WO2001074930A1 - Compositions polymeres reticulables en emulsion - Google Patents

Compositions polymeres reticulables en emulsion Download PDF

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WO2001074930A1
WO2001074930A1 PCT/US2001/010785 US0110785W WO0174930A1 WO 2001074930 A1 WO2001074930 A1 WO 2001074930A1 US 0110785 W US0110785 W US 0110785W WO 0174930 A1 WO0174930 A1 WO 0174930A1
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polymer
composition
latex
group
amine
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PCT/US2001/010785
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WO2001074930A8 (fr
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Chia-Chen Lo
Michael Charles Kaufman
William Charles Arney, Jr.
David Robinson Bassett
Richard D. Jenkins
Teong L. Chan
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Union Carbide Chemicals & Plastics Technology Corporation
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Priority to AU2001253109A priority Critical patent/AU2001253109A1/en
Publication of WO2001074930A1 publication Critical patent/WO2001074930A1/fr
Publication of WO2001074930A8 publication Critical patent/WO2001074930A8/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation

Definitions

  • the present invention generally relates to emulsion polymers and more specifically relates to emulsion polymer compositions which are crosslinkable.
  • Crosslinking of polymer coatings typically enhances the coating's cohesive strength, abrasion resistance, chemical resistance, and exterior durability.
  • a common way to crosslink a polymer is to react a functional group containing reactive polymer with an external multifunctional crosslinker.
  • the external crosslinker can be pre-mixed with the reactive polymer (commonly called a one-package system) or, alternatively, it can be mixed with the reactive polymer immediately prior to the application (commonly called a two-package system).
  • One package systems are often desired because of their simplicity and ease of handling.
  • 5,536,784 discloses the reaction of activated keto methylene groups with araldimines wherein both funtionalities are covalently bonded to polymer backbones.
  • Araldimines are amines blocked by reaction with aromatic aldehydes.
  • U.S. Patent No. 4,772,680 and EP 0 199 087 Al disclose a reaction between keto or aldehyde groups bonded to polymer backbones and amines blocked with ketones or aldehydes.
  • use of blocked amines is typically not desirable because the organic moiety used as the blocking agent is released on curing contributing to the release of volatile organic compounds to the environment.
  • U.S. Patent No. 4,988,762 discloses emulsion polymer particles wherein both reactive groups are on the same polymer chains throughout the latex particle or are on separate polymer chains with the different chains being separated by a core-shell particle morphology. Presumably, premature reaction does not occur because extensive mixing of the polymer chains is required for significant reaction, and this does not occur within a latex particle because of extremely high viscosity within the particle.
  • a disadvantage of this approach is that complete mixing of multiple particles as the coating dries is similarly difficult. See, e.g., p. 114 of J. M. Geurts, J. J. G. S. Van Es, A. L. German; Progress in Organic Coatings, 29, (1996) 107 - 115.
  • WO 97/45490 and WO 98/52980 disclose the use of latexes containing particles containing polymer covalently linked to poly(alkylenimine) groups and particles containing polymers with ketimine functionality. On drying, the particles come into contact and crosslinking can occur. However, this system suffers the disadvantage that it is unstable unless the pH is greater than about 10. See WO 99/14278. Also, such highly caustic latexes can damage skin. Moreover, if the pH is attained by use of the required levels of ammonia or organic amines, noxious and/or polluting materials are released to the environment.
  • crosslinkable coating compositions i.e., one package systems, which are stable in storage and can be crosslinked at ambient and elevated temperatures during or after application to a substrate by crosslinking reactions that preferably do not produce noxious and/or polluting by-products. Furthermore, it is desired that such compositions have low toxicity, and allow properties of coatings made from the compositions to be tailored to fit end-use needs.
  • compositions comprising crosslinkable emulsion polymers are provided.
  • the compositions comprise a blend of a first emulsion polymer having amine groups and a second emulsion polymer having functional groups which are reactive with the amine groups.
  • crosslinkable emulsion polymer compositions which can remain stable during long storage periods e.g., one year or longer. More specifically, when in the emulsion form, i.e., particulate form, the particles which comprise the first polymer are not attracted to particles which comprise the second polymer, thereby leading to little interaction between the reactive groups. As a result, premature crosslinking of the polymer particles during storage can be avoided. Quite desirably in accordance with the present invention, crosslinking occurs during or after film formation of the polymer.
  • compositions of the present invention are useful in a variety of applications including, for example, coatings, adhesives, caulks, sealants, additives and modifiers where properties such as cohesive strength, abrasion resistance, block resistance, chemical resistance, mechanical strength and exterior durability of polymers are often desired.
  • the monomers suitable for making the polymers of the present invention can be any ethylenically unsaturated monomers which comprise or which can be derivatized to comprise the desired amine functionality, or amine-reactive functionality, in accordance with the invention.
  • Typical monomers include vinyl monomers and acrylic monomers.
  • the vinyl monomers suitable for use in accordance with the present invention include any compounds having vinyl functionality, i.e., ethylenic unsaturation, exclusive of compounds having acrylic functionality, e.g., acrylic acid, methacrylic acid, esters of such acids, acrylonitrile and acrylamides.
  • the vinyl monomers are selected from the group consisting of vinyl esters, vinyl aromatic hydrocarbons, vinyl aliphatic hydrocarbons, vinyl alkyl ethers and mixtures thereof.
