# Patent

## Title
Liquid formulations for coating and printing substrates

## Abstract

A formulation for application to a substrate including a mixture of a liquid having a first viscosity and an amine-acid adduct. The mixture has a second viscosity greater than the first viscosity. The amine-acid adduct is evaporative and substantially completely removed from the mixture in a functionally dry state as applied as a deposit on the substrate. In particular, the general nature of the formulation is that of a mixture that includes a viscosity control agent, such as an amine-acid adduct that forms a carbamate, and the formulation is for use in coating or printing wherein the final coated product includes little or no viscosity control agent.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims priority from Provisional Patent Application No. 60/572,333 filed May 19, 2004.


BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to liquid formulations designed for application to substrates as coatings, printed patterns or the like, and is concerned in particular with a formulation comprising a mixture of a liquid and volatile viscosity altering components, the latter being substantially completely evaporative when the mixture is applied to a substrate and processed to its functionally dried state.
2. Description of the Prior Art
There are solutions and dispersions, which are used as coatings or printing inks that are best applied from a very dilute state, such as in a water or non-aqueous medium. In many cases, however, the rheology of these coatings or inks may cause them to flow too freely to allow for proper control of the amount of their application. Further, if discreetly applied, they may flow too freely to maintain their target positions.
There exists an abundance of rheology control agents, commonly referred to as “thickening agents”, which can be incorporated in the continuous liquid phase of a system to modify its viscosity to an appropriate level (i.e. one which meets the requirements of the application method). Unfortunately, when used in systems which are subsequently dried, the thickening agent left behind is often of a high enough concentration to adversely affect the performance of the coating or printing.
The printing of conductive inks and the application of optical coatings are two non-limiting examples where this dichotomy exists between the requirement of elevated viscosity for application purposes and purity in the functionally dried state. The dielectric properties of residual thickening agents can disadvantageously reduce the conductivity of conductive ink deposits, and the opacity of such residual thickening agents can introduce haze that adversely affects the desired clarity of optical coatings.
A need exists, therefore, for coating and ink formulations having rheologies that have been adjusted by the incorporation of thickening agents to achieve viscosities appropriate for the intended application modes, with the thickening agents being substantially completely removed from the resulting coating or ink deposits in their functionally dried states as applied to the substrates.
As herein employed, “functionally dried state” means that the volatile components of a liquid mixture have been evaporated to an extent sufficient to place the mixture in condition for its intended use.
Again, as herein employed, a component of a liquid mixture is considered to have been “substantially completely removed” when any residue of the component does not prevent the mixture, when in its functionally dried state, from performing its intended use.
SUMMARY OF THE INVENTION
In accordance with the present invention, a formulation for application to a substrate as a coating or printed deposit comprises a mixture of a liquid having a first viscosity and an amine-acid adduct in an amount appropriate to the liquid and the intended use of the mixture, preferably greater than 10% by weight of the mixture. The mixture has a second viscosity greater than the first viscosity. The amine-acid adduct is substantially completely removed by evaporation in the course of applying the mixture to a substrate and processing it to its functionally dried state. The residue of the amine-acid adduct can be as low as 0.2%, typically less than about 0.1%, preferably less than 0.01%, and most preferably less than 0.001% by weight of the thus applied and processed mixture.


DETAILED DESCRIPTION
The present invention employs the amine carbamate as a viscosity control agent for a range of solutions/dispersions from hydrocarbons to alcohols to water. Primary and secondary amines are candidates; tertiary amines are not useful.
The amines, when treated with CO2, form the amine carbamate (and with water can form the amine carbonate). This zwitter ion salt formed can, as is the case of fatty acid esters and salts, be used to alter the rheology of a liquid in which such salts are compatible.
The use of amines, especially those that have a boiling point at about the temperature of that of the solvent or the continuous phase of a liquid mixture, allows the carbamate (carbonate) to break down (release CO2) and the amine to evaporate off with the other volatile components of the mixture. In the course of applying the mixture to a substrate and processing it to its functionally dried state, the carbamate (carbonate) is substantially completely removed, with any residue being as low as 0.2%, typically less than 0.1%, preferably less than 0.01%, and most preferably less than 0.001% by weight of the thus applied and processed mixture.
Applications where this type of rheology control is advantageous include, for example:

    
    
        (a) Nanotechnology, where the elements being coated are often in very dilute concentration, but the coatings need a higher viscosity to allow even placement. This is of particular interest when dealing with carbon nanotubes, where viscosity control not only facilitates application, but also has a stabilizing effect in preventing the nanotubes from entangling in the carrier liquid, thus agglomerating and falling out of the carrier liquid before coating, discrete coating, or printing.
        (b) The application of optical coatings, e.g., for film based vision driven user interfaces (displays, touchscreens), clear protective coatings for graphics, etc., where clarity of the functionally dried deposit is a prime requirement.
        (c) Other contamination-sensitive coatings that are used in electronic product fabrication. For example, use of “ink jet” type of coatings (printing) used in placement of resist coatings; or adhesion treatments for discrete placement of conductive elements in a circuit.
    
    


In the following examples, liquid mixtures were prepared using one or more of the following components:

    CNT Ink Concentrate (3000 ppm CNT) obtained from Eikos in Franklin, Mass.
    Solvent Ink Concentrate #7633-41P obtained from Raffi & Swanson in Wilmington, Mass.
    Diluting Acrylate IBOA (Isobornyl Acrylate) obtained from Surface Specialties UCB in Smyrna, Ga.
    UV Coating ECX 4019 obtained from Cognis Corporation in Ambler, Pa.


Example 1










Conductive Ink

















WB Carbamate:





sec-Butyl Amine
90 grams



Water
10 grams



CO2
Bubble through




until viscosity




11,500-12,500 cP


CNT Ink Formula:





CNT Ink Concentrate
 1%



(3000 ppm CNT)




Water
21%



Solvent (IPA)
50%



Carbamate
28%




100% 





Starting viscosity of ink concentrate 30-100 cP


Final viscosity of mixture 1500-2000 cP






Example 2










Optical Coating

















Carbamate:





n-Butyl Amine
50 grams



Solvent
50 grams



CO2
Bubble through




until viscosity




10,000 cP


Solvent Ink Formula:





Solvent Ink Concentrate
10%



Solvent
70%



Carbamate
20%




100% 





Starting viscosity of concentrate 100-200 cP


Final viscosity of mixture 1000-1200 cP






Example 3










Optical Coating



















Carbamate:






n-Propyl Amine
20 grams




Diluting Acrylate
80 grams




CO2
Bubble through





until viscosity





10,000 cP



UV Coating Formula:






UV Coating
79%




Carbamate
21%





100% 





Starting viscosity of UV coating 200-250 cP


Final viscosity of mixture 1500-1800 cP






The mixtures of Examples 1-3 were applied to a clear polyester film using a Meyer drawdown rod and processed to their functionally dried state in a laboratory oven at 70° C. for one minute. The resulting dried deposits were tested for residual carbamate components using a pHydrion Insta-Check Surface pH Pencil (available from VWR International of West Chester, Pa., U.S.A.). In each case, the pH reading ranged between 5 and 6.
Based on the definition of pH (the chemical fact that pH is the negative logarithmic function of the concentration of the hydrogen ion, written as the equation pH=−log [H+] from Holtzclaw et. al. General Chemistry, p. 459, 1984, D. C, Heath and Co., Lexington, Mass.), the higher the concentration of the hydrogen ion, the lower the pH. Any residual amine component of the carbamates would decrease the hydrogen ion concentration and thereby increase the pH as measured in this test.
Using this method of calculation, and based on the pH readings recited above, the residual carbamate concentrations in the functionally dried residues of Examples 1-3 were determined to be in the range of 7.3×10−6%. To the extent present at such reduced levels, any residual carbamate was observed to have no significant adverse impact on the conductivity of the ink of Example 1, or on the clarity of the coatings of Examples 2 and 3.
Zwitter ion adducts of amines can be formed with materials other than CO2. Carbon disulfide (CS2) also forms stable amine salts, as do hydrogen chloride (HCl) and low boiling temperature organic acids (e.g. acetic acid, formic acid, propionic acid). However, CO2 has the advantage of being of minimal toxicity and is a relatively weak acid, which may be a benefit to some of the coatings being treated.
Another advantage is that few amine carbamates/carbonates are stable much above 100° C. Thus a CO2-based adduct, being easier to break down, has an excellent overall fugitive property.
As an alternative to making an amine adduct and then adding the adduct to a coating (or printing) system, the amine may be added directly to the coating, followed by addition of the CO2, CS2, etc. so as to form the amine adduct in-situ. In all cases, upon drying, the amine carbamate would decarboxylate, and then the amine could be driven off. The temperature needed would depend on the amine and whether or not the regenerated amine was needed to play a roll in maintaining coating “wet out” during the drying process.
The printed or coated mixtures of the present invention may be dried to their functionally dried state by various methods, e.g., thermal drying, air drying, infrared drying, microwave drying and vacuum drying.
Amines useful in the present invention may be selected from the group listed below in Table 1.










