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WO2004030801A1 - Utilisation d'esters de cellulose carboxyalkyles tels que l'acetate butyrate de cellulose carboxymethyle pour former des materiaux hydrophobes dans l'eau - Google Patents

Utilisation d'esters de cellulose carboxyalkyles tels que l'acetate butyrate de cellulose carboxymethyle pour former des materiaux hydrophobes dans l'eau Download PDF

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WO2004030801A1
WO2004030801A1 PCT/US2003/031049 US0331049W WO2004030801A1 WO 2004030801 A1 WO2004030801 A1 WO 2004030801A1 US 0331049 W US0331049 W US 0331049W WO 2004030801 A1 WO2004030801 A1 WO 2004030801A1
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water
aqueous
carboxymethyl cellulose
cmcab
acrylated
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Ronald Todd Obie
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Eastman Chemical Co
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Eastman Chemical Co
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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/34—Higher-molecular-weight carboxylic acid esters
    • 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
    • C09D101/32—Cellulose ether-esters
    • 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
    • C08L1/32—Cellulose ether-esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Definitions

  • Carboxyalkyl Cellulose Esters such as Carboxymethyl
  • the present invention relates to methods of dispersing hydrophobic materials into water, using carboxyalkyl cellulose esters such as carboxymethyl cellulose acetate butyrate (CMCAB), and to the resulting aqueous dispersions.
  • CMCAB carboxymethyl cellulose acetate butyrate
  • the invention relates also to finished coating films made from such dispersions, which exhibit reduced water sensitivity without increasing the film dry time beyond that obtained from aqueous dispersions using conventional surfactants.
  • cellulose esters are polymers which are useful in many plastic, film, coating, and fiber applications. In coatings applications, cellulose esters are typically applied as organic solvent solutions.
  • aqueous coating compositions continue to replace traditional organic solvent-based coating compositions. Paints, inks, sealants, and adhesives, for example, that were previously formulated with organic solvents, are now formulated as aqueous compositions, in order to reduce the amount of volatile organic compounds (NOC's) commonly found in such organic solvent-based compositions. While the move from organic solvent-based compositions to aqueous compositions is believed to bring health and safety benefits, the aqueous coating compositions are expected to meet or exceed the performance standards of solvent-based compositions. The need to meet or exceed such performance standards places a premium on the characteristics and properties of these aqueous coating compositions.
  • U.S. Patent ⁇ os. 5,668,273 and 5,994,530 disclose carboxylalkyl cellulose esters, including carboxymethyl cellulose acetate butyrate (CMCAB), and their use in aqueous pigment dispersions and coating compositions.
  • CMCAB carboxymethyl cellulose acetate butyrate
  • U.S. Patent No. 5,668,273 discloses various new ether derivatives of cellulose esters useful in coating compositions as binder resins and rheology modifiers. These esters exhibit 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 describes carboxymethyl cellulose esters of higher acids that are used in aqueous dispersions to formulate waterborne coating compositions containing pigments.
  • U.S. Patent No. 5,792,856 describes a process for preparing carboxyalkyl cellulose esters that involves slurrying water-wet carboxy(C 1 -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.
  • a mixture of water, an alkanoic acid, and optionally a C 2 -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 2 -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.
  • 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, hid. 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.
  • US Patent 5,466,745 discloses coatings made from surface-active olefinic copolymers and polyesters capable of forming an oil-in-water emulsion. These emulsions are used to incorporate hydrophobic polyisocyanate crosslinkers, preferably those having at least one non primary isocyanate group, into an aqueous phase.
  • hydrophobic polyisocyanate crosslinkers preferably those having at least one non primary isocyanate group
  • U.S. Pat. No. 5,880,190 teaches water-based emulsion compositions containing chlorinated polyolefins that are true emulsions, requiring conventional surfactants for emulsion stability.
  • a pH of greater than 7 is said to be necessary for best performance, and a temperature of about 160°F or greater is said to be necessary when the emulsion is to be used as a primer for improved adhesion.
  • the primer is to be coated at about lmil film thickness, and must be overcoated with another coating, or admixed with a polyurethane/acrylic dispersion, in order for the primer to be effective in its role as an adhesion promoter.
  • carboxyalkyl cellulose esters are useful for incorporating non-water soluble materials into water, without the need for conventional surfactants or other surface active agents.
  • conventional surfactants are effective in emulsifying items into water, their very nature causes such emulsions to exhibit unwanted side effects such as water sensitivity.
  • CMCAB is itself a binder polymer, and does not have to be completely solubilized to adequately disperse into water.
  • CMCAB possesses a surface active nature, so that it is capable of incorporating a variety of hydrophobic moieties into aqueous phases.
  • Such moieties range from those considered very hydrophobic, such as hydrocarbon, fluorinated, chlorinated, and silicone-based materials, to those with only a low level of hydrophobicity, such as hydroxylated materials. Further, both monomeric and polymeric materials may be satisfactorily dispersed.