  • Suitable vinyl monomers include vinyl esters, such as, for example, vinyl propionate, vinyl laurate, vinyl pivalate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl butyrates, vinyl benzoates, vinyl isopropyl acetates and similar vinyl esters; vinyl aromatic hydrocarbons, such as, for example, styrene, methyl styrenes and similar lower alkyl styrenes, chlorostyrene, vinyl toluene, vinyl naphthalene and divinyl benzene; vinyl aliphatic hydrocarbon monomers, such as, for example, vinyl chloride and vinylidene chloride as well as alpha olefins such as, for example, ethylene, propylene, isobutylene, as well as conjugated dienes such as 1,3 butadiene, methyl-2-butadiene, 1,3-piperylene, 2,3-dimethyl butadiene, isoprene,
  • the acrylic monomers suitable for use in accordance with the present invention comprise any compounds having acrylic functionality.
  • Preferred acrylic monomers are selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylate acids and methacrylate acids as well as aromatic derivatives of acrylic and methacrylic acid, acrylamides and acrylonitrile.
  • the alkyl acrylate and methacrylic monomers (also referred to herein as "alkyl esters of acrylic or methacrylic acid”) will have an alkyl ester portion containing from 1 to about 12, preferably about 1 to 5, carbon atoms per molecule.
  • Suitable acrylic monomers include, for example, methyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, propyl acrylate and methacrylate, 2 -ethyl hexyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, decyl acrylate and methacrylate, isodecyl acrylate and methacrylate, benzyl acrylate and methacrylate, isobornyl acrylate and methacrylate, neopentyl acrylate and methacrylate, 1-adamatyl methacrylate and various reaction products such as butyl, phenyl, and cresyl glycidyl ethers reacted with acrylic and methacrylic acids, hydroxyl alkyl acrylates and methacrylates such as hydroxyethyl and hydroxypropyl acrylates and methacrylates
  • the amount of the particular monomers used to make the first polymer and the second polymer is not critical to the present invention and is dependent on the particular monomers and their intended function, which amount can be determined by those skilled in the art. Typically the amount of each monomer ranges from about 0.1 to 99 weight percent and more typically from about 0.5 to 80 weight percent based on the total weight of the monomers used to make the polymer.
  • the amine groups which are comprised in the first polymer may be present on one or more monomers used to polymerize the first polymer, or alternatively, may be incorporated into the polymer after polymerization by derivatizing the polymer.
  • the amine groups are primary amine groups or secondary amine groups. It is also preferred that the amine not be a blocked amine, i.e., does not have a nitrogen-carbon double bond.
  • the amine functionality is introduced into the first polymer by an imination reaction involving carboxyl (or carboxylate salt) groups of the precursor polymer and an added aziridine compound.
  • the aziridine compound is commonly referred to as an alkylene imine and preferably has the formula H
  • Rl and R ⁇ which may be the same or different are selected from hydrogen, benzyl, aryl, and alkyl of 1 to 5 carbon atoms; and where R ⁇ is hydrogen or alkyl of 1 to 5 carbon atoms. More preferably Rl is hydrogen, R ⁇ is hydrogen or alkyl of 1 to 5 carbon atoms (particularly methyl) and R ⁇ is hydrogen.
  • the corresponding chain-pendant amino ester groups (providing chain- pendant amine functional groups) formed by the imination reaction have the formulae
  • Rl, R ⁇ , and R ⁇ are as defined above (in the case of using ethylene imine, these two formulae will be the same).
  • the amount of alkylene imine used should be sufficient to iminate the desired proportion of the carboxyl groups to aminoalkyl ester groups. Preferably the amount used should be sufficient to iminate about 5% to 95%, preferably 20% to 80%, of the carboxyl groups on the precursor polymer.
  • the amount of aziridine compound generally should not exceed the amount of carboxyl groups on the latex polymer particle on a molar basis. It is preferred that the amount of carboxyl groups on the latex polymer particles is in an excess on a molar basis compared with the amount of aziridine compound to ensure a complete reaction of aziridine compound.
  • a quantitative yield of the primary amine group containing aqueous latex polymer particles can obtained by direct imination in accordance with this invention. Further details of imination reactions are known to those skilled in the art.
  • Monomers which can be used to provide carboxyl groups in the precursor polymer include for example, olefinically unsaturated carboxylic acids, usually of 3 to 6 carbon atoms, especially acrylic acid, methacrylic acid, beta-carboxyethylacrylate, fumaric acid and itaconic acid.
  • the chain-pendant amine functionality may also be introduced into the vinyl polymer by techniques other than imination.
  • the amine precursor groups are oxazoline groups derived from the polymerization of an olefinically unsaturated oxazoline monomer (i.e. an oxazoline having an unsaturated substituent in the 2-position).
  • an olefinically unsaturated oxazoline monomer i.e. an oxazoline having an unsaturated substituent in the 2-position.
  • An example of such a monomer would be 2-isopropenyl oxazoline.
  • Hydrolysis of oxazoline groups in the precursor polymer will yield aminoalkyl ester groups and hence provide chain-pendant amine groups.
  • the amine precursor groups are ketimine groups derived from the polymerization of a ketimine unsaturated monomer.
  • Such monomers can e.g. be produced by first reacting a ketone or aldehyde with an aliphatic amino compound (selected from primary amines, secondary amines, and ethanolamines) to produce a ketimine, and further reacting the ketimine with an ethylenic derivative containing an ethylenically unsaturated group.
  • a ketimine monomer can also be prepared by reacting an amino- containing olefinically unsaturated monomer with ketones or aldehydes (see U.S. Pat. No. 4,328,144). Hydrolysis of ketimine groups in the precursor polymer will generate chain-pendant amine functional groups.
  • hindered amine monomers i.e. olefinically unsaturated monomers bearing amine groups which are in a sterically hindered environment (e.g. by being bonded to a tertiary or perhaps secondary carbon atom).
  • the first emulsion polymer is polymerized from the following monomers:
  • the polymer is derivatized to convert the carboxyl groups to amine groups as described above.
  • the second polymer in accordance with the present invention can be polymerized from any monomers having functional groups which are reactive with the amine groups in the first polymer.
