcohols as lubricants and release agents for transparent thermoplastics which reduce the transparency of plastics to a far lesser degree than other previously customarily used montan wax esters of aliphatic alcohols. These compounds are made by acid-base reaction, alcohols with carboxylic acids. Montanic acid, which is essentially a mixture of C18-C36-carboxylic acids with a predominant content of C26-C32-carboxylic acids and is obtained by oxidative bleaching of crude montan wax is preferred.

Some of the coatings disclosed above are susceptible to abrasion or scratching during the manufacturing process such as converting, or during the copying process, some of which are visible when the imaged transparencies are projected. Attempts to make the toner-receptive coatings tougher have included crosslinking of the polymers present. However, crosslinking tends to reduce the toner adhesion of the layer to an unacceptable level.

In general, when lubricating agents are present in a toner receptive coating, the coating has less susceptibility to abrasions or scratches. However, typically, the presence of lubricating agents has tended to drastically reduce the toner adhesion to the toner receptive coating.

The present inventors have now discovered a class of lubricants which, when added to compositions for forming toner-receptive coatings, imageable with a variety of toners and binder resins, improve scratch resistance without adversely affecting the toner adhesion, image quality and feedability of the original toner-receptive coating.

Summary of the Invention The invention provides a toner receptive composition, and a transparent image receptor for use in a copying application comprising a transparent polymeric substrate, and coated on at least one major surface of the substrate is a toner receptive composition suitable for electrophotographic or xerographic imaging, comprising: a) from 55 to 95 parts of a transparent film forming imageable polymer; b) from 5 to 10 parts of at least one lubricating agent selected from the group consisting of mono- substituted poly(oxyethylenes) represented by the following general formula:

HO-£-CH₂-CH₂-θ}^CH₂-CH2-R wherein n is an integer ranging from 5 to 200; and R is a straight chained or branched alkylether, containing from 6 to 25 carbon atoms; and poly-substituted poly(oxyethylenes) represented by the following formula:

wherein X is an integer from 50 to 500, and Y is an integer from 1 to 4; Ri, R₂, and R₃ are straight chain or branched alkyl groups, Ri containing from 10 to 15 carbon atoms, R₂ containing from 10 to 24 carbon atoms, and R₃ containing from 5 to 40 carbon atoms; c) from 1 to 15 parts of at least one polymeric particle; and d) from 0 to 20 parts of an antistatic agent selected from the group consisting of cationic agents, anionic agents, and mixtures thereof.

Transparencies having coated thereon toner receptive compositions of the present invention possess improved scratch resistance while maintaining good toner adhesion properties.

Preferred toner-receptive compositions of the invention comprise: a) from 55 parts to 94 parts of an imageable polymer formed from at least one monomer selected from the group consisting of bicyclic alkyl (meth) acrylates, aliphatic alkyl (meth) acrylates having from one to 12 carbon atoms, aromatic (meth) acrylates, and a polar monomer having the formula:

wherein R is hydrogen or methyl, Ri and R₂ may be hydrogen, identical or different alkyl groups having up to 12 carbon atoms, preferably up to 2 carbon atoms, or the quaternary cationic salts thereof; b) at least one lubricating agent selected from the group consisting of mono-substituted poly(oxyethylenes) represented by the following structure:

wherein n is an integer ranging from 5 to 200, R is an alkylether, having a straight chain alkyl group containing from 12 to 25 carbon atoms, and poly- substituted poly(oxyethylenes) represented by the following general formula:

wherein X is an integer ranging from 90 to 500, and Y is an integer ranging from 1 to 4; Ri, R₂, and R₃ are straight chain or branched alkyl groups, Ri containing from 10 to 13 carbon atoms, R₂ containing from 12 to 18 carbon atoms, and R₃ having from 7 to 36 carbons; c) from 1 to 15 parts at least one antifriction polymeric particle; and d) from 0 to 20 parts of an antistatic agent selected from the group consisting of cationic agents, anionic agents, fluorinated agents, and non-ionic agents. Highly preferred toner-receptive compositions of the invention comprise: a) from 55 parts to 94 parts of a core/shell latex polymer comprising:

1) a core formed from: i) from 0 to 30 parts of at least one monomer selected from the group consisting of bicyclic alkyl (meth)acrylates, and aromatic

(meth)acrylates; and ii) 70 to 100 parts of at least one α.β- ethylenically unsaturated monomer having from 1 to 12 carbon atoms; 2) a shell formed from: i) from 0 to 65 parts of at least one monomer selected from the group consisting of bicyclic alkyl (meth)acrylates and aromatic (meth)acrylates; and ii) 35 to 100 parts of at least one α,β- ethylenically unsaturated monomer having from 1 to 12 carbon atoms; and b) at least one lubricating agent selected from the group consisting of mono-substituted poly(oxyethylene)s represented by the following structure:

HO-f-CH₂-CH₂-θ3-CH₂-CH₂-R wherein n is an integer from 5 to 200; R is an straight chain alkylether containing from 12 to 25 carbon atoms; and poly-substituted poly(oxyethylenes) represented by the following general formula:

■ wherein X is an integer ranging from 90 to 500, and Y is an integer ranging from 1 to 4; R_1; R₂, and R₃ are straight chain or branched alkyl groups, Ri containing from 10 to 13 carbon atoms, R₂ containing from 12 to 18 carbon atoms, and R3 containing from 7 to 36 carbons; c) from 1 to 15 parts of at least one antifriction polymeric particle, said particle having a particle size distribution of from 5 to 15 mm; and d) from 0 to 20 parts of an antistatic agent selected from the group consisting of cationic agents, anionic agents, fluorinated agents, and non-ionic agents. These terms as used herein have the following meanings:

1. The term "core/shell latex polymer" means a polymer in spherical form wherein each discrete sphere has a core surrounded by a shell.

2. The term " (meth) acrylate" and the like, as used herein mean both the acrylate and methacrylate versions of the composition are included in the definition. 3. The term "antifriction polymeric particle" means a particle whose presence provides decreased friction to the surface to which it is applied.

All percents parts and ratios herein are by weight unless specifically stated otherwise.

