WO2007145955A2 - Procédés d'amélioration des propriétés de brillance, d'étalement et de résistance à la coulure de compositions de revêtement comprenant des esters mixtes de cellulose de faible poids moléculaire - Google Patents

Procédés d'amélioration des propriétés de brillance, d'étalement et de résistance à la coulure de compositions de revêtement comprenant des esters mixtes de cellulose de faible poids moléculaire Download PDF

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WO2007145955A2
WO2007145955A2 PCT/US2007/013253 US2007013253W WO2007145955A2 WO 2007145955 A2 WO2007145955 A2 WO 2007145955A2 US 2007013253 W US2007013253 W US 2007013253W WO 2007145955 A2 WO2007145955 A2 WO 2007145955A2
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cellulose
esters
degree
cab
coating composition
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PCT/US2007/013253
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English (en)
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WO2007145955A3 (fr
Inventor
Deepanjan Bhattacharya
Hampton Loyd Chip Williams, Iii
Roy Glenn Foulk
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Eastman Chemical Company
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Priority claimed from US11/810,011 external-priority patent/US20080085953A1/en
Priority claimed from US11/810,065 external-priority patent/US20070282038A1/en
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Publication of WO2007145955A2 publication Critical patent/WO2007145955A2/fr
Publication of WO2007145955A3 publication Critical patent/WO2007145955A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/10—Esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/16—Esters of inorganic acids
    • C09D101/18—Cellulose nitrate

Definitions

  • This invention belongs to the field of cellulose chemistry, and more particularly, to low molecular weight cellulose mixed esters that are useful in coating and ink compositions as low viscosity binder resins and rheology modifiers.
  • Cellulose esters are valuable polymers that are useful in many plastic, film, coating, and fiber applications.
  • Cellulose esters (CEs) are typically synthesized by the reaction of cellulose with an anhydride or anhydrides corresponding to the desired ester group or groups, using the corresponding carboxylic acid as diluent and product solvent. Some of these ester groups can afterward be hydrolyzed to obtain a partially-esterified product.
  • These partially substituted cellulose esters have great commercial value, and find use in coatings, where their greater solubility and compatibility with co-resins (in comparison with triesters) and hydroxyl group content (to facilitate crosslinking) are prized.
  • U.S. Pat. No. 2,129,052 advised that hydrolysis under severe conditions such as high temperature or high concentration of catalyst caused degradation of the cellulose, the resulting products being unsuitable for commercial use because of their low strength.
  • U.S. Pat. No. 2,801 ,239 relating to the use of zinc chloride as an esterification catalyst, cited as an advantage that the process minimized the rate of breakdown of the cellulose.
  • U.S. Pat. No. 3,518,249 acknowledged that little interest had been shown in cellulose esters of an extremely low degree of polymerization.
  • conventional cellulose esters When used in coating compositions, conventional cellulose esters provide many benefits, including improved hardness, improved aluminum flake orientation, high clarity, high gloss, decreased dry-to-touch time, improved flow and leveling, improved redissolve resistance, reduced cratering, and reduced blocking.
  • the performance properties of conventional cellulose esters are accompanied by an increase in viscosity, which must be offset by increasing the level of solvents used.
  • a cellulose ester product that provides the benefits of conventional cellulose esters, while providing only a moderate increase in viscosity without the addition of organic solvents. It would clearly be an advance in the art to provide cellulose esters that provide the performance properties of conventional cellulose esters, without an undue increase in viscosity when incorporated into coating compositions.
  • U.S. Pat. No. 3,386,932 discloses a method for reducing the molecular weight of cellulose triacetate with a catalyst such as boron trifluoride, the resulting bifunctional, low molecular weight cellulose triacetate then being used to produce linear block copolymers.
  • This disclosure emphasizes the importance of maintaining the ester substitution at the 2-, 3-, and 6-positions of the triacetate, that is, wherein substantially all of the hydroxyl groups of the cellulose have been esterified, so that the hydroxy! functionality necessary for formation of the linear block copolymers preferentially appears only on the ends of the polymer chains.
  • U.S. Pat. No. 4,532,177 describes base coat compositions that include a film- forming resin component, selected from alkyd, polyester, acrylic and polyurethane resins, from 1.0 to 15.0 % by weight pigment, and from 2.0 % to 50.0 % by weight of a cellulose ester material.
  • the '177 patent suggests a solution viscosity for the cellulose ester material from 0.05 - 0.005 seconds, an acetyl content from 10.0 - 15.0 % by weight, a propionyl content from 0.1 - 0.8 % by weight, a butyryl content from 36.0 - 40.0 % by weight, and a free- hydroxyl content of from 1.0 - 2.0 % by weight.
  • the examples of the '177 patent use a cellulose ester having a solution viscosity of 0.01 , which is approximately equivalent to an inherent viscosity (IV) for such an ester of from about 0.25 to about 0.30 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane (PM95) at 25°C.
  • IV inherent viscosity
  • PM95 phenol/tetrachloroethane
  • WO 91/16356 describes a process for the preparation of low molecular weight, high-hydroxyl cellulose esters by treating a cellulose polymer with trifluoroacetic acid, a mineral acid, and an acyl or aryl anhydride in an appropriate carboxylic solvent, followed by optional in situ hydrolysis.
  • the cellulose esters obtained according to the disclosure are said to have a number average molecular weight (M n ) ranging from about 0.01 x 10 5 (about 1 ,000) to about 1.0 x 10 5 (about 100,000), and an IV (inherent viscosity) from about 0.2 to about 0.6, as measured at a temperature of 25°C for a 0.25 gram sample in 100 ml of a 60/40 by weight solution of phenol/tetrachloroethane.
  • M n number average molecular weight
  • Japanese Kokai Patent Publication No. 51-119089 describes a process for the preparation of a low molecular weight cellulose mixed organic acid ester that involves heating cellulose acetate with a saturated or unsaturated organic acid of 3 or more carbon atoms (propionyl or higher), in the presence of an acid catalyst, with removal of the resulting acetic acid from the reaction mixture, to obtain a lower molecular weight cellulose mixed organic acid ester.
  • the starting material for this process is cellulose acetate.
  • Japanese Kokai Patent Publication No. 51-119088 discloses a method for the manufacture of a low molecular weight cellulose organic acid ester that includes heating cellulose acetate with a saturated or unsaturated organic acid at a temperature above 30 0 C in the presence of a cation exchange resin, the resulting ester having a lower molecular weight than the starting material.
  • the starting material for the disclosed process is cellulose acetate.
  • U.S. Pat. No. 6,303,670 discloses an ultraviolet-curable cellulosic coating composition comprising a cellulose acetate, a diepoxy compound, and a photo cationic polymerization catalyst.
  • the cellulose acetate useful in these compositions is a low molecular weight cellulose acetate, having a number- average molecular weight of from 1 ,500 to 5,000, and is prepared from cellulose triacetate by hydrolysis. According to this disclosure, the degree of substitution of hydroxyl groups must be from 1 to 3, since hydroxyl values of less than 1 are said to result in insufficient crosslinking in the final coating composition.
  • the present applicants have unexpectedly discovered that relatively low molecular weight cellulose mixed esters, which were thought to lack the properties necessary to provide the performance characteristics of conventional molecular weight esters, can be incorporated into coating compositions, without an undue increase in viscosity, and without the high levels of solvent heretofore necessary in the preparation of high solids coatings containing cellulose esters. Also surprisingly, the properties of the resulting coatings, when the coating compositions are applied and cured, are comparable in most respects to those made using conventional molecular weight esters.
  • esters according to the invention exhibit improved solubilities in a variety of organic solvents, compatibility with various co-resins, and suitable melt stability after prolonged exposure to melt temperatures. Further advantages of the inventive esters are set forth in the following.
  • the cellulose mixed esters according to the present invention are low in molecular weight, have a high maximum degree of substitution (are highly substitutable), and provide high solids, low viscosity coating compositions, with none of the drawbacks typically associated with low molecular weight cellulose esters, such as formation of brittle films.
  • the inventive esters do not themselves unduly increase the viscosity of the compositions, providing the advantages of conventional cellulose esters without the drawbacks typically associated with their use, such as an undesirable increase in organic solvent levels to maintain the desired viscosity.
  • the new cellulose mixed esters can be utilized in high solids or low VOC coating compositions as the majority component, thereby reducing or eliminating the amount of resin utilized.
  • coating compositions comprising the new cellulose mixed esters can have at least one of the following advantages: 1 ) polishability tests after 24 hours indicated that a much higher level of 20 degree gloss for the coating compositions comprising the inventive cellulose mixed ester as compared to commercial product offerings;
  • drying rheology is improved over coating compositions without the cellulose mixed ester, which leads to improved anti-sag properties.
  • Coating compositions comprising the inventive cellulose mixed esters are particularly useful in clear coat compositions for refinishing clearcoat/colorcoat finishes of vehicles such as automobiles and trucks.
  • Clearcoat/colorcoat finishes for vehicles have been used and are very popular. Such finishes can be produced by a wet-on-wet method, in which the colorcoat or basecoat which is pigmented is applied and dried for a short period of time but not cured and then the clearcoat, which provides protection for the colorcoat and improves the appearance of the overall finish such as gloss and distinctness of image, is applied thereover and both are cured together. Repair of such clearcoat/colorcoat finishes that have been damaged e.g. in a collision, has been difficult. Using current technology, the clearcoat refinish compositions can take many hours to cure to a sufficiently hard and water resistant state at ambient or slightly elevated temperatures suitable for automobile refinishing. In addition, the vehicle cannot be moved outside to free up work space in the autobody repair shop without risk of water spotting nor can the clearcoat be sanded or buffed to a high gloss finish on the same day of application.
  • Fig. 1 is a graph plotting log viscosity as a function of concentration for solutions of cellulose esters according to the invention and conventional cellulose esters.
  • Fig. 2 is a graph of the 20 degree gloss for an inventive coating composition comprising a cellulose mixed ester in comparison to several commercial products.
  • Fig. 3 is a graph of the 20 degree gloss versus the steps in a typical polishing procedure for an inventive coating composition comprising a cellulose mixed ester in comparison to several commercial products.
  • Fig. 4 is a plot of the variability in 20 degree gloss readings over a 48 hour polishability window for an inventive coating composition comprising a cellulose mixed ester in comparison to several commercial products.
  • Optional or optionally means that the subsequently described event or circumstances may or may not occur.
  • the description includes instances where the event or circumstance occurs, and instances where it does not occur.
  • Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value.
  • CAB means a cellulose acetate butyrate
  • CAP means a cellulose acetate propionate
  • CA means a cellulose acetate
  • CMCAB means a carboxymethylcellulose acetate butyrate
  • CMCAP means a carboxymethylcellulose acetate propionate
  • CMCA means a carboxymethylcellulose acetate
  • HS-CAB means an inventive high solids cellulose acetate butyrate according to the invention, having a high maximum degree of substitution, a low degree of polymerization, a low intrinsic viscosity (IV), and a low molecular weight.
  • HS-CAB-55 refers to an inventive high solids cellulose acetate butyrate with a high maximum degree of substitution, a low degree of polymerization, a low IV, a low molecular weight, and a high butyryl content (high-butyryl, or from about 52 to about 55 wt.%), prepared along the lines of Example 3, unless noted otherwise;
  • HS-CAB-46 refers to an inventive high solids cellulose acetate butyrate with a high maximum degree of substitution, a low degree of polymerization, a low IV, a low molecular weight, and a medium to high butyryl content (high mid-butyryl, or from about 43 to about 51 wt.%), prepared along the lines of Examples 21-22 unless noted otherwise;
  • HS-CAB-38 refers to an inventive high solids cellulose acetate butyrate with a high maximum degree of substitution, a low degree of polymerization, a low IV, a low molecular weight, and a medium
  • the invention relates to cellulose mixed esters having a total degree of substitution per anhydroglucose unit of from about 3.08 to about 3.50, and having the following substitutions: a degree of substitution per anhydroglucose unit of hydroxyl of no more than about 0.70; a degree of substitution per anhydroglucose unit of C3-C4 esters from about 0.80 to about 1.40, and a degree of substitution per anhydroglucose unit of acetyl of from about 1.20 to about 2.34.
