WO2001012712A1 - Nonionic associative thickener composition with improved viscosity retention upon tinting in architectural latex coating - Google Patents
Nonionic associative thickener composition with improved viscosity retention upon tinting in architectural latex coating Download PDFInfo
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- WO2001012712A1 WO2001012712A1 PCT/US2000/022220 US0022220W WO0112712A1 WO 2001012712 A1 WO2001012712 A1 WO 2001012712A1 US 0022220 W US0022220 W US 0022220W WO 0112712 A1 WO0112712 A1 WO 0112712A1
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- aminoplast
- ether copolymer
- hydrophobe
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/32—Modified amine-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
Definitions
- the present invention relates to a water soluble copolymer composition containing a linear aminoplast-ether copolymer possessing a relatively high content of the hydrophobe tristyryl phenol.
- a copolymer contains a unit of the formula:
- the divalent Ro contains a divalent alkyleneoxy containing moiety
- Amp is the skeletal residue of an aminoplast, as stated above, R is hydrogen, alkyl containing 1 to about 4 carbon atoms, or acyl containing 1 to about 4 carbon atoms, RO is bonded to alkylene units of Amp, and a is a number greater than 1 , preferably greater than 2.
- Amp includes any dimer and oligomer component of the aminoplast.
- Ro 2 is tristyryl phenol, that is covalently bonded to Amp through a heteroatom, p 2 is number that is equal to the free valence of Amp minus (2 + q), and q is a positive number
- Nonionic associative thickeners have been used in latex architectural coatings for nearly 20 years. They have replaced the traditional cellulosic thickeners because coatings that utilize nonionic associative thickeners exhibit improved application properties such as brush drag, flow and leveling, and water sensitivity.
- the term "associative thickener' * is recognized in the art to mean a nonionic hydrophobically modified water-soluble polymer capable of interacting in aqueous solution with itself and with other species such as latex particles. Associative thickeners are widely used to enhance the performance properties of paints and coatings.
- RQ i contains a divalent alkyleneoxy containing moiety
- Amp is the skeletal residue of an aminoplast
- R is hydrogen, alkyl containing 1 to about 4 carbon atoms, or acyl containing 1 to about 4 carbon atoms
- p is a positive number that is equal to the free valence of Amp minus 2
- RO is bonded to alkylene units of Amp
- a is a number greater than 1.
- the skeletal unit of the aminoplast is the structure of the aminoplast minus the RO — leaving groups bonded to alkylene of the alkylol or alkylol ether or ester of the aminoplast, regardless of whether any of the RO — groups are removed from the aminoplast. That skeletal unit is referred to herein and in the claims as "Amp.”
- linear when used herein and in the claims to characterize a polymer, relates to a polymer that is devoid of crosslinking or branching that renders the polymer solid and cured.
- a "wholly linear” polymer is apolymerthat is devoid of crosslinking and branching.
- a linear polymer may or may not be a wholly linear polymer.
- acrylic polymer means any polymer wherein at least 50% by weight is an acrylic or methacrylic acid or ester, including mixtures of such acids and esters individually and together.
- vinyl acetate polymer means any polymer containing at least 50% by weight of vinyl acetate.
- the problem with formulating a pre-tmted coating with a very high viscosity is that it creates problems in the manufactu ⁇ ng process
- the problem with additives such as surfactants and solvents, or cellulosics and alkai-swellable thickeners is that it compromises the application properties of the resulting coating
- the additives can also cause problems with the physical properties of the final d ⁇ ed paint film For example, high levels of surfactants or the use of alkai-swellable thickeners can lead to water sensitivity or poor scrub resistance
- nonionic associative thickener that can be used in latex coatings of the mid to neutral base formulations based on small particle size acrylics that does not need the addition of surfactants and solvents, or other thickening agents to achieve a satisfactory viscosity when the colorant is added
- nonionic associative thickener that can be used in latex coatings for the mid to neutral base formulations based on small particle size acrylics that maintains desirable application properties when the colorant is added without compromising the final film properties.