Detailed Description of the Invention Image-receptive sheets of the invention comprise a substrate having a toner-receptive composition coated on at least one major surface of the substrate, said composition comprising at least one lubricating agent selected from the group consisting of mono-substituted poly(oxyethylene) represented by the following structure:

HO-£-CH₂-CH₂-θ3-CH₂-CH₂-R wherein n is an integer ranging from 5 to 200, preferably from 20 to 200; R is an alkylether, said alkyl group preferably being straight chain, having from 6 to 25 carbon atoms, preferably from 12 to 25 carbon atoms; and poly- substituted poly(oxyethylenes) , represented by the following general formula:

wherein X is an integer ranging from 50 to 500, preferably from 90 to 500, and Y is an integer ranging from 1 to 4; Ri, R₂, and R₃ are straight chained or branched alkyl groups, Ri containing from 10 to 15 carbon atoms, preferably from 10 to 13 carbon atoms, R containing from 10 to 24 carbon atoms, preferably from 12 to 18 carbon atoms, and R₃ containing from 5 to 40 carbon atoms, preferably from 7 to 36 carbon atoms.

It has been found that when straight chain alkyl groups are used in mono-substituted poly(oxyethylene) alkylethers, the alkylethers exhibit better scratch resistance performance than do those containing branched chain alkyl groups.

Examples of straight chain alkylethers include stearyl ether, lauryl ether, cetyl ether, oleyl ether and decyl ether, preferably stearyl ether and lauryl ether, and most preferably, stearyl ether. These substances are available from ICI as Brij™ compounds such as Brij^1M-700: [polyoxyethylene]loo stearyl ether, Brij^-SS: [Polyoxyethylene]₂₃ lauryl ether, Brij™-78: [Polyoxyethylene]₂₀ stearyl ether, Brij^-Sδ: [Polyoxyethylene]₂₀ cetyl ether, Brij™-99: [Polyoxyethylene]₂₀ oleyl ether, Synthrapol® KB, [Polyoxyethylene]5.5 decyl ether, and Brij^1M-721: [Polyoxyethylene]₂ι stearyl ether. Useful polysubstituted poly(oxyethylene) urethanes include Acrysol™ RM-825, Acrysol™ SCT-200 and 275, all available from Rhom and Haas.

When lubricating agents are present in a toner receptive coating, the coating has less susceptibility to abrasions or scratches. However, typically the use of these lubricating agents drastically reduces the toner adhesion to the toner receptive coating. The lubricating agents listed above are unique, in that when added to toner-receptive compositions, the compositions may be used with a variety of toners containing differing binder resins, and improve scratch resistance without adversely affecting the toner adhesion, image quality and feedability of the original toner-receptive composition.

The film-forming polymer, copolymer or polymer blend used for toner-receptive compositions of the present invention can be coated out of a water-based emulsion or aqueous solution, using any well-known coating technique. Such polymers can be made from any ethylenically unsaturated monomers, particularly α,β-ethylenically unsaturated monomers, and can include acrylates and methacrylates, styrenes, substituted styrenes and vinylidine chlorides.

Preferably, the film forming polymer contains from 80 parts to 100 parts of at least one monomer selected from the group consisting of bicyclic alkyl (meth) acrylates, aliphatic alkyl (meth)acrylates having from one to twelve carbon atoms, and aromatic (meth)acrylates.

Useful bicyclic (meth) acrylates include, but are not limited to, dicyclopentenyl (meth)acrylate, norbornyl (meth)acrylate, 5-norborene-2-methanol, and isobornyl (meth)acrylate. Preferred bicyclic monomers include dicyclopententyl (meth)acrylate, and isobornyl (meth) acrylate.

Useful aliphatic alkyl (meth) acrylates include, but are not limited to, methyl acrylate, ethyl acrylate, methyl (meth)acrylate, isobutyl (meth) acrylate, isodecyl (meth)acrylate, cyclohexyl (meth) acrylate, and the like. Preferred aliphatic monomers include methyl (meth) acrylate, ethyl (meth)acrylate, and isodecyl (meth) acrylate. Useful aromatic (meth)acrylate include, but not limited to benzyl (meth)acrylate and styrene (meth)acrylate.

The polymer can also contain from 0 to 20 parts of a polar monomer selected from the group consisting of alkyldioldi (meth)acrylates; hydroxyalkyl (meth)acrylates; alkyl(dialkoxy)silane; and Nitrogen-containing compounds including N-alkylacrylamide, N,N-dialkyl monoalkyl amino ethyl (meth)acrylate, and their cationic salt thereof, N,N- dialkyl monoalkyl amino methyl (meth) acrylate, and their cationic salt thereof, N-alkyl amino alkyl (meth)acrylate, all said above alkyl groups having up to 12 carbon atoms, preferably up to 8 carbon atoms.

Preferred polar monomers include butanedioldiacrylate, hexanedioldiacrylate, hydroxyethylacrylate and methacrylate, N-methylacrylamide, n-butylmethacrylamide, N- methylolacrylamide, N-butylaminoethyl (meth) acrylate, N,N'- diethyl aminoethyl (meth)acrylate, and N,N'-dimethyl aminoethyl (meth)acrylate.

In a highly preferred embodiment, the film forming polymer comprises a) from 55 parts to 94 parts of a core/shell latex polymer comprising:

1) a core formed from: i) 0 to 30 parts of at least one monomer selected from the group consisting of bicyclic alkyl (meth) acrylates, and aromatic

(meth) acrylates; and ii) 70 to 100 parts of at least one α,β- ethylenically unsaturated monomer having from 1 to 12 carbon atoms; 2) a shell formed from: i) 0 to 65 parts of at least one monomer selected from the group consisting of bicyclic alkyl (meth)acrylates and aromatic (meth)acrylates; and ii) 35 to 100 parts of at least one α,β- ethylenically unsaturated monomer having from 1 to 12 carbon atoms. The more compliant core/shell image-receptive layer allows the toner particles to come into contact with more surface area of the layer, while the lower T_g of the core material aids a faster softening of the image-receptive layer with high T_g shell at the high temperature of the fuser rollers, thus giving good toner adhesion.

