WO1993019136A1 - Aqueous coatings composition and process for the preparation thereof - Google Patents
Aqueous coatings composition and process for the preparation thereof Download PDFInfo
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- WO1993019136A1 WO1993019136A1 PCT/US1993/002679 US9302679W WO9319136A1 WO 1993019136 A1 WO1993019136 A1 WO 1993019136A1 US 9302679 W US9302679 W US 9302679W WO 9319136 A1 WO9319136 A1 WO 9319136A1
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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
- C09D101/14—Mixed esters, e.g. cellulose acetate-butyrate
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
Definitions
- the present invention relates to novel aqueous coating compositions containing cellulose mixed esters and acrylic resins and to the process for the preparation thereof. More particularly the present invention relates to aqueous coating compositions containing succinated derivatives of cellulose esters and a compatible amine neutralized acrylic resin.
- Cellulose esters are valuable polymers which are useful in many plastic, film, coating and fiber applications. In coatings applications, cellulose esters are generally applied from organic solvent solutions. Because of health and environmental concerns from volatile organic content of solvent based coatings, water based coatings are becoming more in demand. There are waterborne coating formulation available containing polyesters and acrylics, but few contain cellulose esters due to their hydrophobic nature making them difficult to disperse or emulsify. When applied from organic solvent solutions as wood, leather, and metal coatings, cellulose esters impart desired properties such as, improved pigment dispersions, improved metallic flake orientation, improved solvent release, and higher gloss coatings. Cellulose esters also function as an excellent rheology control agent in solvent coating formulations. It would be very desirable to incorporate these excellent properties of cellulose esters into waterborne coating systems.
- Coatings prepared from these cellulose mixed esters are made by neutralizing the cellulose mixed ester with an amine and forming an aqueous dispersion. Coating compositions made from these dispersions are not always stable and have volatile organics content (VOC) above 20 weight percent.
- VOC volatile organics content
- Other cellulose ester systems used in water based coating are disclosed in U.S. 3,318,714 (describing pigment dispersions in a cellulose acetate butyrate lacquer systems) and U.S. 3,220,865 (describing an emulsion coating composition based on cellulose acetate butyrate, and plasticizers) .
- the aqueous coating composition of the present invention comprises:
- a further aspect of the present invention entails a process of producing a composition by mixing in a high shear mixture (a) and (b) above to form a composition having a near neutral pH and a volatile organics content below 20 weight percent.
- aqueous coating compositions containing cellulose mixed esters and compatible amine neutralized acrylic resins that are relatively stable over long periods of time. Additionally, the applicant has discovered that these aqueous coating compositions containing cellulose mixed esters and acrylic resins provide excellent coatings for many substrates such as metal, wood, and plastics, particularly metals when the coating contains metal flake pigment.
- the aqueous coating composition of the present invention are prepared by directly mixing the cellulose mixed ester and the compatible amine neutralized acrylic resin without the need of forming an aqueous dispersion of the cellulose mixed esters and without the need of the amine neutralizing step since sufficient amine is provided by the neutralized acrylic resin.
- the resulting composition has a near neutral pH (preferably neutral) and the individual components are more compatible. Also by avoiding this step it is believed to result in an aqueous coating composition with very low VOC.
- the aqueous coating composition of the present invention provides a coating that drys faster and has a very good metallic appearance.
- the aqueous coating composition results in a coating with good metallic flop. In other words the face angle brightness is high and the low angle brightness is low.
- the aqueous compositions of the present invention generally have 3 to 50 weight percent cellulose mixed ester, based on the total solids.
- the amount of cellulose mixed ester is preferably 5 to 40 weight percent more preferably 10 to 30 weight percent with an amount of 10 to 25 weight percent being most preferred.
- An adequate amount of cellulose mixed ester is required to result in a dispersion that has good stability and good film forming ability. Adequate amounts of cellulose mixed ester also increase the drying characteristics and improve the gloss of the final coating.
- the cellulose ester of the present invention is a cellulose mixed ester that has at least two different ester functionalities thereon.
- the ester functionalities are herein referred to as a first ester residue and a second ester residue.
