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WO2001035719A2 - Utilisation du carboxymethyle cellulose acetate butyrate (cmcab) dans une formulation de mordançage du bois permettant une bonne adhesion sous la couche de finition - Google Patents

Utilisation du carboxymethyle cellulose acetate butyrate (cmcab) dans une formulation de mordançage du bois permettant une bonne adhesion sous la couche de finition Download PDF

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Publication number
WO2001035719A2
WO2001035719A2 PCT/US2000/041774 US0041774W WO0135719A2 WO 2001035719 A2 WO2001035719 A2 WO 2001035719A2 US 0041774 W US0041774 W US 0041774W WO 0135719 A2 WO0135719 A2 WO 0135719A2
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Prior art keywords
ether
ethylene glycol
reds
agents
propylene glycol
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PCT/US2000/041774
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English (en)
Inventor
Ronald Obie
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Eastman Chemical Company
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Priority to PCT/US2000/041774 priority Critical patent/WO2001035719A2/fr
Publication of WO2001035719A2 publication Critical patent/WO2001035719A2/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/06—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood
    • B05D7/08—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood using synthetic lacquers or varnishes
    • 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
    • C09D15/00—Woodstains
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/06—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood
    • B05D7/08—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood using synthetic lacquers or varnishes
    • B05D7/10—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood using synthetic lacquers or varnishes based on cellulose derivatives

Definitions

  • CMCAB CARBOXYMETHYL CELLULOSE ACETATE BUTYRATE
  • Cellulose esters are polymers, which are useful in many plastic, film, coating and fiber applications. In coatings applications, cellulose esters are generally applied from organic solvent solutions.
  • aqueous coating compositions continue to replace traditional organic solvent-based coating compositions. Paints, inks, sealants, and adhesives, for example, previously formulated with organic solvents are now formulated as aqueous compositions. This reduces potentially harmful exposure to volatile organic compounds (VOC's) commonly found in organic solvent-based compositions.
  • VOC's volatile organic compounds
  • the aqueous coating compositions must meet or exceed the performance standards expected from solvent-based compositions. The need to meet or exceed such performance standards places a premium on the characteristics and properties of such aqueous coating compositions.
  • U.S. Patent Nos. 5,668,273 and 5,994,530 disclose the use of carboxylalkyl cellulose esters, as well as their use in aqueous pigment dispersions and coating compositions.
  • U.S. Patent No. 5,668,273 discloses various new ether derivatives of cellulose esters, which are described as being useful in coating compositions as binder resins and rheology modifiers. These esters are described as having good solubility in a wide range of organic solvents, compatibility with a variety of resins, and ease of dispersion in a water-borne formulation.
  • U.S. Patent No. 5,994,530 describe carboxymethyl cellulose esters of higher acids that are used in aqueous dispersions, which are useful in formulating waterborne coating compositions containing pigments.
  • U.S. Patent Nos. 5,973,139; 5,792,856; and 4,590,265 describes carboxylated cellulose esters, and various synthetic processes for their preparation.
  • U.S. Patent No. 5,973,139 describes a process which includes activating an oxidized cellulose with water, followed by dehydration using acetic acid, and optionally displacing at least some of the acetic acid with butyric acid or propionic acid.
  • the activated cellulose ester is then reacted with an esterifying reagent in the presence of a catalyst.
  • the temperature is gradually increased to a level sufficient to complete the esterification.
  • the carboxylated ester is then hydrolyzed to obtain the desired degree of substitution, and precipitated from solution.
  • U.S. Patent No. 5,792,856 describes a process for preparing carboxyalkyl cellulose esters. The process involves slurrying water wet carboxy(C ⁇ -C 3 alkyl) cellulose (acid form) in a solvent, followed by treating the mixture with certain anhydrides in the presence of a strong acid catalyst. The mixture is heated to about 40° to 55°C until the reaction is complete. Next, a mixture of water, an alkanoic acid, and optionally a C -C 5 alkanoic acid salt of an alkali or alkaline earth metal is added, in an amount that does not totally neutralize the strong acid catalyst. The solution is then heated to effect partial hydrolysis, and in an amount depending on the amount of strong acid catalyst, treated with a C -C 5 alkanoic acid salt of an alkali or alkaline earth metal dissolved in water and an alkanoic acid.
  • U.S. Patent No. 4,590,265 relates to a method for the preparation of carboxylated cellulose esters, by reacting a cellulose ester with ozone at a temperature of about 25° to 80°C, for a period of time sufficient to yield the carboxylate cellulose ester product.
  • the patent also discloses applications for the carboxylated cellulose esters, including metal coatings, pigment dispersions, wood coatings, and inks.
  • U.S. Patent No. 4,520, 192 describes a process for preparing carboxyalkyl acetyl celluloses with a carboxyalkyl degree of substitution (DS) per anhydroglucose unit of 0.2-2.5 and an acetyl DS of 0.5-2.8 and the metal salts of these materials.
  • the preparation of the carboxyalkyl acetyl cellulose is accomplished by converting carboxyalkyl cellulose, sodium salt, into its acid form by soaking in an aqueous acid solution of sulfuric acid, hydrochloric acid, nitric acid, or acetic acid.
