[go: up one dir, main page]

WO1999001505A1 - Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins - Google Patents

Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins Download PDF

Info

Publication number
WO1999001505A1
WO1999001505A1 PCT/US1998/013734 US9813734W WO9901505A1 WO 1999001505 A1 WO1999001505 A1 WO 1999001505A1 US 9813734 W US9813734 W US 9813734W WO 9901505 A1 WO9901505 A1 WO 9901505A1
Authority
WO
WIPO (PCT)
Prior art keywords
paint
coating
acrylic
coatings
pvdf
Prior art date
Application number
PCT/US1998/013734
Other languages
English (en)
French (fr)
Inventor
Scott R. Gaboury
Xavier F. Drujon
Original Assignee
Elf Atochem North America, 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 Elf Atochem North America, Inc. filed Critical Elf Atochem North America, Inc.
Priority to CA002264719A priority Critical patent/CA2264719A1/en
Priority to JP50735699A priority patent/JP2002513442A/ja
Priority to BR9806106-2A priority patent/BR9806106A/pt
Priority to EP98933065A priority patent/EP0932645A4/en
Priority to AU82817/98A priority patent/AU735801B2/en
Priority to EA199900181A priority patent/EA001802B1/ru
Publication of WO1999001505A1 publication Critical patent/WO1999001505A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • This invention relates to compositions of matter classified in the art of chemistry as seed polymers based on fluoropolymers, more specifically homo polymers of vinylidene fluoride (VDF) and copolymers of vinylidene fluoride with comonomers selected from hexafluoropropylene (HFP) tetrafluorethylene (TFE) , chlorotrifluorethylene (CTFE) , trifluoroethylene (TrFE) , and/or vinylfluoride (VF) , in combination with polymers based on acrylic acid, acrylic acid esters, methacrylic acid and/or methacrylic acid esters (acrylic polymers) , to compositions containing them, more specifically to liquid coating compositions containing them, and to processes for the preparation and use of the compositions containing the seed polymers of fluoropolymers and acrylic polymers and " for the use of the fluoropolymers and acrylic polymers combinations themselves.
  • VDF vinylidene fluoride
  • HFP he
  • Coatings made through use of paint binders and paint vehicles formulated from polyvinylidene fluoride (PVDF) polymer resins are known to provide good solvent resistance, chemical resistance, weather resistance, heat stability, strength and resilience. However, there is a desire for further improvement, particularly in exterior durability in harsh environments.
  • PVDF polyvinylidene fluoride
  • the mechanism of film formation in conventional polyvinylidene fluoride (PVDF) based dispersion coatings and the industrial conditions under which these coatings are applied lead to medium gloss coatings, typically 30 to 40 as measured with 60 degree gloss geometry.
  • the nature of conventional PVDF dispersion paints is a mixture of discrete PVDF particles into a homogeneous acrylic solution phase or discrete PVDF particles and discrete acrylic particles in an aqueous phase.
  • PVDF and acrylic phases may or may not contain pigments and other additives as well. It is known in the art that in order to develop optimum properties from this type of -paint system, the PVDF and acrylic phases must mix during film formation. In the case of coil coating, which is one common application of this type of coatings system, film formation times of 30 to 60 seconds are typical. Short bake cycles offer little time for complete PVDF and acrylic mixing.
  • paint base or “paint vehicle” comprehend the combination of paint binder and thinner into which pigment is mixed to form a paint.
  • varnish comprehends a liquid composition which is converted to a -transparent solid after application as a thin layer.
  • a paint base or paint vehicle without added pigment can be a varnish.
  • binder or “paint binder” comprehend the nonvolatile portion of a paint base or paint vehicle. It holds pigment particles together and the paint film as a whole to the material on which it is applied.
  • thickner comprehends the portion of paint (or varnish) which volatilizes during the drying process. It includes any solvent (aqueous or non-aqueous) .
  • AMF acrylic modified fluoropolymer
  • AMF solid resin (particles or agglomerated) prepared by polymerizing ethylenically unsaturated monomers selected from the group acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters and mixtures thereof in the presence of a latex of vinylidene fluoride homo- or copolymers as described in more detail below and isolating, if necessary, the resin from the latex resulting from its preparation.
