WO2012089120A1 - Sealing combination and its application in a self-leveling floor product - Google Patents

Sealing combination and its application in a self-leveling floor product Download PDF

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Publication number
WO2012089120A1
WO2012089120A1 PCT/CN2011/084799 CN2011084799W WO2012089120A1 WO 2012089120 A1 WO2012089120 A1 WO 2012089120A1 CN 2011084799 W CN2011084799 W CN 2011084799W WO 2012089120 A1 WO2012089120 A1 WO 2012089120A1
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Prior art keywords
weight
parts
emulsion
acrylate
pore filler
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Application number
PCT/CN2011/084799
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French (fr)
Inventor
Jun Li
Cecile Evju BAGGERUD
Zhimin DAI
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Saint-Gobain Weber S.A.
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Publication of WO2012089120A1 publication Critical patent/WO2012089120A1/en

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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/12—Flooring or floor layers made of masses in situ, e.g. seamless magnesite floors, terrazzo gypsum floors
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • 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

Definitions

  • the invention relates to the field of sealing material, particularly to a high performance sealing combination for use on cement substrate or porous structure widely used on SLF (self-leveling floor) products.
  • the invention further relates to the application of the sealing combination on self-leveling floor products.
  • SLF product is a cement-based material which may be formed into a porous hardened material after curing and drying.
  • a sealing layer for a wide variety of uses is required to afford a final application featuring scratch resistance, fouling resistance and good resistance to household liquids.
  • a solvent borne sealer is thought to be able to permeate more deeply pores and exclude water very well. However, the solvent content (50% to 80% of the total formulation weight) endangers environment and health.
  • a water borne emulsion sealer is usually safer, cheaper and environmental acceptability.
  • United States Patent Application No. 5191002A disclosed a floor care maintenance system utilizing a low zinc or phosphate formulation to lessen its environmental impact and provide useful floor care maintenance properties.
  • European Patent Application No. 1371698A1 disclosed a coating composition for inhibiting the penetration of water into a cementitious material comprising polymeric nano-particles having an average particle diameter between 1 and 50 nm.
  • An object of this invention is to provide a novel sealing combination to overcome the shortcomings in the prior art.
  • the invention provides a sealing combination adapted for forming a protective coating on a floor surface, the protective coating comprising at least one pore filler layer and at least one top coat layer, the pore filler layer being formed in direct contact with the floor surface and the top coat layer being formed on the pore filler layer, the sealing combination comprising a pore filler and a surface covering agent, wherein the pore filler is adapted for forming the pore filler layer on the floor surface and comprises the following components:
  • the surface covering agent is adapted for forming the top coat layer on the pore filler layer and comprises the following components:
  • (a2) an aqueous acrylic emulsion comprising acrylic matrix, wherein the acrylic matrix in the component (a2) is different from the acrylic matrix in the component (al);
  • the acrylic matrix in the component (al) has a molecular weight greater than that of the acrylic matrix in the component (a2).
  • the acrylic matrix in the component (al) and the acrylic matrix in the component (a2) are block or graft polymers, wherein the molecular weight of the acrylic matrix in the component (al) is 200000-350000, and the molecular weight of the acrylic matrix in the component (a2) is 150000-260000.
  • the pore filler comprises the following components:
  • aqueous acrylic emulsion 20-30 parts by weight of an aqueous acrylic emulsion, wherein the aqueous acrylic emulsion is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly (aromatic acrylate), poly (alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof;
  • polymeric wax emulsion 0.5-5 parts by weight of a polymeric wax emulsion, wherein the polymeric wax emulsion is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion and synthetic wax emulsion;
  • the additive (cl) comprises the following components:
  • organometallic chelate complex (el l) 0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
  • (cl3) 0.5-3 parts by weight of an anti-scratching agent, at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant and at most 3 parts by weight of a defoamer.
  • the anti-scratching agent is selected from poly ether modified polydimethylsiloxane.
  • the film forming auxiliary is selected from the group consisting of lactate, 2-butoxyl ethanol, phthalate, ethylene glycol, diethylene glycol, diacetone alcohol, propylene glycol and ethylene glycol phenyl ether.
  • the surfactant is selected from acrylate-co-carboxylate and 2-amino-2-methyl-l-propanol.
  • the defoamer is selected from mineral oil-type defoamer and siloxane deformer.
  • the surface covering agent comprises the following components:
  • the additive (c2) comprises the following components:
  • organometallic chelate complex 0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
  • the anti-scratching agent is selected from poly ether modified polydimethylsiloxane.
  • the film forming auxiliary is selected from the group consisting of lactate, 2-butoxyl ethanol, phthalate, ethylene glycol, diethylene glycol, diacetone alcohol, propylene glycol and ethylene glycol phenyl ether.
  • the surfactant is selected from acrylate-co-carboxylate and 2-amino-2-methyl-l-propanol.
  • the defoamer is selected from mineral oil-type defoamer and siloxane deformer.
  • the aqueous acrylic emulsion in the component (al) is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly (aromatic acrylate), poly (alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof.
  • the polymeric wax emulsion in the component (a2) is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion and synthetic wax emulsion.
  • the aqueous acrylic emulsion in the component (bl) is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly (aromatic acrylate), poly (alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof.
  • the polymeric wax emulsion in the component (b2) is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion and synthetic wax emulsion.
  • the polymeric wax emulsion comprises particles having an average particle size of 0.1-5 ⁇ .
  • the solid content of the pore filler is 20-35 wt%, and the solid content of the surface covering agent is 25 ⁇ 45wt%. In another preferred embodiment, the thickness of the protective layer is 10 ⁇ 80 ⁇ .
  • the pendulum friction coefficient of the protective layer is 45-80.
  • the invention relates to the use of the above sealing combination in self-leveling floor products.
  • the invention provides a method for detecting wear on SLF products, wherein the method comprises:
  • the wearing condition is a simulated traffic load.
  • the wearing condition is an experimental scratching test.
  • the invention provides a protective layer for a self-leveling floor, comprising:
  • a pore filler layer formed on the self-leveling floor, wherein the material used for forming the pore filler layer at least comprises a first aqueous acrylic emulsion
  • top coat layer formed on the pore filler layer, wherein the material used for forming the top coat layer at least comprises a second aqueous acrylic emulsion;
  • first aqueous acrylic emulsion and the second aqueous acrylic emulsion are based on block or graft polymers comprising aqueous acrylic matrices, and the acrylic matrix in the first aqueous acrylic emulsion has a molecular weight greater than that of the acrylic matrix in the second aqueous acrylic emulsion.
  • the molecular weight of the acrylic matrix in the first aqueous acrylic emulsion is 200000-350000
  • the molecular weight of the acrylic matrix in the second aqueous acrylic emulsion is 150000-260000.
  • the first aqueous acrylic emulsion is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly (aromatic acrylate), poly (alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof.
  • the second aqueous acrylic emulsion is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly(aromatic acrylate), poly(alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof.
  • the first aqueous acrylic emulsion is different from the second aqueous acrylic emulsion in their composition.
  • the first aqueous acrylic emulsion is 20-30 parts by weight
  • the material used for forming the pore filler layer further comprises:
  • polymeric wax emulsion 0.5-5 parts by weight of a polymeric wax emulsion, wherein the polymeric wax emulsion is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion and synthetic wax emulsion;
  • the additive comprises the following components:
  • organometallic chelate complex 0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
  • a polyfunctional crosslinking agent wherein the polyfunctional crosslinking agent is polyfunctional aziridine; and 0.5-3 parts by weight of an anti-scratching agent, at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant and at most 3 parts by weight of a defoamer.
  • the second aqueous acrylic emulsion is 20-45 parts by weight
  • the material used for forming the top coat layer further comprises:
  • polymeric wax emulsion 2-8 parts by weight of a polymeric wax emulsion, wherein the polymeric wax emulsion is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion, and synthetic wax emulsion;
  • the additive comprises the following components:
  • organometallic chelate complex 0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
  • polyfunctional crosslinking agent 1-3 parts by weight of a polyfunctional crosslinking agent, wherein the polyfunctional crosslinking agent is polyfunctional aziridine;
  • an anti-scratching agent at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant and at most 3 parts by weight of a defoamer.
  • the polymeric wax emulsion comprises particles having an average particle size of 0.1-5 ⁇ .