TABLE 1







Amine
B.P. ° C.



















Morpholine
129



N-ethyl-n-butyl amine
91



n-butyl amine
78



sec-butyl amine
63



t-butyl amine
46



n-propyl amine
48



n-pentyl amine
104



di-n-butylamine
129



N-methyl-n-butylamine
91



Ethylene diamine
117



AMP
166



(2 amino-2-methyl-1-propanol)




DMEA
135



(dimethyl, ethanol amine)

## Claims

1. An ink or liquid formulation for application to a substrate, said liquid formulation comprising a liquid mixture of:
a continuous phase of a zwitter ion adduct, and
a material having a first viscosity to be deposited onto the substrate, wherein the mixture has a second viscosity that is suitable for use in a liquid application method and wherein the second viscosity is higher than the first viscosity, wherein said continuous phase zwitter ion adduct includes an evaporative component such that the continuous phase zwitter ion adduct is substantially completely removed from said mixture when applied to the substrate and in a functionally dried state such that the material to be deposited remains on the substrate with no measurable remnant of the continuous phase zwitter ion adduct, and wherein the material is a conductive ink, an optical coating, or a dilute dispersion of carbon nanotubes.

2. The ink or coating formulation as claimed in claim 1, wherein said formulation includes less than about 0.1% zwitter ion adduct by weight when substantially evaporated.

3. The ink or coating formulation as claimed in claim 1, wherein said formulation includes less than about 0.01% zwitter ion adduct by weight when substantially evaporated.

4. The liquid formulation as claimed in claim 1, wherein said evaporative zwitter ion adduct further includes a diluting acrylate.

5. The ink or coating formulation as claimed in claim 1, wherein the zwitter ion adduct has a boiling point at about the temperature of the continuous phase of the liquid mixture.

6. The ink or coating formulation as claimed in claim 1, wherein the liquid mixture comprises a hydrocarbon, water, or an alcohol.

7. The ink or coating formulation as claimed in claim 1, wherein the zwitter ion adduct is a carbamate or the carbonate and wherein the carbamate or the carbonate is a viscosity control agent that alters the first viscosity of the liquid.

8. The ink or coating formulation of claim 1, wherein the evaporative zwitter ion adduct includes an amine.

9. The ink or coating formulation of claim 8, wherein the amine is a primary or secondary amine.

10. The ink or coating formulation of claim 8, wherein the amine is selected from the group consisting of morpholine, N-ethyl-n-butylamine, n-butylamine, sec-butylamine, t-butylamine, n-propylamine, n-pentylamine, di-n-butylamine, N-methyl-n-butylamine, ethylene diamine, 2-amino-2-methyl-1-propanol and dimethylethanolamine.