  • U.S. Patent No. 3,435,027 describes a base catalyzed (sodium hydroxide) esterification of carboxymethyl cellulose (in the sodium salt form) in 70-85%) acetone nonsolvent media with acetic, propionic, lactic, or stearyl anhydride. The procedure yields a product with a low degree of ester substitution and falls well short of a fully substituted cellulose.
  • USSR Patent 612933 describes a process for preparation of cellulose acetate ethers wherein an alkali activated cellulose (12% sodium hydroxide) is etherified with mono chloro acetic acid followed by esterification with acetic anhydride in the presence of sulfuric acid catalyst. The process is limited to a low DS of the carboxymethyl substituent.
  • U.S. Patent No. 3,789,117 discloses a process for preparing an enteric medicament coating from an organic solvent soluble cellulose derivative.
  • the cellulose derivative's substitution has a carboxymethyl DS range of 0.3 to 1.2 in conjunction with at least one of the remaining hydroxyl groups being etherified or esterified.
  • Ester groups include acetyl, propionyl, butyryl, nitric, or higher fatty acids. The degree of substitution is not specified.
  • RO 96929 (Romania) describes a carboxymethyl cellulose (CMC) acetate with a carboxymethyl degree of substitution of 0.5-3.0, acetyl DS of 0.4-2.9, and viscosity 150-1500 cP.
  • This material was taught to be useful as an alkaline suspension stabilizer, solution thickener, and alkaline media binder. The material was prepared by mixing 70%o acetic acid with CMC(Na salt), washing the acetic wet CMC with 50% acetic acid to remove the sodium acetate, and esterification of the acetic acid wet CMC--H with acetic anhydride for 1.5 hours at 50-110°C. in the presence of sulfuric acid.
  • U.S. Patent No. 5,008,385 reports cellulose derivatives that can be synthesized by homogeneous reaction in dimethylacetamide and/or N-methylpyrrolidine containing LiCl. Included in their examples was CMC acetate (carboxymethyl DS 0.13-0.23, acetyl DS 2.54-2.15). These materials were tested for use in the production of fibers, filaments, or membranes.
  • Carbohydrate Research, 13, pp.83-88, (1970) describes the preparation of CMC acetate by sulfuric acid catalyzed acetylation of CMC (carboxymethyl DS of 0.07) hydrolysis (acetylation and hydrolysis procedures taken from Maim, Ind. Eng. Chem., 38 (1946) 77), and evaluation of this material in membranes for reverse osmosis.
  • GB 2,284,421 discloses carboxymethyl cellulose alkanoates which are "lightly carboxymethylated", i.e., having a degree of substitution per anhydroglucose unit of less than 0.2.
  • Such polymers are taught to be useful as a coating agent for paper and papermaking or as a bonding agent for non-woven fabric, or can be extruded to form filaments or film, or can be used to produce shaped articles.
  • the invention provides a method for making a stained wood substrate having an overcoat, with improved adhesion of the stained wood substrate to the overcoat.
  • the process comprises the step of applying an aqueous carboxymethyl cellulose acetate butyrate (CMCAB) stain composition to a wood substrate, forming a stained wood substrate.
  • the aqueous CMCAB stain composition contains CMCAB, optionally a colorant, water, and an organic solvent.
  • the stained wood substrate is then dried.
  • an overcoat is applied to the stained wood substrate, forming a coated, stained wood substrate.
  • the coated, stained wood substrate is then cured.
  • This method for improving the adhesion of the stained wood substrate to an overcoat relates to a wide variety of wood substrates.
  • wood substrates include, but are not limited to: oak, maple, yellow pine, birch, spruce, walnut, poplar, and aspen. Other wood substrates may also be used.
  • the stained wood substrate that is formed will be compatible with a variety of overcoats, including, but not limited to: UN-curable overcoats, lacquer overcoats, acid-curable overcoats, nitrocellulose overcoats, thermoplastic overcoats, thermosetting overcoats, polyurethane overcoats, etc.
  • the method of the invention has the advantage of improving the adhesion of the stained wood substrate to an overcoat. Other advantages are reduced grain raising, increased wetting, increased adhesion with topcoats, and improved brightness.
  • the stained wood substrate wipes well, and is compatible with a variety of colors, substrates, and overcoats.
  • the invention solves many of the existing problems with waterborne wood stains currently on the market.
  • the replacement of the acrylic resin in the stain with a lesser total amount of CMCAB makes the waterborne stain behave more like a solventborne stain. It can be applied by a variety of methods known in the art, such as wiping with a rag, brushing, etc. If the CMCAB stain is applied by brush, it has the advantage of not gumming up the brush. In addition, the CMCAB stain raises the wood grain to a lesser extent and provides excellent adhesion to a wide variety of topcoats.
  • This invention relates to a method for making a stained wood substrate having an overcoat, where the substrate displays improved adhesion of the stained wood substrate to the overcoat.
  • the wood substrate formed by this method also exhibits reduced grain raising, increased wetting, increased adhesion with topcoats, and improved brightness.
  • the stain wipes well, and is compatible with a variety of colors, substrates, and overcoats.
  • the invention is used with cellulosic wood substrates.
  • Cellulose is a natural carbohydrate polysaccharide consisting of anhydroglucose units joined by an oxygen linkage to form long molecular chains, which are essentially linear. See Richard J. Lewis, Sr., Hawley's Condensed Chemical Dictionary, Thirteenth Edition, John Wiley & Sons, Inc., New York, 1997.