  • the solid content of the pore filler is 20-35 wt%, and the solid content of the surface covering agent is 25 ⁇ 45wt%.
  • the thickness of the protective layer is 10 ⁇ 80 ⁇ .
  • the invention provides a method for forming the protective layer on a self-leveling floor, comprising:
  • first pore filler layer coating the material used for forming the pore filler layer in the protective layer on the self-leveling floor to form a first pore filler layer; maintaining the first pore filler layer for a period of sufficient to make it dry, and then coating the material used for forming the pore filler layer in the protective layer on the first pore filler layer to form a second pore filler layer, wherein the first and second pore filler layers together constitute the pore filler layer;
  • Fig. 1 illustrates the relationship between wetting ratio and number of customers in a supermarket according to a first example embodiment of the application
  • Fig. 2 illustrates the relationship between wetting ratio and times of friction in a lab according to the first example embodiment of the application.
  • a porous filler may be made by blending an water-borne acrylic polymer emulsion with a series of polyfunctional materials for a sealing layer of a SLF product, which is suitable for filling the porous structure of SLF and useful for preventing household liquids from staining a SLF product; a coating, when applied on SLF, provides a continuous and dense film that may provide better protection for SLF floor against staining from household liquid (such as water, red wine, coffee and ketchup); and the combination of the porous filler and the coating above may form a wear-resistant layer on SLF.
  • the invention is thus achieved on the basis of the above findings.
  • the invention provides a sealing combination for cement substrate or porous structure (widely used for SLF products), which is based on a special water-borne acrylic emulsion formulation and provides low volatile organic components (VOC), low slippery risk, high durability, high resistance to household liquids and good wearing resistance, including: a pore filler layer for sealing the porous structure of SLF to provide water resistance, and a top coat layer for affording durability and anti-scratching performance.
  • VOC volatile organic components
  • the sealing combination comprises the following components:
  • an additive selected from organometallic chelate complex and polyfunctional cros slinking agents for enhancing strength, and
  • additional additives for forming an acceptable film, wherein the additional additives are selected from film-forming auxiliary, defoamer, dispersant, anti-scratching agent and surfactant.
  • the sealing combination may be applied on various geometric surfaces, particularly suitable for cement SLF substrate.
  • the water borne aqueous acrylic matrix exhibits excellent flowability and particular compactness, and shows no surface defects. It has a viscosity of 0.1 ⁇ about lOOOPa *s and is thixotropic. Its solid content is about 20 ⁇ 60wt%. Preferably, the solid content of the pore filler layer is 20-35 wt%, and that of the top coat layer is 25 ⁇ 45wt%.
  • the acrylic matrix is desirably block or graft polymer having a molecular weight of about 60000-800000. Preferably, the molecular weight of the pore filler layer is about 200000-350000, and that of the top coat layer is about
  • the water borne aqueous acrylic matrix is selected from the following polymers and co-polymers: polymethacrylate, poly(styrene acrylate), poly(aromatic acrylate), poly(alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate and mixtures thereof, which are all dispersed in water.
  • a polymeric wax emulsion and various additives may be added into the composition to impart the sealing combination with desirable thixotropic property.
  • the particles in the wax emulsion preferably have an average particle size of 0.1-5 ⁇ .
  • the wax emulsion is added in an amount sufficient to achieve desirable gloss and wear-resistance.
  • the wax emulsion is used in a small amount of no more than 10%, specifically, about 0.5-5% for the pore filler layer and about 2-8% for the top coat layer.
  • polymeric wax emulsions suitable for the invention include: oxidized polyethylene wax (A-C® 316, from Honeywell Co.), high density polyethylene wax emulsion (WE-618B3, from Sino-wax Co.), PTFE wax emulsion (MPF5003, from Joule wax Co.).
  • the functional additives are selected from the group consisting of organometallic chelate complex, polyfunctional crosslinking agent, film-forming auxiliary, defoamer, surfactant and anti-scratching agent.
  • the organometallic chelate complex helps improve the interface behavior of other additives, minimize formation of surface defects and improve the wear-resistance of the composition.
  • organotitanium chelate complex e.g., HY-1803 from Jessica Chem. Co.; TiLCOM TET from Tioxide UK Co.
  • aluminum-zirconium coupling agent e.g. HY-031 from Jessica Chem. Co.
  • concentration of the coupling agent is about 0.1 ⁇ 3wt%, preferably about 0.5-2% for the pore filler layer and about 1-2% for the top coat layer.
  • the polyfunctional crosslinking agent may be added in a large amount to improve the final performances of the composition, including impartment of strength and flexibility, improvement of household liquids resistance, and increase of coating hardness.
  • the crosslinking agent may increase the hardness by at least one level.
  • the film-forming auxiliary may facilitate more continuous formation of film.
  • Some examples of film-forming auxiliary include lactate, 2-butoxyl ethanol, phthalate, ethylene glycol, diethylene glycol, diacetone alcohol, propylene glycol and ethylene glycol phenyl ether.
  • the film-forming auxiliary includes external film-forming auxiliary and internal film-forming auxiliary.
  • External film-forming auxiliary such as 2-butoxyl ethanol may dissolve in the external aqueous phase of the emulsion composition
  • internal film-forming auxiliary such as butyl octyl phthalate may dissolve in the internal phase.
  • Commercially available products including D ALP AD A (from Dow Chemical Co.) and TEXANOL 12 (from Eastman Chemical Co.), may be used in the invention.
  • the defoamer is used to minimize foaming during the process.
  • a variety of defoamers may meet the above requirement.
  • Commercially available defoamer suitable for the invention includes mineral oil-type defoamer (e.g. Colloids 643TM from Colloid Co.), siloxane defoamer (e.g. Bubble Breaker 3056A from Witco Co.).
  • the surfactant may be used to improve the dispersability of the additives and minimize the surface defects of the coating.
  • Henkel 5040 a carboxylate obtained by co-polymerizing acrylate, may be used in the invention.
  • AMP-95 (from ANGUS Chem. Co.) is 2-amino-2-methyl- l-propanol that may be used in the invention as a co- surfactant.
  • anti-scratching agent may strongly enhance surface smoothness, and thus significantly improve substrate wettability.
  • polyether modified polydimethylsiloxane such as commercially available products (BYK-333, from BYK America Co., or BD-3033 from Bald Silicone Co.) may be used as an anti-scratching agent and a second defoamer.
  • composition of the invention may be formulated as follows: first dissolving an organometallic chelate complex in deionized water, followed by addition of an aqueous acrylic substrate with particular solid content; agitating the mixture slowly and adding polymeric wax emulsion; then adding a film-forming auxiliary, a defoamer, a surfactant and an anti-scratching agent into the mixture in sequence; then adding a polyfunctional crosslinking agent; mixing in a planet mixer for 5 minutes with the whole mixing process being carried out preferably at room temperature; and finally filtering the whole mixture using a 150 mesh sieve to separate the unexpected agglomerate.
  • the composition provides a pore filler layer and a top coat layer to fill the porous structure of SLF, prevent staining of SLF products and form a wear-resistant layer to inhibit aging, wearing and staining.
  • a pore filler layer When having lower shear rate and higher molecular weight (generally about 200000-350000), the pore filler layer exhibits significant thixotropic property.
  • the top coat layer has good hardness and high concentration of wax emulsion (preferably about 2-8 wt%).
  • composition of the invention may be applied using various applicators, for example, a coating kit such as 3MTMEasy Shine Applicator System. Alternatively, it may be applied manually using a wax mop. For SLF products, the pore filler layer and the top coat layer may be applied separately for 1-4 times depending on their end use.
  • a coating kit such as 3MTMEasy Shine Applicator System.
  • it may be applied manually using a wax mop.
  • the pore filler layer and the top coat layer may be applied separately for 1-4 times depending on their end use.
  • composition of the invention may form film quickly without the use of any commercially available heaters or ovens. Optimal performances of the composition may be resulted as it actually dries out one week after application.
  • the dried coating has unique and excellent household liquids resistance, no surface defects, better wear resistance and good staining resistance.
  • the invention provides a method for detecting wear on SLF products.
  • the method includes: applying a sealing layer on the SLF product, wearing the sealing layer (exposing the sealing layer to various traffic conditions), indicating with an indicator capable of wetting the worn area, and detecting the wet area by image analysis.