  • functional groups are selected from the group consisting of aldehydes, ketones and oxiranes (also referred to herein as epoxy groups).
  • the functional groups are selected from acetoacetate groups, epoxy groups and mixtures thereof.
  • the epoxy groups are terminal or pendant in structure.
  • Ethylenically unsaturated monomers containing acetoacetate groups useful for the preparation of the second polymer include, but not limited to, vinyl acetoacetate, acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate (AAEM), acetoacetoxypropyl methacrylate (AAPM), allyl acetoacetate, acetoacetoxybutyl methacrylate, 2,3-di(acetoacetoxy) propyl methacrylate, N-(2- acetoacetoxyethyl) acrylamide, and N-(2-acetoacetamidoethyl) methacrylamide .
  • vinyl acetoacetate acetoacetoxyethyl acrylate
  • AAEM acetoacetoxyethyl methacrylate
  • AAPM acetoacetoxypropyl methacrylate
  • allyl acetoacetate acetoacetoxybutyl me
  • Ethylenically unsaturated monomers containing epoxy groups useful for the preparation of the second polymer include, but not limited to, glycidyl acrylate, glycidyl methacrylate, N-glycidyl acrylamide and allyl glycidyl ether.
  • the second emulsion polymer may contain as little as about 0.5 weight percent of the acetoacetate and/or epoxy group containing ethylenically unsaturated monomers to as much as about 45 weight percent or more, based on the total weight of monomers used to make the polymer.
  • the monomers which contain functionality reactive with amine groups may be used individually or in combinations.
  • the acetoacetate and/or epoxy group containing ethylenically unsaturated monomers are preferably present in an amount of from about 1 to 30 weight percent, and more preferably from about 2 to 20 weight percent based on the total weight of monomers.
  • the second emulsion polymer is polymerized from the following monomers:
  • the Tg of the first polymer and the second polymer of the present invention is typically from about -60 to 100°C and more preferably from about -50 to 80 °C. °.
  • x is the weight fraction of component in the copolymer and Tg; is the homopolymer glass transition of component i.
  • the viscosity of the first polymer and the second polymer of the present invention is from about 10 to 3000 and preferably from about 20 to 1500 centipoise ("cP') measured with a 40 to 60 weight percent solids composition using a Brookfield Viscometer with a number 2 spindle at 60 revolutions per minute.
  • cP' centipoise
  • the molecular weight of the first polymer and the second polymer of the present invention is typically from about 10 3 to 10 7 , preferably from about 2,000 to 1,000,000 grams per gram mole.
  • the term "molecular weight” means weight average molecular weight.
  • Techniques for altering molecular weight are well known and include, for example, utilizing multifunctional monomers and chain transfer agents.
  • Techniques for measuring the weight average molecular weight of emulsion polymers is known to those skilled in the art. One such technique is, for example, gel permeation chromatography.
  • the particle size of the first polymer and the second polymer is from about 0.01 to 5 microns, preferably from about 0.02 to 2 microns and more preferably from about 0.02 to 1 microns.
  • the particle size of the first polymer and the second polymer may be different, e.g., one having a small particle size and the other having a large particle size or, alternatively, the particle sizes can be controlled to be nearly identical.
  • the first polymer is substantially free of functional groups which are reactive with amine groups and the second polymer is substantially free of amine groups.
  • substantially free means less than about 5 mole percent, preferably less than about 1 mole percent of the first polymer comprises functional groups which are reactive with amines, and less than about 5 mole percent, preferably less than about 1 mole percent of the second polymer comprises amine groups.
  • the first polymer and second polymer are compatible.
  • the term "compatible" means that the first polymer and second polymer are capable of combining to promote crosslinking when a film is cast of the first polymer and the second polymer.
  • the crosslinking occurs at a temperature in the range of from about 10 to 320°C, more preferably from about 15 to 100°O, and most preferably at ambient conditions, e.g., 25°C.
  • Compatibility in accordance with the present invention can also be evidenced by the degree of light transmission through a film cast from the first polymer and the second polymer wherein the film has a thickness of from about 0.5 mil to 10 mil.
  • the film is translucent, thereby transmitting light so that objects beyond cannot be seen clearly. More preferably, the film is transparent, thereby transmitting light without appreciable scattering so that objects beyond are clearly visible.
  • compatibility of the polymers and hence, crosslinking efficiency can be enhanced by using at least one common monomer in the polymerization of the first polymer and the second polymer.
  • the first polymer and second polymer are polymerized from at least two common monomers.
  • the emulsion polymers in the present invention can be polymerized by any means known to those skilled in the art.
  • the term "emulsion polymer” means a polymer in particulate form comprising a liquid medium.
  • the emulsion polymers are latexes, i.e., polymers polymerized in the presence of water and dispersed in particulate form.
  • the term "emulsion polymer” is intended to include solution polymers which are polymerized in solution form and converted to a dispersion, e.g., such as by the methods described in U.S. Patent No. 5,731,368 issued March 24, 1998.
  • the latex mediums which comprise the emulsion polymers are aqueous, although such liquid mediums may be comprised wholly or partly of other liquids, such as alcohols or hydrocarbons.
  • first polymer and second polymer are not critical to the present invention.
  • first polymer is prepared in a form which comprises carboxyl groups which are then subsequently converted to amine groups.
  • the second polymer is preferable polymerized separately from the first polymer and then subsequently combined to form the compositions of the present invention.
  • the second polymer may be polymerized in the presence of the first polymer or, alternatively, the composition comprising the first polymer may be partly decanted and the second polymerization may be conducted in at least a portion of the liquid medium in which the first polymerization was conducted.
