Electrically conductive and abrasion/scratch resistant polymeric materials, method of fabrication thereof and uses thereof

• US 5,721,299 A
• Filed: 02/09/1994
• Issued: 02/24/1998
• Est. Priority Date: 05/26/1989
• Status: Expired due to Term

• Current Assignee: GlobalFoundries, Inc.
• Original Assignee: International Business Machines Corporation
• Inventors: Pillsbury, Thomas B., Dickerson, Jack A., Afzali-Ardakani, Ali, Angelopoulos, Marie, Gelorme, Jeffrey D., Puttlitz, Karl J., Shaw, Jane M.
• Primary Examiner(s): DEAN JR, RALPH H
• Application Number:
  US08/193,926
• Time in Patent Office: 1,476 Days
• Field of Search: 525/474, 252/500, 252/518, 524/177, 524/166, 524/176, 524/161, 524/159, 524/183
• US Class Current: 524/177
• CPC Class Codes: C08G 61/12 Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• CPC Class Codes: H01B 1/125 comprising aliphatic main chains, e.g. polyactylenes
• CPC Class Codes: H01B 1/127 comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• CPC Class Codes: H01B 1/128 comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• CPC Class Codes: H01J 29/868 Screens covering the input or output face of the vessel, e.g. transparent anti-static coatings, X-ray absorbing layers
• CPC Class Codes: H01L 23/49894 Materials of the insulating layers or coatings
• CPC Class Codes: H01L 23/60 Protection against electrostatic charges or discharges, e.g. Faraday shields
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• CPC Class Codes: H01L 33/40 Materials therefor
• CPC Class Codes: H01L 33/42 Transparent materials
• CPC Class Codes: H05K 9/0079 Electrostatic discharge protection, e.g. ESD treated surface for rapid dissipation of charges

Abstract

Electrically conductive and abrasion resistant polymeric compositions, methods of fabrication thereof and uses thereof are described. Admixtures of abrasion resistant materials and electrically conductive polymeric materials are formed. Many of these admixtures are light transmitting and can be used as an abrasion resistant light transmitting electrostatic discharge layers. The light transmitting discharge layer is useful as a surface coating for visual displays such as CRT screens to avoid electrostatic accumulation of dust and scratching. The compositions can be admixtures of abrasion resistant silicones, polysiloxanes, acrylates, epoxies, methacrylates, epoxyacrylates, epoxymethacrylates, styrenes and electrically conductive polymers selected from the group of substituted and unsubstituted polyanilines, polyparaphenylenevinyles, substituted and unsubstituted polythiophenes substituted and unsubstituted poly-p-phenylene sulfides, substituted and unsubstituted polyfuranes, substituted and unsubstituted polypyrroles, substituted and unsubstituted polyselenophenes, polyacetylines formed from soluble precursors, combinations thereof and blends thereof with other polymers. The compositions can be a layer of an electrically conductive polymer with an abrasion resistant layer thereover.

Claims

1. A composition of matter formed by a process comprising:

admixing an abrasion and scratch resistant material, an electrically conductive polymeric material and a solvent wherein said solvent is removed, said electrically conductive polymer comprise extended conjugation.

2. The composition of matter of claim 1 wherein said abrasion and scratch resistant material is selected from the group consisting of polysiloxanes, acrylates, epoxies and epoxyacrylates, epoxymethacrylates and styrenes.

3. The composition of matter of claim 1, wherein said electrically conductive polymeric material is selected from the group consisting of a substituted and unsubstituted polyparaphenylenevinylenes, substituted and unsubstituted polyanilines, substituted and unsubstituted polyazines, substituted and unsubstituted polythiophenes, substituted and unsubstituted poly-p-phenylene sulfides, substituted and unsubstituted polyfuranes, substituted and unsubstituted polypyrroles, substituted and unsubstituted polyselenophene, polyacetylenes formed from soluble precursors and combinations thereof.

4. The composition of matter of claim 1, wherein said electrically conductive polymer material contains disassociated precursors selected from the group consisting of onium salts, iodonium salts, borate salts, tosylate salts, triflate salts and sulfonoxylimides, said disassociated precursors doping said polymeric material constituent.

5. The composition of matter of claim 1, wherein said composition is light transmitting.

6. The composition of matter of claim 5, wherein said light transmitting composition is disposed on a display screen.

7. The composition of matter of claim 1, wherein said electrically conductive polymeric material is a polyaniline doped with triphenylsulfonium hexafluoroantimonate.

8. The composition of matter of claim 1, wherein said electrically conductive polymeric material is a polyaniline doped with a dopant selected from the group consisting of diethyl-ammonium trifluoromethane sulfonate and diisopropyl ammonium trifluoromethane sulfonate.