  • the wetting ratio of the sealing layer is obtained by dividing the area occupied by the indicator droplet with the area wetted by the indicator.
  • the indicator is deionized water and controlled with a pipette.
  • the wear degree of the coated surface is correlated with the wetting ratio of the sealing layer.
  • the wearing condition is represented by the wetting ratio on the SLF substrate.
  • the image analysis includes image taking, image treatment and calculation of wetting ratio.
  • the region wetted by the indicator is observable.
  • An observer may be allowed to determine information regarding the surface conditions, including coating coverage of the SLF substrate, wear degree of the substrate, as well as various wearing conditions experienced by the coating on any part of the SLF substrate.
  • the wetting ratio of the sealing layer is obtained from the wetting area of indicator divided by droplet area of indicator. Variation of the wetting ratio indicates that a coating, though still on the SLF substrate, has suffered from different degrees of wearing.
  • the wetting ratio of the coating on the SLF substrate may be determined accurately by a variety of methods.
  • an initial zero wetting ratio measurement is made after applying the composition on the SLF substrate.
  • the zero wetting ratios are successively recorded with the function of pedestrian traffic. It could determine the initial invalidating period of the sealing combination corresponding to the wetting ratio is above zero.
  • the wetting ratio for the region with higher traffic load increases along with traffic conditions. This provides information about the wear degree in the region with higher traffic load and whether the surface needs refinishing.
  • the exposing conditions for wearing the composition of the invention may shorten the testing duration in practical use, and may be used to effect fast simulation of the results for practical use in another method.
  • an overwhelming majority of the liquids with low viscosity may be used as the indicator, among which deionized water controlled with a pipette is preferred.
  • the wetting image may be captured using a macro photographing device, preferably a portable camera.
  • the composition of the invention exhibits such good household liquid resistance that no contaminant has been left on SLF products within 24 hours.
  • the dry film formed from the composition of the invention exhibits such good wear resistance that it can endure most forms of scratching and staining from traffic load.
  • the invention provides a protective coating for self-leveling floor, comprising:
  • a pore filler layer formed on the self-leveling floor, wherein the material used for forming the pore filler layer at least comprises a first aqueous acrylic emulsion
  • top coat layer formed on the pore filler layer, wherein the material used for forming the top coat layer at least comprises a second aqueous acrylic emulsion.
  • the invention provides a method for forming the above protective coating on the self-leveling floor, comprising:
  • first pore filler layer maintaining the first pore filler layer for a period of sufficient to make it dry, and then coating the material used for forming the pore filler layer in the protective layer on the first pore filler layer to form a second pore filler layer, wherein the first and second pore filler layers together constitute the pore filler layer;
  • the sealing combination of the invention may provide performances such as household liquid resistance, improved endurance, resistance to scratching and staining from pedestrian traffic, and reduced necessity of maintenance; may be used to prevent household liquids from staining SLF products; when applied on SLF, may provide a continuous and dense film that may provide better protection for SLF floor against staining from household liquid (such as water, red wine, coffee and ketchup); and may form a wear-resistant layer on SLF.
  • performances such as household liquid resistance, improved endurance, resistance to scratching and staining from pedestrian traffic, and reduced necessity of maintenance
  • when applied on SLF may provide a continuous and dense film that may provide better protection for SLF floor against staining from household liquid (such as water, red wine, coffee and ketchup); and may form a wear-resistant layer on SLF.
  • Henkel 5040 a carboxylate obtained by co-polymerizing acrylate, available from Henkel Co., used as a dispersing aid
  • Bubble Breaker 3056 A siloxane-based defoamer available from Witco Co.
  • D ALP AD A as a film-forming auxiliary
  • 2 parts by weight of BD-3033 poly ether modified polydimethylsiloxane as an anti-scratching agent available from Bald Silicone Co.
  • XAMA ® -7 polyfunctional crosslinking agent available from Bayer Material Science Co.
  • the resultant mixture was further agitated until it was homogeneous.
  • the whole mixing process was carried out at room temperature.
  • the whole mixture was filtered through a 150 mesh sieve to separate off the unwanted agglomerate.
  • the above mixture was used in the sealing combination for the pore filler layer.
  • Henkel 5040 a carboxylate obtained by co-polymerizing acrylate, available from Henkel Co., used as a dispersing aid
  • Bubble Breaker 3056 A siloxane-based defoamer available from Witco Co.
  • D ALP AD A as a film-forming auxiliary
  • BD-3033 poly ether modified polydimethylsiloxane as an anti-scratching agent
  • XAMA ® -7 polyfunctional crosslinking agent available from Bayer Material Science Co.
  • the resultant mixture was further agitated until it was homogeneous.
  • the whole mixing process was carried out at room temperature.
  • the whole mixture was filtered through a 150 mesh sieve to separate off the unwanted agglomerate.
  • the above mixture was used in the sealing combination for the top coat layer.
  • the sealing combination was applied on a SLF substrate using a wax mop to obtain a first pore filler layer, ensuring that the applying place have been covered.
  • a second coating was applied, so that the first pore filler layer was covered and invisible. The interval between these two applications was about 1 hour.
  • the second pore filler layer was allowed to dry until it was not thumb print tacky before applying top coat layer.
  • a first top coat layer was applied on the area covered by the pore filler layer by a wax mop. Before over coating, the first top coat layer was dried for at least 1 hour. Then a second top coat layer was applied.
  • the sealing combination exhibited very good household liquid resistance. It left no contaminant on SLF products within 24 hours. In addition, it showed good wear resistance, scratching resistance and staining resistance.
  • Example 2 Using the method in Example 1, 2 parts by weight of HY-1803 organotitanium chelate complex (available from Jessica Chem. Co.) was dissolved in 55 parts by weight of deionized water. Then, the resultant mixture was added into 100 parts by weight of HD2535 epoxy-functional acrylate emulsion (available from HUA JIN SI Trading Co.).
  • the top coat layer derived from the sealing combination was obtained from a premixture which was prepared by dissolving 3 parts by weight of HY-1803 organotitanium chelate complex (available from Jessica Chem. Co.) in 80 parts by weight of deionized water, adding the resultant mixture into 100 parts by weight of TC 106F water borne urethane-functional acrylic emulsion (available from Tianyin Chemical Co.), and adding into this mixture 8 parts by weight of MPF5003 polytetrafluoroethylene wax emulsion (available from Joule wax Co.), 3 parts by weight of Henkel 5040 (a carboxylate obtained by co-polymerizing acrylate), 1 part by weight of Bubble Breaker 3056 A siloxane-based defoamer, 3 parts by weight of D ALP AD A as a film-forming auxiliary (available from Dow Chemical Co.), 3 parts by weight of BD-3033 polyether modified poly dimethyl siloxane as an anti-scratching agent (available from Bald Silicone
  • Example 1 The sealing combination in Example 1 was evaluated using the method of detecting wear on SLF products. Four coatings (including two pore filler layers and two top coat layers) were applied on a SLF floor using the sealing combination. The floor was exposed to high traffic load in a supermarket. The main load came from moving customers. Two months later, the results were obtained as shown in Fig. 1.
  • Example 3 The same sealing combination as in Example 3 was used, and the floor was exposed to a to-and-fro motion in a lab apparatus.
  • the main wearing source was the stroke of the press head. After 8 hours, the results were obtained as shown in Fig. 2.
  • Comparison of Examples 3 and 4 indicates that, the different exposure condition to wear for the sealing combination of the invention could achieve similar degree of wearing. Therefore, the method of detecting wear on SLF products as described herein may be expanded to establish the correlation between the practical application of the sealing combination and the quick evaluating test for the sealing combination.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention discloses a sealing combination and an application thereof in a self-leveling floor product. The sealing combination includes a pore filler and a surface covering agent, wherein the sealing combination is adapted for forming on a floor surface a protective coating which includes at least one pore filler layer and at least one top coat layer, wherein the pore filler layer is formed on the floor surface directly, and the top coat layer is formed on the pore filler layer directly. The invention further provides an application of the above sealing combination on self-leveling floor products and a method for detecting wear on the self-leveling products.

