CN104302717A - Aqueous latex-based coating components - Google Patents
Aqueous latex-based coating components Download PDFInfo
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- CN104302717A CN104302717A CN201380026548.7A CN201380026548A CN104302717A CN 104302717 A CN104302717 A CN 104302717A CN 201380026548 A CN201380026548 A CN 201380026548A CN 104302717 A CN104302717 A CN 104302717A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
Abstract
Disclosed are aqueous latex-based coating components and surfactant stabilized coating components which comprise a non-ionic surfactant, a neutralized phosphate surfactant, and a copolymer of at least a vinyl ester of a C1-13 alkanoic acid and ethylene. The weight ratio of non-ionic surfactant to neutralized phosphate surfactant is greater than 1:1. The components may be free of protective colloids. The coating components may be incorporated into latex paint compositions. The latex paint compositions exhibit high pigment volume concentration and high wet scrub resistance.
Description
Priority request
This application claims the right of priority of the U.S. Provisional Application numbers 60/650,645 submitted on May 23rd, 2012, the full text is incorporated herein by reference for it.
Technical field
The present invention relates to and comprise the multipolymer of vinyl ester and ethene, the nonionic surface active agent of neutralization and the phosphoric acid ester of neutralization or the aqueous latex base coating composition of phosphate surfactant active.The invention still further relates to the method for this component of preparation.The invention further relates to the paint composition comprising this aqueous latex base coating composition.
Background of invention
Because latex-based paint vehicle has the many advantages surmounting solvent based product, this type of paint vehicle has occupied most of indoor and outdoors paint vehicle market.The advantage of latex-based paint vehicle comprises and is easy to cleaning, low smell and quick-drying.
The emulsion polymer of two kinds of main Types is for preparing latex paint vehicle, i.e. (1) acrylic emulsions multipolymer, comprise the alkyl ester of vinylformic acid and methacrylic acid, or this type of ester and vinyl aromatic comonomer are as cinnamic combination, and a small amount of vinylformic acid and methacrylic acid, and (2) vinyl acetate copolymer, comprise the vinyl-acetic ester combined with ethene (VAE), vinylchlorid and/or a small amount of more soft acrylic monomer.This acrylic emulsion polymer is mainly used in high-quality paint vehicle because of the water tolerance of excellence, required levelling property, film hardness and scrub resistance.This vae copolymer thing shows toughness, but has inferior scrub resistance.Vae copolymer thing is often than acrylic copolymer considerably cheaper.
Although use VAE-base latex paint vehicle to there is advantage, have good grounds to be VAE emulsion in paint vehicle product relative to solvent-based paint vehicle and acrylic latex paint vehicle exist that some is not enough.A bit this type of deficiency relates to scrub resistance.Term " scrub resistance " paint vehicle industry for describe paint vehicle coating clean time the resistance to ability weathered.Because pigment volume concentration (PVC) (PVC) is higher, pigment volume increases to maximize coating covering to the ratio of paint vehicle cumulative volume, and scrub resistance reduces.
Past has carried out many effort to improve the scrub resistance ability of latex-based paint vehicle.These effort relate to be attempted to optimize various paint vehicle formulation parameters, as used silane base-material, using the combination of agglomerated solvent and use specific surfactant and protective colloid.
Especially, the U.S. Patent number 4,277,385 authorizing the people such as Carroll discloses and comprises plastic pigment particle to provide high PVC acrylic acid or the like base-material preparation, keeps good physical properties simultaneously.Said preparation can also comprise agglomerated solvent.
Authorize the U.S. Patent number 6 of the people such as Pierre; 673; 854 disclose aqueous acetic acid vinyl acetate-ethene polymers dispersion, and it comprises vinyl-acetic ester, ethene and optional Third monomer, has the alcohol ether phosphate of 4 to 70 ethylene oxide units or phosphate surfactant active, at least one protective colloid and water.The people such as Pierre disclose the phosphoric acid ester or phosphate surfactant active that use neutralization, but teach and need protective colloid to stablize this polymkeric substance.This protective colloid especially can be Natvosol (HEC), polyvinyl alcohol (PVA).
Although above-mentioned prior art is for improving the scrub resistance of VAE base latex paint vehicle, still need to find new coating formulation (being especially the preparation of paint vehicle form), this coating formulation uses VAE and provides high PVC and high scrub resistance equally.
Astonishing and against expectation, having been found that by using nonionic surface active agent and the phosphoric acid ester of neutralization or the combination of phosphate surfactant active, the scrub resistance of VAE base latex paint vehicle can be improved while maintenance high PVC.Astonishing and against expectation find further, this type of combination of tensio-active agent can reduce or eliminate the needs by protective colloid-stabilised dispersion.
Summary of the invention
In the first embodiment, the present invention relates to a kind of aqueous latex base coating composition, comprise: (a) at least one C
1-13the vinyl ester of paraffinic acid and the multipolymer of ethene; (b) nonionic surface active agent; (c) phosphoric acid ester neutralized or phosphate surfactant active, wherein nonionic surface active agent is greater than 1:1 to the phosphoric acid ester of neutralization or the weight ratio of phosphate surfactant active.
In this second embodiment, the present invention relates to a kind of paint composition, comprise: the aqueous latex base coating composition that (i) first describes in embodiment; (ii) with the pigment component being selected from mineral dye, mineral filler and composition thereof that the amount making this paint composition have the pigment volume concentration (PVC) (PVC) of about 25 volume % to 90 volume % exists; (ii) at least one is selected from the auxiliary component of wetting agent, dispersion agent, emulsifying agent, filler, thickening material, defoamer, dyestuff and sanitas.
In the 3rd embodiment, the present invention relates to a kind of coating composition of surfactants stabilize, described composition comprises: (a) comprises at least one C
1-13the vinyl ester of paraffinic acid and the multipolymer of ethene; (b) nonionic surface active agent; (c) phosphoric acid ester neutralized or phosphate surfactant active, wherein said composition is not containing protective colloid.