- ester residue refers to those portions of the mixed ester which are added as a result of the reaction of a carboxylic functionality (located on a reactant) with a hydroxyl functionality which is located on the cellulose molecule.
- the result of this reaction is the esterification of the cellulose molecule, with the ester being that portion of the reactant which resides on the cellulose ester.
- the first ester residue is a ester residue of an anhydride of a dicarboxylic acid.
- the anhydride can be a cyclic dicarboxylic acid anhydride, or an oligomer or polymer containing the anhydride of at least one such dicarboxylic acid.
- the first ester residue is linked to the cellulose molecule with an ester functionality, and the first ester residue further comprises a carboxylic acid functionality. This carboxylic acid functionality allows the resulting mixed ester to be associated with a basifying agent such as an amine and then used in a waterborne coating formulation without further modification of the cellulose mixed ester.
- the cellulose ester used in a waterborne coating is associate with other elements in the coating particularly an acrylic polymer to impart the desired rheological properties.
- One such desired rheological property for a coating which contains metal flake pigment(s) results in an improvement in the parallel alignment of the metal flakes in the applied coating i.e. good metallic flop.
- Cellulose esters which do not have such a first ester residue do not impart the desired rheological properties to waterborne coating formulations.
- the first ester residue can be formed, in general, from the reaction of any anhydride of a dicarboxylic acid with cellulose.
- useful anhydrides are succinic anhydride including its derivatives such as methylsuccinic anhydride, dodecenylsuccinic anhydride, and octadecenylsuccinic anhydride; phthalic anhydride including its derivatives such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylhexahydrophthalic anhydrides such as methylhexahydroph—thalic anhydride, endomethylene tetrahydrophthalic anhydride, and 3— nitrophthalic anhydride; maleic anhydride including its derivatives such as citraconic anhydride; glutaric anhydride; adipic anhydride; itaconic anhydride;
- 5 noborene—2,3—dicaroxylic anhydride including its derivatives such as chlorendic anhydride; and diglycolic acid anhydride.
- Other useful anhydrides include those anhydrides having a free carboxyl group in addition to the anhydride group such as trimellitic anhydride, aconitic anhydride, 2,6,7—naphthalene tricarboxylic anhydride, 1,2,4—butane tricarboxylic anhydride, and 1,3,4—cyclopentane tricarboxylic anhydride.
- any oligomeric or polymeric compounds which comprise cyclic anhydrides of dicarboxylic acids could be used.
- preferred cyclic anhydrides of dicarboxylic acids comprise one or more members selected from the group consisting of: succinic anhydride, trimellitic anhydride, glutaric anhydride, adipic anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and diglycolic acid anhydride.
- Still more preferred anhydrides of dicarboxylic acids comprise one or more members selected from the group consisting of: succinic anhydride, glutaric anhydride, adipic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and diglycolic acid anhydride.
- the most preferred anhydride of a dicarboxylic acid is succinic anhydride.
- the first ester residue makes up from 3 weight percent to 35 weight percent of the mixed cellulose ester. These weight percent values are based on the weight of the mixed ester.
- the first ester residue is present in an amount of from 3 weight percent to 17 weight percent, based on the weight of the mixed ester.
- the first ester residue is present in an amount of from 8 weight percent to 17 weight percent, based on the weight of the mixed ester.
- the most preferable amount of first ester residue present in the mixed ester depends upon the particular coating composition which is being formulated, because it affects the interactions of the mixed cellulose ester with the other components as well as the stability of the mixed cellulose ester in the particular dispersion.
- the second ester residue is a residue of an oleophilic monocarboxylic acid and/or a hydrophilic monocarboxylic acid.
- the second residue is linked to the cellulose molecule with an ester functionality.
- the second ester residue does not further comprise a carboxylic acid functionality.
- the presence of the second residue on the mixed ester has the effect of promoting interactions with other components in the coating composition, particularly with any other polymer(s) present, to effect desirable rheological characteristics. In this regard, its function is similar to that of the first ester residue.