  • the invention provides a method for dispersing hydrophobic polymers and moieties into an aqueous phase using carboxyalkyl cellulose esters, such as carboxymethyl cellulose acetate butyrate, which are themselves relatively hydrophobic, carboxyl-containing polymers, in the substantial absence of conventional surfactant.
  • hydrophobic moieties susceptible to being dispersed include waxes; silicones; fluorocarbons; UN absorbers; photoinitiators; chlorinated and nonchlorinated polyolefins; hydroxy-functional resins such as acrylics, polyesters, and polyethers; acrylate-functional resins such as' acrylated crylics, acrylate olyesters, acrylated polyethers, acrylated polyurethanes, and acrylated epoxies; amine-modified acrylated acrylics, polyesters and polyethers; unsaturated polyesters; allyl functional polymers; a inoplast resins, and the like; and any other chemical entity that is not typically soluble in water.
  • These dispersions may then, dependent upon the chemical or polymer dispersed, be used as additives for compatible compositions, or as coatings for most any substrate.
  • the invention provides a method for dispersing hydrophobic polymers and moieties into an aqueous phase using carboxyalkyl cellulose esters, such as CMCAB, as polymeric surfactants.
  • carboxyalkyl cellulose esters such as CMCAB
  • the carboxyalkyl cellulose ester is dissolved in a compatible solvent, the hydrophobic polymer to be incorporated is added, the ester is neutralized to a given percent neutralization, and the solution inverted from a solvent continuous phase to an aqueous continuous phase.
  • esters of carboxy ( -C 3 alkyl) cellulose used according to the invention which are known to be useful also as binder components of coating compositions, preferably have an inherent viscosity of 0.20 to 0.70 dL/g, preferably 0.35 to 0.60 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25°C, a degree of substitution per anhydroglycose unit of carboxy -C 3 alkyl) of about 0.20 to 0.75, and a degree of substitution per anhydroglucose unit of C 2 -C esters of about 1.5 to about 2.7. As is described below, these resins are useful in coating and ink formulations.
  • a carboxymethyl cellulose butyrate having a degree of substitution per anhydroglucose unit 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 1.50 to 2.70, and having an inherent viscosity of 0.20 to 0.70 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25°C. It is preferred that the inherent viscosity be 0.35 to 0.60 dL/g.
  • a carboxymethyl cellulose propionate having a degree of substitution per anhydroglucose unit 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 propionyl of about 1.50 to 2.70, and having an inherent viscosity of 0.20 to 0.70 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25°C. It is preferred that the inherent viscosity be 0.35 to 0.60 dL/g.
  • 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 nhydroglucose 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 0.70 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol tetrachloroethane at 25°C.
  • the inherent viscosity be 0.35 to 0.60 dL/g. 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.
  • a carboxymethyl cellulose acetate propionate having a degree of substitution per anhydroglucose unit 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 propionyl of about 0.10 to 2.60 and a degree of substitution per anhydroglucose unit of acetyl of about 0.10 to 2.65, and having an inherent viscosity of 0.20 to 0.70 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25°C.
  • the inherent viscosity be 0.35 to 0.60 dL/g. 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 carboxy (Ci -C 3 alkyl) alkyl cellulose esters used in the invention may be prepared by a multi-step process.
  • the free acid form of, for example, carboxymethyl 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.
  • CMC- H carboxymethyl cellulose
  • the high alpha content is important for the quality of the final products prepared therefrom. We have found that low alpha cellulose pulps lead to poor solubility in organic solvents and consequently poor formulations.
  • 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 CMC 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 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 the 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.
  • Neutralization of the strong acid catalyst is important for optimal thermal and hydrolytic stability of the final product.
  • either the fully substituted or partially hydrolyzed forms of carboxy (Ci -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 deionized water to efficiently remove residual organic acids and inorganic salts.
  • C 2 -C 4 esters of carboxy (Ci -C 3 alkyl) cellulose ester having an inherent viscosity of about 0.2 to 0.70 dL/g, as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25°C, and having a degree of substitution per anhydroglucose unit (DS/AGU) of carboxy (Ci. -C. 3 alkyl) of about 0.20 to 0.75, made by a process which includes:
  • 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.
  • This powder is thus free from any significant amount of residual organic acids and inorganic salts.
  • CMCAB is capable of incorporating a wide variety of hydrophobic moieties into the aqueous phase.
  • the method generally described above has successfully been used to incorporate many different types of materials into aqueous dispersions. Examples of some specific dispersions, and some of their representative uses, are described in detail below. Further, to show the breadth of the types and kinds of materials that may be dispersed according to the invention, Table 1 below provides an extended list of representative materials that can be incorporated into the aqueous phase according to the invention. The list in Table 1 is representative only, and is not intended to be a comprehensive listing.