  • the emulsion polymerization may be used to prepare the emulsion polymer of the present invention include semi-batch, staged feed, power feed, full batch, continuous, seeded emulsion polymerization or any other suitable procedure. Any suitable polymerization conditions may be used. Typically, the reaction temperature will range from 0°C to about 100°C, and preferably from about 40°C to about 90°C. The polymerization normally will be conducted using polymerization initiators.
  • Suitable polymerization initiators include, but are not limited to: water-soluble persulfates and peroxides capable of generating free radicals such as ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, peracetic acid, perbenzoic acid, diacetyl peroxide, t-butyl peracetate, t-butyl perbenzoate, and the like; azo initiators, such as 2,2- azobisisobutyronitrile, and the like; and other radiation and transition metal compounds capable of generating free radicals.
  • water-soluble persulfates and peroxides capable of generating free radicals such as ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, peracetic acid, perbenzoic
  • the amount of such free radical initiators used generally ranges from about 0.05% to about 6% by weight based on the weight of all monomers present.
  • redox initiators may be used, especially when polymerization is carried out at lower temperatures.
  • reducing agents may be used in addition to the persulfate and peroxide initiators mentioned above.
  • Typical reducing agents include, but are not limited to: alkali metal salts of hydrosulfites, sulfoxylates, thiosulfates, sulfites, bisulfites, reducing sugar such as glucose, sorbose, ascorbic acid, erythorbic acid, and the like.
  • the reducing agents are used at levels from about 0.01% to about 6% by weight.
  • Suitable surfactants include, but are not limited to, one or more: alkyl and/or aryl sulfates, sulfonates, phosphates, or carboxylates such as sodium lauryl sulfate, sodium salt of alkylaryl polyether sulfates, linear alcohol ethoxylate phosphates, alkylphenol ethoxylate phosphates, and the like; oxyalkylated fatty amines, fatty acid amides and/or monoalkylphenols such as oxyethylated lauryl alcohol, oxyethylated oleyl alcohol, oxyethylated stearyl alcohol, oxythylated p-iso-octylphenol, oxyethylated p-n
  • the reactive surfactants useful in the preparation of the polymers may be any compound which contains ethylenically unsaturated double bonds for free radical reaction with the ethylenically unsaturated monomers during polymerization while also containing hydrophilic and hydrophobic moieties similar to conventional surfactants which impart surface activity.
  • Example of compounds which are useful as reactive surfactants in the present invention include, but not limited to, the compounds prepared by reacting sulfonated half esters of maleic anhydride with alkoxylated alkyl arylols described in U.S. Pat. No.
  • the amount of surfactants may range from about 0.5% to about 15% by weight, and preferably from about 1% to about 7% by weight.
  • Any polymeric stabilizers capable of stabilizing latex particles may be used, these include, but not limited to, cellulose ethers such as hydroxyethyl cellose, alkyl modified hydroxyethyl cellulose, aryl alkyl modified hydroxyethylcellose, carboxymethylcellose, alginate, starch, poly(vinyl alcohol), polyacrylates, polymethacr lates, styrene-maleic anhydride copolymers, polyvinyl pyrrolidones, polyacrylamides, polyethers, and the like.
  • the amount of polymeric stabilizers may range from about 0% to about 25% by weight, and preferably from about 0% to about 5% by weight.
  • a highly reactive one-package aqueous coating system with an excellent storage stability can be made by placing amine reactive functional groups on one latex polymer particle and placing the amine groups on a different latex polymer particle. The two populations of particles can then be readily blended to form a one- package coating system.
  • the latex polymer particles with highly reactive functional groups are separated by charge and/or steric repulsion in aqueous medium resulting in excellent shelf stability.
  • the location of the amine groups on the particles is important to achieving optimum performance.
  • the preferred location of the amine groups is on the surface of the particles.
  • the preferred reactive functional group for the acetoacetate and epoxy group reactions is the primary amine group.
  • the primary amine group containing monomers are generally water soluble. These monomers are prone to aqueous phase homopolymerization to generate water soluble amine containing oligomers and polymers. There are also rearrangement reactions that can occur with common amine containing monomers that destroy the reactivity of the amine. These water soluble oligomers and polymers in the aqueous phase increase the water sensitivity of the polymer film. They can also diffuse into the latex polymer particles and cause premature crosslinking with acetoacetate and/or epoxy groups within the aqueous latex polymer particles.
  • the primary amine group containing ethylenically unsaturated monomers are often unstable in aqueous solution due to acyl migration of the amine groups to form a much less reactive N- hydroxyethyl acrylamide (see J. M. Geurts, J. J. G. S. Van Es, A. L. German; Progress in Organic Coatings, 29, (1996) 107 - 115).
  • the amine functionality is easily oxidizable by the common persulfate and peroxide initiators employed in the manufacturing of the commercial aqueous latex polymer particles. Typically, only less common and expensive azo initiators can be used for reactions with these monomers. Often, much less amine groups can be incorporated into the first polymer particles by copolymerizing with these monomers. The resulting latex polymer particles also often tend to show very little crosslinking reactions with acetoacetate and epoxy groups.
  • the primary amine groups on one set of aqueous latex polymer particles are found very reactive towards the aectoacetate and epoxy functional groups on a different set of aqueous latex polymer particles prepared in the present invention.
  • Water soluble multi-functional amines or water soluble polymeric amines have a tendency to diffuse into the latex polymer particles causing pre-mature crosslinking and weakening the mechanical strength and solvent resistance of the films, as well as causing the gellation of the coating on a prolonged storage.
  • the coatings in the present invention are cost effective, environmental friendly and do not generate toxic byproduct as in the conventional melamine formaldehyde crosslinked coatings, and has a high flexibility for adjusting the desirable properties for specific end applications.
  • the polymer compositions of the present invention are stable for long periods of time, e.g., two months or more, preferably, six months or more, and more preferable one year or more.
