FIELD OF THE INVENTION

The present invention relates generally to aqueous cellulose compositions and, more particularly, to aqueous cellulose-based coatings and methods of making.

BACKGROUND OF THE INVENTION Nitrocellulose has long been used as a base film forming material for various films and coatings. One of its many applications is in lacquer emulsions used in the manufacture of nail coatings or polishes.

Nitrocellulose emulsions used in coatings are generally obtained through either direct emulsification or indirectly through various inversion techniques. For example, a conventional lacquer of nitrocellulose and solvent with emulsifiers is emulsified with the addition of water, inverting from a water-in-lacquer to a lacquer-in-water emulsion. Another inversion technique begins with water-wet nitrocellulose which is dissolved in the solvent system, with water from the mixture dispersing throughout the solvent phase. Additional water containing an emulsifying agent is added forming a lacquer-in-water emulsion by inversion. Although many improvements have been made in nail coatiηg performance, conventional nail coatings still employ a relatively high percentage of volatile water- immiscible solvents which are relatively toxic, in order to emulsify the nitrocellulose based material. Water-miscible solvents are not ordinarily used because they promote formation of water-in-lacquer rather than lacquer-in-water emulsions. Due to the high percentage of water-immiscible solvents ordinarily employed to emulsify the nitrocellulose, the resultant coatings are flammable and potentially toxic, with a high rate of volatilization and an unpleasant odor. In addition, some individuals become sensitized and develop reactions to these nail coatings.

It is therefore desirable to provide a method for preparing cellulose solutions with less reliance on a high percentage of harsh solvents. It is also desirable to provide cellulose-based compositions which have reduced environmental impact by employing a greater percentage of water. It is further desirable to provide nitrocellulose-based compositions for coatings with a lower percentage of solvent. It is further desirable to

provide improved nail coatings with a lower percentage of solvents, but which do not sacrifice durability and hardness characteristics.

SUMMARY OF THE INVENTION The present invention provides novel aqueous cellulose compositions and methods of making such compositions. The present invention also encompasses the use of aqueous cellulose compositions in coatings and the method of making. The coating compositions are free-flowing liquids which may be either pigmented or non-pigmented and applied to human nails in a conventional manner. The coating compositions may also be employed as polishes and protective coatings. The method for preparing cellulose in water, hereinafter "aqueous cellulose solution," generally comprises the steps of mixing solid nitrocellulose, ethylcellulose or cellulose acetate butyrate and a substantial amount of water, adding more water with continued mixing and adding a small amount of solvent with continued mixing. The water and solvent may also be added simultaneously. The above steps are performed at an elevated temperature of about 95°C to boiling. The resulting mixture is azeotropic-like.

Nitrocellulose-based coatings of the present invention are obtained by mixing a proportional amount of acrylic-based polymers and aqueous nitrocellulose solution.

Various additives such as wetting agents, germicides and thickeners may also be added.

Pigmented coatings are formed by adding dispersed treated pigments to the nitrocellulose- based coatings. The dispersed treated pigments are obtained by repeatedly mixing the pigments with silanes, and titanates, desiccating and then, milling the treated pigments with a wetting agent and a dispersing surfactant.

The nail coatings of the present invention are primarily aqueous rather than solvent- based and employ generally gentler, low volatile organic solvents. The hardness, durability and water resistance of the nail coatings of the invention are equal to or surpass those of nail coatings presently on the market. The coatings of the present invention are also less affected by humidity than solvent-based coatings. In addition, the coatings of the present invention have a high solid content (28% - 43% solids), which affords better coverage of imperfections in the nail. The coatings of the present invention do not appear to form a continuous film as do solvent-based coatings and do not easily chip due to their adhesive and flexible qualities. The decrease in the high percentage of solvents reduces solvent-related problems. The coatings of the present invention also more readily permit the exchange of body fluids with the atmosphere, i.e. allowing the nail bed to "breathe."

The coatings of the present invention may also be used as a polish on vinyl, leather, finished and unfinished wood, formica and flooring, including linoleum, ceramic tile,

marble and mineral flooring and the like. The coatings are also useful as polishes for automobiles.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS I. Preparation of The Aqueous Cellulose Solution The aqueous cellulose solution is made with solvents selectively compatible with polymers to which it will be added, to enhance the properties of the particular polymer being used. The invention can include nitrocellulose, ethylcellulose or cellulose acetate butyrate, although it will be appreciated that in alternative embodiments, other suitable cellulose compounds or complexes may be used. Examples of solvents that may be employed in the present invention include but are not limited to propylene glycol monopropyl ether, ethylene glycol monopropyl ether, ethyl 3-ethoxypropionate, isopropyl or ethyl alcohol (32g) with ethylene glycol monobutyl ether (26g), dipropylene glycol monobutyl ether, dipropylene glycol methyl ether, propylene glycol methyl acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, isopropyl acetate, N-methyl-2-pyrrolidone, isopropyl or ethyl alcohol and propylene glycol methyl ether. Examples of preferred solvents include propylene glycol monobutyl ether, ethylene glycol monobutyl acetate, ethylene glycol monobutyl ether and diethylene glycol monoethyl ether. The solvents of the present invention may also act as a freeze-thaw factor. The present invention may also employ surfactants including but not limited to El 620, available from Rhone Poulenc of Cranbury, NJ, FC129 Fluorad, available from 3M of St. Paul, MN, Surfynol S-104E, available from Air Products, Inc. of Allentown, PA, L-7001 , available from Union Carbide Corp. of Danbury, CT, and A-196, available from American Cyanamid. The invention can also include other additives such as ammonium hydroxide, 28%. The pH of the solution is in the range of from about 2.0 to about 6.0. Nitrocellulose, ethylcellulose and cellulose acetate butyrate (hereinafter referred to generally as "cellulose compounds") were put into aqueous solutions according to the following general technique wherein the amount of distilled water varied from about 2 parts by weight to about 20 parts by weight for every part by weight of cellulose compound (all measurements are based on employing an open vessel in the preparation of the compositions). The nitrocellulose was 80% by weight, water packed. Ethylcellulose and cellulose acetate butyrate were 100% by weight. An example of preferred nitrocellulose is that sold by Aqualon, a Hercules Corporation. An example of preferred ethylcellulose is that sold by Dow Chemical Co. of Midland, Ml. An example of preferred cellulose acetate butyrate is that sold by Eastman Kodak Co. of Rochester, NY. The solvents employed range from about 2 parts by weight to about 20 parts by weight for every part

by weight of cellulose compound. The surfactants employed vary from about 0.05g to about 1.0g without dilution for every part by weight of cellulose compound. The general technique consists of applying heat in the range of from about 70°C to about boiling, preferably at about 95°C to about boiling and mixing at a mixer speed of around 8.5 or at a speed great enough to form a vortex in the mixture. The cellulose compound and distilled water are mixed for about five minutes. More water is added and the solution is mixed for about five more minutes. Solvent is added and mixed for about twenty more minutes. Variations of this method may be employed as illustrated by the foregoing examples with similar results obtained. The following are examples of the most preferred methods of preparing aqueous nitrocellulose solutions:

Specific Example 1 10g of nitrocellulose and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was added and the resulting solution mixed for 5 minutes. 40g of ethylene glycol monobutyl acetate was poured into this solution and mixed for 20 minutes.

Specific Example 2 10g of nitrocellulose and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was added and the resulting solution mixed for 5 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes. Specific Example 3

10g of nitrocellulose and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was added and the resulting solution mixed for 5 minutes. 0.5g of CMC-7H- 1 % was added and this solution was mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was then poured into the solution and mixed for 20 minutes. Specific Example 4

10g of nitrocellulose and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed in for 8 minutes. 40g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 20 minutes. Specific Example 5

10g of nitrocellulose and 40g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 40g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1% was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

Specific Example 6

10g of nitrocellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of

NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 30g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

The following are examples of the most preferred methods of preparing aqueous ethylcellulose solutions:

Specific Example 7 10g of ethylcellulose and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was added and the resulting solution mixed for 5 minutes. 40g of ethylene glycol monobutyl acetate was poured into this solution and mixed for 20 minutes.

Specific Example 8 10g of ethylcellulose and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was added and the resulting solution mixed for 5 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

Specific Example 9 10g of ethylcellulose and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was added and the resulting solution mixed for 5 minutes. 0.5g of CMC-7H- 1% was added and this solution was mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was then poured into the solution and mixed for 20 minutes. Specific Example 10

10g of ethylcellulose and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed in for 8 minutes. 40g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 20 minutes.

Specific Example 11 10g of ethylcellulose and 40g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 40g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

Specific Example 12 10g of ethylcellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 30g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

The following are examples of the most preferred methods of preparing aqueous cellulose acetate butyrate solutions:

Specific Example 13 10g of cellulose acetate butyrate and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was added and the resulting solution mixed for 5 minutes. 40g of ethylene glycol monobutyl acetate was poured into this solution and mixed for 20 minutes.

Specific Example 14 10g of cellulose acetate butyrate and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was added and the resulting solution mixed for 5 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

Specific Example 15

10g of cellulose acetate butyrate and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was added and the resulting solution mixed for 5 minutes.

0.5g of CMC-7H-1 % was added and this solution was mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was then poured into the solution and mixed for 20 minutes.

Specific Example 16 10g of cellulose acetate butyrate and 20g of distilled water were mixed for 5 minutes. 20g of distilled Water was poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1% was added and mixed in for 8 minutes. 40g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 20 minutes.

Specific Example 17 10g of cellulose acetate butyrate and 40g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 40g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes. Specific Example 18

10g of cellulose acetate butyrate and 16.44g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8

minutes. 30g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

The following are examples of the preferred method of preparing aqueous nitrocellulose solutions: Specific Example 19

10g of nitrocellulose and 30g of distilled water were mixed for 5 minutes. 5g of

NH ₄ OH (28%) and 45g of distilled water were combined and poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 20 minutes. Specific Example 20

10g of nitrocellulose and 30g of distilled water were mixed for 5 minutes. 5g of

NH ₄ OH (28%) and 45g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes. Specific Example 21

10g of nitrocellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of

NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 46g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 30 minutes. Specific Example 22

10g of nitrocellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of

NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 46g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes. Specific Example 23

10g of nitrocellulose and 25g of distilled water were mixed for 5 minutes. 25g of distilled water was poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 20 minutes. Specific Example 24

10g of nitrocellulose and 25g of distilled water were mixed for 5 minutes. 25g of distilled water was poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

The following are examples of the preferred method of preparing aqueous ethylcellulose solutions:

Specific Example 25

10g of ethylcellulose and 30g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 45g of distilled water were combined and poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 20 minutes.

Specific Example 26

10g of ethylcellulose and 30g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 45g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

Specific Example 27

10g of ethylcellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 46g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 30 minutes.

Specific Example 28 10g of ethylcellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1% was added and mixed for 8 minutes. 46g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

Specific Example 29 10g of ethylcellulose and 25g of distilled water were mixed for 5 minutes. 25g of distilled water was poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 20 minutes.

