CA2583268C - Self crosslinking waterborne coatings - Google Patents
Self crosslinking waterborne coatings Download PDFInfo
- Publication number
- CA2583268C CA2583268C CA2583268A CA2583268A CA2583268C CA 2583268 C CA2583268 C CA 2583268C CA 2583268 A CA2583268 A CA 2583268A CA 2583268 A CA2583268 A CA 2583268A CA 2583268 C CA2583268 C CA 2583268C
- Authority
- CA
- Canada
- Prior art keywords
- coating composition
- monomer
- weight
- polyvinyl chloride
- monomers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
Abstract
An aqueous coating composition comprising (i) a binder resin having latent crosslinking functionality, (ii) crosslinker for the resin, and (iii) polymeric extender particles is disclosed.
Description
SELF CROSSLINKING WATERBORNE COATINGS
[0002] This invention relates to waterborne coatings having improved performance properties. Conventional latex paints are widely used because they provide reduced volatile organic compound emission and because they allow easier clean up than solvent borne coatings. However, when compared to solvent borne coating systems, typical latex coatings may lack certain performance properties, such as the chemical resistance and durability provided by such solvent borne coatings.
[0003] It has now been found that latex coating compositions having improved properties, such as improved stain and chemical resistance and durability, can be produced by formulating a chemical coating comprising a binder resin having post crosslinking groups; a suitable crosslinker for the binder resin; and polymeric extender particles such as polyvinyl chloride extender particles.
[0004] The present invention is directed to an aqueous coating composition in which the binder resin has functional groups that further react with one or more co-dispersed crosslinkers some time after initial formation of the binder resin.
In certain applications the substantive crosslinking will be delayed until application of the coating to a substrate and evaporation of at least some of the aqueous carrier.
[0004a] More specifically, according to one aspect of the invention there is provided an aqueous coating composition comprising:
(i) a binder resin having carbonyl latent crosslinking functionality;
(ii) an effective crosslinking amount of a crosslinker selected from the group consisting of di and poly amines, di and poly hydrazides, and di and poly hydrazines and mixtures thereof for the binder resin;
(iii) solid polyvinyl chloride polymeric extender particles.
[0004b] According to another aspect of the invention there is provided a coating composition comprising:
(i) a binder resin obtained by polymerizing a monomer mixture comprising:
(a) about 1 to about 25% by weight of a monomer having carbonyl latent crosslinking functionality;
(b) about 0.5 to about 15% by weight of an acid functional monomer;
(c) about 0.1 to about 10% of a wet adhesion promoting monomer; and (d) about 50 to about 98.4% of at least one other copolymerizable monomer.
(ii) a crosslinker selected from the group consisting of di and polyamines, di and poly hydrazides, and di and poly hydrazines and mixtures thereof;
(ii) solid polyvinyl chloride extender particles.
In certain applications the substantive crosslinking will be delayed until application of the coating to a substrate and evaporation of at least some of the aqueous carrier.
[0004a] More specifically, according to one aspect of the invention there is provided an aqueous coating composition comprising:
(i) a binder resin having carbonyl latent crosslinking functionality;
(ii) an effective crosslinking amount of a crosslinker selected from the group consisting of di and poly amines, di and poly hydrazides, and di and poly hydrazines and mixtures thereof for the binder resin;
(iii) solid polyvinyl chloride polymeric extender particles.
[0004b] According to another aspect of the invention there is provided a coating composition comprising:
(i) a binder resin obtained by polymerizing a monomer mixture comprising:
(a) about 1 to about 25% by weight of a monomer having carbonyl latent crosslinking functionality;
(b) about 0.5 to about 15% by weight of an acid functional monomer;
(c) about 0.1 to about 10% of a wet adhesion promoting monomer; and (d) about 50 to about 98.4% of at least one other copolymerizable monomer.
(ii) a crosslinker selected from the group consisting of di and polyamines, di and poly hydrazides, and di and poly hydrazines and mixtures thereof;
(ii) solid polyvinyl chloride extender particles.
[0005] As reactive elements, the aqueous coating composition contains (a) a binder resin comprising the polymerization reaction product of at least one or more copolymerizable monoethylenically unsaturated monomers, wherein at least one of the monoethylenically unsaturated monomers contains latent crosslinking functionality; and (b) a crosslinking amount of at least one crosslinker reactive with the crosslinking functionality. As a coating, this invention comprises the crosslinkable binder resin, the crosslinker, and polymeric extender particles.
[0006] The latent crosslinking functionality can be imparted to the binder resin by incorporating monomers having reactive functional groups known in the art. For example (i) the pendent functional group could be a carbonyl group, such as ketone, or aldehyde, la or acetoacetoxy and the crosslinker could representatively have amino or hydrazide groups; (ii) the pendent functional group could be epoxy and the crosslinker could representatively have carboxylic acid, thiol or amino groups; (iii) the pendent functional group could be silane and the crosslinker could representatively have hydroxyl groups;
and (iv) the pendent functional groups could be hydroxyl groups and the crosslinker could representatively have isocyanate groups or methylol groups or etherified methylol groups.
and (iv) the pendent functional groups could be hydroxyl groups and the crosslinker could representatively have isocyanate groups or methylol groups or etherified methylol groups.
[0007] Alternatively, the functional groups identified as useful in the crosslinkers could be incorporated into the binder resin and the corresponding identified reactive group could be present in the crosslinker. The exact nature of the coreactive groups is not critical. Any coreactive groups are possible as pendent functional groups and crosslinking groups, provided the coating composition remains fluid until application to a substrate. If desired, the crosslinker can be withheld from the coating composition until immediately prior to application to ensure that the coating composition remains fluid. In some embodiments, such as the use of pendent carbonyl groups on the binder resin, and the use of a water-soluble polyhydrazide, it is convenient to incorporate the hydrazide into the aqueous coating to provide a single package which will cure upon application.
Binder Resins [0008] The latex polymers used as binder resins in accordance with the present invention (also referred to herein as "binders") include those polymers polymerized from one or more suitable monomers. Typically, the binders are polymerized from one or more copolymerizable monoethylenically unsaturated monomers such as, for example, vinyl monomers and/or acrylic monomers.
Binder Resins [0008] The latex polymers used as binder resins in accordance with the present invention (also referred to herein as "binders") include those polymers polymerized from one or more suitable monomers. Typically, the binders are polymerized from one or more copolymerizable monoethylenically unsaturated monomers such as, for example, vinyl monomers and/or acrylic monomers.
[0009] The vinyl monomers suitable for use in accordance with the present invention include any compounds having vinyl functionality, i.e., ethylenic unsaturation, exclusive of compounds having acrylic functionality, e.g., acrylic acid, methacrylic acid, esters of such acids, acrylonitrile and acrylamides. Preferably, the vinyl monomers are selected from the group consisting of vinyl esters, vinyl aromatic hydrocarbons, vinyl aliphatic hydrocarbons, vinyl alkyl ethers and mixtures thereof.
[0010] Suitable vinyl monomers include vinyl esters, such as, for example, vinyl propionate, vinyl laurate, vinyl pivalate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl butyrates, vinyl benzoates, vinyl isopropyl acetates and similar vinyl esters; vinyl aromatic hydrocarbons, such as, for example, styrene, methyl styrenes and similar lower alkyl styrenes, chlorostyrene, vinyl toluene, vinyl naphthalene and divinyl benzene; vinyl aliphatic hydrocarbon monomers, such as, for example, vinyl chloride and vinylidene chloride as well as alpha olefins such as, for example, ethylene, propylene, isobutylene, as well as conjugated dienes such as 1,3 butadiene, methyl-2-butadiene, 1,3-piperylene, 2,3-dimethyl butadiene, isoprene, cyclohexene, cyclopentadiene, and dicyclopentadiene; and vinyl alkyl ethers, such as, for example, methyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether.