  • silicone resins can be classified depending upon structure and molecular weight as silicone resins, oils, rubbers, silanes, defoamers, and hammertone additives. All of these silicones are useful according to the invention. Also useful are silicones described as polydimethylsiloxanes, phenylpolysiloxanes, phenyl modified polydimethylsiloxanes, polymethyalkylsiloxanes, organically modified polymethyalkyl siloxanes such as polyether, polyester, aralkyl modified materials. Also useful are siloxanes having combinations of the above mentioned functional groups. Reactive siloxanes include, but are not limited to, those having hydroxyl, carboxyl, isocyanato, amine, and vinyl functionality.
  • Michem Wax 433 Michelman, Inc. Carnauba Wax Cincinnati, OH
  • waxes that are useful according to the invention include, but are not limited to, natural waxes such as petroleum waxes, which include the macrocrocrystalline and microcrystallme paraffin waxes; Lignite, peat, and montan wax and their acid, ester and saponified derivatives; animal waxes such as bees wax, shellac, and wool wax; and vegetable waxes such as camauba, candelilla and rice wax; synthetic waxes useful for the invention include fatty acid amide waxes, polyolefin waxes such as polyethylene and polypropylene, fischer-tropsch waxes and oxidized polyethylenes, grafted polyolefin and copolymer waxes. Waxes with curing functionality, such as those having UN-reactive functional groups, are also useful in the invention. Chlorinated polymers
  • Desmophen 1300-75 ® Bayer Corporation Polyester polyol Pittsburgh, PA
  • polyols that can be dispersed according to the invention include acrylic polyols, polyester polyols, polyether polyols, and copolymers made from these polymers.
  • Cellulose Acetate Butyrate esters are also advantageously dispersed according to the invention, as are alkyd resins.
  • oils useful according to the invention include lauric oils, palm oils, and drying oils such as chinawood oil, linseed oil, oiticia oil and dehydrated castor oils.
  • Unsaturated vegetable oils are also useful; these include soybean, corn, canola, safflower, sunflower, peanut, menhaden, rapeseed, avocado, and walnut oils.
  • Monomeric and polymeric plasticizers are also useful for incorporation into aqueous dispersions. These plasticizers include chlorinated paraffins, epoxides, adipates, azelates, phosphates, phthalates, sebacates, trimellitates, glutarates, and polymeric-mixed dibasic acids. Hydrogenated terphenyl, and 2,2,4-trimethyl-l,3-pentanediol diisobutyrate, available as TXCB from Eastman Chemical Company, are also useful. Unsaturated and UV curable resins and oligomers
  • Also useful for dispersion into the aqueous phase according to the invention are unsaturated polyesters, acrylated acrylics, acrylated polyesters, acrylated polyethers, acrylated epoxies, acrylated urethanes, amine-modified acrylated polyethers, acrylated cellulosics, and the like. Allyl functional resins such as CN9101 ® available from the Sartomer Company, are also useful according to the invention.
  • Vinyl monomers that are useful according to the invention include, but are not limited to, examples such as isobornyl acrylate, isodecyl acrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipropylene glycol diacrylate, and their ethoxylated and propoxylated derivatives; acrylate modified phosphate esters, methacrylate modified phosphate esters, carboxyethyl acrylate; methacrylate and vinyl-functional polymers and monomers are useful as well, as are styrene and vinyl
  • Photoinitiators useful according to the invention will be known by their trade names by those skilled in the art. Although the listed names are given, they are exemplary only and do not serve to limit the scope of the invention: Esacure BO, Daitocure EE , Vicure 30, Daitocure IP, Esacure EB1, Trigonal 14, Vicure 10, Esacure EB2, Daitocure IB, Esacure EB3, Esacure EB4, Irgacure 651, Lucirin DBK, Esacure KBl, Esacure KB, Micure 3K-6, Hicure BDK, Uvatone 8302, Deap, Uvatone 8301, Irgacure 184, Darocure 1173, Micure HP-8, Darocure 1116, Darocure 2959, Irgacure 500, Darocure 4665, Darocure 1664, Darocure 4043, Irgacure 907, Irgacure 369, Florcur
  • UV absorbers benzyliden-malonates
  • substituted benzophenones benzotriazoles
  • triazines phenyltriazines
  • oxalanilides and the like.
  • Other useful additives and stabilizers include hindered-amine light stabilizers, known in the industry as HALS, and antioxidants.
  • Suitable antioxidant types include, but are not limited to, phenols and hindered phenolics, phosphites, diphosphonites, tertiary butylhydroquinone, propyl gallate, butylated hydroxyanisole, and butylated hydroxytoluene.