In the 4th embodiment; the present invention relates to a kind of method manufacturing aqueous latex base coating composition, copolymerization at least one C under being included in the phosphoric acid ester of nonionic surface active agent and neutralization or the existence of phosphate surfactant active and when there is not protective colloid
1-13the vinyl ester of paraffinic acid and ethene.
In the 5th embodiment, the present invention relates to a kind of method manufacturing aqueous latex base coating composition, under being included in the phosphoric acid ester of nonionic surface active agent and neutralization or the existence of phosphate surfactant active, with the nonionic surface active agent being greater than 1:1, at least one C is closed to the phosphoric acid ester neutralized or phosphate surfactant active copolymerization weight ratio
1-13the vinyl ester of paraffinic acid and ethene.
Detailed Description Of The Invention
Usually, the present invention relates to a kind of aqueous latex base coating composition and preparation method thereof, wherein this component is stablized by nonionic surface active agent and the phosphoric acid ester of neutralization or the combination of phosphate surfactant active.Especially, this component comprises this tensio-active agent and at least one C
1-13the vinyl ester of paraffinic acid and the multipolymer of ethene.Nonionic surface active agent is greater than 1:1 to the phosphoric acid ester of neutralization or the weight ratio of phosphate surfactant active.In some embodiments, nonionic surface active agent can be 3:2 to the phosphoric acid ester of neutralization or the weight ratio of phosphate surfactant active.Advantageously, the invention provides a kind of industrial feasible aqueous latex base coating composition, it can be mixed in paint composition or coating composition.
The invention still further relates to a kind of coating composition of surfactants stabilize.This component is stablized by the phosphoric acid ester of neutralization or phosphate surfactant active and nonionic surface active agent.This component comprises at least one C
1-13the vinyl ester of paraffinic acid and the multipolymer of ethene.This component is not containing protective colloid.Advantageously, the invention provides a kind of industrial feasible aqueous latex base coating composition, this component is avoided using protective colloid and can being mixed in paint composition or coating composition.
The multipolymer used in the coating composition of this aqueous latex base coating composition and this surfactants stabilize can comprise at least one C
1-13the vinyl ester of paraffinic acid and ethene.In some embodiments, this vinyl ester is vinyl-acetic ester.This multipolymer and preparation thereof are described below in detail.This multipolymer can account for 1 to 20 % by weight, and such as 3 to 12 % by weight.
tensio-active agent
Phosphoric acid ester that this coating composition comprises nonionic surface active agent and neutralization, that such as neutralize completely or phosphate surfactant active.In some embodiments, nonionic surface active agent is greater than 1:1 to the phosphoric acid ester of neutralization or the weight ratio of phosphate surfactant active.In scope, nonionic surface active agent can be 1:1 to 3:1 to the phosphoric acid ester of neutralization or the weight ratio of phosphate surfactant active.In further embodiment, nonionic surface active agent is about 3:2 to the phosphoric acid ester of neutralization or the weight ratio of phosphate surfactant active.
The suitable nonionic surface active agent that can be used as emulsifying agent in copolymer emulsion stabilising system in this article and coating composition comprises polyethylene oxide condensate.The nonionic surface active agent of this type multiple is disclosed in above-mentioned U.S. Patent number 5,849, in 389.Although can nonionic emulsifier be used as in the preparation of polyethylene oxide condensate copolymer emulsion in this article and coating composition, emulsion herein and composition can substantially containing alkylphenol ethoxylate (APE) as octylphenol ethoxylate.These represent the compound being typically used as tensio-active agent that a class is degraded to alkylphenol.Environmental problem is there is in this compounds because of its quasi-estrin characteristic.
In some embodiments, this nonionic surface active agent comprises to have and connects the side chain of functional group or the C of straight chain
1-50carbyl component and 4 to 100 ethylene oxide units.This connection functional group can be ether or ester.In further embodiment, this nonionic surface active agent can comprise the straight-chain fatty alcohol of ethoxylation.An example of this nonionic surface active agent with
a3065 form is sold, and it is the straight chain fatty acid of ethoxylation and the mixture of 30 moles of ethylene oxide.
This phosphoric acid ester or phosphate surfactant active are neutralizations, such as, neutralize completely.In some embodiments, this phosphoric acid ester or phosphate surfactant active can neutralize with sodium hydroxide.This phosphoric acid ester or phosphate surfactant active can comprise the C of phosphoric acid
1-15ester, the C of such as phosphoric acid
12ester.In other embodiments, this phosphoric acid ester or phosphate surfactant active can comprise 4 to 20 ethylene oxide units, such as 6 to 10 ethylene oxide units.An example of this phosphoric acid ester or phosphate surfactant active with
rS-610A25 form is sold,
rS-610A25 is polyoxyethylene tridecyl ether phosphate, ammonium salt, and it can neutralize completely.
Except the phosphoric acid ester neutralized or phosphate surfactant active and nonionic surface active agent, component of the present invention can also comprise aniorfic surfactant.The suitable aniorfic surfactant that can be used as emulsifying agent in emulsion copolymers emulsion-stabilizing system in this article and coating composition comprises alkylaryl sulphonate/ester, alkali metal alkyl sulfate, sulfonated alkyl ester and fatty acid soaps.This type of aniorfic surfactant multiple is also disclosed in above-mentioned U.S. Patent number 5,849, in 389.
protective colloid
Conventionally, various protective colloid is if the material of polyvinyl alcohol and the formation protective colloid of other routine is also for replacing this surfactant emulsifiers or stablize the emulsion polymer latexes composition of aforementioned type together with this surfactant emulsifiers.In some preferred embodiments, emulsion herein and composition can substantially containing this type of protective colloid as stablizer.Protective colloid can comprise Natvosol and polyvinyl alcohol.If based on by the total amount of multipolymer in stable emulsion or composition, what protective colloid accounted for this emulsion and composition is no more than 0.5 % by weight, this type of emulsion is considered to " substantially not containing " protective colloid.Use emulsifying agent and tensio-active agent, stablizer not substantially to be characterized by this article containing the latex emulsion herein of protective colloid and composition be emulsion and the composition of " basic full tensio-active agent-Ji ".