Description

Sealing Combination and Its Application in a Self-leveling
Floor Product
Technical Field
The invention relates to the field of sealing material, particularly to a high performance sealing combination for use on cement substrate or porous structure widely used on SLF (self-leveling floor) products. The invention further relates to the application of the sealing combination on self-leveling floor products. Background Art
SLF product is a cement-based material which may be formed into a porous hardened material after curing and drying. In order to keep it from aging, wearing and permanent staining from any spilling on it, a sealing layer for a wide variety of uses is required to afford a final application featuring scratch resistance, fouling resistance and good resistance to household liquids.
A solvent borne sealer is thought to be able to permeate more deeply pores and exclude water very well. However, the solvent content (50% to 80% of the total formulation weight) endangers environment and health. A water borne emulsion sealer is usually safer, cheaper and environmental acceptability.
However, while the transformation from organic solvent-based compositions to aqueous compositions brings health and safety benefits, the water borne emulsion compositions should meet or even exceed the performance standards expected from solvent-based compositions.
United States Patent Application No. 5191002A disclosed a floor care maintenance system utilizing a low zinc or phosphate formulation to lessen its environmental impact and provide useful floor care maintenance properties.
European Patent Application No. 1371698A1 disclosed a coating composition for inhibiting the penetration of water into a cementitious material comprising polymeric nano-particles having an average particle diameter between 1 and 50 nm.
However, the prior technical methods mentioned above deal exclusively with
- l - partial performances of a sealing layer and can not satisfy the all-around requirements for a SLF product.
What is desired, therefore, is a coating formulation which can be applied to a SLF product to impart household liquid resistance, improve durability, withstand scratch and fouling from pedestrian traffic and decrease maintenance requirements.
Meanwhile, there exists an urgent need in the art for a method adapted to evaluate the performance of sealing layers changing along with pedestrian traffic. Since these sealing layers are often clean and colorless, it is very difficult to determine the wear degree. The method would be helpful to determine which point of a sealing layer has worn and in need of refinishing. Furthermore, the method could also distinguish the discrepancy of different sealing layers.
Summary of the Invention
An object of this invention is to provide a novel sealing combination to overcome the shortcomings in the prior art.
In one aspect, the invention provides a sealing combination adapted for forming a protective coating on a floor surface, the protective coating comprising at least one pore filler layer and at least one top coat layer, the pore filler layer being formed in direct contact with the floor surface and the top coat layer being formed on the pore filler layer, the sealing combination comprising a pore filler and a surface covering agent, wherein the pore filler is adapted for forming the pore filler layer on the floor surface and comprises the following components:
(al) an aqueous acrylic emulsion comprising acrylic matrix;
(bl) a polymeric wax emulsion;
(cl) an additive; and
(dl) water;
the surface covering agent is adapted for forming the top coat layer on the pore filler layer and comprises the following components:
(a2) an aqueous acrylic emulsion comprising acrylic matrix, wherein the acrylic matrix in the component (a2) is different from the acrylic matrix in the component (al);
(b2) a polymeric wax emulsion; (c2) an additive; and
(d2) water.
In a preferred embodiment, the acrylic matrix in the component (al) has a molecular weight greater than that of the acrylic matrix in the component (a2).
In another preferred embodiment, the acrylic matrix in the component (al) and the acrylic matrix in the component (a2) are block or graft polymers, wherein the molecular weight of the acrylic matrix in the component (al) is 200000-350000, and the molecular weight of the acrylic matrix in the component (a2) is 150000-260000.
In another preferred embodiment, the pore filler comprises the following components:
(al) 20-30 parts by weight of an aqueous acrylic emulsion, wherein the aqueous acrylic emulsion is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly (aromatic acrylate), poly (alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof;
(bl) 0.5-5 parts by weight of a polymeric wax emulsion, wherein the polymeric wax emulsion is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion and synthetic wax emulsion;
(c 1) 1.1-18 parts by weight of an additive; and
(dl) 47-78.4 parts by weight of water.
In another preferred embodiment, the additive (cl) comprises the following components:
(el l) 0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
(cl2) 0.5-1 part by weight of a polyfunctional crosslinking agent, wherein the polyfunctional crosslinking agent is polyfunctional aziridine; and
(cl3) 0.5-3 parts by weight of an anti-scratching agent, at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant and at most 3 parts by weight of a defoamer.
In another preferred embodiment, the anti-scratching agent is selected from poly ether modified polydimethylsiloxane.
In another preferred embodiment, the film forming auxiliary is selected from the group consisting of lactate, 2-butoxyl ethanol, phthalate, ethylene glycol, diethylene glycol, diacetone alcohol, propylene glycol and ethylene glycol phenyl ether.
In another preferred embodiment, the surfactant is selected from acrylate-co-carboxylate and 2-amino-2-methyl-l-propanol.
In another preferred embodiment, the defoamer is selected from mineral oil-type defoamer and siloxane deformer.
In another preferred embodiment, the surface covering agent comprises the following components:
(a2) 20-45 parts by weight of an aqueous acrylic emulsion;
(b2) 2-8 parts by weight of a polymeric wax emulsion;
(c2) 1.6-20 parts by weight of an additive; and
(d2) 27-76.4 parts by weight of water.
In another preferred embodiment, the additive (c2) comprises the following components:
(c21) 0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
(c22) 1-3 parts by weight of a polyfunctional crosslinking agent, wherein the polyfunctional crosslinking agent is polyfunctional aziridine; and
(c23) 0.5-3 parts by weight of an anti-scratching agent, at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant and at most 3 parts by weight of a defoamer.
In another preferred embodiment, the anti-scratching agent is selected from poly ether modified polydimethylsiloxane. In another preferred embodiment, the film forming auxiliary is selected from the group consisting of lactate, 2-butoxyl ethanol, phthalate, ethylene glycol, diethylene glycol, diacetone alcohol, propylene glycol and ethylene glycol phenyl ether.
In another preferred embodiment, the surfactant is selected from acrylate-co-carboxylate and 2-amino-2-methyl-l-propanol.
In another preferred embodiment, the defoamer is selected from mineral oil-type defoamer and siloxane deformer.
In another preferred embodiment, the aqueous acrylic emulsion in the component (al) is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly (aromatic acrylate), poly (alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof.
In another preferred embodiment, the polymeric wax emulsion in the component (a2) is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion and synthetic wax emulsion.
In another preferred embodiment, the aqueous acrylic emulsion in the component (bl) is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly (aromatic acrylate), poly (alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof.
In another preferred embodiment, the polymeric wax emulsion in the component (b2) is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion and synthetic wax emulsion.
In another preferred embodiment, the polymeric wax emulsion comprises particles having an average particle size of 0.1-5 μιη.
In another preferred embodiment, the solid content of the pore filler is 20-35 wt%, and the solid content of the surface covering agent is 25~45wt%. In another preferred embodiment, the thickness of the protective layer is 10~80μιη.
In another preferred embodiment, the pendulum friction coefficient of the protective layer is 45-80.
In another aspect, the invention relates to the use of the above sealing combination in self-leveling floor products.
In still another aspect, the invention provides a method for detecting wear on SLF products, wherein the method comprises:
coating the pore filler in the sealing combination on a self-leveling floor to form a pore filler layer;
coating the surface covering agent in the sealing combination on the pore filler layer to form a top coat layer;
exposing the top coat layer and the pore filler layer thereunder to a wearing condition;
indicating the wear degree with an indicator which permeates and wets the worn area; and
detecting the wetting ratio of the coated surface by image analysis.
In a preferred embodiment, the wearing condition is a simulated traffic load.
In another preferred embodiment, the wearing condition is an experimental scratching test.
In yet another aspect, the invention provides a protective layer for a self-leveling floor, comprising:
a pore filler layer formed on the self-leveling floor, wherein the material used for forming the pore filler layer at least comprises a first aqueous acrylic emulsion; and
a top coat layer formed on the pore filler layer, wherein the material used for forming the top coat layer at least comprises a second aqueous acrylic emulsion;
wherein the first aqueous acrylic emulsion and the second aqueous acrylic emulsion are based on block or graft polymers comprising aqueous acrylic matrices, and the acrylic matrix in the first aqueous acrylic emulsion has a molecular weight greater than that of the acrylic matrix in the second aqueous acrylic emulsion. In a preferred embodiment, the molecular weight of the acrylic matrix in the first aqueous acrylic emulsion is 200000-350000, and the molecular weight of the acrylic matrix in the second aqueous acrylic emulsion is 150000-260000.