  • stable means that the compositions will not exhibit any appreciable crosslinking during storage. Crosslinking can be evidenced by a decrease in MEK Double Rub test, the details of which test are known to those skilled in the art.
  • the emulsion polymer compositions of the present invention can have a variety of end uses including, for example, as protective or decorative coatings, e.g., latex paints, adhesives, e.g., PSA's, and personal care applications, e.g., hair fixatives.
  • protective or decorative coatings e.g., latex paints
  • adhesives e.g., PSA's
  • personal care applications e.g., hair fixatives.
  • caulks and sealants paper coatings, masonry additives, leather applications, textiles such as nonwoven, pigment printing, back coatings and laminatings, as additives to improve the flow of crude oil and middle distillates, in corrosion- resistant primer coatings for metals, adhesives for hard-to-adhere surfaces, such as plastics, e.g., polypropylene and polyvinyl chloride, and in water-proofing coatings for concrete, wood, tile, brick and metal.
  • a preferred end use application for the latex compositions of the present invention is in a latex paint.
  • the amount of latex compositions in the latex paint is at least about 1, preferably about 2 to 50 and most preferably about 3 to 40 weight percent of the total paint composition.
  • the latex paint may also contain from about 20 to 90 weight percent water and from about 0.1 to 10 weight percent of other additives including for example, thickeners, pigments, preservatives, surfactants, dispersants and the like.
  • Typical components include, but are not limited to, one or more of the following: solvents such as aliphatic or aromatic hydrocarbons, alcohols, esters, ketones, glycols, glycol ethers, nitroparaffins or the like; pigments; fillers, dryers, flatting agents; plasticizers; stabilizers; dispersants; surfactants; viscosifiers including other polymeric additives, cellulose ether based thickeners and so on; suspension agents; flow control agents; defoamers; anti-skinning agents; preservatives; extenders; filming aids; other crosslinkers; surface improvers; corrosion inhibitors; and other ingredients useful in latex compositions. Further details concerning the preparation of latex paints are known to those skilled in the art.
  • films made from the latex compositions can have enhanced scrub resistance relative to films made other polymers.
  • scrub resistance means wet abrasion resistance as measured by ASTM D2486-79.
  • PSA's are soft ductile materials which in the dry state are permanently tacky at room temperature and adhere to a variety of surfaces under only slight pressure. They have low glass transition temperature (Tg) less than - 20° C and low to medium molecular weight. These are being increasingly used in consumer, automotive and construction areas. PSA's are generally polymers derived from acrylic, vinyl acetate, ethylene, styrene, butadiene and isoprene type of monomers. In many cases, depending on the nature of base copolymer they are formulated with tackifiers, plasticizers, and curing agents to enhance adhesive properties.
  • a typical PSA end-use system consists of the adhesive, the carrier (polymeric or metallic film or paper backing) and, in many cases, silicone release liner. They find applications in tapes, labels, decals, floor tiles, wall coverings and wood grained film.
  • a typical PSA composition in accordance with the present invention comprises from about 75 to 100 weight percent of the polymer composition, and from about 0 to 25 weight percent of other common ingredients, based on the total weight of the adhesive composition.
  • Other common ingredients found in adhesive compositions include for example, surfactants, defoamers, tackifiers, pigments, plasticizers, etc. Further details concerning the preparation of adhesive compositions are known to those skilled in the art.
  • EXAMPLE 1 This example illustrates the preparation of aqueous latex particles with reactive acetoacetate groups.
  • a reaction kettle was equipped with an agitator, thermocouple, reflux condenser, nitrogen inlet, water jacket, and suitable addition ports.
  • a monomer pre- emulsion was prepared by mixing together 58.38 parts of deionized water, 1.58 parts of a sodium dodecyl benzene sulfonate (Rhodacal DS- 10 supplied by Rhodia Inc.), 2.56 parts of an ethoxylated nonylphenol (Tergitol NP-40 (70AQ) supplied by Union Carbide Corp.), 0.55 part of a 28% solution of ammonium hydroxide, 49.94 parts of n-butyl acrylate, 39.34 parts of methyl methacrylate, 1.34 parts of methacrylic acid, and 9.38 parts of acetoacetoxyethyl methacrylate.
  • the reaction kettle was charged with 65.26 parts of deionized water and was heated to 60°C. A solution of 0.05 part of ammonium persulfate in 1.22 parts of deionized water, 2.24% of the above prepared monomer pre-emulsion, and a solution of 0.04 part of sodium formaldehyde sulfoxylate in 1.22 parts of deionized water were then added to the reaction kettle. The reaction kettle was heated to 70°C with continued agitation and nitrogen purge.
  • This example describes the preparation of an aqueous latex polymer composition with primary amino groups on the surface of the latex particle.
  • the reaction kettle setup described in Example 1 was used.
  • a monomer preemulsion was prepared by mixing together 58.59 parts of deionized water, 0.55 part of a 28% solution of ammonium hydroxide, 1.59 parts of a sodium dedocyl benzene sulfonate (Rhodacal DS-10 supplied by Rhodia Inc.), an ethoxylated nonylphenol (Tergitol NP-40 (70AQ) supplied by Union Carbide Corp.), 50.12 parts of n-butyl acrylate, 44.25 parts of methyl methacrylate, and 5.62 parts of methacrylic acid.
  • the reaction kettle was charged with 65.00 parts of deionized water and was heated to 60°C. A solution of 0.06 part of ammonium persulfate in 1.22 parts of water, 2.25% of the above prepared monomer preemulsion, and a solution of 0.04 part of sodium formaldehyde sulfoxylate in 1.22 parts of deionized water were then charged to the reaction kettle. The reaction kettle was heated to 70°C with continued agitation and nitrogen purge.