In other embodiments, this coating composition can not contain protective colloid.Without being bound by theory, protective colloid can be removed from coating composition, because the phosphoric acid ester of nonionic surface active agent and neutralization or the combination of phosphate surfactant active are used for stablizing this coating composition.
ethane-acetic acid ethyenyl ester (VAE) multipolymer
The multipolymer of vinyl-acetic ester and ethene is comprised at the emulsion copolymers forming the type used in the copolymer blend of composition herein.The vinyl-vinyl acetate copolymer can being abbreviated as " EVA " or " VAE " is well known in the art.
This vae copolymer thing is the aqueous emulsion polymerisate of other unsaturated comonomer optional of ethene, vinyl-acetic ester and formation emulsion copolymers.Amount for the preparation of the vinyl monomer of this vae copolymer thing can be about 5 % by weight to about 20 % by weight of the comonomer gross weight for the preparation of this vae copolymer thing, such as about 10 % by weight to about 15 % by weight.Amount for the preparation of the vinyl-acetic ester of this vae copolymer thing can be about 70 % by weight to about 95 % by weight of the comonomer gross weight for the preparation of this vae copolymer thing, such as about 75 % by weight to about 90 % by weight.
This vae copolymer thing used in composition blend in this article can also containing 0 % by weight to about 10 % by weight of the comonomer gross weight for the preparation of this vae copolymer thing, such as one or more optional unsaturated comonomers of about 0.1 % by weight to about 5 % by weight.Examples of such optional comonomer can comprise such as (methyl) acrylic acid C
1-C
12ester, as also for the formation of (methyl) acrylic acid C of the acrylic copolymer of this copolymer blend
1-C
12ester.Optional comonomer for the formation of other type of this VAE emulsion copolymers describes hereinafter in more detail.But preferably, forming this vae copolymer thing used in the blend of composition herein should substantially containing the comonomer containing nonesterified carboxy moiety.
optional additional comonomer
This VAE emulsion copolymers used in the co-blended of formation composition herein can contain multiple optional comonomer.The comonomer of examples of such optional can be promote that better film forming or coating formation performance maybe can realize having those of the film of desirable properties and coating by composition herein.This type of desirable film/coating performance can comprise the adhesivity of effects on surface or the substrate such as improved, improvement wet adhesion, to cleaning or the better tolerance of removal that the weathering of other type or wearing and tearing cause, and the tolerance to film or coating cracking improved.
The optional comonomer that can be used in the emulsion copolymers of the composition be mixed into herein is containing those of at least one polymerizable double bond and one or more additional functional moiety.Examples of such optional or additional comonomer can comprise the combination of unsaturated silane comonomer, glycidyl comonomer, urea groups comonomer and these auxiliary optional comonomer thus.
Unsaturated silane as optional comonomer corresponds to the substituted silane of structural formula I usually:
Wherein R representative is at ω-undersaturated organic group of position olefinic, and R
1, R
2and R
3(it can be identical or different) represents halogen, preferred chlorine, or group-OZ, Z represent hydrogen or uncle or secondary alkyl or acyl group, and its optional alkoxy replaces.The unsaturated silane compound of suitable formula I be preferably radicals R in formula represent 2 to 10 carbon atoms, particularly 2 to 4 carbon atoms ω-unsaturated chain thiazolinyl or formed by the unsaturated carboxylic acid of maximum 4 carbon atoms and the alcohol carrying Si group of maximum 5 carbon atoms those.Suitable radicals R
1, R
2, R
3preferably group-OZ, Z represent the uncle of maximum 10 carbon atoms, preferably maximum 4 carbon atoms and/or secondary alkyl, or the alkyl of preferably maximum 3 carbon atoms of alkoxy replacement, or the acyl group of maximum 6 carbon atoms, preferably maximum 3 carbon atoms, or hydrogen.Most preferred unsaturated silane comonomer is vinyl trialkyl oxysilane.
The example of the silane compound of preferred formula I comprises γ-methacryloxypropyl three (2-methoxy ethoxy) silane, vinyl methoxy silane, vinyltriethoxysilane, methylvinyldiethoxysilane alcohol, vinylethoxysilane glycol, allyltriethoxysilane, vinyl tripropoxy silane, vinyl silane triisopropoxide, vinyltributoxysilane, vinyltriacetoxy silane, trimethylammonium ethylene glycol vinyl silane, γ-methacryloxypropyl trimethylammonium ethylene glycol silane, γ-acryloxypropyl triethoxyl silane and γ-methacryloxypropyl trimethoxy silane.
Glycidyl compound also can be used as optional additional comonomer in this VAE emulsion copolymers.Glycidyl compound is containing epoxy-based material, and can promote the crosslinked of emulsion copolymers in copolymer blend.The example of suitable optional glycidyl comonomer comprises glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, vinyl glycidyl ether, the Vinyl toluene replaced with glycidyl in aromatic fractions and vinylbenzene, and with the vinyl benzoate that glycidyl replaces in aromatic fractions.