In another preferred embodiment, the first aqueous acrylic emulsion is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly (aromatic acrylate), poly (alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof.
In another preferred embodiment, the second aqueous acrylic emulsion is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly(aromatic acrylate), poly(alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof.
In another preferred embodiment, the first aqueous acrylic emulsion is different from the second aqueous acrylic emulsion in their composition.
In another preferred embodiment, the first aqueous acrylic emulsion is 20-30 parts by weight, and the material used for forming the pore filler layer further comprises:
0.5-5 parts by weight of a polymeric wax emulsion, wherein the polymeric wax emulsion is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion and synthetic wax emulsion;
1.1-18 parts by weight of an additive.
In another preferred embodiment, the additive comprises the following components:
0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
0.5-1 part by weight of a polyfunctional crosslinking agent, wherein the polyfunctional crosslinking agent is polyfunctional aziridine; and 0.5-3 parts by weight of an anti-scratching agent, at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant and at most 3 parts by weight of a defoamer.
In another preferred embodiment, the second aqueous acrylic emulsion is 20-45 parts by weight, and the material used for forming the top coat layer further comprises:
2-8 parts by weight of a polymeric wax emulsion, wherein the polymeric wax emulsion is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion, and synthetic wax emulsion;
1.6-20 parts by weight of an additive .
In another preferred embodiment, the additive comprises the following components:
0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
1-3 parts by weight of a polyfunctional crosslinking agent, wherein the polyfunctional crosslinking agent is polyfunctional aziridine; and
0.5-3 parts by weight of an anti-scratching agent, at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant and at most 3 parts by weight of a defoamer.
In another preferred embodiment, the polymeric wax emulsion comprises particles having an average particle size of 0.1-5 μιη.
In another preferred embodiment, the solid content of the pore filler is 20-35 wt%, and the solid content of the surface covering agent is 25~45wt%.
In another preferred embodiment, the thickness of the protective layer is 10~80μιη.
In yet another aspect, the invention provides a method for forming the protective layer on a self-leveling floor, comprising:
coating the material used for forming the pore filler layer in the protective layer on the self-leveling floor to form a first pore filler layer; maintaining the first pore filler layer for a period of sufficient to make it dry, and then coating the material used for forming the pore filler layer in the protective layer on the first pore filler layer to form a second pore filler layer, wherein the first and second pore filler layers together constitute the pore filler layer;
maintaining the second pore filler layer for a period of sufficient to make it dry, and then coating the material used for forming the top coat layer in the protective layer on the second pore filler layer to form a first top coat layer;
maintaining the first top coat layer for a period of sufficient to make it dry, and then coating the material used for forming the top coat layer in the protective layer on the first top coat layer to form a second top coat layer, wherein the first and second top coat layers together constitute the top coat layer; and
maintaining the second top coat layer for a period of sufficient to make it dry.
Brief Description of the Drawings
Fig. 1 illustrates the relationship between wetting ratio and number of customers in a supermarket according to a first example embodiment of the application;
Fig. 2 illustrates the relationship between wetting ratio and times of friction in a lab according to the first example embodiment of the application. Detailed Description of the Invention
After extensive and intensive study, the inventors have found that a porous filler may be made by blending an water-borne acrylic polymer emulsion with a series of polyfunctional materials for a sealing layer of a SLF product, which is suitable for filling the porous structure of SLF and useful for preventing household liquids from staining a SLF product; a coating, when applied on SLF, provides a continuous and dense film that may provide better protection for SLF floor against staining from household liquid (such as water, red wine, coffee and ketchup); and the combination of the porous filler and the coating above may form a wear-resistant layer on SLF. The invention is thus achieved on the basis of the above findings.
According to one aspect, the invention provides a sealing combination for cement substrate or porous structure (widely used for SLF products), which is based on a special water-borne acrylic emulsion formulation and provides low volatile organic components (VOC), low slippery risk, high durability, high resistance to household liquids and good wearing resistance, including: a pore filler layer for sealing the porous structure of SLF to provide water resistance, and a top coat layer for affording durability and anti-scratching performance. Specifically, the sealing combination comprises the following components:
a film forming water borne acrylic matrix,
a polymeric wax emulsion to be mixed with the matrix for providing various gloss and wear-resistance,
an additive selected from organometallic chelate complex and polyfunctional cros slinking agents for enhancing strength, and
one or more additional additives for forming an acceptable film, wherein the additional additives are selected from film-forming auxiliary, defoamer, dispersant, anti-scratching agent and surfactant.
According to the invention, the sealing combination may be applied on various geometric surfaces, particularly suitable for cement SLF substrate.
According to the invention, the water borne aqueous acrylic matrix exhibits excellent flowability and particular compactness, and shows no surface defects. It has a viscosity of 0.1~about lOOOPa *s and is thixotropic. Its solid content is about 20~60wt%. Preferably, the solid content of the pore filler layer is 20-35 wt%, and that of the top coat layer is 25~45wt%. The acrylic matrix is desirably block or graft polymer having a molecular weight of about 60000-800000. Preferably, the molecular weight of the pore filler layer is about 200000-350000, and that of the top coat layer is about
150000-260000.
According to the invention, the water borne aqueous acrylic matrix is selected from the following polymers and co-polymers: polymethacrylate, poly(styrene acrylate), poly(aromatic acrylate), poly(alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate and mixtures thereof, which are all dispersed in water. According to the invention, a polymeric wax emulsion and various additives may be added into the composition to impart the sealing combination with desirable thixotropic property. The particles in the wax emulsion preferably have an average particle size of 0.1-5 μιη. Generally, the wax emulsion is added in an amount sufficient to achieve desirable gloss and wear-resistance. The wax emulsion is used in a small amount of no more than 10%, specifically, about 0.5-5% for the pore filler layer and about 2-8% for the top coat layer.
Examples of some commercially available polymeric wax emulsions suitable for the invention include: oxidized polyethylene wax (A-C® 316, from Honeywell Co.), high density polyethylene wax emulsion (WE-618B3, from Sino-wax Co.), PTFE wax emulsion (MPF5003, from Joule wax Co.).
According to the invention, the functional additives are selected from the group consisting of organometallic chelate complex, polyfunctional crosslinking agent, film-forming auxiliary, defoamer, surfactant and anti-scratching agent.
According to the invention, the organometallic chelate complex (used as coupling agent) helps improve the interface behavior of other additives, minimize formation of surface defects and improve the wear-resistance of the composition. Examples of commercially available organometallic chelate complex suitable for the invention include organotitanium chelate complex (e.g., HY-1803 from Jessica Chem. Co.; TiLCOM TET from Tioxide UK Co.); aluminum-zirconium coupling agent (e.g. HY-031 from Jessica Chem. Co.). The concentration of the coupling agent is about 0.1~3wt%, preferably about 0.5-2% for the pore filler layer and about 1-2% for the top coat layer.
According to the invention, the polyfunctional crosslinking agent may be added in a large amount to improve the final performances of the composition, including impartment of strength and flexibility, improvement of household liquids resistance, and increase of coating hardness. For example, when water borne aqueous acrylic matrix such as poly(styrene acrylate) is used, addition of polyfunctional aziridine (e.g. XAMA®-7 from Bayer Material Science Co., or F-0082 from Yoowe Chemical Co.) as the crosslinking agent may increase the hardness by at least one level.
According to the invention, the film-forming auxiliary may facilitate more continuous formation of film. Some examples of film-forming auxiliary include lactate, 2-butoxyl ethanol, phthalate, ethylene glycol, diethylene glycol, diacetone alcohol, propylene glycol and ethylene glycol phenyl ether. The film-forming auxiliary includes external film-forming auxiliary and internal film-forming auxiliary. External film-forming auxiliary such as 2-butoxyl ethanol may dissolve in the external aqueous phase of the emulsion composition, while internal film-forming auxiliary such as butyl octyl phthalate may dissolve in the internal phase. Commercially available products, including D ALP AD A (from Dow Chemical Co.) and TEXANOL 12 (from Eastman Chemical Co.), may be used in the invention.
According to the invention, the defoamer is used to minimize foaming during the process. A variety of defoamers may meet the above requirement. Commercially available defoamer suitable for the invention includes mineral oil-type defoamer (e.g. Colloids 643™ from Colloid Co.), siloxane defoamer (e.g. Bubble Breaker 3056A from Witco Co.).