Specific Example 30 10g of ethylcellulose and 25g of distilled water were mixed for 5 minutes. 25g of distilled water was poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

The following are examples of the preferred method of preparing aqueous cellulose acetate butyrate solutions:

Specific Example 31

10g of cellulose acetate butyrate and 30g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 45g of distilled water were combined and poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 20 minutes.

Specific Example 32 10g of cellulose acetate butyrate and 30g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 45g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes. Specific Example 33

10g of cellulose acetate butyrate and 16.44g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 46g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 30 minutes.

Specific Example 34

10g of cellulose acetate butyrate and 16.44g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 46g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

Specific Example 35 10g of cellulose acetate butyrate and 25g of distilled water were mixed for 5 minutes. 25g of distilled water was poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 20 minutes.

Specific Example 36 10g of cellulose acetate butyrate and 25g of distilled water were mixed for 5 minutes. 25g of distilled water was poured into the mixture and mixed for 5 minutes. 0.5g

of CMC-7H-1 % was added and mixed for 8 minutes. 40g of ethylene glycol monobutyl ether was poured into the mixture and mixed for 20 minutes.

The following are additional examples of the method of preparing aqueous nitrocellulose solutions: Specific Example 37

10g of nitrocellulose and 30g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 45g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H 1 % was added and mixed for 8 minutes. 2g of Zn(NH ₃ )3x(C0 ₃ )x(Zinc Ammonia Carbonate Complex) and 8g of distilled water were mixed in for 10 minutes. 35g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 40 minutes.

Specific Example 38

10g of nitrocellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of

NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 20g of ethylene glycol monobutyl ether and 26g of isopropyl acetate were combined, poured into the mixture and mixed for 20 minutes.

Specific Example 39

10g of nitrocellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 30g of ethylene glycol monobutyl ether and 16g of diethylene glycol monoethyl ether were combined, poured into the mixture and mixed for 20 minutes.

Specific Example 40 10g of nitrocellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of

NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 30g of ethylene glycol monobutyl ether and 16g of ethylene glycol monobutyl acetate were combined, poured into the mixture and mixed for 25 minutes. Specific Example 41

10g of nitrocellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of

NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 23g of ethylene glycol monobutyl ether and 23g of ethylene glycol monobutyl acetate were combined, poured into the mixture and mixed for 25 minutes.

Specific Example 42

10g of nitrocellulose and 16.44g of distilled water were mixed for 5 minutes. 5g of

NH ₄ OH (28%) and 24.52g of distilled water were combined, poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 30g of ethylene glycol monobutyl ether and 16g of ethylene glycol monobutyl acetate were combined, poured into the mixture and mixed for 25 minutes.

Specific Example 43 10g of nitrocellulose and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 40g of N-methyl-2-pyrrolidone was poured into the mixture and mixed for 20 minutes.

Specific Example 44 10g of nitrocellulose and 20g of distilled water were mixed for 5 minutes. 20g of distilled water was poured into the mixture and mixed for 5 minutes. 0.5g of CMC-7H-1 % was added and mixed for 8 minutes. 1g of CO 630 was added. 40g of ethylene glycol monobutyl acetate was poured into the mixture and mixed for 20 minutes. II. Cellulose Based Coatings

Nitrocellulose-based coatings according to the present invention are obtained by mixing a proportional amount of acrylic-based polymers and aqueous nitrocellulose solution. It will be appreciated that alternatively, a proportional amount of acrylic-based polymers may be mixed with an aqueous ethylcellulose solution or aqueous cellulose acetate butyrate solution in a similar fashion to form ethylcellulose-based coatings and cellulose acetate butyrate-based coatings. Examples of polymers used in the present invention include but are not limited to A 1054, A 5050, R960 and BT 44, available from Zeneca Resins of Wilmington, DE, KRS 2411 and KPS 5545, available from Kane

International Corp. of Larchmont, NY, Zinpol 259, available from Zinchem, Inc. of Somerset,

NJ, and Carboset 525 and Carboset 526, available from B.F. Goodrich Co. of Akron, OH.

The preferred acrylic-based polymers are A621 , A 622, A623, A630, A633, A645, A 655 and

A 1054, available from Zeneca Resins and Joncryl 77 and Joncryl 89, available from SC Johnson of Racine, Wl. The invention can also include surfactants such as El 620, available from Rhone Poulenc, FC129 Fluorad, available from 3M, Surfynol DF-75, Surfynol

S-104E and Surfynol S-104PG, available from Air Products, Inc., L 7001 , and L7602, available from Union Carbide Corp., and A-196 and OT75, available from American

Cyanamid, and Span 80, available from ICI Specialties of Wilmington, DE, and others known in the art. Specific silanes such as Z 6040, 25-additive and Z-6020, available from

Dow Corning Corp. of Midland, Ml and A 1100, available from Union Carbide Corp. as well as those known in the art may also be employed. The invention can also include titanates such as Tysor LA and Tysor LE, available from E.I. duPont deNemours & Co., Inc. of Wilmington, DE. (Silanes and titanates are hydrolyzed 24 hours prior to usage to prevent concentrated areas in solution.) Colloidal silicas such as Nalco 2326, Nalco 1115 and Nalco 1140, available from Nalco Chemical Co. of Chicago, IL, and dispersants such as CT 136, available from Air Products, Inc. and L 7602, available from Union Carbide Corp., may also be employed. Defoamers such as S-104E and S-104 PG from Air Products (also used as a wetting agent) may also be employed. Germicides such as Dowicide, parabens, ammonium hydroxide and others known in the art may also be added. A preferred germicide is Suttocide A, sold by Sutton Laboratory, Inc., a GAF Company (aka ISP Manufacturing). Thickeners such as SCT 270 and SCT 275, available from Union Carbide Corp., CMC-7H, available from Aqualon Co., and others known in the art may be added. A preferred thickener is Keltrol T, sold by Kelco Company, a division of Merck. The amount of germicides and thickeners added to the solution is based on the percentage level of solids in the solution. The amount of thickener used is in the range of about .4 to about 1.5% by weight and the amount of germicide used is also in the range of about .4 to about 1.5% weight. Solvents may be added to retard film formation and to allow better flow and freeze-thaw properties of the coating. Preferred solvents include ethanol (100%) or propylene glycol in the range of from about 8% by weight to about 10% by weight. Ultraviolet (UV) absorbers may also be employed to retard degradation of the coatings caused by UV radiation. Examples of suitable UV absorbers include Spectrasorb UV 5411 and UV 531 sold by American Cyanamid, and Uvinol N-35, Etocrylene, sold by BASF. The amount of UV absorber used is in the range of about .2 to about 2% by weight. The following methods were employed to formulate the nitrocellulose-based coatings. Generally, the material was placed in a 1000 ml beaker and a standard laboratory mixer was employed using a standard propeller, at room temperature. The mixer speed was set at 8.5 or at a speed great enough to form a vortex in the mixture. The solution was poured in a steady stream. A further step of decanting may be employed if necessary. Further illustrations of the basic method are depicted in the following examples.

Specific Example 45 20g of Carboset 525 (15%) and 10g of distilled water were mixed together in a vessel and added to 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) and mixed for 10 minutes. 20g of Zinpol 259 was added

and mixed for 10 minutes with the mixer speed increased to 8 setting. 10g of KRS 2411 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of distilled water and 10g of ammonia hydroxide (10%) were poured together, mixed in a vessel, added to the above mixture and mixed for 10 minutes. 15g of BT 44 was added and mixed for 10 minutes. 2.52g of DF-75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.04g of S-104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 5.04g of FC-129 (.01 %) at 0.05% level of solids was added and mixed for 15 minutes. 2.52g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.04g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 2.52g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.52g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 2.52g of L 7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 0.3g of N 2326 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.3g of N 1115 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.52g of A 196 (1%) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of CMC-7H (1%) at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 46 16g of C 525 and 10g of distilled water were combined. 2.9g solid weight (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added. 10g of BT 44 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 15g of Z 259 was added and mixed for 10 minutes. 5g of KRS 2411 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 2.2g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 4.4g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 4.4g of FC 129 (.01 %) at 0.05% level of solids was added and mixed for 30 minutes. 2.2g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 4.4g of Tysor LA( 10%) at 1 % level of solids was added and mixed for 15 minutes. 2.2g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.2g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 0.5% level of solids was added

and mixed for 15 minutes. 2.2g of A 196 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of CMC-7H (1 %) at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 47 16g of C 525 (15%) and 10g of distilled water were combined. 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added. 20g of Z 259 was added and mixed for 10 minutes. 10g of KRS 2411 was added and mixed for 10 minutes. 25g of A 622 and 15g of A 655 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 15g of BT 44 was added and mixed for 10 minutes. 15g of A 5050 was added and mixed for 10 minutes. 2.8g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.6g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 5.6g of FC 129 (.01 %) at 0.05% level of solids was added and mixed for 30 minutes. 2.8g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.6g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 2.8g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of L 7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol 10% of solids was added and mixed for 15 minutes. 1g of 25- additive (3%) at 0.05% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of A 196 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of CMC-7H (1 %) at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 48 15g of BT 44 and 25g of A 622 were mixed together for 10 minutes. 10g of A 1054 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 10g of KRS 2411 was added and mixed for 10 minutes. 15g of C 525 and 10g of distilled water were combined, added to the above mixture and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added and mixed for 10 minutes. 4.72g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 2.56g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15

minutes. 4.72g of FC 129 (.01 %) at 0.5% level of solids was added and mixed for 30 minutes. 2.36g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 4.72g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 2.36g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.36g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.36g of L 7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 4.6g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 1.02g of 25-additive at 0.05% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.36g of A 196 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 0.47g of CMC-7H-1 % at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 49 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added to the vessel. 16g of C 525 and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 15g of Z 259 was added and mixed for 10 minutes. 15g of BT 44 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 2.25g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 4.5g of S 104E (1%) at 0.05% level of solids was added and mixed for 30 minutes. 4.5g of FC 129 (.01%) at 0.05% level of solids was added and mixed for 30 minutes. 2.25g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 4.5g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 2.25g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.25g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.25g of L 7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 1 g of 25-additive at 0.05% of solids was added and mixed for 15 minutes. 0.5g of N 2325 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.25g of A 190 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of CMC-7H-1 % at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 50

20g of A 1054 was added to the vessel. 20g of C 525 and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 15g of BT 44 was added and mixed for 10 minutes. 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 10g of KRS 2411 was added and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 10g of KRS 5545 was added and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 2.71 g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.42g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 5.42g of FC 129 (.01 %) at 0.05% level of solids was added and mixed for 30 minutes. 2.71 g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.42g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 2.71 g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.71 g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.71 g of L7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 4.86g of ethylene glycol at 8% of solids was added and mixed for 15 minutes. 1.25g of 25-additive at 0.05% level of solids was added and mixed for 15 minutes. 0.54g of N 2325 (10%) at 0.5% volume of solids was added and mixed for 15 minutes. 0.54g of N 1115 (10%) at 0.5% volume of solids was added and mixed for 15 minutes. 2.71 g of A 196 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 0.54g of CMC-7H-1 % at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 51 20g of A 1054 and 15g of BT 44 were combined and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 10g of KRS 2411 was added and mixed for 10 minutes. 10g of KRS 5545 was added and mixed for 10 minutes. 20g of C 525 was added and mixed for 10 minutes. 2.71 g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.42g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 5.42g of FC 129 (.01%) at 0.05% level of solids was added and mixed for 30

minutes. 2.71 g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.42g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 2.71 g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.71 g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.71 g of L 7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 4.86g of ethylene glycol at 8% of solids was added and mixed for 15 minutes. 1.25g of 25-additive at 0.05% of solids was added and mixed for 15 minutes. 0.54g of N 2326 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.54g of N 1115 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.71 g of A 196 (1 %) at 0.5% level of solids was added and mixed for 10 minutes. 0.54g of CMC-7H-1 % at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 52 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added to the vessel. 16g of C 525 and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 10g of BT 44 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 15g of Z 269 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 2.2g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 4.4g of FC 129 (.01 %) at. 0.05% level of solids was added and mixed for 30 minutes. 2.2g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 4.4g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 2.2g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.2g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 4.4g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. Specific Example 53

2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) and 15g of BT 44 were combined and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 10g of KRS 2411 was added and mixed for 10 minutes. 10g of KRS 5545 was added and mixed for 10 minutes.