[0011] The acrylic monomers suitable for use in accordance with the present invention comprise any compounds having acrylic functionality. Preferred acrylic monomers are selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylate acids and methacrylate acids as well as aromatic derivatives of acrylic and methacrylic acid, acrylamides and acrylonitrile. Typically, the alkyl acrylate and methacrylic monomers (also referred to herein as "alkyl esters of acrylic or methacrylic acid") will have an alkyl ester portion containing from 1 to about 18, preferably about 1 to 8, carbon atoms per molecule.
[0012] Suitable acrylic monomers include, for example, methyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, propyl acrylate and methacrylate, 2-ethyl hexyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, decyl acrylate and methacrylate, isodecyl acrylate and methacrylate, benzyl acrylate and methacrylate, isobornyl acrylate and methacrylate, neopentyl acrylate and methacrylate, and 1-adamantyl methacrylate.
[0013] In addition to the specific monomers described above, those skilled in the art will recognize that other monomers such as, for example, allylic monomers, or monomers which impart wet adhesion, such as monomers having teritiary amine, ethylene ureido, or N-heterocyclic groups, can be used in place of, or in addition to, the specifically described monomers in the preparation of the binders. Representative wet adhesion promoting monomers include methacrylamidoethyl ethylene urea, dimethylaminoethyl methacrylate, vinyl imidizole and 2-ethyleneuriedo-ethyl methacrylate. The amount of such other monomers is dependent on the particular monomers and their intended function, which amount can be determined by those skilled in the art. In one embodiment of this invention, a wet adhesion promoting monomer, if desired, could be present at levels ranging up to about 5% of the total monomer mix by weight.
[0014] The monomer mix polymerized to create the binder resin of the present invention will comprise at least one ethylenically unsaturated monomer containing "latent crosslinking" capabilities, which as used herein means a monomer which possesses the ability to further react with a crosslinker some time after initial formation of the polymer.
The crosslinking reaction can occur through the application of energy, e.g., through heat or radiation. Also, drying can activate the crosslinking polymer through changes in pH, oxygen content, evaporation of solvent or carrier, or other changes that causes a reaction to occur. The particular method of achieving crosslinking in the binder polymer is not critical to the present invention. A variety of chemistries are known in the art to produce crosslinking in latexes.
The crosslinking reaction can occur through the application of energy, e.g., through heat or radiation. Also, drying can activate the crosslinking polymer through changes in pH, oxygen content, evaporation of solvent or carrier, or other changes that causes a reaction to occur. The particular method of achieving crosslinking in the binder polymer is not critical to the present invention. A variety of chemistries are known in the art to produce crosslinking in latexes.
[0015] Representative examples of latent crosslinking carbonyl-containing monomers include acrolein, methacrolein, diacetone acrylamide, diacetone methacrylamide, 2 butanone methacrylate, formyl styrol, diacetone acrylate, diacetone methacrylate, acetonitrile acrylate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate and vinylaceto acetate. These monomers normally do not affect crosslinking until during final film formation, for example, when the aqueous polymer emulsion simultaneously contains an appropriate added amount of a reactive material such as a polyamine compound as crosslinker. Particularly suitable compounds of this type are the dihydrazides and trihydrazides of aliphatic and aromatic dicarboxylic acids of 2 to 20 carbon atoms. Polyamine compounds useful as crosslinkers for the carboxyl functional groups include those having an average of at least two carbonyl-reactive groups of the formula - NH2 and carbonyl reactive groups derived from such groups. Examples of useful amine functional groups include R-NH2, R-O-NH2, R-O-N=C<, R-NH-C(=O)-O-NH2, wherein R is alkylene, alicyclic or aryl and may be substituted.
Representative useful polyamines include ethylene diamine, isophorone diamine, diethylenetriamine and dibutylenetriamine. In one embodiment of this invention it is useful to utilize polyhydrazides as the polyamine compounds. Representative useful polyhydrazides include oxalic dihydrazide, adipic dihydrazide, succinic dihydrazide, malonic dihydrazide, glutaric dihydrazide, phthalic or terephthalic dihydrazide and itaconic dihydrazide. Additionally, water-soluble hydrazines such as ethylene-l,2-dihydrazine, propylene-1,3-dihydrazine and butylene-1,4-dihydrazine can also be used as one of the crosslinking agents.
[00161 Additional building blocks which are suitable for postcrosslinking are those which contain hydrolyzable organosilicon bonds. Examples are the copolymerizable monomers methacryloyloxypropyltrimethoxysilane and vinyltrimethoxysilane.
[00171 Epoxy-, hydroxyl- and/or N-alkylol-containing monomers, for example, glycidyl acrylate, N-methylolacrylamide and -methacrylamide and monoesters of dihydric alcohols with c~ fl-monoethylenically unsaturated carboxylic acids of 3 to 6 carbon atoms, such as hydroxyethyl, hydroxy-n-propyl or hydroxy-n-butyl acrylate and methacrylate are also suitable for postcrosslinking. Primary or secondary amino containing acrylates or methacrylates such as t-butyl amino ethyl methacrylate are also suitable.
[00181 In one embodiment the binder resin can be obtained by the polymerization of a mixture of monomers, which mixture contains about 0.5 to about 25% by weight, based on the total weight of the polymer, of at least one monomer having latent crosslinking functionality.
[00191 In one embodiment of the present invention, the binder resin is an acid functional latex. Specific acid functional monomers suitable for use in accordance with the present invention include, for example, acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, dimeric acrylic acid or the anhydrides thereof.
Besides carboxylic acids and anhydrides, monomers possessing other acid groups such as sulfonic or phosphoric acid groups are also useful. Representative monomers include ethylmethacrylate-2-sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, methyl-2-propenoic acid ethyl-2-phosphate ester (HEMA-phosphate), (1-phenylvinyl)-phosphonic acid, or (2-phenylvinyl)-phosphonic acid. Mixtures of acids are also practical.
[00201 For many applications, typically, the particle size,of the binder resins would range from about 0.1 to 1.0 microns. The Tg of some useful representative binder resins, of the present invention would typically be from about -60 to 100 C. Binder resins having a Tg less than about 20 C typically require less volatile organic compounds (solvents and coalescents) to form a smooth film compared to higher Tg polymers. In one useful embodiment the Tg would be less than about 10 C. In another useful embodiment the Tg is less than about 1 C. As used herein, the term "Tg" means polymer glass transition temperature.
[0021] Preparation of latex compositions is well known in the paint and coatings art.
Any of the well known free-radical emulsion polymerization techniques used to formulate latex polymers can be used in the present invention. Such procedures include, for example, single feed, core-shell, and inverted core-shell procedures which produce homogeneous or structured particles.
[0022] In one useful embodiment the binder resin would be obtained by polymerizing a monomer mixture of about 1-25% by weight of a monomer having latent crosslinking functionality, 0.5 to about 15% of an acid functional monomer and about 60 to 98.5%
other monomers. In another useful embodiment the monomer mixture would also comprise about 0.1 to about 10% of a wet adhesion promoting monomer. In another embodiment, the monomer mixture would comprise about 1-25% by weight of a monomer having latent crosslinking functionality, 0.5 to about 15% of an acid functional monomer, 0.1 to about 10% of a wet adhesion monomer, 1 to about 55 parts styrene, and the remainder selected from other copolymerizable monomers.
[0023] The crosslinker for reaction with the latent crosslinking functionality need only be present in an amount necessary to achieve the desired degree of cure.
For many applications, the crosslinker will typically be present at a level to provide at least 0.1 equivalent for each equivalent of latent crosslinking functionality.
[0024] In one of the embodiments of this invention, the crosslinker would be present at a level to provide between about 0.2 to about 2.0 equivalents for each equivalent of latent crosslinking functionality. In some useful embodiments the crosslinker will be present at a level to provide 0.4 to about 1.2 equivalents for each equivalent of latent crosslinking functionality.
[0025] In another useful embodiment the crosslinker would be present at a level to provide about 0.4 to about 1.0 equivalent for each equivalent of latent crosslinking functionality.