  • This example describes the preparation of aqueous latex particles with reactive epoxy groups.
  • the equipment and procedure described in Example 1 were used.
  • a monomer preemulsion was prepared by mixing together 55.87 parts of deionized water, 0.53 part of a 28% ammonium hydroxide solution, 1.52 parts of a sodium dodecyl benzene sulfonate (Rhodacal DS-10 supplied by Rhodia Inc.), 2.44 parts of an ethoxylated nonylphenol (Tergitol NP-40 (70AQ) supplied by Union Carbide Corp.), 51.01 parts of n-butyl acrylate, 38.5 parts of methyl methacrylate, 1.31 parts of methacrylic acid, and 9.18 parts of glycidyl methacrylate.
  • the reaction kettle was charged with 66.77 parts of deionized water and was heated to 60°C. A solution of 0.05 part of ammonium persulfate in 1.19 part of deionized water, 2.21% of the above prepared monomer preemulsion, and a solution of 0.04 part of sodium formaldehyde sulfoxylate in 1.19 part of deionized water were then added to the reaction kettle. The reaction kettle was heated to 70°C with continued agitation and nitrogen purge.
  • This example describes the preparation of a novel one-package, ambient and elevated temperature crosslinkable stable aqueous latex composition with mutually reactive acetoacetate and primary amine functional groups on different latex particles.
  • a 100 parts of latex in Example 2 containing primary amine groups was charged into a container equipped with a variable speed agitator.
  • a 100 parts of the latex in Example 1 containing acetoacetate groups was neutralized to pH 9.1 with ammonium hydroxide and slowly added to the latex in Example 2 with agitation. The latex was let stand to release the foam.
  • a defoamer can be added optionally to accelerate the defoaming process.
  • the properties of the resulting one-package latex with mutually reactive acetoacetate and primary amine functional groups on different latex particles are presented in Table 1.
  • the solvent resistance of the dried film is listed in Table 2 and Table 3.
  • the novel one-package latex with mutually reactive functional groups in Example 4 was highly stable for more than six months without any signs of settlement and coagulation nor any pre-mature crosslinking. The solvent resistance was maintained after prolonged storage.
  • EXAMPLE 5 This example describes the preparation of a novel one-package, ambient and elevated temperature crosslinkable stable aqueous latex composition with mutually reactive epoxy and primary amine groups on different latex particles.
  • a 100 parts latex in Example 2 containing primary amine groups was charged into a container equipped with a variable speed agitator.
  • a 100 parts of the latex in Example 3 containing epoxy groups was neutralized to pH 9.2 with ammonium hydroxide and slowly added to latex in Example 1 with agitation. The latex was let stand to release the foam.
  • a defoamer can be added optionally to accelerate the defoaming process.
  • Table 1 The properties of the resulting one-package latex with mutually reactive epoxy and primary amine functional groups on different latex particles are presented in Table 1.
  • the solvent resistance of the dried film is listed in Table 2 and Table 3.
  • the novel one-package latex with mutually reactive functional groups in Example 5 was highly stable for more than six months without any signs of settlement and coagulation nor ant pre-mature crosslinking. The solvent resistance was maintained after prolonged storage.
  • a common way to examine the solvent resistance of a coating is by wetting the coating with methyl ethyl ketone (MEK) solvent followed by abrading the solvent swelled coating with a mild pressure.
  • MEK methyl ethyl ketone
  • a simple way to examine the solvent resistance is by rubbing a dried coating film with a fiber tipped applicator swab soaked with MEK solvent. A back and forth rubbing is counted as one double-rub. The rubbing process continues until the coating film breaks.
  • the uncrosslinked coating generally dissolves in solvent, thus exhibits week resistance to MEK rubbing. As the polymer chains in a coating film formed a network by crosslinking reaction, the solvent resistance of the coating increases.
  • the solvent resistance of a coating is also effected by the rate of crosslinking reaction, temperature of crosslinking reaction and crosslinking density.
  • the aqueous coating latexes from Example 1 to Example 5 were casted on Leneta charts with a 7-mil draw down bar. The coatings were dried at room temperature for various time and then rubbed with MEK soaked fiber tipped applicator swab. Table 2 shows the solvent resistance of the above prepared aqueous coatings at room temperature crosslinking.
  • Latex (Film dried 1 (Film dried 4 (Film dried day at room days at room 14 days at temperature) temperature) room temperature)
  • the novel one-package aqueous coatings with compatible polymer compositions in this invention as shown in Example 4 and Example 5 crosslinked even at room temperature and showed excellent solvent resistance towards MEK comparing with coatings without crosslinking.
  • a substantial crosslinking and solvent resistance was obtained with relatively short drying time.
  • the solvent resistance further increased as the drying time increased.
  • the results are surprising since most of the conventional wisdom (or theories) predicts that the polymer chain diffusion would be retarded as soon as the two latex particles approaching each other and the first crosslinking reaction occurs at the point of contact.
  • the conventional theories predict that the crosslinking reactions will be severely affected due to a lack of polymer chain diffusion across the interparticle interface resulting in a coating film with inferior solvent resistance.
  • the crosslinking reaction of the novel one-package aqueous coatings in this invention can be accelerated with increasing of crosslinking temperature.
  • the aqueous coating latexes from Example 1 to Example 5 were casted on Leneta charts with a 7-mil draw down bar.
  • the wet coating films were dried at room temperature for 30 minutes to flush off water.
  • the panels were then put in an air- vented 100°C oven for different lengths of time.
  • Table 3 shows the solvent resistance of the novel aqueous coatings of this invention cured at 100°C at different cure time.
  • the crosslinking reaction for the novel one-package aqueous coatings in this invention was extremely fast at 100°C. A substantial crosslinking and solvent resistance were obtained within 10 minutes of cure as shown in Example 4 and Example 5.