Another kind of optional comonomer for this VAE emulsion copolymers component comprises ring-type urea groups comonomer.Known ring-type urea groups comonomer is give the wet adhesion improved matter by the film formed containing the multipolymer of these comonomers and coating.Ring-type urea-based compound and they are as promoting that the purposes of adhering comonomer is disclosed in U.S. Patent number 4,104,220; 4,111,877; 4,219,454; 4,319,032; 4,599,417 and 5,208, in 285.The disclosure of all these United States Patent (USP)s is incorporated to herein through this incorporated.
prepared by coating composition
Comprise aforementioned vae copolymer thing that is basic and optional comonomer can adopt and cause the conventional emulsion polymerization flow process preparing copolymer emulsion to be prepared.These emulsions can be mixed in the coating composition herein of aqueous latex form subsequently.This type of flow process is described in such as U.S. Patent number 5,849, and in 389, its disclosure is incorporated to herein through this incorporated.
Usually, by nonionic surface active agent with in and phosphoric acid ester or phosphate surfactant active existence under and when there is not protective colloid copolymerization at least one C
1-13aqueous latex base coating composition prepared by the vinyl ester of paraffinic acid and ethene.In other method, this aqueous latex based coating composition by nonionic surface active agent with in and phosphoric acid ester or phosphate surfactant active existence under copolymerization at least one C
1-13prepared by the vinyl ester of paraffinic acid and ethene.Nonionic surface active agent is greater than 1:1 to the phosphoric acid ester of neutralization or the weight ratio of phosphate surfactant active, such as 1:1 to 3:1 or approximately 3:2.Vinyl ester in two kinds of preparation methods can be vinyl-acetic ester.
Amount for the preparation of the vinyl monomer of this vae copolymer thing can be about 5 % by weight to about 20 % by weight of the comonomer gross weight for the preparation of this vae copolymer thing, such as about 10 % by weight to about 15 % by weight.Amount for the preparation of the vinyl-acetic ester of this vae copolymer thing can be about 70 % by weight to about 95 % by weight of the comonomer gross weight for the preparation of this vae copolymer thing, such as about 75 % by weight to about 90 % by weight.
Vae copolymer thing for composition blend herein can also containing 0 % by weight to about 10 % by weight of the comonomer gross weight for the preparation of this vae copolymer thing, such as one or more optional unsaturated comonomers of about 0.1 % by weight to about 5 % by weight.
In typical polymerization process, this vinyl ester, ethene and other optional comonomer can be polymerized being no more than under the existence at catalyst component and at least one emulsifying agent under 100 atmospheric pressure in water-bearing media in suitable aggregation container.Aqueous reaction mixture in aggregation container can remain on the pH of about 2 to 9 by suitable buffer reagent under.
Combine several polymeric composition, namely the mode of emulsifying agent, comonomer, catalyst system component etc. can have a great difference.Usually, be initially at the water-bearing media being formed in aggregation container and contain (one or more) emulsifying agent at least partially, other polymeric composition various joins in this container subsequently.
Comonomer can join in aggregation container continuously, incrementally, or adds the comonomer of stand-by whole amount with single charge form.Comonomer can use with pure monomer form, or can use with pre-mixing emulsion form.Ethene as comonomer can be pumped in aggregation container and also keep wherein at suitable pressures.
Catalyst system component also can incrementally or as single charging be added in this aggregation container continuously, stage by stage.Suitable polymerizing catalyst comprises the water-soluble free radical forming agent (initiator) being generally used for letex polymerization, as hydrogen peroxide, Sodium Persulfate, Potassium Persulphate and ammonium persulphate, and tert-butyl hydroperoxide, its amount is emulsion total amount 0.01 % by weight to 3 % by weight, preferably 0.01 % by weight to 1 % by weight.These materials can with reductive agent as together with formaldehyde-sodium hydrosulfite 90min, ferrous salt, V-Brite B, sodium bisulfite, S-WAT, Sulfothiorine as redox catalyst, with 0.01 % by weight to 3 % by weight of emulsion total amount, preferably the amount of 0.01 % by weight to 1 % by weight uses.This free radical forming agent can join in the emulsifier aqueous solution be initially present in aggregation container, or can the stage is metered in the course of the polymerization process.When forming redox system in aggregation container, initiator should separate with (one or more) reductive agent and add, such as, add with independent solution.
As described, the whole amount with the water-bearing media of polymeric additive can be present in aggregation container before introducing comonomer.Or this water-bearing media, or its part, can add in the course of the polymerization process continuously or incrementally.
In typical polymerization process, polymerization reactor can be filled with emulsifier aqueous solution.Add comonomer to be polymerized at least partially subsequently.In this initial reaction mixture after stirring homogenizing, polymerization can start by adding catalyst system at least partially, prepares seed crystal material with original position.Can increase progressively or add continuously remaining comonomer and catalyst system component subsequently to complete the preparation of emulsion polymer.Or replace original position and prepare seed crystal material, the water-bearing media containing crystal seed dispersion can be prepared separately and add in aggregation container, again adds remaining comonomer and catalystic material subsequently.
Emulsion polymerization for the preparation of the multipolymer of aqueous latex form carries out under the existence of stabilising system, and described stabilising system comprises the phosphoric acid ester of neutralization or phosphate surfactant active and nonionic surface active agent as described herein.
paint/lacquer feed composition preparation
This coating composition is prepared by the blend forming the emulsion copolymers of moisture (namely water base) latex disclosed herein.Term " latex " uses with its conventional sense in this article, namely means that particulate material is being prepared and the dispersion stablized in the emulsifying agent of this latex or the aqueous phase of tensio-active agent containing being suitable for.Latex coating composition herein comprises the specific copolymer blend be dispersed in the aqueous phase with suitable emulsifier system.
The basal component of coating composition herein mixes with conventional other composition for the formation of paint composition the most usually.The technology preparation paint vehicle known to the skilled manufacturing paint vehicle field can be used.Usually, by the combination of water, defoamer, pigment, filler (also referred to as extender pigment) and surfactant stabilisers (except the emulsifying agent used in the emulsion polymerization process of copolymer blend) to form abrasive material (grind), wherein pigment and filler is milled to by the desired particle size indicated by the Hegman reading of 2 to 6.