  • the inventive mixed esters exhibit an inherent viscosity from about 0.05 to about 0.15 dl_/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25 0 C; a number average molecular weight (M n ) of from about 1 ,000 to about 5,600; a weight average molecular weight (M w ) of from about 1 ,500 to about 10,000; and a polydispersity of from about 1.2 to about 3.5.
  • the ester may comprise butyryl, or propionyl, or mixtures of the two.
  • the degree of substitution per anhydroglucose unit of hydroxyl may be from about 0.05 to about 0.70; the inherent viscosity may be from about 0.05 to about 0.12 dl_/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25 0 C; or the number average molecular weight (M n ) may be from about 1 ,500 to about 5,000.
  • a preferred polydispersity may be from 1.2 to 2.5; a preferred inherent viscosity from 0.07 to 0.11 dL/g; or a preferred number average molecular weight (M n ) from about 1,000 to about 4,000.
  • a preferred inherent viscosity may be from about 0.07 to about 0.11 dl_/g; or a preferred number average molecular weight (M n ) from about 1 ,000 to 4,000.
  • the invention relates to cellulose mixed esters having a total degree of substitution per anhydroglucose unit of from about 3.08 to about 3.50, and having the following substitutions: a degree of substitution per anhydroglucose unit of hydroxyl of no more than about 0.70; a degree of substitution per anhydroglucose unit of C 3 -C 4 esters from about 1.40 to about 2.45, and a degree of substitution per anhydroglucose unit of acetyl of from 0.20 to about 0.80.
  • the inventive mixed esters exhibit an inherent viscosity of from about 0.05 to about 0.15 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25 0 C; a number average molecular weight (M n ) of from about 1 ,000 to about 5,600; a weight average molecular weight (M w ) of from about 1 ,500 to about 10,000; and a polydispersity of from about 1.2 to about 3.5.
  • the ester may comprise butyryl, or propionyl, or mixtures of the two.
  • the degree of substitution per anhydroglucose unit of hydroxyl may be from about 0.05 to about 0.70; the inherent viscosity may be from about 0.05 to about 0.12 dl_/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25 ?C; or the number average molecular weight (M n ) may be from about 1 ,500 to about 5,000.
  • a preferred polydispersity may be from 1.2 to 2.5; a preferred inherent viscosity from 0.07 to 0.11 d!_/g; or a preferred number average molecular weight (M n ) from about 1 ,000 to about 4,000.
  • a preferred inherent viscosity may be from about 0.07 to about 0.11 dL/g; and a preferred number average molecular weight (M n ) from about 1 ,000 to 4,000.
  • the invention relates to cellulose mixed esters having a total degree of substitution per anhydroglucose unit of from about 3.08 to about 3.50, and having the following substitutions: a degree of substitution per anhydroglucose unit of hydroxyl of no more than about 0.70; a degree of substitution per anhydroglucose unit of C 3 -C 4 esters from about 2.11 to about 2.91, and a degree of substitution per anhydroglucose unit of acetyl of from 0.10 to about 0.50.
  • the inventive mixed esters may exhibit an inherent viscosity of from about 0.05 to about 0.15 dL/g, as measured in a 60/40 (wtJwt.) solution of phenol/tetrachloroethane at 25 0 C; a number average molecular weight (M n ) of from about 1 ,000 to about 5,600; a weight average molecular weight (M w ) of from about 1 ,500 to about 10,000; and a polydispersity of from about 1.2 to about 3.5.
  • the ester may comprise butyryl, or propionyl, or mixtures of the two.
  • the degree of substitution per anhydroglucose unit of hydroxyl may be from about 0.05 to about 0.70; the inherent viscosity may be from about 0.05 to about 0.12 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25 0 C; or the number . average molecular weight (M n ) may be from about 1 ,500 to about 5,000.
  • a preferred polydispersity may be from 1.2 to 2.5; a preferred inherent viscosity from 0.07 to 0.11 dl_/g; and a preferred number average molecular weight (M n ) from about 1 ,000 to about 4,000.
  • a preferred inherent viscosity may be from about 0.07 to about 0.11 dl_/g; and a preferred number average molecular weight (M n ) from about 1,000 to 4,000.
  • these resins are especially useful in coating and ink formulations. They are soluble in a wide range of solvents and solvent blends, as demonstrated in the examples of this application, making them particularly suited for custom coating formulations.
  • a cellulose mixed ester having a maximum degree of substitution of from about 3.08 to about 3.50, a degree of substitution per anhydroglucose unit of hydroxy! from about 0.01 up to about 0.70, a degree of substitution per anhydroglucose unit Of C 3 -C 4 esters of about 0.8 to about 3.50, a degree of substitution per anhydroglucose unit of acetyl from about 0.05 to about 2.00, and having an inherent viscosity of about 0.05 to about 0.15 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25 0 C.
  • a cellulose mixed ester having a maximum degree of substitution of from about 3.08 to about 3.50, a degree of substitution per anhydroglucose unit of hydroxyl from about 0.01 up to about 0.70, a degree of substitution per anhydroglucose unit of C 3 -C 4 esters of about 0.8 to about 3.50, a degree of substitution per anhydroglucose unit of acetyl from about 0.05 to about 2.00, and having an inherent viscosity of about 0.05 to about 0.15 dl_/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25 0 C.
  • a cellulose acetate butyrate having a maximum degree of substitution of from about 3.08 to about 3.50, and a degree of substitution per anhydroglucose unit of hydroxyl from about 0.01 to about 0.70, and a degree of substitution per anhydroglucose unit of butyryl of about 0.80 to about 3.44, and a degree of substitution per anhydroglucose unit of acetyl of about 0.05 to about 2.00, and having an inherent viscosity of 0.05 to 0.15 dl_/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25 °C.
  • the inherent viscosity may be from 0.07 to 0.11 dL/g, the degree of substitution per anhydroglucose unit of hydroxyl from 0.10 to 0.70, butyryl from 1.10 to 3.25, or acetyl from 0.10 to 0.90.
  • esters according to this embodiment exhibit solubility in a wide range of solvents and solvent blends.
  • a cellulose acetate propionate having a degree of substitution per anhydroglucose unit of hydroxyl from about 0.01 to about 0.70, and a degree of substitution per anhydroglucose unit of propionyl of about 0.80 to about 3.44 and a degree of substitution per anhydroglucose unit of acetyl of from about 0.05 to about 2.00, and having an inherent viscosity of about 0.05 to about 0.15 dl_/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25 0 C.
  • the inherent viscosity may be from 0.07 to 0.11 dl_/g, the degree of substitution per anhydroglucose unit of hydroxyl from 0.10 to 0.70, the degree of substitution per anhydroglucose unit of propionyl from 1.10 to 3.25, or the degree of substitution per anhydroglucose unit of acetyl of from 0.10 to 0.90.
  • Various esters according to this embodiment exhibit solubility in a wide range of solvents and solvent blends.
  • the source of cellulose be a natural cellulose as just described, and that the source of cellulose not be a modified cellulose such as a cellulose ether, e.g. an alkyl cellulose.
  • the cellulose starting material not be a carboxyalkylcellulose, such as carboxymethylcellulose, or any cellulose derivative having acid functionality.
  • the cellulose esters of the invention may be prepared by a multi-step process.
  • cellulose is water-activated, followed by water displacement via solvent exchange with an alkanoic acid such as acetic acid, followed by treatment with a higher alkanoic acid (propionic acid or butyric acid) to give a cellulose activate wet with the appropriate alkanoic acid.
  • the cellulose activate is treated with the desired anhydride, in the presence of a strong acid catalyst such as sulfuric acid, to give essentially a fully- substituted cellulose ester having a lower molecular weight than conventional esters.
  • a solution consisting of water and an alkanoic acid is added slowly to the anhydrous "dope" solution so as to allow removal of combined sulfur from the cellulose backbone.
  • the final addition allows a slow transition through the hydrous point to give a period of low water concentration and high temperature (as a result of the exotherm from water reacting with excess anhydride) in the reaction medium.
  • This is important for hydrolysis of combined sulfur from the cellulose backbone.
  • This product is then hydrolyzed using sulfuric acid to provide a partially substituted cellulose ester.
  • Hydrolysis is important to provide gel-free solutions in organic solvents, and to provide better compatibility with other resins in coatings applications.
  • the hydroxyl groups exposed during hydrolysis are also important crosslinking sites in many coatings applications.
  • either the fully substituted or partially hydrolyzed forms of cellulose ester are isolated by diluting the final neutralized "dope" with an equal volume of acetic acid followed by precipitation of the diluted "dope" into a volume of water about 20 to 30 times its weight, to give a particle that can be easily washed with deionized water to efficiently remove residual organic acids and inorganic salts.
  • a fairly sticky precipitate is initially formed.
  • the precipitate can be hardened by exchanging the precipitation liquid for fresh water and allowing the precipitate to stand. The hardened precipitate can then be easily washed and ground up as necessary.
  • the key descriptors of the composition of a cellulose ester are the level of substitution of the various ester groups (i.e. degree of substitution or wt. % are commonly used and are discussed in detail in other parts of this application), the level of hydroxyl groups, and the size of the polymer backbone, which can be inferred from IV, viscosity, and GPC data.
  • the key factors that influence the resulting composition of the inventive cellulose mixed esters thus produced are: acetic anhydride level, acetic acid level, butyric (or propionic) anhydride level, butyric (or propionic) acid level, water level, cellulose level, catalyst type, catalyst level, time, and temperature.
  • higher catalyst loadings, higher temperatures, and/or longer reaction times during esterification are used to produce the inventive cellulose esters, having lower molecular weights than conventional esters.
  • the sulfuric acid is neutralized after the esterification or hydrolysis reactions are complete by addition of a stoichiometric amount of an alkali or alkaline earth metal alkanoate, for example magnesium acetate, dissolved in water and an alkanoic acid such as acetic acid.
  • an alkali or alkaline earth metal alkanoate for example magnesium acetate
  • an alkanoic acid such as acetic acid.
  • either the fully substituted or partially hydrolyzed forms of cellulose ester are isolated by diluting the final neutralized "dope" with an equal volume of acetic acid followed by precipitation of the diluted "dope" into a volume of water about 20 to 30 times its weight, to give a particle that can be easily washed with deionized water to efficiently remove residual organic acids and inorganic salts.
  • a fairly sticky precipitate is initially formed.
  • the precipitate can be hardened by exchanging the precipitation liquid for fresh water and allowing the precipitate to stand. The hardened precipitate can then be easily washed and ground up as necessary.
  • the cellulose esters according to the invention have a weight average molecular weight, M w> as measured by GPC, of from about 1,500 to about 10,000; or from about 2,000 to about 8,500; a number average molecular weight, M n , as measured by GPC, of from about 1,500 to about 6,000; and a polydispersity, defined as M w /M n , from about 1.2 to about 7, or from about 1.2 to about 3.5, or from about 1.2 to about 2.5.
  • cellulose mixed esters according to the invention exhibit compatibility with a wide variety of co-resins, compatibility being defined as the ability of two or more resins, when mixed together, to form a stable homogeneous mixture useful as a coating composition.
  • an HS-CAB with approximately 38 wt.% butyryl exhibits compatibilities with Eastman's Acrylamac 2328, Akzo Nobel's Microgel, Eastman's Duramac 2314, Bayer's Desmodur 3300, Rhodia's XIDT, and Bayer's Desmodur IL, equal to or better than commercial higher-butyryl-content samples such as CAB-551-0.01 (cellulose acetate butyrate containing approximately 55 wt. % butyryl, available from Eastman Chemical Company).
  • inventive cellulose mixed esters having approximately 38 wt. % butyryl, or approximately 55 wt.