[0026] The coatings of this invention will also comprise a polymeric extender particle. In one embodiment of this invention, the polymeric extender particle would comprise solid polyvinyl chloride particles. Polyvinyl chloride particles are taught in U.S. Published Application 2004/0034158 Al (Reuter et al.).
[0027] In one embodiment of this invention, the polyvinyl chloride extender particles would have an average particle size in a range from about 5 to about 150 microns. The coating composition incorporating the polyvinyl chloride extender particles would be free of plasticizers. In the absence of plasticizers, the polyvinyl chloride extender particles remain as discrete particles in the film after the coating has cured or dried.
In some embodiments, it is useful to utilize polymeric extender particles which are substantially free of any colored pigments dispersed therein.
[0028] As used herein, the term "plasticizer" means a nonaqueous, nonvolatile liquid medium that is compatible with polyvinyl chloride and when added to a coating composition containing polyvinyl chloride becomes a part of the dried film and increases film flexibility. Plasticizers, when admixed with the polyvinyl chloride would produce a gel by solublizing the polyvinyl chloride, and ultimately a fully fused solid when the composition is heated. Examples of plasticizers include phthalic acid esters, dibasic esters, phosphoric acid esters, polyester-based plasticizers and especially dioctyl phthalate and diisononyl phthalate.
[0029] As used herein, the term "polyvinyl chloride" shall mean a homopolymer of vinyl chloride, or a copolymer of at least 80 weight percent of units derived from vinyl chloride, with up to about twenty weight percent of one or more other vinyl monomers.
[0030] As defined above, the polyvinyl chloride extender particles may be homopolymers of vinyl chloride or copolymers of at least 80 weight percent of units derived from vinyl chloride, with up to about twenty weight percent of one or more other vinyl monomers. Suitable vinyl monomers include alpha-olefins, such as ethylene and propylene; vinyl esters, such as vinyl acetate, vinyl propionate, and vinyl benzoate;
vinylidene chloride; alkyl (meth)acrylates, such as methyl acrylate, lauryl acrylate, methyl methacrylate and cetyl methacrylate; vinyl aromatic monomers, such as styrene and vinyl toluene; acrylonitrile; methacrylonitrile; and maleimides, such as N-cyclohexyl maleimide, N-phenylamaleimide, or maleimide. Preferably, however, the polyvinyl chloride extender particles are vinyl chloride homopolymers. Polyvinyl chloride polymers can be prepared by suspension polymerization or other techniques as is known in the art and are commercially available from a number of suppliers. One useful polyvinyl chloride resin extender particle is Geon 217 available from Poly One Corporation.
[0031] In some useful embodiments, the polyvinyl chloride extender particles will have an average particle size greater than 3 microns. For some applications, the polyvinyl chloride extender particles have an average particle size in a range from about 5 microns to about 150 microns, and frequently in a range from about 10 microns to about microns. The polyvinyl chloride extender particles are solid and remain as discrete particles in the coatings of this invention even after the coating has cured or dried.
[0032] Preferably, the polyvinyl chloride extender particles have a Fikentscher K
value between about 50 and about 80, more preferably between about 60 and about 70.
The Fikentscher K value is determined by solution viscosity measurements and provides a measure of molecular weight. The correlation between the Fikentscher K value and number average molecular weight (Mn) is as follows: a Fikentscher K value of 50 is roughly equal to a Mn of 28,000 and a Fikentscher K value of 80 is roughly equal to a Mn of 80,000.
[0033] The amount of polymeric extender particles in the coating composition of the present invention, on a solids basis, is typically from about 5 to about 60 weight percent, and often from about 25 to about 50 weight percent, based on the total weight of solids of the coating composition.
[0034] The coating composition of the present invention is manufactured using techniques known to those skilled in the art of manufacturing paint. The coatings of this invention may also include conventional pigments and flattening agents as well as various additives. Examples of suitable inorganic flatting agents include silicates, such as talc, and various forms of silica, such as amorphous, aerogel, diatomaceous, hydrogel and fumed silicas. Conventional pigments include titanium dioxide, zinc oxide, and other inorganic or organic pigments. The coatings of this invention also may incorporate one or more polymeric opacifying agents. The polymeric opacifiers are generally small particle size non-film forming polymerized beads which are insoluble in the coating in which they are dispersed. Typically the polymeric opacifying agents will replace some of the hiding pigments which would otherwise be incorporated into the coating.
The beads may be solid or they may contain vesicles or dispersed pigments within the polymerized bead. Representative polymeric particles useful as opacifying agents include beads of polystyrene, polyacrylic, polyethylene, polyamide, poly(vinylacetate ethylene), melamine formaldehyde, urea formaldehyde, polyester and polyurethane. Representative commercially available polymeric pigments are sold under the Ropaque, Dylex (polystyrene) and Pergopak (urea formaldehyde) trademarks. If polymeric opacifying agents are incorporated they typically will comprise between about 1% and about 85% by weight of the total amount of opacifying agents and pigments. Typical additives include dispersants, preservatives, anti foaming agents, thickeners, etc. The coatings of this invention can be applied to any substrate such as wood, wallboard, metal, etc.
by any application method including spraying, brushing, rolling, etc. in one embodiment the coatings are especially useful as interior or exterior paints, especially house paints.
[0035] The present invention will be better understood by reference to the following examples, which are provided for purposes of illustration only and are not to be construed as limiting the scope of the present invention.
[0036] A latex polymer was prepared as follows. A reaction vessel was charged with 124.75 parts water and heated to 85 C under a nitrogen blanket. A first mixture of 6.14 parts water, 1.39 parts surfactant (Abex EP-110, an anionic surfactant available from Rhodia), 0.082 parts 28% aqueous ammonia, and 0.30 parts ammonium persulfate was then added to the heated water. A feed mixture of 50.88 parts water, 8.08 parts Abex EP-110, 3.72 parts methacrylic acid, 1.49 parts Sipomer PAM 100 (phosphate ester of 2-hydroxyethyl methacrylate from Rhodia), 5.98 parts Rohamere 6844 (25% aqueous solution of N-(2-methacryloxyethyl)ethylene urea from Rohm Tech, Inc.), 79.05 parts 2-ethyl hexyl acrylate, 54.70 parts styrene, 3.07 parts water and 4.48 parts diacetone acrylamide was prepared, as was an initiator mixture of 0.30 parts ammonium persulfate and 15.36 parts water. The feed mixture and the initiator mixture were then simultaneously added to the heated (85 C) reaction mixture over a period of 3 hours.
Upon completion of the additions, the reaction was maintained at 85 C for an additional hour. The reaction was then allowed to cool to 65 C and a chase oxidizer mixture of 0.21 parts t-butyl hydroperoxide in 2.4 parts water and a chase reducer mixture of 0.15 parts isoascorbic acid, 2.40 parts water, and 0.07 parts 28% aqueous ammonia were both added over 45 minutes and the reaction was held at 65 C for 45 minutes thereafter.
The reaction was then allowed to cool to 35 C and 0.22 parts Proxel GXL and 0,75 parts 28%
aqueous ammonia were added. 1.72 parts adipic dihydrazide was pre-dissolved in 5.16 parts water by heating to 60 C and mixing for 15 minutes, and that solution was then added to the reaction mixture over a three minute period. The reaction was mixed for an additional 15 minutes and then filtered to provide the final self-crosslinking latex mixture. The latex product had a Tg of approximately -4 C, and an NVM of 41.600%.
[0037] A latex mixture could be prepared by the process as shown in Example 1 except replacing the Abex EP-110 with a comparable solids amount of Rhodafac (a nonyl-phenol ethoxylated phosphate ester from Rhodia) and the monomer mix to provide, on a weight solids basis, 4% diacetone acrylamide, 1.0% methacrylic acid, 2.2%
PAM 100, 52.8% 2-ethyl hexyl acrylate, and 40% styrene. The same equivalent ratio of adipic dihydrazide as in Example 1 could be utilized.
