WO2001042358A1 - Storage stable, foamable, single latex/epoxy emulsion - Google Patents

Storage stable, foamable, single latex/epoxy emulsion Download PDF

Info

Publication number
WO2001042358A1
WO2001042358A1 PCT/US2000/031618 US0031618W WO0142358A1 WO 2001042358 A1 WO2001042358 A1 WO 2001042358A1 US 0031618 W US0031618 W US 0031618W WO 0142358 A1 WO0142358 A1 WO 0142358A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
styrene
acrylic acid
butadiene
latex
Prior art date
Application number
PCT/US2000/031618
Other languages
English (en)
French (fr)
Inventor
James G. Kennedy
Christian Piechocki
Kenneth W. Hester
Paulus C. J. M. Van Bellegem
Original Assignee
Dow Global Technologies Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies Inc. filed Critical Dow Global Technologies Inc.
Priority to CA002392589A priority Critical patent/CA2392589A1/en
Priority to KR1020027007391A priority patent/KR20020064929A/ko
Priority to EP00980476A priority patent/EP1244747A1/en
Priority to JP2001543648A priority patent/JP2003517511A/ja
Priority to BR0016480-1A priority patent/BR0016480A/pt
Priority to AU17731/01A priority patent/AU1773101A/en
Publication of WO2001042358A1 publication Critical patent/WO2001042358A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00Compositions of rubbers containing carboxyl groups
    • C08L13/02Latex
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the invention relates to a novel single latex/epoxy emulsion.
  • Latex foam is a well known material.
  • the latex is in the form of an emulsion when delivered to an end user.
  • the emulsion is employed in the manufacture of flooring, wall covering, shoe lining and non-woven materials.
  • the end user may add fillers to enhance desired properties prior to coating a given substrate with a foam layer made from the emulsion. Since products may be stored for extended periods of time, stable emulsions would be highly desirable. Previous attempts to provide stable emulsions required use of curing pastes, gelling agents, accelerators or stabilizers. Latex emulsions that are stable and that do not require such curing pastes, gelling agents, accelerators or stabilizers would be highly desirable. Especially desirable are latex emulsions that will cross-link in the backing process to ensure final end properties have sufficient strength.
  • the present invention provides a solution to one or more of the disadvantages and deficiencies described above.
  • this invention is an emulsion comprising a latex and an epoxy compound.
  • the latex is preferably a carboxylated styrene-butadiene polymer with a bimodal particle size.
  • the composition may also contain stabilizing surfactants as the cross- linking agent to improve physical properties of the resulting foam.
  • the composition may employ a dual catalyst system.
  • the composition may include performance enhancing additives, such as paraffin wax and silicone detackifier.
  • the latex emulsion may be supplied to the point of manufacture where inorganic or organic filler can be added to enhance desired properties. More advantageously, no additional curing pastes, gelling agents, accelerators or stabilizers are required in the practice of this invention.
  • the emulsion in one non-limiting embodiment, is stable for twelve months at ambient temperatures.
  • the resulting foam will cross-link in the backing process to improve final end properties such that the product has sufficient strength.
  • this invention provides a simplified manufacturing process and need not employ any heavy metals, sulfur or nitrosamine releasing accelerators which are conventionally used for making such foams.
  • this invention is a process useful for forming an article of manufacture comprising applying a foam to a substrate wherein the foam is formed from a composition comprising a bimodal latex and an epoxy emulsion.
  • this invention is a process useful for forming a composition useful for preparing a latex foam, comprising: combining a bimodal latex and an epoxy emulsion.
  • the bimodal latexes used in this invention may be characterized as having two separate and distinct particle size distributions have high solids content, good high shear rheology and good low shear viscosity.
  • the large size polymer particles of the bimodal latex have a heterogeneous character.
  • the bimodal latex used in this invention may comprise a proportion of large size latex particles and a proportion of small size latex particles. It is desirable to employ large size particles whose diameter is in the range of from 2.5 to 10, most preferably from 3 to 4, times that diameter of the small size particles. It is also desirable that the weight percentage of large size particles in the latex formulation exceed the weight percentage of the small size particles.