  • butyryl are compatible at a 1:1 ester to resin loading with acrylic resins that are not compatible with many conventional molecular weight cellulose esters. Such dramatic shifts in compatibility allow formulators to use a mid-butyryl ester (about 38 wt. %) in applications that might otherwise require a higher butyryl CAB for compatibility purposes.
  • An advantage to being able to use a mid-butyryl ester instead of a high-butyryl ester is that when all properties aside from butyryl level and acetyl level remain constant, i.e. hydroxyl value and molecular weight, the mid-butyryl CAB has a higher T 9 than its high-butyryl counterpart.
  • Another advantage to using a mid-butyryl ester over a high-butyryl ester is that mid-butyryl commercial esters are often less soluble in particular solvents and solvent blends than their high-butyryl counterparts. This same trend is generally observed when comparing mid-butyryl HS-CAB's with high-butyryl HS-CAB's of equivalent molecular weight and hydroxyl content.
  • inventive mid-butyryl esters (HS-CAB-38) according to the invention have better compatibility with co-resins than a conventional molecular weight high butyryl cellulose ester such as a CAB-551-0.01 , while exhibiting a similar solubility.
  • coatings formulators can use the inventive esters of the invention in basecoat formulations that cannot tolerate the viscosity increase imparted by the addition of conventional CAB's, while providing the redissolve resistance typical of conventional esters having a higher butyryl content.
  • inventive mixed esters likewise demonstrate better-than- expected redissolve resistance in certain systems. This is surprising, since the inventive mixed esters have a molecular weight lower than conventional cellulose mixed esters. One would instead expect to see a decrease in redissolve resistance with a lowering in molecular weight.
  • coatings formulators can use the inventive esters of the invention in basecoat formulations that cannot tolerate the viscosity increase imparted by the addition of conventional CAB's, while providing the necessary redissolve resistance.
  • cellulose esters according to the invention have excellent melt stability after prolonged exposure to melt temperatures.
  • inventive esters exhibit a better-defined melting point, as further described herein, making them especially suitable for uses where a well-defined melting point is necessary. Not being bound by theory, we attribute this to a lower polydispersity value than conventional esters.
  • cellulose esters are considered to have a maximum degree of substitution of 3.0.
  • a DS of 3.0 indicates that there are 3.0 reactive hydroxyl groups in cellulose that can be derivatized.
  • Native cellulose is a large polysaccharide with a degree of polymerization from 700 - 2,000, and thus the assumption that the maximum DS is 3.0 is approximately correct.
  • Table 1 gives the DSwiax at various degrees of polymerization. Mathematically, a degree of polymerization of 401 is required in order to have a maximum DS of 3.00. As the table indicates, the increase in DSwi a x that occurs with a decrease in DP is slow, and for the most part, assuming a maximum DS of 3.00 is acceptable. However, once the DP is low enough, for example a DP of 21 , then it becomes appropriate to use a different maximum DS for all calculations.
  • the present invention thus provides a cellulose ester with a high maximum degree of substitution and a low degree of polymerization.
  • the inventive esters of the present application having a high maximum degree of substitution and a low degree of polymerization, unexpectedly exhibit rheological performance similar to conventional cellulose esters having a much higher degree of polymerization. It is quite surprising that an HS-CAB with such a low degree of polymerization would display such rheological performance.
  • the cellulose esters according to the invention exhibit a fairly random substitution pattern of hydroxyl groups. We believe that this random substitution pattern of hydroxy! groups is achieved by performing the molecular weight reduction step prior to hydrolysis of the ester groups.
  • the low molecular weight cellulose ester products of the prior art processes generally exhibit a non-random substitution pattern, particularly at C-4 of the non-reducing terminus and at C-1 (RT1) of the reducing terminus.
  • the products of the prior art generally have a hydroxyl group at C-4 and either a hydroxyl or ester at C-1 (RT-1) depending on whether the process is a hydrolysis or an acetolysis reaction.
  • the widely accepted mechanism presented in Scheme 1 may help the reader to visualize the explanation above.
  • the proposed mechanism presented in Scheme 1 depicts the reaction of a polysaccharide with a high degree of polymerization, the nature of the groups at C4 and RT1 being influenced by the amount of cleavage that occurs.
  • the substitution at the two carbons of interest, C4 and RT1 increases to large levels as more and more glycosidic bonds are cleaved.
  • Scheme 1 shows only a single glycosidic bond being cleaved and thus only one C4 and one RT1 site have the substitution pattern displayed by products generated by the prior art. As more and more sites are cleaved, the effect of the substitution pattern at C4 and RT1 becomes more important.
  • Cellulose mixed esters of the invention have utility in pigment dispersions by blending the cellulose ester and a pigment with heat and/or shear to disperse the pigment.
  • pigments can be easily dispersed in coating formulations and plastics, thereby providing high coloring power and good transparency while using a minimal amount of pigment.
  • Such pigment dispersions can be improved by the use of the cellulose esters of the present invention in place of conventional cellulose esters.
  • the cellulose mixed esters of the present invention impart markedly improved wetting properties to the pigment dispersion.
  • Mixtures of C2 - C 4 esters of cellulose and pigments at pigment: ester weight ratios of about 20:80 to 50:50 may be prepared.
  • These dispersions can be prepared on a two-roll mill or in a ball mill, Kady mill, sand mill, or the like.
  • the high DSMBX, low DP cellulose esters of this invention have an advantage over conventional cellulose esters in that they have less of an impact on the viscosity, and thus allow formulations with a higher binder (resin) loading to be used.
  • the present invention provides a pigment dispersion comprising about 20 to 77 weight percent of a pigment and correspondingly about 33 to 80 percent by weight of a C2 - C4 ester of cellulose having an inherent viscosity of about 0.05 to 0.15 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25 0 C, and a degree of substitution per anhydroglucose unit of C2 - C4 esters of about 0.8 to about 3.5.
  • esters of the invention are easily formulated into either lacquer or enamel type coatings where they are used as rheology modifiers and/or binder components providing improved aluminum flake orientation and improved hardness. They can provide a water-clear, high gloss, protective coating for a variety of substrates, especially metal and wood.
  • An additional advantage when used for example to prepare pigments for use in plastics or coatings, relates to an increase in melt stability exhibited by the esters of the invention.
  • the inventive HS-CABs have a sharper melting range than commercial CAB's, possibly due to the tighter polydispersity of HS-CAB's versus conventional CAB's.
  • HS-CAB's can be blended with a pigment to produce a pigment dispersion.
  • the pigment dispersions can be prepared by a number of routes including a slurry method and by extrusion.
  • the improved melt stability is advantageous in extruder applications, since yellowing of the cellulosic is reduced or eliminated.
  • Cellulose esters of this invention exhibit improved solubility and compatibility (i.e., film clarity) characteristics over many conventional cellulose esters (cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, or cellulose acetate butyrate).
  • conventional mid-butyryl cellulose esters such as CAB-381-0.1 (available from Eastman Chemical Company, Kingsport, TN), as evidenced for example in Comparative Example 31 and Example 49, are not readily soluble in Eastman C-11 ketone (a mixture of saturated and unsaturated, linear and cyclic ketones), Eastman DIBK (diisobutyl ketone), PP (propylene glycol monopropyl ether), Eastman EP solvent (ethylene glycol monopropyl ether), Eastman EB solvent (ethylene glycol monobutyl ether), methanol, Tecsol C solvent, 95 % (ethanol with methanol, methyl isobutyl ketone, and ethyl acetate as denaturants with 5% water), toluene, or a 90/10 isopropyl alcohol/ water blend.
  • Eastman C-11 ketone a mixture of saturated and unsaturated, linear and cyclic ketones
  • Eastman DIBK diisobutyl ketone
  • inventive esters such as certain of the HS-CAB-38s (as exemplified in Example 28 and Example 49) of the invention are soluble in each of the solvents or solvent systems described above.
  • soluble as used throughput the specification, we mean that a clear solution is obtained when a 10 % (wt/wt) mixture of the cellulose ester in the desired solvent is prepared, unless stated otherwise.
  • conventional high-butyryl cellulose esters such as CAB- 551-0.01 (available from Eastman Chemical Company), as evidenced in Comparative Example 32 and Example 49, are not readily soluble in methanol, Tecsol C solvent, 95 %, toluene (the ester gels), or a 90/10 isopropyl alcohol/ water blend.
  • certain inventive esters such as certain of the high-butyryl cellulose esters (HS-CAB-55's), as evidenced in Example 29 and some of the inventive esters of Example 49, are soluble in each of the solvents or solvent systems described above.
  • low-butyryl cellulose esters such as CAB-171-15S (available from Eastman Chemical Company), as evidenced in Comparative Example 33, are not readily soluble in Eastman PM solvent (propylene glycol monomethyi ether), and only partially soluble in Eastman PM acetate (propylene glycol methyl acetate) and Eastman DM solvent (diethylene glycol methyl ether).
  • certain inventive esters such as certain of the low- butyryl cellulose esters HS-CAB-17s and HS-CAB-20s, as evidenced in Example 30 and Example 49, are soluble in each of these solvents or solvent systems.
  • the inventive esters are soluble in most classes of typical coating solvents, including ketones, esters, alcohols, glycol ethers, and glycol ether esters, while tolerating dilution with water or aromatic hydrocarbons.
  • the esters of the present invention exhibit viscosities in organic solutions that in many cases differ substantially from those of conventional molecular weight esters.
  • the viscosities of an HS-CAB-38 (Sample 4, Table 4) and an HS-CAB-55 (Sample 5, Table 4) are compared to the lowest viscosity commercial cellulose esters, CAB-381-0.1 and CAB-551-0.01 , of comparable butyryl content, using as solvent a 90/10 by weight mixture of n-butyl acetate/xylene.
  • Figure 1 shows a representative comparison of the relative viscosity at each measured concentration. The log viscosities vs.
  • mid-butyryl cellulose esters such as CAB-381-0.1 (available from Eastman Chemical Company, Kingsport, TN), as evidenced in Example 34, exhibit a viscosity greater than 500,000 centipoise (in a 90/10 by weight mixture of n-butyl acetate/xylene) as a 50 wt. % solution.
  • certain inventive esters having comparable butyryl content exhibit viscosities in the same solution of less than 500 centipoise at a 50 wt.% solution.
  • certain inventive low-butyryl cellulose esters such as HS-CAB-17, as can be seen in Table 6A of Example 34, exhibit viscosities no greater than 6,000 centipoise, and others no greater than 3,000 ce ⁇ tipose, as a 50 wt.% solution in a 90/10 by weight mixture of n-butyl acetate/xylene.
  • esters of the present invention are relatively hard polymers, i.e., about 12 Knoop Hardness Units (KHU), and have high glass transition temperatures. They can be added to other resins to improve the coating hardness, and to improve properties such as slip, sag resistance, and mar resistance. To further improve the toughness, crosslinkers such as melamines or isocyanates may be added to react with these esters or with other resins.
  • KHU Knoop Hardness Units
  • the esters of the present invention may possess free hydroxyl groups, and thus may be utilized in conjunction with crosslinking agents such as melamines and isocyanates.
  • crosslinking agents such as melamines and isocyanates.
  • Such melamines are preferably compounds having a plurality of -N(CH 2 OR) 2 functional groups, wherein R is C 1 - C 4 alkyl, preferably methyl.
  • the melamine cross-linking agent may be selected from compounds of the following formula, wherein R is independently C 1 - C 4 alkyl:
  • preferred cross-linking agents include hexamethoxymethylamine, tetramethoxymethylbenzo-guanamine, tetramethoxymethylurea, mixed butoxy/methoxy substituted melamines, and the like.
  • the most preferred melamine cross-linking agent is hexamethoxymethylamine.
  • Typical isocyanate crosslinking agents and resins include hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), and toluene diisocyanate.
  • HMDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • toluene diisocyanate hexamethylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • toluene diisocyanate toluene diisocyanate
  • the cellulose esters of this invention are effective flow additives for high solids coatings formulations. Addition of the cellulose esters according to the invention to high solids coatings formulations generally results in the elimination of surface defects in the film upon curing/drying (i.e. elimination of pinholing and orange peel).
