Carboxylated cellulose ester and manufacture thereof

A process for the preparation of carboxylated cellulose esters comprising the steps of

• (a) providing a cellulose ester in solid particulate form to a reaction zone;
• (b) intimately contacting said cellulose ester in said reaction zone with a gaseous stream comprising at least about 0.25 weight percent ozone;
• and
• (c) reacting said cellulose ester with said ozone at a temperature of about 25.degree. to 80.degree. C. for a period of time sufficient to yield a carboxylated cellulose ester having an acid number of at least about 5.

A process for the preparation of carboxylated cellulose esters comprising the steps of

• (a) providing a cellulose ester in the form of a powder to a reaction zone;
• (b) fluidizing said cellulose ester in said reaction zone with a gaseous stream comprising at least about 0.25 weight percent ozone;
• and
• (c) reacting said cellulose ester with ozone at a temperature of about 25.degree. to 80.degree. C. for a period of time of about 0.5 to 24 hours.

A process for the preparation of carboxylated cellulose esters comprising the steps of

• (a) providing to a reaction zone a cellulose ester in the form of a powder having a moisture content less than about 5 percent by weight;
• (b) fluidizing said cellulose ester in said reaction zone with a gaseous stream comprising about 1 to 3 percent by weight of ozone;
• and
• (c) reacting said cellulose ester with ozone at a temperature of about 50.degree. to 75.degree. C. for a period of time of about 1 to 12 hours.

The process for preparing carboxylated cellulose ester material comprising contacting at from about 50.degree. C. to about 75.degree. C., cellulose ester material with ozone fed to a fluidized bed reactor for a sufficient period to carboxylate said material, converting said reactor to a closed loop system wherein the ozone feed is terminated, recirculating the gasses present in said system at from about 70.degree. C. to about 100.degree. C. and adding a volatile organic acid thereto in vapor form to a concentration of from about 0.2% to about 2.2% by weight of the initial ester material charge, continuing said recirculation until the Hoeppler viscosity of the carboxylated material is between about 20 and about 200 cps. determined using a 20% by wt. solution of said material in an 85/15 weight ratio of n-butyl acetate/n-butyl alcohol and calculated from the equation

• N=T(S-D)K
• wherein:
• T=time in seconds for the ball to pass between the reference marks in the sample;
• S=specific gravity of ball used;
• D=density of XAE sample solution at temperature of determination;
• and
• K=tube constant for the particular ball used,
• and purging the system at elevated temperature until the total free acid content is less than about 0.5% by weight of said initial material charge.

A clear-on-base metal coating system comprising:

• (A) a nonaqueous base film comprising
• (a) a first film-forming material comprising
• (i) about 20 to 50 percent by weight of a carboxylated cellulose ester having an acid number of at least about 5 and an inherent viscosity of about 0.01 to 1.00 determined according to ASTM D2857-70 procedure at 25.degree. C. using a polymer concentration of 0.5% by weight in 60/40 by weight, phenol/tetrachloroethane solvent, and
• (ii) correspondingly about 50 to 80 percent by weight of a film-forming resin comprising an alkyd resin, a melamine resin, a polyester resin, an acrylic resin, a urethane resin, or a mixture thereof,
• (b) uniformly dispersed pigments, and
• (c) volatile organic solvents for said first film-forming material, and
• (B) a transparent coating composition deposited on said base film without substantial intermixing or intersolution of said base film and said transparent coating composition, said transparent coating composition comprising
• (a) a second film-forming material comprising an alkyd resin, a polyester resin, an acrylic resin, a urethane resin, or a mixture thereof, and
• (b) volatile organic solvents for said second film-forming material.

A metal coating which is the reaction product of approximately stoichiometric quantities of

• (A) a first component consisting essentially of a reactive polyfunctional isocyanate material, and
• (B) a second component comprising
• (i) about 20 to 100% by weight of a carboxylated cellulose ester having an acid number of at least about 5 and an inherent viscosity of about 0.01 to 1.00 determined according to ASTM D2857-70 procedure at 25.degree. C. using a polymer concentration of 0.5% by weight in 60/40 by weight, phenol/tetrachloroethane solvent, and
• (ii) correspondingly about 0 to 80% by weight of a thermosetting acrylic resin.