  • a latex composition comprised substantially of styrene butadiene comprising from 50 to 98, preferably from 60 to 80, weight percent large size particles and from 2 to 50, preferably from 20 to 40, weight percent small size particles can be used. It is understood that the proportion of large size particles and the proportion of small size particles, the size distribution of particles, and the amount of solids in the formulation employed can depend on the particular latex which is employed and/or the particular coating device which is employed.
  • the large size latex particles can vary in size from 1500 A (0.15 micrometers) to 10,000 A (1 micrometer), more preferably from 1800 A (0.18 micrometers) to 3,000 A (0.3 micrometers) in diameter.
  • the small size latex particle can vary in size from 500 A (0.05 micrometers) to 1000 A (0.1 micrometers) , more preferably from 600 A (0.06 micrometers) to 800 A (0.08 micrometers) in diameter.”
  • Heterogeneous polymer particles may be employed in the practice of this invention to provide the large size polymer particles of the bimodal latex.
  • the heterogeneous polymer particles are characterized as having a hard resinous polymer of interpolymer forming a core or core-type region, and a soft preferably interpolymer shell or shell-type region.
  • the coalescence capable heterogeneous polymer particles which particles have hard core or core-type regions and soft shell or shell-type regions.
  • the large size heterogeneous polymer particles have a relatively soft polymer domain and a relatively hard polymer domain. It is believed that the hard polymer domain provides a desirable gloss characteristic to the coating formulation; while the soft, deformable polymer domain provides a desirable binding characteristic to the coating formulation.
  • the heterogeneous polymer particles typically comprise from 10 to 90, preferably 40 to 75 weight percent of a hard polymer domain, and 10 to 90, preferably 25 to 60 weight percent of a soft polymer domain.
  • the hard polymer domain comprises from 80 to 100 weight percent types of monomers (for example, monovinylidene aromatic monomers) which form a hard component of the hard polymer domain when polymerized; from 0 to 20 weight percent, preferably from 10 to 20 weight percent monomers such as open chain aliphatic conjugated diene monomers or other such monomers which when polymerized provide a softening character to the hard domain; and from 0 to 10, preferably 0.5 to 5 weight percent of a hydrophilic, hydrolyzable or ionizable monomer such as acrylic acid.
  • monomers for example, monovinylidene aromatic monomers
  • the soft polymer domain comprises from 30 to 70, preferably 40 to 60 weight percent of a monoethylenically unsaturated monomer which (for example, a monomer which can form a hard component of the polymer domain such as a monovinylidene aromatic monomer, or a monomer which can form a soft component of the soft polymer domain such as an acrylate monomer, or a combination thereof); from 70 to 30, preferably from 60 to 40 weight percent of a soft monomer such as a conjugated open chain diene; and from 0.1 to 10, preferably 2 to 6 weight percent of a hydrophilic, hydrolyzable or ionizable monomer.
  • the minimum film formation temperature of the latex composition is less than about 30°C.
  • Preferred heterogeneous polymer particles comprise carboxylated monovinylidene/conjugated diene containing polymer particles.
  • carboxylated styrene/butadiene containing polymer particles having a heterogeneous character are particularly useful.
  • the small size polymer particles of this invention are prepared from combinations of monomers such that the resulting particles have sufficient adhesive properties for foam coating applications, such as for application to a backing material to provide for example a resilient foam backing layer which is adhered to a second structure, the second structure being the subst-rate for the foam layer.
  • foam coating applications such as for application to a backing material to provide for example a resilient foam backing layer which is adhered to a second structure, the second structure being the subst-rate for the foam layer.
  • Virtually any latex that can be used as a foam coating and can be prepared for use in a bimodal composition can be employed. It is also desirable that the latex be carboxylated in order to increase colloidal stability and, hence, the degree of binding efficiency to the paper and pigments.
  • suitable monomers for providing a carboxylate character include acrylic acid, methacrylic acid, itaconic acid and fumaric acid.
  • the minimum film formation temperature of the latex composition is less than about 25 C.
  • Representative monomers useful in preparing the latexes of this invention and methods for preparing the individual separate particles are described in U.S. Pat. Nos. 3,404,1 16 and 3,399,080.
  • Examples of monomers suitable for preparing the latexes of this invention can include the olefins such as ethylene and propylene, vinyl acetate, alkyl acrylates, hydroxyalkyl acrylates, alkyl methacrylates, hydroxyalkyl methacrylates, acrylamide, n-methyloylacrylamides, as well as monomers such as vinyl chloride and vinylidene chloride.