- the oleophilic and hydrophilic properties. of the second ester residue may be changed and balanced to suit a particular coating composition. Because of the nature of the first residue, it contributes strongly to the hydrophilicity of the mixed cellulose ester.
- the second ester residue can be formed, in general, from the reaction of any oleophilic monocarboxylic acid and/or any hydrophilic monocarboxylic acid, with cellulose.
- the second ester residue makes up from 1 weight percent to 95 weight percent, based on the weight of the mixed cellulose ester.
- residues of oleophilic monocarboxylic acids, if present should in general be present in an amount of from 10 weight percent to 65 weight percent, based on the weight of the mixed ester.
- residues of hydrophilic monocarboxylic acids, if present should in general be in an amount of from 1 weight percent to 45 weight percent based on the weight of the mixed ester.
- Preferred oleophilic monocarboxylic acids comprise at least one member selected from the group consisting of monocarboxylic acids having at least 3 carbon atoms therein (as well as derivatives of such monocarboxylic acids) . Still more preferred oleophilic monocarboxylic acids comprises at least one member selected from the group consisting of: butyric acid, propionic acid, valeric acid, hexanoic acid, and other aliphatic monocarboxylic acids.
- the selection of the most preferred oleophilic monocarboxylic acid depends upon the particular formulation being produced because of its contribution to the interactions which bring the rheological properties desired in the coating. Among the most preferred oleophilic monocarboxylic acids are propionic acid and butyric acid.
- the amount of oleophilic monocarboxylic acid residue present in the mixed ester is, as stated above, generally from 10 weight percent to 65 weight percent, based on the weight of the mixed ester.
- the amount of oleophilic monocarboxylic acid residue present is from 30 weight percent to 55 weight percent. Still more preferably, the amount of oleophilic monocarboxylic acid residue is from 30 weight percent to 46 weight percent.
- the selection of the most preferred amount of oleophilic monocarboxylic acid residue present depends upon the particular coating formulation being produced, the particular oleophilic monocarboxylic acid chosen, and the types and amounts of the other residues on the mixed cellulose ester.
- the hydrophilic monocarboxylic acid residue comprises one or more members selected from the group consisting of: acetic acid residues and residues that are derivatives of acetic acid.
- the selection of the most preferred hydrophilic monocarboxylic acid depends likewise upon the particular formulation being produced, the amount of hydrophilic monocarboxylic acid used, and the types and amounts of the other residues on the mixed cellulose ester.
- the hydrophilic monocarboxylic acid residue is acetic acid residue.
- the amount of hydrophilic monocarboxylic acid residue present in the mixed ester is, as stated above, generally from 0.5 weight percent to 45 weight percent, based on the weight of the mixed ester.
- the amount of hydrophilic monocarboxylic acid residue present is from 1 weight percent to 15 weight percent. The selection of the most preferred amount of hydrophilic monocarboxylic acid residue present depends upon the particular coating formulation being produced, the particular hydrophilic monocarboxylic acid chosen, and the types and amounts of the other residues on the mixed cellulose ester.
- the cellulose mixed ester used in the present invention has an acid number of at least 50, determined by the milligrams of KOH required to neutralize one gram of resin.
- the acid number is preferably high and can be as high as 105 to 110.
- the acid number of the cellulose mixed ester is preferably greater than 55 more preferably between 60 to 65.
- the cellulose mixed ester of the present invention can be further characterized as having a number average molecular weight of from 5,000 to 100,000, as determined by standard methods of gel permeation chromatography as measured against polystyrene standards.
- the number average molecular weight is from 10,000 to 100,000.
- the number average molecular weight is 10,000 to 30,000.
- the cellulose mixed ester of the present invention can be further characterized as having a degree of substitution of from 2 to 3.
- the degree of substitution is from 2.2 to 3 .
- the degree of substitution is 2.5 to 3.
- the cellulose mixed ester of the present invention is neutralized partially or fully with a basifying agent that is present with the acrylic polymer.
- the basifying agent is preferable an amine.
- the amine employed is preferably one which will be volatilized during the curing of the coating and will not remain in the cured coating.
- One preferred amine is ammonia.