" Hegman " reading is the modal mode characterizing abrasive dispersion (relative to polymeric dispersions).Hegman number relates to the fineness of the abrasive dispersion of micron measurement.Hegman number is higher, means that abrasive material is thinner.The Hegman number of about 2 to about 3 is almost unique concerning flat enamel.Clear lacquer and eggshell paint depend on that formula can have the Hegman number of about 3 to about 6, are preferably 3 to being less than 5.The Hegman number of about 6 represents lower semi-gloss scope.Additional water, this latex copolymer blend, rheology modifier, sterilant etc. join in this abrasive material subsequently, will expect blended by the gross and be adjusted to required Hegman reading and viscosity, and forming this paint composition thus.
Coating composition of the present invention can be mixed in paint composition, and this paint composition comprises this coating composition, pigment component and at least one auxiliary component.This pigment component can be selected from mineral dye, mineral filler and composition thereof.Add this pigment component with the pigment volume concentration (PVC) making this paint composition have about 25 volume % to 90 volume %.This at least one auxiliary component can be selected from wetting agent, dispersion agent, emulsifying agent, filler, thickening material, defoamer, dyestuff and sanitas.
The preferred filler that can be used for paint composition herein can be such as calcium carbonate, magnesite, rhombspar, kaolin, mica, talcum, silicon-dioxide, calcium sulfate, feldspar, barium sulfate and Opacifying polymers.The example that can be used for the white pigment of paint composition herein can be zinc oxide, zinc sulphide, white lead carbonate, ANTIMONY TRIOXIDE SB 203 99.8 PCT, lithopone (zinc sulphide+barium sulfate) and preferred titanium dioxide.The example being preferred for the inorganic colored pigments of paint composition herein comprises ferriferous oxide, carbon black, graphite, luminous pigment, zinc yellow, zinc green, prussian blue, ultramarine, manganese black, antimony black, manganese violet or schweinfurt green.The metal complex pigment of suitable organic colored pigments preferably such as squid ink, gamboge, your palm fibre of jam, toluidine red, p-nitroaniline red, hansa yellow, indigo, azoic dyestuff, anthraquinone and bipseudoindoxyl dye and dioxazine, quinacridone, phthalocyanine pigment, isoindolinone and azomethine series.
This filler can use as independent component.Mixture such as calcium carbonate/kaolin and the calcium carbonate/kaolin/talcum of filler are also considered to particularly useful in practice.In order to improve the opacifying power of coating and save titanium dioxide, usually use filler in small, broken bits as calcium carbonate in small, broken bits and the mixture with the various calcium carbonate that different grain size distributes.Calcined clay is generally used for improving film and does opaqueness, because they contribute to entrained air space in dry film.Air void produces large refractive index difference and scattered light in film, once film is solidificated in film produce higher opaqueness.In order to regulate the opacifying power of the coating of formation, the tone of color and the degree of depth, the white pigment of this filler and appropriate amount and inorganic and/or organic colored pigments are mixed.
In order to dispersed filler and pigment in water, the auxiliary agent based on anionic or non-ionic wetting agent of 0.1 to 0.6 % by weight of this aqueous compositions gross weight can be added, preference is as trisodium phosphate, sodium polyphosphate, naphthalenesulfonate, sodium polyacrylate, polymaleic acid sodium and polyphosphate, as 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid sodium and nitrilo three (methylene phosphonic acid) sodium.
Paint composition herein preferably has about 25 volume % to about 90 volume %, the pigment volume concentration (PVC) (PVC) of such as about 50 volume % to about 90 volume % or about 75 volume % to about 90 volume %.PVC represents that volume that in paint composition, pigment is filled is divided by the volume of pigment, filler and film forming copolymer, is multiplied by 100%.In U.S. Patent Publication No. 2010/0056696, describe in further detail PVC, it is incorporated herein by this reference.
Thickening material can also be joined in paint vehicle preparation herein.Operable thickening material especially preferably includes derivatived cellulose as methylcellulose gum (MC), Natvosol (HEC) and carboxymethyl cellulose.Other thickening material operable comprises casein, Sudan Gum-arabic, Tragacanth, starch, sodiun alginate, polyvinyl alcohol, Polyvinylpyrolidone (PVP), sodium polyacrylate and the water solubility copolymer based on vinylformic acid and methacrylic acid, as acrylic acid/acrylamide and methacrylic acid/acrylate copolymer.Caustic solubility (vinylformic acid) emulsion (HASE) of hydrophobically modified, ethoxylation (gathering) the ammonia ester (HEUR) of hydrophobically modified and polyether glycol (PEPO) are also available.Inorganic thickening agent such as wilkinite or hectorite also can use.This type of thickening material uses with the amount that is about 0.1 % by weight to 3 % by weight, preferably approximately 0.1 % by weight to 1 % by weight of aqueous latex paint vehicle total formulation weight amount usually.
In other embodiments, the thickening material also serving as protective colloid can be got rid of from this paint vehicle preparation.The thickening material that can get rid of comprises methylcellulose gum, Natvosol, carboxymethyl cellulose and polyvinyl alcohol.
For many application, sometimes also desirably comprise other additive a small amount of of the latex paint feed composition be mixed into herein, as sterilant, pH adjusting agent and defoamer.This can in a usual manner and anyly in the preparation process of this latex to carry out when an opportunity arises.
Commercial latices paint vehicle can contain other component of the volatile organic content for improving this paint vehicle preparation.The volatile organic content of paint vehicle preparation refers to exists volatile organic constituents; Namely contain carbon and be not classified as any volatile constituent of exempting solvent by EPA.VOC source can comprise cosolvent, comprises glycols, it contributes to, and wet limit applies, open hour and anti-freezing-thawing property, and coalescing agent, and it reduces T when film is dry
g, thus contribute to this latex polymer formation film; The emulsion components of low levels and most of additive.Such as, aminomethylpropanol is the volatile compound for regulating pH.