10g of distilled water was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 2.8g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.6g of S 104E (1%) at 0.05% level of solids was added and mixed for 30 minutes. 5.6g of FC 129 (.01 %) at 0.05% level of solids was added and mixed for 30 minutes. 2.8g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.6g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 2.8g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of L 7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 1 g of 25- additive (3%) at 0.05% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of A 196 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of CMC-7H (1 %) at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 54 20g of A 1054 was added to the vessel. 20g of C 525 and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 15g of BT 44 was added and mixed for 10 minutes. 2.9g solid weight (based on solid content) aqueous nitrocellulose solution (prepared as described above) was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 10g of KRS 2411 was added and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 10g of KRS 5545 was added and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 2.71 g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.42g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 5.42g of FC 129 (.01 %) at 0.05% level of solids was added and mixed for 30 minutes. 2.71 g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.42g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 2.71 g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.71 g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.71 g of L 7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 4.86g of ethylene glycol at 8% of solids was added and mixed for 15 minutes. 1.25g of 25-additive at 0.05% of solids was added and mixed for 15 minutes. 0.54g of N

2326 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.54g of N 1115 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.71 g of A 196 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 0.54g of CMC-7H (1 %) at 0.0625% level of solids was added and mixed for 30 minutes. Specific Example 55

20g of A 1054 was added to the vessel. 20g of C 525 and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 15g of BT 44 was added and mixed for 10 minutes. 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 10g of KRS 2411 was added and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 10g of KRS 5545 was added and mixed for 10 minutes. 10g of distilled water was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 2.8g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.6g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 5.6g of FC 129 (.01 %) at 0.05% level of solids was added and mixed for 30 minutes. 2.8g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.6g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 2.8g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of L 7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 1g of 25-additive (3%) at 0.05% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at - 0.5% level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of A 196 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of CMC-7H (1 %) at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 56 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added to the vessel. 16g of C 525 (15%) and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 15g of BT 44 was added and' mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of KRS 2411 was added and mixed for 10 minutes. 10g of NH ₄ 0H (10%) was added and mixed for 10

minutes. 2.8g of DF 75 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.6g of S 104E (1 %) at 0.05% was added and mixed for 30 minutes. 5.6g of FC 129 (.01 %) at 0.05% level of solids was added and mixed for 30 minutes. 2.8g of Z 6040 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 5.6g of Tysor LA (10%) at 1% level of solids was added and mixed for 15 minutes. 2.8g of Z 6020 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of A 1100 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of L 7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 2.8g of A 196 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 0.5g of CMC-7H (1 %) at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 57 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added to the vessel. 20g of C 525 (15%) and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 15g of BT 44 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of KRS 2411 was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 3g of DF 75 (10%) at 0.6% level of solids was added and mixed for 15 minutes. 5.02g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 5.02g of FC 129 (.01 %) at 0.05% level of solids was added and mixed for 30 minutes. 5.01 g of Z 6040 (10%) at 1.02% level of solids was added and mixed for 15 minutes. 10g of Tysor LA (10%) at 2% level of solids was added and mixed for 15 minutes. 5.01 g of Z 6020 (10%) at 1.02% level of solids was added and mixed for 15 minutes. 5.01 g of A 1100 (10%) at 1.02% level of solids was added and mixed for 15 minutes. 2.5g of L 7001 (1 %) at 0.5% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 0.25g of N 2326 (10%) at 0.5% level of solids was added and mixed for 15 minutes. 0.25g of N 1115 (10%) at 0.5% level of solids

was added and mixed for 15 minutes. 2.5g of A 196 (1 %) at 0.5% level of solids was added and mixed for 30 minutes.

Specific Example 58 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added to the vessel. 20g of C 525 (15%) and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 12g of KRS 2411 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of BT 44 was added and mixed for 10 minutes. 10g of NH ₄ OH (10%) was added and mixed for 10 minutes. 3g of DF 75 (10%) at 0.6% level of solids was added and mixed for 15 minutes. 5.6g of FC 129 (.01 %) at 0.06% level of solids was added and mixed for 30 minutes. 5.01 g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 4g of Z 6040 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 10g of Tysor LA (10%) at 1% level of solids was added and mixed for 15 minutes. 4g of Z 6020 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 4g of A 1100 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 3g of L 7001 (1 %) at 0.06% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 1 % level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 1 % level of solids was added and mixed for 15 minutes. 3g of A 196 (1 %) at 0.06% level of solids was added and mixed for 15 minutes. 0.5g of CMC-7H (1 %) at 0.0625% level of solids was added and mixed for 30 minutes.

Specific Example 59 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added to the vessel. 20g of C 525 (15%) and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 10g of C 526 (10%) was added and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 12g of KRS 2411 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of BT 44 was added and mixed for 10 minutes. 5g of NH ₄ OH (10%) was added and mixed for 10 minutes. 3.05g of DF 75 (10%) at 0.6% level of solids was added and mixed for 15 minutes. 5.01 g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 6g of FC 129 (.01 %) at 0.06% level of solids was added and mixed for 30 minutes. 4g of Z 6040 (10%) at 0.8% level of solids was

added and mixed for 15 minutes. 10g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 4g of Z 6020 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 4g of A 1100 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 3g of L 7001 (1 %) at 0.06% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 1 % level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 1 % level of solids was added and mixed for 15 minutes. 3g of A 196 (1 %) at 0.06% level of solids was added and mixed for 30 minutes.

Specific Example 60 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added to the vessel. 20g of C 525 (15%) and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 10g of C 526 (10%) was added and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 12g of KRS 2411 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of BT 44 was added and mixed for 10 minutes. 5g of NH ₄ OH (10%) was added and mixed for 10 minutes. 3.05g of DF 75 (10%) at 0.6% level of solids was added and mixed for 15 minutes. 5.01 g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 6g of FC 129 (.01 %) at 0.06% level of solids was added and mixed for 30 minutes. 4g of Z 6040 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 10g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 4g of Z 6020 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 4g of A 1100 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 3g of L 7001 (1 %) at 0.06% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 1 % level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 1 % level of solids was added and mixed for 15 minutes. 3g of A 196 (1 %) at 0.06% level of solids was added and mixed for 15 minutes. 3.01 g of SCT 270 1 % of solids was added and mixed for 30 minutes. Specific Example 61

2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added to the vessel. 20g of C 525 (15%) and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 10g of C 526 (10%) was added and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 12g of KRS 2411 was added and mixed for 10 minutes. 25g of A 622 was added and mixed

for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of BT 44 was added and mixed for 10 minutes. 5g of NH ₄ OH (10%) was added and mixed for 10 minutes. 3.05g of DF 75 (10%) at 0.6% level of solids was added and mixed for 15 minutes. 5.01 g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 6g of FC 129 (.01 %) at 0.06% level of solids was added and mixed for 30 minutes. 4g of Z 6040 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 10g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 4g of Z 6020 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 4g of A 1100 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 3g of L 7001 (1 %) at 0.06% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 1 % level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 1 % level of solids was added and mixed for 15 minutes. 3g of A196 (1 %) at 0.06% level of solids was added and mixed for 15 minutes. 2.20g of SCT 270 0.75% of solids was added and mixed for 30 minutes.

Specific Example 62 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added to the vessel. 20g of C 525 (15%) and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 10g of C 526 (10%) was added and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 12g of KRS 2411 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of BT 44 was added and mixed for 10 minutes. 5g of NH ₄ OH (10%) was added and mixed for 10 minutes. 3.05g of DF 75 (10%) at 0.6% level of solids was added and mixed for 15 minutes. 5.01 g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 6g of FC 129 (.01 %) at 0.06% level of solids was added and mixed for 30 minutes. 4g of Z 6040 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 10g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 4g of Z 6020 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 4g of A 1100 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 3g of L 7001 (1 %) at 0.06% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 1 % level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 1 % level of solids was added and mixed for 15 minutes. 3g of A 196 (1 %)

at 0.06% level of solids was added and mixed for 15 minutes. 2.04g of SCT 270 at 0.75% level of solids was added and mixed for 30 minutes.

Specific Example 63 2.9g (based on solid content) of aqueous nitrocellulose solution (prepared as described above) was added to the vessel. 20g of C 525 (15%) and 10g of distilled water were combined, added to the vessel and mixed for 10 minutes. 10g of C 526 (10%) was added and mixed for 10 minutes. 20g of Z 259 was added and mixed for 10 minutes. 12g of KRS 2411 was added and mixed for 10 minutes. 25g of A 622 was added and mixed for 10 minutes. 15g of A 655 was added and mixed for 10 minutes. 20g of A 1054 was added and mixed for 10 minutes. 10g of BT 44 was added and mixed for 10 minutes. 5g of NH ₄ OH (10%) was added and mixed for 10 minutes. 3.05g of DF 75 (10%) at 0.6% level of solids was added and mixed for 15 minutes. 5.01 g of S 104E (1 %) at 0.05% level of solids was added and mixed for 30 minutes. 6g of FC 129 (.01 %) at 0.06% level of solids was added and mixed for 30 minutes. 4g of Z 6040 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 10g of Tysor LA (10%) at 1 % level of solids was added and mixed for 15 minutes. 4g of Z 6020 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 4g of A 1100 (10%) at 0.8% level of solids was added and mixed for 15 minutes. 3g of L 7001 (1 %) at 0.06% level of solids was added and mixed for 15 minutes. 5g of ethylene glycol at 10% of solids was added and mixed for 15 minutes. 0.5g of N 2326 (10%) at 1 % level of solids was added and mixed for 15 minutes. 0.5g of N 1115 (10%) at 1 % leverof solids was added and mixed for 15 minutes. 3g of A 196 (1 %) at 0.06% level of solids was added and mixed for 15 minutes. 2.73g of SCT 270 at 1 % level of solids was added and mixed for 30 minutes. III. Modified Polymers in Cellulose Based Coatings. In a preferred method, polymers were modified with an aqueous nitrocellulose solution or aqueous ethylcellulose solution or aqueous cellulose acetate butyrate solution in a range between 0.01 g and 1.0g of aqueous cellulose solution per gram polymer. This is determined by the viscosity of the resulting mix, which is allowed to react from three to twenty days and is determined by clarity of film on glass prior to formulating the coatings. The modification optimizes the amount of cellulose in solution producing an increase in the percent of cellulose in the coating. The modified method produces coatings with increased clarity, viscosity, flexibility and hardness. The same basic method for formulating the coatings, as described above, is employed with the exception of using the modified polymers.