- the coating composition of the present invention is a coating composition which comprises the cellulose mixed ester of the present invention an acrylic polymer component.
- the coating composition preferably further comprises materials chosen from the group consisting of other polymers, crosslinkers, water, organic solvents, basifying agents, flake pigments, other pigments, and additives.
- Suitable cellulose mixed esters include of cellulose such as cellulose acetate butyrate (CAB) , cellulose acetate propionate (CAP) , cellulose acetate valerate (CAV) , cellulose acetate isovalerate (CAIV) , cellulose acetate propionate butyrate (CAPB) , and the like, with CAP and CAB being more preferred and CAB being most preferred.
- CAB cellulose acetate butyrate
- CAP cellulose acetate propionate
- CAV cellulose acetate valerate
- CAIV cellulose acetate isovalerate
- CAB cellulose acetate propionate butyrate
- the preferred cellulose mixed esters are the succinated derivatives of cellulose esters.
- CAB succinate is CAB succinate.
- the most preferred example of CAB succinate used in the present invention is CAB—SU160 available from Eastman Chemical Company of Kingsport, Tennessee.
- These succinate-substituted CAB's are produced by reacting a cellulose acetate butyrate having a hydroxyl functionality with succinic anhydride. Reactions between hydroxyl groups and acid anhydrides, such as this reaction, can typically be carried out under mild conditions (i.e. room temperature to 150°C and atmospheric pressure) .
- CAB—SU160 typically has a butyryl content of 41.6 weight percent, and acetyl content of 1.2 weight percent, a hydroxyl content of 3 weight percent, a degree of succination of 11.5 weight percent, an acid number of 60, a free acid weight percent of less than 0.1, and molecular weight Mn of 20,000.
- the aqueous coating composition of the present invention has a acrylic polymer or resin component content of at least 50 weight percent based on the total weight of solids.
- the amount of this acrylic resin component is preferably 60 to 95 weight percent preferably 70 to 90 weight percent with an amount of 75 weight percent being most preferred.
- This acrylic resin component contains a compatible amine neutralized acrylic resin can have a minor amount of a polyurethane such that the aqueous coating composition has no more than 20 weight percent polyurethane, based on total solids, preferably less than 15 weight percent.
- the resulting aqueous composition has at least a minor amount of polyurethane so that the resulting coating is not too stiff or brittle but not so much as to interfere with the qualities of the cellulose mixed ester.
- the amount of polyurethane is more preferably 5 to 15 weight percent based on total solids.
- a compatible acrylic resin is one that remains dispersed with the cellulose mixed ester when the composition is stored. Suitable examples of acrylic resins that are useful in the present invention are copolymers containing acrylic acid, methacrylic acid, hydroxyethylmethacrylate, and the like, including vinyl monomers thereof.
- the acrylic resins used in the dispersion composition of the present invention have free acid functionalities. However, these free acid functionalities are at least partially neutralized prior to forming the final dispersion composition. The acrylic resins are partially neutralized to be able to form ionic dispersions in the resulting dispersion composition.
- Acrylic resins preferably have an acid number prior to partial neutralization of 10 to 80, more preferably 40 to 60 with an acid number of 50 to 60 being the most preferred.
- the acrylic resins are preferably neutralized by 5 to 100 %, preferably 10 to 80 % with a neutralization percent of 10 to 30 being most preferred.
- the acrylic resins are preferably neutralized using amines including ammonia. Suitable amines include ammonia, diethylaminoethanol, dimethylaminoethanol, N,N—dimethylethylamine, 2— dimethylamino—2—methyl—1—propanol, triethylamine, and the like, with ammonia being most preferred due to availability and effectiveness.
- the amine neutralized acrylic resin is preferably non acidic prior to being combined and mixed with the cellulose mixed ester.
- the amine neutralized acrylic resin preferably has a pH in solution of 7.5 to 8.5.
- a surfactant is not required by the present invention and cross—linking is optional.
- the water content in the dispersion of the present invention depends upon the desired viscosity of the dispersion.
- the amount of water is the amount of water sufficient to render the dispersion usable in the particular coating application.
