Composites and methods for conductive transparent substrates

• US 7,955,696 B2
• Filed: 12/18/2007
• Issued: 06/07/2011
• Est. Priority Date: 12/19/2006
• Status: Active Grant

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Original Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Inventors: Mahdi, Syed Z., Baikerikar, Kiran, Dermody, Daniel L., Oner-Deliormanh, Didem
• Primary Examiner(s): Speer; Timothy M
• Assistant Examiner(s): ROBINSON, LAUREN E
• Application Number:
  US11/959,208
• Publication Number:
  US 20080152926A1
• Time in Patent Office: 1,267 Days
• Field of Search: 428/328, 428/689, 524/444, 524/589, 522/91, 522/99, 525/29, 525/301, 525/925
• US Class Current: 428/328
• CPC Class Codes: C08L 2666/52 Metal-containing compounds
• CPC Class Codes: C08L 33/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: C08L 33/10 Homopolymers or copolymers of methacrylic acid esters
• CPC Class Codes: C08L 33/14 of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C08L 83/10 Block- or graft-copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00
• CPC Class Codes: H01B 1/22 the conductive material comprising metals or alloys
• CPC Class Codes: H05B 2203/013 Heaters using resistive films or coatings
• CPC Class Codes: H05B 2203/017 Manufacturing methods or apparatus for heaters
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials
• CPC Class Codes: Y10T 428/256 Heavy metal or aluminum or compound thereof
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31547 Of polyisocyanurate
• CPC Class Codes: Y10T 428/31786 Of polyester [e.g., alkyd, etc.]

Abstract

The present invention is directed to a conductive article and method of making the same that includes a substrate; a conductive composite including a conductive material in a matrix that includes one or more film forming resins having at least one functional group capable of polymerization; one or more adhesion promoters; and one or more compounds, which are reactive with the film forming resin and which also contain at least one acidic moiety.

Claims

1. A conductive article, comprising:

a. a substrate;

b. a conductive composite including a conductive material in a matrix that includes;

i) one or more film forming resins having at least one functional group capable of polymerization;

ii) an initiator for causing the formation of free radicals or cations;

iii) one or more compounds, which are reactive with the film forming resin and which also contain at least one acidic moiety; and

iv) one or more adhesion promoters comprising a Michael Addition Product of an amino alkoxy silane and a compound having two or more acrylate groups the reaction product having 4 or greater alkoxy silane groups, at least one unsaturated group and all of the amine groups are tertiary.

2. The article of claim 1, wherein the substrate is selected from a glass, a plastic, coated plastic, metal, or any combination thereof.

3. The article of claim 2, wherein the one or more film forming resins includes one or more aliphatic urethane acrylate oligomers, one or more aromatic urethane acrylates, one or more epoxy acrylates, one or more melamine acrylates, one or more polyester acrylates, one or more polyether acrylates, one or more silicone acrylates one or more dendritic acrylates, one or more polybutadiene acrylates, one or more amine acrylates, one or more acrylic acrylates, one or more metallic acrylates, one or more amido acrylates, one or more chlorinated polyester acrylates, one or more allylic oligomers, one or more anhydride/carboxylic acid-containing aromatic acid acrylate/methacrylate half ester oligomers, one or more hyperbranched acrylates, one or more imide/ester/amide-containing acrylates self-initiating oligomers, one or more acrylated phenoxy oligomers, one or more acrylamidomethyl substituted cellulose esters, one or more dual-functional acrylated oligomers, one or more spiro-ortho carbonate esters, or any mixture thereof.

4. The article of claim 3, wherein the initiator includes one or more alpha hydroxyl ketones, one or more alpha amino ketones, one or more phosphine oxides, one or more phenyl glyoxylates, one or more thioxanthones, one or more benzophenones, one or more oxime esters, one or more benzyldimethyl ketals, or any mixture thereof.

5. The article of claim 1, wherein the compounds reactive with the film forming resins containing at least one acidic moiety are selected from the group of methacrylic acids, acrylic acids, acrylated phosphate acid esters, mono-2-(methacryloxy)ethyl maleate, mono-2-(methacryloyloxy)ethyl maleate, or phosphoric monoacrylate, maleic acids, itaconic acids, vinyl phosphonic acid, 2-sulfoethylmethacrylate, beta-carboxyethyl acrylate, 3-butenoic acid, 4-pentenoic acid, acrylamido glycolic acid, crotonic acid, tiglic acid, 2-(Trifluoromethyl)acrylic acid, dimethylacrylic acid, undecylenic acid, —

and any mixture thereof.

