Electrically conductive composition and elements containing solubilized polyaniline complex and solvent mixture

• US 5,716,550 A
• Filed: 01/05/1996
• Issued: 02/10/1998
• Est. Priority Date: 08/10/1995
• Status: Expired due to Fees

• Current Assignee: Eastman Kodak Company
• Original Assignee: Eastman Kodak Company
• Inventors: Gardner, Sylvia Alice, Brady, Brian Kenneth, Shaw-Klein, Lori Jeanne
• Primary Examiner(s): Lieberman, Paul
• Assistant Examiner(s): KOPEC, MARK T
• Application Number:
  US08/583,266
• Time in Patent Office: 767 Days
• Field of Search: 252/500, 252/518, 252/519, 528/422, 528/423, 524/80, 524/104, 524/173, 524/379
• US Class Current: 252/500
• CPC Class Codes: B41M 5/41 Base layers supports or substrates
• CPC Class Codes: B41M 5/44 characterised by the macromolecular compounds
• CPC Class Codes: C09D 179/02 Polyamines
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: G03C 1/85 characterised by antistatic additives or coatings
• CPC Class Codes: G03C 1/89 Macromolecular substances therefor
• CPC Class Codes: G11B 5/633 of cinematographic films or slides with integral magnetic track
• CPC Class Codes: H01B 1/128 comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• CPC Class Codes: H01J 2229/8632 characterised by the material
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31768 Natural source-type polyamide [e.g., casein, gelatin, etc.]
• CPC Class Codes: Y10T 428/31775 Paper
• CPC Class Codes: Y10T 428/31786 Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31895 Paper or wood
• CPC Class Codes: Y10T 428/31971 Of carbohydrate
• CPC Class Codes: Y10T 428/31982 Wood or paper

Abstract

Electrically conductive elements, such as imaging elements, can be prepared by applying electrically conductive coating compositions to a suitable support. The coating compositions include a polyaniline-protonic counter-ion complex in a first solvent that has certain Hansen solubility parameters, and a film-forming binder in a second common coating solvent. The total solids in the coating composition is less than or equal to about 10 weight %, and the weight ratio of the binder to the complex is at least about 1:1. Under these formulation conditions, the polyaniline protonic counter-ion complex is solubilized, rather than being in dispersed form, and is readily applied to form a thin, relatively transparent, electrically conductive film. Antistatic layers of photographic elements can be prepared in this manner.

Claims

1. An electrically conductive coating composition comprising a solution of:

a) a complex of a polymeric polyaniline and a protonic acid that has a counter-ion that imparts conductivity to said composition,

said complex being dissolved in a first solvent, that has a Hansen polar solubility parameter of from 13 to about 17 MPa^1/2, and a Hansen hydrogen bonding solubility parameter of from about 5 to about 14 MPa^1/2, and

b) a film-forming binder dissolved in a second solvent, wherein said first and second solvents are different,

provided that the total solids in said composition is less than or equal to about 10 weight % of the total composition, and the weight ratio of said binder to said complex is at least about 2;

1,

wherein said first solvent is dimethylsoulfoxide, a γ

-butyrolactone/lower alcohol blend, a propylene carbonate/lower alcohol blend, an ethylene carbonate/lower alcohol blend, a propylene carbonate/ethylene carbonate/lower alcohol blend, or a mixture thereof, wherein said lower alcohol has up to 4 carbon atoms,

said second solvent is water, a chlorinated solvent, or a mixture of a chlorinated solvent with a lower alcohol or acetone, wherein said lower alcohol has up to 4 carbon atoms,

the weight ratio of said second solvent to said first solvent is from about 5;

1 to about 19;

1, and

said composition provides a dried conductive layer having a resistivity of less than or equal to 10.9 log ohms/square.

2. The coating composition of claim 1 wherein the total solids is said composition is from about 0.1 to about 6 weight % of the total composition.

3. The coating composition of claim 1 wherein the total solids in said composition is from about 1 to about 4 weight % of the total composition.

4. The coating composition of claim 1 wherein the weight ratio of said binder to said complex is from about 9:

1 to about 99;

1.

5. The coating composition of claim 1 wherein the weight ratio of said second solvent to said first solvent is from about 7:

1 to about 19;

1.