- the overall total solids content of the aqueous coating composition of the present invention including cellulose mixed ester and acrylic resin is 5 to 50 weight percent.
- the overall solids content, based on the total dispersion, is preferably 10 to 40 weight percent more preferably 20 to 40, with an overall total solids content of 25 to 35 weight percent being most preferred.
- the VOC of the aqueous coating composition of the present invention is very low, below 20 weight percent, preferably below 15 weight percent, more preferably below 10 weight percent, with a VOC near zero being most preferred.
- the amount of organic solvent and any cosolvent used in the organic coating composition of the present invention is below 20 weight percent, preferably below 15 weight percent.
- suitable organic solvents include cyclohexanone, methylethylketone, acetone, methylamylketone, ethylacetate, propylacetate, butylacetate, ethylene glycol monobuty1ether, ethylene glycol monopropylether, ethylene glycol monoethylether, propylene glycol monomethylether, xylene, ethyl—3— ethoxypropionate, and alcohols such as 2—propanol, 2— butanol, and 2—methyl—1—propanol and the like.
- the slower drying solvents are more preferred in that they produce a better final coating.
- the most preferred slower drying solvent is 2—butanol, particularly for pigmented coatings.
- additives include polymer thermal stabilizers, UV stabilizers, antioxidants, colorants, carbon black, metal flake (including aluminum flake) , and pigments.
- Preferred pigments include titanium dioxide, chromium oxide, chromium yellow, and cadmium red. The amount of pigments and additives depends upon each particular end- use application.
- Common thermal stabilizers include epoxide— containing compounds such as glycidyl ether of aromatic hydrocarbons and, alcohols, for example, EPON 828, a Bisphenol—A type epoxy compound produced by Shell Chemical Company.
- Other suitable epoxide—containing compounds include epoxidized soybean oil or epoxidized tallate.
- Antioxidants generally used in the dispersion composition of the present invention include hindered phenol—type compounds, for example, 4—methyl—2,6—di— tert—butylphenol and tetrakis[methylene(3,5-di—tert— butyl—4—hydroxyhydrocinnamate) ]methane (Irganox 1010 by Ciba—Geigy Corporation) .
- Other compounds such as
- Tinuvin 770 a hindered amine, are also effective as antioxidants.
- the aqueous coating composition of the present invention is preferably a pigmented composition containing up to 30 parts pigment per 100 parts resin (a plus b) .
- the amount of pigment is preferably up to 20 parts per 100 parts, more preferably 5 aid 15 parts per 100, with 10 to 15 parts per 100 parts resin being most preferred.
- At least a portion of the pigment up to 100 % of the pigment is a metal flake.
- Metal flake flop is greatly enhanced by the present invention thus a significant amount of metal flake in the aqueous coating composition is preferred.
- Aluminum flake is the most preferred metal flake.
- the aqueous coating composition of the present invention is a dispersion and is preferably prepared at a temperature of 25 to 60°C, more preferably 25 to 60°C, with a temperature of 50°C being most preferred due to the solubility of the cellulose mixed ester in the preferred solvent 2—butanol.
- the dispersion preparation time or mixing time is generally between a few seconds and 30 minutes, with a time between 1 and 10 minutes being most preferred. Times shorter than a few seconds are possible but are limited by the speed of adding the cellulose mixed ester composition to the acrylic resin composition whereas times longer than 30 minutes do not significantly increase the homogeneity of the dispersion.
- the dispersions according to the present invention are generally low viscosity and milky in appearance. When coated on wood, metal, leather, and the like, they have good adhesion and dry to form clear, transparent films with good appearance and hardness.
- the dispersion of the present invention can be applied to any suitable substrate by standard methods such as spraying, rolling, and brushing. Among the more useful substrates are metal, wood, leather, plastics, paper, fabrics, and glass.
- the aqueous dispersion of the present invention is applied to a suitable substrate, it is solidified by evaporation of the liquid component or other solidification methods known in the art of coatings and film forming. After solidification the coating can then be cured at elevated temperatures. The curing or drying temperature can vary depending upon the application.