[0038] A representative flat latex coating composition could be prepared by admixing the following materials in the order shown:
Raw Material Parts by Weight Self-crosslinking latex of Example 2 39.50 Defoamerl 0.20 Polymeric opacifying pigment2 9.50 Water 9.15 Attapulgite clay 0.50 Hydroxyethyl cellulose thickener 0.08 Microbiocide 0.05 Surfactant3 1.26 Nonionic surfactant4 0.20 2 amino-2-methyl-l-proponol 0.30 Defoamer' 0.20 Ground feldspar 9.50 Polyvinyl chloride particles5 4.00 Water 0.83 Ethylene glycol 1.10 Associative thickener6 1.60 Water 0.08 20% active fungicide 0.20 Titanium dioxide slurry? 30.00 Water 0.62 Defoamerl 0.10 I Sher-Defoam, proprietary defoamer of the assignee of this application 2 Ropaque OP-96 from Rohm and Haas 3 Tamol 165-A from Rohm and Haas 4 Triton N-57 nonionic surfactant from Rohm and Haas Geon 217 from Poly One Corporation. Vinyl chloride homopolymer having an average particle size of about 35 microns 6 Acrysol RM-2020 NPR polymer solution from Rohm and Haas 7 R-746 from Rohm and Haas [0039] While the invention has been shown and described with respect to particular embodiments thereof, those embodiments are for the purpose of illustration rather than limitation, and other variations and modifications of the specific embodiments herein described will be apparent to those skilled in the art, all within the intended spirit and scope of the invention. Accordingly, the invention is not to be limited in scope and effect to the specific embodiments herein described, nor in any other way that is inconsistent with the extent to which the progress in the art has been advanced by the invention.
Representative useful polyamines include ethylene diamine, isophorone diamine, diethylenetriamine and dibutylenetriamine. In one embodiment of this invention it is useful to utilize polyhydrazides as the polyamine compounds. Representative useful polyhydrazides include oxalic dihydrazide, adipic dihydrazide, succinic dihydrazide, malonic dihydrazide, glutaric dihydrazide, phthalic or terephthalic dihydrazide and itaconic dihydrazide. Additionally, water-soluble hydrazines such as ethylene-l,2-dihydrazine, propylene-1,3-dihydrazine and butylene-1,4-dihydrazine can also be used as one of the crosslinking agents.
[00161 Additional building blocks which are suitable for postcrosslinking are those which contain hydrolyzable organosilicon bonds. Examples are the copolymerizable monomers methacryloyloxypropyltrimethoxysilane and vinyltrimethoxysilane.
[00171 Epoxy-, hydroxyl- and/or N-alkylol-containing monomers, for example, glycidyl acrylate, N-methylolacrylamide and -methacrylamide and monoesters of dihydric alcohols with c~ fl-monoethylenically unsaturated carboxylic acids of 3 to 6 carbon atoms, such as hydroxyethyl, hydroxy-n-propyl or hydroxy-n-butyl acrylate and methacrylate are also suitable for postcrosslinking. Primary or secondary amino containing acrylates or methacrylates such as t-butyl amino ethyl methacrylate are also suitable.
[00181 In one embodiment the binder resin can be obtained by the polymerization of a mixture of monomers, which mixture contains about 0.5 to about 25% by weight, based on the total weight of the polymer, of at least one monomer having latent crosslinking functionality.
[00191 In one embodiment of the present invention, the binder resin is an acid functional latex. Specific acid functional monomers suitable for use in accordance with the present invention include, for example, acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, dimeric acrylic acid or the anhydrides thereof.
Besides carboxylic acids and anhydrides, monomers possessing other acid groups such as sulfonic or phosphoric acid groups are also useful. Representative monomers include ethylmethacrylate-2-sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, methyl-2-propenoic acid ethyl-2-phosphate ester (HEMA-phosphate), (1-phenylvinyl)-phosphonic acid, or (2-phenylvinyl)-phosphonic acid. Mixtures of acids are also practical.
[00201 For many applications, typically, the particle size,of the binder resins would range from about 0.1 to 1.0 microns. The Tg of some useful representative binder resins, of the present invention would typically be from about -60 to 100 C. Binder resins having a Tg less than about 20 C typically require less volatile organic compounds (solvents and coalescents) to form a smooth film compared to higher Tg polymers. In one useful embodiment the Tg would be less than about 10 C. In another useful embodiment the Tg is less than about 1 C. As used herein, the term "Tg" means polymer glass transition temperature.
[0021] Preparation of latex compositions is well known in the paint and coatings art.
Any of the well known free-radical emulsion polymerization techniques used to formulate latex polymers can be used in the present invention. Such procedures include, for example, single feed, core-shell, and inverted core-shell procedures which produce homogeneous or structured particles.
[0022] In one useful embodiment the binder resin would be obtained by polymerizing a monomer mixture of about 1-25% by weight of a monomer having latent crosslinking functionality, 0.5 to about 15% of an acid functional monomer and about 60 to 98.5%
other monomers. In another useful embodiment the monomer mixture would also comprise about 0.1 to about 10% of a wet adhesion promoting monomer. In another embodiment, the monomer mixture would comprise about 1-25% by weight of a monomer having latent crosslinking functionality, 0.5 to about 15% of an acid functional monomer, 0.1 to about 10% of a wet adhesion monomer, 1 to about 55 parts styrene, and the remainder selected from other copolymerizable monomers.
[0023] The crosslinker for reaction with the latent crosslinking functionality need only be present in an amount necessary to achieve the desired degree of cure.
For many applications, the crosslinker will typically be present at a level to provide at least 0.1 equivalent for each equivalent of latent crosslinking functionality.
[0024] In one of the embodiments of this invention, the crosslinker would be present at a level to provide between about 0.2 to about 2.0 equivalents for each equivalent of latent crosslinking functionality. In some useful embodiments the crosslinker will be present at a level to provide 0.4 to about 1.2 equivalents for each equivalent of latent crosslinking functionality.
[0025] In another useful embodiment the crosslinker would be present at a level to provide about 0.4 to about 1.0 equivalent for each equivalent of latent crosslinking functionality.
[0026] The coatings of this invention will also comprise a polymeric extender particle. In one embodiment of this invention, the polymeric extender particle would comprise solid polyvinyl chloride particles. Polyvinyl chloride particles are taught in U.S. Published Application 2004/0034158 Al (Reuter et al.).
[0027] In one embodiment of this invention, the polyvinyl chloride extender particles would have an average particle size in a range from about 5 to about 150 microns. The coating composition incorporating the polyvinyl chloride extender particles would be free of plasticizers. In the absence of plasticizers, the polyvinyl chloride extender particles remain as discrete particles in the film after the coating has cured or dried.
In some embodiments, it is useful to utilize polymeric extender particles which are substantially free of any colored pigments dispersed therein.
[0028] As used herein, the term "plasticizer" means a nonaqueous, nonvolatile liquid medium that is compatible with polyvinyl chloride and when added to a coating composition containing polyvinyl chloride becomes a part of the dried film and increases film flexibility. Plasticizers, when admixed with the polyvinyl chloride would produce a gel by solublizing the polyvinyl chloride, and ultimately a fully fused solid when the composition is heated. Examples of plasticizers include phthalic acid esters, dibasic esters, phosphoric acid esters, polyester-based plasticizers and especially dioctyl phthalate and diisononyl phthalate.
[0029] As used herein, the term "polyvinyl chloride" shall mean a homopolymer of vinyl chloride, or a copolymer of at least 80 weight percent of units derived from vinyl chloride, with up to about twenty weight percent of one or more other vinyl monomers.
[0030] As defined above, the polyvinyl chloride extender particles may be homopolymers of vinyl chloride or copolymers of at least 80 weight percent of units derived from vinyl chloride, with up to about twenty weight percent of one or more other vinyl monomers. Suitable vinyl monomers include alpha-olefins, such as ethylene and propylene; vinyl esters, such as vinyl acetate, vinyl propionate, and vinyl benzoate;
vinylidene chloride; alkyl (meth)acrylates, such as methyl acrylate, lauryl acrylate, methyl methacrylate and cetyl methacrylate; vinyl aromatic monomers, such as styrene and vinyl toluene; acrylonitrile; methacrylonitrile; and maleimides, such as N-cyclohexyl maleimide, N-phenylamaleimide, or maleimide. Preferably, however, the polyvinyl chloride extender particles are vinyl chloride homopolymers. Polyvinyl chloride polymers can be prepared by suspension polymerization or other techniques as is known in the art and are commercially available from a number of suppliers. One useful polyvinyl chloride resin extender particle is Geon 217 available from Poly One Corporation.