The core is made from at least one α,β-ethylenically unsaturated monomer having from 1 to 12 carbon atoms. This monomer makes up from 70 to 100 parts, preferably from 75 to 90 parts of the core. Where this monomer comprises less than 100%, the core also contains at least one monomer selected from the group consisting of bicyclic alkyl (meth)acrylates, and aromatic (meth)acrylates. This monomer can comprise up to 40 parts, preferably from 10 to 25 parts.

The shell is likewise formed from at least one α,β- ethylenically unsaturated monomer containing from 1 to 12 carbon atoms. This monomer may comprise up to 100 parts of the shell, preferably from 45 to 80 parts. Where this monomer comprises less than 100 parts, the shell can also comprise up to 65 parts, preferably from 20 to 55 parts, of at least one monomer selected from the group consisting of bicyclic alkyl (meth)acrylates, and aromatic (meth) acrylates.

Useful α,β-ethylenically unsaturated monomers include, but are not limited to, methyl acrylate, ethyl acrylate, methyl (meth)acrylate, isobutyl (meth)acrylate, isodecyl (meth)acrylate, cyclohexyl (meth) acrylate, n-butyl acrylate, styrene, vinyl esters, and the like. Preferred monomers include methyl (meth)acrylate, ethyl (meth)acrylate and isodecyl (meth)acrylate.

Useful bicyclic (meth)acrylates include, but are not limited to, dicyclopentenyl (meth)acrylate, norbornyl

(meth) acrylate, and isobornyl (meth)acrylate. Preferred bicyclic monomers include dicyclopentenyl (meth) acrylate. Useful aromatic (meth)acrylates include, but not limited to benzyl (meth)acrylate. The core polymer, and/or the shell polymer, can also contain from 0 to 20 parts of a polar monomer selected from the group consisting of acrylic (meth)acrylic acid; or hydroxyalkyl (meth)acrylates; and nitrogen-containing compounds including N-alkylacrylamide, N,N-dialkyl amino monoalkyl (meth)acrylate, N-alkyl amino alkyl

(meth) acrylate, and their cationic salts thereof, all said above alkyl groups having up to 8 carbon atoms, preferably up to 2 carbon atoms. Preferred polar monomers include hydroxyethylacrylate and methacrylate, N-methylacrylamide, n-butylmethacrylamide, N-methylolacrylamide, N-butylaminoethyl (meth)acrylate, N,N'- diethylaminoethyl (meth)acrylate, N,N'-dimethyl aminoethyl (meth) acrylate, N,N'-dimethyl amino ethyl (meth)acrylate, and isobutoxy(meth)acrylamide.

When these polar monomers are present in the shell polymer, the shell polymer is preferably crosslinked. Some of the polar monomers, e.g., n-methylolacrylamide and isobutoxy methacrylamide can undergo self-crosslinking during the drying stage, while others required an additional crosslinker to be present. Useful crosslinkers include poly-functional aziridines such as trimethylolpropane-tris-

(β-(N-Aziridinyl)propionate) , Pentaerythritol-tris-(β-(N- aziridinyl)propionate) , trimethylolpropane-tris-(β-(N- methylaziridinyl)propionate) , and the like; ureaformaldehyde, melamine formaldehyde, isocyanate, multifunctional epoxy polymers, alkyldialkoxy silane, γ- aminopropyl trimethoxysilane, vinyl triethoxy silane, vinyl tris(β-methoxy ethoxy)-silane, vinyl triacetoxy silane, γ- methacryloxypropyltrimethyoxy silane, γ-(β-amino ethyl)aminopropyl trimethoxysilane, and the like.

Polymeric particles, other than the core/shell spheres, are also present in the toner receptive coating. These can range in size from 1 mm to 15 mm in diameter and can include poly(methylmethacrylate) (PMMA) , modified poly(methylmethacrylate) , poly(tetrafluorethylene) , polyethylene, particles produced from diol di (meth)acrylate homopolymers which impart antifriction characteristics when coated on image recording sheets. The diol di(meth)acrylates can be reacted with long-chain fatty alcohol esters of (meth)acrylic acid.

Preferred embodiments contain particles selected from PMMA, modified PMMA, and particles produced from either diol-di (meth)acrylate homopolymers or copolymers of diol di (meth)acrylates and long-chain fatty alcohol esters of (meth)acrylic acid.

Other useful particles include inorganic particles such as silica, polymeric particles such as PMMA, modified PMMA, polyethylene and tetrafluoropolyethylene, porous organic particles such as ureaformaldehyde, and coated silicas. For good feedability under all conditions, a bimodal particle distribution is preferred. The mean particle size preferably ranges from 0.25 mm to 15 mm. Particles smaller than 0.25 mm would require the use of more particles to produce an effective coefficient of friction, this would tend to also produce more haze. Larger particles than 15 mm would require thicker coatings to anchor the particles firmly in the coatings, which would increase haze and coating cost. For optimal performance, the particles preferably have narrow particle size distributions, i.e., a standard deviation of up to 20% of the average particle size. These ranges are preferably 0.1-0.7 mm, 1-6 mm, 3-6 mm, 4-8 mm, 6-10 mm, 8-12 mm, 10-15 mm. More preferred particles are those having bimodal particle size distributions. This is made by mixing particles having 2 different particle size distributions such as particles having a distribution of sizes from 1-4 mm mixed with 6-10 mm. When bimodal particles are used, both particles can be selected from the long chain alkyl polymeric beads described above, or one of the particles can be selected from such beads and one selected from other beads such as PMMA and polyethylene beads, or inorganic particles such as silica particles, the second type of bead or particle also preferably having a narrow particle size distribution.

Whatever particle combination is used, suitable particle size combinations include particle size distributions of from 1 to 4 mm and from 6 to 10 mm, or from 2 to 6 mm and from 8 to 12 mm, or from 0.20 to 0.5 mm and from 1-6 mm.