- CABSU160 into the rapidly stirred solvent over a period of 1 or 2 minutes.
- the energy imparted by the mixer caused the temperature to rise and allowed more rapid solution to be obtained.
- the final temperature of the 40 % solids solution was 50°C.
- Neocryl XK62 resin (42 % solids acrylic emulsion from ICI Resins) was then slowly poured into the rapidly stirred CABSU160 solution.
- the viscosity increase caused by the addition of the Neocryl XK62 resin was controlled by adding deionized water intermittently with the resin so that at all times the mixture could be adequately stirred.
- the mixture was poured from the mixing vessel into a bottle and stored until required.
- Preparation of the paint involved adding aluminum flake i.e. Aquavex 516—107P from Silverline Company, which had first been dispersed 1:1 into butyl glycol (ethylene glycol mono butyl ether) to the above dispersion such that the ratio of resin (acrylic + CABSU160) to aluminum flake was 100:15 on a solids basis. This was mixed with gentle agitation until the mixture was homogeneous. Deionized water was added until the viscosity was 20 sec flow time through Din 4 standard viscosity cup.
- aluminum flake i.e. Aquavex 516—107P from Silverline Company, which had first been dispersed 1:1 into butyl glycol (ethylene glycol mono butyl ether) to the above dispersion such that the ratio of resin (acrylic + CABSU160) to aluminum flake was 100:15 on a solids basis. This was mixed with gentle agitation until the mixture was homogeneous. Deionized water was added until the viscosity was 20 sec flow time
- the paint was filtered through a gauze so as to remove any undispersed aluminum flake or other undispersed species and sprayed onto phosphated steel test panels, using an air pressure of 4 bar (60 psi) .
- the air temperature and humidity was 21°C and 45 % RH.
- a dry coating thickness of 15 ⁇ a was obtained from 2 spraying applications with air dried (17 ins after beginning to apply the first coat) a clear solvent based acrylic/melamine paint was applied so as to produce a glossy appearance. After coating to a thickness of 50 ⁇ m, the panel was heated in an oven at 135°C for 30 minutes.
- the paint exhibited excellent metallic appearance with good brightness and flop.
- a similar paint without the addition of CABSU160 was very mottled, grey in appearance and dried more slowly.
- a composition was prepared as above but with 30 weight percent solids in 2—butanol. This facilitated the dissolving of the CABSU but resulted in increased VOC in the paint. The appearance was unaffected.
- Example 3 A composition was prepared as above except that the CABSU160 solution may be poured into the (acrylic or acrylic:polyurethane) dispersion in order to produce the CABSU/acrylic blend. The final dispersion appeared identical to that produced with the reverse additional described.
- CABSU1105 (105 acid number) (8g) powder was slowly poured into a rapidly stirred mixture, using a Silverson High Shear Mixer, of deionized water (140g) to which 35 % ammonia (1.6g) had been added. The viscosity of the clear solution was further reduced with 120.5g of deionized water. The dispersion was labelled D54.
- XPD1162 solid acrylic resin from BF Goodrich
- granules (65.3g) were slowly poured into a rapidly stirred mixture of deionized water (105g) to which 35 % ammonia (13g) had been added. The mixing was carried out using a Silverline High Shear Mixer. This dispersion was labelled XPD1162.