  • Other useful additives include optical brightners, algaecides, biocides, and fungicides. Aminoplasts and phenoplasts resins
  • aminoplast and phenolplast resins that are useful in the invention. Examples include, but are not limited to, urea-formaldehyde crosslinking agents, melamine crosslinking agents, benzoguanamine formaldehyde crosslinking agents, and glycoluril formaldehyde crosslinking agents, and phenol-formaldehyde crosslinking agents. These resins are often modified with various alkylation groups such as methly, butyl, and isobutyl type groups among others. Useful materials include monomeric and polymeric species.
  • silicones are dispersed in the aqueous phase using CMCAB.
  • various waxes that are otherwise insoluble in water are dispersed in the aqueous phase using CMCAB.
  • a further embodiment according to the invention relates to a method and composition for incorporating chlorinated polyolefins into aqueous dispersions and/or aqueous coating compositions.
  • CMCAB is used to prepare an aqueous/ chlorinated polyolefin/ CMCAB dispersion (Aq/CPO/CMCAB).
  • the Aq/CPO/CMCAB dispersion can be pigmented and or crosslinked.
  • the dispersion can be used to coat plastic substrates such as TPO, polypropylene, and polyethylene.
  • the coated plastic can then be further coated with itself and/or with a further coating.
  • This Aq/CPO/CMCAB provides improved adhesion to the plastic and plastic composite substrates.
  • the invention thus provides a method for dispersing chlorinated polyolefin into an aqueous phase utilizing CMCAB.
  • the invention also provides a method of coating a substrate with an aqueous adhesion promoter and/or a coating composition, resulting in improved adhesion.
  • the present invention relates to an aqueous dispersion of chlorinated polyolefin, rather than to an emulsion.
  • the dispersion of the invention does not require conventional surfactants for stability, but rather uses a hydrophobic cellulosic polymer, such as CMCAB, that is capable of dispersing the hydrophobic chlorinated polyolefin.
  • the dispersion of the invention may be used as a film forming coating or a primer. It may also be crosslinked.
  • the dispersion of the present invention does not require temperatures of 160°F in order for adhesion to be obtained, nor must the dispersion be maintained at a pH above 7.
  • CMCAB is dissolved in a compatible solvent, a solution of chlorinated polyolefin in a compatible solvent (such as toluene, xylene, aromatic 100, aromatic 150, or DPMA) is added; the CMCAB is then neutralized to a given percent neutralization; and the solution inverted from a solvent continuous phase to an aqueous continuous phase.
  • a compatible solvent such as toluene, xylene, aromatic 100, aromatic 150, or DPMA
  • the invention provides a method of incorporating polyols, such as styrene allyl alcohol, cellulose acetate butyrate, or AU608S acrylic polyols, for example, into the aqueous phase.
  • polyols such as styrene allyl alcohol, cellulose acetate butyrate, or AU608S acrylic polyols
  • the invention provides a large number of such polyols to be used in water-based coating compositions, and to be used with polyisocyanates.
  • the invention thus provides a method for dispersing a non water-soluble polyol for use with polyisocyanates.
  • Polyurethane coatings provide outstanding performance and durability in all segments of the coatings industry.
  • Typical 2K polyurethane coatings are solvent-based, but considerable efforts have recently been made to develop 2K water-based technology in order to be more environmentally friendly. Examples of this technology include the Bayer water-dispersible polyisocyanates such as Bahydur XP7063, and the Cytec tertiary isocyanate crosslinkers such as Cythane 3174.
  • Compatible polyols are the Rohm and Haas Acrylic Roshield 3275 and Air Products Adura Polyols. Other polyols available are as described above.
  • aqueous polyurethane technologies just described are somewhat limited, in that the variety of resins available for use in water-based systems limits the types of properties that can be obtained with these systems. That is, typically, specific polyisocyanates andor specific polyols have to be used. In solvent-based 2K polyisocyanate systems, there are a variety of polyols and polyisocyanates that may be used, allowing one to develop coatings and systems with a variety of cure and performance properties. Thus, there remains a need for aqueous urethane technology that will allow an increase in the breadth and flexibility in choice of technologies for obtaining a variety of cure and performance properties, more like solvent-based systems. This need is filled according to the present invention.
  • the present invention thus provides a method of incorporating a non water-soluble polyol into water.
  • a relatively hydrophobic polymer such as CMCAB
  • CMCAB a relatively hydrophobic polymer
  • a polyol such as styrene allyl alcohol
  • CMCAB/SAA/Aq aqueous dispersion
  • the CMCAB/SAA Aq can then be crosslinked with a polyisocyanate (such as Bayhydur XP7063 or TMXDI, or Desmodur N-100), or with any crosslinker capable of crosslinking hydroxyl groups.
  • a crosslinked coating system having outstanding mar resistance and gloss was developed by addition of Bayhydur XP7063 to CMCAB/SAA/Aq, at a theoretical NCO/OH of 1/1, and cured by air-drying.