  • Especially preferred latexes include modified styrene butadiene latexes such as, for example, styrene butadiene/acrylic acid, styrene/butadiene/acrylic acid/itaconic acid, styrene butadiene/vinylidene chloride, styrene/butadiene beta-hydroxyethyl acrylate, styrene/butadiene/beta- hydroxyethylacrylate/acrylic acid, styrene/n-butylacrylate/acrylic acid, methyl methacrylate/n-butylacrylate/acrylic acid, vinyl acetate/acrylic acid, vinyl acetate/n- buty'acrylate/acryiic acid, and/or styrene/n-butyl acrylate/butadiene/acrylic acid.
  • Mixtures of carboxylic acids can be employed in the aforementioned latexes.
  • bimodal latexes can be prepared by intermediate addition of a seed latex during the heterogeneous particle emulsion polymerization process.
  • the core domain of the large size particle can be prepared, and either simultaneously to or after the shell domain of the large size particle is formed, the seed latex can be added in order to provide large size heterogeneous polymer particles having a hard core domain and a soft shell domain, and small size polymer particles having a soft character which is similar to that shell character of the large size particles.
  • the seed latex can be added in order to provide large size heterogeneous polymer particles having a hard core domain and a soft shell domain, and small size polymer particles having a soft character which is similar to that shell character of the large size particles.
  • Any of the latex formulations can be concentrated, if desired.
  • carboxylated latex comprised of a copolymer of a vinyl aromatic monomer and an unsaturated carboxylic acid monomer.
  • the copolymer may further comprise a diene monomer.
  • the vinyl aromatic monomer may be selected from styrene, alpha-methylstyrene, a,r- methylstyrene, a,r-ethylstyrene, alpha-a,r-dimethylstyrene, a,r,a,r-dimethylstyrene, a,r-t- butylstyrene, vinylnaphthalene, methoxystyrene, cyanostyrene, acetylstyrene, monochlorostyrene, dichlorostyrene, and other halostyrenes, and mixtures thereof.
  • the vinyl aromatic monomer may be present in any effective amount.
  • the vinyl aromatic monomer may be present in amounts of from approximately 0 to 75 percent by weight, based on the total weight of the polymer resin. Preferably the vinyl aromatic monomer is present in amounts of from approximately 35 to 70 percent by weight.
  • the ethylenically unsaturated carboxylic acid may be a monocarboxylic acid, or a dicarboxylic acid or a polycarboxylic acid, such as, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, derivatives thereof and mixtures thereof.
  • the ethylenically unsaturated carboxylic acid monomer may be present in amounts of from approximately 0.5 to 25 percent by weight, based on the total weight of the polymeric resin.
  • the ethylenically unsaturated acid monomer is present in amounts of from approximately 1 to 5 percent by weight and, more preferably, from 3 to 5 percent by weight, based on the total weight of the copolymer.
  • the diene monomer when present, may be selected from butadiene, isoprene, divinylbenzene, derivatives thereof and mixtures thereof.
  • the 1,3 -butadiene monomer is preferred.
  • the diene monomer may be present in amounts of from approximately 0 to 85 percent by weight, preferably from approximately 30 to 65 percent by weight, based on the total weight of the polymer resin.
  • the latex may comprise an additional ethylenically unsaturated monomeric component or components.
  • ethylenically unsaturated compounds include methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, phenyl acrylate, acrylonitrile, methacrylonitrile, ethyl- chloroacrylate, diethyl maleate, polyglycol maleate, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide, vinyl methyl ketone, methyl isopropenyl ketone and vinyl ethylester. Derivatives thereof or mixtures thereof may be included.
  • the latex may comprise a styrene/butadiene/-acrylic acid copolymer or a styrene/butadiene/hydroxy-ethylacrylate/itaconic acid copolymer.
  • the latex may also include a mixture of copolymers.
  • a mixture of styrene/butadiene/acrylic acid and styrene/butadiene/-hydroxyethylacrylate/itaconic acid polymers in approximately equal amounts by weight may be used.
  • Such monomers are copolymerized in an aqueous emulsion containing surfactants and modifiers under conditions of time, temperature, pressure and agitation in accordance with well known principles of emulsion polymerization.
  • the epoxy resin component is suitably any compound which possesses more than one 1 ,2-epoxy group.
  • the epoxy resin component is saturated or unsaturated aliphatic or cycloaliphatic, aromatic or heterocyclic and can be substituted or unsubstituted.
  • the epoxy resins may be selected from the polyglycidyl ethers of bisphenol compounds, the polyglycidyl ethers of a novolac resin, and the polyglycidyl ethers of a polyglycol. Mixtures of two or more epoxy resins may also be used.