- a clear top coat consisting of an acrylic/melamine paint was spray applied to a dry film thickness of 50 ⁇ m. Curing was carried out in an oven at 135°C for 30 mins. The coating was bright metallic with good flop appearance. The base coat did not contain any volatile organic material. A similar paint which did not contain any CABSU1105 was grey and mottled.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP93908504A EP0631604A1 (en) | 1992-03-18 | 1993-03-02 | Aqueous coatings composition and process for the preparation thereof |
JP5516798A JPH07506134A (en) | 1992-03-18 | 1993-03-02 | Water-based paint composition and its manufacturing method |
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US07/854,501 US5286768A (en) | 1992-03-18 | 1992-03-18 | Aqueous coatings composition contianing cellulose mixed ester and amine neutralized acrylic resin and the process for the preparation thereof |
US854,501 | 1992-03-18 |
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WO1993019136A1 true WO1993019136A1 (en) | 1993-09-30 |
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PCT/US1993/002679 WO1993019136A1 (en) | 1992-03-18 | 1993-03-02 | Aqueous coatings composition and process for the preparation thereof |
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US (1) | US5286768A (en) |
EP (1) | EP0631604A1 (en) |
JP (1) | JPH07506134A (en) |
CA (1) | CA2131913A1 (en) |
WO (1) | WO1993019136A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5384163A (en) * | 1991-10-23 | 1995-01-24 | Basf Corporation | Cellulose esters moidified with anhydrides of dicarboxylic acids and their use in waterborne basecoats |
US5334638A (en) * | 1992-01-21 | 1994-08-02 | Eastman Chemical Company | Aqueous dispersion useful in coatings containing hydrolyzed cellulose ester and acyrlic resin |
US20050166794A1 (en) * | 2004-02-04 | 2005-08-04 | Bauer Richard D. | Binder additive for inkjet ink |
US9273195B2 (en) | 2010-06-29 | 2016-03-01 | Eastman Chemical Company | Tires comprising cellulose ester/elastomer compositions |
US9068063B2 (en) | 2010-06-29 | 2015-06-30 | Eastman Chemical Company | Cellulose ester/elastomer compositions |
US9708472B2 (en) | 2011-12-07 | 2017-07-18 | Eastman Chemical Company | Cellulose esters in highly-filled elastomeric systems |
US10077342B2 (en) | 2016-01-21 | 2018-09-18 | Eastman Chemical Company | Elastomeric compositions comprising cellulose ester additives |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3320865A (en) * | 1964-06-30 | 1967-05-23 | Minnesota Mining & Mfg | Self-developing photographic camera |
US3318714A (en) * | 1965-10-23 | 1967-05-09 | Eastman Kodak Co | Pigment dispersions |
JPS5321225A (en) * | 1976-08-12 | 1978-02-27 | Nippon Oil & Fats Co Ltd | Water-dispersed coating compositions |
JPS5554301A (en) * | 1978-10-17 | 1980-04-21 | Daicel Chem Ind Ltd | Preparation of aqueous dispersion of synthetic resin solubilized with cellulose acetate alkylate |
JPS5823847A (en) * | 1981-08-04 | 1983-02-12 | Kansai Paint Co Ltd | Cellulose derivative-containing emuslion composition |
US4590265A (en) * | 1984-02-17 | 1986-05-20 | Eastman Kodak Company | Carboxylated cellulose ester and manufacture thereof |
GB2156829B (en) * | 1984-04-02 | 1987-08-19 | Kodak Ltd | Base coat compositions for wet-on-wet applicatons, and articles coated therewith |
JPH0793134B2 (en) * | 1987-02-06 | 1995-10-09 | 三菱マテリアル株式会社 | Ceramic molds and punches for dry cell fuel molding |
US4960814A (en) * | 1988-06-13 | 1990-10-02 | Eastman Kodak Company | Water-dispersible polymeric compositions |
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1992
- 1992-03-18 US US07/854,501 patent/US5286768A/en not_active Expired - Fee Related
-
1993
- 1993-03-02 EP EP93908504A patent/EP0631604A1/en not_active Ceased
- 1993-03-02 WO PCT/US1993/002679 patent/WO1993019136A1/en not_active Application Discontinuation
- 1993-03-02 JP JP5516798A patent/JPH07506134A/en active Pending
- 1993-03-02 CA CA002131913A patent/CA2131913A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
WORLD SURFACE COATINGS ABSTRACTS 1984, OXFORD GB page 1422 SAVASTENKO ET AL 'light sensitivity of layers containing acidic mixed acetate esters of cellulose and polyvinyl alcohol' * |
Also Published As
Publication number | Publication date |
---|---|
EP0631604A1 (en) | 1995-01-04 |
CA2131913A1 (en) | 1993-09-30 |
JPH07506134A (en) | 1995-07-06 |
US5286768A (en) | 1994-02-15 |
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