  • a distinct advantage that high DSwiax, low DP cellulose esters have over conventional cellulose esters is that the inventive esters have a minimal impact on solution and/or spray viscosity when added to high solids coatings formulations.
  • the percent solids can be increased, thus reducing the VOC of the formulation.
  • Conventional cellulose esters can be used in these same applications as flow additives, but a reduction in solids must generally accompany the addition of the conventional cellulose esters. That is, the solvent level must be increased so as to maintain a desirable viscosity.
  • the present invention provides a coating composition
  • a coating composition comprising
  • compositions of the invention the total weight of (a), (b), and (c) will of course equal 100%.
  • the cellulose mixed esters of the present invention may also be utilized in waterborne coating compositions.
  • the inventive esters may be dissolved in organic solvents, treated with either an amine or a surfactant, and dispersed in water.
  • solvents include, but are not limited to, 2-butanone, methyl amyl ketone, methanol, ethanol, ethyl 3-ethoxypropionate, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, and the like.
  • Dispersion of the cellulose esters of the present invention in water is facilitated by addition of an amine or a surfactant.
  • dispersing agents and surfactants include sodium bis(tridecyl) sulfosuccinnate, di(2-ethyl hexyl) sodium sulfosuccinnate, sodium dihexylsulfosuccinnate, sodium dicyclohexyl sulfosuccinnate, diamyl sodium sulfosuccinnate, sodium diisobutyl sulfosuccinate, disodium iso-decyl sulfosuccinnate, disodium ethoxylated alcohol half ester of sulfosuccinnic acid, disodium alkyl amido polyethoxy sulfosuccinnate, tetrasodium N-(1,2- dicarboxy-ethyl)-N-oxtadecyl sulfosuccinnamate, disodium N- octasulfosuccinnamate, sulfated ethoxylated nony
  • inventive cellulose esters may be combined with one or more co-resins to assist dispersion.
  • the amount of suitable aqueous solvent in the dispersed coating composition of such embodiments may be from about 50 to about 90 wt %, or from about 75 to about 90 wt %, of the total coating composition.
  • a waterborne coating composition comprising:
  • a coating composition comprising at least one cellulose mixed ester, at least one crosslinking agent, and optionally, at least one resin; wherein the cellulose mixed ester is in an amount ranging from about 51% by weight to about 100% by weight, based on the total weight of the cellulose mixed ester and the resin.
  • the cellulose mixed ester and crosslinking agent can be any compound previously disclosed.
  • the cellulose mixed ester is cellulose acetate butyrate.
  • the crosslinking agent is a polyisocyanate or melamine.
  • the resin can be any resin known in the art for use in coating compositions.
  • examples of such resin include, but are not limited to, polyesters, polyester- amides, cellulose esters other than those disclosed herein, alkyds, polyurethanes, epoxy resins, polyamides, acrylics, vinyl polymers, polyisocyantes, melamines, phenolics, urea resins, urethane resins, polyamides, and mixtures thereof.
  • a coating composition comprises at least one cellulose mixed ester, at least one crosslinking agent, at least one solvent, and optionally, at least one resin; wherein the cellulose mixed ester is in an amount ranging from about 51 % by weight to about 100% by weight, based on the total weight of said cellulose mixed ester and the resin.
  • the cellulose mixed ester, crosslinking agent, and solvent can be any compound previously disclosed as such.
  • the cellulose mixed ester is cellulose acetate butyrate.
  • the crosslinking agent is a polyisocyanate or a melamine.
  • the amount of cellulose mixed ester and resin is about 5 weight percent to about 95 weight percent of the total weight of cellulose mixed ester, solvent, and resin.
  • the solvent can be an organic solvent or a solvent mixture.
  • the amount of crosslinki ⁇ g agent ranges from about 5 weight percent to about 40 weight percent based on the total weight of cellulose mixed ester and resin, preferably from about 10 weight percent to about 30 weight percent.
  • the amount of resin can range from about 0 weight percent to about 49 weight percent based on the total weight of cellulose mixed ester and resin, preferably from about 10 weight percent to about 40 weight percent.
  • the coating composition comprises at least one cellulose mixed ester, at least one hydroxy-containing acrylic polymer, at least one crosslinking agent, and at least one curing catalyst.
  • the cellulose mixed ester has previously been described in this disclosure.
  • the hydroxy-containing acrylic polymer can be any that is known in the art capable of being used in a coating composition.
  • the hydroxy-containing acrylic polymer can be prepared by conventional solution polymerization techniques in which monomers, solvents, and polymerization catalyst are charged into a conventional polymerization reactor and heated to about 60 0 C to about 200 0 C for about 0.5 to about 6 hours to form a hydroxy-containing acrylic polymer having a weight average molecular weight of about 2,000 to about 13,000. Another range for weight average molecular weight is from about 3,000 to about 11 ,000. The weight average molecular weight was determined by gel permeation chromatography using a polymethyl methacrylate standard.
  • the hydroxy-containing acrylic polymer can have a glass transition temperature (Tg) of at least 30 0 C. Another range for the Tg is from about 40 0 C to about 80 0 C. All glass transition temperatures disclosed herein are determined by differential scanning calorimetry (DSC).
  • Typical useful polymerization catalysts are azo type catalysts, such as, azo- bis-isobutyronitrile, 1 ,1'-azo-bis(cyanocyclohexane); acetates, such as, t-butyl peracetate; peroxides, such as, di-t-butyl peroxide; benzoates, such as, t-butyl perbenzoate; octoates, such as, t-butyl peroctoate, and the like.
  • azo type catalysts such as, azo- bis-isobutyronitrile, 1 ,1'-azo-bis(cyanocyclohexane)
  • acetates such as, t-butyl peracetate
  • peroxides such as, di-t-butyl peroxide
  • benzoates such as, t-butyl perbenzoate
  • octoates such as, t-butyl peroctoate, and the like.
  • the hydroxy-containing acrylic polymer comprises polymerized monomers of styrene, a first methacrylate, a second methacrylate, and a hydroxyl alkyl methacrylate or acrylate having 1-8 carbon atoms in the alkyl group.
  • the first methacrylate can be at least one selected from the group consisting of methyl methacrylate, isobornyl methacrylate, cyclohexy methacrylate, and mixtures thereof.
  • the second methacrylate can be at least one selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, ethyl hexyl methacrylate, and mixtures thereof.
  • the hydroxyl alkyl methacrylate or acrylate can be at least one selected from the group consisting of hydroxyl ethyl methacrylate, hydroxyl propyl methacrylate, hydroxyl butyl methacrylate, hydroxyl ethyl acrylate, hydrox propyl acrylate, hydroxyl butyl acrylate, and mixtures thereof.
  • the amount of polymerized monomers comprising the hydroxy-containing acrylic polymer ranges from about 5 to about 30% by weight styrene residues, about 1 to about 50% by weight of a first methacrylate residues, about 30 to about 60% by weight the second methacrylate residues, and about 10 to about 40% by weight of the hydroxyl alkyl methacrylate residues.
  • the total percentage of monomer residues in the hydroxy-containing acrylic polymer equal 100%.
  • the amount of polymerized monomers comprising the hydroxy-containing acrylic polymer ranges from about 5 to about 30% by weight styrene residues; about 1 to about 50% by weight isobomyl methacrylate residues, about 30 to about 60% ethyl hexyl methacrylate residues, and about 10 to about 40% by weight hydroxyl ethyl methacrylate residues and hydroxyl propyl methacrylate residues combined.
  • the amount of polymerized monomers comprising the hydroxy-containing acrylic polymer ranges from about 5 to about 30% by weight styrene residues; about 1 to about 50% by weight of at least one first methacrylate residue selected from the group consisting of methyl methacrylate, isobutyl methacrylate, isobornyl methacrylate, and ethyl hexyl methacrylate; about 30 to about 60% of at least one second methacrylate residue selected from the group consisting of methyl methacrylate, isobutyl methacrylate, isobornyl methacrylate, and ethyl hexyl methacrylate, and about 10 to about 40% by weight hydroxyl ethyl methacrylate residues.
  • Blends of more than one hydroxy-containing acrylic polymer can be utilized.
  • the hydroxy-containing acrylic polymer can contain about 0.5% to about 2% by weight of acrylamide or methacrylamide such as n-tertiary butyl acrylamide or methacrylamide.
  • crosslinking agent was previously described in this disclosure.
  • the curing catalyst can be any catalyst known in the art capable of increasing the reaction time between the hydroxy-containing acrylic polymer and the crosslinking agent.
  • the curing catalyst can be any catalyst known in the art capable of curing the coating composition in about 6 hours or less. Other ranges of curing times are less than or equal to about 4 hours; less than or equal to about 2 hours; less than or equal to 1 hour; and less than or equal to 30 minutes.
  • the curing catalyst is capable of yielding a pot life of at least 30 minutes at ambient temperatures.
  • a pot life of at least 30 minutes at ambient temperatures is generally sufficient for completion of a refinish job.
  • the curing catalyst is at least one selected from the group consisting of an organotin compound, a tertiary amine, and an organic acid.
  • organotin compounds include, but are not limited to, organotin carboxylates, particularly dialkyl tin carbosylates of aliphatic carboxylic acids, such as, dibutyl tin dilaurate, dibutyl tin dioctoate, dibutyl tin diacetate, and the like.
  • organotin carboxylates particularly dialkyl tin carbosylates of aliphatic carboxylic acids, such as, dibutyl tin dilaurate, dibutyl tin dioctoate, dibutyl tin diacetate, and the like.
  • Zn, Cd, Pd organometallic
  • tertiary amines include, but are not limited to, tertiary aliphatic monoamines or diamines, particularly trialkylene diamines, such as, triethylene diamine, N'alkyl trimethylenediamine, such as, N,N,N'-trimethyl-N'- tallow-I .S-diaminopropane, and the like; and trialkylamines such as, tridodecylamine, trihexadecylamine, N,N'-dimethylalkyl amine, such as N 1 N'- dimethyldodecyl amine, and the like.
  • the alkyl or alkylene portions of these amines may be linear or branched and may contain 1 to about 20 carbon atoms.
  • Ultraviolet and infrared light can also be utilized as a curing catalyst.
  • the amount of hydroxy-containing acrylic polymer is that which is sufficient to give hardness and chemical resistance to a coating composition given the particular use of the coating composition.
  • the amount of hydroxy-containing acrylic polymer ranges from about 60% by weight to about 95% by weight based on the weight of the coating composition. Another range is from about 60% by weight to about 90% by weight based on the weight of the coating composition, and another range is from about 70% to about 85%.
  • the amount of cellulose mixed ester can range from about 3% by weight to about 40% by weight based on the weight of the coating composition. Another range is from about 10% by weight to about 40% by weight based on the weight of the coating composition, and another range is from about 15% to about 30%.
  • the amount of the crosslinking agent depends on the amount of hydroxy- containing acrylic polymer utilized in the coating composition.
  • the amount of the crosslinking agent is typically less than about 2% by weight based on the weight of the hydroxy-containing acrylic polymer.
  • the amount of the curing catalyst is typically less than or equal to about 10% by weight based on the weight of the coating composition. Other ranges for the amount of curing catalyst is less than or equal to 5% and less than or equal to 2% by weight based on the weight of the coating composition.
  • the inventive coating composition can be a liquid or a powder. If in a liquid state, the coating composition further comprises at least one solvent.
  • the solvent can be any that is known in the art for producing coating compositions. Solvents have been previously described in this disclosure. If in powder form, the coating composition can be utilized as a powered coating composition.
  • a method of improving the gloss of a coating composition comprises contacting at least one hydroxy-containing acrylic polymer, at least one cellulose mixed ester, at least one crosslinking agent, and at least one curing catalyst to produce the coating composition; applying the coating composition to a substrate; and drying the coating composition; wherein the 20 degree gloss of the coating composition is improved over a coating composition without the cellulose mixed ester.