  • the cellulose may be chemically modified, i.e. chemical groups (carboxyl, alkyl, acetate, nitrate, ether, etc) may be substituted for the hydroxyl groups along the carbon chain.
  • the invention may also be practiced with a broad variety of substrates, made from various materials, such as wood, plastic, paper or cardboard.
  • the invention relates to wood substrates.
  • wood substrates include, but are not limited to: oak, maple, yellow pine, birch, spruce, walnut, poplar, and aspen.
  • Other wood substrates may also be used, as well as various veneer substrates.
  • the process of the invention comprises the step of applying a carboxymethyl cellulose acetate butyrate (CMCAB) stain composition to the wood substrate to form a stained wood substrate.
  • the CMCAB stain composition comprises CMCAB, and optionally one or more colorants, / ' . e. one or more organic or inorganic pigments and/or dyes, water and an organic solvent.
  • the CMCAB stain composition will be applied as a wet coat, and contain about 12% solids, with pigment to binder in a ratio of about 0: 1 to 2.5: 1.
  • the CMCAB stain composition will contain up to about 30% solids, up to about 15% solids, or about 10%> solids.
  • the CMCAB stain composition will be a natural stain without any colorants.
  • the aqueous CMCAB stain composition may be applied by any means known in the art.
  • the CMCAB coating composition may be applied by spray, wiping with a rag, or by painting with a brush or a roller. Other methods known in the art for applying a coating composition are also acceptable.
  • the CMCAB stain composition to be applied to the substrate will comprise certain esters of carboxy(C ⁇ -C 3 alkyl) cellulose, which are useful as components of coating compositions.
  • esters preferably have an inherent viscosity of 0.20 to 1.7 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol tetrachloroethane at 25°C, a degree of substitution per anhydroglucose unit of carboxy(d -C 3 alkyl) of about 0.20 to 0.75, and a degree of substitution per anhydroglucose unit of C -C 4 esters of about 1.5 to about 2.7.
  • the CMCAB stain composition comprises a carboxymethyl cellulose acetate butyrate having a degree of substitution of carboxymethyl of 0.20 to 0.75, preferably 0.25 to 0.35, a degree of substitution per anhydroglucose unit of hydroxyl from about 0.10 to 0.70, and a degree of substitution per anhydroglucose unit of butyryl of about 0.10 to 2.60 and a degree of substitution per anhydroglucose unit of acetyl of 0.10 to 1.65, and having an inherent viscosity of 0.20 to 1.70 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25°C. It is preferred that the degree of substitution per anhydroglucose unit of hydroxyl is 0.10 to 0.70, butyryl is 1.10 to 2.55, and acetyl is 0.10 to 0.90.
  • the C -C 4 esters of carboxy(C ⁇ -C 3 alkyl) cellulose of the invention may be prepared by any method known in the art. As an example, they may be prepared by the following multi-step process. In this process, the free acid form of, for example, carboxy-methyl 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 aliphatic acid (propionic acid or butyric acid) to give a carboxymethyl cellulose (CMC— H) activate wet with the appropriate aliphatic acid.
  • an alkanoic acid such as acetic acid followed by treatment with a higher aliphatic acid (propionic acid or butyric acid) to give a carboxymethyl cellulose (CMC— H) activate wet with the appropriate aliphatic acid.
  • the starting carboxymethyl cellulose be prepared from cellulose with a 95 to 99%o alpha content, preferably about 96 to 97% alpha cellulose content.
  • the high alpha content is important for the quality of the final products prepared therefrom.
  • the CMC--H is treated with the desired anhydride in the presence of a strong acid catalyst such as sulfuric acid to give a fully substituted carboxymethyl cellulose ester.
  • a strong acid catalyst such as sulfuric acid
  • a final solution consisting of water and an aliphatic acid
  • the final addition allows a slow transition through the hydrous point to give 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 crucial for hydrolysis of combined sulfur from the cellulose backbone.
  • This product is then hydrolyzed using sulfuric acid to provide a partially substituted carboxymethyl cellulose ester. Hydrolysis is necessary to provide gel free solutions in organic solvents and to provide better compatibility with other resins in coatings applications.
  • 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 carboxy(C ⁇ -C 3 alkyl) 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 1.5 to 3.0 times its weight. This is followed by addition of 1.5 to 3.0 volumes of water to give a particle that can be easily washed with de-ionized water to efficiently remove residual organic acids and inorganic salts.
  • the fully substituted or partially hydrolyzed forms of carboxy(C ⁇ -C 3 alkyl) cellulose ester are isolated by precipitation of the diluted dope by addition of about 2.0 times its volume of 10% aqueous acetic acid, followed by an additional 2.0 times the dope volume of water.
  • the reaction mixture is diluted with an equal volume of acetic acid, followed by precipitation of the diluted product into a volume of water about 1.5 to 3.0 times its weight, followed by an additional volume of water about 1.5 to 3.0 times its weight, washed with deionized water and dried to provide the desired product as a powder or granules.
  • This powder is thus free from any significant amount of residual organic acids and inorganic salts.
  • the reaction mixture is diluted with an equal volume of acetic acid, followed by precipitation of the diluted product by the addition of about 2.0 times its volume of aqueous acetic acid, followed by about 2.0 times its volume of water, washed with deionized water and dried to provide the desired product as a powder.
  • the CMCAB stain composition may optionally contain one or more colorants, i.e. one or more organic or inorganic pigments and/or dyes, including extender pigments. Any colorants known to one of ordinary skill in the art may be used.