  • a paint base for a dispersion coating means a coating where the paint base or vehicle is made from substantially dry resin, isolated from the latex resulting from its preparation, dissolved or suspended in thinner.
  • a paint base for a dispersion coating will be one wherein the paint base will contain substantially only resin isolated from any latex it -was initially formed in, if necessary, and substantially dried.
  • the invention provides in a first composition aspect, a paint base or paint vehicle for dispersion coating which comprises in an amount of from 10% to 90% by weight of the dry resin content, an acrylic modified fluoropolymer resin.
  • the invention provides in a second composition aspect a paint comprising the paint base or paint vehicle of the first composition aspect of the invention and a pigment mixed therein.
  • the invention provides in a third composition aspect, a coating derived by applying a paint as defined in the second composition aspect of the invention or a varnish consisting essentially of a paint base or paint vehicle as defined in the first composition aspect of the invention to a surface on which a coating is desired and evaporating the solvent contained in said paint or varnish.
  • the invention provides in a fourth composition aspect, an article of manufacture comprising an article having adhered on at least one surface thereof a coating as defined in the third composition aspect of the invention.
  • the invention provides in a process aspect, a process for applying an improved acrylic modified fluoropolymer binder containing coating on a surface which comprises applying a paint as defined in the second composition aspect of the invention or a varnish consisting essentially of a paint base or paint vehicle as defined in the first composition aspect of the invention to said surface and evaporating the thinner from said paint or varnish.
  • the vinylidene fluoride homo- and copolymer emulsions employed as a starting material are known, as are their methods of preparation. See, for example, Humphrey and Dohany, Vinylidene Fluoride Polymers, Encyclopedia of Polymer Science and
  • the latices so prepared may be homopolymer PVDF or copolymer PVDF with suitable monomers for copolymerization with VDF being selected from HFP, TFE, TrFE, VF or mixtures thereof.
  • HFP is a preferred comonomer.
  • Up to about 30% by weight comonomer (s) may be incorporated in PVDF copolymers with from about 0% to about 25% by weight being preferred.
  • Seed particles having Tg less than 25°C are preferred for this invention.
  • Techniques for controlling Tg are well known in the art and are not per se part of this invention.
  • the most common method of control of Tg for fluorocopolymers is by control of the fluorocopolymer composition.
  • the seed particle size should be less than 250 nm. in order to obtain a final AMF polymer particle size of less than 350 nm.
  • the acrylic and methacrylic monomer that are seed polymerized in the presence of the fluoropolymer latex are acrylic acid, acrylic acid alkyl esters, methacrylic acid and methacrylic acid alkyl esters wherein the alkyl group in the ester portion of the molecule is from 1 to about 10 carbon atoms, with from 1 to about 4 carbons being preferred.
  • Suitable acrylic esters include, without limitation, ethylacrylate, methylacrylate, butylacrylate, propylacrylate, isobutylacrylate, amylacrylate, 2-ethylhexylacrylate, and hexylacrylate.
  • Suitable methacrylic acid esters include without limitation, ethyl methylacrylate, methyl methacrylate, butyl methacrylate, propyl methacrylate, isobutyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate and hydroxyethyl methacrylate .
  • Preferred monomers are acrylic acid methacrylic acid, ethyl acrylate, methyl acrylate, butyl acrylate, methyl methacrylate and glycidyl methacrylate.
  • the acrylate and methacrylate ester monomers may be used singly or in combination.
  • small quantities of other copolymerizable monomers and/or oligomers may be copolymerized with the acrylic and/or methacrylic acid and ester monomers.
  • these include, without limitation, acrylonitrile, conjugated dienes, such as, 1,3- butadiene and isoprene, fluoroalkyl acrylates, fluoroacrylalkyl methacrylates, aromatic alkenyl compounds, such as, styrene, ⁇ -methylstyrene, styrene halides and divinyl hydrocarbon compounds, such as, divinyl benzene.
  • Reactive emulsifiers such as those available under the tradenames, Burenna, Eliminol, NK ester, may be used.