  • the CMCAB/SAA/Aq displayed easy incorporation of the NCO component. This system is useful, for example, to obtain reduced VOC 2K polyurethane coatings.
  • the invention provides a method and composition for incorporating an air oxidizable initiator/crosslinker into aqueous systems.
  • water based coatings are composed of high molecular weight emulsion polymers. Although the physical properties of these polymers are quite good, these polymers often lack the necessary chemical resistance, such as solvent resistance, to be used in more aggressive environments.
  • solvent resistance There are a variety of means used to improve the solvent resistance of these polymers, particularly crosslinking of some sort. Many times the crosslinkers used result in the release of formaldehyde, or require the addition of a second component at the time of coating application. These procedures usually result in a limited coating shelf life or pot-life.
  • EP 0,537,910,A2 describes latex polymers that use copolymerized olefinically unsaturated monomers to develop the polymer. There nonetheless remains a need for improved crosslink density and cure speed for coatings that cure by air oxidation.
  • the present invention provides a method and composition for incorporating an air- oxidizable initiator/crosshnker into aqueous systems, resulting in improved performance properties of the aqueous systems.
  • a relatively hydrophobic polymer, CMCAB is used to incorporate Santolink XII 00 into an aqueous dispersion (CMCAB/XIlOO/Aq).
  • CMCAB/XIlOO/Aq can then be blended with an air-oxidizable polymer such as Roshield 3188.
  • the Roshield 3188 polymer blended with CMCAB/XH 00/Aq displays about twice the MEKrubs as does Roshield 3188 blended with CMCAB- plasticizer, thus indicating that the CMCAB/XIlOO/Aq yields improved crosslink density.
  • CMCAB/XIlOO/Aq yields improved crosslink density.
  • Other polymers and monomers that cure by air oxidation may also be incorporated into the system.
  • the invention relates also to methods of incorporating photoinitiators into aqueous compositions.
  • CMCAB is used to incorporate a hydrophobic photoinitiator, such as KIP100F, poly[2-hydroxy-2-methyl-l-[4(l- methylvinyl)phenyl]propan- 1 -one/2-Hydroxy-2-methyl- 1 -phenylpropanone blend, into an aqueous phase (Aq/PI/CMCAB).
  • the Aq/PI/CMCAB can then be added to an aqueous, UV-curable latex, or a polymer or dispersion, and cured with UV irradiation.
  • This method allows the use of photoinitiators that cannot normally be used in aqueous coatings to be used, including, but not limited to, photoinitiators useful for curing pigmented coatings.
  • Aqueous UV-cure systems are used to obtain low weight curable coatings on substrates such as wood, plastic, textile, and printing compositions, and require the incorporation of suitable photoinitiators.
  • the photoinitiator of choice is typically Darocure 1173 from Ciba. This photoinitiator has a tendency to volatilize upon stoving (to drive off water), resulting in decreased curing efficiency.
  • WO 01/29093 teaches the use of mono and/or bis-acylphosphine oxide solids as suspensions in water.
  • the cited publication teaches the use of surfactants, along with a grinding process, to stabilize the suspension.
  • CMCAB being capable of forming films that are not water sensitive, is used to incorporate photoinitiators of any type into a water medium, without adversely impacting the water sensitivity of the resulting film.
  • This embodiment of the invention generally involves dissolving a hydrophobic photoinitiator such as Irgacure 184 in solvent or monomer, mixing the resulting solution with a CMCAB solution (alternatively, the PI may be dissolved directly in the CMCAB solution), followed by inversion with water to an aqueous CMCAB dispersion. This CMCAB dispersion is then added to a UV-curable latex or emulsion and cured by UV irradiation.
  • a hydrophobic photoinitiator such as Irgacure 184 in solvent or monomer
  • the resulting aqueous photoinitiator dispersion allows the incorporation of photoinitiators not normally capable of being used in aqueous latexes. It is therefore unnecessary to use photoinitiators such as Darocure 1173 that, although they may be used in aqueous coatings, tend to sublime upon stoving.
  • a major advantage of the present invention is that photoinitiators can be easily incorporated into aqueous compositions that, until now, could not be used in water-based compositions. Table 1 provides a representative list of such photoinitiators.
  • the invention relates to methods of making high solids, low VOC, aqueous UV-cure systems.
  • a relatively hydrophobic polymer, CMCAB is dissolved into UV monomer and/or solvent, and the system is then inverted to an aqueous dispersion.
  • Other monomers, oligomers, and photoinitiators, as set out above in Table 1, may be added to the composition prior to the,inversion process, followed by subsequent inversion to the dispersion.
  • CMCAB can be dissolved into acrylate monomer, which subsequently assists in the inversion process.
  • the dispersion may be used as a coating itself, or added to an aqueous emulsion, dispersion, or other aqueous polymer.
  • the dispersion may be added to other water-miscible polymers.