  • the preferred epoxy resins are the polyglycidyl ethers of bisphenol compounds.
  • the polyglycidyl ethers of bisphenol A or bisphenol F have been found to be suitable.
  • the epoxy resins may be formed as the reaction products of epichlorohydrin and bisphenol A or bisphenol F or derivatives thereof.
  • the epoxy resin component of the curable latex composition may further include an emulsifier or surfactant.
  • An anionic or a nonionic surfactant may be used.
  • a nonionic surfactant is preferred.
  • An ethoxylated nonionic surfactant is more preferred.
  • An ethoxylated nonionic surfactant having an HLB of approximately 16 to 20 is most preferred.
  • the non-ionic surfactant sold under the trade designation "Capcure 65" and available from Diamond Shamrock Corporation has been found to be suitable.
  • the emulsifying agent or surfactant may be present in amounts of from approximately 5 to 10 percent by weight, based on the weight of the epoxy resin.
  • the emulsifying agent or surfactant is present in amounts of from approximately at least 8 percent by weight.
  • the epoxy resin emulsion so formed provides a relatively reduced particle size.
  • the reduced particle size provides an improvement in the stability of the epoxy resin and in turn in the curable latex composition.
  • the epoxy resin and surfactant or emulsifier are homogenized by means of a suitable high shear blender.
  • the particle size of the epoxy resin emulsion thus produced may be approximately two to five times that of tile latex (for example approximately three times that of the latex (for example, less than 1000 nm)). High shear homogenization may continue during phase inversion in order to assist in achieving small particle size.
  • the level of epoxy resin employed will vary over a wide range depending upon the properties of the final product required, as well as the types of epoxy resin and carboxylic acid used.
  • Low viscosity resins are preferred as it is easier to produce a stable emulsion from them.
  • Representative commercial epoxy resins include those sold under the trade designations D.E.R.® 351 -A and D.E.R.® 330 available from The Dow Chemical Company.
  • the epoxy resin emulsion component as described above comprises an organo- soluble or organo-miscible catalyst.
  • Suitable organo-soluble or organo-miscible catalysts include the phosphonium salts, such as, for example, ethyltriphenyl phosphonium acetate and ethyltriphenyl phosphonium phosphate and the quaternary ammonium salts, such as, for example, alkylbenzyl dimethyl ammonium chloride, benzyltrimethyl ammonium chloride, methyltrioctyl ammonium chloride, tetraethyl ammonium bromide, N-dodecyl pyridinium chloride and tetraethyl ammonium iodide.
  • the preferred organo-soluble or organo-miscible catalysts are ethyltriphenyl phosphonium acid acetate, ethyltriphenyl phosphonium phosphate and methyltrioctyl ammonium chloride.
  • Ethyltriphenyl phosphonium phosphate is not readily available but it can be manufactured from ethyltriphenyl phosphonium acetate by reaction with phosphoric acid.
  • the organo-soluble or organo-miscible catalyst may be present in an amount of from approximately 0.1 to approximately 10.0 percent, preferably from 0.3 to 2.0 percent, by weight, based on the weight of the epoxy resin.
  • the water-soluble catalytic curing agent may be present in an amount of from approximately 0.1 to approximately 15 percent by weight, based on the weight of the copolymer.
  • Suitable catalytic curing agents include tridimethyl aminomethyl phenol, dimethyl aminomethyl phenol, dicyandiamide, polyamines such as, for example, ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and isophorone diamine.
  • the curable latex composition according to the present invention may further include standard compounding ingredients such as, for example, fillers, thickening agents, antioxidants, dispersants, pH modifiers and flame retarding agents.
  • standard compounding ingredients such as, for example, fillers, thickening agents, antioxidants, dispersants, pH modifiers and flame retarding agents.
  • An adjustment of the pH of the mixture of the reactive latex and the coreactive material may be made, if desired, by the addition of usual acidifying or alkalizing agents such as, for example, acetic acid, citric acid, dilute mineral acids, ammonium hydroxide and dilute aqueous solutions of alkali metal hydroxides.
  • acidifying or alkalizing agents such as, for example, acetic acid, citric acid, dilute mineral acids, ammonium hydroxide and dilute aqueous solutions of alkali metal hydroxides.
  • the shelf life of the blend of latex and epoxy resin emulsion may be improved by selecting the pH of the blend such that a substantial proportion of the carboxyl groups on the latex copolymer are protonized. It has been found that if the pH is maintained in the range of approximately 6 to 6.5, extended shelf life may be achieved.