  • the primary amine containing latex in Example 2 also showed some self-crosslinking under the high temperature curing.
  • a good stable crosslinkable aqueous coating should exhibit at least six months storage stability without showing any signs of coagulation, agglomeration, pre -mature crosslinking, and losing of the crosslinking efficiency.
  • the pre-mature crosslinking and losing of crosslinking efficiency during storage decrease the crosslinking density of coating film and adversely affecting its solvent resistance.
  • the aqueous coating latexes from Example 1 to Example 4 were stored at room temperature for nine months and were casted on Leneta charts with a 7-mil draw down bar. The coatings were dried at room temperature for various time and then rubbed with MEK soaked fiber tipped applicator swabs. Table 4 shows the solvent resistance of these aged coatings at the room temperature crosslinking.
  • a combination of high crosslinking reactivity with excellent storage stability in a single package coating is difficult to achieve in any coating systems.
  • the novel one-package aqueous coating compositions with mutually reactive functional groups on different latex particles in this invention as shown in Example 4 were perfectly stable after a prolonged storage and showed a surprisingly good crosslinking reactivity without any signs of pre-mature crosslinking of polymers.
  • the rate of crosslinking reaction and solvent resistance for the novel one-package aqueous coatings were maintained even after nine months storage.
  • This example illustrates the preparation of aqueous latex particles with reactive acetoacetate groups.
  • a reaction kettle was equipped with an agitator, thermocouple, reflux condenser, nitrogen inlet, water jacket, and suitable addition ports.
  • a monomer preemulsion was prepared by mixing together 34.13 parts of deionized water, 0.94 parts of a linear alkyl benzene sulfonic acid,0.06 parts of an ethoxylated nonylphenol (Tergitol NP-10 ) supplied by Union Carbide Corp.), 48.25 parts of n-butyl acrylate, 47.75 parts of ethyl acrylate, 4.00 parts acetoacetoxyethyl methacrylate.
  • the reaction kettle was charged with 62.50 parts of deionized water and 0.04 part of sodium bicarbonate, purge nitrogen for 15 minutes then heated to 56°C. 2.00% of the above prepared monomer preemulsion, and solution of 0.10 part of sodium persulfate in 1.33 parts of deionized water, and a solution of 0.10 part of sodium formaldehyde sulfoxylate in 1.33 parts of deionized water were then added to the reaction kettle. After initial reaction, the reaction kettle was control to 55°C with continued agitation.
  • the latex was then cooled to room temperature and adjust with 0.75 part of 28% ammonium hydroxide in 2.50 parts of deionized water to pH 7-8.
  • the properties of the latex obtained are presented in Table 5.
  • the solvent resistance and tensile strength of the dried film is listed in Table 6.
  • EXAMPLE 7 This example describes the preparation of an aqueous latex polymer composition with primary amino groups on the surface of the latex particle.
  • the reaction kettle setup described in Example 6 was used.
  • a monomer preemulsion was prepared by mixing together 34.13 parts of deionized water, 0.94 parts of a linear alkyl benzene sulfonic acid,0.06 parts of an ethoxylated nonylphenol (Tergitol NP-10 supplied by Union Carbide Corp.), 48.25 parts of n-butyl acrylate, 47.75 parts of ethyl acrylate, 4.00 parts methacrylic acid.
  • the reaction kettle was charged with 62.50 parts of deionized water and 0.04 part of sodium bicarbonate, purge nitrogen for 15 minutes then heated to 56°C. 2.00% of the above prepared monomer preemulsion, and solution of 0.10 part of sodium persulfate in 1.33 parts of deionized water, and a solution of 0.10 part of sodium formaldehyde sulfoxylate in 1.33 parts of deionized water were then added to the reaction kettle. After initial reaction, the reaction kettle was control to 55°C with continued agitation.
  • the latex was adjusted to pH 7-8 with 0.75 part of 28% ammonium hydroxide pre- dissolved in 2.5 parts of water. The temperature of the reaction kettle was then raised to 80°C. 0.97 parts of propyleneimine in 2.88 parts of deionized water was added to the reaction kettle through a dropping funnel over a 30 minutes period. The temperature was maintained at 80°C for 60 minutes. A sample was taken to check the residual propyleneimine. When no propyleneimine was detected, a complete propyleneimine was achieved. The latex was then cooled to room temperature. The properties of the latex obtained are presented in Table 5. The solvent resistance and tensile strength of the dried film is listed in Table 6.
  • This example describes the preparation of a conventional one- package self-crosslinking, elevated temperature crosslinkable stable aqueous latex composition with functional monomer N-methylol acrylamide for the comparison studies. This is the most common crosslinker currently being used in textile latexes. This sample act as a control to demonstrate the finished latex solvent up -take and tensile strength of sample 4.
  • a monomer preemulsion was prepared by mixing together 34.13 parts of deionized water, 0.94 parts of a linear alkyl benzene sulfonic acid,0.06 parts of an ethoxylated nonylphenol (Tergitol NP-10 ) supplied by Union Carbide Corp.), 48.25 parts of n- butyl acrylate, 47.75 parts of ethyl acrylate, 6.25 parts of N-methylol acrylamide (48% in aqueous), and 1.25 parts of itaconic acid.
  • the reaction kettle was charged with 62.50 parts of deionized water and 0.04 part of sodium bicarbonate, purge nitrogen for 15 minutes then heated to 56°C.
  • the temperature was maintained at 55°C to 60°C for 30 minutes more after all additions.
  • 0.17 part of t-butyl hydroperoxide in 2.50 parts of deionized water and 0.17 part of sodium formaldehyde sulfoxylate in 2.50 parts of deionized water were added to the reaction kettle over half hour period.