6. The article of claim 5, wherein the at least one acidic moiety is unsaturated.

7. The article of claim 1, wherein the matrix includes:

a. from about 10 to about 70 parts by weight of the one or more of the film forming resin;

b. from about 2 to about 30 parts by weight of one or more reactive diluents;

c. from about 1 to about 30 parts by weight of the one or more adhesion promoters;

d. from about 1 to about 10 parts by weight of the one or more compounds containing at least one acidic moiety; and

e. from about 2 to about 20 parts by weight of one or more catalysts or initiators;

wherein the composition contains 100 parts.

8. The article of claim 7 wherein the matrix includes at least one acidic moiety comprising one or more carboxylic acid moieties, one or more phosphonic acids, one or more sulfonic acids, or any mixture thereof, and a high molecular weight Michael adduct having multiple alkoxysilanes.

9. The article of claim 7, wherein the one or more reactive diluents includes one or more isobornyl acrylates, one or more tripropylene glycol diacrylates, one or more 2(2-ethoxyethoxy) ethyl acrylates, one or more 2-phenoxyethyl acrylates, one or more hydroxyethyl acrylates, one or more hexanediol diacrylates, one or more nonanediol diacrylates, one or more butylene glycol diacrylates, one or more tricyclodecane dimethanol diacrylate, one or more propoxylated neopentyl glycol diacrylates, one or more butanediol diacrylates, one or more cyclohexanedimethanol diacrylates, one or more cis/trans 1,3/1,4 cyclohexanedimethanol diacrylates, one or more alkoxylated cyclohexanedimethanol diacrylates, one or more tetraethylene glycol diacrylates, one or more triethylene glycol diacrylates, one or more dipropylene glycol diacrylates, one or more diethylene glycol diacrylates, one or more 3,3,5-trimethylcyclohexyl acrylates, one or more cyclic trimethylolpropane formal acrylates, one or more propoxylated glyceryl triacrylates, one or more ditrimethylolpropane tetra acrylates, one or more tris(2-hydroxyethyl)isocyanurate triacrylates, one or more trimethylolpropane triacrylates, one or more alkoxylated trimethylolpropane triacrylates, or any mixture thereof.

10. The article of claim 9, further comprising one or more of fluorosilanes, fluorinated additives, polybutadiene acrylates, silylated polymers, titanates, zirconates, zircon-aluminates, silane-treated fillers, hindered amine light stabilizers, ultraviolet absorbers, antioxidants, vinyltrimethoxysilanes, oligomeric vinyl trimethoxysilanes, triethyl orthoformates, triethyl orthoacetates, molecular sieve powders, polyether modified polydimethylsiloxanes, modified silica, or any mixture thereof.

11. The article of claim 7, wherein the substrate is a window and the composite defines a pattern used on the window as at least one of a window defogger or an antenna, and a coating about the periphery of the window.

12. An article according to claim 1 wherein the Michael Addition Product contains 6 or greater alkoxy silane groups.

13. An article according to claim 1 wherein the relative amounts in parts by weight of the conductive material relative to the matrix are greater than about 2:

1.

14. An article according to claim 1 wherein the conductive composite contains conductive material in an amount of at least about 50% by weight of overall conductive composite.

15. A conductive composition, comprising a conductive material in a matrix that includes:

i) one or more film forming resins having at least one functional group capable of polymerization;

ii) an initiator for causing the formation of free radicals or cations;

iii) one or more compounds, which are reactive with the film forming resin and which also contain at least one acidic moiety; and

iv) one or more adhesion promoters comprising a Michael Addition Product of an amino alkoxy silane and a compound having two or more acrylate groups the reaction product having 4 or greater alkoxy silane groups, at least one unsaturated group and all of the amine groups are tertiary.

16. The composition of claim 15, wherein the one or more film forming resins includes one or more aliphatic urethane acrylate oligomers, one or more aromatic urethane acrylates, one or more epoxy acrylates, one or more melamine acrylates, one or more polyester acrylates, one or more polyether acrylates, one or more silicone acrylates one or more dendritic acrylates, one or more polybutadiene acrylates, one or more amine acrylates, one or more acrylic acrylates, one or more metallic acrylates, one or more amido acrylates, one or more chlorinated polyester acrylates, one or more allylic oligomers, one or more anhydride/carboxylic acid-containing aromatic acid acrylate/methacrylate half ester oligomers, one or more hyperbranched acrylates, one or more imide/ester/amide-containing acrylates self-initiating oligomers, one or more acrylated phenoxy oligomers, one or more acrylamidomethyl substituted cellulose esters, one or more dual-functional acrylated oligomers, one or more spiro-ortho carbonate esters, or any mixture thereof.