9. The composition of matter of claim 7, wherein said polyaniline is an emeraldine base form of polyaniline.

10. The composition of matter of claim 8, wherein said polyaniline is an emeraldine base form of polyaniline.

11. The composition of matter of claim 3 wherein said polythiophene is selected from the group consisting of poly(3-butylthiophene), and 3-methylthiophene-3-butylthiophene-copolymer doped with a precursor selected from the group consisting of MDT and triphenyl sulfonium hexafluoroantimonate.

12. The composition of matter of claim 2, wherein said silicones/polysiloxanes are selected from the group consisting of

(R_n SiO.sub.(4-n)/2)_m wherein n=1-3 and m≧

2 (oligomeric and polymeric) and R=hydrogen methyl, longer alkyl, fluoroalkyl, phenyl, vinyl, chlorine, alkoxy, acyloxy, alkylamino and hydroxyl,

hexamethyldisiloxane

octamethyltrisiloxane

decamethyltetrasiloxane

octamethylcyclotetra-siloxane

octaphenylcyclotetra-siloxane

2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-cyclotetrasiloxane

methyltris(trimethyl-siloxy) silane

1,1,1,3,5,5,5-heptamethyl-trisiloxane

1,1,3,5,5-pentamethyl-1,3,5-triphenyltrisiloxane

polydimethylsiloxane,

silsesquioxanes

polysiloxanediols

allyl methacrylate

tetrahydrofurfuryl methacrylate

cyclohexyl methacrylate

n-hexyl methacrylate

cyclohexyl acrylate

2-ethoxyethyl acrylate

2-ethoxyethyl methacrylate

isodecyl methacrylate

2-methoxyethyl acrylate

2(2-ethoxyethoxy) ethylacrylate

stearyl acrylate

tetrahydrofurfuryl acrylate

lauryl methacrylate

stearyl methacrylate

octyl acrylate

lauryl acrylate

2-phenoxyethyl acrylate

2-phenoxyethyl methacrylate

2-hydroxyethyl methacrylate

2-dimethyl aminoethyl methacrylate

2-dodecylthioethyl methacrylate

N-methacryloyl-2-pyrrolidinone

urethane acrylates

isodecyl acrylate

isobornyl methacrylate

benzyl acrylate

hexyl acrylate

isooctyl acrylate

isobornyl acrylate

triethylene glycol

dimethacrylate

ethylene glycol dimethacrylate

tetraethylene glycol dimethacrylate

polyethylene glycol

dimethacrylate

1,3 butylene glycol diacrylate

1,4-butanediol diacrylate

1,4-butanediol dimethacrylate

diethylene glycol dimethacrylate

1,6 hexanediol diacrylate

1,6 hexanediol dimethacrylate

neopentyl glycol diacrylate

neopentyl glycol dimethacrylate

polyethylene glycol (200) diacrylate

tetraethylene glycol diacrylate

triethylene glycol diacrylate

1,3 butylene glycol dimethacrylate

tripropylene glycol diacrylate

ethoxylated bisphenol A dimethacrylate

ethoxylated bisphenol A diacrylate

reactive polyester (diacrylate)

tris (2-1-hydroxy ethyl) isocyanurate trimethacrylate

pentaerythritol tetraacrylate

trimethylolpropane trimethacrylate

trimethylolpropane triacrylate

tris (2-hydroxy ethyl) isocyanurate triacrylate

dipentaerythritol pentaacrylate

pentaerythritol triacrylate

2,3 epoxy butyl methacrylate

2,3 epoxycyclohexyl methacrylate

10,11 epoxyundecyl methacrylate

glycidyl methacrylate and

epoxy novolak acrylate.

13. The composition of matter of claim 1, wherein said electrically conducting polymeric material is an ethoxypolyaniline.

14. The composition of matter of claim 2, wherein said acrylates and methacrylates are selected from the group consisting of

(R_n SiO.sub.(4-n)/2)_m wherein n=1-3 and m≧

2 (oligomeric and polymeric) and R=hydrogen methyl, longer alkyl, fluoroalkyl, phenyl, vinyl, chlorine, alkoxy, acyloxy, alkylamino and hydroxyl,