The following method was employed to formulate the modified polymers. Generally, polymer and aqueous nitrocellulose are mixed in a 1000 ml beaker. A water bath with a temperature of from about 70° to about 95°C may be employed to accelerate the reaction. The solution is then placed in a container and sits for a few days to several weeks to allow for reaction. A further step of decanting may be employed if necessary. The ratio of aqueous nitrocellulose solution to polymer varies for particular polymers. The most preferred ratio of aqueous nitrocellulose solution to polymer is as follows: 0.066g aqueous nitrocellulose solution per 1 g A622 0.04g aqueous nitrocellulose solution per 1 g A655 0.039g aqueous nitrocellulose solution per 1 g A1054 0.0213g aqueous nitrocellulose solution per 1 g KRS2411 0.022g aqueous nitrocellulose solution per 1 g Z259 0.05748g aqueous nitrocellulose solution per 1 g C525 0.0678g aqueous nitrocellulose solution per 1 g BT44 0.0201 g aqueous nitrocellulose solution per 1 g R960 0.0615g of aqueous nitrocellulose solution per 1 g A621 0.06g of aqueous nitrocellulose solution per 1 g A630

As described above, the general method for formulating nitrocellulose based coatings is employed using modified polymers. Illustrations of this basic method using modified polymers in the most preferred embodiment of the present invention is depicted in the following examples.

The following are examples of the methods of making the most preferred modified coatings:

Specific Example 64 60g of modified A630 and 60g of modified A655 were mixed for 10 minutes. 40g of modified A622 was added and mixed for 10 minutes. 20g of modified A1054 was added and mixed for 10 minutes. 0.44g of FC129 5% at 0.015% of solids at 50% active was added and mixed for 25 minutes. 2.04g of L7602 5% at 0.14% of solids was added and mixed for 20 minutes. 0.364g of Z6040 100% at 0.5% of solids was added and mixed for 20 minutes. 1.45g of Tysor La 100% at 1 % of solids at 50% active was added and mixed for 20 minutes. 0.73g of Suttocide A 100% at 0.5% of solids at 50% active was added and mixed for 20 minutes. 9.09g of Nalco 1140 40% at 5% of solids was added and mixed for 20 minutes. 3.42g of A196 100% at 0.4% of solids at 85% active was added and mixed for 20 minutes. 0.29g of OT75 100% at 0.3% of solids at 75% active was added and mixed for 20 minutes. 0.15g of Span80 100% at 0.2% of solids was added and mixed for 20

minutes. 63.95g of A630, unmodified, at 31.5% of total volume was added and mixed for 15 minutes. 19.61 g of A633, unmodified, at 9.66% of total volume was added and mixed for 15 minutes. 28.28g of A645, unmodified, at 20% of total volume was added and mixed for 15 minutes. 0.7g of S104-PG 2% at 0.03% of solids at 50% active was added and mixed for 25 minutes. The amount of solvent (distilled water and ethanol, 100%), defoamer, germicide and thickener and pigment was based on 40% of solids, as required.

Specific Example 65 60g of modified A630 and 60g of modified A655 were mixed for 10 minutes. 40g of modified A622 was added and mixed for 10 minutes. 20g of modified A1054 was added and mixed for 10 minutes. 0.44g of FC129 5% at 0.015% of solids at 50% active was added and mixed for 25 minutes. 2.04g of L7602 5% at 0.14% of solids was added and mixed for 20 minutes. 0.364g of Z6040 100% at 0.5% of solids was added and mixed for 20 minutes. 1.45g of Tysor La 100% at 1% of solids at 50% active was added and mixed for 20 minutes. 0.73g of Suttocide A 100% at 0.5% of solids at 50% active was added and mixed for 20 minutes. 9.09g of Nalco 1140 40% at 5% of solids was added and mixed for 20 minutes. 3.42g of A196 100% at 0.4% of solids at 85% active was added and mixed for 20 minutes. 0.29g of OT75 100% at 0.3% of solids at 75% active was added and mixed for 20 minutes. 0.15g of SpanδO 100% at 0.2% of solids was added and mixed for 20 minutes. 63.95g of A630, unmodified, at 31.5% of total volume was added and mixed for 15 minutes. 19.61 g of A633, unmodified, at 9.66% of total volume was added and mixed for 15 minutes. 28.28g of A623, unmodified, at 20% of total volume was added and mixed for 15 minutes. 0.7g of S104-PG 2% at 0.03% of solids at 50% active was added and mixed for 25 minutes. The amount of solvent (distilled water and ethanol, 100%), defoamer, germicide and thickener and pigment was based on 40% of solids. Specific Example 66

360g of modified A622 and 216g of modified A655 was mixed for 20 minutes. 8.154g of L7602 4% at 0.15% level of solids was added and mixed for 25 minutes. 6.53g of S-77 1 % at 0.03% level of solids was added and mixed for 30 minutes. 0.75g of N1115 100% at 0.05% level of solids at 15% active was added and mixed for 25 minutes. 120g of modified A1054 was added and mixed for 25 minutes. 57.3g of ethanol 200% proof and 14.32g of distilled water were added and mixed for 25 minutes. 2.18g of Suttocide A 100% at 0.5% level of solids at 50% active was added and mixed for 25 minutes. Thickener was added in quantum sufficient, 0.2% to 0.8% of total solids. The amount of solvent, defoamer, germicide and thickener was based on 37.75% of solids.

Specific Example 67

180g of modified A622 and 108g of modified A655 were mixed together for 10 minutes. 60g of modified A1054 was added and mixed for 10 minutes. 4.54g of L76024% at 0.15% of solids was added and mixed for 15 minutes. 3.63g of Silwet 77 1 % at 0.03% of solids was added and mixed for 25 minutes. 4.03g of N1115 10% at 0.05% of solids at 15% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 37.75% of solids. UN. absorber 1 % level of 10% solution is 6.795g of Spectrasorb UV 5411.

Specific Example 68 180g of modified A622 and 108g of modified A655 were mixed together for 10 minutes. 60g of modified A1054 was added and mixed for 10 minutes. 60g of modified R960 was added and mixed for 10 minutes. 4.54g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 3.63g of Silwet 77 1 % at 0.03% of solids was added and mixed for 25 minutes. 4.03g of Ν11 15 10% at 0.05% of solids at 15% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 37.75% of solids. UN. absorber 1 % level of 10% solution is 6.795g of Spectrasorb UV 5411.

Specific Example 69

360g of modified A622 and 216g of modified A655 was mixed for 20 minutes. 120g of modified A1054 was added and mixed for 20 minutes. 4.76g of L7602 10% at 0.18% level of solids was added and mixed for 25 minutes. 7.93g of S77 1 % at 0.03% level of solids was added and mixed for 30 minutes. 0.88g of Ν1115 100% at 0.05% level of solids at 15% active was added and mixed for 25 minutes. 2.12g of Z6040 100% at 0.8% level of solids was added and mixed for 25 minutes. 8.46g of Tysor LA 100% at 1.6% level of solids at 50% active was added and mixed for 25 minutes. 21.16g of propylene glycol

100% at 0.8% level of solids was added and mixed for 25 minutes. 2.64g of Suttocide A

100% at 0.5% level of solids at 50% active was added and mixed for 25 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38% of solids.

The following are examples of methods of making the preferred modified coatings: Specific Example 70

50.2g of modified A621 and 50.2g of modified A655 were mixed for 10 minutes.

36g of modified A622 was added and mixed for 10 minutes. 30g of modified A1054 was added and mixed for 10 minutes. 2.05g of FC129 1 % at 0.015% of solids at 50% active was added and mixed for 25 minutes. 0.96g of L7602 10% at 0.14% of solids was added and mixed for 20 minutes. 0.364g of Z6040 100% at 0.5% of solids was added and mixed

- 28 - for 20 minutes. 1.37g of Tysor La 100% at 1% of solids at 50% active was added and mixed for 20 minutes. 0.7g of Suttocide A 100% at 0.5% of solids at 50% active was added and mixed for 20 minutes. 2.06g of Propylene glycol 100% at 3% of volume was added and mixed for 20 minutes. 8.53g of Nalco 1140 40% at 5% of solids was added and mixed for 20 minutes. 3.22g of A196 100% at 0.4% of solids at 85% active was added and mixed for 20 minutes. 0.27g of OT75 100% at 0.3% of solids at 75% active was added and mixed for 20 minutes. 0.14g of SpanδO 100% at 0.2% of solids was added and mixed for 20 minutes. 82.7g of A655, unmodified, at 45% of total volume was added and mixed for 15 minutes. 24.51 g of A621 , unmodified, at 13.5% of total volume was added and mixed for 15 minutes. 35.56g of A623, unmodified, at 19.4% of total volume was added and mixed for 15 minutes. 0.7g of S104-PG 2% at 0.03% of solids at 50% active was added and mixed for 25 minutes. The amount of solvent (distilled water and ethanol, 100%), defoamer, germicide and thickener and pigment was based on 40% of solids.

Specific Example 71 52g of modified A630 and 52g of modified A655 were mixed for 10 minutes. 38g of modified A622 was added and mixed for 10 minutes. 30g of modified A1054 was added and mixed for 10 minutes. 2.17g of FC129 1% at 0.015% of solids at 50% active was added and mixed for 25 minutes. 1.02g of L7602 10% at 0.14% of solids was added and mixed for 20 minutes. 0.364g of Z6040 100% at 0.5% of solids was added and mixed for 20 minutes. 1.46g of Tysor La 100% at 1 % of solids at 50% active was added and mixed for 20 minutes. 0.73g of Suttocide A 100% at 0.5% of solids at 50% active was added and mixed for 20 minutes. 9.07g of Nalco 1140 40% at 5% of solids was added and mixed for 20 minutes. 3.41 g of A196 100% at 0.4% of solids at 85% active was added and mixed for 20 minutes. 0.28g of OT75 100% at 0.3% of solids at 75% active was added and mixed for 20 minutes. 0.147g of Span80 100% at 0.2% of solids was added and mixed for 20 minutes. 43.42g of A655, unmodified, at 23.6% of total volume was added and mixed for 15 minutes. 29.44g of A630, unmodified, at 16.% of total volume was added and mixed for 15 minutes. 29.44g of A623, unmodified, at 16% of total volume was added and mixed for 15 minutes. 0.7g of S104-PG 2% at 0.03% of solids at 50% active was added and mixed for 25 minutes. The amount of solvent (distilled water and ethanol, 100%), defoamer, germicide and thickener and pigment was based on 40% of solids.