  • other systems may be added to the dispersion. The process is useful for the development of clear and pigmented mixtures, and yields aqueous UV coatings having a low VOC content, and exhibiting fast cure.
  • UV-curable compositions thus include fast cure speeds, low VOC content, and high performance properties.
  • Traditional compositions are approximately 100% nonvolatile. These systems typically use oligomers to obtain the bulk physical property requirements, and use suitable monomers to obtain the proper application viscosity. Alternatively, these systems may be diluted with organic solvent, in order to obtain low film weights for such substrates as wood and printing-type substrates. Water can be utilized to reduce viscosity and film weight for these systems, but only if a method of incorporation of the UV-curable components into an aqueous phase is available. The state of the art in such systems is to use emulsifiers to develop oil-in- ater emulsions of conventional 100% solids UV-curable systems. One drawback of these systems is that the resulting films may be water sensitive.
  • U.S. Pat. No. 5,306,744 teaches the development of methacrylate functional latex compositions for use in UV-curable coatings and compositions.
  • U.S. Pat. No. 5,095,066 teaches the use of hydrophilic polyurethanes containing (meth)acryloyl groups as reactive emulsifiers for radically curable synthetic resins.
  • CMCAB can be used to incorporate a variety of UV oligomers and photoiniators, to develop relatively high solids, relatively low VOC UV-curable compositions useful to obtain low weight curable coatings on substrates such as wood, plastic, metal, textile, and printing-type operations.
  • the invention involves dissolving together a photoinitiator, solvent, monomer, oligomer, and CMCAB, followed by inversion with water to an aqueous CMCAB dispersion.
  • This UV-curable CMCAB dispersion is then cured by UV irradiation, or added to a UV curable latex or emulsion, and cured by UV irradiation.
  • Pigments, additives, or any item typically used in such coatings may be added to the dispersion, either before or after inversion, to make the final coating.
  • the composition may be crosslinked with crosslinkers compatible with carboxyl and hydroxyl groups.
  • a further embodiment of the invention relates to a method of incorporating crosslinkers and resins into the aqueous phase.
  • Aminoplast and phenolplast resins are used to crosslink a variety of polymer binders, resulting in improved cure speed and improved physical properties. These crosslinkers are used in solvent-based as well as water-based systems.
  • the aminoplast resins typically require high methylol functionality. These resins often result in a limited pot life. Better moisture resistance properties are obtained with butylated melamine resins. These resins are difficult to disperse into water, however.
  • Melamine resins for water-based systems require the use of monomeric aminoplast resins in conjunction with special carboxy acrylic polymers.
  • This invention provides a method of incorporating aminoplast crosslinkers and resins into the aqueous phase.
  • a relatively hydrophobic polymer containing acid groups is used to incorporate the aminoplast crosslinker into an aqueous phase.
  • CMCAB is used to incorporate an aminoplast such as Cymel 300 into water, (CMCAB/Amino/Aq).
  • the CMCAB/Amino/Aq can then be treated with a catalyst solution, such as blocked PTSA, and applied to a substrate and cured.
  • the CMCAB/Amino/Aq can be pigmented, and applied as a coating, or added to other polymers and resins.
  • the cured CMCAB/Amino/Aq provides outstanding MEK resistance, water resistance, adhesion, and tannin stain resistance.
  • Example 1 thus demonstrates how a hydrophobic material such as a silicone modified polyacrylate may be easily dispersed into water according to the invention.
  • Example 2 shows how Tego 90 IW maybe dispersed by the invention at a factor of about 10 times the recommended amount, without causing cratering.
  • Other examples of defoamers include those set forth above in Table 1.
  • the MPK, anhydrous isopropanol, Eastman EB and CMCAB are mixed until the CMCAB is dissolved, after which the Saniticizer 160 is added.
  • Example 5 demonstrates a synthetic polyethylene wax dispersed according to the invention
  • Example 6 demonstrates Camauba wax, a vegetable wax, dispersed according to the invention.
  • Examples 5 through 8 thus demonstrate how various waxes may be dispersed according to the invention.
  • Other types of waxes as indicated previously, can also be dispersed according to the invention.
  • There appears to be no limit on the particle size of the wax that may be dispersed the examples displaying dispersions of waxes from solution (submicron) to greater than 12.5 micron. Larger particle size waxes are expected to be just as easily dispersed.
  • Examples 9-30 relate to methods and compositions for incorporating chlorinated polyolefins into aqueous dispersions, and to the corresponding aqueous coating compositions.
  • Aqueous acid cure Primer (B10P117A) Air dry 20min, 20min @125F, 3min @79C, cool
  • Aqueous acid cure Enamel B10P117B Air dry 20, 20min @125F, 3min @79C, cool
  • Examples 9 - 18 show how the invention can be used to develop coating systems with improved adhesion to TPO plastic.