Volatile organic content in units of grams per liter calculates according to the formula proposed in previously mentioned U.S. Patent Publication No. 2010/0056696, and its content is incorporated herein by this reference.Commercial latices paint vehicle can have the VOC level higher than 150 grams per liters.On the contrary, coating described herein and paint composition can have low-down volatile organic content (VOC), as lower than about 50 grams per liters or even lower than 5 grams per liters.
This VAE emulsion copolymers being used as film-forming components in composition in this article can exist in the process of dispersed color and filler.But in most of the cases, this copolymer blend advantageously fast or add under slower stirring still heat or in the filler/pigment thickener that cooled.
Do not wish to be bound by theory, a feature that can affect the bulk property combination in latex paint vehicle preparation is the size range existed in emulsion.When the ratio height of macroparticle, the scrub resistance of the coating formed by gained paint vehicle can reduce.When fine particle fraction (i.e. size be less than 0.1 micron those particles) is high, this paint vehicle can have inferior flowing and levelling characteristic.Can by the size of particles regulating the surfactant concentration of protective colloid level or initial interpolation or increment interpolation in the course of the polymerization process to affect latex in copolymer emulsion.Stirring is another variable that can affect size of particles in copolymer emulsion.These factors can be regulated where necessary by methods known in the art.In some embodiments, the granularity of this aqueous latex base coating composition is less than 1 micron, such as, be less than 500 nanometers.
paint/lacquer feed composition performance
When solidifying, multipolymer in aqueous latex paint/lacquer feed composition herein forms film or coating, this film or coating by adhere to apply this paint/lacquer feed composition above substrate on.This film or coating encapsulates also protect this substrate.
In latex, multipolymer formation coating or the minimum temperature needed for film are called minimum film-forming temperature or MFT.The second-order transition temperature T of emulsion copolymers in MFT and copolymer blend
grelevant, but also can by other component in this type of paint/lacquer feed composition as the impact of coalescing agent.Paint/lacquer feed composition herein preferably has and is equal to or less than about 10 DEG C, such as, be equal to or less than the MFT of about 5 DEG C.
Paint/lacquer feed composition herein will form film or coating, and this film or coatings go out the excellent adhesion to the dry substrate be applied thereto by such composition or hard surface.At least 400 circulations that this film shows the testing method B according to ASTM D 2486 revision (being referred to herein as the amendment testing method B of ASTM D 2486) when drying records, such as at least 425 circulations, at least 435 circulations or the wet scrub resistance (" WSR ") circulated at least 437 times.The testing method B of amendment ASTM D 2486 is to test wet scrub resistance when there is no scouring media and there is no (one or more) pad (shim).In scope, this film shows 400 to 600 circulations when drying, such as 425 to 575 circulations, 435 to 565 circulations or the WSR circulated for 437 to 560 times.In this testing method, measure paint vehicle of the present invention relative to object of reference BATF 998A.Result is reported in units of cycle number, also can report with the per-cent of cycle number to reference surfaces promoting agent cycle number.In the WSR of the function of the % as reference surfaces promoting agent, the tensio-active agent of neutralization is at least 140% of object of reference, such as at least 145%, at least 150% or at least 155%.In scope, this film shows 140 to 300% when drying, the WSR of the function of the % as reference surfaces promoting agent of such as 145 to 250%, 150 to 225% or 155 to 210%.
The performance of paint/lacquer feed composition of the present invention and herein this type of paint/lacquer feed composition is illustrated by following non-limiting examples.
prepared by embodiment 1
3.5 kg water are loaded, 241 grams in 10.2 boosting force containers
a 3065,105 grams neutralization phosphoric acid ester/salt A (
rS 710), 88 grams of moisture 33% sodium vinyl sulfonates, 13 grams of sodium acetates, 1 gram
fF6,0.21 gram of Mohr's salt, 0.52 gram of EDTA tetra-na salt and 2.1 grams
282.Add the sodium hydroxide solution of 10% subsequently, until observe pH neutral.This container is emptying subsequently and use nitrogen wash.Open stirring subsequently.
a 3065 is mixtures of the ethoxylated linear lipid acid of the nonionic surface active agent with 65 % by weight.
rS 710 is organophosphates of a kind of complexity, comprises the polyoxyethylene tridecyl ether phosphate of free acid.
a 3065 is right
the weight ratio of RS 710 is about 3:2.
fF6 is the mixture of the organic acid salt of mineral acid and replacement.
4.7 kg of vinyl acetate and 21 grams of trimethoxyvinyl silane are loaded in the slow addition vessel of monomer.
Vinyl-acetic ester/trimethoxyvinyl silane mixture and 0.55 kg ethylene of 5% is loaded in this reactor.
0.19 kg water and 4.2 grams are loaded in reductive agent addition vessel
the solution of FF6.
The solution of 0.19 kg water and 10.5 grams of Sodium Persulfates is loaded in oxygenant addition vessel.
Through the time periods of 270 minutes by adding the solution from reductive agent addition vessel and the solution by adding to come autoxidator addition vessel, and retain the monomer mixture of 95% through the time period of 200 minutes, thus be polymerized at 70 DEG C.After end is added, this batch of material is heated to 85 DEG C, and is cooled to 60 DEG C subsequently.This batch of material is transferred in aftertreatment container.
By add comprise 52 grams of water, 2 grams
the reductant solution of FF6 and 0.1 gram Mohr's salt, and the aftertreatment being carried out this batch of material by the oxidizing agent solution adding 70% aqueous solution comprising 52 grams of water and 7.5 grams of tert-butyl hydroperoxides.
prepared by embodiment 2-10
Prepare embodiment 2 by the method identical with for embodiment 1, except not by phosphoric acid ester/salt A (
rS 710) neutralization.