  • a method of improving the gloss of a refinish clearcoat composition comprises contacting at least one hydroxy-containing acrylic polymer, at least one cellulose mixed ester, at least one crosslinking agent, and at least one curing catalyst to produce a refinish clearcoat composition; applying the coating composition to a substrate; and drying the coating composition; wherein the 20 degree gloss of the coating composition is improved over a coating composition with the cellulose mixed ester.
  • a method of improving the 20 degree gloss variability of a coating composition is provided.
  • a method of improving the 20 degree gloss variability of a refinish clearcoat composition comprises contacting at least one hydroxy-containing acrylic polymer, at least one cellulose mixed ester, at least one crosslinking agent, and at least one curing catalyst to produce a refinish clearcoat composition; applying the coating composition to a substrate; and drying the coating composition; wherein the variability of the 20 degree gloss over a period of 48 hours is improved over a coating composition without the cellulose mixed ester.
  • the cellulose mixed ester is dissolved in solvent.
  • the order of addition is such that the crosslinking agent and hydroxy-containing acrylic polymer are contacted in the last step.
  • the hydroxy-containing acrylic polymer and the curing agent can be added in a first step followed by the crosslinking agent.
  • the crosslinking agent and curing catalyst can be added first then the hydroxy-containing acrylic polymer.
  • the cellulose mixed ester can be added with the hydroxy-containing acrylic polymer.
  • Other additives can be added at any time and in any order. These additives to coating compositions are described subsequently in this disclosure.
  • the following order of addition is made: 1) hydroxy-containing acrylic polymer; 2) curing catalyst; 3) antioxidant; 4) flow additive; 5) cellulose mixed ester; and 6) crosslinking agent.
  • the above compositions are further comprised of one or more coatings additives.
  • coatings additives are generally present in a range of about 0.1 to 15 weight percent, based on the total weight of the composition.
  • coatings additives include leveling, rheology, and flow control agents such as silicones, fluorocarbons or cellulosics; flatting agents; pigment wetting and dispersing agents; surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti-skinning agents; anti-flooding and anti-floating agents; fungicides and mildewcides; corrosion inhibitors; thickening agents; or coalescing agents.
  • flatting agents examples include synthetic silica, available from the Davison Chemical Division of W. R. Grace & Company under the trademark SYLOIDTM; polypropylene, available from Hercules Inc., under the trademark HERCOFLATTM; synthetic silicate, available from J. M Huber Corporation under the trademark ZEOLEXTM; and polyethylene.
  • dispersing agents and surfactants include sodium bis(tridecyl) sulfosuccinnate, di(2-ethylhexyl) sodium sulfosuccinnate, sodium dihexylsulfosuccinnate, sodium dicyclohexyl sulfosuccinnate, diamyl sodium sulfosuccinnate, sodium diisobutyl sulfosuccinate, disodium isodecyl sulfosuccinnate, disodium ethoxylated alcohol half ester of sulfosucci ⁇ nic acid, disodium alkyl amido polyethoxy sulfosuccinnate, tetrasodium ⁇ /-(1 ,2- dicarboxy-ethyl)- ⁇ /-oxtadecyl sulfosuccinnamate, disodium N- octasulfosuccinnamate, sulfated ethoxy
  • viscosity, suspension, and flow control agents examples include polyaminoamide phosphate, high molecular weight carboxylic acid salts of polyamine amides, and alky I amine salt of an unsaturated fatty acid, all are available from BYK Chemie U.S.A. under the trademark ANTI TERRATM.
  • Further examples include polysiloxane copolymers, polyacrylate solution, cellulose esters, hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide wax, polyolefin wax, carboxymethyl cellulose, ammonium polyacrylate, sodium polyacrylate, and polyethylene oxide.
  • fungicides examples include 4,4- dimethyloxazolidine, 3,4,4-trimethyl-oxazolidine, modified barium metaborate, potassium /V-hydroxy-methyl-N-methyldithiocarbarnate, 2-(thiocyano- methylthio) benzothiazole, potassium dimethyl dithiocarbamate, adamantane, ⁇ /-(trichloromethylthio) phthalimide, 2,4,5,6-tetrachloroisophthalonitrile, orthophenyl phenol, 2,4,5-trichlorophenol, dehydroacetic acid, copper naphthenate, copper octoate, organic arsenic, tributyl tin oxide, zinc naphthenate, and copper 8-quinolinate.
  • U.V. absorbers and U.V. light stabilizers include substituted benzophenone, substituted benzotriazole, hindered amine, and hindered benzoate, available from American Cyanamide Company under the trade name Cyasorb UV, and available from Ciba Geigy under the trademark
  • TINUVIN diethyl-S-acetyW-hydroxy-benzyl-phosphonate, 4-dodecyloxy- 2-hydroxy benzophenone, and resorcinol monobenzoate.
  • a formulated coating composition containing the cellulose esters of the present invention is applied to a substrate and allowed to dry.
  • the substrate can be, for example, wood; plastic; metal, such as aluminum or steel; cardboard; glass; cellulose acetate butyrate sheeting; and various blends containing, for example, polypropylene, polycarbonate, polyesters such as polyethylene terephthalate, acrylic sheeting, as well as other solid substrates.
  • Pigments suitable for use in the coating compositions according to the present invention are the typical organic and inorganic pigments, well-known to one of ordinary skill in the art of surface coatings, especially those set forth by the Colour Index, 3d Ed., 2d Rev., 1982, published by the Society of Dyers and Colourists in association with the American Association of Textile Chemists and Colorists. Examples include, but are not limited to the following: Cl Pigment White 6 (titanium dioxide); Cl Pigment Red 101 (red iron oxide); Cl Pigment Yellow 42, Cl Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 (copper phthalocyanines); Cl Pigment Red 49:1 ; and Cl Pigment Red 57:1.
  • the conventional cellulose acetate butyrates described in this invention were commercial samples from Eastman Chemical Company, Kingsport, Tennessee, as follows: CAB-171-15, CAB-381-0.1 , CAB-381-0.5, CAB-381- 20, CAB-551-0.01 and CAB-551-0.2.
  • Commercial CMCAB samples were from Eastman Chemical Company as follows: CMCAB-641-0.5 and CMCAB- 641-0.2.
  • Desmodur HL was obtained from Bayer as a 60% solution in butyl acetate.
  • Eastman's Polymac HS 220-2010 (polyester), Eastman's Duramac HS 2706 (alkyd resin), Eastman's Polymac HS 5776 (polyester), Eastman's Acrylamac 232-1700 (acrylic resin), Versamid 750 (polyamide), UCAR's VYHD (polyvinyl chloride/acetate), Eastman's Duramac 207-2706 (TOFA short oil alkyd resin), Eastman's Duramac 5205 (coconut medium oil alkyd resin), Cytec's Cymel 303 (HMM melamine), Cytec's Beetle 65 (urea-formaldehyde), Bayer's Des N 3300 (polyisocyante), DuPont's
  • Strike-in means redissolve of the basecoat caused by the solvents in a clearcoat and typically results in a mottled or muddy appearance of the basecoat pigment/metal flakes.
  • High Solids Coatings are coatings with a higher % solids in the formulation than traditional coatings, this typically means coatings formulations with a % solids level greater than or equal to 60 %.
  • Medium Solids Coatings are coatings with a higher % solids in the formulation than low solids coatings, this typically means coatings formulations with a % solids level between 40 % and 60 %.
  • Low Solids Coatings are coatings with a low % solids in the formulation, this typically means coatings formulations with a % solids level less than 40 %.
  • Gloss is a subjective term used to describe the relative amount and nature of mirror like reflection.
  • Orange Peel is a paint surface appearance resembling an orange skin texture.
  • a Surface Defect is any abnormality on the surface of a coating that adversely affects the appearance of the coating; examples include pinholes, craters, and orange peel.
  • Pinholes are film surface defects characterized by small pore-like flaws in a coating, which extend entirely through the coating and have the general appearance of pinpricks.
  • Craters are small bowl-shaped depressions frequently having drops or bands of material at their centers and raised circular edges in a coating film.
  • Craterinq is the formation in a wet coating film of small bowl-shaped depressions that persist after drying.
  • Terminus means the terminal saccharide of a disaccharide, trisaccharide, oligosaccharide or polysaccharide that has no other saccharide attached at C1.
  • the C1 can be functionalized with either a hydroxyl group or an ester group.
  • Non-reducing Terminus means the terminal saccharide of a disaccharide, trisaccharide, oligosaccharide or polysaccharide that has no other saccharide attached at C4.
  • the C4 can be functionalized with either a hydroxyl group or an ester group.
  • Acetolvsis means the cleavage of a glycosidic bond in the absence of water and in the presence of a catalyst and a carboxylic acid, including but not limited to acetic acid.
  • Hydrolysis means the cleavage of a glycosidic bond in the presence of water and a catalyst. Hydrolysis also means the cleavage of an ester linkage of a cellulose ester in the presence of water and a catalyst to generate a free hydroxyl group on the cellulosic backbone.
  • Flop means where two different painted panels appear to be a good match for color when viewed at a given angle, but appear different at all other angles.
  • Mandrel Bends is a test for determining the flexibility and adhesion of surface coatings, so named because it involves the bending of coated metal panels around mandrels, [adapted from ASTM procedure D-522]
  • the 1 H NMR results are obtained using a JEOL Model GX-400 NMR spectrometer operated at 400 MHz. Sample tube size is 5 mm. The sample temperature is 80 0 C, the pulse delay 5 sec. and 64 scans are acquired for each experiment. Chemical shifts are reported in ppm from tetramethylsilane, with residual DMSO as an internal reference. The chemical shift of residual DMSO is set to 2.49 ppm.
  • the weight percent acyl is calculated as follows, where:
  • F, relative response factor for component I
  • F s relative response factor for isovaleric acid
  • This GC method is used, along with NMR, to determine weight % acetyl, propionyl, and butyryl, and the method used is indicated.
  • wt. % substitutions may be converted to degree of substitution (DS) values, according to the fof lowing:
  • Wt. % Bu (DS ⁇ u * MW B u)/((DS Ac * MW AcKe t) + (DS Bu * MW BuKe t) + MW a nhydroglu)
  • Wt. % AC (DS Ac * MW Ac )/((DSAc * MW A cKet) + (DS B u * MWBuKet) + MWanhydroglu)
  • DS M a ⁇ Maximum degree of substitution (DS Max is assumed to be 3.22 for all calculations, to be more accurate, the degree of polymerization should be determined and the DSwiax used in the calculations should be appropriately adjusted. To simplify the calculations, a DSM a x of 3.22 is assumed. As is evidenced by the negative values of Wt % Hydroxyl for several of the HS-CAB samples that were isolated in the fully esterified state, 3.22 is not completely accurate.
  • Method 1 determines the degree of substitution of acetyl and of butyryl by analyzing the NMR spectrum and comparing the peak area of the integrated alkyl ester protons with the peak area of the cellulose backbone protons.
  • acetyl can be distinguished from the higher esters such as butyryl or propionyl, but butyryl cannot be distinguished from propionyl.
  • propionyl one must assume that all the higher esters peaks come from either butyryl or propionyl, depending upon the anhydride used. This is a reasonable assumption for cellulose acetate butyrates since the level of propionyl in CAB's is near zero when butyric anhydride is a reactant.
  • Ester substitutions for conventional molecular weight cellulose esters are easily calculated. Since they have a higher degree of substitution, it is accepted that the DSwiax is 3.0.
  • the maximum degree of substitution is greater than 3.0 and is on a steeper part of the curve, that is small changes in DP have a greater impact on DS Ma ⁇ than is seen with conventional esters.
  • the degree of polymerization based on molecular weight
  • the DS Ma x is assumed to be equal to 3.22 for this purpose.
  • Method 2 utilizes the weight percent data determined by GC (acetyl, propionyl, and butyryl) and by titration (hydroxyl), and DS values are calculated from these data.