Specific Example 72 52g of modified A630 and 52g of modified A655 were mixed for 10 minutes. 38g of modified A622 was added and mixed for 10 minutes. 30g of modified A1054 was added and mixed for 10 minutes. 2.17g of FC129 1 % at 0.015% of solids at 50% active was

added and mixed for 25 minutes. 1.02g of L7602 10% at 0.14% of solids was added and mixed for 20 minutes. 0.364g of Z6040 100% at 0.5% of solids was added and mixed for 20 minutes. 1.46g of Tysor La 100% at 1 % of solids at 50% active was added and mixed for 20 minutes. 0.73g of Suttocide A 100% at 0.5% of solids at 50% active was added and mixed for 20 minutes. 9.07g of Nalco 1140 40% at 5% of solids was added and mixed for 20 minutes. 3.41 g of A196 100% at 0.4% of solids at 85% active was added and mixed for 20 minutes. 0.28g of OT75 100% at 0.3% of solids at 75% active was added and mixed for 20 minutes. 0.147g of Span80 100% at 0.2% of solids was added and mixed for 20 minutes. 67.68g of A655, unmodified, at 36% of total volume was added and mixed for 15 minutes. 30.08g of A630, unmodified, at 16.% of total volume was added and mixed for 15 minutes. 30.08g of A623, unmodified, at 16.% of total volume was added and mixed for 15 minutes. 0.7g of S104-PG 2% at 0.03% of solids at 50% active was added and mixed for 25 minutes. The amount of solvent (distilled water and ethanol, 100%), defoamer, germicide and thickener and pigment was based on 40% of solids. Specific Example 73

52g of modified A630 and 52g of modified A655 were mixed for 10 minutes. 38g of modified A622 was added and mixed for 10 minutes. 30g of modified A1054 was added and mixed for 10 minutes. 2.17g of FC129 1 % at 0.015% of solids at 50% active was added and mixed for 25 minutes. 1.02g of L7602 10% at 0.14% of solids was added and mixed for 20 minutes. 0.364g of Z6040 100% at 0.5% of solids was added and mixed for 20 minutes. 1.46g of Tysor La 100% at 1 % of solids at 50% active was added and mixed for 20 minutes. 0.73g of Suttocide A 100% at 0.5% of solids at 50% active was added and mixed for 20 minutes. 9.07g of Nalco 1140 40% at 5% of solids was added and mixed for 20 minutes. 3.41 g of A196 100% at 0.4% of solids at 85% active was added and mixed for 20 minutes. 0.28g of OT75 100% at 0.3% of solids at 75% active was added and mixed for 20 minutes. 0.147g of Span80 100% at 0.2% of solids was added and mixed for 20 minutes. 78.426g of A630, unmodified, at 41.72% of total volume was added and mixed for 15 minutes. 50.06g of A633, unmodified, at 26.63% of total volume was added and mixed for 15 minutes. 51.17g of A623, unmodified, at 27.22% of total volume was added and mixed for 15 minutes. Added nitocellulose solution at 0.125g of total volume of solution, mixed 20 minutes. 0.7g of S104-PG 2% at 0.03% of solids at 50% active was

added and mixed for 25 minutes. The amount of solvent (distilled water and ethanol, 100%), defoamer, germicide and thickener and pigment was based on 40% of solids.

Specific Example 74 52g of modified A630 and 52g of modified A655 were mixed for 10 minutes. 38g of modified A622 was added and mixed for 10 minutes. 30g of modified A1054 was added and mixed for 10 minutes. 2.17g of FC129 1 % at 0.015% of solids at 50% active was added and mixed for 25 minutes. 1.02g of L7602 10% at 0.14% of solids was added and mixed for 20 minutes. 0.364g of Z6040 100% at 0.5% of solids was added and mixed for 20 minutes. 1.46g of Tysor La 100% at 1 % of solids at 50% active was added and mixed for 20 minutes. 0.73g of Suttocide A 100% at 0.5% of solids at 50% active was added and mixed for 20 minutes. 9.07g of Nalco 1140 40% at 5% of solids was added and mixed for 20 minutes. 3.41 g of A196 100% at 0.4% of solids at 85% active was added and mixed for 20 minutes. 0.28g of OT75 100% at 0.3% of solids at 75% active was added and mixed for 20 minutes. 0.147g of Span 80 100% at 0.2% of solids was added and mixed for 20 minutes. 94g of Joncryl 89, unmodified, at 50% of total volume was added and mixed for 15 minutes. 41.83g of Joncryl 77, unmodified, at 22.25% of total volume was added and mixed for 15 minutes. 45.12g of BT44, unmodified, at 24% of total volume was added and mixed for 15 minutes. 18.91 g of N1 140 40% at 5% of solids was added and mixed for 20 minutes. 0.756g of Z6040 100% at 0.5% of solids was added and mixed for 20 minutes. 7.567g of S104-PG 2% at 0.05% of solids at 50% active was added and mixed for 25 minutes. The amount of solvent (distilled water and ethanol, 100%), defoamer, germicide and thickener and pigment was based on 40% of solids.

Specific Example 75 480g of modified A622 and 288g of modified A655 was mixed for 20 minutes. 160g of modified A1054 was added and mixed for 20 minutes. 160g of modified KRS241 1 was added and mixed for 20 minutes. 16.04g of S104E 10% at 0.0205% level of solids at 50% active was added and mixed for 30 minutes. 23.27g of FC129 0.2% at 0.006% level of solids at 50% active was added and mixed for 30 minutes. 14.67g of L7602 4% at 0.15% level of solids was added and mixed for 25 minutes. 2.51 g of Z6040 100% at 0.64% of solids was added and mixed for 25 minutes. 10.09g of Tysor LA 100% at 1.29% level of solids at 50% active was added and mixed for 25 minutes. 3.03g of L7001 10% at 0.058% level of solids at 75% active was added and mixed for 25 minutes. 4.49g of A196 10% at 0.068% level of solids at 85% active was added and mixed for 25 minutes. '3.92g of N115 100% at 0.15% level of solids at 15% active was added and mixed for 25 minutes. 97.44g of ethanol 200 proof was added and mixed for 25 minutes. Suttocide A was added in

quantum sufficient. Thickeners were added in quantum sufficient. The amount of solvent, defoamer, germicide and thickener was based on 35.94% of solids.

Specific Example 76 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 60g of modified A1054 was added and mixed for 10 minutes. 60g of modified KRS2411 was added and mixed for 10 minutes. 5.78g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 4.62g of Silwet 77 1 % at 0.03% of solids was added and mixed for 25 minutes. 5.14g of N1115 10% at 0.05% of solids at 15% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 37.75% of solids.

Specific Example 77 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 60g of modified A1054 was added and mixed for 10 minutes. 72g of modified KRS 2411 was added and mixed for 10 minutes. 6.07g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 6.63g of S-104E 1 % at 0.0205% of solids at 50% active was added and mixed for 25 minutes. 19.40g of FC129 0.1 % at 0.006% of solids at 50% active was added and mixed for 25 minutes. 4.62g of Z604020% at 0.64% of solids was added and mixed for 15 minutes. 13.91 g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 12.51 g of L7001 1 % at 0.058% of solids at 75% active was added and mixed for 15 minutes. 15.42g of N1115 10% at 0.143% of solids at 15% active was added and mixed for 15 minutes. 12.37g of A196 1 % at 0.065% level of solids at 85% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38.50% of solids.

Specific Example 78 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 60g of modified A1054 was added and mixed for 10 minutes. 72g of modified KRS2411 was added and mixed for 10 minutes. 5.78g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 4.62g of Silwet 77 1 % at 0.03% of solids was added and mixed for 25 minutes. 5.18g of Z604020% at 0.64% of solids was added and mixed for 15 minutes. 13.91 g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 5.14g of N1115 10% at 0.05% of solids at 15% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38.50% of solids.

Specific Example 79

360g of modified A622 and 216g of modified A655 were mixed for 20 minutes. 120g of modified A1054 was added and mixed for 20 minutes. 60g of modified KRS2411 was added and mixed for 20 minutes. 5.17g of L7602 10% at 0.18% level of solids was added and mixed for 25 minutes. 8.62g of S77 10% at 0.03% level of solids was added and mixed for 30 minutes. 0.96g of N1115 100% at 0.05% level of solids at 15% active was added and mixed for 25 minutes. 2.3g of Z6040 100% at 0.8% level of solids was added and mixed for 25 minutes. 9.19g of Tysor LA 100% at 1.6% level of solids at 50% active was added and mixed for 25 minutes. 22.98g of propylene glycol 0.8% level of solids was added and mixed for 25 minutes. 2.87g of Suttocide A 100% at 0.5% level of solids at 50% active was added and mixed for 25 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38% of solids.

Specific Example 80

180g of modified A622 and 108g of modified A655 were mixed for 20 minutes. 60g of modified A1054 was added and mixed for 20 minutes. 2.38g of L7602 10% at 0.18% of solids was added and mixed for 25 minutes. 3.97g of S77 1 % at 0.03% level of solids was added and mixed for 30 minutes. 0.44g of N1115 100% at 0.05% level of solids at

15% active was added and mixed for 25 minutes. 30g of modified KRS2411 was added and mixed for 20 minutes. 10.58g of propylene glycol 100% at 0.8% level of solids was added and mixed for 25 minutes. 1.32g of suttocide A 100% at 0.5% level solids at 50% active was added and mixed for 25 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38% of solids.

Specific Example 81

180g of modified A622 and 108g of modified A655 were mixed for 20 minutes. 60g of modified A1054 was added and mixed for 20 minutes. 30g of modified KRS2411 was added and mixed for 20 minutes. 2.59g of L7602 10% at 0.18% level of solids was added and mixed for 25 minutes. 4.31 g of S77 1 % at 0.03% level of solids was added and mixed for 30 minutes. 0.48g of N1115 100% at 0.05% level of solids at 15% active was added and mixed for 25 minutes. 11.49g of propylene glycol at 0.8% level of solids was added and mixed for 25 minutes. 1.44g of Suttocide A 100% at 0.5% level of solids at 50% active was added and mixed for 25 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38% of solids.

Specific Example 82 180g of modified A622 and 108g of modified A655 were mixed for 20 minutes. 1.97g of L7602 10% at 0.18% level of solids was added and mixed for 25 minutes. 3.28g

of S77 1 % at 0.03% level of solids was added and mixed for 30 minutes. 0.36g of N1115 100% at 0.05% level of solids at 15% active was added and mixed for 25 minutes. 20g of modified A1054 was added and mixed for 20 minutes. 0.88g of Z6040 100% at 0.8% level of solids was added and mixed for 25 minutes. 3.5g of Tysor LA 100% at 1.6% level of solids at 50% active was added and mixed for 25 minutes. 8.76g of propylene glycol 100% at 0.8% level of solids was added and mixed for 25 minutes. 1.09g of Suttocide A 100% at 0.5% level of solids at 50% active was added and mixed for 25 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38% of solids.

Specific Example 83 180g of modified A622 and 108g of modified A655 were mixed for 20 minutes.