According to the invention, the surfactant (or dispersant) may be used to improve the dispersability of the additives and minimize the surface defects of the coating. Henkel 5040, a carboxylate obtained by co-polymerizing acrylate, may be used in the invention. AMP-95 (from ANGUS Chem. Co.) is 2-amino-2-methyl- l-propanol that may be used in the invention as a co- surfactant.
According to the invention, anti-scratching agent may strongly enhance surface smoothness, and thus significantly improve substrate wettability. According to the invention, polyether modified polydimethylsiloxane such as commercially available products (BYK-333, from BYK America Co., or BD-3033 from Bald Silicone Co.) may be used as an anti-scratching agent and a second defoamer.
The composition of the invention may be formulated as follows: first dissolving an organometallic chelate complex in deionized water, followed by addition of an aqueous acrylic substrate with particular solid content; agitating the mixture slowly and adding polymeric wax emulsion; then adding a film-forming auxiliary, a defoamer, a surfactant and an anti-scratching agent into the mixture in sequence; then adding a polyfunctional crosslinking agent; mixing in a planet mixer for 5 minutes with the whole mixing process being carried out preferably at room temperature; and finally filtering the whole mixture using a 150 mesh sieve to separate the unexpected agglomerate.
According to the invention, the composition provides a pore filler layer and a top coat layer to fill the porous structure of SLF, prevent staining of SLF products and form a wear-resistant layer to inhibit aging, wearing and staining. When having lower shear rate and higher molecular weight (generally about 200000-350000), the pore filler layer exhibits significant thixotropic property. The top coat layer has good hardness and high concentration of wax emulsion (preferably about 2-8 wt%).
The composition of the invention may be applied using various applicators, for example, a coating kit such as 3M™Easy Shine Applicator System. Alternatively, it may be applied manually using a wax mop. For SLF products, the pore filler layer and the top coat layer may be applied separately for 1-4 times depending on their end use.
The composition of the invention may form film quickly without the use of any commercially available heaters or ovens. Optimal performances of the composition may be resulted as it actually dries out one week after application. The dried coating has unique and excellent household liquids resistance, no surface defects, better wear resistance and good staining resistance.
In another aspect, the invention provides a method for detecting wear on SLF products. The method includes: applying a sealing layer on the SLF product, wearing the sealing layer (exposing the sealing layer to various traffic conditions), indicating with an indicator capable of wetting the worn area, and detecting the wet area by image analysis. The wetting ratio of the sealing layer is obtained by dividing the area occupied by the indicator droplet with the area wetted by the indicator.
Preferably, the indicator is deionized water and controlled with a pipette.
In the method of the invention, the wear degree of the coated surface is correlated with the wetting ratio of the sealing layer.
According to the invention, the wearing condition is represented by the wetting ratio on the SLF substrate.
According to the invention, the image analysis includes image taking, image treatment and calculation of wetting ratio.
In the above method of the invention, the region wetted by the indicator is observable. An observer may be allowed to determine information regarding the surface conditions, including coating coverage of the SLF substrate, wear degree of the substrate, as well as various wearing conditions experienced by the coating on any part of the SLF substrate. The wetting ratio of the sealing layer is obtained from the wetting area of indicator divided by droplet area of indicator. Variation of the wetting ratio indicates that a coating, though still on the SLF substrate, has suffered from different degrees of wearing.
According to the invention, the wetting ratio of the coating on the SLF substrate may be determined accurately by a variety of methods. In one of such methods, an initial zero wetting ratio measurement is made after applying the composition on the SLF substrate. The zero wetting ratios are successively recorded with the function of pedestrian traffic. It could determine the initial invalidating period of the sealing combination corresponding to the wetting ratio is above zero. This represents the wear resistance of various compositions before wearing. In other methods, the wetting ratio for the region with higher traffic load increases along with traffic conditions. This provides information about the wear degree in the region with higher traffic load and whether the surface needs refinishing. In addition, the exposing conditions for wearing the composition of the invention may shorten the testing duration in practical use, and may be used to effect fast simulation of the results for practical use in another method.
According to the invention, an overwhelming majority of the liquids with low viscosity may be used as the indicator, among which deionized water controlled with a pipette is preferred. The wetting image may be captured using a macro photographing device, preferably a portable camera. The composition of the invention exhibits such good household liquid resistance that no contaminant has been left on SLF products within 24 hours.
The dry film formed from the composition of the invention exhibits such good wear resistance that it can endure most forms of scratching and staining from traffic load.
In another aspect, the invention provides a protective coating for self-leveling floor, comprising:
a pore filler layer formed on the self-leveling floor, wherein the material used for forming the pore filler layer at least comprises a first aqueous acrylic emulsion; and
a top coat layer formed on the pore filler layer, wherein the material used for forming the top coat layer at least comprises a second aqueous acrylic emulsion.
In another aspect, the invention provides a method for forming the above protective coating on the self-leveling floor, comprising:
coating the material used for forming the pore filler layer in the protective layer on the self-leveling floor to form a first pore filler layer;
maintaining the first pore filler layer for a period of sufficient to make it dry, and then coating the material used for forming the pore filler layer in the protective layer on the first pore filler layer to form a second pore filler layer, wherein the first and second pore filler layers together constitute the pore filler layer;
maintaining the second pore filler layer for a period of sufficient to make it dry, and then coating the material used for forming the top coat layer in the protective layer on the second pore filler layer to form a first top coat layer;
maintaining the first top coat layer for a period of sufficient to make it dry, and then coating the material used for forming the top coat layer in the protective layer on the first top coat layer to form a second top coat layer, wherein the first and second top coat layers together constitute the top coat layer; and
maintaining the second top coat layer for a period of sufficient to make it dry.
The main advantages of the invention lie in that:
the sealing combination of the invention may provide performances such as household liquid resistance, improved endurance, resistance to scratching and staining from pedestrian traffic, and reduced necessity of maintenance; may be used to prevent household liquids from staining SLF products; when applied on SLF, may provide a continuous and dense film that may provide better protection for SLF floor against staining from household liquid (such as water, red wine, coffee and ketchup); and may form a wear-resistant layer on SLF.
Examples
The invention will be further illustrated with reference to the following specific examples. However, it is to be understood that these examples are used only to demonstrate the invention without limiting the scope of the invention. The testing methods in the following examples, for which if no specific conditions are indicated, will be carried out under conventional conditions or under those conditions suggested by the manufacturers. Unless otherwise specified, all percentages and parts are based on weight.
In the examples of the invention, unless otherwise specified, the preparing and applying procedures of the samples, and the detecting of the wetting ratios are carried out at room temperature (23 °C±2°C) and atmospheric pressure. Example 1
First, 3 parts by weight of HY- 1803 organotitanium chelate complex (from Jessica Chem. Co.) was dissolved in 150 parts by weight of deionized water. Then, the transparent solution and 100 parts by weight of YODOSOL AD12S water-borne acrylic emulsion (available from National Starch & Chemical Co.) were placed into a planet mixer. After homogenized, 8 parts by weight of WE-618B3 polymeric wax emulsion (available from Sino-wax Co.) was added to adjust the gloss and wear resistance of the mixture. The mixture was agitated slowly until it was homogeneous. Into this homogeneous mixture were added 3 parts by weight of Henkel 5040 (a carboxylate obtained by co-polymerizing acrylate, available from Henkel Co., used as a dispersing aid), 1 part by weight of Bubble Breaker 3056 A siloxane-based defoamer (available from Witco Co.), 3 parts by weight of D ALP AD A as a film-forming auxiliary (available from Dow Chemical Co.), 2 parts by weight of BD-3033 poly ether modified polydimethylsiloxane as an anti-scratching agent (available from Bald Silicone Co.) and 2 parts by weight of XAMA®-7 polyfunctional crosslinking agent (available from Bayer Material Science Co.). The resultant mixture was further agitated until it was homogeneous. The whole mixing process was carried out at room temperature. Finally, the whole mixture was filtered through a 150 mesh sieve to separate off the unwanted agglomerate. The above mixture was used in the sealing combination for the pore filler layer.