  • the latex was adjusted with ammonium hydroxide to pH 7-8 and cooled to room temperature.
  • the properties of the latex obtained are presented in Table 5.
  • the solvent resistance and tensile strength of the dried film is listed in Table 6 .
  • This example describes the preparation of a novel one- package, ambient and elevated temperature crosslinkable stable aqueous latex composition with mutually reactive acetoacetate and primary amine functional groups on different latex particles.
  • a 100 parts of latex in Example 7 containing primary amine groups was charged into a container equipped with a variable speed agitator.
  • a 100 parts of the latex in Example 6 containing acetoacetate groups was charge into the container with the latex in Example 7, Stir to get homogeneous mix.
  • the latex was let stand to release the foam.
  • a defoamer can be added optionally to accelerate the defoaming process.
  • Table 5 The properties of the resulting one-package latex with mutually reactive acetoacetate and primary amine functional groups on different latex particles are presented in Table 5.
  • the solvent resistance of the dried film is listed in Table 6 and Table 7.
  • the novel one-package latex with mutually reactive functional groups in Example 8 was highly stable for more than six months without any signs of settlement and coagulation nor any pre-mature crosslinking.
  • the solvent resistance was maintained after prolonged storage.
  • Table 7 showed the capability of crosslinking at ambient temperature as well as high temperature.
  • the stability of the latex at 50 °C in oven as well as in ambient temperature showed the invented novel one-pack crosslinked system was stable without any gelation.
  • a common way to examine the solvent resistance of a textile binder is by soaking the cured binder membrane with acetone solvent and water for 24 hours, the solvent uptake was measured in term of weight percentage of the dry binder weight.
  • the solvent uptake is normally at 300-1000% for a crosslinked polymer depending on the type and the dosage of crosslinking monomer and the types of monomer being used in the polymer.
  • a uncrosslinked film will normally dissolved into solution or forming soft gel.
  • latex was pour into a Teflon mold and allowed it to dry to clear film in ambient temperature to form a membrane with thickness approximately 1.0-1.3 mm, it was further cured in oven at 140°C for 3 minutes and removed from oven to cool down for 15 minutes, then a 1 inch by 1 inch sample was cut and weight before soaking in solvent. After soaking for a 24 hours, dry the wet sample by tissue paper and re-weight the sample and the up-take liquid in the membrane was measured and calculated. Latex cured film tensile strength was also measured, it reflexes the degree of crosslinking in a polymer.
  • Table 6 showed the crosslinking capability of Sample 4 at ambient temperature and accelerated higher temperature.
  • Sample 4 the novel one-pack system with compatible polymer composition in this invention as shown in Table 8 is a stable polymer over a period of time without any sign of gelation especially at the accelerated oven test at 50 °C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions polymères en émulsion, comprenant un premier polymère qui renferme des groupes amine, et un second polymère qui renferme des groupes fonctionnels réagissant avec les groupes amine du premier polymère. Ces compositions sont capables de réticulation efficace à des températures ambiantes et élevées, et présentent une résistance excellente à une réticulation prématurée pendant le stockage. Elles sont utiles, par exemple, dans les revêtements, les adhésifs, les matériaux d'étanchéité, les additifs, et les modificateurs. L'invention concerne également des procédés permettant de préparer lesdites compositions.
PCT/US2001/010785 2000-04-04 2001-04-03 Compositions polymeres reticulables en emulsion WO2001074930A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017191131A1 (fr) 2016-05-02 2017-11-09 Allnex Netherlands B.V. Dispersion de polymère anionique à fonctionnalité amine et compositions de revêtement associées
WO2019097041A1 (fr) * 2017-11-20 2019-05-23 Basf Se Latex polymères acryliques aqueux et leur utilisation en tant que liants

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07256206A (ja) * 1994-03-23 1995-10-09 Kawasaki Steel Corp 加熱接着用表面被覆電磁鋼板の製造方法
WO1997045495A1 (fr) * 1996-05-28 1997-12-04 Eastman Chemical Company Utilisation de latex a fonction amino dans des encres a base aqueuse
WO1998052980A1 (fr) * 1997-05-21 1998-11-26 Eastman Chemical Company Procede de preparation de melanges de latex chimiquement et physiquement stables jusqu'a la formation de films
EP0989163A1 (fr) * 1998-09-25 2000-03-29 Akzo Nobel N.V. Composition aqueuse réticulable utilisable dans des revêtements

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07256206A (ja) * 1994-03-23 1995-10-09 Kawasaki Steel Corp 加熱接着用表面被覆電磁鋼板の製造方法
WO1997045495A1 (fr) * 1996-05-28 1997-12-04 Eastman Chemical Company Utilisation de latex a fonction amino dans des encres a base aqueuse
WO1998052980A1 (fr) * 1997-05-21 1998-11-26 Eastman Chemical Company Procede de preparation de melanges de latex chimiquement et physiquement stables jusqu'a la formation de films
EP0989163A1 (fr) * 1998-09-25 2000-03-29 Akzo Nobel N.V. Composition aqueuse réticulable utilisable dans des revêtements

Non-Patent Citations (1)

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Title
DATABASE WPI Section Ch Week 199549, Derwent World Patents Index; Class A14, AN 1995-378924, XP002172953 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017191131A1 (fr) 2016-05-02 2017-11-09 Allnex Netherlands B.V. Dispersion de polymère anionique à fonctionnalité amine et compositions de revêtement associées
WO2019097041A1 (fr) * 2017-11-20 2019-05-23 Basf Se Latex polymères acryliques aqueux et leur utilisation en tant que liants
US11613644B2 (en) 2017-11-20 2023-03-28 Basf Se Aqueous acrylic polymer latexes and their use as binders

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