1.97g of L7602 10% at 0.18% level of solids was added and mixed for 25 minutes. 3.28g of S77 1 % at 0.03% level of solids was added and mixed for 30 minutes. 0.36g of N1115 100% at 0.05% level of solids at 15% active was added and mixed for 25 minutes. 60g of modified A1054 was added and mixed for 20 minutes. 30g of modified KRS2411 was added and mixed for 20 minutes. 0.88g of Z6040 100% at 0.8% level of solids was added and mixed for 25 minutes. 3.5g of Tysor LA 100% at 1.6% level of solids at 50% active was added and mixed for 25 minutes. 8.76g of propylene glycol 8% level of solids was added and mixed for 25 minutes. 1.09g of Suttocide A 100% at 0.5% level of solids at 50% active was added and mixed for 25 minutes. Specific Example 84

180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 4.54g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 3.63g of Silwet 77 1 % at 0.03% of solids was added and mixed for 25 minutes. 4.03g of N1115 10% at 0.05% of solids at 15% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38% of solids.

Specific Example 85 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 6.07g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 6.63g of S- 104E 1 % at 0.0205% of solids at 50% active was added and mixed for 25 minutes. 19.40g of FC129 1 % at 0.006% of solids at 50% active was added and mixed for 25 minutes. 4.62g of Z6040 20% at 0.64% of solids was added and mixed for 15 minutes. 13.91 g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 12.51 g of L7001 1 % at 0.058% of solids at 75% active was added and mixed for 15 minutes. 15.42g of N1115 10% at 0.143% of solids at 15% active was added and mixed for 15 minutes. 12.37g of A196 1 % at 0.065% of solids at 85% active was added and

mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38% of solids.

Specific Example 86 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 14.18g of DF75 1 % at 0.5435% of solids was added and mixed for 15 minutes. 10.70g of S-104E 1% at 0.0205% of solids at 50% active was added and mixed for 25 minutes. 31.33g of FC129 1% at 0.006% of solids at 50% active was added and mixed for 25 minutes. 8.35g of Z6040 20% at 0.64% of solids was added and mixed for 15 minutes. 22.45g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 20.19g of L7001 1 % at 0.058% of solids at 75% active was added and mixed for 15 minutes. 24.89g of N1115 10% at 0.143% of solids at 15% active was added and mixed for 15 minutes. 19.96g of A196 1 % at 0.065% of solids at 85% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38% of solids. The following are additional examples of the method of making the modified coatings:

Specific Example 87 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 60g of modified A1054 was added and mixed for 10 minutes. 60g of modified Z259 was added and mixed for 10 minutes. 5.78g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 4.62g of Silwet 77 1 % at 0.03% of solids was added and mixed for 25 minutes. 5.14g of N1115 10% at 0.05% of solids at 15% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 37.75% of solids. Specific Example 88

180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 60g of modified A1054 was added and mixed for 10 minutes. 60g of modified C525 was added and mixed for 10 minutes. 5.78g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 4.62g of Silwet 77 1 % at 0.03% of solids was added and mixed for 25 minutes. 5.14g of N1115 10% at 0.05% of solids at 15% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 37.75% of solids.

Specific Example 89 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 60g of modified A1054 was added and mixed for 10 minutes. 60g of modified BT44 was added

and mixed for 10 minutes. 5.78g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 4.62g of Silwet 77 1 % at 0.03% of solids was added and mixed for 25 minutes. 5.14g of N1115 10% at 0.05% of solids at 15% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 37.75% of solids.

Specific Example 90 180g of modified A622 and 108g of modified A655 were mixed together for 10 minutes. 120g of modified A1054 was added and mixed for 10 minutes. 90g of modified KRS2411 was added and mixed for 10 minutes. 90g of modified of BT44 was added and mixed for 10 minutes. 90g of modified Z259 was added and mixed for 10 minutes. 90g of modified C525 was added and mixed for 10 minutes. 16.06g of DF75 10% at 0.5435% of solids was added and mixed for 15 minutes. 12.13g of S-104E 1 % at 0.0205% of solids at 50% active was added and mixed for 25 minutes. 35.48g of FC129 0.1 % at 0.006% of solids at 50% active was added and mixed for 25 minutes. 9.46g of Z6040 20% at 0.64% of solids was added and mixed for 15 minutes. 25.43g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 22.87 of L7001 1 % at 0.058% of solids at 75% active was added and mixed for 15 minutes. 28.19g of N1115 10% at 0.143% of solids at 15% active was added and mixed for 15 minutes. 22.61 g of A196 1 % at 0.065% of solids at 85% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38.50% of solids.

Specific Example 91 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 120g of modified A1054 was added and mixed for 10 minutes. 90g of modified KRS2411 was added and mixed for 10 minutes. 90g of modified BT44 was added and mixed for 10 minutes. 90g of modified C525 was added and mixed for 10 minutes. 14.18g of DF75 1 % at 0.5435% of solids was added and mixed for 15 minutes. 10.70g of S-104E 1 % at 0.0205% of solids at 50% active was added and mixed for 25 minutes. 31.33g of FC129 0.1 % at 0.006% of solids at 50% active was added and mixed for 25 minutes. 8.35g of Z6040 20% at 0.64% of solids was added and mixed for 15 minutes 22.45g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 20.19g of L7001 1 % at 0.058% of solids at 75% active was added and mixed for 15 minutes. 24.89g of N1115 10% at 0.143% of solids at 15% active was added and mixed for 15 minutes. 19.96g of A196 1 % at 0.065% of solids at 85% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38.50% of solids.

Specific Example 92

180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 120g of modified A1054 was added and mixed for 10 minutes. 90g of modified KRS2411 was added and mixed for 10 minutes. 90g of modified Z259 was added and mixed for 10 minutes. 90g of modified C525 was added and mixed for 10 minutes. 14.18g of DF75 1 % at 0.5435% of solids was added and mixed for 15 minutes. 10.70g of S-104E 1 % at 0.0205% of solids at 50% active was added and mixed for 25 minutes. 31.33g of FC129 0.1 % at 0.006% of solids at 50% active was added and mixed for 25 minutes. 8.35g of Z6040 20% at 0.64% of solids was added and mixed for 15 minutes 22.45g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 20.19g of L7001 1 % at 0.058% of solids at 75% active was added and mixed for 15 minutes. 24.89g of N1115 10% at 0.143% of solids at 15% active was added and mixed for 15 minutes. 19.96g of A196 1 % at 0.065% of solids at 85% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38.50% of solids. Specific Example 93

180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 120g of modified A1054 was added and mixed for 10 minutes. 90g of modified KRS2411 was added and mixed for 10 minutes. 90g of modified Z259 was added and mixed for 10 minutes. 90g of modified C525 was added and mixed for 10 minutes. 9.79g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 7.83g of Silwet 77 1 % at 0.03% of solids was added and mixed for 25 minutes. 8.35g of Z6040 20% at 0.64% of solids was added and mixed for 15 minutes. 22.45g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 20.19g of L7001 1 % at 0.058% of solids at 75% active was added and mixed for 15 minutes. 24.89g of N1115 10% at 0.143% of solids at 15% active was added and mixed for 15 minutes. 19.96g of A196 1 % at 0.065% of solids at 85% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38.50% of solids.

Specific Example 94 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 120g of modified A1054 was added and mixed for 10 minutes. 90g of modified KRS2411 was added and mixed for 10 minutes. 90g of modified Z259 was added and mixed for 10 minutes. 90g of modified C525 was added and mixed for 10 minutes. 9.79g of L7602 4% at 0.15% of solids was added and mixed for 15 minutes. 10.71 g of S-104E 1 % at 0.0205% of solids at 50% active was added and mixed for 25 minutes. 31.33g of FC129 0.1 % at 0.006% of solids at 50% active was added and mixed for 25 minutes. 8.35g of Z604020%

at 0.64% of solids was added and mixed for 15 minutes 22.45g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 20.19g of L7001 1 % at 0.058% of solids at 75% active was added and mixed for 15 minutes. 26.11 g of N11 15 10% at 0.15% of solids at 15% active was added and mixed for 15 minutes. 19.96g of A196 1 % at 0.065% of solids at 85% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38.50% of solids.

Specific Example 95 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 120g of modified A1054 was added and mixed for 10 minutes. 90g of modified KRS2411 was added and mixed for 10 minutes. 90g of modified Z259 was added and mixed for 10 minutes. 90g of modified C525 was added and mixed for 10 minutes. 9.79g of L7602 4% at 15% of solids was added and mixed for 15 minutes. 7.83g of Silwet 77 1 % at 0.03% of solids was added and mixed for 25 minutes. 8.35g of Z6040 20% at 0.64% of solids was added and mixed for 15 minutes. 22.45g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 26.03g of N1115 10% at 0.15% of solids at 15% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38.50% of solids.

Specific Example 96 180g of modified A622 and 108g of modified A655 were mixed for 10 minutes. 120g of modified A1054 was added and mixed for 10 minutes. 90g of modified KRS2411 was added and mixed for 10 minutes. 90g of modified Z259 was added and mixed for 10 minutes. 90g of modified C525 was added and mixed for 10 minutes. 14.18g of DF75 1 % at 0.5435% of solids was added and mixed for 15 minutes. 10.70g of S-104E 1 % at 0.0205% of solids at 50% active was added and mixed for 25 minutes. 31.33g of FC129 0.1 % at 0.006% of solids at 50% active was added and mixed for 25 minutes. 8.35g of Z6040 20% at 0.64% of solids was added and mixed for 15 minutes 22.45g of Tysor LA 30% at 1.29% of solids at 50% active was added and mixed for 15 minutes. 20.19g of L7001 1 % at 0.058% of solids at 75% active was added and mixed for 15 minutes. 24.89g of N1115 10% at 0.143% of solids at 15% active was added and mixed for 15 minutes. 19.96g of A196 1 % at 0.065% of solids at 85% active was added and mixed for 15 minutes. The amount of solvent, defoamer, germicide and thickener was based on 38.50% of solids. IV. Pigmented Coatings

Pigmented coatings are obtained by adding dispersed treated pigments to the cellulose-based coatings. The dispersed treated pigments are obtained by repeatedly mixing the pigments with silanes, titanates and other additives, and heating until

desiccation. Distilled water may be added at each step to allow for proper mixing. The treated pigments are then milled with a wetting agent and dispersing surfactant. The milled pigment is added to the appropriate coating formula.