Using the procedure as described above, 3 parts by weight of HY-1803 organotitanium chelate complex (available from Jessica Chem. Co.) was dissolved in 81 parts by weight of deionized water. Then, the transparent solution and 100 parts by weight of TC 106F water borne urethane-functional acrylic emulsion (containing fluoropolymer particles, available from Tianyin Chemical Co.) were placed into a planet mixer. After homogenized, 8 parts by weight of WE-618B3 polymeric wax emulsion (available from Sino-wax Co.) was added to adjust the gloss and wear resistance of the mixture. The mixture was agitated slowly until it was homogeneous. Into this homogeneous mixture were added 3 parts by weight of Henkel 5040 (a carboxylate obtained by co-polymerizing acrylate, available from Henkel Co., used as a dispersing aid), 1 part by weight of Bubble Breaker 3056 A siloxane-based defoamer (available from Witco Co.), 3 parts by weight of D ALP AD A as a film-forming auxiliary (available from Dow Chemical Co.), 3 parts by weight of BD-3033 poly ether modified polydimethylsiloxane as an anti-scratching agent (available from Bald Silicone Co.) and 3 parts by weight of XAMA®-7 polyfunctional crosslinking agent (available from Bayer Material Science Co.). The resultant mixture was further agitated until it was homogeneous. The whole mixing process was carried out at room temperature. Finally, the whole mixture was filtered through a 150 mesh sieve to separate off the unwanted agglomerate. The above mixture was used in the sealing combination for the top coat layer.
Subsequently, the sealing combination was applied on a SLF substrate using a wax mop to obtain a first pore filler layer, ensuring that the applying place have been covered. A second coating was applied, so that the first pore filler layer was covered and invisible. The interval between these two applications was about 1 hour. The second pore filler layer was allowed to dry until it was not thumb print tacky before applying top coat layer. A first top coat layer was applied on the area covered by the pore filler layer by a wax mop. Before over coating, the first top coat layer was dried for at least 1 hour. Then a second top coat layer was applied.
The sealing combination exhibited very good household liquid resistance. It left no contaminant on SLF products within 24 hours. In addition, it showed good wear resistance, scratching resistance and staining resistance.
Example 2
Using the method in Example 1, 2 parts by weight of HY-1803 organotitanium chelate complex (available from Jessica Chem. Co.) was dissolved in 55 parts by weight of deionized water. Then, the resultant mixture was added into 100 parts by weight of HD2535 epoxy-functional acrylate emulsion (available from HUA JIN SI Trading Co.). Into this mixture were added premixture of 5 parts by weight of WE-618B3 polymeric wax emulsion (available from Sino-wax Co.), 2 parts by weight of Henkel 5040 (a carboxylate obtained by co-polymerizing acrylate), 1 part by weight of Bubble Breaker 3056A siloxane-based defoamer, 2 parts by weight of DALPAD A as a film-forming auxiliary (available from Dow Chemical Co.) and 2 parts by weight of XAMA®-7 polyfunctional crosslinking agent (available from Bayer Material Science Co.). The above mixture was used in the sealing combination for the pore filler layer.
The top coat layer derived from the sealing combination was obtained from a premixture which was prepared by dissolving 3 parts by weight of HY-1803 organotitanium chelate complex (available from Jessica Chem. Co.) in 80 parts by weight of deionized water, adding the resultant mixture into 100 parts by weight of TC 106F water borne urethane-functional acrylic emulsion (available from Tianyin Chemical Co.), and adding into this mixture 8 parts by weight of MPF5003 polytetrafluoroethylene wax emulsion (available from Joule wax Co.), 3 parts by weight of Henkel 5040 (a carboxylate obtained by co-polymerizing acrylate), 1 part by weight of Bubble Breaker 3056 A siloxane-based defoamer, 3 parts by weight of D ALP AD A as a film-forming auxiliary (available from Dow Chemical Co.), 3 parts by weight of BD-3033 polyether modified poly dimethyl siloxane as an anti-scratching agent (available from Bald Silicone Co.) and 3 parts by weight of F-0082 polyfunctional crosslinking agent (available from Yoowe Chemica Co.).
Example 3
The sealing combination in Example 1 was evaluated using the method of detecting wear on SLF products. Four coatings (including two pore filler layers and two top coat layers) were applied on a SLF floor using the sealing combination. The floor was exposed to high traffic load in a supermarket. The main load came from moving customers. Two months later, the results were obtained as shown in Fig. 1.
Example 4
The same sealing combination as in Example 3 was used, and the floor was exposed to a to-and-fro motion in a lab apparatus. The main wearing source was the stroke of the press head. After 8 hours, the results were obtained as shown in Fig. 2.
Comparison of Examples 3 and 4 indicates that, the different exposure condition to wear for the sealing combination of the invention could achieve similar degree of wearing. Therefore, the method of detecting wear on SLF products as described herein may be expanded to establish the correlation between the practical application of the sealing combination and the quick evaluating test for the sealing combination.
The documents mentioned above are all incorporated herein by reference in their entirety as if each was incorporated individually. Further, it should be understood, after referring to the above disclosure of this invention, the ordinary skilled technicians in the art should be able to make various changes or modifications to the invention. These equivalent forms also fall into the scope of the attached claims of this application.

Claims

What is claimed is:
1. A sealing combination adapted for forming a protective coating on a floor surface, the protective coating comprising at least one pore filler layer and at least one top coat layer, the pore filler layer being formed in direct contact with the floor surface and the top coat layer being formed on the pore filler layer, the sealing combination comprising a pore filler and a surface covering agent, wherein
the pore filler is adapted for forming the pore filler layer on the floor surface and comprises the following components:
(al) an aqueous acrylic emulsion comprising acrylic matrix;
(bl) a polymeric wax emulsion;
(cl) an additive; and
(dl) water; and
the surface covering agent is adapted for forming the top coat layer on the pore filler layer and comprises the following components:
(a2) an aqueous acrylic emulsion comprising acrylic matrix, wherein the acrylic matrix in the component (a2) is different from the acrylic matrix in the component (al);
(b2) a polymeric wax emulsion;
(c2) an additive; and
(d2) water.
2. The sealing combination of Claim 1, wherein the acrylic matrix in the component (al) has a molecular weight greater than that of the acrylic matrix in the component (a2).
3. The sealing combination of Claim 2, wherein the acrylic matrix in the component (al) and the acrylic matrix in the component (a2) are block or graft polymers, and the molecular weight of the acrylic matrix in the component (al) is 200000-350000 while the molecular weight of the acrylic matrix in the component (a2) is 150000-260000.
4. The sealing combination of Claim 1, wherein the pore filler comprises the following components: (al) 20-30 parts by weight of an aqueous acrylic emulsion;
(bl) 0.5-5 parts by weight of a polymeric wax emulsion;
(cl) 1.1-18 parts by weight of an additive; and
(dl) 47-78.4 parts by weight of water.
5. The sealing combination of Claim 1, wherein the additive (cl) comprises the following components:
(el l) 0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
(cl2) 0.5-1 part by weight of a polyfunctional crosslinking agent, wherein the polyfunctional crosslinking agent is polyfunctional aziridine; and
(cl3) 0.5-3 parts by weight of an anti-scratching agent, at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant and at most 3 parts by weight of a defoamer.
6. The sealing combination of Claim 5, wherein the anti-scratching agent is selected from polyether modified polydimethylsiloxane.
7. The sealing combination of Claim 5, wherein the film forming auxiliary is selected from the group consisting of lactate, 2-butoxyl ethanol, phthalate, ethylene glycol, diethylene glycol, diacetone alcohol, propylene glycol and ethylene glycol phenyl ether.
8. The sealing combination of Claim 5, wherein the surfactant is selected from acrylate-co-carboxylate and 2-amino-2-methyl-l-propanol.
9. The sealing combination of Claim 5, wherein the defoamer is selected from mineral oil-type defoamer and siloxane deformer.
10. The sealing combination of Claim 1, wherein the surface covering agent comprises the following components:
(a2) 20-45 parts by weight of an aqueous acrylic emulsion;
(b2) 2-8 parts by weight of a polymeric wax emulsion;
(c2) 1.6-20 parts by weight of an additive; and (d2) 27-76.4 parts by weight of water.