Embodiment 3 is prepared, except using the phosphoric acid ester/salt A of reduction by the method identical with for embodiment 1.
Embodiment 4 is prepared, except not neutralising phosphoric acid ester/salt A by the method identical with for embodiment 3.
Prepare embodiment 5 by the method identical with for embodiment 1, except use neutralization phosphoric acid ester/salt B (
rS 610, a kind of organophosphate of complexity, comprises the polyoxyethylene tridecyl ether phosphate of free acid) replace the phosphoric acid ester/salt A of neutralization.
Embodiment 6 is prepared, except not neutralising phosphoric acid ester/salt B by the method identical with for embodiment 5.
Embodiment 7 is prepared, except using the phosphoric acid ester/salt B of reduction by the method identical with for embodiment 5.
Embodiment 8 is prepared, except not neutralising phosphoric acid ester/salt B by the method identical with for embodiment 5.
Prepare embodiment 9 by the method identical with for embodiment 1, except use phosphoric acid ester/salt C (
a16, a kind of branched dodecylbenzene sulfonic acid sodium) replace phosphoric acid ester/salt A.
Embodiment 10 is prepared, except using the phosphoric acid ester/salt C of reduction by the method identical with for embodiment 9.
As shown in Table 1 below, when neutralizing this phosphoric acid ester or phosphate surfactant active and be greater than 1:1 when the weight ratio of nonionic surface active agent to the phosphoric acid ester neutralized or phosphate surfactant active, WSR cycle number improves, and the WSR of reference surfaces promoting agent % form improves.Each tensio-active agent (" PPHM ") is reported in units of the number of every hundred parts of monomers.
Although specifically described exemplary of the present disclosure, should be understood that, when not departing from spirit of the present disclosure and scope, other amendment various it will be apparent to those skilled in the art that and can easily be made by those skilled in the art.Therefore, the scope of claims being not intended to is limited to the embodiment and explanation enumerated herein, this claim interpretation be contain that exist in this specification sheets all have can the feature of novelty of granted patent, comprise all features that disclosure those skilled in the art can be considered its equivalent features.
Claims (22)
1. aqueous latex base coating composition, comprises:
(a) at least one C
1-13the vinyl ester of paraffinic acid and the multipolymer of ethene;
(b) nonionic surface active agent; With
C phosphoric acid ester that () neutralizes or phosphate surfactant active,
Wherein nonionic surface active agent is greater than 1:1, preferred 1:1 to 3:1 to the phosphoric acid ester of neutralization or the weight ratio of phosphate surfactant active, most preferably about 3:2.
2. the component of claim 1, wherein this vinyl ester is vinyl-acetic ester.
3. the component of claim 2, wherein this multipolymer comprise the vinyl-acetic ester of 70 % by weight to 95 % by weight, the ethene of 5 % by weight to 30 % by weight and 0 % by weight to 10 % by weight the emulsion polymeric product of additional comonomer.
4. the component of claim 3, wherein this vinyl-acetic ester, ethene and additional comonomer nonionic surface active agent with in and phosphoric acid ester or phosphate surfactant active existence under be polymerized.
5. the component of arbitrary aforementioned claim, with 1 to 20 % by weight, preferably the amount of 3 to 12 % by weight comprises this multipolymer.
6. the component of arbitrary aforementioned claim, wherein this phosphoric acid ester or phosphate surfactant active are the C of phosphoric acid
1-15ester.
7. the component of arbitrary aforementioned claim, wherein this phosphoric acid ester or phosphate surfactant active comprise 4 to 20 ethylene oxide units, preferably 6 to 10 ethylene oxide units.
8. the component of arbitrary aforementioned claim, wherein this phosphoric acid ester or phosphate surfactant active sodium hydroxide neutralize.
9. the component of arbitrary aforementioned claim, wherein this nonionic surface active agent comprises ethoxylated linear fatty alcohol.
10. the component of arbitrary aforementioned claim, wherein this nonionic surface active agent comprise reduction, the C comprising 4 to 100 ethylene oxide units of side chain or straight chain
1-C
50ether or ester.
The component of 11. arbitrary aforementioned claims, wherein said composition is not substantially containing protective colloid.
The component of 12. arbitrary aforementioned claims, wherein said composition is not substantially containing Natvosol and polyvinyl alcohol.
The component of 13. arbitrary aforementioned claims, wherein said composition has the mean particle size being less than 1 micron, being preferably less than 500 nanometers.
The component of 14. arbitrary aforementioned claims, wherein this multipolymer is not substantially containing nonesterified carboxy moiety.
The component of 15. arbitrary aforementioned claims, wherein this multipolymer comprises at least one additional comonomer, described additional comonomer is selected from unsaturated silane comonomer, glycidyl comonomer, ring-type urea groups comonomer and combination thereof, preferred wherein said at least one additional comonomer is selected from vinyl trialkyl oxysilane monomer, glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, vinyl glycidyl ether, with the vinylbenzene that glycidyl replaces in aromatic fractions, with the vinyl benzoate of glycidyl replacement and Vinyl toluene in aromatic fractions, and combination.
The component of 16. arbitrary aforementioned claims, comprise at least one auxiliary component further, described auxiliary component is selected from wetting agent, dispersion agent, emulsifying agent, filler, thickening material, defoamer, dyestuff and sanitas.
The component of 17. arbitrary aforementioned claims, comprises calcium carbonate further.
The component of 18. arbitrary aforementioned claims, wherein said composition is not substantially containing alkylphenol ethoxylate.
The component of 19. arbitrary aforementioned claims, wherein this copolymer blend has and is equal to or less than 10 DEG C, is preferably equal to or less than the minimum film-forming temperature (MFT) of 5 DEG C.
