Modified antistatic compositions and thermally developable materials containing same

Abstract

Antistatic compositions include a fluorochemical that is a reaction product of R f CH 2 CH 2 —SO 3 H with an amine wherein R f comprises 4 or more fully fluorinated carbon atoms. These antistatic compositions can be formulated in organic solvent-based conductive coating compositions, with or without hydrophobic binders, that can be used to form conductive layers in thermally developable materials including thermographic and photothermographic materials.

We claim:  
     
         1 . An antistatic composition comprising one or more solvents, at least 50 volume % being organic solvent(s), and a fluorochemical that is a reaction product of R f CH 2 CH 2 —SO 3 H with an amine wherein R f  comprises 4 or more fully fluorinated carbon atoms.  
     
     
         2 . The antistatic composition of  claim 1  wherein said amine comprises one or more aliphatic amino groups, is non-fluorinated, and has a molecular weight of from about 31 to about 2000 and R f  comprises 4 or more even-numbered fully fluorinated carbon atoms.  
     
     
         3 . The antistatic composition of  claim 1  wherein R f  comprises a fluoroaliphatic chain comprising one or more straight-chain, branched-chain, or cyclic aliphatic chains or combinations thereof that are joined together by heteroatoms or heteroatom-containing groups.  
     
     
         4 . The antistatic composition of  claim 2  wherein R f  comprises a single fluoroalkyl chain comprising 6, 8, 10, 12, 14, or 16 fully fluorinated carbon atoms.  
     
     
         5 . The antistatic composition of  claim 2  wherein R f  comprises a single fully fluorinated fluoroalkyl chain comprising 6, 8, or 10 carbon atoms.  
     
     
         6 . The antistatic composition of  claim 2  comprising first and second fluorochemicals wherein said first fluorochemical is a reaction product of R f  a-CH 2 CH 2 —SO 3 H with an aliphatic amine wherein R f  a comprises 4 or more even-numbered fully fluorinated carbon atoms, and said second fluorochemical is a reaction product of R fb -CH 2 CH 2 —SO 3 H with the same or different aliphatic amine wherein R fb  comprises 4 or more even-numbered fully fluorinated carbon atoms.  
     
     
         7 . The antistatic composition of  claim 2  comprising first and second fluorochemicals wherein said first fluorochemical is a reaction product of R f  a-CH 2 CH 2 —SO 3 H with an aliphatic amine wherein R f  a comprises 6 fully fluorinated carbon atoms, and said second fluorochemical is a reaction product of R fb -CH 2 CH 2 —SO 3 H with the same or different aliphatic amine wherein R f  b comprises 8 or 10 fully fluorinated carbon atoms.  
     
     
         8 . The antistatic composition of  claim 1  wherein said amine is an aliphatic amine and comprises one or more straight-chain, branched-chain, or cyclic aliphatic groups, or a combination of such groups that are joined together by heteroatoms or heteroatom-containing groups.  
     
     
         9 . The antistatic composition of  claim 1  wherein said aliphatic amine comprises two amino groups.  
     
     
         10 . The antistatic composition of  claim 2  wherein said aliphatic amine is a polyoxyalkylenediamine.  
     
     
         11 . The antistatic composition of  claim 2  wherein said aliphatic amine is polyoxyalkyleneamine, polyoxypropylenediamine, propoxylated{poly(oxypropylene)} diamine, alkylethertriamine, or ethoxylated tallow alkylamine, and R f  is C 6 F 13 —.  
     
     
         12 . The antistatic composition of  claim 2  further comprising one or more hydrophobic binders.  
     
     
         13 . The antistatic composition of  claim 12  wherein at least one of said hydrophobic binders is a cellulose acetate butyrate binder.  
     
     
         14 . A thermally developable material comprising a support and having thereon at least one thermally developable layer, and a first conductive layer comprising a fluorochemical that is a reaction product of R f CH 2 CH 2 —SO 3 H with an amine wherein R f  comprises 4 or more fully fluorinated carbon atoms.  
     
     
         15 . The thermally developable material of  claim 14  wherein said amine comprises one or more amino groups, is non-fluorinated, and has a molecular weight of from about 31 to about 2000 and R f  comprises 4 or more even-numbered fully fluorinated carbon atoms.  
     
     
         16 . The thermally developable material of  claim 14  wherein R f  comprises a fluoroaliphatic chain comprising one or more straight-chain, branched-chain, or cyclic aliphatic chains or combinations thereof that are joined together by heteroatoms or heteroatom-containing groups.  
     
     
         17 . The thermally developable material of  claim 15  wherein R f  comprises a single fluoroalkyl chains comprising 6, 8, 10, 12, 14, or 16 fully fluorinated carbon atoms.  
     
     
         18 . The thermally developable material of  claim 15  wherein R f  comprises a single fully fluorinated fluoroalkyl chain comprising 6, 8, or 10 carbon atoms.  
     