[0031] In some useful embodiments, the polyvinyl chloride extender particles will have an average particle size greater than 3 microns. For some applications, the polyvinyl chloride extender particles have an average particle size in a range from about 5 microns to about 150 microns, and frequently in a range from about 10 microns to about microns. The polyvinyl chloride extender particles are solid and remain as discrete particles in the coatings of this invention even after the coating has cured or dried.
[0032] Preferably, the polyvinyl chloride extender particles have a Fikentscher K
value between about 50 and about 80, more preferably between about 60 and about 70.
The Fikentscher K value is determined by solution viscosity measurements and provides a measure of molecular weight. The correlation between the Fikentscher K value and number average molecular weight (Mn) is as follows: a Fikentscher K value of 50 is roughly equal to a Mn of 28,000 and a Fikentscher K value of 80 is roughly equal to a Mn of 80,000.
[0033] The amount of polymeric extender particles in the coating composition of the present invention, on a solids basis, is typically from about 5 to about 60 weight percent, and often from about 25 to about 50 weight percent, based on the total weight of solids of the coating composition.
[0034] The coating composition of the present invention is manufactured using techniques known to those skilled in the art of manufacturing paint. The coatings of this invention may also include conventional pigments and flattening agents as well as various additives. Examples of suitable inorganic flatting agents include silicates, such as talc, and various forms of silica, such as amorphous, aerogel, diatomaceous, hydrogel and fumed silicas. Conventional pigments include titanium dioxide, zinc oxide, and other inorganic or organic pigments. The coatings of this invention also may incorporate one or more polymeric opacifying agents. The polymeric opacifiers are generally small particle size non-film forming polymerized beads which are insoluble in the coating in which they are dispersed. Typically the polymeric opacifying agents will replace some of the hiding pigments which would otherwise be incorporated into the coating.
The beads may be solid or they may contain vesicles or dispersed pigments within the polymerized bead. Representative polymeric particles useful as opacifying agents include beads of polystyrene, polyacrylic, polyethylene, polyamide, poly(vinylacetate ethylene), melamine formaldehyde, urea formaldehyde, polyester and polyurethane. Representative commercially available polymeric pigments are sold under the Ropaque, Dylex (polystyrene) and Pergopak (urea formaldehyde) trademarks. If polymeric opacifying agents are incorporated they typically will comprise between about 1% and about 85% by weight of the total amount of opacifying agents and pigments. Typical additives include dispersants, preservatives, anti foaming agents, thickeners, etc. The coatings of this invention can be applied to any substrate such as wood, wallboard, metal, etc.
by any application method including spraying, brushing, rolling, etc. in one embodiment the coatings are especially useful as interior or exterior paints, especially house paints.
[0035] The present invention will be better understood by reference to the following examples, which are provided for purposes of illustration only and are not to be construed as limiting the scope of the present invention.
[0036] A latex polymer was prepared as follows. A reaction vessel was charged with 124.75 parts water and heated to 85 C under a nitrogen blanket. A first mixture of 6.14 parts water, 1.39 parts surfactant (Abex EP-110, an anionic surfactant available from Rhodia), 0.082 parts 28% aqueous ammonia, and 0.30 parts ammonium persulfate was then added to the heated water. A feed mixture of 50.88 parts water, 8.08 parts Abex EP-110, 3.72 parts methacrylic acid, 1.49 parts Sipomer PAM 100 (phosphate ester of 2-hydroxyethyl methacrylate from Rhodia), 5.98 parts Rohamere 6844 (25% aqueous solution of N-(2-methacryloxyethyl)ethylene urea from Rohm Tech, Inc.), 79.05 parts 2-ethyl hexyl acrylate, 54.70 parts styrene, 3.07 parts water and 4.48 parts diacetone acrylamide was prepared, as was an initiator mixture of 0.30 parts ammonium persulfate and 15.36 parts water. The feed mixture and the initiator mixture were then simultaneously added to the heated (85 C) reaction mixture over a period of 3 hours.
Upon completion of the additions, the reaction was maintained at 85 C for an additional hour. The reaction was then allowed to cool to 65 C and a chase oxidizer mixture of 0.21 parts t-butyl hydroperoxide in 2.4 parts water and a chase reducer mixture of 0.15 parts isoascorbic acid, 2.40 parts water, and 0.07 parts 28% aqueous ammonia were both added over 45 minutes and the reaction was held at 65 C for 45 minutes thereafter.
The reaction was then allowed to cool to 35 C and 0.22 parts Proxel GXL and 0,75 parts 28%
aqueous ammonia were added. 1.72 parts adipic dihydrazide was pre-dissolved in 5.16 parts water by heating to 60 C and mixing for 15 minutes, and that solution was then added to the reaction mixture over a three minute period. The reaction was mixed for an additional 15 minutes and then filtered to provide the final self-crosslinking latex mixture. The latex product had a Tg of approximately -4 C, and an NVM of 41.600%.
[0037] A latex mixture could be prepared by the process as shown in Example 1 except replacing the Abex EP-110 with a comparable solids amount of Rhodafac (a nonyl-phenol ethoxylated phosphate ester from Rhodia) and the monomer mix to provide, on a weight solids basis, 4% diacetone acrylamide, 1.0% methacrylic acid, 2.2%
PAM 100, 52.8% 2-ethyl hexyl acrylate, and 40% styrene. The same equivalent ratio of adipic dihydrazide as in Example 1 could be utilized.
[0038] A representative flat latex coating composition could be prepared by admixing the following materials in the order shown:
Raw Material Parts by Weight Self-crosslinking latex of Example 2 39.50 Defoamerl 0.20 Polymeric opacifying pigment2 9.50 Water 9.15 Attapulgite clay 0.50 Hydroxyethyl cellulose thickener 0.08 Microbiocide 0.05 Surfactant3 1.26 Nonionic surfactant4 0.20 2 amino-2-methyl-l-proponol 0.30 Defoamer' 0.20 Ground feldspar 9.50 Polyvinyl chloride particles5 4.00 Water 0.83 Ethylene glycol 1.10 Associative thickener6 1.60 Water 0.08 20% active fungicide 0.20 Titanium dioxide slurry? 30.00 Water 0.62 Defoamerl 0.10 I Sher-Defoam, proprietary defoamer of the assignee of this application 2 Ropaque OP-96 from Rohm and Haas 3 Tamol 165-A from Rohm and Haas 4 Triton N-57 nonionic surfactant from Rohm and Haas Geon 217 from Poly One Corporation. Vinyl chloride homopolymer having an average particle size of about 35 microns 6 Acrysol RM-2020 NPR polymer solution from Rohm and Haas 7 R-746 from Rohm and Haas [0039] While the invention has been shown and described with respect to particular embodiments thereof, those embodiments are for the purpose of illustration rather than limitation, and other variations and modifications of the specific embodiments herein described will be apparent to those skilled in the art, all within the intended spirit and scope of the invention. Accordingly, the invention is not to be limited in scope and effect to the specific embodiments herein described, nor in any other way that is inconsistent with the extent to which the progress in the art has been advanced by the invention.
Claims (14)
1. An aqueous coating composition comprising:
(i) a binder resin having carbonyl latent crosslinking functionality;
(ii) an effective crosslinking amount of a crosslinker selected from the group consisting of di and poly amines, di and poly hydrazides, and di and poly hydrazines and mixtures thereof for the binder resin;
(iii) solid polyvinyl chloride polymeric extender particles.