  • Typical white pigments include titanium dioxide, zinc oxide, zinc sulfide, white lead, lithophone, and modifications thereof.
  • Black pigments are selected from the group of mineral blacks, bone blacks, iron oxide blacks, and carbon blacks, for example.
  • Inorganic colored pigments include lead chromates, metal oxides, sulfides and sulfoselenides, iron blue, cobalt blue, ultramarine blue, manganese violet, bismuth vanadate, and molybdate yellow, for example.
  • organic colored pigments include metallized azo reds including lithol reds, permanent red 2B, lithol rubine red, BON reds, BON maroon-nonmetallized azo reds including toluidine red, para reds, napthol reds, quinacridone reds, vat reds, anthraquinone red, brominated pyranthrone red, perylene reds, benzimidazolon based reds, diazo condensation reds, thioindigoid reds, pigment red 251, 252, and 257.
  • Blue pigments include, but are not limited to, copper phthalocyanine blues, indanthrone blue, and carbazole violet.
  • yellow pigments examples include monoarylide yellows, diarylide yellows, benzimidazolone yellows, and heterocyclic yellows.
  • Orange pigments include azo-based oranges, bisazo-based oranges, bisazo condensation-based oranges, perinone type orange, quinacridone type orange, pyranthrone type orange, heterocyclic hydroxy-based orange, and pyrazoloquinazolone-based orange.
  • green pigments include copper phthalocyanine greens, and triphenylmethane-phospho tungsto molybdic acid (PTMA) complexes.
  • PTMA triphenylmethane-phospho tungsto molybdic acid
  • Extender pigments include calcium carbonate, kaolin or china clay, talc, silica, mica, barium sulfate, wollastonite, sodium alumino silicates, alumina trihydrate, and aluminum oxide.
  • Metallic Pigments include, but are not limited to, aluminum, zinc, gold, bronze, nickel, and stainless steel.
  • pearlescent pigments include titanium dioxide and ferric oxide coatings on mica, bismuth oxychloride crystals grown from a solution of bismuth salts, natural pearl essence, guanine, and hypoxanthane purines from fish scales. This list is not meant to be exclusive.
  • Dyes that might be used are included in the following classes, i.e., Acid dyes, Azoic Coupling Components, Azoic Diazoic Components, Basic dyes, Direct Dyes, Reactive dyes, Solubilized Nat Dyes, Solvent Dyes, Sulfur Dyes, Nat Dyes, and Aniline Dyes.
  • Specific dyes by C.I. number and dyes of both domestic and foreign manufacture can be found in the Colour index and its Additions and Amendments, published jointly by the American Association of Textile Chemist and Colorists, Research Triangle Park, ⁇ C and The Society of Dyers and Colourists in Bradford, England.
  • Other suitable pigments and dyes are known in the art.
  • Pigment dispersions may be prepared by blending the cellulose ester and a pigment with heat and/or shear to disperse the pigment. In this manner, pigments can be easily dispersed in coating formulations, thereby providing high coloring power and good transparency while using a minimal amount of pigment.
  • CMC esters and pigments may be prepared at pigment to ester ratios of from about 10:90 to about 90:10 weight percent. In a high shear environment, such as when using organic pigments, it is preferable to use pigments in an amount from about 10 to 20 weight percent, and esters in an amount from about 90 to 80 weight percent. These dispersions may be prepared on two-roll mill, ball mill, Kady mill, sand mill, Cowles mixers, and the like.
  • the pigments may be present in an amount from about 50 to 90 weight percent and the C 2 -C 4 esters of carboxy(Ci -C 3 alkyl) cellulose in an amount from about 50 to 10 weight percent.
  • a typical pigment dispersion may be formed by blending either a solution or a dispersion of the esters with the pigment with the necessary shear required in order to disperse the pigment.
  • the coatings may be applied to a substrate in the form of an organic solvent solution, an amine neutralized waterborne dispersion, a fully neutralized aqueous/organic colloidal dispersion, or as a zero NOC-exempt solvent dispersion in acetone with aqueous ammonia.
  • the coatings may also act as a protective coating for a variety of substrates, especially metal and wood.
  • solvents include: acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, 2-propoxy- ethanol, 2-butoxyethanol, ethyl 3-ethoxypropionate, 2-butanone, methanol, ethanol, propanol, isopropyl alcohol, butanol, 2-ethyl-hexanol, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethyl ether, propyl ether, propyl glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, dipropylene glycol ether, dipropylene glycol methyl ether, ethylene glycol, ethylene glycol butyl ether, ethylene glycol,
  • the amount of solvent will be adjusted in order to dissolve and/or suspend the various components of the composition in a uniform liquid suspension or liquid.
  • organic solutions of the esters of this invention may be prepared by adding 1 to 1000 parts of solvent per part of ester; 1.5 to 9 parts of solvent per part of ester is preferred.
  • the CMCAB stain composition will be aqueous, which will reduce VOCs.
  • minor amounts of an organic solvent may help to reduce grain raising. Grain raising results in the roughening of the surface of the wood substrate. It is usually initiated by the absorption of moisture or water, which is absorbed by cellulosic material in the wood cell wall. Because the amount of cell wall substance varies across the wood substrate, variations in the amount of moisture/water absorption takes place resulting in differential swelling and shrinking hence resulting in a grain raised or roughened surface.