11. The ink or coating formulation of claim 8, wherein the amine is a butyl amine.

12. The ink or coating formulation of claim 8, wherein the amine is a propyl amine.

13. The ink or coating formulation of claim 1, wherein the evaporative zwitter ion adduct includes carbon dioxide (CO2).

14. The ink or coating formulation of claim 1, wherein the evaporative zwitter ion adduct includes one of: carbon disulfide (CS2), hydrochloric acid (HCL), or a low boiling temperature organic acid.

15. The ink or coating formulation of claim 14, wherein the low boiling temperature organic acid is one of: acetic acid, formic acid, or propionic acid.

16. An ink or coating formulation for application to a substrate, said formulation comprising a mixture of:
a liquid including carbon nanotubes and having a first viscosity, and
an evaporative zwitter ion adduct that includes amine, wherein the ink or coating formulation in liquid form has a second viscosity that is greater than said first viscosity, and in a functionally dried state the zwitter ion adduct is substantially evaporated from the ink or coating formulation that is applied to the substrate.

17. The ink or coating formulation as claimed in claim 16, wherein said formulation includes less than about 0.1% zwitter ion adduct by weight when substantially evaporated.

18. The ink or coating formulation as claimed in claim 16, wherein said evaporative zwitter ion adduct further includes a diluting acrylate.

19. The ink or coating formulation as claimed in claim 16, wherein said formulation includes less than about 0.01% zwitter ion adduct by weight when substantially evaporated.

20. The ink or coating formulation as claimed in claim 16, wherein the mixture comprises zwitter ion adduct of greater than 10% by weight of the mixture.

21. The ink or coating formulation as claimed in claim 16, wherein the liquid comprises a hydrocarbon, water, or an alcohol.

22. The ink or coating formulation as claimed in claim 16, wherein the mixture comprises a volatile component such that the zwitter ion adduct is substantially evaporated from the ink or coating formulation in a functionally dried state.

23. The ink or coating formulation as claimed in claim 16, wherein the zwitter ion adduct is a carbamate or the carbonate and wherein the carbamate or the carbonate is a viscosity control agent that alters the first viscosity of the liquid.

24. The ink or coating formulation of claim 16, wherein the amine is a primary or secondary amine.

25. The ink or coating formulation of claim 16, wherein the amine is selected from the group consisting of morpholine, N-ethyl-n-butylamine, n-butylamine, sec-butylamine, t-butylamine, n-propylamine, n-pentylamine, di-n-butylamine, N-methyl-n-butylamine, ethylene diamine, 2-amino-2-methyl-1-propanol and dimethylethanolamine.

26. The ink or coating formulation of claim 16, wherein the amine is a butyl amine.

27. The ink or coating formulation of claim 16, wherein the amine is a propyl amine.

28. The ink or coating formulation of claim 16, wherein the evaporative zwitter ion adduct further includes carbon dioxide (CO2).

29. The ink or coating formulation of claim 16, wherein the evaporative zwitter ion adduct further includes one of: carbon disulfide (CS2), hydrochloric acid (HCL), or a low boiling temperature organic acid.

30. The ink or coating formulation of claim 29, wherein the low boiling temperature organic acid is one of: acetic acid, formic acid, or propionic acid.

31. A conductive ink or coating formulation for application to a substrate, said formulation comprising a mixture of:
a liquid including a conductive ink material and having a first viscosity, and
an evaporative zwitter ion adduct that includes amine, wherein
the conductive ink or coating formulation in liquid form has a second viscosity that is greater than said first viscosity, and in a functionally dried state the zwitter ion adduct is substantially evaporated from the ink or coating formulation that is applied to the substrate.

32. The ink or coating formulation as claimed in claim 31, wherein said evaporative zwitter ion adduct further includes a diluting acrylate.

33. The ink or coating formulation as claimed in claim 31, wherein said formulation includes less than about 0.1% zwitter ion adduct by weight when substantially evaporated.

34. The ink or coating formulation as claimed in claim 31, wherein said formulation includes less than about 0.01% zwitter ion adduct by weight when substantially evaporated.

35. The conductive ink or coating formulation as claimed in claim 31, wherein the liquid comprises a hydrocarbon, water, or an alcohol.