11. The sealing combination of Claim 1, wherein the additive (c2) comprises the following components:
(c21) 0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
(c22) 1-3 parts by weight of a polyfunctional crosslinking agent, wherein the polyfunctional crosslinking agent is selected from polyfunctional aziridine; and
(c23) 0.5-3 parts by weight of an anti-scratching agent, at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant and at most 3 parts by weight of a defoamer.
12. The sealing combination of Claim 11, wherein the anti-scratching agent is a poly ether modified polydimethylsiloxane.
13. The sealing combination of Claim 11, wherein the film forming auxiliary is selected from the group consisting of lactate, 2-butoxyl ethanol, phthalate, ethylene glycol, diethylene glycol, diacetone alcohol, propylene glycol and ethylene glycol phenyl ether.
14. The sealing combination of Claim 11, wherein the surfactant is selected from the group consisting of acrylate-co-carboxylate and 2-amino-2-methyl-l-propanol.
15. The sealing combination of Claim 11, wherein the defoamer is selected from the group consisting of mineral oil-type defoamer and siloxane deformer.
16. The sealing combination of Claim 1, wherein the aqueous acrylic emulsion in the component (al) is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly(aromatic acrylate), poly(alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers, and mixtures thereof.
17. The sealing combination of Claim 1, wherein the polymeric wax emulsion in the component (a2) is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, PTFE wax emulsion, silicone emulsion and synthetic wax emulsion.
18. The sealing combination of Claim 1, wherein the aqueous acrylic emulsion in the component (bl) is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly(aromatic acrylate), poly(alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers and mixtures thereof.
19. The sealing combination of Claim 1, wherein the polymeric wax emulsion in the component (b2) is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion and synthetic wax emulsion.
20. The sealing combination of Claim 1, wherein the polymeric wax emulsion comprises particles having an average particle size of 0.1-5 μιη.
21. The sealing combination of Claim 1, wherein the solid content of the pore filler is 20-35 wt%, and the solid content of the surface covering agent is 25-45 wt%.
22. The sealing combination of Claim 1, wherein the thickness of the protective layer is 10~80μιη.
23. The sealing combination of Claim 1, wherein the pendulum friction coefficient of the protective layer is 45-80.
24. An application of the sealing combination of any one of Claims 1-23 in a self-leveling floor product.
25. A method for detecting wear of a protective layer formed by applying a sealing combination as claimed in any of claims 1-24 on a floor surface comprising:
coating the pore filler on a self-leveling floor to form a pore filler layer;
coating the surface covering agent in the sealing combination of any one of Claims 1-24 on the pore filler layer to form a top coat layer;
exposing the top coat layer and the pore filler layer thereunder to a wearing condition;
indicating the wear degree with an indicator which permeates and wets the worn area; and detecting the wetting ratio of the coated surface by image analysis.
26. The method of Claim 25, wherein the wearing condition is a simulated traffic load.
27. The method of Claim 26, wherein the wearing condition is an experimental scratching test.
28. A protective layer adapted for a self-leveling floor, comprising
a pore filler layer formed on the self-leveling floor, wherein the material used for forming the pore filler layer at least comprises a first aqueous acrylic emulsion; and
a top coat layer formed on the pore filler layer, wherein the material used for forming the top coat layer at least comprises a second aqueous acrylic emulsion;
wherein the first aqueous acrylic emulsion and the second aqueous acrylic emulsion are based on block or graft polymers comprising aqueous acrylic matrices, and the acrylic matrix in the first aqueous acrylic emulsion has a molecular weight greater than that of the acrylic matrix in the second aqueous acrylic emulsion.
29. The protective layer of Claim 28, wherein the molecular weight of the acrylic matrix in the first aqueous acrylic emulsion is 200000-350000, and the molecular weight of the acrylic matrix in the second aqueous acrylic emulsion is 150000-260000.
30. The protective layer of Claim 28, wherein the first aqueous acrylic emulsion is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly(aromatic acrylate), poly(alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers, and mixtures thereof.
31. The protective layer of Claim 28, wherein the second aqueous acrylic emulsion is selected from the group consisting of polymethacrylate, poly(styrene acrylate), poly(aromatic acrylate), poly(alkyd acrylate), epoxy-functional acrylate, urethane-functional acrylate, hydroxyl functional acrylate, self-crosslinking acrylate, and copolymers, and mixtures thereof.
32. The protective layer of Claim 28, wherein the first aqueous acrylic emulsion is different from the second aqueous acrylic emulsion in their compositions.
33. The protective layer of Claim 28, wherein the first aqueous acrylic emulsion is 20-30 parts by weight, and the material used for forming the pore filler layer comprises:
0.5-5 parts by weight of a polymeric wax emulsion, wherein the polymeric wax emulsion is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion, and synthetic wax emulsion; and
1.1-18 parts by weight of an additive.
34. The protective layer of Claim 33, wherein the additive comprises the following components:
0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent;
0.5-1 part by weight of a polyfunctional crosslinking agent, wherein the polyfunctional crosslinking agent is selected from polyfunctional aziridine; and
0.5-3 parts by weight of an anti-scratching agent, at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant, and at most 3 parts by weight of a defoamer.
35. The protective layer of Claim 28, wherein the second aqueous acrylic emulsion is 20-45 parts by weight, and the material used for forming the top coat layer comprises:
2-8 parts by weight of a polymeric wax emulsion, wherein the polymeric wax emulsion is selected from the group consisting of oxidized polyethylene wax emulsion, paraffin emulsion, high density polyethylene wax emulsion, polytetrafluoroethylene wax emulsion, silicone emulsion, and synthetic wax emulsion; and
1.6-20 parts by weight of an additive.
36. The protective layer of Claim 35, wherein the additive comprises the following components:
0.1-3 parts by weight of an organometallic chelate complex, wherein the organometallic chelate complex is selected from organotitanium chelate complex and aluminum-zirconium coupling agent; 1-3 parts by weight of a polyfunctional crosslinking agent, wherein the polyfunctional crosslinking agent is polyfunctional aziridine; and
0.5-3 parts by weight of an anti-scratching agent, at most 5 parts by weight of a film forming auxiliary, at most 3 parts by weight of a surfactant and at most 3 parts by weight of a defoamer.
37. The protective layer of Claim 28, wherein the polymeric wax emulsion comprises particles having an average particle size of 0.1-5 μιη.
38. The protective layer of Claim 28, wherein the solid content of the pore filler is 20-35 wt%, and the solid content of the surface covering agent is 25-45 wt%.
39. The protective layer of Claim 28, wherein the thickness of the protective layer is 10~80μηι.
40. A method for forming the protective layer of any one of Claims 28-39 on a self-leveling floor, comprising:
coating the material used for forming the pore filler layer in the protective layer of any one of Claims 28-39 on the self-leveling floor to form a first pore filler layer;
maintaining the first pore filler layer for a period of sufficient to make it dry, and then coating the material used for forming the pore filler layer in the protective layer of any one of Claims 28-39 on the first pore filler layer to form a second pore filler layer, wherein the first and the second pore filler layers together constitute the pore filler layer; maintaining the second pore filler layer for a period of sufficient to make it dry, and then coating the material used for forming the top coat layer in the protective layer of any one of Claims 28-39 on the second pore filler layer to form a first top coat layer; maintaining the first top coat layer for a period of sufficient to make it dry, and then coating the material used for forming the top coat layer in the protective layer of any one of Claims 28-39 on the first top coat layer to form a second top coat layer, wherein the first and second top coat layers together constitute the top coat layer; and maintaining the second top coat layer for a period of sufficient to make it dry.
PCT/CN2011/084799 2010-12-31 2011-12-28 Sealing combination and its application in a self-leveling floor product WO2012089120A1 (en)

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CN102094514A (en) * 2010-12-31 2011-06-15 圣戈班研发（上海）有限公司 Sealing agent composition and application thereof to self-leveling ground product
CN102633533B (en) * 2012-04-17 2013-11-27 滨州学院 Cement concrete penetration repair cream
CN103382331B (en) * 2013-07-08 2015-12-23 四川亿欣新材料有限公司 Automobile water-based property resistance to broken fall coating
CN109082174A (en) * 2018-08-13 2018-12-25 上海英诺威新材料科技有限公司 High performance floor coatings
CN110815961A (en) * 2019-11-18 2020-02-21 天津市嘉惠宝地毯有限公司 Carpet with good antistatic performance

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