hexamethyldisiloxane

octamethyltrisiloxane

decamethyltetrasiloxane

octamethylcyclotetra-siloxane

octaphenylcyclotetra-siloxane

2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-cyclotetrasiloxane

methyltris(trimethyl-siloxy)silane

1,1,1,3,5,5,5-heptamethyl-trisiloxane

1,1,3,5,5-pentamethyl-1,3,5-triphenyltrisiloxane

polydimethylsiloxane,

silsesquioxanes

polysiloxanediols

allyl methacrylate

tetrahydrofurfuryl methacrylate

cyclohexyl methacrylate

n-hexyl methacrylate

cyclohexyl acrylate

2-ethoxyethyl acrylate

2-ethoxyethyl methacrylate

isodecyl methacrylate

2-methoxyethyl acrylate

2(2-ethoxyethoxy) ethylacrylate

stearyl acrylate

tetrahydrofurfuryl acrylate

lauryl methacrylate

stearyl methacrylate

octyl acrylate

lauryl acrylate

2-phenoxyethyl acrylate

2-phenoxyethyl methacrylate

2-hydroxyethyl methacrylate

2-dimethylaminoethyl methacrylate

2-dodecylthioethyl methacrylate

N-methacryloyl-2-pyrrolidinone

urethane acrylates

isodecyl acrylate

isobornyl methacrylate

benzyl acrylate

hexyl acrylate

isooctyl acrylate

isobornyl acrylate

triethylene glycol

dimethacrylate

ethylene glycol dimethacrylate

tetraethylene glycol dimethacrylate

polyethylene glycol

dimethacrylate

1,3 butylene glycol diacrylate

1,4-butanediol diacrylate

1,4-butanediol dimethacrylate

diethylene glycol dimethacrylate

1,6 hexanediol diacrylate

1,6 hexanediol dimethacrylate

neopentyl glycol diacrylate

neopentyl glycol dimethacrylate

polyethylene glycol (200) diacrylate

tetraethylene glycol diacrylate

triethylene glycol diacrylate

1,3 butylene glycol dimethacrylate

tripropylene glycol diacrylate

ethoxylated bisphenol A dimethacrylate

ethoxylated bisphenol A diacrylate

reactive polyester (diacrylate)

tris (2-hydroxy ethyl) isocyanurate trimethacrylate

pentaerythritol tetraacrylate

trimethylolpropane trimethacrylate

trimethylolpropane triacrylate

tris (2-hydroxy ethyl) isocyanurate triacrylate

dipentaerythritol pentaacrylate

pentaerythritol triacrylate

2,3 epoxy butyl methacrylate

2,3 epoxycyclohexyl methacrylate

10,11 epoxyundecyl methacrylate

glycidyl methacrylate and

epoxy novolak acrylate.

15. The composition of matter of claim 2 wherein said epoxies are selected from the group consisting of:

aromatic glycidyl ether resins,

aromatic glycidyl amine resins,

glycidyl esters,

cycloaliphatic epoxy resins,

3,4-epoxycyclohexyloxirane,

2-(3'"'"',4'"'"'-epoxycyclo-hexyl)-5,1"-spiro-3",4"-epoxycyclohexane-1,3-dixoane, and

bis(3,4-epoxy-cyclohexylmethyl) adipate.

16. The composition of matter of claim 1, wherein said abrasion and scratch resistant material is a polymeric material.

17. The composition of matter of claim 1, wherein the weight percent ratio of said conductive polymeric material to said abrasion and scratch resistant material is from about 2% to about 50%.

18. The composition of matter of claim 1, wherein said abrasion and scratch resistant material is an organic material.

19. The composition of claim 1, wherein said styrenes are selected from the group consisting of O-chlorostyrene, P-chlorostyrene, Chloromethylstyrene and methylstyrene.

20. The composition of matter of claim 1, wherein said admixture is substantially resistant to loss of electrical conductivity when exposed to aqueous solutions, alkaline solutions and solvents.

21. The composition of matter of claim 2, wherein said acrylate is a methacrylate.

24. A composition of matter according to claims 1, 22 or 23, wherein:

said abrasion and scratch resistant material is selected from the group consisting of silicones/polysiloxanes acrylates, methacrylates, epoxyacrylates, epoxymethacrylates, epoxies and styrenes;

said electrically conductive polymeric material is selected from the group consisting of substituted and unsubstituted polyparaphenylenevinylenes, substituted and unsubstituted polyanilines, substituted and unsubstituted polyazines, substituted and unsubstituted polythiophenes, substituted and unsubstituted poly-p-phenylene sulfides, substituted and unsubstituted polyfuranes, substituted and unsubstituted polypyrroles, substituted and unsubstituted polyselenophene, polyacetylenes formed from soluble precursors and combinations thereof;

the weight percent ratio of electrically conductive polymeric material to said abrasion resistant being from about 2% to 50%.

22. A composition of matter formed by a process comprising:

admixing an abrasion and scratch resistant material selected from the group consisting of a solution and a dispersion and an electrically conductive polymeric material selected from the group consisting of a solution and a dispersion to form an admixture, and curing said admixture, said electrically conductive polymer comprises extended conjugation.

23. A composition of matter formed by a process comprising:

admixing an abrasion and scratch resistant non-elastomeric and non-thermoplastic material selected from the group consisting of a solution and a dispersion and an electrically conductive polymeric material selected from the group consisting of a solution and a dispersion to form an admixture, and curing said admixture, said electrically conductive polymer comprises extended conjugation.