     
         19 . The thermally developable material of  claim 15  wherein said first conductive layer comprises first and second fluorochemicals wherein said first fluorochemical is a reaction product of R fa -CH 2 CH 2 —SO 3 H with an amine wherein R fa  comprises 6 fully fluorinated carbon atoms, and said second fluorochemical is a reaction product of R fb -CH 2 CH 2 —SO 3 H with the same or different amine wherein R b  comprises 8 or 10 fully fluorinated carbon atoms.  
     
     
         20 . The thermally developable material of  claim 19  wherein said first fluorochemical is present in said first conductive layer in an amount of from about 50 to about 95 weight % based on total fluorochemical weight.  
     
     
         21 . The thermally developable material of  claim 15  wherein said aliphatic amine comprises one or more straight-chain, branched-chain, or cyclic aliphatic groups, or a combination of such groups that thereof that are joined together by heteroatoms or heteroatom-containing groups.  
     
     
         22 . The thermally developable material of  claim 15  wherein said aliphatic amine is a polyoxyalkylenediamine.  
     
     
         23 . The thermally developable material of  claim 15  wherein said first conductive layer comprises one or more fluorochemicals, each fluorochemical being a reaction product of R f CH 2 CH 2 —SO 3 H with a non-fluorinated polyoxyalkyleneamine comprising two or more amino groups and having a molecular weight of from about 17 to about 2000, and each R f  is the same or different fully fluorinated fluoroalkyl group having 6, 8, or 10 carbon atoms.  
     
     
         24 . The thermally developable material of  claim 23  wherein said aliphatic amine is polyoxyalkyleneamine, polyoxypropylenediamine, propoxylated {poly(oxypropylene)} diamine, alkylethertriamine, or ethoxylated tallow alkylamine, and at least one R f  is C 6 F 3 —.  
     
     
         25 . The thermally developable material of  claim 15  wherein said first conductive layer further comprises one or more hydrophobic binders.  
     
     
         26 . The thermally developable material of  claim 25  wherein at least one of said hydrophobic binders is a cellulose acetate butyrate binder.  
     
     
         27 . The thermally developable material of  claim 15  wherein said first conductive layer is disposed over said thermally developable layer on the same side of said support.  
     
     
         28 . The thermally developable material of  claim 15  comprising a second conductive layer on the opposite side of said support as said first conductive layer, said first and second conductive layers containing the same or different reaction product fluorochemical that is a reaction product of R f CH 2 CH 2 —SO 3 H with an aliphatic amine wherein R f  comprises 4 or more even-numbered fully fluorinated carbon atoms.  
     
     
         29 . The thermally developable material of  claim 15  that is a non-photosensitive thermographic material comprising a non-photosensitive source of reducible silver ions and a reducing composition for said non-photosensitive source of reducible silver ions.  
     
     
         30 . A black-and-white thermographic material that comprises a support having thereon one or more thermally-developable imaging layers comprising a binder and in reactive association, a non-photosensitive source of reducible silver ions, and a reducing composition for said non-photosensitive source of reducible silver ions, and 
 a first conductive layer comprising a fluorochemical that is a reaction product of R f CH 2 CH 2 —SO 3 H with an aliphatic amine wherein R f  comprises 4 or more even-numbered fully fluorinated carbon atoms.    
     
     
         31 . A photothermographic material that comprises a support having thereon one or more thermally developable imaging layers comprising a binder and in reactive association, a photosensitive silver halide, a non-photo-sensitive source of reducible silver ions, a reducing composition for said non-photosensitive source reducible silver ions, and 
 a first conductive layer comprising a fluorochemical that is a reaction product of R f CH 2 CH 2 —SO 3 H with an amine wherein R f  comprises 4 or more even-numbered fully fluorinated carbon atoms.    
     
     
         32 . The photothermographic material of  claim 31  wherein said amine comprises one or more amino groups, is non-fluorinated, and has a molecular weight of from about 31 to about 2000.  
     
     
         33 . The photothermographic material of  claim 32  wherein said first conductive layer is disposed on said support opposite said one or more thermally developable imaging layers.  
     
     
         34 . The photothermographic material of  claim 32  wherein said non-photosensitive source of reducible silver ions is a silver fatty acid carboxylate having 10 to 30 carbon atoms in the fatty acid or a mixture of said silver carboxylates.  
     
     
         35 . The photothermographic material of  claim 32  wherein said support is composed of a transparent polyester and said first conductive layer further comprises a cellulose ester binder.  
     
     
         36 . The photothermographic material of  claim 35  wherein the weight ratio of fluorochemical to cellulose ester binder in said first conductive layer is from about 0.04:1 to about 0.2:1.  
     
     
         37 . The photothermographic material of  claim 32  further comprising a protective layer over said one or more thermally-developable imaging layers, an antihalation layer on the backside of said support, or both.  
     