- the present invention relates to a water soluble copolymer composition containing a linear aminoplast-ether copolymer possessing a relatively high content of the hydrophobe t ⁇ styryl phenol
- a copolymer contains a unit of the formula
- the divalent Ro contains a divalent alkyleneoxy containing moiety
- Amp is the skeletal residue of an aminoplast, as stated above, R is defined above, RO is bonded to alkylene units of Amp, and a is a number greater than 1, preferably greater than 2 Amp includes any dimer and oligomer component of the aminoplast R ⁇ , 2 J s t ⁇ styryl phenol, that is covalently bonded to Amp through a heteroatom, p 2 is number that is equal to the free valence of Amp minus (2+ q), and q is a positive number
- the relatively high content of the hydrophobe means a copolymer that contains more than about 3 % t ⁇ styryl phenol based on weight.
- the copolymer contains about 4% t ⁇ styryl phenol to about 10% t ⁇ styryl phenol based on weight when the polymer is produced usmg polyethylene oxide and a glycolu ⁇ l compound
- the invention relates to a novel water-based coating composition that contains a linear aminoplast-ether copolymer possessing end groups characte ⁇ zed by a component of the units making up the copolymer, or a monofunctional group that effectively end-caps the copolymer, forming the end group This yields a copolymer of the formula
- each R, )0 is the same or different terminal group, such as hydrogen, — R ⁇ , — H, Amp bonded — (OR) pb — Amp — (OR) p ⁇ , tristyryl phenol, or any other mono functional organic groups, such asalkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkyoxyalkyl, aroxyalkyl, cycloalkoxyalkyl, and the like, and p , is a positive number that is equal to the free valence of Amp minus 1
- a particularly preferred linear aminoplast-ether copolymer comprises units of the formula:
- n has a value of at least 2
- x is 0 or 1
- s+ 1 equals (i) the free valence of the
- the linear aminoplast-ether copolymer employed in the coating composition of the invention comprises a copolymer that possesses end groups as illustrated by the following structure:
- each R ⁇ 01 is the same or different terminal group, such as hydrogen, — R ⁇ — H, — (OR) p ⁇ , — Amp 0 — (OR) p i , tristyryl phenol, or any other mono functional organic groups, such as alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkyoxyalkyl, aroxyalkyl, cycloalkoxyalkyl, and the like, and p , is a positive number that is equal to the free valence of Amp 0 minus 1. Amp 0 is depicted in formula V.
- the present invention further relates to a latex coating for the mid to neutral base formulations based on small particle size acrylics.
- the present invention improves on this type of latex coatings by reducing the drop in viscosity that normally occurs when the colorant is added to latex coating for the mid to neutral base formulations based on small particle size acrylics.
- the present invention also yields overall improved color acceptance compared to other compositions and competitive products.
- This invention relates to the use of any aminoplast, including those specifically recited in FIG. 1 above, to make the copolymer of the invention.
- aminoplasts exceptional performing associative thickeners, for use in latex coatings for the mid to neutral base formulations based on small particle size acrylics, are obtained from the reaction of glycolu ⁇ ls with alkylene oxide glycols to w uch are incorporated the t ⁇ styryl phenol pendant moieties
- the linear aminoplast-ether copolymers of formula I et seq are made by the novel condensation reaction of a polyfunctional aminoplast with a di-functional polyether (alone or with another polyol, as characte ⁇ zed with respect to formulae XII and XIII) in the presence of an acid catalyst
- ammoplasts are condensed with polyfunctional compounds to produce thermosetting resins or thermoset products (1 e , C-stage res )
- This reaction produces a linear copolymer
- the copolymers of formulae I, II, III, IV, and V are either liquid or thermoplastic solids that are solvent soluble and water soluble or dispersible
- the linear aminoplast-ether copolymer are made by the copolyme ⁇ zation reaction of a polyfunctional aminoplast with an ether containing two active hydrogen terminal groups, m the presence of an acid catalyst, especially a Bronsted-Lowery acid provided in catalytically effective amounts The reaction is continued until the desired molecular weight is achieved
- the desired molecular weight of the copolymer is dependent on the mtended use of the copolymer
- the molecular weight of the copolymer may range from about 12,000 to about 800,000, preferably from about 20,000 to about 100,000, and most preferably from about 30,000 to about 80,000
- the aminoplast is a polymenzable resin of the general formula
- z is a positive number having a value of at least 2.