17. The composition of claim 16, wherein the initiator includes one or more alpha hydroxyl ketones, one or more alpha amino ketones, one or more phosphine oxides, one or more phenyl glyoxylates, one or more thioxanthones, one or more benzophenones, one or more oxime esters, one or more benzyldimethyl ketals, or any mixture thereof.

18. The composition of claim 15, wherein the compounds reactive with the film forming resin and containing at least one acidic moiety are selected from the group of methacrylic acids, acrylic acids, acrylated phosphate acid esters, mono-2-(methacryloxy)ethyl maleate, mono-2-(methacryloyloxy)ethyl maleate, or phosphoric monoacrylate, maleic acids, itaconic acids, vinyl phosphonic acid, 2-sulfoethylmethacrylate, beta-carboxyethyl acrylate, 3-butenoic acid, 4-pentenoic acid, acrylamido glycolic acid, crotonic acid, tiglic acid, 2-(Trifluoromethyl)acrylic acid, dimethylacrylic acid, undecylenic acid, and any mixture thereof.

19. The composition of claim 18, wherein the at least one acidic moiety is unsaturated.

20. The composition of claim 15, wherein the matrix includes:

b. from about 10 to about 70 parts by weight of the one or more of the film forming resin;

c. from about 2 to about 30 parts by weight of one or more reactive diluents;

d. from about 1 to about 30 parts by weight of the one or more of an adhesion promoter;

e. from about 1 to about 10 parts by weight of the one or more compounds containing at least one acidic moiety; and

f. from about 2 to about 20 parts by weight of one or more catalysts or initiators;

wherein the composition contains 100 parts.

21. The composition of claim 20, wherein the composition is one cured upon exposure to ultraviolet light, an electron beam, or both.

22. The composition of claim 21, wherein the matrix includes at least one acidic moiety comprising one or more carboxylic acid moieties, one or more phosphonic acids, one or more sulfonic acids, or any mixture thereof, and a high molecular weight Michael adduct having multiple alkoxysilanes.

23. The a composition of claim 20, wherein the one or more reactive diluents includes one or more isobornyl acrylates, one or more tripropylene glycol diacrylates, one or more 2(2-ethoxyethoxy) ethyl acrylates, one or more 2-phenoxyethyl acrylates, one or more hydroxyethyl acrylates, one or more hexanediol diacrylates, one or more nonanediol diacrylates, one or more butylene glycol diacrylates, one or more tricyclodecane dimethanol diacrylate, one or more propoxylated neopentyl glycol diacrylates, one or more butanediol diacrylates, one or more cyclohexanedimethanol diacrylates, one or more cis/trans 1,3/1,4 cyclohexanedimethanol diacrylates, one or more alkoxylated cyclohexanedimethanol diacrylates, one or more tetraethylene glycol diacrylates, one or more triethylene glycol diacrylates, one or more dipropylene glycol diacrylates, one or more diethylene glycol diacrylates, one or more 3,3,5-trimethylcyclohexyl acrylates, one or more cyclic trimethylolpropane formal acrylates, one or more propoxylated glyceryl triacrylates, one or more ditrimethylolpropane tetra acrylates, one or more tris(2-hydroxyethyl)isocyanurate triacrylates, one or more trimethylolpropane triacrylates, one or more alkoxylated trimethylolpropane triacrylates, or any mixture thereof.

24. The composition of claim 20, further comprising one or more of fluorosilanes, fluorinated additives, polybutadiene acrylates, silylated polymers, titanates, zirconates, zircon-aluminates, silane-treated fillers, hindered amine light stabilizers, ultraviolet absorbers, antioxidants, vinyltrimethoxysilanes, oligomeric vinyl trimethoxysilanes, triethyl orthoformates, triethyl orthoacetates, molecular sieve powders, polyether modified polydimethylsiloxanes, modified silica, or any mixture thereof.

25. A composition according to claim 15 wherein the Michael Addition Product contains 6 or greater alkoxy silane groups.

26. A composition according to claim 15 wherein the relative amounts in parts by weight of the conductive material relative to the matrix are greater than about 2:

1.

27. A composition according to claim 15 wherein the conductive composite contains conductive material in an amount of at least about 50% by weight of the overall conductive composite.