  • the pH may be adjusted in any suitable manner. Addition of an approximate amount of ammonia has been found to be suitable for pH adjustment.
  • the epoxy emulsion may comprise additional components and additives.
  • additional components may include, but not limited to, 0.1 to 10 parts per 100 dry parts of a bimodal latex, preferably about 1 to 4 parts of a paraffin wax emulsion to improve cell tack and water resistance.
  • the composition may include from 0.1 to 5 parts, preferably about 1 part, of a cell detackifier, such as a silicone based cell detackifier, used to prevent the cell walls of the foam from sticking together.
  • the composition may include from 0.1 to 5 parts, preferably about 3 parts, of a froth stabilizer such as a suspension of disodium N-cetostearyl sulphosuccinimate.
  • the composition may include from 0.1 to 5 parts, preferably about 1 part, of a froth booster.
  • the composition may include from 0.1 to about 2, preferably about 0.4 part, of a dispersant for any filler, if present, such as a polyphosphate dispersant added to improve dispersion of a inorganic (mineral) filler.
  • the composition may include 0.1 to 5 parts, preferably about 1.5 parts, of a catalyst or dual catalyst which improves curing time during processing, such as a water based mixture composed of 2,4,6-tri(dimethylaminomethyl)phenol and ethtriphenylphosphonium acid ester.
  • the composition may include 0.1 to 2 parts, preferably 0.5 part of ammonium sulfate to reduce viscosity.
  • the composition may include 0.1 to 10 parts, preferably about 4 parts of the epoxy emulsion, which serves as a cross-linker.
  • the composition may include a compound to improve resilience, such as 0.1 to 5 parts, preferably 1.5 parts, of ammonium oleate.
  • the composition may include 0.1 to 5 parts of one or more antioxidants, such as about 1.2 parts of a blend of a polymeric hindered phenol and ditridecyl di thio diproprionate.
  • compositions of this invention may additionally comprise one or more mineral fillers.
  • mineral fillers include those known in the art such as clay, titanium dioxide, carbon, silicates, zinc oxide, calcium carbonate, zinc sulfide, potassium titanate and titanate whiskers, glass flakes, clays, kaolin and glass fibers.
  • the amount of filler which is employed can vary, depending upon the density of the filler and the coating properties desired.
  • Each of the aforementioned components is mixed in an aqueous medium to yield a formulation which is about 10 to about 90 percent solids by weight.
  • the various components of the curable latex compositions of the present invention may be maintained separately until shortly before use because of their ambient temperature curing properties.
  • two or more components which do not react with each other can be premixed.
  • the latex and the water- soluble catalytic curing agent may be provided as one component and the epoxy emulsion containing the organo-soluble or organo-miscible catalyst as the other component.
  • the latex may also be combined with the epoxy emulsion containing the organo-soluble or organo- miscible catalyst and then the water-soluble catalytic curing agent may be added separately immediately prior to use.
  • the composition may be used directly or may be further diluted with water depending on the solids level desired for the particular method of application to be employed.
  • the composition of this invention containing a bimodal latex and an epoxy emulsion may be admixed and stored for long periods of time, for example, up to a year.
  • the curing temperature may be any suitable temperature above ambient temperature. Indeed, some curing may occur at ambient temperature, but since the reaction time is extremely slow, such a temperature is impractical.
  • the preferred temperature range is from approximately 120°C to 180°C.
  • the residence time is variable. Factors influencing residence time include temperature, film thickness, water content and the components of the curable coating composition. With temperatures in that range, a total residence time of approximately five to ten minutes has been found to be suitable.
  • the generality of the invention should not in any way be restricted by theory based on the results of our experiments; however, it can be postulated that the water-soluble catalytic curing agent will to some extent be transferred into the epoxy resin phase upon drying, and promote polymerization of the epoxy resin, as well as carboxyl-epoxy reaction. It also makes the latex more miscible with the epoxy resin.
  • the organic soluble catalyst had shown reasonable activity for the acid-epoxy reaction only, hence resin emulsions pre- catalyzed with the organo-soluble catalyst yield a long shelf life.
  • the organic soluble catalyst also makes the carboxylated latex polymer more miscible with the epoxy resin. It is therefore reasonable to assume, that the latex particles are crosslinked with a built-in network of homopolymerized epoxy resin.