  • the amounts of organic solvents are generally minimized in order to minimize volatile organic content (V.O.C.).
  • Preferred embodiments of the compositions of the invention have N.O.C. less than 3 g/gallon, most preferably less than 2.6 g/gallon.
  • the CMCAB esters used in the invention possess free hydroxyl groups and thus can also be utilized in conjunction with crosslinking agents such as melamines and isocyanates.
  • melamines are preferably compounds having a plurality of — ⁇ (CH 2 OR) functional groups, wherein R is Ci -C 4 alkyl, preferably methyl.
  • the melamine cross-linking agent may be selected from those known in the art. Examples of crosslinking agents include hexamethoxymethylmel amine, tetramethoxymethylbenzoguanamine, tetramethoxymethylurea, mixed butoxy/methoxy substituted melamines, and the like.
  • melamine cross-linking agent is hexamethoxymethylmelamine and urea-formaldehyde.
  • Typical isocyanate crosslinking agents and resin include hexamethylene diisocyanate (HMDI), isophorone diisocyanate (LPDI), and toluene diisocyanate, and their adducts.
  • Preferred epoxy functional resins generally have a molecular weight of about 300 to about 4000, and have approximately 0.05 to about 0.99 epoxy groups per 100 g of resin (i.e., 100-2000 weight per epoxy (WPE)).
  • WPE weight per epoxy
  • Such resins are widely known and are commercially available under the EPONTM trademark of the Shell Chemical Company, the ARALDITETM trademark of CIBA-Geigy, and D.E.R. resins of the Dow Chemical Company.
  • resins include polyester resins, including water extended polyesters, polystyrene, vinyl resins including polyvinylacetate, polyvinylchloride, vinylchloride-vinylacetate copolymers and the like; polyamide resins, polyurea resins, and acrylic resins; phenolic resins, maleic resins, coumerone-indene resins, urea-formaldehyde; melamine-formaldehyde resins; epoxy resins, silicone resins, ionomer resins, acetal resins, polyethylene, polypropylene, hydrocarbon resins, rubber derivatives, polycarbonate resins, phenoxy resins, fluorol plastics, styrene-butadiene resins, polyurethane resins, furane resins, polysulfone resins, pentaerythritol resins, ester gum, co-polyesters, UN-curable oligomers with corresponding photoinitiators, and the like.
  • 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 waxes, leveling, flow control agents and rheology modifiers such as silicones, clays, fluorocarbons, cellulosics, and organic rheology modifiers such as acrylics, and mixtures thereof; flatting agents; pigment wetting and dispersing agents; surfactants; ultraviolet (UN) absorbers; UN 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.
  • Specific examples of additional coatings additives can be found in Raw Materials Index, published by the National Paint & Coatings Association,
  • 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.
  • Coating compositions of the invention may also contain any compatible plasticizer known in the art.
  • plasticizers include, but are not limited to, texanol isobutyrate, diisononyl phthalate, dioctyl phthalate, butyl benzyl phthalate, dibutyl phthalate, diethylene glycol, dioctyl terephthalate, and mixtures thereof.
  • plasticizers include TXEB (Texanol Isobutyrate, commerically available from Eastman Chemical Company), DINP (Diisononyl Phthalate, commerically available from Exxon Mobile Chemical Company), DOP (Dioctyl Phthalate, commerically available from Eastman Chemical Company), BBP (Butyl Benzyl Phthalate, commerically available from Solutia, Inc.), DBP (Dibutyl Phthalate, commerically available from Eastman Chemical Company), EMN-425 (a blend of 75/25 DOTP/Benzoate ester, commerically available from Eastman Chemical Company), DOA (dioctyl adipate), and TEG-2EH (triethylene glycol di-2- ethylhexanoate).
  • 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, tetra-sodium N-(l,2-dicarboxy- ethyl)-N-octadecyl sulfosuccinnamate, disodium N-octasulfo-succinnamate, sulfated ethoxyl
  • viscosity, suspension, and flow control agents examples include polyaminoamide phosphate, high molecular weight carboxylic acid salts of polyamine amides, and alkyl amine salt of an unsaturated fatty acid, all 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 1,2- benzisothiazolin-3-one, 4,4-dimethyloxazolidine, 3,4,4-trimethyloxazolidine, modified barium metaborate, potassium N-hydroxy-methyl-N-methyldithiocarbamate, 2-(thiocyanomethylthio) benzothiazole, potassium dimethyl dithio-carbamate, adamantane, N-trichloro-methylthio) phthalimide, 2,4,5, 6-tetra-chloroisophthalo- nitrile, 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 UN. light stabilizers include substituted benzophenone, substituted benzotriazole, hindered amine, and hindered benzoate, available from American Cyanamide Company under the tradename Cyasorb UV, and available from Ciba Geigy under the trademark TINUVIN, and diethyl-3-acetyl- 4hydroxy-benzyl-phosphonate, 4-dodecyl-oxy-2-hydroxy benzophenone, and resorcinol monobenzoate.
  • the stained wood substrate is then dried by any means known in the art. Typical drying methods include providing combinations of heat and/or air and/or UN light in order to speed the rate of drying.
  • overcoats are applied to the stained wood substrate.
  • overcoats include, but are not limited to, UN- curable clearcoats, lacquers, acid cures, nitrocellulose coatings, etc.