     
         38 . The photothermographic material of  claim 32  wherein said support is composed of a transparent polyester film, said photosensitive silver halide is a photosensitive silver bromide, silver bromoiodide, or both, said non-photosensitive source of reducible silver ions is a silver salt of an aliphatic carboxylic acid, or a mixture of such salts, at least one of which is silver behenate, said reducing composition for said non-photosensitive source reducible comprises a hindered phenol, and 
 on one or both sides of said support, the same or different conductive layers each comprising a cellulose acetate butyrate binder, and the same or different fluorochemical that is a reaction product of R f -CH 2 CH 2 —SO 3 H with a non-fluorinated polyoxyalkyleneamine comprising two or more amino groups and having a molecular weight of from about 31 to about 2000, and each R f  is the same or different fully fluorinated fluoroalkyl group having 6, 8, or 10 carbon atoms.  
 
     
     
         39 . The photothermographic material of  claim 27  that provides a black-and-white image.  
     
     
         40 . A black-and-white photothermographic material that comprises a support having thereon: 
 a) one or more thermally developable imaging layers each comprising a binder, and in reactive association, 
 a photosensitive silver bromide or silver iodobromide,  
 a non-photosensitive source of reducible silver ions that includes one or more silver carboxylates at least one of which is silver behenate,  
 a reducing composition for said non-photosensitive source reducible silver ions that includes at least one hindered phenol, and  
 at least one toner, antifoggant, spectral sensitizing dye, or high contrast agent, or any combination thereof,  
   b) a protective overcoat disposed over said one or more thermally developable imaging layers,    c) on the backside, a first conductive layer comprising a fluorochemical that is a reaction product of R f CH 2 CH 2 —SO 3 H with a polyoxyalkylenediamine wherein R f  comprises a single fully fluorinated fluoroalkyl chain comprising 6, 8, or 10 carbon atoms, or a mixture of two or more fluorochemicals that are reaction products of the same or different R f CH 2 CH 2 —SO 3 H with the same or different polyoxyalkylenediamine, and    d) also on said backside, an antihalation layer disposed over said first conductive layer.    
     
     
         41 . A black-and-white thermographic material that comprises a support having thereon: 
 a) one or more thermally developable imaging layers each comprising a binder, and in reactive association, 
 a non-photosensitive source of reducible silver ions that includes one or more silver carboxylates at least one of which is silver behenate,  
 a reducing composition for said non-photosensitive source reducible silver ions that includes at least one di- or tri-hydroxy compound having at least two hydroxy groups in ortho- or para-relationship on the same aromatic nucleus,  
 at least one toner, antifoggant, or high contrast agent, or any combination thereof,  
   b) a protective overcoat disposed over said one or more thermally developable imaging layers, and    c) on the backside, a first conductive layer comprising a fluorochemical that is a reaction product of R f  CH 2 CH 2 —SO 3 H with a polyoxyalkylenediamine wherein R f  comprises a single fully fluorinated fluoroalkyl chain comprising 6, 8, or 10 carbon atoms, or a mixture of two or more fluorochemicals that are reaction products of the same or different R f CH 2 CH 2 —SO 3 H with the same or different polyoxyalkylenediamine.    
     
     
         42 . A method of forming a visible image comprising: 
 A) thermal imaging of the thermally developable material of  claim 15 .    
     
     
         43 . The method of  claim 42  wherein said thermographic material comprises a transparent support, and said image-forming method further comprises: 
 B) positioning said thermal imaged thermographic material between a source of imaging radiation and an imageable material that is sensitive to the imaging radiation, and  
 C) exposing said imageable material to the imaging radiation through the visible image in said thermal imaged thermographic material to provide an image in the imageable material.  
 
     
     
         44 . A method of forming a visible image comprising: 
 A) imagewise exposing the photothermographic material of  claim 32  to electromagnetic radiation to form a latent image,    B) simultaneously or sequentially, heating said exposed photothermographic material to develop said latent image into a visible image.    
     
     
         45 . The method of  claim 44  wherein said photothermographic material comprises a transparent support, and said image-forming method further comprises: 
 C) positioning said exposed and heat-developed photothermographic material with the visible image therein between a source of imaging radiation and an imageable material that is sensitive to said imaging radiation, and  
 D) exposing said imageable material to said imaging radiation through the visible image in said exposed and heat-developed photothermographic material to provide an image in said imageable material.  
 
     
     
         46 . A method of preparing an antistatic composition comprising dispersing R f CH 2 CH 2 —SO 3 H wherein R f  comprises 4 or more even-numbered fully fluorinated carbon atoms and an amine in one or more solvents, at least 50 volume % being organic solvent(s), said one or more solvents further comprising one or more hydrophobic binders, and reacting said amine and R f CH 2 CH 2 —SO 3 H to provide a fluorochemical in an antistatic composition.  
     
     
         47 . A method of coating an antistatic composition comprising: 
 dispersing R f CH 2 CH 2 —SO 3 H wherein R f  comprises 4 or more even-numbered fully fluorinated carbon atoms and an amine in one or more solvents, at least 50 volume % being organic solvent(s), said one or more solvents further comprising one or more hydrophobic binders, and reacting said amine and R f CH 2 CH 2 —SO 3 H to provide a fluorochemical in an antistatic composition, and    without isolation or purification of said fluorochemical, applying said antistatic composition to a substrate.