- the ether containing two active hydrogen terminal groups comp ⁇ ses a wide va ⁇ ety of compositions
- a preferred class is nonionic
- Illustrative of a preferred class of such ethers are polyalkylene oxides of the formula
- alkylene oxide is a divalent moiety containing at least two alkylene oxide units in which
- the alkylene oxide units form a linear chain and provide a terminal OH, or
- the alkylene oxide units are bonded to a starter molecule, such as a diamine, urea, carbamate, phenoxy, amide, bis-imide, and the like, and providing a terminal OH, and/or
- alkylene oxide are bonded to a terminal group that possesses a moiety that provides the active hydrogen ( — H in formula VII).
- X is an active hydrogen functional moiety such as oxy ( — O — ), sulfidyl ( — S — ), amino ( — N ⁇ ), carboxy
- R Q4 and Ro 8 are alkyl of 2 to about 8 carbon atoms
- R ⁇ and R ⁇ are one or more alkylene oxide units, e.g., such as water soluble or dispersible ethylene oxide, propylene oxide, mixed ethylene oxide/1 ,2-propylene oxide, mixed ethylene oxide/1 ,3-propylene oxide, mixed ethylene oxide/1, 2-butylene oxide, mixed ethylene oxide/ 1,4-butylene oxide, and the like;
- alkylene oxide units e.g., such as water soluble or dispersible ethylene oxide, propylene oxide, mixed ethylene oxide/1 ,2-propylene oxide, mixed ethylene oxide/1 ,3-propylene oxide, mixed ethylene oxide/1, 2-butylene oxide, mixed ethylene oxide/ 1,4-butylene oxide, and the like;
- Rog is a divalent group such as alkyleneoxy, alkylen ⁇ olyamine, cycloalkylene polyamine, phenoxy, uriedo, carbamate, amide, and the like; xl and x2 are each equal to the free valence of X; x3, x4, x5, x6 and x7 are each 0 or 1, and one or more of x4 and x6 is 1.
- Specific illustrations of a limited class of polyethers encompassed by formula VIII are the Carbowax® and Pluracol® polyether diols sold by Union Carbide Chemicals & Plastics, Inc. and BASF Performance Chemicals, respectively.
- the molecular weight of the polyether reagent may range from about 106 and lower, to about 35,000, and higher.
- polyfunctional compounds i.e., polyfunctional compounds
- thermosetting resins or thermoset products i.e., C-stage resin
- the above method produces a linear copolymer.
- the copolymers of formulae I, II, III, IV, and V are either liquid or thermoplastic solids that are solvent soluble and water soluble or dispersible.
- Aminoplast reagents include, but are not restricted to, aldehyde reaction products of melamines, ureas, benzoguanamines, glycolurils, and the like, to produce the array of aminoplasts, including but not limited to those described in FIG. 1 above. While any of these can be used to make associative thickeners, the glycolurils, such as those of formula IX
- Suitable polyethers include polyalkylene polyethers.
- the preferred polyethers are water soluble.
- the most preferred polyethers are the alkylene polyethers where the predominant alkylene groups are ethylene.
- the most desirable polyethers are polyethylene oxide diols that possess molecular weights from about 1,000 to about 35,000.
- polyethylene oxide diols are those of the formula:
- xl 1 has a value of about 20 to about 800, preferably from about 50 to about 500, and most preferably from about 100 to about 300.
- R ]5 is the residue of a diol possessing greater hydrophobicity than R Q ,, thereby providing for a linear copolymer containing the structure
- x29 has a value that is greater than x30.
- x30/x29 is less than about 1 , preferably less than about 0.33.
- R 15 groups are H(0CH 2 CH wherein x31 has a value of about 8 to about 20, x32 has a value of about 8 to about 23, x33 and x34 have values of 0 to about 8.
- the linear copolymer of formula XII may be modified to possess the terminal groups of formulae II and V, discussed above.
- the linear aminoplast-ether copolymers of this invention contains a hydrophobe pendant group.
- Acceptable hydrophobe groups include aliphatic to alkyl phenol to tristyryl phenol.
- the most preferred hydrophobic pendant group is tristyryl phenol.
- Tristyryl phenol extends from aminoplast component of the linear backbone of the aminoplast-ether copolymer. Tristyryl phenol groups are typically bonded to the backbone through ether or ester groups, as illustrated in formula II.
- tristyryl phenol enhances the performance of the resulting aminoplast-ether copolymer as an associative thickener in architectural coating compositions for the mid to neutral base formulations based on small particle size acrylics where the level of colorant added is in large amounts for about the 5 to 16 oz per gallon range.