  • the foaming step may be undertaken in any suitable manner conventional manner.
  • a foam or froth may be generated by methods well known in the art, for example by releasing a noncoagulating gas such as nitrogen, or by causing the decomposition of a gas- liberating material to chemically react with an ingredient in the mixture with the liberation of a non-coagulable gas as a reaction product.
  • the mixture of the reactive latex and the coreactive material is also foamed by whipping or by use of apparatus having commercially available foam heads.
  • foaming aids such as sodium lauryl sulfate, or foam stabilizers, such as potassium oleate, may be added if desired.
  • such added materials should be non-reactive with the reactive group in the latex polymer or in the coreactive material and thus the preference may vary with the composition of the mixture.
  • Other soaps, emulsifiers, wetting agents, and surfactants may be used, even though they may be reactive to a limited extent.
  • the frothed mixture may be poured into molds, spread on a flat tray or belt, or coated onto substrates.
  • substrate is defined as any material such as cloth, fabric, leather, wood, glass or metal or any form of backing to which the frothed mixture will adhere when applied and after it is cured.
  • the foam may be applied to the textile prior to drying and curing.
  • a typical froth formed from the continuous foam will have a density in the range of from approximately 200 to 400 grams per liter in its wet state, preferably approximately 350 grams per liter.
  • the foam may be applied to the substrate utilizing a doctor blade.
  • the foam may be dried and cured at a temperature of approximately 110°C to 150°C.
  • the drying and curing may be undertaken in a forced air circulation oven.
  • the internal temperature of the oven should be maintained preferably at or above approximately 120°C.
  • Aerosol 108 surfactant from ICI
  • Disponil TA 430 Henkel
  • Aerosol TO 75 An end epoxy equivalent weight (EEW) value of 500 plus/minus 20 was obtained.
  • the resin product was dispersed in a centrifugal pump to yield an epoxy emulsion having volume average particle size below 0.6 micron; an EEW value of 780-910 and a solid content of 56- 61 percent.
  • An emulsion in accordance with this invention was prepared by admixing the following components: 100 dry parts of a bimodal carboxylated styrene-butadiene latex, 4 parts of a paraffin wax emulsion to improve cell tack and water resistance (IMPERMAX T940, from Govi), 1 part of a silicone based cell detackifier used to prevent the cell walls of the foam from sticking together (PROSIL E70, from Stephenson Brothers), 3 parts of a froth stabilizer (EMPINIM MKB, a suspension of disodium N-cetostearyl sulphosuccinimate, from Albright and Wilson Surfactants Group), 1 part of a froth booster (SLS), 0.4 part of a dispersant for filler (CALGON PT, a polyphosphate dispersant added to improve dispersion of a inorganic filler), 1.5 parts of a dual catalyst which improves curing time during processing (ETPPAAc/Ancamine K54,
  • the emulsion was employed in a foam backing process by combining 100 parts by dry weight of the emulsion of the preceding paragraph and 160 parts by dry weight of calcium carbonate filler to provide a product having a solids content of 78 percent and a viscosity of 3,500 cps (Brookfield spindle 4 at 20 rpm).
  • the filler was employed to improve resilience and strength of the final foam.
  • Calcium carbonate was used as an extender in the foam manufacturing process.
  • the calcium carbonate was preferably selected to be readily dispersible, exhibit low froth viscosity and stability and provide good final foam properties at high loadings of up to 200 parts per 100 parts dry latex.
  • a representative calcium carbonate filler may currently be obtained from Omya as BL 200.
  • the product was mechanically foamed using air to reduce density, spread onto the substrate and the dried in an oven at approximately 140°C to remove the water from the system.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)
PCT/US2000/031618 1999-12-10 2000-11-17 Storage stable, foamable, single latex/epoxy emulsion WO2001042358A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002392589A CA2392589A1 (en) 1999-12-10 2000-11-17 Storage stable, foamable, single latex/epoxy emulsion
KR1020027007391A KR20020064929A (ko) 1999-12-10 2000-11-17 저장 안정한 발포성 단일 라텍스/에폭시 에멀젼
EP00980476A EP1244747A1 (en) 1999-12-10 2000-11-17 Storage stable, foamable, single latex/epoxy emulsion
JP2001543648A JP2003517511A (ja) 1999-12-10 2000-11-17 保存安定性に優れた発泡性単一ラテックス/エポキシエマルション
BR0016480-1A BR0016480A (pt) 1999-12-10 2000-11-17 Emulsão única de latex/epóxi, espumável, estável na armazenagem e seu uso
AU17731/01A AU1773101A (en) 1999-12-10 2000-11-17 Storage stable, foamable, single latex/epoxy emulsion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US17029399P 1999-12-10 1999-12-10
US60/170,293 1999-12-10