  • the total amount of acrylic acid, acrylic esters, methacrylic acid, methacrylic acid esters or mixtures thereof should be 80% or greater, preferably 90% or greater by weight of the total monomer mixture .
  • the total monomer mixture for polymerization or copolymerization in the presence of the fluoropolymer seed particles should be 10 to 200 parts by weight, preferably 20 to 80 parts by weight per 100 parts by weight of seed particles.
  • the seed polymerization can be carried out under the same conditions as for conventional emulsion polymerizations.
  • the desired acrylic and/or methacrylic monomer (s) and a polymerization initiator and, optionally, a surfactant, a chain transfer agent, a pH regulator, and, also optionally, eventually a solvent and a chelating agent, are added to the seed latex, and reaction is carried out under atmospheric pressure, 0.5 to 6 hours at temperatures of 20 to 90°C, preferably 40 to 80°C.
  • the emulsion polymerization using the fluoropolymer as a seed can be performed according to standard methods :
  • the ingredients may be added to the reactor neat, solubilized in a suitable solvent (organic or aqueous) or as a dispersion in a suitable solvent.
  • stirred tank reactor operating in the semi-continuous mode is preferred because of its convenience and flexibility.
  • the process used to manufacture the products of the invention involves at least two stages. At least one stage is required for the emulsion polymerization of the fluoropolymer and at least one is required for the seeded emulsion polymerization of the acrylic monomer (s) .
  • Each stage can be performed in the same reactor or different reactors.
  • Each stage may contain its specific monomers, surfactant, initiator, chain transfer agent, pH regulator, solvent and/or chelating agents . It is preferred that the same reactor be employed for the various stages .
  • the final latex may be composed of dispersed particles, homogeneous in size and composition, or of dispersed particles having several populations of size and/or of composition. Latex having- a homogeneous composition distribution of the dispersed particles is preferred. A broad particle size distribution, or a multi-modal particle size distribution allowing efficient packing of the particles, may be preferred to a homogeneous particle size distribution.
  • the final latex particles may be composed of one, two or more phases of various morphologies such as single phase morphology, core-shell, half-moon, inverse core shell, strawberry, snow ball men, interpenetrating network and the like, all of which are well known in the art as are the techniques of obtaining same.
  • the preferred morphologies are fluoropolymer cores/acrylic shells, latex particles and homogeneous latex particles.
  • a single phase latex particle morphology can ' be obtained with miscible fluoropolymer/acrylic polymer pairs or with interpenetrating networks.
  • the surfactant that can be used includes anionic surfactants, cationic surfactants, non-ionic surfactants and amphoteric surfactants. They can be used separately or in combinations of two or more, with the proviso that obviously incompatible types cannot be combined. They can be mixed with the seed latex, or with the monomer mixture, or in any suitable combination with other polymerization ingredients.
  • the anionic surfactant includes esters of higher alcohol sulfates (e.g.
  • Suitable cationic surfactants are an alkyl pyridinium chloride or an alkylammonium chloride.
  • the non-ionic surfactant includes polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, glycerol esters, sorbitan alkyl esters, and derivatives thereof.
  • a suitable amphoteric surfactant is lauryl betaine .
  • Reactive emulsifiers which are able to copolymerize with the above-mentioned monomers, can also be used (e.g. sodium styrene sulfonate, sodium alkyl sulfonate, sodium aryl alkyl sulfonate) .
  • the amount of surfactant usually used is 0.05 to 5 parts by weight per 100 parts by weight of total fluoropolymer particles .
  • Any kind of initiator which produces radicals suitable for free radical polymerization in aqueous media, for temperatures from 20 to 100°C, can be used as the polymerization initiator. They can be used alone or in combination with a reducing agent (e.g. sodium hydrogenobisulfite, sodium L-ascorbate, sodium thiosulfate, sodium hydrogenosulfite) .
  • a reducing agent e.g. sodium hydrogenobisulfite, sodium L-ascorbate, sodium thiosulfate, sodium hydrogenosulfite
  • persulfates hydrogen peroxide
  • water- soluble initiators can be used as water- soluble initiators
  • cumene hydroperoxide diisopropyl peroxy carbonate
  • benzoyl peroxide 2,2'azobis methyl butanenitrile, 2,2'- azobisisobutyronitrile, 1,1' azobiscyclohexane-1- carbonitrile, isopropylbenzenehydroperoxyde
  • Preferred initiators are 2,2'azobis methylbutanenitrile and 1, 1' azobiscyclohexane-1-carbonitrile.