- This invention relates to the use of any aminoplast, including those specifically recited in FIG. 1 above, to make the copolymer of the invention.
- exceptional performing associative thickeners are obtained from the reaction of glycolurils with alkylene oxide glycols to which are incorporated tristyryl phenol pendant moieties at a relatively high concentration.
- the relatively high concentration of tristyryl phenol means about 3% or greater based on weight.
- the concentration of tristyrl phenol is at a concentration of about 4% to about 10% based on weight.
- the production of the aminoplast-ether copolymers are made by solvent or melt polymerization.
- an aminoplast- such as glycoluril-, based associative thickener
- dissolving the aminoplast e.g., glycoluril
- a polyether compounds within the scope of formula IX such as a Carbowax ⁇ polyether sold by Union Carbide Chemical and Plastics, Inc., Danbury, Conn.
- a more hydrophobic polyol within the scope of formula XI with the addition of ethoxylated tristyryl phenol (such as Soprophor BSU)
- a stripping solvent such as alkylated benzene (e.g., toluene or xylenes).
- each may be dried by azeotropic distillation with toluene, xylenes, or a mixture of them, or by any other drying procedure.
- Total concentration of the reagents in the solvent may be maintained from about 10 to about 60 weight %.
- the temperature of the mixture may be brought to about 60°- 140° C, preferably to about 80°- 120° C.
- An acid catalyst such as a sulfonic acid catalyst, is then added.
- the reaction mixture is placed under reduced pressure to bring about a steady distillation of the toluene/xylenes which azeotropes the alcohol byproduct that must be removed in order for the reaction to proceed.
- Fresh solvent is constantly added to maintain a constant level.
- the reaction is allowed to proceed until a given high viscosity is achieved as measured by Gardner bubble tubes or until viscosity increase ceases. Such viscosity increase indicates an increase in the molecular weight of the copolymer.
- step 1 Polyether polyol, ethoxylated tristyryl phenol, and azeotroping solvent (e.g., toluene) are added to an appropriately sized container that accommodates a heater, temperature reading device, a nitrogen inlet, and a Dean Stark water trap and condenser. 2. The mixture of step 1 is heated to reflux to dry the mixture by azeotropic distillation. When water removal ceases, the mixture is cooled to about 100° C, and the water trap is removed. A distillation column and receiving vessel are installed in the container.
- azeotroping solvent e.g., toluene
- Glycoluril e.g., Powderlink 1 174.
- the catalyst is added and vacuum is applied. The pressure is reduced to a level that causes a steady distillation of solvent at about 100° C. The solvent is continually replenished from a pressure equalizing add funnel.
- the dried polymer is cut into strips and redissolved in water or water/cosolvent mixture.
- Polymerization in the melt involves the admixture of the same reagents in the absence of a solvent with a heavy duty laboratory mixer (such as an Universal Sigma Blade Mixer, sold by Baker Perkins Guittard S A, Paris, France) at a temperature sufficient to generate leaving groups and remove the reaction condensation products.
- a heavy duty laboratory mixer such as an Universal Sigma Blade Mixer, sold by Baker Perkins Guittard S A, Paris, France
- the removal of volatile byproducts by vacuum is necessary in order to shift the reaction to the right and prevent an equilibrium reaction from occurring that impedes the reaction before the desired degree of polymerization is achieved.
- Catalysts useable for effecting the copolymerization reaction includes the standard Br ⁇ onsted-Lowery acid catalysts typically used for the condensation of aminoplast resins.
- Such acid catalysts include mineral acids (e.g., HC1, H 2 S0 4 , H 3 PO 4 , and the like), aryl sulfonic and alkylated aryl sulfonic acids, such as benzene sulfonic acid, p-toluene sulfonic acid, 1 -naphthalene sulfonic acid, 2-naphthalene sulfonic acid, naphthalene- 1,5-disulfonic acid, naphthalene-2,7-disulfonic acid, 1,3,6-naphthalene trisulfonic acid, naphtholsulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid, oxalic acid, maleic acid, hexamic acid, alkyl phosphate ester, phthalic acid, and copolymerized acrylic acid.
- the sulfonic acid catalyst e
- Cymel 1170, 1171, 1175 and Powderlink 1174 are marketed by Cytec Industries as Cymel 1170, 1171, 1175 and Powderlink 1174.