36. The conductive ink or coating formulation as claimed in claim 31, wherein the mixture comprises a volatile component such that the zwitter ion adduct is substantially evaporated from the ink or coating formulation in a functionally dried state.

37. The conductive ink or coating formulation as claimed in claim 31, wherein the zwitter ion adduct is a carbamate or the carbonate and wherein the carbamate or the carbonate is a viscosity control agent that alters the first viscosity of the liquid.

38. The conductive ink or coating formulation of claim 31, wherein the amine is a primary or secondary amine.

39. The conductive ink or coating formulation of claim 31, wherein the amine is selected from the group consisting of morpholine, N-ethyl-n-butylamine, n-butylamine, sec-butylamine, t-butylamine, n-propylamine, n-pentylamine, di-n-butylamine, N-methyl-n-butylamine, ethylene diamine, 2-amino-2-methyl-1-propanol and dimethylethanolamine.

40. The conductive ink or coating formulation of claim 31, wherein the amine is a butyl amine.

41. The conductive ink or coating formulation of claim 31, wherein the amine is a propyl amine.

42. The conductive ink or coating formulation of claim 31, wherein the evaporative zwitter ion adduct further includes carbon dioxide (CO2).

43. The conductive ink or coating formulation of claim 31, wherein the evaporative zwitter ion adduct further includes one of: carbon disulfide (CS2), hydrochloric acid (HCL), or a low boiling temperature organic acid.

44. The conductive ink or coating formulation of claim 43, wherein the low boiling temperature organic acid is one of: acetic acid, formic acid, or propionic acid.

45. An optical ink or coating formulation for application to a substrate, said formulation comprising a mixture of:
a liquid including an optical coating material and having a first viscosity, and an evaporative zwitter ion adduct that includes amine, wherein the optical ink or coating
formulation in liquid form has a second viscosity that is greater than said first viscosity, and in a functionally dried state the zwitter ion adduct is substantially evaporated from the ink or coating formulation that is applied to the substrate.

46. The optical ink or coating formulation as claimed in claim 45, wherein the liquid comprises a hydrocarbon, water, or an alcohol.

47. The optical ink or coating formulation as claimed in claim 45, wherein the mixture comprises a volatile component such that the zwitter ion adduct is substantially evaporated from the ink or coating formulation in a functionally dried state.

48. The optical ink or coating formulation as claimed in claim 45, wherein the zwitter ion adduct is a carbamate or the carbonate and wherein the carbamate or the carbonate is a viscosity control agent that alters the first viscosity of the liquid.

49. The optical ink or coating formulation as claimed in claim 45, wherein said evaporative zwitter ion adduct further includes a diluting acrylate.

50. The optical ink or coating formulation as claimed in claim 45, wherein said formulation includes less than about 0.1% zwitter ion adduct by weight when substantially evaporated.

51. The optical ink or coating formulation as claimed in claim 45, wherein said formulation includes less than about 0.01% zwitter ion adduct by weight when substantially evaporated.

52. The optical ink or coating formulation of claim 45, wherein the amine is a primary or secondary amine.

53. The optical ink or coating formulation of claim 45 wherein the amine is selected from the group consisting of morpholine, N-ethyl-n-butylamine, n-butylamine, sec-butylamine, t-butylamine, n-propylamine, n-pentylamine, di-n-butylamine, N-methyl-n-butylamine, ethylene diamine, 2-amino-2-methyl-1-propanol and dimethylethanolamine.

54. The optical ink or coating formulation of claim 45, wherein the amine is a butyl amine.

55. The optical ink or coating formulation of claim 45, wherein the amine is a propyl amine.

56. The optical ink or coating formulation of claim 45, wherein the evaporative zwitter ion adduct further includes carbon dioxide (CO2).

57. The optical ink or coating formulation of claim 45, wherein the evaporative zwitter ion adduct further includes one of: carbon disulfide (CS2), hydrochloric acid (HCL), or a low boiling temperature organic acid.

58. The optical ink or coating formulation of claim 57, wherein the low boiling temperature organic acid is one of: acetic acid, formic acid, or propionic acid.