  • the uncertainty with the use of this method is that the DS calculations are dependent on the accuracy and precision of the GC and titration test methods.
  • the calculated DS M3X is less than 3.0.
  • the acid number of any carboxy(Ci-C3)alkylcellulose esters are determined by titration as follows. An accurately weighed aliquot (0.5-1.Og) of the carboxy (C1-C3) alkylcellulose ester is mixed with 50 ml_ of pyridine and stirred. To this mixture is added 40 ml_ of acetone followed by stirring. Finally, 20 ml_ of water is added and the mixture stirred again. This mixture is titrated with 0.1 N sodium hydroxide in water using a glass/combination electrode. A blank consisting of 50 ml_ of pyridine, 40 ml_ of acetone, and 20 ml_ of water is also titrated. The acid number is calculated as follows where:
  • IV The inherent viscosity (IV) of the cellulose esters described in this application, except where indicated otherwise, are determined by measuring the flow time of a solution of known polymer concentration and the flow time of a solvent- blank in a capillary viscometer, and then calculating the IV. IV is defined by the following equation:
  • Samples are prepared to a concentration of 0.50 g per 100 mL of solvent (60% phenol and 40% 1,1 ,2,2-tetrachloroethane by weight, also described herein as "PM95").
  • the sample (0.25 g) is weighed into a culture tube containing a stir bar.
  • 50.0 mL of 60% phenol and 40% 1 ,1 ,2,2- tetrachloroethane by weight (also described in the application as "PM95") is added.
  • the mixture is placed in a heater and heated with stirring (300 rpm) to 125 0 C (7 minutes to reach the target temperature and 15 minute hold at 125 0 C).
  • the molecular weight distributions of cellulose ester and carboxy(Ci- C 3 )alkylcellulose ester samples are determined by gel permeation chromatography (GPC) using one of two methods listed below.
  • THF The molecular weight distributions of cellulose ester samples indicated as being tested by GPC with THF as a solvent are determined at ambient temperature in Burdick and Jackson GPC-grade THF stabilized with BHT, at a flow rate of 1 ml/min. All other samples-are determined using GPC with NMP as a solvent, as set forth in Method 2 below. Sample solutions are prepared by dissolution of about 50 mg of polymer in 10 ml of THF, to which 10 ⁇ l of toluene is added as a flow-rate marker.
  • An autosampler is used to inject 50 ⁇ l of each solution onto a Polymer Laboratories PLgel ® column set consisting of a 5 ⁇ m Guard, a Mixed-C ® and an Oligopore ® column in series.
  • the eluting polymer is detected by differential refractometry, with the detector cell held at 30 0 C.
  • the detector signal is recorded by a Polymer Laboratories Caliber ® data acquisition system, and the chromatograms are integrated with software developed at Eastman Chemical Company.
  • a calibration curve is determined with a set of eighteen nearly monodisperse polystyrene standards with molecular weight from 266 to 3,200,000 g/mole and 1 -phenyl hexane at 162 g/mole.
  • the molecular weight distributions and averages are reported either as equivalent polystyrene values or as true molecular weights calculated by means of a universal calibration procedure with the following parameters:
  • NMP The molecular weight distributions of all samples not otherwise indicated are determined by GPC with NMP as a solvent, as follows. The molecular weight distributions of cellulose ester samples are determined by gel permeation chromatography at 40 0 C in Burdick and Jackson N-Methylpyrrolidone with 1 % Baker glacial acetic acid by weight, at a flow rate of 0.8 ml/min. Sample solutions are prepared by dissolution of about 25 mg of polymer in 10 ml of NMP, to which 10 ⁇ l of toluene is added as a flow-rate marker.
  • An autosampier is used to inject 20 ⁇ l of each solution onto a Polymer Laboratories PLgel ® column set consisting of a 10 ⁇ m Guard, a Mixed-B ® column.
  • the eluting polymer is detected by differential refractometry, with the detector cell held at 40 0 C.
  • the detector signal is recorded by a Polymer Laboratories Caliber ® data acquisition system, and the chromatograms are integrated with software developed at Eastman Chemical Company.
  • a calibration curve is determined with a set of eighteen nearly monodisperse polystyrene standards with molecular weight from 580 to 3,200,000 g/mole. The molecular weight distributions and averages are reported as equivalent polystyrene values.
  • the neutralized dope was filtered at approximately 50 0 C through a glass wool- covered coarse fritted funnel.
  • the product was precipitated by pouring, with rapid mixing, the clear, neutralized dope into 20 - 30 volumes of water. Decanting away the filtration liquid and adding fresh deionized water and then allowing the precipitate to stand in the fresh water for several hours hardened the precipitate. The precipitate was washed extensively with deionized water for at least 4 hours. The product was dried in a vacuum oven at approximately 50°C overnight to yield 95 g of the final product.
  • the neutralized dope was filtered at approximately 50 °C through a glass wool-covered coarse fritted funnel.
  • the product was precipitated by pouring, with rapid mixing, the clear, neutralized dope into 20 - 30 volumes of water. Decanting away the filtration liquid and adding fresh deionized water and then allowing the precipitate to stand in the fresh water for several hours hardened the precipitate. The precipitate was washed extensively with deionized water for at least 4 hours. The product was dried in a vacuum oven at approximately 50 °C overnight to yield 132 g of the final product.
  • the neutralized dope was filtered at approximately 50 °C through a glass wool-covered coarse fritted funnel.
  • the product was precipitated by pouring, with rapid mixing, the clear, neutralized dope into 20 - 30 volumes of water. Decanting away the filtration liquid and adding fresh deionized water and then allowing the precipitate to stand in the fresh water for several hours hardened the precipitate. The precipitate was washed extensively with deionized water for at least 4 hours.
  • the product was dried in a vacuum oven at approximately 50 0 C overnight to yield 110 g of the final product.
  • the neutralized dope was filtered at approximately 50 0 C through a glass wool-covered coarse fritted funnel.
  • the product was precipitated by pouring, with rapid mixing, the clear, neutralized dope into 20 - 30 volumes of water. Decanting away the filtration liquid and adding fresh deionized water and then allowing the precipitate to stand in the fresh water for several hours hardened the precipitate. The precipitate was washed extensively with deionized water for at least 4 hours. The product was dried in a vacuum oven at approximately 50 0 C overnight to yield 136 g of the final product.
  • a 2L-reaction kettle was charged with a butyric acid-wet, water-activated cellulose (457.14 g), prepared according to Example 1.
  • Butyric acid (18.10 g) and acetic acid (55.58 g) were added to the kettle.
  • the mixture was cooled to 0 °C.
  • a mixture of butyric anhydride (572.00 g), acetic anhydride (145.60 g), and sulfuric acid (5.28 g) were cooled to -15 0 C and then added to the reaction kettle.
  • the mixture was stirred for 1 hour at room temperature.
  • the mixture was then heated to 62.8 0 C and stirred for 24 hours.
  • the catalyst was neutralized by the addition of Mg(OAc) 4 (42.29 g) dissolved in HOAc (500 g) and water (500 g).
  • the product was precipitated by pouring the clear, neutralized dope with rapid mixing, into 20 - 30 volumes of water. The precipitate was washed extensively with deionized water for at least 4 hours. The product was dried in a vacuum oven at approximately 50 0 C overnight.
  • a 2L-reaction kettle was charged with a butyric acid-wet, water-activated cellulose (457.14 g) (prepared according to Example 1). Butyric acid (18.10 g) and acetic acid (55.58 g) were added to the kettle. The mixture was cooled to 0 0 C. A mixture of butyric anhydride (572.00 g), acetic anhydride (145.60 g), and sulfuric acid (5.28 g) were cooled to -15 0 C and then added to the reaction kettle. The mixture was stirred for 1 hour at room temperature. The mixture was then heated to 79.4 °C and stirred for 21.2 hours.
  • the catalyst was neutralized by the addition of Mg(OAc) 4 (42.29 g) dissolved in HOAc (500 g) and water (500 g).
  • the product was precipitated by pouring the clear, neutralized dope with rapid mixing, into 20 - 30 volumes of water. The precipitate was washed extensively with deionized water for approximately 15 hours. The product was dried in a vacuum oven at approximately 50 0 C overnight.
  • the catalyst was neutralized by the addition of Mg(OAc) 4 (42.29 g) dissolved in HOAc (500 g) and water (500 g).
  • the product was precipitated by pouring the clear, neutralized dope with rapid mixing, into 20 - 30 volumes of water. The precipitate was washed extensively with deionized water for at least 4 hours. The product was dried in a vacuum oven at approximately 50 0 C overnight.
  • Example 8 Preparation of a fully-esterified, high-butyryl cellulose ester (HS-C AB-55) according to the invention
  • a 2L-reaction kettle was charged with a butyric acid-wet, water-activated cellulose (338.70 g), prepared according to Example 1.
  • Butyric acid 22.78 g was added to the kettle.
  • the mixture was cooled to 0 0 C.
  • a mixture of butyric anhydride (614.41 g), acetic anhydride (0.61 g), and sulfuric acid (5.28 g) were cooled to -15 0 C and then added to the reaction kettle.
  • the mixture was stirred for 1 hour at room temperature.
  • the mixture was then heated to 79.4 0 C and stirred for 5 hours.
  • the catalyst was neutralized by the addition of Mg(OAc) 4 (42.29 g) dissolved in HOAc (500 g) and water (500 g).
  • the product was precipitated by pouring the clear, neutralized dope with rapid mixing, into 20 - 30 volumes of water. The precipitate was washed extensively with deionized water for at least 4 hours. The product was dried in a vacuum oven at approximately 50 0 C overnight.
  • Wt. % Bu (DS Bu * MW B u)/((DSAc * MW Ac ⁇ et) + (DS B u * MW B u ⁇ et) +
  • Wt. % Ac (DS Ac * MW A c)/((DS A c * MW Ac ⁇ et ) + (DS Bu * MW Bu ⁇ et) +
  • DSOH DS Max - DS Ac - DS Bu
  • DSwiax Maximum degree of substitution (DS Ma ⁇ is assumed to be 3.22 for all calculations, to be more accurate, the degree of polymerization could be determined and the DS M ax used in the calculations appropriately adjusted. To simplify the calculations, a DSM a x of 3.22 is assumed. As is evidenced by the negative values of Wt % Hydroxyl for several of the HS- CAB samples isolated in the fully esterified state, 3.22 is not completely accurate.
  • the HS-CAB samples and commercial CAB samples are dissolved in a variety of solvents and solvent blends (see Table 5 and 6) at 10% by weight at approximately 22 0 C (72 0 F) (room temperature).
  • the samples are checked visually for solubility and rated as soluble-clear (9), soluble-slight haze (7), gels (5), partially soluble (3), and insoluble (1).
  • the inventive cellulose esters are considerably more soluble in some solvents than current commercial cellulose esters of similar acetyl/butyryl content (e.g.
  • CAB-381-0.1 , CAB-551- 0.01, and CAB-171-15 all available from Eastman Chemical Company, Kingsport, TN), particularly the HS CAB-38 and HS CAB-17 type ester for the following solvents: toluene, methanol, ethanol, isopropyl alcohol, Eastman EB, Eastman EP, PB, PP, DIBK, C-11 ketone, EB acetate, PM acetate, and /?- butyl acetate.
  • Table 4 Properties of HS-CAB's evaluated
  • MEK methyl ethyl ketone
  • MPK methyl propyl ketone
  • MAK methyl amyl ketone
  • PM acetate propylene glycol methyl acetate
  • EB acetate ethylene glycol butyl acetate
  • PM propylene glycol monomethyl ether
  • DM diethylene glycol methyl ether
  • PB propylene glycol monobutyl ether
  • DE diethylene glycol ethyl ether
  • PP propylene glycol monopropyl ether
  • Eastman EP Solvent ethylene glycol monopropyl ether
  • Eastman EB Solvent ethylene glycol monobutyl ether
  • 95% Tecsol C ethanol with methanol, MIBK and ethyl acetate as denaturants with 5% water
  • NMP n-methyl pyrrolidone
  • Eastman EEP Solvent ethyl 3-ethoxypropionate
  • the viscosities of an HS-CAB-38 (Sample 4, Table 4) and an HS-CAB-55 (Sample 5, Table 4) are compared to the lowest viscosity commercial cellulose esters, CAB-381-0.1 and CAB-551-0.01 , of comparable butyryl content, using as solvent an n-butyl acetate/xylene in a 90/10 by weight mixture, using Brookfield viscosity as a function of concentration.