An antistatic agent may also be present in the coating. Useful agents are selected from the group consisting of nonionic antistatic agents, cationic agents, anionic agents, and fluorinated agents. Useful agents include such as those available under the trade name ATMER™, e.g., ATMER™ 110, 1002, 1003, 1006, and the like, derivatives of Jeffamine™ ED-4000, 900, 2000 with FX8 and FX10, available from 3M, Larostat™ 60A, and Markastat™ AL-14, available from Mazer Chemical Co., with the preferred antistatic agents being steramido-propyldimethyl-β-hydroxy-ethyl ammonium nitrate, available as Cyastat SN, N,N'-bis(2-hydroxyethyl)-N-(3'- dodecyloxy-2'2-hydroxylpropyl) methylammonium methylsulfate, available as Cyastat™ 609, both from American Cyanamid. When the antistatic agent is present, amounts of up to 20% (solids/solids) may be used. Preferred amounts vary, depending on coating weight. When higher coating weights are used, 1-10% is preferred, when lower coating weights are used, 5-15% is preferred.

When the film forming polymer is made by emulsion polymerization, an emulsifier is also present. The emulsifiers include nonionic, or anionic emulsifiers, and mixtures thereof, with nonionic emulsifiers being preferred. Suitable emulsifiers include those having a HLB of at least 10, preferably from 12 to 18. Useful nonionic emulsifiers include C_π to Cis polyethylene oxide ethanol, such as Tergitol™, especially those designated series "S" from Union Carbide Corp, those available as Triton™ from Union Carbide Corp., and the Tween™ series available from ICI America. Useful anionic emulsifiers include sodium salts of alkyl sulfates, alkyl sulfonates, alkylether sulfates, oleate sulfates, alkylarylether sulfates, alkylarylpolyether sulfates, and the like. Commercially available examples include such as those available under the trade names Siponate™ and Siponic™ from Alcolac, Inc. When used, the emulsifier is present at levels of from 1% to 7%, based on polymer, preferably from 2% to 5%.

Additional wetting agents with HLB values of 7-10 may be present in the emulsion to improve coatability. These additional surfactants are added after polymerization is complete, prior to coating of the polymeric substrate. Preferred additional wetting agents include fluorochemical surfactants such as

wherein n is from 6 to 15 and R can be hydrogen or methyl. Useful examples include FC-170C and FC-171, available from 3M. Another useful wetting agent is Triton™ X-100, available from Union Carbide.

Addition of a coalescing agent is also preferred for emulsion based layers to insure that the coated material coalesces to form a continuous and integral layer and will not flake in conventional printing process. Compatible coalescing agents include propylcarbitol, available from Union Carbide as the Carbitol™ series, as well as the Cellusolve™ series, Propasolve™ series, and Ektasolve series of coalescing agents, also from Union Carbide. Other useful agents include the acetate series from Eastman Chemicals Inc., the Dowanol™ E series, Dowanol™ E acetate series, Dowanol™ PM series and their acetate series from Dow Chemical, N-methyl-2-pyrrolidone from GAF, and 3-hydroxy- 2,2,4-trimethyl pentyl isobutryate, available as Texanol™, from Eastman Chemicals Inc. These coalescing agents can be used singly or as a mixture.

Other optional ingredients may be present in the imaging polymer for the purposes of improving coatability, or other features. Useful additives include such as crosslinking agents, catalysts, thickeners, adhesion promoters, glycols, defoamers and the like.

One preferred optional ingredient in the emulsion polymerized embodiment of the invention is an additional adhesion promotor to enhance durability of thicker coatings to the substrate. Useful adhesion promoters include organofunctional silanes having the following general formula:

wherein R R₂, and R₃ are selected from the group consisting of an alkoxy group and an alkyl group with the proviso that at least one alkoxy group is present, n is an integer from 0 to 4, and Y is an organofunctional group selected from the group consisting of chloro, methacryloxy, amino, glycidoxy, and mercapto. Useful silane coupling agents include such as γ-aminopropyl trimethoxysilane, vinyl triethoxy silane, vinyl tris(β-methoxy ethoxy)-silane, vinyl triacetoxy silane, γ-methacryloxypropyltrimethyoxy silane, γ-(β-amino ethyl) aminopropyl trimethoxysilane, and the like. The adhesion promotor may be present at levels of from 0.5% to 15% of the total resin, preferably from 0.5% to 10%.

Film substrates may be chosen from any polymer capable of forming a self-supporting sheet, e.g., films of cellulose esters such as cellulose triacetate or diacetate, polystyrene, polyamides, vinyl chloride polymers and copolymers, polyolefin and polyallomer polymers and copolymers, polysulphones, polycarbonates, polyesters, and blends thereof. Suitable films may be produced from polyesters obtained by condensing one or more dicarboxylic acids or their lower alkyl diesters in which the alkyl group contains up to 6 carbon atoms, e.g., terephthalic acid, isophthalic, phthalic, 2,5-,2, 6-, and 2, 7-naphthalene dicarboxylic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, with one or more glycols such as ethylene glycol, 1,3-propanediol, 1, 4-butanediol, and the like. Preferred film substrates or backings are cellulose triacetate or cellulose diacetate, polyesters, especially polyethylene terephthalate, and polystyrene films. Polyethylene terephthalate is most preferred. It is preferred that film backings have a caliper ranging from 50 mm to 150 mm. Film backings having a caliper of less than 50 mm are difficult to handle using conventional methods for graphic materials. Film backings having calipers over 150 mm are very stiff, and present feeding difficulties in certain commercially available copying machines. When polyester film substrates are used, they can be biaxially oriented to impart molecular orientation before the imaging layer is coated thereon, and may also be heat set for dimensional stability during fusion of the image to the support. These films may be produced by any conventional extrusion method.

To promote adhesion of the layer to the film substrate, it may be desirable to treat the surface of the film substrate with one or more primers, in single or multiple layers. Useful primers include those known to have a swelling effect on the substrate polymer. Examples include halogenated phenols dissolved in organic solvents. Alternatively, the surface of the film substrate may be modified by treatment such as corona treatment or plasma treatment. The primer layer, when used, should be relatively thin, preferably less than 2 mm, most preferably less than 1 mm, and may be coated by conventional coating methods.

Transparencies of the invention are particularly useful in the production of imaged transparencies for viewing in a transmission mode or a reflective mode, i.e., in association with an overhead projector.

The following examples are for illustrative purposes, and do not limit the scope of the invention, which is that defined by the claims.