Generally, the pigments are placed in a glass beaker and silane is added. Pigments employed in the present invention include but are not limited to D & C red 21 , D & C yellow, D & C cosmetic iron blue, D & C T102 and D & C cosmetic dioxide. Silanes used in the present invention include but are not limited to Z 6040, 25-additive, A 1100, and Z 6020. After mixing the pigments and silane for about 5 minutes, the vessel is heated with occassional stirring until all the liquid is desiccated. Titanate is then added and the mass is mixed for about 5 minutes. The titanates employed in the present invention include Tysor TE, and Tysor LA. The mass is then heated with occassional stirring until all the liquid has dried. Again, silane is added and the mass is mixed for about 5 minutes. The mass is heated and stirred until desiccated. Silane is added and mixed for about 5 minutes. The mass is again heated and stirred until desiccated. The material is placed in a mill, then dispersed with a wetting agent for about 30 minutes. The preferred wetting agent of the present invention is S-104E but others known in the art may be employed. Finally, a dispersing surfactant is added and the material is placed in a mill for about 90 minutes. The preferred dispersing surfactants of the present invention are CT 136 and L7602. The dispersed treated pigments are then added to the coating prepared as described above and mixed for about 20 minutes. The following examples employ the general technique described above to formulate the dispersed treated pigments:

Specific Example 97 .55g D&C red 6, 0.45g D&C red 34 and 1 g Z6040 (10%) at 10% of solids were combined in a glass beaker, mixed for 5 minutes and microwaved at high for 5 minutes. 4g Tysor TE (10%) at 26% of solids at 50% active was added, mixed for 5 minutes and microwaved for 5 minutes at high. 5g of distilled water was added. 0.5g of CMC-7H (1 %) at 0.0625% level of solids was added and mixed for 5 minutes and microwaved for 5 minutes at high.

Specific Example 98 12g D&C red 6 and 24g Z 6040 (10%) at 20% of solids were combined in a glass beaker, mixed for 20 minutes and microwaved at high for 10 minutes. 24g of Tysor TE (10%) at 10% of solids at 50% active was added. 60g of distilled water was added. The combination was mixed for 5 minutes and microwaved at high for 10 minutes. 6g of CMC- 7H (1 %) at 0.5% of solids was added and mixed for 5 minutes and microwaved for 5 minutes at high.

Specific Example 99

14g of D&C red 6 and 14g of Z 6040 (10%) at 10% of solids were combined in a glass beaker, mixed for 5 minutes and microwaved at high for 10 minutes. 28g of Tysor LA (10%) at 10% of solids at 50% active was added. The combination was mixed for 5 minutes and microwaved at high for 10 minutes. 14g of Z 6020 (10%) at 10% of solids was added, mixed for 5 minutes and microwaved at high for 10 minutes. 7g of CMC-7H (1%) at 0.5% solids was mixed for 5 minutes and microwaved for 10 minutes at high.

Specific Example 100

14g of D&C red 6 and 14g of Z 6040 (10%) at 10% of solids were combined in a glass beaker, mixed for 5 minutes and microwaved at high for 10 minutes. 28g of Tysor

LA (10%) at 10% of solids at 50% active was added. The combination was mixed for 5 minutes and then microwaved at high for 10 minutes. 14g of Z 6020 (10%) at 10% of solids was added, mixed for 5 minutes and microwaved at high for 10 minutes. 14g of A

1100 (10%) at 10% of solids was added, mixed for 5 minutes and microwaved at high for 10 minutes. 7g of CMC-7H (1%) at 0.5% solids was added, mixed for 5 minutes and microwaved for 10 minutes at high.

Specific Example 101 4.02g of D&C red 7, 0.8g of D&C red 6, 1.8g of D & C Ti0 ₂ , 3.13g of D&C red 34, 0.01 g of D&C cosmetic iron blue, 0.25g of D&C yellow 5 and 0.02g of D&C cosmetic dioxide (total of 10g of pigment) and 10g of Z 6040 (10%) at 10% of solids were combined in a glass beaker, mixed for 5 minutes and microwaved at high for 10 minutes. 30g of Tysor LA (10%) at 15% of solids at 50% active was added. The combination was mixed for 5 minutes and microwaved at high for 10 minutes. 10g of Z 6020 (10%) at 10% of solids was added, mixed for 5 minutes and microwaved at high for 10 minutes. 10g of A 1100 (10%) at 10% of solids was added, mixed for 5 minutes and microwaved at high for 10 minutes. 5g of CMC-7H (1 %) at 0.5% of solids was added and mixed for 5 minutes and microwaved for 5 minutes at high. 6.67g of NAIco 1115 100% at 10% of solids at 15% active and 10g of distilled water were added, mixed for 5 minutes and microwaved at high for 5 minutes. Specific Example 102

4.02g of D&C red 7, 0.8g of D&C red 6, 1.8g of D&C Ti0 ₂ , 3.13g of D&C red 34,

0.01 g of D&C cosmetic iron blue, 0.25g of D&C yellow 5, 0.02 of D&C cosmetic dioxide

(total of 10g of pigment) and 10g of Z 6040 (10%) at 10% of solids were combined in a glass beaker, mixed for 5 minutes and microwaved at high for 10 minutes. 30g of Tysor LA (10%) at 15% of solids at 50% active was added. The combination was mixed for 5

minutes and microwaved at high for 10 minutes. 10g of Z 6020 (10%) at 10% of solids was added, mixed for 5 minutes and microwaved at high for 10 minutes. 10g of A 1100 (10%) at 10% of solids was added, mixed for 5 minutes and microwaved at high for 10 minutes. 50g of CMC-7H (1 %) at 5% of solids was added and mixed for 5 minutes and microwaved for 5 minutes at high.

Specific Example 103 4.02g of D&C red 7, 0.08 of D&C red 6, 1.8g of D&C Ti0 ₂ , 3.13g of D&C red 34, 0.01 g of D&C cosmetic iron blue, 0.25g of D&C yellow 5, 0.02g of D&C cosmetic dioxide (total of 10g of pigment) and 20g of Z 6040 (10%) of 20% of solids were combined in a glass beaker, mixed for 10 minutes and microwaved at high for 5 minutes. 80g of Tysor LA (10%) at 40% of solids at 50% active was added. The combination was mixed for 5 minutes and microwaved at high for 10 minutes. 20g of Z 6020 (10%) at 20% of solids was added, mixed for 5 minutes and microwaved at high for 10 minutes. 20g of A 1100 (10%) at 20% of solids was added, mixed for 5 minutes and microwaved at high for 10 minutes.

Specific Example 104 10g of pigment, 5g of Z6040 20% at 10% level of solids and 10g of distilled water were combined in a glass beaker, mixed for 5 minutes and microwaved for 4 minutes at high. 20g of Tysor LA or Tysor TE 30% at 30% of solids at 50% active, 1 g of 25-additive 100% at 10% of solids, 5g of Z6020 20% at 10% level of solids and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved for 4 minutes at high. 5g of A1100 20% at 10% level of solids and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved for 4 minutes at high. 30g of CMC-7H 1 % at 3% of solids was then mixed for 5 minutes and microwaved for 4 minutes at high. 20g of Nalco 1115 100% at 30% of solids at 15% active and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved at high for 4 minutes.

Specific Example 105 10g of pigment, 10g of Z6040 20% at 20% level of solids and 10g of distilled water were combined in a glass beaker, mixed for 5 minutes and microwaved for 4 minutes at high. 33.3g of Tysor LA or Tysor TE 30% at 50% of solids at 50% active, 2g of 25-additive 100% at 20% of solids, 10g of Z6020 20% at 20% level of solids and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved for 4 minutes at high. 10g of A1100 20% at 20% level of solids

and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved for 4 minutes at high. 40g of CMC-7H 1 % at 4% of solids was then mixed for 5 minutes and microwaved for 4 minutes at high. 26.67g of Nalco 1115 100% at 40% of solids at 15% active and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved at high for 4 minutes.

Specific Example 106 10g of pigment, 15g of Z604020% at 30% level of solids and 10g of distilled water were combined in a glass beaker, mixed for 5 minutes and microwaved for 4 minutes at high. 40g of Tysor LA or Tysor TE 30% at 60% of solids at 50% active, 5g of 25-additive 100% at 50% of solids, 20g of Z6020 20% at 40% level of solids and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved for 4 minutes at high. 20g of A1100 20% at 40% level of solids and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved for 4 minutes at high. 10g of CMC-7H 1 % at 1 % of solids was then mixed for 5 minutes and microwaved for 4 minutes at high. 10g of Nalco 1115 100% at 15% of solids at 15% active and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved at high for 4 minutes. Specific Example 107

10g of pigment, 20g of Z6040 20% at 40% level of solids and 10g of distilled water were combined in a glass beaker, mixed for 5 minutes and microwaved for 4 minutes at high. 46.67g of Tysor LA or Tysor TE 30% at 70% of solids at 50% active, 6g of 25- additive 100% at 60% of solids, 20g of Z6020 20% at 40% level of solids and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved for 4 minutes at high. 20g of A1100 20% at 40% level of solids and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved for 4 minutes at high. 50g of CMC-7H 1 % at 5% of solids was then mixed for 5 minutes and microwaved for 4 minutes at high. 36.67g of Nalco 1115 100% at 55% of solids at 15% active and 10g of distilled water were combined and added to the above mixture. The mixture was then mixed for 5 minutes and microwaved at high for 4 minutes.

The following examples employ the most preferred method of formulating the pigmented coatings:

Specific Example 108

The coating is prepared by the following method.

60g of modified A630 and 60g of modified A655 were mixed for 10 minutes. 40g of modified A622 was added and mixed for 10 minutes. 20g of modified A1054 was added and mixed for 10 minutes. 0.44g of FC129 5% at 0.015% of solids at 50% active was added and mixed for 25 minutes. 2.04g of L7602 5% at 0.14% of solids was added and mixed for 20 minutes. 0.364g of Z6040 100% at 0.5% of solids was added and mixed for 20 minutes. 1.45g of Tysor La 100% at 1 % of solids at 50% active was added and mixed for 20 minutes. 0.73g of Suttocide A 100% at 0.5% of solids at 50% active was added and mixed for 20 minutes. 9.09g of Nalco 1140 40% at 5% of solids was added and mixed for 20 minutes. 3.42g of A196 100% at 0.4% of solids at 85% active was added and mixed for 20 minutes. 0.29g of 0T75 100% at 0.3% of solids at 75% active was added and mixed for 20 minutes. 0.15g of Span 80 100% at 0.2% of solids was added and mixed for 20 minutes. 63.95g of A630, unmodified, at 31.5% of total volume was added and mixed for 15 minutes. 19.61 g of A633, unmodified, at 9.66% of total volume was added and mixed for 15 minutes. 28.28g of A645, unmodified, at 20% of total volume was added and mixed for 15 minutes. 0.7g of S104-PG 2% at 0.03% of solids at 50% active was added and mixed for 25 minutes. The amount of solvent (distilled water and ethanol, 100%), defoamer, germicide and thickener and pigment was based on 40% of solids, as required. The pigments are treated by the following technique.

10g of Red 27 Alumina Lake/Ti0 ₂ /Zirconium lake. 2g of Z6040 100% at 20% level of solids, 20g of distilled water and the pigment were mixed for 5 minutes and heated until dessicated while mixing. 8.08g of Tysor LA 100% at 40% level of solids at 50% active and 20g of distilled water were added, mixed for 5 minutes and heated until dessicated while mixing. 2g of Z6020 20% at 100% level of solids and 20g of distilled water was added, mixed for 5 minutes and heated until dessicated while mixing. 2g of A1100 100% at 20% level of solids and 20g of distilled water was added, mixed for 5 minutes and heated until dessicated while mixing. 10g of CMC7H 1 % at 1 % level of solids and 20g of distilled was added, mixed for 5 minutes and heated until dessicated while mixing. 5g of N1140 40% at 20% level of solids and 20g of distilled water were added, mixed for 5 minutes and heated until dessicated while mixing.