  • the overcoat may be applied by any acceptable method known in the art, i.e. application by spraying or coating.
  • the overcoat in the form of a powder, may be sprayed onto the substrate by well known electrostatic powder spray techniques, such as corona discharge or triboelectric electrostatic spray techniques. After the overcoat is applied, the stained, coated substrate is cured.
  • the coated, stained substrate produced according to the invention will exhibit improved adhesion of the stained wood substrate to an overcoat.
  • Other advantages are reduced grain raising, increased wetting, increased adhesion with topcoats, and improved brightness.
  • the stain produced by the method of the invention wipes well, and is compatible with a variety of colors, substrates, and overcoats.
  • CMCAB esters usable in this invention may be prepared as described in U.S. Patent No. 5,994,530, which is hereby incorporated in its entirety.
  • the CMCAB esters used in the following examples were prepared according to the following description.
  • CMC— H free acid
  • the activate was transferred to a 2 liter round bottom flask and chilled in ice for 1 hour.
  • the activate was esterified by treating with 264 grams of butyric anhydride, 30 grams of acetic anhydride, and 2.94 grams of sulfuric acid at 0°C.
  • the reaction was allowed to warm as a result of the exotherm and proceeded to dissolution after 2.1 hours at 45° C. (additional heat was required to hold the temperature at 43° C).
  • a solution of 74 grams of water and 74 grams of acetic acid was added dropwise to the reaction mixture over 30 minutes generating an exotherm of approximately 15° C. as a result of reaction of excess anhydride with water.
  • the contents were hydrolyzed by heating to 60° C. for 4.5 hours.
  • the sulfuric acid catalyst was then neutralized by the addition of 7.1 grams of magnesium acetate (tetrahydrate) in 20 mL of water and 19 mL of acetic acid.
  • the reaction contents were diluted with an equal weight of acetic acid and precipitated by adding 3,000 mL of 10% aqueous acetic acid.
  • the precipitated particles were hardened by the addition of 3,000 mL of water.
  • CMC — H Activation of CMC (CMC— H):
  • CMC — H was washed in water with stirring for 5 minutes to 1 hour. The water was drained to approximately 20%> solids. The water-wet CMC — H was dewatered by washing 3 times with 200-500 grams of acetic acid followed by 3 washes with 200-500 grams of butyric acid. In between each wash the sample was drained to approximately 16-18% solids. After the final butyric acid wash, vacuum was applied to obtain the butyric acid wet CMC — H activate at 15-40%> solids.
  • the butyric acid wet CMC — H was combined with 31 grams of acetic anhydride, and 253 grams of butyric anhydride at 0° C.
  • a catalyst solution consisting of 3.44 grams of sulfuric acid in 3.44 grams of acetic acid was added slowly to the reaction mixture keeping the temperature below 30° C. After completion of the catalyst addition, the temperature was ramped from 30° C. to 35° C. over 150 minutes. The temperature was then ramped from 35° to 45° C. over a 60 minute period. The reaction mass was heated at 45° C. until complete dissolution of the solids to an acid dope.
  • the resulting dope was diluted with acetic acid and water to give about a 1 : 1 ratio of acetyl/butyryl and approximately 20%> water concentration.
  • the acid dope was held at 65° C. and circulated through a 0.5 micron filter to remove any particulates. 6. Precipitation:
  • the dope from above was added to water with agitation to give a flake precipitate. This material was allowed to harden, washed with water, and dried at 60° C.
  • An optional precipitation method is to add 10% aqueous acetic in sufficient volume to yield about 30% organic acid in the final precipitation bath followed by the addition of an equal amount of water. The precipitate is then washed with water and dried at 60° C.
  • the acid number of a carboxy(C]-C 3 alkyl) cellulose ester is determined by titration as follows. An accurately weighted aliquot (0.5-1.0 g) of the carboxy(C ⁇ -C 3 alkyl) cellulose ester was mixed with 50 mL of pyridine and stirred. To this mixture was added 40 mL of acetone followed by stirring. Finally, 20 mL of water was added and the mixture stirred again. This mixture was titrated with 0.1N sodium hydroxide in water using a glass/combination electrode. A blank consisting of 50 mL pyridine, 40 mL of acetone and 20 mL water was also titrated. The acid number was calculated as follows where:
  • acetyl, propionyl, and butyryl weight percents were determined by a hydrolysis GC method. In this method, about 1 g of ester was weighed into a weighing bottle and dried in a vacuum oven at 105° C. for at least 30 minutes. Then
  • Ci concentration of I(acyl group)
  • Ci ((Fi*Ai)/Fs*As))*R*100
  • This GC method was used instead of NMR because the methylene of the carboxymethyl group cannot be separated from the ring protons of the cellulose backbone making absolute DS measurements by NMR difficult.
  • the DS values were calculated by converting the acid number to percent carboxymethyl.
  • the CMCAB dispersion was made by mixing 563.81 g EB (ethylene glycol butyl ether, commercially available from Eastman Chemical Company), and 241.63 g of CMCAB for 30 minutes, until dissolved. Next, 5.96 g of AMP-95 (2-amino-2- methyl- 1-propanol) was added, followed by the slow addition of 1188.60 g of distilled water, added at a rate of approximately 4 teaspoons at a time. The pH of the resulting dispersion was about 4.70.