20. paint compositions, comprise:
The aqueous latex base coating composition of (i) arbitrary aforementioned claim;
(ii) with the pigment component being selected from mineral dye, mineral filler and composition thereof that the amount making this paint composition have 25 volume % to 90 volume %, the preferably pigment volume concentration (PVC) (PVC) of 75 volume % to 90 volume % exists; With
(ii) at least one is selected from the auxiliary component of wetting agent, dispersion agent, emulsifying agent, filler, thickening material, defoamer, dyestuff and sanitas.
The paint composition of 21. claims 20, has the volatile organic content (VOC) being less than 50 grams per liters, being preferably less than 5 grams per liters.
The paint composition of any one of 22. claims 20 to 21, it forms the film of the wet scrub resistance showing at least 400 circulations recorded according to the amendment testing method B of ASTM D 2486 when drying.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261650645P | 2012-05-23 | 2012-05-23 | |
| US61/650,645 | 2012-05-23 | ||
| PCT/EP2013/060642 WO2013174934A1 (en) | 2012-05-23 | 2013-05-23 | Aqueous latex-based coating components |
Publications (1)
| Publication Number | Publication Date |
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| CN104302717A true CN104302717A (en) | 2015-01-21 |
Family
ID=48485191
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380026548.7A Pending CN104302717A (en) | 2012-05-23 | 2013-05-23 | Aqueous latex-based coating components |
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| CN (1) | CN104302717A (en) |
| WO (1) | WO2013174934A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019080475A1 (en) * | 2017-10-23 | 2019-05-02 | 北新集团建材股份有限公司 | Exterior wall coating, and preparation method and wetting agent therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| MX2019002506A (en) | 2016-09-06 | 2019-12-05 | Ocv Intellectual Capital Llc | A corrosion-resistant non-woven for pipe liner pultrusion applications. |
| EP3722377A1 (en) * | 2019-04-09 | 2020-10-14 | Clariant International Ltd | Additives for extending the open time of aqueous dispersion paints and varnishes |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4228047A (en) * | 1978-10-31 | 1980-10-14 | Air Products And Chemicals, Inc. | Starch compatible polyvinyl acetate latices |
| US20030100671A1 (en) * | 2001-10-05 | 2003-05-29 | Dorian Pierre | Vinyl acetate/ethylene emulsion stabilized with a phosphate surfactant |
| KR100500151B1 (en) * | 2002-11-20 | 2005-07-11 | 순경석 | Method of preparing waterproof admixture for waterproofing and anticorrosive treatment of concrete, and waterproof admixture prepared thereby |
| CN1687265A (en) * | 2005-04-15 | 2005-10-26 | 宁波广用纳米涂料有限公司 | Emulsion for environmental protection type latex paint and preparation method |
| CN101041704A (en) * | 2007-04-20 | 2007-09-26 | 上海三瑞化学有限公司 | Novel ethane-acetic acid ethyenyl ester copolymer emulsion |
| CN101163757A (en) * | 2005-04-22 | 2008-04-16 | 巴斯福股份公司 | Low-voc emulsion polymer coating compositions |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104220A (en) | 1976-07-29 | 1978-08-01 | Air Products & Chemicals, Inc. | Alkenyl 1-(2-Aminoethyl) alkyleneureido succinamates, their synthesis, and use in aqueous emulsion polymer systems |
| US4111877A (en) | 1976-07-29 | 1978-09-05 | Air Products & Chemicals, Inc. | Allyl esters of n-alkyl-omega-(alkyleneureido) amic acids and their synthesis and use in aqueous emulsion polymer systems |
| US4219454A (en) | 1978-09-05 | 1980-08-26 | Air Products And Chemicals, Inc. | Vinyl acetate copolymer emulsions for paint |
| US4277385A (en) | 1979-02-09 | 1981-07-07 | Scm Corporation | High PVC latex paint |
| US4319032A (en) | 1980-06-06 | 1982-03-09 | Alcolac Inc. | Derivatives of aminoalkyl alkylene ureas |
| US4599417A (en) | 1984-11-05 | 1986-07-08 | Desoto, Inc. | Ureido-functional adhesion promoting amide monomers |
| US5208285A (en) | 1989-02-17 | 1993-05-04 | National Starch And Chemical Investment Holding Corporation | Vinyl acetate polymer with wet adhesion |
| US5849389A (en) | 1997-03-10 | 1998-12-15 | National Starch And Chemical Investment Holding Corporation | Carpet coating compositions |
| EP2277959B1 (en) | 2008-09-02 | 2013-10-16 | Celanese International Corporation | Low emission, high scrub VAE latex paints |
-
2013
- 2013-05-23 WO PCT/EP2013/060642 patent/WO2013174934A1/en active Application Filing
- 2013-05-23 CN CN201380026548.7A patent/CN104302717A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4228047A (en) * | 1978-10-31 | 1980-10-14 | Air Products And Chemicals, Inc. | Starch compatible polyvinyl acetate latices |
| US20030100671A1 (en) * | 2001-10-05 | 2003-05-29 | Dorian Pierre | Vinyl acetate/ethylene emulsion stabilized with a phosphate surfactant |
| KR100500151B1 (en) * | 2002-11-20 | 2005-07-11 | 순경석 | Method of preparing waterproof admixture for waterproofing and anticorrosive treatment of concrete, and waterproof admixture prepared thereby |
| CN1687265A (en) * | 2005-04-15 | 2005-10-26 | 宁波广用纳米涂料有限公司 | Emulsion for environmental protection type latex paint and preparation method |
| CN101163757A (en) * | 2005-04-22 | 2008-04-16 | 巴斯福股份公司 | Low-voc emulsion polymer coating compositions |
| CN101041704A (en) * | 2007-04-20 | 2007-09-26 | 上海三瑞化学有限公司 | Novel ethane-acetic acid ethyenyl ester copolymer emulsion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019080475A1 (en) * | 2017-10-23 | 2019-05-02 | 北新集团建材股份有限公司 | Exterior wall coating, and preparation method and wetting agent therefor |
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