Publications (1)

Publication Number Publication Date
WO2001042358A1 true WO2001042358A1 (en) 2001-06-14

Family

ID=22619318

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/031618 WO2001042358A1 (en) 1999-12-10 2000-11-17 Storage stable, foamable, single latex/epoxy emulsion

Country Status (9)

Country Link
EP (1) EP1244747A1 (zh)
JP (1) JP2003517511A (zh)
KR (1) KR20020064929A (zh)
CN (1) CN1409742A (zh)
AR (1) AR026758A1 (zh)
AU (1) AU1773101A (zh)
BR (1) BR0016480A (zh)
CA (1) CA2392589A1 (zh)
WO (1) WO2001042358A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007060462A1 (en) * 2005-11-28 2007-05-31 The University Of Sheffield Particle-stabilised foams
EP1867676A1 (fr) 2006-06-16 2007-12-19 Hutchinson Composition de mastic expansible pour le renforcement structural de corps creux métalliques
CN100387653C (zh) * 2005-08-16 2008-05-14 广东鸿昌化工有限公司 一种单组分自交联环氧丙烯酸复合乳液及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100779883B1 (ko) * 2006-12-19 2007-11-28 제일모직주식회사 토너 및 그 제조방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0245021A2 (en) * 1986-05-02 1987-11-11 The Dow Chemical Company Curable latex composition, films and foams formed therefrom and method for curing the composition
JPH09291484A (ja) * 1996-04-22 1997-11-11 Dainippon Ink & Chem Inc ホットカーペット
US5733944A (en) * 1995-05-26 1998-03-31 Basf Aktiengesellschaft Aqueous polymer dispersions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0245021A2 (en) * 1986-05-02 1987-11-11 The Dow Chemical Company Curable latex composition, films and foams formed therefrom and method for curing the composition
US5733944A (en) * 1995-05-26 1998-03-31 Basf Aktiengesellschaft Aqueous polymer dispersions
JPH09291484A (ja) * 1996-04-22 1997-11-11 Dainippon Ink & Chem Inc ホットカーペット