A urethane wood finish comprising

• (A) about 1 to 60 percent by weight, based upon the total weight of film-forming components, of a carboxylated cellulose ester having an acid number of at least about 5 and an inherent viscosity of about 0.01 to 1.00 determined according to ASTM D2857-70 procedure at 25.degree. C. using a polymer concentration of 0.5% by weight in 60/40 by weight, phenol/tetrachloroethane solvent;
• (B) 0 to about 50 percent by weight, based upon the total weight of film-forming components, of a urethane-forming polyol;
• and
• (C) about 15 to 65 percent by weight, based upon the total weight of film-forming components, of a urethane-forming polyfunctional isocyanate.

A urethane wood finish comprising

• (A) about 40 to 55 percent by weight of a carboxylated cellulose ester having an acid number of at least about 5 and an inherent viscosity of about 0.01 to 1.00 determined according to ASTM D2857-70 procedure at 25.degree. C. using a polymer concentration of 0.5% by weight in 60/40 by weight, phenol/tetrachloroethane solvent;
• (B) about 2 to 10 percent by weight of a urethane-forming polyol;
• (C) about 35 to 60 percent by weight of a urethane-forming polyfunctional isocyanate;
• and
• (D) a quantity of a solvent which is substantially free of reactive hydroxyl groups, or a mixture of such solvents, which is sufficient to solvate components (A) and (B).

A wood finish modifying lacquer which is compatible with nitrocellulose-based furniture lacquers, said modifying lacquer comprising

• (A) about 20 to 80 percent by weight, based upon the total weight of components (A), (B), (C), and (D), of a carboxylated cellulose ester having an acid number of at least about 5 and an inherent viscosity of about 0.01 to 1.00 determined according to ASTM D2857-70 procedure at 25.degree. C. using a polymer concentration of 0.5% by weight in 60/40 by weight, phenol/tetrachloroethane solvent;
• (B) 0 to about 50 percent by weight, based upon the total weight of components (A), (B), (C), and (D), of an alkyd resin;
• (C) 0 to about 50 percent by weight, based upon the total weight of components (A), (B), (C), and (D), of a maleic resin;
• (D) 0 to about 30% by weight, based upon the total weight of components (A), (B), (C), and (D), of a plasticizer;
• and
• (E) a solvating quantity of a solvent comprising a lower alkyl ester of a lower carboxylic acid, a lower alkyl ketone, a hydrocarbon having about 5 to 12 carbon atoms, a lower aliphatic alcohol, or a mixture thereof, provided that one or both of components (B) and (C) is present in a total concentration of at least about 10% by weight, based upon the total weight of components (A), (B), (C), and (D), and further provided that the total concentration of components (B) and (D) is at least about 20% by weight, based upon the total weight of components (A), (B), (C), and (D).

An ink composition having improved color development and improved adhesion to plastic substrates, said ink composition comprising

• (A) about 30 to 70 percent by weight of a carboxylated cellulose ester having an acid number of at least about 5 and an inherent viscosity of about 0.01 to 1.00 determined according to ASTM D2857-70 procedure at 25.degree. C. using a polymer concentration of 0.5% by weight in 60/40 by weight, phenol/tetrachloroethane solvent;
• (B) correspondingly about 30 to 70 percent by weight of an ink pigment;
• (C) an ink solvent in a quantity sufficient to provide a viscosity which is suitable for applying said ink composition;
• and
• (D) up to about 15 percent by weight, based upon the total weight of the composition, of each of one or more modifiers comprising maleic resins, acrylic resins, sucrose ester resins, phthalate plasticizers, polyester resins, urea-formaldehyde resins, or mixtures thereof, provided that the total concentration of said modifiers in said composition does not exceed about 60 percent by weight.