4g of the above treated pigments was added to a plastic container with metal balls. 4g of S104PG 2% at 1 % level of solids at 50% active was added with 2g ethanol 10% at 5% level and 2g distilled water at 5% of solids. This was milled for 30 minutes. 11.2g of L7602 5% at 14% level of solids was added and milled for 120 minutes.

The above coating was added at 3g of pigment to 100g of coating.

Specific Example 109 The coating is prepared by the following method.

360g of modified A622 and 216g of modified A655 were mixed for 20 minutes. 120g of modified A1054 was added and mixed for 25 minutes. 8.154g of L7602 4% at

0.15% level of solids was added and mixed for 25 minutes. 6.53g of S-77 1 % at 0.03% level of solids was added and mixed for 30 minutes. 0.75g of N1115 100% at 0.05% level of solids at 15% active was added and mixed for 25 minutes. 15.76g of propylene glycol at 8% level were added and mixed for 25 minutes. 2.18g of suttocide A 100% at 0.5% level of solids at 50% active was added and mixed for 25 minutes. Thickener was added in quantum sufficient, 0.2% to 0.8% of total solids. The amount of solvent, defoamer, germicide and thickener was based on 37.75% of solids.

The pigments are treated by the following technique.

6g of Ba lake #6 red, 2g of Orange #5 AL lake, 2g of red #34 Ca lake and 10g of red #7 Ca lake were combined (20g of pigment). 20g of Z604020% at 20% level of solids,

10g of distilled water and the pigment were mixed for 5 minutes and microwaved for 6 minutes at high. 16.08g of Tysor LA 100% at 40% level of solids at 50% active and 10g of distilled water were added, mixed for 5 minutes and microwaved for 6 minutes at high.

20g of Z6020 20% at 20% level of solids and 10g of distilled water was added, mixed for 5 minutes and microwaved for 6 minutes at high. 20g of A110020% at 20% level of solids and 10g of distilled water was added, mixed for 5 minutes and microwaved for 6 minutes at high. 40.2g of CMC7H 1 % at 2% level of solids was added, mixed for 10 minutes and microwaved for 6 minutes at high. 40g of N1115 100% at 30% level of solids at 15% active and 20g of distilled water were added, mixed for 10 minutes and microwaved for 6 minutes at high. 8g of the above treated pigments was added to a metal cylinder with metal balls.

8g of 77 Silwet 1% at 1% level of solids was added and milled for 60 minutes. 1.44g of

L7602 100% at 18% level of solids was added and milled for 120 minutes.

The treated pigments from above are dispersed by the following technique.

8g of treated pigment and 4g of CMC7H 10% at 0.5% level of solids were mixed and milled for 15 minutes. 8g of S104E 2% at 1 % level of solids at 50% active was added and milled for 30 minutes. 1.44g of L7602 100% at 18% level of solids was added and milled for 90 minutes. The coating from above was added in quantum sufficient for desired intensity of color.

The following examples employ a preferred method of formulating the pigmented coatings:

Specific Example 110

52g of modified A630 and 52g of modified A655 were mixed for 10 minutes. 38g of modified A622 was added and mixed for 10 minutes. 30g of modified A1054 was added and mixed for 10 minutes. 2.17g of FC129 1 % at 0.015% of solids at 50% active was added and mixed for 25 minutes. 1.02g of L7602 10% at 0.14% of solids was added and mixed for 20 minutes. 0.364g of Z6040 100% at 0.5% of solids was added and mixed for 20 minutes. 1.46g of Tysor La 100% at 1 % of solids at 50% active was added and mixed for 20 minutes. 0.73g of Suttocide A 100% at 0.5% of solids at 50% active was added and mixed for 20 minutes. 9.07g of Nalco 1140 40% at 5% of solids was added and mixed for 20 minutes. 3.41 g of A196 100% at 0.4% of solids at 85% active was added and mixed for 20 minutes. 0.28g of OT75 100% at 0.3% of solids at 75% active was added and mixed for 20 minutes. 0.147g of Span 80 100% at 0.2% of solids was added and mixed for 20 minutes. 78.426g of A630, unmodified, at 41.72% of total volume was added and mixed for 15 minutes. 50.06g of A633, unmodified, at 26.63% of total volume was added and mixed for 15 minutes. 51.17g of A623, unmodified at 27.22% of total volume was added and mixed for 15 minutes. Added nitocellulose solution at 0.125g of total volume of solution, mixed 20 minutes. 0.7g of S104-PG 2% at 0.03% of solids at 50% active was added and mixed for 25 minutes. The amount of solvent (distilled water and ethanol, 100%), defoamer, germicide and thickener and pigment was based on 40% of solids. The pigments are treated by the following technique.

10g of Red 27 Alumina Lake/Ti0 ₂ /Zirconium lake. 2g of Z6040 100% at 20% level of solids, 20g of distilled water and the pigment were mixed for 5 minutes and heated until dessicated while mixing. 8.08g of Tysor LA 100% at 40% level of solids at 50% active and 20g of distilled water were added, mixed for 5 minutes and heated until dessicated while mixing. 2g of Z6020 20% at 100% level of solids and 20g of distilled water was added, mixed for 5 minutes and heated until dessicated while mixing. 2g of A1100 100% at 20% level of solids and 20g of distilled water was added, mixed for 5 minutes and heated until dessicated while mixing. 20g of CMC7H 1% at 2% level of solids and 20g of distilled was added, mixed for 5 minutes and heated until dessicated while mixing. 5g of N1140 40% at 20% level of solids and 20g of distilled water were added, mixed for 5 minutes and heated until dessicated while mixing.

4g of the above treated pigments was added to a plastic container with metal balls. 4g of S104PG 2% at 1 % level of solids at 50% active was added with 2g ethanol 10% at 5% level and 2g distilled water at 5% of solids. This was milled for 30 minutes. 11.2g of L7602 5% at 14% level of solids was added and milled for 120 minutes.

The above coating was added at 3g of pigment to 100g of coating.

Specific Example 111 The coating is prepared by the following method.

360g of modified A622 and 216g of modified A655 were mixed for 20 minutes. 120g of modified A1054 was added and mixed for 25 minutes. 120g of modified R960 was added and mixed for 25 minutes. 8.154g of L7602 4% at 0.15% level of solids was added and mixed for 25 minutes. 6.53g of S-77 1 % at 0.03% level of solids was added and mixed for 30 minutes. 0.75g of N1115 100% at 0.05% level of solids at 15% active was added and mixed for 25 minutes. 15.76g of propylene glycol at 8% level were added and mixed for 25 minutes. 2.18g of suttocide A 100% at 0.5% level of solids at 50% active was added and mixed for 25 minutes. Thickener was added in quantum sufficient, 0.2% to 0.8% of total solids. The amount of solvent, defoamer, germicide and thickener was based on 37.75% of solids.

The pigments are treated by the following technique. 6g of Ba lake #6 red, 2g of Orange #5 AL lake, 2g of red #34 Ca lake and 10g of red #7 Ca lake were combined (20g of pigment). 20g of Z604020% at 20% level of solids,

10g of distilled water and the pigment were mixed for 5 minutes and microwaved for 6 minutes at high. 16.08g of Tysor LA 100% at 40% level of solids at 50% active and 10g of distilled water were added, mixed for 5 minutes and microwaved for 6 minutes at high. 20g of Z6020 20% at 20% level of solids and 10g of distilled water was added, mixed for

5 minutes and microwaved for 6 minutes at high. 20g of A1100 20% at 20% level of solids and 10g of distilled water was added, mixed for 5 minutes and microwaved for 6 minutes at high. 40.2g of CMC7H 1 % at 2% level of solids was added, mixed for 10 minutes and microwaved for 6 minutes at high. 40g of N1115 100% at 30% level of solids at 15% active and 20g of distilled water were added, mixed for 10 minutes and microwaved for 6 minutes at high. 8g of the above treated pigments was added to a metal cylinder with metal balls.

8g of 77 Silwet 1 % at 1% level of solids was added and milled for 60 minutes. 1.44g of

L7602 100% at 18% level of solids was added and milled for 120 minutes.

The treated pigments from above are dispersed by the following technique. 8g of treated pigment and 4g of CMC7H 10% at 0.5% level of solids were mixed and milled for 15 minutes. 8g of S104E 2% at 1 % level of soϋds at 50% active was added and milled for 30 minutes. 1.44g of L7602 100% at 18% level of solids was added and milled for 90 minutes. The coating from above was added in quantum sufficient for desired intensity of color.

Specific Example 112

The coating is prepared by the following method.

480g of modified A622 and 288g of modified A655 were mixed for 20 minutes.

160g of modified A1054 was added and mixed for 20 minutes. 160g of modified KRS2411 was added and mixed for 20 minutes. 16.04g of S104E 10% at 0.0205% level of solids at

50% active was added and mixed for 30 minutes. 23.27g of FC129 0.2% at 0.006% level of solids at 50% active was added and mixed for 30 minutes. 14.67g of L7602 4% at

0.15% level of solids was added and mixed for 25 minutes. 2.51 g of Z6040 100% at 0.64% of solids was added and mixed for 25 minutes. 10.09g of Tysor LA 100% at 1.29% level of solids at 50% active was added and mixed for 25 minutes. 3.03g of L7001 10% at

0.058% level of solids at 75% active was added and mixed for 25 minutes. 4.49g of A196

10% at 0.068% level of solids at 85% active was added and mixed for 25 minutes. 3.92g of N115 100% at 0.15% level of solids at 15% active was added and mixed for 25 minutes.

97.44g of ethanol 200 proof was added and mixed for 25 minutes. Suttocide A was added in quantum sufficient. Thickeners were added in quantum sufficient.

The pigments are treated by the following technique.

20g of pigment, 20g of Z604020% at 20% level of solids and 10g of distilled water were mixed for 5 minutes and microwaved for 6 minutes at high. 40g of Tysor LA 40% at

40% level of solids at 50% active was added, mixed for 5 minutes and microwaved for 6 minutes at high. 6g of #25 (Dow Corning) at 100% at 30% level of solids, 20g of Z6020

20% at 20% level of solids and 10g of distilled water was added, mixed for 5 minutes and microwaved for 6 minutes at high. 20g of A1100 20% at 20% level of solids and 10g of distilled water was added, mixed for 5 minutes and microwaved for 6 minutes at high. 40g of CMC7H 1% at 20% level of solids and 20g of distilled water were added, mixed for 5 minutes and microwaved for 6 minutes at high. 40g of N1115 100% at 30% level of solids at 15% active was added, mixed for 5 minutes and microwaved for 6 minutes at high.

The treated pigments from above are dispersed by the following technique.

5g of treated pigment, 5g of S77 1 % at 1 % level of solids, and 20g of distilled water were placed in a shaker and were shaken for 60 minutes. 0.9g of L7602 100% at 18% level of solids was added and shaken for 120 minutes. The treated and dispersed pigments were then added to 120g of the above coating.