- the Cymel versions are either mixed methylolated species and typically contain a relatively high dimer or oligomer content of up to about 20 weight percent.
- Powderlink 1174 is a purer form that is solely the methyl ester of the formula:
- dimer-oligomer of the monomer form.
- x is 0, and such monomer form is trifunctional.
- the dimer-oligomer forms provide greater amounts of methoxy per molecule.
- the dimer contains 6 methoxy functional groups.
- Such tri- and hexa- functionality does not alter this invention.
- the glycoluril ether linkage is much more resistant to hydrolysis than other aminoplast ether bonds.
- the higher dimer-oligomer content of the less pure glycolurils is not as favored as the lower dimer-oligomer content of Powder link 1 174. ' Further reduction of oligomers can be effected by recrystallization.
- 'Powderlink 1 174 is called a "resin” and "crosslinker” by Cytec, and has been sold under the Cymel® name (i.e., Cymel 1174). Its empirical structure is C ]2 H 22 N 4 0 6 . Its chemical name is Imidazo [4,5-D] imidazole-2,5 ( 1 H,3H)-dione, tetrahydro- 1 ,3 ,4,6-tetrakis (methoxymethyl)-. CAS 17464-88-9.
- Glycoluril 1 ,3,4,6 tetrakis methoxymethyl
- Glycoluril tetrakis methoxymethyl
- Glycoluril N,N,N,N tetrakis methoxymethyl
- Glyoxal diuriene tetrakis methoxymethyl
- Tetramethoxytetramethylol acetylenediurea Tetramethoxytetramethylol acetylenediurea.
- the favored name is (i) and such skeletal structure is called glycoluril.
- the ratio of aminoplast resin to the difunctional polyether is not critical. Typically, either the aminoplast resin or the difunctional polyether may be used in molar excess or stoichiometrically equivalent amounts in making the linear copolymer of the invention. In characterizing stoichiometry of the aminoplast resin, the resin is treated as being difunctional since linearity, according to the invention, is achieved when the aminoplast resin functions as a difunctional monomer even though the resin has the capability ofhigher functionality, e.g. , tri- and tetrafunctionality, as the case may be.
- more than one mole of a polyether diol to one mole of, e.g., a glycoluril such as Powderlink 1174, represents a stoichiometric excess of the polyether to the glycoluril.
- a glycoluril such as Powderlink 1174
- Either the polyether or the aminoplast may be in excess.
- one employs a molar excess ofthe aminoplast resin because one may incorporate more hydrophobicity into the copolymer this way.
- the copolymer is dimeric to oligomeric (e.g., possessing less than about 15 repeating units).
- the amount of ethoxylated tristyryl phenol should not exceed about 2.0 moles, nor be less than about 0.4 mole per mole of reacted aminoplast resin in the copolymer ofthe invention.
- the amount of ethoxylated tristyryl phenol ranges from about 0.7 mole to about 1.5 mole per mole of reacted aminoplast.
- Waterbome coatings may be defined as coatings that contain water as the major volatile component and utilize water to dilute the coating to application consistency. These coatings consist mainly of resinous binder, pigments, water, and organic solvent. The type of pigmentation and the method of incorporation of the pigment vary widely.
- Waterbome coatings can be made by dispersing, emulsifying or emulsion polymerizing the resin binder by use of added surfactants. This technique leads to opaque liquids. Because some hard resins are difficult or impossible to disperse directly into water, the resin sometimes can be dissolved in a water- immiscible solvent, and the resulting solution dispersed by the use of added surfactants. In this case, the solvent aids subsequent film coalescence. Surface activity or water dispersability also can be introduced into resin molecules by chemical modification ofthe resin by introducing functional polar groups such as the carboxyl group.
- Some very finely dispersed resins appear as clear or slightly hazy liquids; they frequently are described as soluble, solubilized, colloidal dispersions, micro-emulsions, hydrosols, etc. These resins contain built-in functional groups that confer water ' 'solubility' ' upon the resin, and, normally, external added surfactants are not used.
- Waterbome resin binders can be classified as anionic, cationic, or non-ionic.
- Anionic dispersions are characterized by negative charges on the resin or by negative charges on the surfactant associated with the resin.
- Cationic dispersions have a positive charge on the resin or on the surfactant associated with the resin.