(i) a binder resin having carbonyl latent crosslinking functionality;
(ii) an effective crosslinking amount of a crosslinker selected from the group consisting of di and poly amines, di and poly hydrazides, and di and poly hydrazines and mixtures thereof for the binder resin;
(iii) solid polyvinyl chloride polymeric extender particles.
2. The coating composition of Claim 1 wherein the binder resin is a latex resin.
3. The coating composition of Claim 2 wherein the latex resin is a polymerized reaction product of a mixture of monomers comprising:
(i) about 1 to about 25% by weight of a monomer having latent crosslinking functionality;
(ii) about 0.5 to about 15% by weight of an acid functional monomer;
(iii) about 60 to about 98.5% of at least one other copolymerizable monomer.
(i) about 1 to about 25% by weight of a monomer having latent crosslinking functionality;
(ii) about 0.5 to about 15% by weight of an acid functional monomer;
(iii) about 60 to about 98.5% of at least one other copolymerizable monomer.
4. The coating composition of Claim 2 wherein the latex resin is the polymerized reaction product of a mixture of monomers comprising:
(i) about 1 to about 25% by weight of a monomer having carbonyl latent crosslinking functionality;
(ii) about 0.5 to about 15% by weight of an acid functional monomer;
(iii) about 0.1 to about 10% of a wet adhesion promoting monomer; and (iv) about 50 to about 98.4% of at least one other copolymerizable monomer.
(i) about 1 to about 25% by weight of a monomer having carbonyl latent crosslinking functionality;
(ii) about 0.5 to about 15% by weight of an acid functional monomer;
(iii) about 0.1 to about 10% of a wet adhesion promoting monomer; and (iv) about 50 to about 98.4% of at least one other copolymerizable monomer.
5. The coating composition of Claim 2 wherein the latex resin is the polymerized reaction product of a mixture of monomers comprising:
(i) about 1 to about 25% by weight of a monomer having carbonyl latent crosslinking functionality;
(ii) about 0.5 to about 15% by weight of an acid functional monomer;
(iii) about 0.1 to about 10% of a wet adhesion promoting monomer;
(iv) about 1 to about 55% by weight of styrene; and (v) zero to about 98.4% by weight of at least one other copolymerizable monomer.
(i) about 1 to about 25% by weight of a monomer having carbonyl latent crosslinking functionality;
(ii) about 0.5 to about 15% by weight of an acid functional monomer;
(iii) about 0.1 to about 10% of a wet adhesion promoting monomer;
(iv) about 1 to about 55% by weight of styrene; and (v) zero to about 98.4% by weight of at least one other copolymerizable monomer.
6. The coating composition of Claim 1 wherein the polyvinyl chloride particles have an average particle size greater than 5 microns.
7. The coating composition of Claim 1 wherein the polyvinyl chloride particles have an average particle size of 5 to about 150 microns.
8. The coating composition of Claim 1 wherein the polyvinyl chloride extender particles are homopolymers of vinyl chloride.
9. The coating composition of Claim 1 wherein the polyvinyl chloride polymeric extender particles are present at about 5 to about 60 weight percent on a solids basis of the coating composition.
10. The coating composition of Claim 1 wherein the polyvinyl chloride polymeric extender particles are present at a level of about 25 to about 50 weight per cent on a solids basis of the coating composition.
11. The coating composition of Claim 1 wherein the crosslinker is present at a level to provide at least 0.1 equivalent for each equivalent of latent crosslinking functionality.
12. The coating composition of Claim 1 wherein the crosslinker is present at a level to provide about 0.2 to about 2.0 equivalents for each equivalent of latent crosslinking functionality.
13. The coating composition of Claim 1 wherein the crosslinker is present at a level to provide about 0.4 to about 1.2 equivalents for each equivalent of latent crosslinking functionality.
14. A coating composition comprising:
(i) a binder resin obtained by polymerizing a monomer mixture comprising:
(a) about 1 to about 25% by weight of a monomer having carbonyl latent crosslinking functionality;
(b) about 0.5 to about 15% by weight of an acid functional monomer;
(c) about 0.1 to about 10% of a wet adhesion promoting monomer; and (d) about 50 to about 98.4% of at least one other copolymerizable monomer.
(ii) a crosslinker selected from the group consisting of di and polyamines, di and poly hydrazides, and di and poly hydrazines and mixtures thereof;
(iii) solid polyvinyl chloride extender particles.
(i) a binder resin obtained by polymerizing a monomer mixture comprising:
(a) about 1 to about 25% by weight of a monomer having carbonyl latent crosslinking functionality;
(b) about 0.5 to about 15% by weight of an acid functional monomer;
(c) about 0.1 to about 10% of a wet adhesion promoting monomer; and (d) about 50 to about 98.4% of at least one other copolymerizable monomer.
(ii) a crosslinker selected from the group consisting of di and polyamines, di and poly hydrazides, and di and poly hydrazines and mixtures thereof;
(iii) solid polyvinyl chloride extender particles.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US61745004P | 2004-10-08 | 2004-10-08 | |
US60/617,450 | 2004-10-08 | ||
PCT/US2005/036404 WO2006042220A1 (en) | 2004-10-08 | 2005-10-07 | Self crosslinking waterborne coatings |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2583268A1 CA2583268A1 (en) | 2006-04-20 |
CA2583268C true CA2583268C (en) | 2011-02-22 |
Family
ID=35696011
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2583268A Expired - Fee Related CA2583268C (en) | 2004-10-08 | 2005-10-07 | Self crosslinking waterborne coatings |
Country Status (6)
Country | Link |
---|---|
US (1) | US20070135567A1 (en) |
EP (1) | EP1799782B1 (en) |
BR (1) | BRPI0518234A2 (en) |
CA (1) | CA2583268C (en) |
MX (1) | MX2007004011A (en) |
WO (1) | WO2006042220A1 (en) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101104766B (en) * | 2006-07-12 | 2010-08-11 | 上海雅达特种涂料有限公司 | Colorful coating for purifying indoor air and producing method thereof |
JP4941672B2 (en) * | 2008-03-11 | 2012-05-30 | Jsr株式会社 | Nonspecific adsorption preventive coating agent for biological substances |
US9790374B2 (en) | 2010-06-04 | 2017-10-17 | Columbia Insurance Company | Aqueous cross-linking compositions and methods |
US9040617B2 (en) | 2010-06-04 | 2015-05-26 | Columbia Insurance Company, Inc. | Aqueous cross-linking compositions and methods |
US9000069B1 (en) | 2010-07-02 | 2015-04-07 | The Sherwin-Williams Company | Self-stratifying coatings |
BR112013015240A2 (en) | 2010-12-17 | 2016-09-13 | Celanese Int Corp | aqueous latex coating compositions |
JP5713502B2 (en) * | 2011-09-03 | 2015-05-07 | 関西ペイント株式会社 | Water-based paint composition |
US9115265B2 (en) * | 2011-09-19 | 2015-08-25 | Columbia Insurance Company | Ambient self-crosslinkable latex |
US9394460B1 (en) | 2011-09-19 | 2016-07-19 | Columbia Insrancc Company | Ambient self-crosslinkable latex |