  • the examples that include the aqueous dispersion of CPO show dramatically improved adhesion of both a water-based primer and a solvent- based 2K polyurethane system, both of which typically show difficulty in adhering to TPO.
  • Examples 31-69 relate to methods of incorporating polyols, such as styrene allyl alcohol, acrylic polyol, polyester polyols and the like, into the aqueous phase.
  • the examples relate also to the use of such dispersed polyols with polyisocyanates.
  • Desmophen R221-75 polyester was dispersed and evaluated, as shown below.
  • Roskydal 502BA unsaturated polyester resin containing OH groups
  • Irgacure 184 1-Hydroxy-cyclohexyl-phenyl ketone
  • the crosslinkers were added at 2% on solid Roskydal 502B A plus the amount needed to have a 1.1/1.0 NCO/OH ratio on CMCAB.
  • B13P177A - Example 54 was evaluated again, but by UV cure.
  • Crosslinkers were added to portions of B13P177A - Example 54 and then a three mil drawdown on Leneta Chart Form 7b was performed.
  • the drawdown flashed for 20 minutes, cured at 66°C for 15 minutes, then UV cured at 13 FPI with one pass through an American Ultraviolet UN Curing unit with a 300WPI mercury lamp.
  • the formulations and the evaluations are shown below.
  • Castor oils were evaluated as shown below.
  • Examples 31 - 69 show that a variety of polyols maybe dispersed into aqueous compositions by use of the invention. Additionally, the examples show that these aqueous polyol dispersions can be crosslinked and used as resins and coatings. Additionally, Examples 54 - 59 show that if the dispersed polymer has unsaturated groups present, by dispersing a photoinitiator and exposing the coating system to UV irradiation, a dual cure coating may be obtained. Further examples of UV curable polymers and oligomers that may be dispersed into aqueous phase have been set forth above in the list of dispersible materials. Examples 70-75 relate to methods for incorporating an air oxidizable initiator/crosslinker into aqueous systems.
  • Examples 76-88 relate to methods of incorporating photoinitiators into aqueous compositions.
  • An ideal photoinitiator for waterbased systems should exhibit high compatibility in an aqueous polymer environment, high photoreactivity, low water vapor volatility, and low odor, and be non-yellowing.
  • Examples 76 - 88 clearly show how non water soluble photoinitiators may be incorporated into an aqueous dispersion, and made into aqueous coatings according to the invention. As set forth above in Table 1, there are a variety of photoinitiators that may be dispersed according to the invention.
  • Examples 89- 116 relate to methods of incorporating crosslinkers and other resins into the aqueous phase.
  • the panel was cured for approx. 6min with oven ramping from 66°C to 99°C, then 60 sec at 130°C - although coating was dry, sample was not mar free
  • the aminoplast/CMCAB product appears better than the nitrocellulose lacquer for water resistance.
  • aqueous basecoat although not as good for softening resistance, seems to show less fiber swell than the nitrocellulose lacquer. However, there was much more water/moisture permeation into the board with the water-based basecoat, in terms of wicking through the board.
  • Example 115 - 3mil Draw Down of Example 113 (B12P74A)
  • Examples 89 - 116 show that it is possible to incorporate a variety of aminoplast crosslinkers into aqueous phases with subsequent coating formation

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Abstract

La présente invention concerne des procédés pour disperser des matériaux hydrophobes dans l'eau en utilisant des esters de cellulose carboxyalkyles tels que l'acétate butyrate de cellulose carboxyméthyle (CMCAB), et des dispersions aqueuses ainsi obtenues. L'invention concerne aussi des films de revêtement finis faits à partir de ces dispersions, qui manifestent une moindre sensibilité à l'eau sans augmenter la durée de séchage du film au-delà du temps de séchage des dispersions aqueuses obtenues avec les surfactants traditionnels.