- Nonionic dispersions are those that have been dispersed by addition of nonionic surfactants or that contain a built-in hydrophilic segment such as polyethylene oxide which is part ofthe main chain of a relatively hydrophobic resin molecule.
- the coating compositions may be ofthe thermosetting or thermoplastic varieties.
- the resin used in forming the coating may be insoluble in water, and the conversion of such a resin into a waterbome system typically involves com erting the resin into an emulsion or dispersion hi the context of this invention, the waterbome composition contains the aminoplast-ether copolymer associative thickener ofthe invention
- the aqueous polymer dispersions may be prepared according to well known emulsion polyme ⁇ zation procedures using one or more emulsifiers of an anionic, cationic, or nonionic type Mixtures of two or more non-neutralizing emulsifiers regardless of type may be used
- the amount of emulsifier may range from about 0 1 to 10% by weight or sometimes even more, based on the weight ofthe total monomer charge
- the molecular weight of these emulsion polymers is high, e g , from about 100,000 to 10,000,000 number average molecular weight, most commonly above 500,000
- the water insoluble resm may be any of those known in the art, and may be a conventional natural or synthetic polymer latex emulsified with one of a nonionic, cationic or anionic surfactant
- the primary resins are based on homopolyme ⁇ zed and copolyme ⁇ zed olefinic monomers such as vmyl acetate, vmyl chlo ⁇ de, styrene, butadiene, vinyhdene chloride, acrylonit ⁇ le, methacrylonit ⁇ le, acrylic acid, methacrylic acid, alkyl acrylates, alkyl methacrylates, acrylamide, methacrylamide, hydroxyethyl methacrylate (“HEMA”), glycidyl methacrylate, dihydroxypropyl methacrylate, homopolymers of C 2 -C 40 alpha-olefins such as ethylene, isobutylene, octene, nonene, and s
- the vinyl acetate copolymers are well-known and include copolymers such as vmyl acetate/butyl acrylate/2-ethylhexyl acrylate, vinyl acetate/butyl maleate, vmyl acetate/ethylene, vmyl acetate/vmyl chlo ⁇ de / butyl acrylate and vmyl acetate/vinyl chlo ⁇ de/ethylene
- Other waterbome systems involve reactive copolymers that are crosslinked by the presence of complementary functional groups in the system.
- a copolymer of acrylic ester/glycidylmethacrylate can be emulsified and crosslinked by the presence of a melamine-formaldehyde resin similarly emulsified in the system.
- a copolymer of HEMA and another acrylate, hydroxyl terminated polyesters, polyethers, or polyurethanes can be emulsified and crosslinked by the presence of either an aminoplast resin, a polyisocyanate or blocked polyisocyanate.
- ' 'acrylic polymer means any polymer wherein at least 50% by weight is an acrylic or methacrylic acid or ester, including mixtures of such acids and esters individually and together.
- vinyl acetate polymer means any polymer containing at least 50% by weight of vinyl acetate.
- Small particle size (about 0.1-0.15 micron) acrylic and other latices are thickened effectively, and flow and leveling improved, by thickeners ofthe invention.
- the use of this invention for producing architectural coatings for the mid to neutral base formulations based on small particle size acrylics where the level of colorant added is in large amounts for about the 5 to 16 oz per gallon range eliminates the need to incorporate other thickener systems, such as cellulosics and alkai-swellable thickeners or large amounts of surfactants.
- the amount ofthe aminoplast-ether copolymer described herein that is employed in the coating composition ofthe invention is not critical. That amount will vary based on the resin system used, the water concentration, the amount of fillers and the choice of fillers, the presence or absence of thixotropic agents, and the like. In that respect, the amount ofthe aminoplast-ether copolymer in the composition is sufficient to thicken the composition. However, in general, the amount ofthe copolymer will range from about 0.1 weight percent to about 15 weight percent, preferably from about 0.5 weight percent to about 10 weight percent, and most preferably from about 1 weight percent to about 8 weight percent, ofthe weight ofthe coating composition, exclusive of fillers, pigments and like additives.
- Optiflo H600 is the aminoplast-ether copolymer described above.
- Quality Control checks usually consist of viscosity (Stormer & ICI), pH, weight per gallon (WPG), hiding power and color acceptance
- the 17.5% solution from example 1 was evaluated in a semi-gloss neutral base formulation which contained Rhopex SG-20M acrylic latex.