EP2825380A4 (en) * | 2012-03-14 | 2015-12-09 | Valspar Sourcing Inc | Modified crush resistant latex topcoat composition for fiber cement substrates |
WO2013159098A1 (en) | 2012-04-20 | 2013-10-24 | Valspar Sourcing, Inc. | Method for making titanium dioxide pigment grind dispersion and paint |
AU2013248980B2 (en) | 2012-04-20 | 2016-07-07 | Swimc Llc | Titanium dioxide pigment grind dispersion and paint |
US20140031486A1 (en) * | 2012-07-26 | 2014-01-30 | The Sherwin-Williams Company | Waterborne coatings |
JP6137734B2 (en) * | 2013-02-27 | 2017-05-31 | 株式会社リコー | Inkjet ink |
US11180649B1 (en) * | 2014-12-19 | 2021-11-23 | The Sherwin-Williams Company | Nanosilica-organic polymer composite latex |
US10421872B1 (en) * | 2015-09-09 | 2019-09-24 | The Sherwin-Williams Company | Stain resistant coating composition |
US10035946B2 (en) * | 2016-02-23 | 2018-07-31 | Ecolab Usa Inc. | Hydrazide crosslinked polymer emulsions for use in crude oil recovery |
AU2017232029B2 (en) * | 2016-10-05 | 2021-12-09 | Rohm And Haas Company | Aqueous dispersion of adsorbing polymer particles and crosslinkable polymer particles |
US10662273B2 (en) | 2016-12-19 | 2020-05-26 | Celanese International Corporation | Waterborne acrylic dispersions with high biorenewable content |
CN109096440A (en) * | 2017-06-21 | 2018-12-28 | 广东华润涂料有限公司 | Water-based latex, preparation method containing the polymer beads with core-shell structure and the coating formed by the water-based latex |
EP3655486B8 (en) * | 2017-07-17 | 2022-05-18 | Covestro (Netherlands) B.V. | Aqueous crosslinkable coating composition |
WO2019069404A1 (en) * | 2017-10-04 | 2019-04-11 | 日立化成株式会社 | Coating liquid, coating film production method, and coating film |
CN112004878A (en) * | 2018-04-20 | 2020-11-27 | 巴斯夫欧洲公司 | Adhesive composition having a gel content based on crosslinking by ketone or aldehyde groups |
Family Cites Families (73)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3150110A (en) * | 1958-02-14 | 1964-09-22 | Celanese Corp | High gloss latex paints |
DE1495706A1 (en) * | 1963-01-11 | 1969-05-08 | Hoechst Ag | Process for the production of crosslinked polymers |
US3277056A (en) * | 1963-11-27 | 1966-10-04 | Lubrizol Corp | N-3-oxohydrocarbon-substituted acrylamides and polymers thereof |
US3687885A (en) * | 1970-04-15 | 1972-08-29 | Du Pont | Water base paints having an improved balance of anti-drip and leveling qualities |
US3896073A (en) * | 1970-08-10 | 1975-07-22 | Lubrizol Corp | Aqueous dispersions of film-forming |
US3959224A (en) * | 1971-02-01 | 1976-05-25 | The Lubrizol Corporation | Water-soluble hydroxyalkylated and alkoxyalkylated compositions and the like derived from N-3-oxohydrocarbon-substituted acrylamides, and polymers thereof |
US3663472A (en) * | 1971-03-15 | 1972-05-16 | Minnesota Mining & Mfg | Composition and method for surfacing leathers and leather substitutes based on filled polyurethane latex |
US3736165A (en) * | 1971-07-21 | 1973-05-29 | Minerals & Chemicals Corp | Method for processing kaolin clay |
GB1421130A (en) * | 1972-11-16 | 1976-01-14 | Harlow Chemical Ltd | Surface coating compositions |
US3984485A (en) * | 1973-10-09 | 1976-10-05 | Neefe Charles W | Wettable polymeric materials prepared from 2-50% by wt. N-(1,1-dimethyl-3-oxobutyl)acrylamide, 2.5% by wt. crosslinking agent and methyl methacrylate |
US4025483A (en) * | 1975-10-06 | 1977-05-24 | Scm Corporation | Stabilizing aqueous titanium dioxide pigment slurries by blending therewith plastic particles |
US4107120A (en) * | 1976-06-17 | 1978-08-15 | Rohm And Haas Company | Heteropolymer acrylic latices and textiles treated therewith |
US4102843A (en) * | 1977-01-07 | 1978-07-25 | Rohm And Haas Company | Dispersing paint pigments |
USRE31936E (en) * | 1977-01-07 | 1985-07-02 | Rohm And Haas Company | Dispersing paint pigments |
US4144212A (en) * | 1978-03-06 | 1979-03-13 | Alcolac Inc. | Air-curing copolymer latices |
US4283320A (en) * | 1979-06-04 | 1981-08-11 | Scm Corporation | Semi-gloss latex paint |
US4384096A (en) * | 1979-08-27 | 1983-05-17 | The Dow Chemical Company | Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems |
US4522962A (en) * | 1980-09-08 | 1985-06-11 | Scm Corporation | Epoxy modified emulsion polymers |
US4771086A (en) * | 1982-09-02 | 1988-09-13 | Union Carbide Corporation | Encapsulating finely divided solid particles in stable suspensions |
US4517098A (en) * | 1983-04-15 | 1985-05-14 | Rohm And Haas Company | Method of dispersing inorganic materials in aqueous systems with low molecular weight acrylic acid copolymers |
US4514552A (en) * | 1984-08-23 | 1985-04-30 | Desoto, Inc. | Alkali soluble latex thickeners |
US4600761A (en) * | 1985-04-04 | 1986-07-15 | Alco Chemical Corporation | Acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein |
US4703080A (en) * | 1985-04-29 | 1987-10-27 | Desoto, Inc. | Aqueous latices having improved coating rheology |
EP0215565B1 (en) * | 1985-08-12 | 1991-07-24 | Ciba Specialty Chemicals Water Treatments Limited | Dispersing agents |
US4743698A (en) * | 1985-10-01 | 1988-05-10 | Alco Chemical Corp. | Acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein |
US4616074A (en) * | 1985-10-01 | 1986-10-07 | Alco Chemical Corporation | Acrylic-methylene succinic ester emulsion copolymers for thickening aqueous systems |
US4789694A (en) * | 1986-01-30 | 1988-12-06 | The Glidden Company | Ambient cure latex paint |
US4722962A (en) * | 1986-06-12 | 1988-02-02 | Desoto, Inc. | Nonionic associative thickeners |
US4801671A (en) * | 1987-06-25 | 1989-01-31 | Desoto, Inc. | Production of alkali-soluble, carboxyl-functional aqueous emulsion thickeners |
US4844952A (en) * | 1987-12-30 | 1989-07-04 | Ppg Industries, Inc. | Multilayered finish having good stain resistance |
DE68910842T2 (en) * | 1988-01-29 | 1994-03-17 | Ici Plc | Dispersions from composite particles. |
US5191051A (en) * | 1989-01-09 | 1993-03-02 | Union Carbide Chemicals & Plastics Technology Corporation | Propoxylated alkali-soluble thickeners |
US5155185A (en) * | 1989-02-06 | 1992-10-13 | The B. F. Goodrich Company | Process for producing dust free polyvinyl chloride resins |
GB2235459B (en) * | 1989-08-09 | 1993-06-23 | Toa Gosei Chem Ind | Process for producing an aqueous resin dispersion |
DE3935137A1 (en) * | 1989-10-21 | 1991-04-25 | Hoechst Ag | COPOLYMERISATES CONTAINING URETHAN GROUPS BASED ON ETHYLENICALLY UNSATURATED MONOMERS, METHODS FOR THEIR PRODUCTION AND THEIR USE |
DE4117487A1 (en) * | 1991-05-28 | 1992-12-03 | Wacker Chemie Gmbh | AMINOOXY CROSSLINKER CONTAINING AQUEOUS DISPERSIONS OF COPOLYMERISATES CONTAINING CARBONYL GROUPS |
EP0618238B1 (en) * | 1991-10-09 | 1996-12-18 | Mitsubishi Chemical BASF Company Limited | Aqueous crosslinking resin composition |
US5385960A (en) * | 1991-12-03 | 1995-01-31 | Rohm And Haas Company | Process for controlling adsorption of polymeric latex on titanium dioxide |
US5320672A (en) * | 1991-12-17 | 1994-06-14 | Whalen Shaw Michael | Associatively dispersed pigments and coatings containing said pigments |
GB9127293D0 (en) * | 1991-12-23 | 1992-02-19 | Ici Plc | Coating pigment particles with polymers |