PCT/US2003/031049 2002-10-01 2003-09-30 Utilisation d'esters de cellulose carboxyalkyles tels que l'acetate butyrate de cellulose carboxymethyle pour former des materiaux hydrophobes dans l'eau Ceased WO2004030801A1 (fr)

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AU2003275345A AU2003275345A1 (en) 2002-10-01 2003-09-30 Use of carboxyalkyl cellulose esters, such as carboxymethyl cellulose acetate butyrate, to form aqueous dispersions of hydrophobic materials in water

Applications Claiming Priority (2)

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US41521502P 2002-10-01 2002-10-01
US60/415,215 2002-10-01

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004104121A1 (fr) * 2003-05-16 2004-12-02 Eastman Chemical Company Systemes de revetement reticulables contenant des esters de carboxyalkylcellulose
WO2007056125A3 (fr) * 2005-11-04 2007-06-28 Eastman Chem Co Esters de cellulose carboxyalkyle destines a une administration prolongee de substances actives sur le plan pharmaceutique
WO2007056205A3 (fr) * 2005-11-04 2007-10-25 Eastman Chem Co Esters de carboxyalkylcellulose pour administration d'agents pharmaceutiquement actifs peu solubles
US8263677B2 (en) 2009-09-08 2012-09-11 Creative Nail Design, Inc. Removable color gel basecoat for artificial nail coatings and methods therefore
US8367742B2 (en) 2009-10-05 2013-02-05 Creative Nail Design, Inc. Removable color layer for artificial nail coatings and methods therefore
US8541482B2 (en) 2009-10-05 2013-09-24 Creative Nail Design, Inc. Removable multilayer nail coating system and methods therefore
US8901198B2 (en) 2010-11-05 2014-12-02 Ppg Industries Ohio, Inc. UV-curable coating compositions, multi-component composite coatings, and related coated substrates
US8901199B2 (en) 2009-09-08 2014-12-02 Creative Nail Design, Inc. Compositions and methods for UV-curable cosmetic nail coatings
CN104592812A (zh) * 2014-12-26 2015-05-06 上海乘鹰新材料有限公司 一种醇水溶性转移涂料及其制备方法
CN116003807A (zh) * 2023-01-04 2023-04-25 西南林业大学 一种生物质单宁/醋酸纤维素塑料薄膜及其制备方法
WO2024094419A1 (fr) * 2022-11-04 2024-05-10 Kemira Oyj Procédé de fabrication d'une dispersion aqueuse

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998033821A1 (fr) * 1996-01-29 1998-08-06 Eastman Chemical Company Esters de cellulose carboxyalkyle
US5994530A (en) * 1998-06-25 1999-11-30 Eastman Chemical Corporation Carboxyalkyl cellulose esters for use in aqueous pigment dispersions
WO2002036637A1 (fr) * 2000-11-01 2002-05-10 Eastman Chemical Company Utilisation de carboxymethyle cellulose acetate butyrate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998033821A1 (fr) * 1996-01-29 1998-08-06 Eastman Chemical Company Esters de cellulose carboxyalkyle
US5994530A (en) * 1998-06-25 1999-11-30 Eastman Chemical Corporation Carboxyalkyl cellulose esters for use in aqueous pigment dispersions
WO2002036637A1 (fr) * 2000-11-01 2002-05-10 Eastman Chemical Company Utilisation de carboxymethyle cellulose acetate butyrate

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004104121A1 (fr) * 2003-05-16 2004-12-02 Eastman Chemical Company Systemes de revetement reticulables contenant des esters de carboxyalkylcellulose
WO2007056125A3 (fr) * 2005-11-04 2007-06-28 Eastman Chem Co Esters de cellulose carboxyalkyle destines a une administration prolongee de substances actives sur le plan pharmaceutique
WO2007056205A3 (fr) * 2005-11-04 2007-10-25 Eastman Chem Co Esters de carboxyalkylcellulose pour administration d'agents pharmaceutiquement actifs peu solubles
US8901199B2 (en) 2009-09-08 2014-12-02 Creative Nail Design, Inc. Compositions and methods for UV-curable cosmetic nail coatings
US8399537B2 (en) 2009-09-08 2013-03-19 Creative Nail Design, Inc. Compositions and methods for nail coatings
US8263677B2 (en) 2009-09-08 2012-09-11 Creative Nail Design, Inc. Removable color gel basecoat for artificial nail coatings and methods therefore
US9717672B2 (en) 2009-09-08 2017-08-01 Creative Nail Design, Inc. Compositions and methods for UV-curable cosmetic nail coatings
US8367742B2 (en) 2009-10-05 2013-02-05 Creative Nail Design, Inc. Removable color layer for artificial nail coatings and methods therefore
US8492454B2 (en) 2009-10-05 2013-07-23 Creative Nail Design, Inc. Removable color layer for artificial nail coatings and methods therefore
US8541482B2 (en) 2009-10-05 2013-09-24 Creative Nail Design, Inc. Removable multilayer nail coating system and methods therefore
US8901198B2 (en) 2010-11-05 2014-12-02 Ppg Industries Ohio, Inc. UV-curable coating compositions, multi-component composite coatings, and related coated substrates
CN104592812A (zh) * 2014-12-26 2015-05-06 上海乘鹰新材料有限公司 一种醇水溶性转移涂料及其制备方法
WO2024094419A1 (fr) * 2022-11-04 2024-05-10 Kemira Oyj Procédé de fabrication d'une dispersion aqueuse
CN116003807A (zh) * 2023-01-04 2023-04-25 西南林业大学 一种生物质单宁/醋酸纤维素塑料薄膜及其制备方法
CN116003807B (zh) * 2023-01-04 2023-12-05 西南林业大学 一种生物质单宁/醋酸纤维素塑料薄膜及其制备方法

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