  • Formulation A is summarized in Table 1, below. Table 1. Formulation A (CMCAB Dispersion - Approx. 2000 Grams)
  • a LAPONITE RDSTM thickener solution was made by mixing 171 g of tap water with 19 g of LAPONITE RDSTM (commercially available from Southern Clay Products, Inc. Gonzales, Texas), until clear and homogeneous.
  • Formulation B is summarized in Table 2, below.
  • Viscosity was measured using a #2 Zahn dip cup, signature series at 74°F.
  • Batch (i) had a viscosity of 17.34 seconds (under agitation), while Batch (ii) had a viscosity of 18.91 seconds (without agitation).
  • Batch (i) and (ii) had a pH of about 7.41 and 7.42, respectively. Both batches were slow to gravity filter.
  • Formulation C is summarized in Table 3, below.
  • the CMCAB dispersion was made by mixing 140 g EB (ethylene glycol butyl ether, commercially available from Eastman Chemical Company), and 60 g of CMCAB for 30 minutes, until dissolved. Next, 1.48 g of AMP-95 (2-amino-2- methyl- 1-propanol) was added, followed by the slow addition of 295.14 g of distilled water. The formulation was filtered through nylon mesh. Formulation D is summarized in Table 4, below. 7 ⁇ b/e 4. Formulation D
  • the formulation was made by mixing 245.198 g of distilled water, 12.9 g of
  • Formulation B and 10.26 g of ACRYSOL SCT-275TM (commercially available from Rohm and Haas Co, Philadelphia, PA). Next, 120.0 g of Formulation D was added, with mixing. Next, 77.39 g of TINT-AYD CW5509TM (commercially available from Elementis Specialties, Jersey City, NJ) was added and mixed. The resulting formulation had a viscosity of 18.22 when measured using a #2 Zahn dip cup, signature series at 77°F.
  • Formulation E is summarized in Table 5, below.
  • Formulation F was prepared by combining 151 ,07g of Formulation E, and
  • Formulation G was prepared by combining 70g of ethylene glycol butyl ether and 30g of CMCAB, and mixing for thirty minutes. Next, 0.74 g of AMP-95 (2- amino-2-methyl- 1-propanol) was added, followed by the slow addition of 147.57 g of distilled water. The pH of the resulting dispersion was about 5.3-5.4. Formulation G is summarized in Table 7, below.
  • a clear base was made by mixing 353.04 g distilled water, 0.54 g of PROXEL
  • Formulation I was prepared by combining 46. Og of distilled water, 41.20 g
  • DISPERBYK 190TM commercially available from Byk Chemie, Wallingford, CT
  • 2.0 g of BYK 019 commercially available from Byk Chemie, Wallingford, CT
  • BYK 019 commercially available from Byk Chemie, Wallingford, CT
  • PROXEL GXLTM l,2-benzisothiazolin-3-one
  • AEROSIL 200TM commercially available from Degussa Corp., Akron, OH
  • Burnt Umber 5250 (commercially available from Harcross Pigments, Fairview
  • Sunsperse WHD 9507TM is commercially available from Sun Chemical Corporation, Cincinnati, OH; Sunsperse RHD 9584TM is commercially available from Sun Chemical Corporation, Cincinnati, OH; RBH 509901TM is commercially available from Hilton Davis/B.F. Goodrich; Cincinnati, OH; Creanova 877-0019TM is commercially available from Creanova, Somerset, NJ; BFG 13464-07-7TM is commercially available from Hilton Davis/B.F. Goodrich, Cincinnati, OH; Tint-Ayd CW5509TM is commercially available from Elementis Specialties, Jersey City, NJ; and Tint-Ayd CW5003TM is commercially available from Elementis Specialties, Jersey City, NJ.
  • the Nickel adhesion test was conducted by placing a nickel in contact with the coated substrate at about a 45-degree angle so that the sharp edge of the nickel was in contact with the coating surface. The nickel was then pulled toward the operator at a moderate rate and with moderate to heavy pressure. The scraped coating area was observed for delamination/whitening, surface mar and/or coating removal, i.e. topcoating removal from undercoating or removal of the entire coating system from the substrate.
  • D3359 which is hereby incorporated by reference.
  • the test was conducted by making 2 sets of 6 parallel cuts (spaced 2mm apart), at right angles to one another, into the coated substrate with sufficient pressure to just go through the coating to the substrate.
  • a cutting tool kit purchased from Paul N. Gardner Co. of Pompano Beach,
  • Formulation C stains were tested by applying the stains to red oak veneer that had been scuff sanded with 220 stearated paper.
  • Formulation C, batch (i) and batch (ii) were applied at 21°C and 48% relative humidity.
  • the Formulation C stain was compared to Formulation E (aged) stain.
  • a UN- curable coating based on a polyester acrylate/urethane acrylate blend was applied with a 5 RDS rod.
  • the UN-clear coating was cured by passing through an American ultraviolet UV conveyor in one pass at 14 ft/minute using a 300 Watt lamp. The cure energy that the product was exposed to was 887mj/cm 2 , UNA.
  • the coated veneer was sponge sanded with a fine sanding sponge from 3M company.
  • the UV coating was applied a second time, and the substrate was again cured as described above.