- the paints were tinted with 8 oz of F Colorant (red iron oxide) from CreaNova (888).
Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU66397/00A AU772095B2 (en) | 1999-08-13 | 2000-08-11 | Nonionic associative thickener composition with improved viscosity retention upon tinting in architectural latex coating |
MXPA02001461A MXPA02001461A (en) | 1999-08-13 | 2000-08-11 | Nonionic associative thickener composition with improved viscosity retention upon tinting in architectural latex coating. |
JP2001517602A JP2003507509A (en) | 1999-08-13 | 2000-08-11 | Nonionic associative thickener composition with improved viscosity retention upon coloring with architectural latex paint |
EP00954049A EP1208147A4 (en) | 1999-08-13 | 2000-08-11 | Nonionic associative thickener composition with improved viscosity retention upon tinting in architectural latex coating |
CA002384180A CA2384180A1 (en) | 1999-08-13 | 2000-08-11 | Nonionic associative thickener composition with improved viscosity retention upon tinting in architectural latex coating |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US37359299A | 1999-08-13 | 1999-08-13 | |
US09/373,592 | 1999-08-13 |
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WO2001012712A1 true WO2001012712A1 (en) | 2001-02-22 |
WO2001012712B1 WO2001012712B1 (en) | 2001-05-03 |
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PCT/US2000/022220 WO2001012712A1 (en) | 1999-08-13 | 2000-08-11 | Nonionic associative thickener composition with improved viscosity retention upon tinting in architectural latex coating |
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EP (1) | EP1208147A4 (en) |
JP (1) | JP2003507509A (en) |
AU (1) | AU772095B2 (en) |
CA (1) | CA2384180A1 (en) |
MX (1) | MXPA02001461A (en) |
WO (1) | WO2001012712A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002012363A1 (en) * | 2000-08-04 | 2002-02-14 | Süd-Chemie AG | Graft polymers or graft copolymers |
EP1291399A2 (en) * | 2001-09-11 | 2003-03-12 | Faber- Castell AG | Powderstick with a porous lead base body |
WO2003055928A1 (en) * | 2001-12-24 | 2003-07-10 | Süd-Chemie AG | Copolymers containing aminoplast units and use thereof as a dispersing agent or stabilizer |
WO2004078858A2 (en) * | 2003-03-08 | 2004-09-16 | Süd-Chemie AG | Associative thickener preparation |
US6900255B2 (en) | 2003-05-16 | 2005-05-31 | Hercules Incorporated | Suppression of aqueous viscosity of nonionic associative thickeners |
EP1541643A1 (en) | 2003-12-10 | 2005-06-15 | Rohm And Haas Company | Nonionic associative thickener containing condensation polymer backbone |
US7741402B2 (en) | 2007-03-21 | 2010-06-22 | Rohm And Haas Company | Thickener composition and method for thickening aqueous systems |
US7803864B2 (en) | 2006-01-05 | 2010-09-28 | Rohm And Haas Company | Associative thickener compositions and methods of use |
US7868122B2 (en) | 2008-06-19 | 2011-01-11 | Southern Clay Products, Inc. | Tint-viscosity stabilization polymeric thickeners |
WO2013134497A1 (en) | 2012-03-08 | 2013-09-12 | Hercules Incorporated | Viscosity suppression of associative thickeners using organophosphates |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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AU2017239546B2 (en) | 2016-10-21 | 2022-01-13 | Rohm And Haas Company | Deep base paint formulation |
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US4289811A (en) * | 1980-02-21 | 1981-09-15 | Celanese Corporation | Stable aqueous dispersions of mixed resins and process for use as coating compositions |
US5627232A (en) * | 1995-06-07 | 1997-05-06 | United Catalysts, Inc. | Water-based composition containing an aminoplast-ether copolymer |
US5629373A (en) * | 1995-06-07 | 1997-05-13 | United Catalysts, Inc. | Water based coating composition containing an aminoplast-ether copolymer |
US5914373A (en) * | 1995-06-07 | 1999-06-22 | United Catalysts, Inc. | Water soluble aminoplast-ether copolymers |