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199804, Derwent World Patents Index; Class A12, AN 1998-037400, XP002161920 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100387653C (zh) * 2005-08-16 2008-05-14 广东鸿昌化工有限公司 一种单组分自交联环氧丙烯酸复合乳液及其制备方法和应用
WO2007060462A1 (en) * 2005-11-28 2007-05-31 The University Of Sheffield Particle-stabilised foams
EP1867676A1 (fr) 2006-06-16 2007-12-19 Hutchinson Composition de mastic expansible pour le renforcement structural de corps creux métalliques

Also Published As

Publication number Publication date
AU1773101A (en) 2001-06-18
KR20020064929A (ko) 2002-08-10
CN1409742A (zh) 2003-04-09
JP2003517511A (ja) 2003-05-27
CA2392589A1 (en) 2001-06-14
EP1244747A1 (en) 2002-10-02
AR026758A1 (es) 2003-02-26
BR0016480A (pt) 2002-09-10

Similar Documents

Publication Publication Date Title
US4857566A (en) Curable latex composition, films and foams formed therefrom and method for curing the composition
US3215647A (en) Synthetic rubber latex foam containing a coreactive material and process of making same
CA1244569A (en) High solids latexes for paper coatings
EP0031964B1 (en) Sequential emulsion polymerization process for structured particle latex products
US6753355B2 (en) Latex crosslinking with blocked nitrile oxides or epoxy silanes
US5767176A (en) Aqueous dispersion composition containing microcrystalline cellulose and composition using the same
JPH0233042B2 (zh)
JPH0433285B2 (zh)
CN105294947A (zh) 一种造纸用高性能丁苯胶乳的制备方法
EP0245021A2 (en) Curable latex composition, films and foams formed therefrom and method for curing the composition
CN110483676B (zh) 一种多相结构的丁二烯-苯乙烯共聚物胶乳及其制备方法和应用
EP1244747A1 (en) Storage stable, foamable, single latex/epoxy emulsion
US4417016A (en) Frothing aid composition
JPH05311024A (ja) アクリル系フォーム用組成物
JP2000230146A (ja) 制振塗料用水性樹脂組成物
JPH10316715A (ja) エポキシ変性重合体の水性分散液
CN110483673B (zh) 一种纸张涂布用多相结构的丁苯胶乳及其制备方法和应用
JPH11292978A (ja) 樹脂粉末の製造方法および樹脂粉末
KR900007782B1 (ko) 경화성 라텍스 조성물
AU593100B2 (en) Curable latex composition, films and foams formed therefrom and method for curing the composition
JP3700037B2 (ja) 防湿加工用組成物
JP3274760B2 (ja) エステル化ロジン物質の水性分散液
JP3803780B2 (ja) 防湿加工用樹脂組成物
JPH06107910A (ja) エポキシ樹脂組成物、その製造方法および接着剤
JPH0250935B2 (zh)

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2000980476

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2392589

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 17731/01

Country of ref document: AU

ENP Entry into the national phase

Ref country code: JP

Ref document number: 2001 543648

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 008169209

Country of ref document: CN

Ref document number: 1020027007391

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1020027007391

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 10130077

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 2000980476

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 2000980476

Country of ref document: EP