  • Figure 1 shows the relative viscosity at each measured concentration. Note how the log viscosities vs. concentration plots are parallel for each of the esters.
  • each of the esters has a similar exponential viscosity rise with concentration, except that the lower the molecular weight of the ester is, the higher the concentration becomes to display the same behavior. Because the inventive esters exhibit a lower viscosity than conventional esters at the same concentration, they allow coating formulations having a higher ester content at the target viscosity.
  • HS-CAB-55 (EMT02-117) gels at 65, 67, 69, and 70 % HS-CAB-55 (EMT02-128) gels at 70 % HS-CAB-17 (EMT02-084) gels at 70 % HS-CAB-17 (EMT02-085) gels at 60 % and 70 % HS-CAB-38 (EMT02-121) is very viscous at 70 % HS-CAB-38 (EMT02-122) is very viscous at 70 % HS-CAB-17 (EMT02-084) is very viscous at 60 %
  • Blends of HS-CAB-38 (Sample 1 , Table 4) and HS-CAB-55 (Sample 2, Table 4) with commercial resins (Duramac HS 2706, Polymac HS 5776, and Acrylamac 232-1700) (1:1 CAB to resin, at 20 % and 40 % solids levels) are prepared and the viscosities of the solutions are determined using a Brookfield viscometer.
  • Comparison blends of CAB-381-0.1 and CAB-551- 0.01 with commercial resins (Duramac HS 2706, Polymac HS 5776, and Acrylamac 232-1700) (1:1 CAB to resin, at 20 % solids levels) are prepared and the viscosities of the solutions are determined using a Brookfield viscometer. The results are presented in Table 7.
  • the HS-CABs have very little impact on solution or spray viscosity and can thus be added at much higher levels than conventional esters. This results in an increase in the % non-volatiles in the system.
  • Example 47 Compatibility of HS-CAB's with Various Coatings Resins
  • Solutions are prepared using ratios of cellulosic to modifying resin of 1/9, 1/3, 1/1, and 3/1 at 10% solids in a mixture of n-butyl acetate/ MEK/ MPK/ EEP/ MAK (35/20/20/15/10). Films are cast on glass at 10 mil thickness. The films are allowed to air dry for 24 hours. The resulting films are evaluated visually under good room lights (Tables 8 and 9) for film clarity.
  • HS-CAB-55 (Sample 2, Table 4) and HS-CAB-38 (Sample 1, Table 4) have good compatibility with most resins tested: acrylics, polyesters, melamine type resins, urea formaldehyde resins, alkyds, isocyanate resin, phenolics and epoxies, and limited compatibility in vinyls and polyamides.
  • HS-CAB-17s (Sample 3, Table 4) are less compatible than HS-CAB-55 and HS-CAB-38, but still can be used with the resins tested in limited amounts.
  • Example 48 HS-CAB Solubilities.
  • Solutions are prepared using ratios of cellulosic to modifying resin ratio of 1/1 at 10% solids in one of four solvent blends, Solvent 1 (MEK/PMAc/EEP, 5/4/1), Solvent 2 (MEK/Xylene/EEP, 5/4/1), Solvent 3 (MEK/PMAc/Toluene, 1/1/2), Solvent 4 (PMAc/EtOH/n-BuOH, 2/1/1). Films are cast on glass at 10 mil thickness. The films are allowed to air dry for 24 hours. The resulting films are evaluated visually under good room lights and the results are presented in Tables 10-16 for film clarity.
  • Solvent 1 MEK/PMAc/EEP 5/4/1
  • Solvent 2 MEK/Xylene/EEP 5/4/1
  • Solvent 3 MEK/PMAc/Toluene 1/1/2
  • Solvent 4 PMAc/EtOH/n-BuOH 2/1/1
  • Solvent 1 MEK/PMAc/EEP 5/4/1
  • Solvent 2 MEK/Xylene/EEP 5/4/1
  • Solvent 3 MEK/PMAc/Toluene 1/1/2
  • Solvent 4 PMAc/EtOH/n-BuOH 2/1/1
  • Solvent 1 MEK/PMAc/EEP 5/4/1
  • Solvent 2 MEK/Xylene/EEP 5/4/1
  • Solvent 3 MEK/PMAc/Toluene 1/1/2
  • Solvent 4 PMAc/EtOH/n-BuOH 2/1/1
  • Solvent 1 MEK/PMAc/EEP 5/4/1
  • Solvent 2 MEK/Xylene/EEP 5/4/1
  • Solvent 3 MEK/PMAc/Toluene 1/1/2
  • Solvent 4 PMAc/EtOH/n-BuOH 2/1/1
  • Solvent 1 MEK/PMAc/EEP 5/4/1
  • Solvent 2 MEK/Xylene/EEP 5/4/1
  • Solvent 3 MEK/PMAc/Toluene 1/1/2
  • Solvent 4 PMAc/EtOH/n-BuOH 2/1/1
  • Solvent 1 MEK/PMAc/EEP 5/4/1
  • Solvent 2 MEK/Xylene/EEP 5/4/1 ' .
  • Solvent 3 MEK/PMAc/Toluene 1/1/2
  • Solvent 4 PMAc/EtOH/n-BuOH 2/1/1
  • Solvent 1 MEK/PMAc/EEP 5/4/1
  • Solvent 2 MEK/Xylene/EEP 5/4/1
  • Solvent 3 MEK/PMAc/Toluene 1/1/2
  • Solvent 4 PMAc/EtOH/n-BuOH 2/1/1
  • HS-CAB's described in Tables 2-3 are treated with solvents and solvent blends (0.2 g of ester in 1.8 g of solvent) to prepare 10 wt % solutions of the CAB's and conventional CAB's (CAB-381-0.1 and CAB- 551-0.01).
  • solvents and solvent blends 0.2 g of ester in 1.8 g of solvent
  • the samples are placed on a roller overnight to allow them to go into solution. Samples are removed from the roller and the solubility of each HS-CAB in each solvent or solvent blend is determined according to the following criteria:
  • Inventive HS-CAB-17 and HS-HS-CAB-38 esters are evaluated as pigment grinding vehicles for inks or coating. Eight millbases and eight ink formulations are prepared as described in Table 20. Compared to conventional CAB grades, color development (color strength) of inventive HS- CAB's is equal or better.
  • Example 51 Improved Melt Stability of HS-CAB's
  • An inventive HS-CAB-38 having a glass transition temperature (T 9 ) of 89 °C and a melt temperature of 120 0 C 1 is placed on a preheated 2-roll horizontal mill (80 0 C).
  • T 9 glass transition temperature
  • a melt temperature of 120 0 C 1 is placed on a preheated 2-roll horizontal mill (80 0 C).
  • the HS-CAB powder adheres to the Roll and the temperature is gradually increased until the HS-CAB begins to soften and flow ( ⁇ 100 "C). It is noted that this material appears to have good thermal stability. After nearly 30 minutes on the mill, the CAB has not yellowed.
  • Example 52 HS-CAP-48: HIGH PROPIONYL, LOW DP CAP
  • a 2L-reaction kettle was charged with a propionic acid-wet activated cellulose (311.77 g total, 16O g dry cellulose), prepared according to Example 1 , except that the butyric acid wash was replaced with a propionic acid wash.
  • Propionic acid (262.5 g) and acetic acid (5.22 g) were added to the kettle. The mixture was cooled to -10 0 C.
  • a mixture of propionic anhydride (757.69 g) and sulfuric acid (5.44 g) were cooled to -30 0 C and then added to the reaction kettle. The mixture was stirred for 1 hour at room temperature. The mixture was then heated to 70 0 C.
  • Example 53 Coating Formulations with HS-CAB-38 and Evaluation
  • Clearcoat formulations are prepared according to Tables 21-22 and the resulting coatings are evaluated to determine the effect different levels of HS- CAB-38 (Sample 4, Table 4) have on dry-to-touch time, hardness development, and gloss.
  • Coatings re prepared (Tables 21 - 22) with an OH:NCO stoichiometry of 1:1 , and a DIN 4 viscosity of 18-20 seconds. Coatings are prepared with 0% CAB and with 2%, 4% and 8% of the hydroxy-functional acrylic substituted with the HS-CABs. Each of the coatings is spray applied to Chemetall Gold Seal, high zinc phosphate 1.0 mm steel panels using a DeVilbiss JGA 545 spray gun at 55 psi air pressure. Three panels are coated for each test ratio, such that a range of dry film thickness including 45 ⁇ m is obtained. The dry-to-touch time is evaluated by a thumb print test (according to ASTM D 1640 section 7.4.2).
  • Each of the panels is also assessed for hardness development by Konig pendulum hardness evaluations. Tests are carried out after 24 hours and continued every 24 hours up to 168 hours. The panels are stored at 23 0 C during this period.
  • a white-pigmented high solids coating using a hybrid acrylic-isocyanate- polyester system is developed which can be sprayed at 70% solids and 18 second Ford Cup #4 viscosity (Tables 25 and 26).
  • An ultra high solids master batch consisting of TRONOX CR828 (titanium dioxide pigment), Rohm and Haas AU608X (acrylic polyol), and Sherwin-Williams US-2 solvent (paint thinner) are mixed together under high shear.
  • TRONOX CR828 titanium dioxide pigment
  • Rohm and Haas AU608X acrylic polyol
  • Sherwin-Williams US-2 solvent paint thinner
  • CAB, BYK ® 325, or a combination of the two are added along with the isocyanate portion, (Bayer Desmodur N 3300) and Bayer Desmophen 800 (polyester polyol) used to keep the OH/CN balance.
  • the Brookfield viscosities are measured at the same solids prior to the addition of the isocyanate. After the isocyanate is added, the spray viscosities are adjusted with the addition of Sherwin- Williams US-2 thinner to 18-20 second Ford Cup #4 and sprayed using a DeVibliss air assisted spray gun at 35 pounds of pressure. Two panels of each formulation are sprayed. After flash-off for 40 minutes at room temperature, the panels are baked in an oven at 82 0 C (180 0 F) for 30 minutes. Before any of the panels are tested, the baked panels are laid horizontally in a constant temperature-humidity room at 24 0 C (70 0 F) and 50 % relative humidity for 7 days.
  • TRONOX 828 Tianium Dioxide Pigment 56.66 Sherwin Williams US-2 Thinner 1.92
  • the pigment dispersion is mixed in an Eiger High Speed Disperser until the particle size is ⁇ 0.1 micron on a Hegmann gauge. This is achieved by mixing at 300 rpm for 5 minutes, allowing the solution to cool and repeating 5 times.
  • HS-CAB-55 (Sample 5, Table 4) and HS-CAB-38 (Sample 4, Table 4) provide the same anti-cratering, anti-mounding and anti-pinholing property as CAB-
  • CAB-17 (Sample 3, Table 4) and HS-CAB-38 (Sample 1 , Table 4) are evaluated as metallic flake control agents in a high solids basecoat useful for automotive coatings.
  • Five formulations are prepared as described in Table 27. The formulations are sprayed onto metal panels using a spray technique altered to accommodate for the higher solids. The formulations are reduced with xylene/n-BuOAc to obtain the same solids level as Example 55 (i.e. 69 %).
  • Example 55 contains HS-CAB-17
  • Example 56 contains HS-CAB-38,
  • Example 57 (Comparative) is the control and contains no metallic flake control agent, and Examples 58 and 59 contain the microgel metallic flake control agent R-1623-M3.