US6103816A (en) * | 1992-10-30 | 2000-08-15 | Ppg Industries Ohio, Inc. | Aqueous aminoplast curable film-forming compositions providing films having resistance to acid etching |
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2000
- 2000-08-11 JP JP2001517602A patent/JP2003507509A/en active Pending
- 2000-08-11 EP EP00954049A patent/EP1208147A4/en not_active Withdrawn
- 2000-08-11 MX MXPA02001461A patent/MXPA02001461A/en not_active Application Discontinuation
- 2000-08-11 AU AU66397/00A patent/AU772095B2/en not_active Ceased
- 2000-08-11 CA CA002384180A patent/CA2384180A1/en not_active Abandoned
- 2000-08-11 WO PCT/US2000/022220 patent/WO2001012712A1/en not_active Application Discontinuation
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US4289811A (en) * | 1980-02-21 | 1981-09-15 | Celanese Corporation | Stable aqueous dispersions of mixed resins and process for use as coating compositions |
US6103816A (en) * | 1992-10-30 | 2000-08-15 | Ppg Industries Ohio, Inc. | Aqueous aminoplast curable film-forming compositions providing films having resistance to acid etching |
US5627232A (en) * | 1995-06-07 | 1997-05-06 | United Catalysts, Inc. | Water-based composition containing an aminoplast-ether copolymer |
US5629373A (en) * | 1995-06-07 | 1997-05-13 | United Catalysts, Inc. | Water based coating composition containing an aminoplast-ether copolymer |
US5914373A (en) * | 1995-06-07 | 1999-06-22 | United Catalysts, Inc. | Water soluble aminoplast-ether copolymers |
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Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002012363A1 (en) * | 2000-08-04 | 2002-02-14 | Süd-Chemie AG | Graft polymers or graft copolymers |
EP1291399A3 (en) * | 2001-09-11 | 2004-02-04 | Faber- Castell AG | Powderstick with a porous lead base body |
EP1291399A2 (en) * | 2001-09-11 | 2003-03-12 | Faber- Castell AG | Powderstick with a porous lead base body |
US7335699B2 (en) | 2001-12-24 | 2008-02-26 | Sud-Chemie Ag | Copolymers containing aminoplast units and use thereof as a dispersing agent or stabilizers |
AU2002361003B2 (en) * | 2001-12-24 | 2007-04-05 | Sud-Chemie Ag | Copolymers containing aminoplast units and use thereof as a dispersing agent or stabilizer |
WO2003055928A1 (en) * | 2001-12-24 | 2003-07-10 | Süd-Chemie AG | Copolymers containing aminoplast units and use thereof as a dispersing agent or stabilizer |
WO2004078858A2 (en) * | 2003-03-08 | 2004-09-16 | Süd-Chemie AG | Associative thickener preparation |
WO2004078858A3 (en) * | 2003-03-08 | 2005-04-21 | Sued Chemie Ag | Associative thickener preparation |
US6900255B2 (en) | 2003-05-16 | 2005-05-31 | Hercules Incorporated | Suppression of aqueous viscosity of nonionic associative thickeners |
EP1541643A1 (en) | 2003-12-10 | 2005-06-15 | Rohm And Haas Company | Nonionic associative thickener containing condensation polymer backbone |
US7803864B2 (en) | 2006-01-05 | 2010-09-28 | Rohm And Haas Company | Associative thickener compositions and methods of use |
US7741402B2 (en) | 2007-03-21 | 2010-06-22 | Rohm And Haas Company | Thickener composition and method for thickening aqueous systems |
US7868122B2 (en) | 2008-06-19 | 2011-01-11 | Southern Clay Products, Inc. | Tint-viscosity stabilization polymeric thickeners |
WO2013134497A1 (en) | 2012-03-08 | 2013-09-12 | Hercules Incorporated | Viscosity suppression of associative thickeners using organophosphates |
US9249280B2 (en) | 2012-03-08 | 2016-02-02 | Hercules Incorporated | Viscosity suppression of associative thickeners using organophosphates |
Also Published As
Publication number | Publication date |
---|---|
AU6639700A (en) | 2001-03-13 |
WO2001012712B1 (en) | 2001-05-03 |
CA2384180A1 (en) | 2001-02-22 |
AU772095B2 (en) | 2004-04-08 |
MXPA02001461A (en) | 2003-07-21 |
EP1208147A1 (en) | 2002-05-29 |
EP1208147A4 (en) | 2002-10-16 |
JP2003507509A (en) | 2003-02-25 |
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