Glossary

BHT 2 TERT-BUTYL -METHYL PHENOL

DMAEMA DIMETHYLAMINOETHYL METHACRYLATE

EA ETHYL ACRYLATE

GMA GLYCIDYL METHYLACRYLATE

HBA HYDROXYBUTYLACRYLATE

HEA HYDROXYETHYLACRYLATE

HEMA HYDROXYETHYL METHACRYLATE

IBOA ISOBORNYL ACRYLATE

IBOMA ISOBORNYL METHACRYLATE

LA/BDDA LAURYLACRYLATE BUTANEDIOLDIACRYLATE

MA METHYL ACRYLATE

MMA METHYL METHACRYLATE

NMP N-METHYLPYRROLIDONE

PC PROPYLCARBITOL

PMMA POLYMETHYL METHACRYLATE

SMA A 50/50 HEXANEDIOLDIACRYLATE/STEARYL

METHACRYLATE BEAD

Z6040 GLYCIDOXYPROPYL TRIMETHOXYSILANE

Test Methods

Coefficient of Friction The Coefficient of Friction or COF of two stationary contacting bodies is defined as the ratio of the normal force "N", which holds the bodies together and the tangential force "Fi", which is applied to one of the bodies such that sliding against each other is induced.

A model SP-102B-3M90 Slip/Peel Tester, from Imass Co. was used to test the COF of articles of the invention. The bead-coated sides of two sheets are brought into contact with each other, with 1 sheet attached to a 1 kg brass sled, tethered to a force gauge and the second sheet attached to the moveable platen. The platen is drawn at a constant speed of 15.24 cm/min., and the maximum and average COF values are obtained from the tester readout and recorded.

Haze Haze is measured with the Gardner Model XL-211 Hazeguard hazemeter or equivalent instrument. The procedure is set forth in ASTM D 1003-61 (Reapproved 1977) . This procedure measures haze of the receptor construction without an image receptive coating.

Coating Durability Test Durability is measured using the SP-102B-3M90 Slip/Peel Tester available from I ass, equipped with an MB-5 load cell. The platen speed was set at 15.24 cm/minute. A 1 cm x 2 cm rubber was attached by a piece of double-coated tape to the middle of the sled with the 2 cm side parallel to the direction of the sliding motion. Test samples of the image receptive film were cut into 5 cm x 20 cm and 2.5 by 5 cm pieces. The 5 cm x 20 cm test piece is attached with double-coated tape to the left end of the platen and both sides of the 200 gms sled weight just above and below the 1 cm x 2 cm rubber. The 2 cm x 5 cm test piece is then attached to the 200 gm sled such that the 2 cm side is parallel to the 5 cm side of the rubber. Both test pieces are pressed to assure that they are flat and centered. They are then labeled and marked. One end of a 20 cm long 12 kg steel finishing line leader was permanently connected to the 200 gms sled and the other end to the load cell. The sled is positioned above the left end of the platen and aligned with it to assure that the leader is in a relaxed state. The sled is then gently laid onto the test sample. 500 gms of additional weight is added to the sled and the platen is activated. After travelling for a distance of 8 cm, the platen is stopped and the sample removed to rate the durability. The ratings are according to the following scale:

1 - positive for both coating removal and particle flaking.

2 - negative for coating removal, positive to particle flaking.

3 - positive for scratches, negative for both coating removal and particle flaking.

4 - negative for scratches, coating removal and particle flaking.

Stack Feeding Test This test defines the number of failures per total number of sheets fed. Receptor sheets were tested in a stack at various temperature and relative humidity conditions. Any jamming, misfeed or other problems during the printing process was recorded as a failure.

Scratch Test This test is carried out on transparency films after they have been imaged through a copier. First, 100 sheets of paper are run through a Xerox 1090 copier. Then 6 sheets of each test film are run, punctuated by 10 sheets of paper. A reference is run each time to insure that variations in copier conditions are taken into account. The films are then projected using an overhead projector (3M M9000), and the intensity of the projected scratch is then judged according to the following standards: 0 = No scratch 1 = Extremely faint scratch, non-continuous

2 = Faint continuous scratch

3 = Visible and continuous scratch.

4 = Very noticeable, continuous scratch. 5 = Very noticeable scratch with signs of coating removal or debris. Any number lower than 2 is acceptable.

Toner Adhesion Test ASTM D2197-86 "Adhesion of Organic Coatings by Scope Adhesion" was used to measure toner adhesion to the coated surface of the film. The measurements were done on samples after the coated film was imaged on a variety of commercially available copiers, specifically Xerox 5065. The results were recorded in grams. A measurement of 200 gms or more is acceptable.

Toner Adhesion by Crease Test

A. Preparation for the test

This test is conducted at ambient conditions of 25°C and 50% relative humidity. A special original is used for this test, having a 2.5 cm x 3 cm black square printed in such a fashion as to be centered with respect to the short edge of the sheet, e.g., the 8 1/2 in. edge of an 81/2 by 11 in. sheet and a 3M logo in the upper left area of the sheet. The original is placed in the copier (Xerox 1090) with the 3M logo away from the operator. 100 sheets of paper are run first to warm up the machine. Then for each test set, 5 sheets of a test sample are run followed by 10 sheets of paper. After all samples are run, they are allowed to cool under ambient conditions for at least 30 minutes prior to crease measurement.

B. Crease measurement

The imaged sheet is loosely folded in such a way that the small solid block in the middle of the bottom of the sheet is doubled over itself. A brass cylinder weighing 862 gms is slowly rolled three times over the folded sheet. Then the sheet is unfolded and the crease area is thoroughly wiped with a tissue paper to remove any loose toner. Using a ruler, calibrated in millimeters (mm) , the width along the crease where the toner is removed is measured under a microscope. 4 to 5 random readings along the crease is done and the average is recorded in mm. Good toner adhesion is any measurement smaller than 2.