6. The coating composition of claim 1 wherein said film-forming binder is a methyl methacrylate polymer, an ethyl methacrylate polymer, polyvinyl acetate, a styrene-olefin copolymer, a polyurethane, polyvinyl formal, polyvinyl butyral, polycarbonate, a cellulose ester, a cellulose ether, an acrylamide polymer, a fluorinated vinyl ether polymer, a vinyl pyrrolidone polymer, an ionic polyester, an ionic acrylonitrile-vinylidene chloride polymer, methylcellulose, cellulose nitrate, gelatin, a gelatin derivative, or a polysaccharide.

7. The coating composition of claim 6 wherein said binder is present in an amount of up to about 5 weight % of the total composition.

8. The coating composition of claim 1 wherein said polyaniline having a number average molecular weight of at least about 1000 daltons, and is prepared by polymerizing an aniline having the structure I:

##STR5## wherein R is the same or different at each occurrence and is an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, a cycloalkenyl group, an alkanoyl group, an alkylthio group, an aryloxy group, an alkylthioalkyl group, an alkylaryl group, an arylalkyl group, an alkylsulfinyl group, an alkoxyalkyl group, an alkylsulfonyl group, an aryl group, an arylthio group, an arylsulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylsulfonyl group, carboxy, halo or cyano, or any two R groups, taken together, are an alkylene group or alkenylene group completing a 3- to 7-membered aromatic or alicyclic ring fused to the central ring of structure I, and having carbon, nitrogen, sulfur or oxygen atoms or a sulfinyl group,

m is an integer of from 1 to 5, and

n is an integer of from 0 to 4, provided that the sum of m and n is 5.

9. The coating composition of claim 8 wherein m is 5 and n is 0.

10. The coating composition of claim 1 wherein said protonic acid has any of structures ##STR6## wherein A is sulfonic acid,

R¹ is an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, a cycloalkenyl group, an alkanoyl group, an alkylthio group, an aryloxy group, an alkylthioalkyl group, an alkylaryl group, an arylalkyl group, an alkylsulfinyl group, an alkoxyalkyl group, an alkylsulfonyl group, an aryl group, an arylthio group, an arylsulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylsulfonyl group, carboxy, halo or cyano, or a 3- to 7-membered heterocyclic ring having carbon, nitrogen, sulfur or oxygen atoms,

R'"'"' is an alkylene group of 1 to 10 carbon atoms,

R² is the same or different at each occurrence and is an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, a cycloalkenyl group, an alkanoyl group, an alkylthio group, an aryloxy group, an alkythioalkyl group, an alkylaryl group, an arylalkyl group, an alkylsulfinyl group, an alkoxyalkyl group, an alkylsulfonyl group, an aryl group, an arylthio group, an arylsulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylsulfonyl group, carboxy, halo, oxo or cyano, or R² is a divalent aliphatic group bonded to two different, nonadjacent carbon atoms of the central ring to form an aromatic or alicyclic ring fused to the central ring of structure III or IV, and having carbon, nitrogen, sulfur or oxygen atoms or a sulfinyl group,

p is an integer of from 1 to 5,

q is an integer of from 0 to 4, provided that the sum of p and q is 5, and

t is 0 or 1.

11. The coating composition of claim 10 wherein said protonic acid is hexanesulfonic acid, octanesulfonic acid, 4-dodecylbenzenesulfonic acid, 10-camphorsulfonic acid, ethylbenzenesulfonic acid, p-toluenesulfonic acid, o-anisidine-5-sulfonic acid, p-chlorobenzenesulfonic acid, hydroxybenzenesulfonic acid, trichlorobenzenesulfonic acid, 2-hydroxy-4-methoxybenzophenonesulfonic acid, 4-nitrotoluene-2-sulfonic acid, dinonylnaphthalenesulfonic acid, 4-morpholineethanesulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, C₈ F₁₇ -sulfonic acid, 3-hydroxypropanesulfonic acid, dioctylsulfosuccinate, 3-pyridinesulfonic acid or p-polystyrenesulfonic acid.

12. The coating composition of claim 1 wherein said protonic acid is 10-camphorsulfonic acid, said first solvent is dimethylsulfoxide, said second solvent is dichloromethane, and said film-forming binder is polymethyl methacrylate.

13. The coating composition of claim 1 further comprising uniformly dispersed ferromagnetic particles in an amount of up to about 5% solids of the total composition.

14. The coating composition of claim 13 wherein said ferromagnetic particles are comprised of ferromagnetic iron oxides with or without cobalt or zinc in solid solution or surface treated, chromium dioxides with or without metallic elements or halogen atoms in solid solution.

15. The coating composition of claim 14 wherein said ferromagnetic particles are cobalt doped γ

-iron oxide particles.