  • Example 55 exhibits excellent appearance and good holdout from the OEM clear. The coating also exhibits good travel or flop. The appearance is poor with Examples 57-59 when sprayed at 69 % solids. The appearance of Example 56 is fair.
  • Example 57 Further reduction is done with the control formulations and the formulations containing the microgels until a good appearance is obtained.
  • the amount of solids for Example 57 is 52.4 in order to obtain similar appearance as Example 55.
  • Example 59 When sprayed at 69 % solids and Example 59 (HS-CAB-38) has fair appearance and poor travel, indicating that there is "strike in” of the basecoat by the topcoat solvents.
  • a new CAB/Acrylic/Urethane formulation is developed loosely based on a combination of two Eastman Publications (E-321 & TT-96-SOL-2A).
  • the purpose of this new formulation is to show the improved flow properties and quicker dry-to-touch time of acrylic isocyanate formulation when CAB-551- 0.01 is added. Then, determine if the HS-CAB will give similar improvements without contributing as greatly to viscosity.
  • DBTDL Dibutyltin Dilaurate
  • DBTDL catalyst level 0.01% based on solids
  • a series of formulations containing HS-CAB (Sample 4, Table 4), at 4 different levels), CAB-381-0.1 , and no CAB, are prepared as described in Table 30.
  • Table 36 shows the viscosity of the systems at 22.3% solids for the CAB-381- 0.1 and 24.3 % solids for the rest.
  • the use of HS-CAB-38 gives formulations with viscosities approximately one tenth that of formulations using the CAB- 381-0.1 control and one third that of the control without CAB.
  • the HS-CAB- 38 samples are applied at a solids level of 40 %, approximately twice that of the controls.
  • the samples are spray applied and allowed to cure for one week prior to evaluation. All samples pass chemical resistance tests with greater than 200 MEK double rubs.
  • Table 31 also lists the 60° gloss for each example. Gloss is not reduced appreciably even at high levels of HS-CAB-38. The one exception is the 25:45 ratio of AU608X to HS-CAB-38. This sample yields values that are up to 9 points lower.
  • DuPont 12375S Refinish Reducer was added to a 16 ounce jar according to the formulation amount show in Table 32. This was followed by the polyester resin (Polymac 220-2010) and dibutyl tin dilaurate (DBTDL catalyst) and agitated with a Cowles-type mixer. HS-CAB-55 (Batch EMT02-131) was then weighed out and slowly added to the stirring solution while maintaining high speed stirring (Part 1 below). This was continued until the HS-CAB was in solution.
  • Part 2 The stochiometric amount of Desmodur N-75 hexamethylene diisocyanate (Part 2) for a 1.1:1 isocyanate/ hydroxyl molar ratio based on the hydroxyl contained in both the HS-CAB and the polyester resin was then added to Part I under agitation to produce a mixture. Acetone (15% by weight) was added to the mixture to produce the clear coat composition.
  • the viscosity of Part 1 was approximately 27-28 sec, and the viscosity Part 1 and Part 2 was approximately 35 -36 sec.
  • the viscosity of the clear coat composition was about 16-17 sec.
  • the viscosity was measured with a #4 Ford Viscosity Cup as per ASTM D-1200. Table 32 Part i
  • Polymac 220-2010 saturated polyester
  • Desmodur N-75 polyisocyanate crosslinker 17.2
  • the clearcoat compositions were drawn down on clear glass plates using a 10-mil wet drawdown cup.
  • the films were allowed to dry at ambient condition and Tukon® hardness was determined using a Tukon Microhardness Tester. The readings are given in knops, and are shown in Table 33. Hardness was determined after 24 hours, 72 hours, and 1 week.
  • the following example demonstrates the utility of the low molecular weight cellulose mixed esters of the invention as the sole polyol in a melamine-cured coating formulation.
  • Two batches of HS-CAB-55 were selected and each was formulated as the sole polyol component of an acid-cured melamine clearcoat.
  • the coating formulations were spray applied to steel panels, cured for 30 minutes at 140 0 C, and tested for solvent resistance (MEK double-rubs) and Tukon hardness within 2 hours of curing.
  • Example 68A >200 8.9
  • Example 68B >200 7.8
  • Aromatic Solvent supplied by:
  • comparative example 69.1 a commercial clear coat system was utilized with corresponding reducer and hardener.
  • comparative example 69.2 another commercial clear coat system was utilized with corresponding reducer and hardener.
  • comparative example 69.3 another commercial clear coat system was utilized with corresponding reducer and hardener in a mix ratio of clear coat to reducer to hardener of 3:1 :1.
  • the coating compositions comprise Uracron CY 430 hydroxy-containing acrylic polymer(70 wt%) obtained from DSM Coating Resins, Eastman DPA 2100 cellulose mixed ester (50% in Solvent Blend) obtained from Eastman Chemical Company, dibutyl tin dilaurate (curative catalyst) (10wt% in n-butyl acetate), Desmodur N3390 crosslinking agent (90wt%) obtained from Bayer Corporation, a solvent blend, BYK-331 flow additive obtained from BYK Chemie, and Irganox 1010 antioxidant obtained from CIBA Specialty Chemicals in the amounts shown in Table 36.
  • the solvent blend contained 30% by volume n-butyl acetate, 20% by volume methyl isobutyl ketone (MIBK), and 50% by volume methyl amyl ketone (MAK).
  • the viscosity of the solvent blend and the final coating composition was measure using a 18(s) Ford Cup method. Paint and Pol ⁇ shability Procedure and Tests
  • a Sata Jet RP Digital 2 Model #09026840 gravity fed spray gun obtained from Sata located in London, UK, was utilized with a maximum pressure of 35psig.
  • the air pressure utilized was between 29-30 psig, and a 1.3 mm air nozzle was utilized.
  • Step Action 1 Wet sanded the painted panels by hand for about 5 min. with 2000 grit 3M 401 Q paper obtained from 3M;
  • the painted panels were tested for 20° Gloss utilizing a BYK Gardner Micro- Tri-Gloss instrument (Model # 4522) obtained from BYK Gardner, located in Columbia, Maryland.
  • the 20° Gloss was measured at a 24 hour cure and at a 48 hour cure time, which means the time lapse after the application of the clear coat composition.
  • the data are tabulated in Table 37 and shown graphically in Figure 2.
  • Figure 3 is a graphic representation of the 20° gloss data for the comparative and inventive examples. It should be noted that the inventive example 68.4 had a higher level of gloss than the comparative examples after the 3 rd polishing step (Step 5 in Polishing Procedure).
  • the storage modulus of the coating compositions were also evaluated.
  • a 10 mil applicator was utilized to produce a 10 ml thick wet film on a glass panel.
  • the film was allowed to dry overnight, and then water was applied to the film to remove it from the glass panel.
  • the storage modulus was determined on the films for coating compositions of Comparative Example 68.1 and Inventive Example 68.4 utilizing a Rheometrics Solid Analyzer (RSAII).
  • the RSA Il is a dynamic mechanical analyzer dedicated to characterizing rheological properties of solid materials.
  • the films were cut into strips approximately 0.100 mm thick, 6.35 mm wide, and 22 mm long.
  • the Tukon Hardness of the coating compositions of Examples 69.1-69.5 was also determined by ASTM D1474 - Standard Test Methods for Indentation
  • ASTM D1474 covers the determination of the indentation hardness of organic materials such as dried paint, varnish and lacquer coatings, when applied to an acceptable plane rigid surface, for example, metal or glass.
  • a hardness tester consisting of a load applicator, a Knoop indenter, and a microscope fitted with a movable micrometer stage is required for these determinations.
  • the Knoop indenter is a pyramidal diamond and provides hardness values in terms of Knoop Hardness Number (KHN).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé d'amélioration des propriétés de brillance, d'étalement et de résistance à la coulure d'une composition de revêtement. Le procédé comprend les étapes consistant à mettre en contact au moins un polymère acrylique contenant des groupements hydroxy, au moins un ester mixte de cellulose, au moins un agent de réticulation et au moins un catalyseur de durcissement afin d'obtenir la composition de revêtement, à appliquer la composition de revêtement sur un substrat, et à sécher la composition de revêtement, la brillance à 20 degrés de la composition de revêtement étant améliorée par rapport à une composition de revêtement ne comprenant pas l'ester mixte de cellulose.
PCT/US2007/013253 2006-06-05 2007-06-05 Procédés d'amélioration des propriétés de brillance, d'étalement et de résistance à la coulure de compositions de revêtement comprenant des esters mixtes de cellulose de faible poids moléculaire WO2007145955A2 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US81092306P 2006-06-05 2006-06-05
US81092406P 2006-06-05 2006-06-05
US60/810,923 2006-06-05
US60/810,924 2006-06-05
US11/810,011 US20080085953A1 (en) 2006-06-05 2007-06-04 Coating compositions comprising low molecular weight cellulose mixed esters and their use to improve anti-sag, leveling, and 20 degree gloss
US11/810,065 US20070282038A1 (en) 2006-06-05 2007-06-04 Methods for improving the anti-sag, leveling, and gloss of coating compositions comprising low molecular weight cellulose mixed esters
US11/810,011 2007-06-04
US11/810,065 2007-06-04

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PCT/US2007/013212 WO2007145929A2 (fr) 2006-06-05 2007-06-05 Compositions de revêtement comprenant des esters mélangés de cellulose à faible poids moléculaire et leur utilisation pour améliorer les propriétés d'anti-coulures, d'étalement et de brillance sous 20 degrés

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WO2013085397A1 (fr) * 2011-12-05 2013-06-13 Resene Paints Limited Composés organiques

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US7893138B2 (en) 2003-03-14 2011-02-22 Eastman Chemical Company Low molecular weight carboxyalkylcellulose esters and their use as low viscosity binders and modifiers in coating compositions
US8039531B2 (en) 2003-03-14 2011-10-18 Eastman Chemical Company Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions
US8124676B2 (en) 2003-03-14 2012-02-28 Eastman Chemical Company Basecoat coating compositions comprising low molecular weight cellulose mixed esters
US8461234B2 (en) 2003-03-14 2013-06-11 Eastman Chemical Company Refinish coating compositions comprising low molecular weight cellulose mixed esters
US20080090960A1 (en) * 2006-09-18 2008-04-17 Eastman Chemical Company Low voc coating compositions comprising low molecular weight cellulose mixed esters and low molecular weight hydroxyl-containing polymers
MX2011001517A (es) * 2008-09-15 2011-03-29 Eastman Chem Co Composiciones de recubrimiento base que comprenden esteres mezclados de celulosa de bajo peso molecular.
CN111560221A (zh) * 2020-05-16 2020-08-21 英科﹒卡乐油墨（苏州）有限公司 一种水性转移涂层
KR102340547B1 (ko) * 2020-06-02 2021-12-20 주식회사 케이씨씨 자동차 중도용 유성 도료 조성물
CN116410640B (zh) * 2023-05-10 2023-10-10 惠州市鸿高化工有限公司 一种水性丙烯酸涂料及其制备方法

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US4170663A (en) * 1978-03-13 1979-10-09 Ppg Industries, Inc. Method for producing coatings of low gloss
US4975300A (en) * 1987-12-31 1990-12-04 Minnesota Mining And Manufacturing Company Method for curing an organic coating using condensation heating and radiation energy
US6303670B1 (en) * 2000-02-25 2001-10-16 Nippon Paper Industries Co., Ltd. Cellulose based coating composition curable with ultraviolet ray

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Publication number Priority date Publication date Assignee Title
WO2013085397A1 (fr) * 2011-12-05 2013-06-13 Resene Paints Limited Composés organiques
CN104093745A (zh) * 2011-12-05 2014-10-08 氧化树脂涂料有限公司 有机化合物
US9458248B2 (en) 2011-12-05 2016-10-04 Resene Paints Limited Cellulose mixed esters

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WO2007145929A2 (fr) 2007-12-21
WO2007145955A3 (fr) 2008-04-03
WO2007145929A3 (fr) 2008-03-20

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