Examples

Example 1 A transparency film having a toner receptive layer is prepared and tested as follows: A. PREPARATION OF THE CORE/SHELL LATEX POLYMER

2544 gms of deionized water, 58 gms of Triton™ X405 (available from Union Carbide) and 5.1 gms of Siponate™ DS 10 (available from Rhone-Polenc) were added to a four-neck flask equipped with a reflux condenser, thermometer, stirrer, metering pump and nitrogen gas inlet. The mixture is then stirred and heated to 60°C under nitrogen atmosphere. During heating, the core monomer pre-mix containing 40 gms of isobornylacrylate (IBOA) and 363 gms of ethylacrylate (EA) was charged into the reactor. When the batch temperature reached 60°C, the initiator was added to the reactor to initiate the polymerization. The reaction is allowed to exotherm. At the exotherm peak, the batch temperature set point was raised to 70°C for the rest of the polymerization period, and the shell monomer premix containing 330 gms of IBOA, 518 gms methylmethacrylate

(MMA) , and 94 gms of EA was fed into the reaction using a metering pump. The shell monomer feed took about 60 to 70 minutes to complete. When the shell monomer feed was completed, the polymerization was continued for two hours at 70°C to eliminate residual monomers. The latex was then cooled to room temperature and filtered through 25 mm filter to remove coagulum. The latex having a ratio of core:shell of 30:70 was then ready. -27-

B. MIXING OF LATEX COATING SOLUTION

38.7 gms of N-methylpyrrolidone (NMP) was slowly added to 379.4 gms of core/shell latex from part 1 with stirring. 64.5 gms of a 10% solids solution of Cyastat™ 609, 30 gms of 10% solids FC 170C premix was then introduced into the latex with stirring, along with 40 gms of a 30% solution of SMA beads having a particle size of 8 mm, 51.6 gms of a 10% solution of A1120 adhesion promotor (available from Union Carbide), 96 gms of a 10% solution of Brij™ 35 (available from ICI) .

To this solution was added 2280.4 gms of D.I. water. Finally, 6.5 gms of 10% solids solution of ammonium hydroxide was added with mixing, to keep the PH at 9, followed by 12.9 gms of a 10% solution of XAMA-7 (available from Sancor) prior to coating.

C. COATING OF THE LATEX COATING SOLUTION

Using a gravure roll coating device, the coating solution was applied on polyvinylidine treated 100 mm poly(ethylene terephthalate) (PET) film, and dried. The drying of the coated web was done in two steps inside the oven with zone 1 set at 93°C and zone 2 set at 149°C. The web remained in each zone for 12 seconds. The dried coating weight was 0.26 gms/m².

D. MEASUREMENT OF PROPERTIES All the properties, both functional and nonfunctional, were measured using various commercially available copiers.

The results are summarized in Table 1.

Receptor sheets of the invention were fed into five different copiers at various temperatures and relative humidities. The following table shows the number of misfeeds for each machine, and the total sheets fed.

Example 2 A transparency film having a toner receptive layer is prepared and tested as follows: A. PREPARATION OF THE CORE/SHELL LATEX POLYMER

2544 gms of deionized water, 58 gms of Triton™ X405 (available from Union Carbide) and 5.1 gms of Siponate™ DS 10 (available from Rhone-Polenc) were added to a four-neck flask equipped with a reflux condenser, thermometer, stirrer, metering pump and nitrogen gas inlet. The mixture is then stirred and heated to 60°C under nitrogen atmosphere. During heating, the core monomer pre-mix containing 40 gms of IBOA and 363 gms of EA were charged into the reactor. When the batch temperature levelled off at 60°C, the initiator is added to the reactor to initiate the polymerization. The reaction is allowed to exotherm. At the exotherm peak, the batch temperature set point was raised to 70°C for the rest of the polymerization period, and the shell monomer premix containing 330 gms of IBOA, 471 gms methylmethacrylate (MMA) , 47 gms of hydroxyethylmethacrylate (HEMA) and 94 gms of EA was fed into the reaction using a metering pump. The shell monomer feed took about 60 to 70 minutes to complete. When the shell monomer feed was completed, the polymerization was continued for two hours at 70°C to eliminate residual monomers. The latex was then cooled to room temperature and filtered through 25 mm filter to remove coagulum. The latex having a ratio of core:shell of 30:70 was then ready. B. MIXING OF LATEX COATING SOLUTION

38.7 gms of N-methylpyrrolidone (NMP) was slowly added to 364.7 gms of core/shell latex from part 1 with stirring. 64.5 gms of a 10% solids solution of Cyastat™ 609, and 30 gms of 10% solids FC 170C premix was then introduced into the latex with stirring, along with 20 gms of a 30% solution of SMA beads having a particle size of 8 mm, 30 gms of a 20% solution of Syloid™ 620 (available from Grace Davidson) having a particle size of 10-12 mm, 49.6 gms of a 10% solution of A1120 adhesion promotor, 96 gms of a 10% solution of Brij™ 35 (available from ICI) . This gave the lubricant content of 7.4 parts per 100 parts of core/shell latex polymer.

To this solution was added 2287.6 gms of D.I. water. Finally, 6.5 gms of 10% solids solution of ammonium hydroxide was added with mixing, to keep the PH at 9, followed by 12.4 gms of a 10% solution of XAMA-7 (available from Sancor) prior to coating.

C. COATING OF THE LATEX COATING SOLUTION

Using a gravure roll coating device, the coating solution was applied on polyvinylidine treated 100 mm poly(ethylene terephthalate) (PET) film, and dried. The drying of the coated web was done in two steps inside the oven with zone 1 set at 93°C and zone 2 set at 149°C. The web remained in each zone for 12 seconds. The dried coating weight was 0.26 g/m².

D. MEASUREMENT OF PROPERTIES

All the properties, both functional and nonfunctional, were measured using various commercially available copiers. The results are summarized in Table 2.

Examples 3C and 4

These examples were made in the same manner as Example 2, except with the following compositions:

EX. Core/ A1120 XAMA-7 FC170 Cyastat SMA Cymel Brij NMP NH3 shell (g) (g) (g) 609 (g) 8mm 303 35 (g) (g)

(g) (g⁾ (g⁾ (g)

1 ^3c 364.7 49.6 12.7 30 64.5 40 - - 38.7 6.5

4 364.7 49.6 12.4 30 64.5 40 24.8 96 38.7 6.5

The examples were coated and tested in the same manner, and the results are shown in Table 1.