WO1993024545A1 (en) * | 1992-05-29 | 1993-12-09 | Union Carbide Chemicals & Plastics Technology Corporation | Aqueous latexes containing macromonomeres |
US5292843A (en) * | 1992-05-29 | 1994-03-08 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers |
US5292828A (en) * | 1992-05-29 | 1994-03-08 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing complex hydrophobic groups |
US5739378A (en) * | 1992-05-29 | 1998-04-14 | Union Carbide Chemicals & Plastics Technology Corporation | Complex hydrophobe-containing oligomers |
US5478602A (en) * | 1992-05-29 | 1995-12-26 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers and their use in a method of coating substrates |
US5426182A (en) * | 1992-05-29 | 1995-06-20 | Union Carbide Chemical & Plastics Technology Corporation | Polysaccharides containing complex hydrophobic groups |
US5488180A (en) * | 1992-05-29 | 1996-01-30 | Union Carbide Chemicals & Plastics Technology Corporation | Complex hydrophobe compounds |
FR2693203B1 (en) * | 1992-07-01 | 1994-08-26 | Coatex Sas | Partially or completely water-soluble acrylic copolymer, crosslinked or not and its use. |
US5432229A (en) * | 1993-03-26 | 1995-07-11 | Mitsubishi Yuka Badische Co., Ltd. | Aqueous crosslinkable resin composition |
US5399618A (en) * | 1993-06-28 | 1995-03-21 | Union Carbide Chemical & Plastics Technology Corporation | Processes for preparing aqueous polymer emulsions |
US5356683A (en) * | 1993-10-28 | 1994-10-18 | Rohm And Haas Company | Expandable coating composition |
DE4340648A1 (en) * | 1993-11-30 | 1995-06-01 | Hoechst Ag | Aqueous polymer dispersions as binders for block-resistant, scratch-resistant and chemical-resistant coatings |
US5414041A (en) * | 1994-04-08 | 1995-05-09 | Rohm And Haas Company | Waterborne coating composition |
GB9408725D0 (en) * | 1994-05-03 | 1994-06-22 | Zeneca Resins Bv | Production of aqueous polymer compositions |
EP0697448B1 (en) * | 1994-08-12 | 1999-01-13 | Kansai Paint Co., Ltd. | Two-component composition for aqueous paint |
US5912293A (en) * | 1994-08-18 | 1999-06-15 | Allied Colloids Limited | Aqueous polymer dispersions for coating wood |
GB2295781B (en) * | 1994-12-09 | 1998-07-22 | Kansai Paint Co Ltd | Process for forming cured paint film |
US5639841A (en) * | 1995-02-28 | 1997-06-17 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomer mixtures |
DE19517777A1 (en) * | 1995-05-15 | 1996-11-21 | Hoechst Ag | Polyvinyl ester dispersion with metal salt hydrosols as seed base |
US5739196A (en) * | 1995-11-30 | 1998-04-14 | Union Carbide Chemicals & Plastics Technology Corporation | Latex compositions having wet adhesion and other improved rheological properties and methods of producing same |
FR2744125B1 (en) * | 1996-01-30 | 1998-06-05 | Peintures Jefco | GRAFT COPOLYMERS, THEIR MANUFACTURING METHOD, THE COMPOSITIONS CONTAINING THEM AND THEIR USE FOR THE PREPARATION OF PIGMENTAL DISPERSIONS IN AQUEOUS AND / OR ORGANIC MEDIA |
DE19625774A1 (en) * | 1996-06-27 | 1998-01-02 | Hoechst Ag | Self-crosslinking aqueous dispersions of polyesters and vinyl polymers |
EP0927198B1 (en) * | 1996-09-18 | 2001-05-23 | Akzo Nobel N.V. | Aqueous polymer dispersion for use in water based glossy lacquers |
US5763012A (en) * | 1996-10-16 | 1998-06-09 | Basf Aktiengesellschaft | Coating of substrates |
US6262169B1 (en) * | 1998-05-14 | 2001-07-17 | Eastman Chemical Company | Protonated amines for controlled crosslinking of latex polymers |
US6610784B1 (en) * | 1999-03-23 | 2003-08-26 | Avecia Bv | Crosslinkable coating compositions |
US6869996B1 (en) * | 1999-06-08 | 2005-03-22 | The Sherwin-Williams Company | Waterborne coating having improved chemical resistance |
DK1125949T3 (en) * | 2000-02-16 | 2006-08-21 | Nuplex Resins Bv | Aqueous dispersions of polymers with glass transition temperature gradient |
GB0005612D0 (en) * | 2000-03-09 | 2000-05-03 | Avecia Bv | Aqueous polymer compositions |
AU2001267876A1 (en) * | 2000-06-29 | 2002-01-08 | Kyowa Yuka Co., Ltd. | Resin composition |
AU785282B2 (en) * | 2001-06-20 | 2006-12-21 | Rohm And Haas Company | Coating with improved hiding, compositions prepared therewith, and processes for the preparation thereof |
AU2003203420B2 (en) * | 2002-04-09 | 2008-12-11 | Rohm And Haas Company | Aqueous polymer blend composition |
ATE408656T1 (en) * | 2002-06-12 | 2008-10-15 | Sherwin Williams Co | COATING COMPOSITION CONTAINING POLYVINYL CHLORIDE FILLER PARTICLES |
-
2005
- 2005-10-07 CA CA2583268A patent/CA2583268C/en not_active Expired - Fee Related
- 2005-10-07 WO PCT/US2005/036404 patent/WO2006042220A1/en active Application Filing
- 2005-10-07 EP EP05804238A patent/EP1799782B1/en active Active
- 2005-10-07 BR BRPI0518234-4A patent/BRPI0518234A2/en not_active Application Discontinuation
- 2005-10-07 US US11/246,929 patent/US20070135567A1/en active Pending
- 2005-10-07 MX MX2007004011A patent/MX2007004011A/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
BRPI0518234A2 (en) | 2008-11-11 |
EP1799782B1 (en) | 2012-12-12 |
WO2006042220A1 (en) | 2006-04-20 |
CA2583268A1 (en) | 2006-04-20 |
MX2007004011A (en) | 2007-05-23 |
EP1799782A1 (en) | 2007-06-27 |
US20070135567A1 (en) | 2007-06-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2583268C (en) | Self crosslinking waterborne coatings | |
US5478601A (en) | Waterborne coating composition | |
US9000069B1 (en) | Self-stratifying coatings | |
US6992121B1 (en) | Aqueous, polymodal, multistage polymer emulsions | |
AU700150B2 (en) | Aqueous paint composition | |
US20090105409A1 (en) | Aqueous secondary polymer dispersions for the production of coatings | |
MXPA97005437A (en) | Composition of aqueous coating fastening and pinting | |
WO2014172050A1 (en) | Fast drying aqueous amine free coating composition(s) | |
JP2016020509A (en) | Hydrophilizing treatment agent | |
EP3452519B1 (en) | Amine functional anionic polymer dispersion and coating compositions thereof | |
US10457763B2 (en) | Aqueous polymer emulsion | |
JP4358739B2 (en) | Acrylic beads for automobiles having improved storage stability and physical properties of coating film, method for producing the same, and acrylic sol composition containing the same | |
CN113646396B (en) | Aqueous coating composition | |
US11421101B2 (en) | Aqueous resin dispersion, method for producing aqueous resin dispersion, aqueous coating material, and adhesive | |
CN104080859B (en) | Polyurethane coating composition | |
JP4688565B2 (en) | Emulsion, its production method and its use | |
JP3448306B2 (en) | Aqueous emulsion containing allyl-based crosslinked copolymer fine particles | |
AU2016299363A1 (en) | Coating compositions | |
JP3523281B2 (en) | Paint resin | |
JP2005154772A (en) | Method of making emulsion coating containing solid crosslinking agent and article made by the method | |
JP3242177B2 (en) | Paint resin | |
US11180649B1 (en) | Nanosilica-organic polymer composite latex | |
JP7129481B2 (en) | Aqueous dispersion, method for producing the same, coating composition and coating film | |
CN111491984B (en) | Aqueous crosslinkable dispersions | |
JP2003096390A (en) | Aqueous coating composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |
Effective date: 20161007 |