  • Formulation C was run on a production-type sponge roller machine with 2 brushes following. The stain applied well. The stain brushed out well. The stain was run on red oak veneer and solids. Two grades of veneer were utilized, i.e. good veneer and poor veneer; the good veneer was of much higher quality than the poor veneer. All parts were scuffed with 220 stearated prior to staining. The stained parts were run through an oven twice at some temperature. It was estimated that the board surface temperature out of the oven the second time was about 130°F. The grain raising results for the good veneer and the poor veneer are summarized as follows:
  • the grain raising of the solid oak and the highest quality veneer was satisfactory; however, the grain raising of the poor quality veneer was unsatisfactory. However, it is noted that the poor quality veneer would typically be filled with UV filler.
  • the stains were applied to red oak veneer with a rag. Formulation J was used as the control.
  • the stained panels were dried at 120°F for 19 minutes and cooled for 10 minutes.
  • a UV topcoat was applied by 5 RDS draw down.
  • the UN-clear coating was cured by passing through an American ultraviolet UV conveyor in one pass at 10 ft/minute using a 300 Watt lamp.
  • the cure energy that the product was exposed to was 1206mj/cm 2 , UNA.
  • the first coat was sponge sanded and a second coat applied and cured in the same manner.
  • the following table summarizes stain application and adhesion results.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un procédé permettant de réaliser un substrat de bois mordancé pourvu d'une couche de finition aux qualités d'adhésion accrues. Selon ce procédé on applique d'abord sur un substrat de bois une composition aqueuse de mordançage à base de carboxyméthyle cellulose acétate butyrate, de façon à obtenir un substrat de bois mordancé, puis à le laisser sécher. On applique ensuite sur le substrat de bois mordancé la couche de finition, ce qui donne un substrat de bois mordancé fini, et on le laisse durcir. Selon l'invention, la composition aqueuse de mordançage à base de carboxyméthyle cellulose acétate butyrate utilisée pour le traitement comprend du carboxyméthyle cellulose acétate butyrate, éventuellement un colorant, de l'eau, et un solvant organique.
PCT/US2000/041774 2000-11-02 2000-11-02 Utilisation du carboxymethyle cellulose acetate butyrate (cmcab) dans une formulation de mordançage du bois permettant une bonne adhesion sous la couche de finition WO2001035719A2 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004061021A1 (fr) * 2002-12-27 2004-07-22 Eastman Chemical Company Dispersions minerales contenant du butyrate d'acetate carboxymethylcellulose et leur utilisation en tant qu'agents de matite dans des compositions de revetement
WO2004083253A1 (fr) * 2003-03-14 2004-09-30 Eastman Chemical Company Esters melanges a du cellulose a bas poids moleculaire et leur utilisation en tant que liants a faible viscosite et agents de modification dans des compositions de revetement
WO2005085341A1 (fr) * 2004-03-02 2005-09-15 Poly Coat Pty Ltd Systeme d'appret pouvant etre peint
WO2018064669A1 (fr) * 2016-09-30 2018-04-05 The Sherwin-Williams Company Teinture à bois hydrocompatible à base de polysaccharide
US10793737B2 (en) 2017-12-29 2020-10-06 Behr Process Corporation Fast dry stain formula

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004061021A1 (fr) * 2002-12-27 2004-07-22 Eastman Chemical Company Dispersions minerales contenant du butyrate d'acetate carboxymethylcellulose et leur utilisation en tant qu'agents de matite dans des compositions de revetement
CN103145856A (zh) * 2003-03-14 2013-06-12 伊士曼化工公司 低分子量纤维素混合酯及其作为低粘度基料和改性剂在涂料组合物中的应用
WO2004083253A1 (fr) * 2003-03-14 2004-09-30 Eastman Chemical Company Esters melanges a du cellulose a bas poids moleculaire et leur utilisation en tant que liants a faible viscosite et agents de modification dans des compositions de revetement
WO2004083254A1 (fr) * 2003-03-14 2004-09-30 Eastman Chemical Company Esters de carboxyalkylcellulose a faible poids moleculaire et leur utilisation en tant que liants et modificateurs a faible viscosite dans des compositions de revetement
JP2006523752A (ja) * 2003-03-14 2006-10-19 イーストマン ケミカル カンパニー 低分子量セルロース混合エステル並びに低粘度結合剤及び改質剤としての被覆組成物へのそれらの使用
US7585905B2 (en) 2003-03-14 2009-09-08 Eastman Chemical Company Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions
EP2301973A3 (fr) * 2003-03-14 2011-11-09 Eastman Chemical Company Esters mélangés à faible poids moléculaire et leur utilisation en tant que liants à faible viscosité et modificateurs dans les compositions de revêtement
WO2005085341A1 (fr) * 2004-03-02 2005-09-15 Poly Coat Pty Ltd Systeme d'appret pouvant etre peint
US8158703B2 (en) 2004-03-02 2012-04-17 Poly Coat Pty. Ltd. Paintable primer system
WO2018064669A1 (fr) * 2016-09-30 2018-04-05 The Sherwin-Williams Company Teinture à bois hydrocompatible à base de polysaccharide
GB2569480A (en) * 2016-09-30 2019-06-19 Swimc Llc Polysaccharide-based water-compatible wood stain
US10519334B2 (en) 2016-09-30 2019-12-31 The Sherwin-Williams Company Polysaccharide-based water-compatible wood stain
GB2569480B (en) * 2016-09-30 2023-02-15 Swimc Llc Polysaccharide-based water-compatible wood stain
US10793737B2 (en) 2017-12-29 2020-10-06 Behr Process Corporation Fast dry stain formula

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