Comparative Example 5C This was prepared according to the following procedure: -30-

A. PREPARATION OF EMULSION POLYMER

The following ingredients were admixed according to the procedures described below to make a latex binder for coating on plain paper copier transparency film.

To prepare the present emulsion polymer, Deionized water (DI water) and surfactant (Triton X405) were charged into a four-neck flask equipped with a reflux condenser, thermometer, stirrer, metering pump and a nitrogen gas inlet. This was stirred and heated to 70°C under nitrogen atmosphere. In the meantime the monomers, IBOA, MMA, EA, DMAEMA and carbon tetrabromide (a chain transfer agent) , were pre-mixed in a separate container at room temperature to make the monomer premix. When the reaction temperature leveled off at 70°C, 20% of the monomer premix and the initiator (ammonium persulfate) were charged into the reactor to start the polymerization. The reaction was allowed to exotherm. At the exotherm peak, the remaining 80% monomer premix was fed into the reaction using a metering pump over a two-hour period while the reaction temperature was maintained at 70°C. After the monomer addition, the polymerization was continued for two hours at 70°C to eliminate residual monomers. The latex was then cooled to 25°C and filtered through a 25 mm filter.

B. MIXING OF LATEX COATING SOLUTION

16.54 gms of Texanol™ was slowly added to 661.67 gms of latex with stirring. 3.57 gms of 50% solids solution of Cyastat™ SN was then added along with 3.57 gms of 50% solids solution Cyastat™ 609. 85.0 gms of 10% solids FC 170C premix was then introduced into the latex with stirring, along with 16 gms of SMA beads having a particle size of 4 mm, 16 gms of SMA beads having a particle size of 8 mm, and 39.7 gms of A1120 adhesion promotor, available from Union Carbide.

To this solution was added D.I. water, to make up a total of 3400 gms. Finally, 2.6 gms of 10% solids solution of Dow 65 defoamer was added with mixing. The final coating solution of latex had a concentration of 5.7% solids.

C. COATING OF THE LATEX COATING SOLUTION

Using a gravure roll coating device, the coating solution was applied on an air corona treated 100 mm poly(ethylene terephthalate) (PET) film, and dried. The drying of the coated web was done in two steps inside the oven with zone 1 set at 93°C and zone 2 set at 149°C. The web remained in each zone for 12 seconds. The dried coating weight was 0.26 gms/m². D. MEASUREMENT OF PROPERTIES

All the properties, both functional and nonfunctional, were measured using various commercially available copiers. The results are summarized in the following Table 1. -32-

Table 1

Examples 5-16 These image-receptive sheets were made in the same manner as Example 2, except that various amounts of different lubricants were used as shown in Table 2.

Table 2

Example 17C This was made in the same manner as Example 5, except that a Carbowax™ lubricant, 3350, available from Union Carbide, was used in place of Brij™ 99. The scratch test yielded a value of 1, but the toner adhesion was only 760 g, rather than the measurement of 1600 gms for Example 5.

Examples 18-19 These image-receptive sheets were made in the same manner as Example 2, except that the core/shell latex polymers were made with N-methylolacrylamide (NMA) instead of HEMA, as shown in Table 3.

Table 3

Example Core/shell latex Core/shell T_g (°C) composition Ratio IBOA/MMA/EA/NMA

18 core 10/0/90/0 40 -5 shell 35/40/20/5 60 ⁷⁷

19 core 10/0/90/0 30 -6 shell 35/50/10/5 70 79

These image-receptive sheets were also tested in the same manner as Example 2 and the results are shown in Table 6.

Examples 20-25 These image-receptive sheets were made in the same manner as Example 2, except with different ingredients as shown in Table 4.

Table 4 _β

Example core/shell latex composition core/shell τ_g Co IBOA/MMA/EA/DMAEMA/CBr4 ratio

20 core 10/10/75/5/0.2 40 1 shell 35/40/20/5/0.2 60 49

21 core 10/10/75/5/0.2 6 shell 35/40/20/5/0.2 54

22 core 10/7.5/77.5/5/0.2 3 shell 35/37.5/22.5/5/0.2 50

23 core 10/5/80/5/0.2 40 -2 shell 35/35/25/5/0.2 60 43

24 core 0/15/80/5/0.2 40 4 shell 0/75/20/5/0.2 60 55

25 core 0/20/75/5/0.2 40 3 shell 0/70/25/5/0.2 60 51

These examples were also tested in the same manner as Example 2 and the results are listed in Table 6.

Example 26 This image-receptive sheet was made in the same manner as Example 2, except with the following composition as shown in Table 5.

Table 5

Example core/shell latex composition core/shell ratio IBOA/MMA/EA/AA/CBr4

26 core 0/10/90/0/.2 40 shell 35/25/35/5/.2 60

This image-receptive sheets was also tested in the same manner as Example 2 and the results are shown in Table 6. Table 6

Examples 27-32 These image-receptive sheets were made in the same manner as Example 1, except that different lubricating agents were used as shown in Table 7. These image-receptive sheets were also tested in the same manner as Example 1, and the results are also listed in Table 7.

Table 7

Exa ples 33 and 34C These image-receptive sheets were made in the following manner:

A. PREPARATION OF SHELL ONLY POLYMER 2544 gms of deionized water, 58 gms of Triton™ X405 and 5.1 gms of Siponate™ DS 10 were added to a four-neck flask equipped with a reflux condenser, thermometer, stirrer, metering pump and nitrogen gas inlet. The mixture was then stirred and heated to 60°C under nitrogen atmosphere. During heating, the shell monomer pre-mix containing 330 gms of IBOA, 518 gms of MMA and 94 gms of EA were charged into the reactor. When the batch temperature reached at 60°C, the initiator was added to the reactor to initiate the polymerization. The reaction was allowed to exotherm. At the exotherm peak, the batch temperature set point was raised to 70°C for the rest of the polymerization period.

B. PREPARATION OF COATING SOLUTION

This was carried out in the same manner as in Example 1, except with 379.4 gms of shell polymer and 51.6 gms of A1120, and no Brij was present in 35C. These image-receptor sheets were also coated in the same manner and tested. The results are shown in Table 8. Although even the image receptive sheet with the lubricant has a higher than desirable scratch value, the improvement over a sample without the lubricant can clearly be seen, and is a substantial improvement.

Table 8

Ex. COF Scratch % Haze Toner adhesion (g) Crease (mm)

33 .26 3 2.1 979 0.7

34C .24 4.6 2.8 832 1.6

Claims

What is Claimed is:

1. A water-based toner-receptive composition comprising: a) from 55 to 95 parts of a transparent film-forming imageable polymer formed from at least one monomer selected from the group consisting of bicyclic alkyl (meth)acrylates, aliphatic alkyl (meth) acrylates having from one to 12 carbon atoms, aromatic (meth) acrylates, and a polar monomer having the formula:

wherein R is hydrogen or methyl, Ri and R₂ are selected from the group consisting of hydrogen, alkyl groups having up to 12 carbon atoms, and the quaternary cationic salts thereof; b) from 5 to 10 parts of at least one lubricating agent selected from the group consisting of i) mono-substituted poly(oxyethylenes) represented by the following general formula:

wherein n is an integer ranging from 5 to 200; R is selected from straight chained or branched alkylether, containing from 6 to 25 carbon atoms, and ii) poly-substituted poly(oxyethylenes) represented by the following formula:

wherein X is an integer ranging from 50 to 500, and Y is an integer ranging from 1 to 4; Ri, R₂, and R₃ are straight chained or branched alkyl groups, Ri containing from 10 to 15 carbon atoms, R₂ containing from 10 to 24 carbon atoms, and R₃ containing from 5 to 40 carbon atoms; c) from 1 to 15 parts polymeric particles; and d) from 0 to 20 parts of an antistatic agent selected from the group consisting of cationic agents, anionic agents, and mixtures thereof.

2. A water-based toner-receptive composition according to claim 1 wherein said imeagable polymer comprises from 55 parts to 94 parts of a core/shell latex polymer comprising: a) a core formed from: i) from 0 to 30 parts of at least one monomer selected from the group consisting of bicyclic alkyl (meth) acrylates and aromatic (meth) acrylates; and ii) 70 to 100 parts of at least one α,β- ethylenically unsaturated monomer having from 1 to

12 carbon atoms; and b) a shell formed from: i) from 0 to 100 parts of at least one monomer selected from the group consisting of bicyclic alkyl (meth) acrylates, and aromatic

(meth) acrylates; and ii) 35 to 70 parts of at least one α,β- ethylenically unsaturated monomer having from 1 to 12 carbon atoms.

3. A toner-receptive composition according to claim 1 wherein said monosubstituted polyoxyethylene comprises a straight chain alkylether selected from the group consisting of [polyoxyethylene]100 stearyl ether, [Polyoxyethylene]₂₃ lauryl ether, [Polyoxyethylene]₂₀ stearyl ether, [Polyoxyethylene]₂₀ cetyl ether, [Polyoxyethylene]₂₀ oleyl ether, [Polyoxyethylene]5.5 decyl ether, and [Polyoxyethylene]21 stearyl ether.

4. A toner-receptive composition according to claim 1 wherein said polysubstituted polyoxyethylene is selected from the group consisting of poly(oxyethylene) urethanes.

5. A toner-receptive composition according to claim 2 wherein said core/shell latex polymer comprises a bicyclic monomer selected from the group consisting of dicyclopentenyl (meth)acrylate, norbornyl (meth) acrylate, and isobornyl (meth)acrylate, an aromatic monomer selected from the group consisting of benzyl (meth)acrylate and styrene (meth)acrylate, and an α,β-ethylenically unsaturated monomer selected from the group consisting of aliphatic acrylates selected from the group consisting of aliphatic alkyl (meth) acrylates include, but are not limited to, methyl acrylate, methyl acrylate, ethyl (meth)acrylate, n- butyl acrylate, isobutyl (meth)acrylate, isodecyl (meth) acrylate, and cyclohexyl (meth) acrylate.

6. A toner-receptive composition according to claim 2 wherein said core/shell latex polymer comprises an α,β- ethylenically unsaturated monomer selected from the group consisting of styrene and vinyl esters.

7. A toner-receptive composition according to claim 2 wherein said core/shell latex polymer comprises a polar monomer selected from the group consisting of (meth)acrylic acid, hydroxyalkyl (meth)acrylate, N-alkylacrylamide, N,N'- dialkyl aminoalkyl (meth)acrylate, monoalkyl amino alkyl

(meth)acrylate, the cationic salt of N,N-dialkylamino alkyl (meth) acrylate, N-methylol acrylamide, isobutoxy

(meth)acrylamide, and N-alkyl aminoalkyl (meth)acrylate, all of said alkyl groups containing up to 12 carbon atoms.

8. A transparent water-based toner-receptive composition according to claim 1 wherein the antistatic agent is selected from the group consisting of steramido- propyldimethyl-β-hydroxy-ethyl ammonium nitrate, N,N'-bis(2- hydroxyethyl)-N- (3'-dodecyloxy-2'2-hydroxylpropyl) methylammonium methylsulfate, and mixtures thereof.

9. A transparent water-based toner-receptive composition according to claim 1 wherein said particle is selected from the group consisting of a 50/50 poly(hexanediol-diacrylate/stearyl methacrylate) particle, a 50/50 poly(butanedioldiacrylate)/lauryl (meth)acrylate particle, an 80/20 poly(hexanediol- diacrylate)/stearyl (meth)acrylate particle, a 50/50 polymethylmethacrylate/1, 6 hexanedioldiacrylate particle, a C dioldiacrylate particle, and a Cι₂ dioldi (meth)acrylate particle.

10. A transparent water-based toner-receptive composition according to claim 11 wherein an additional particle is also present, said additional particle having an average particle size which differs by at least 4 mm from the average particle size of said novel polymeric particle, said additional particle comprising a polymer selected from the group consisting of a copolymer of hexanedioldiacrylate and stearylmethacrylate and polymethylmethacrylate.

11. A transparent water-based toner-receptive composition according to claim 1 further comprising a silica particle.

12. A transparent recording sheet comprising a transparent film substrate having two major opposing surfaces, at least one of said surfaces having coated thereon a water-based toner-receptive composition according to claim 1.