  • the oil-soluble initiator could be dissolved in a small quantity of solvent if desired.
  • the amount of initiator used is 0.1 to 2 parts by weight per 100 parts by weight of the monomer mixture added.
  • chain transfer agents there are no limitations in the type of chain transfer agents that can be used, as long as they do not excessively slow down the reaction.
  • the chain transfer agents that can be used include for example mercaptans (e.g. dodecyl mercaptan, octylmercaptan) , halogenated hydrocarbon (e.g. carbon tetrachloride, chloroform), xanthogen (e.g. dimethylxanthogen disulfide) .
  • the quantity of chain transfer agent used is usually 0 to 5 parts by weight per 100 parts by weight of the monomer mixture added.
  • a small quantity of solvent can be added during the reaction in order to help swell the seed particle.
  • the quantity of solvent added should be in such ranges that workability, environmental safety, production safety, fire hazard prevention, are not impaired.
  • pH adjusting agents e.g. sodium carbonate, potassium carbonate, sodium hydrogenocarbonate
  • chelating agents e.g. ethylene diamine tetraacetic acid, glycine, alanine
  • Isolation of the acrylic modified fluoropolymer resin from the seed polymer latex may be accomplished -by standard methods well known in the art such as, drying of the latex, coagulation by high shear mixing, centrifugation, and/or altering the ionic balance and/or freezing followed by filtration and optional washing and the like.
  • the paint base or paint vehicle composition may be left unpigmented to form a varnish, or it may be mixed with one or more 'pigments to form a paint.
  • the same pigments useful in other PVDF based coatings may satisfactorily be used in the practice of the present invention.
  • the pigments include, for example, those pigments identified in U.S. Patent No. 3,340,222.
  • the pigment may be organic or inorganic .
  • the pigment may comprise titanium dioxide, or titanium dioxide in combination with one or more other inorganic pigments wherein titanium dioxide comprises the major part of the combination.
  • Inorganic pigments which may be used alone or in combination with titanium dioxide include, for example, silica, iron oxides of various colors, cadmiums, lead titanate, and various silicates, for example, talc, diatomaceous earth, asbestos, mica, clay, and basic lead silicate.
  • Pigments which may be used in combination with titanium dioxide include, for example, zinc oxide, zinc sulfide, zirconium oxide, white lead, carbon black, lead chromate, leafing and non-leafing metallic pigments, molybdate orange, calcium carbonate and barium sulfate.
  • the preferred pigment category is the ceramic metal oxide type pigments which are calcined. Chromium oxides and some iron oxides of the calcined type may also be satisfactorily utilized. For applications where a white coating is desired, a non- chalking, non-yellowing rutile-type of titanium dioxide is recommended. Lithopones and the like are inadequate as they suffer from lack of chalk resistance and/or from inadequate hiding. Anastase Ti0 2 is similarly not recommended.
  • the pigment component when present, is advantageously present in the composition in the amount of from about 0.1 to about 50 parts by weight per 100 parts of resin component. While for most applications the preferred range is from about 25 to about 35 parts by weight pigment per 100 parts of resin component, for white and light colored pigment the amount of pigment is generally in the higher ranges of the preferred amount, and may be as high as 35 parts by weight per 100 parts of resin component or higher .
  • compositions of the invention with be in liquid form.
  • the binder comprising the fluoropolymer resin and any optional other resins contained therein will be, dispersed, partially or completely dissolved in a thinner which may comprise either aqueous or non- aqueous based solvents.
  • a thinner which may comprise either aqueous or non- aqueous based solvents.
  • solvents may either be single solvents or mixtures of solvents.
  • Suitable aqueous based solvents are described in U.S. Patent "4,128,519.
  • Suitable non-aqueous based solvents are described in WO 93/13178 and U.S. Patent 3,324,069.
  • solvents employed are not per se part of this invention and any conventional solvent or mixture of solvents including latent solvents conventionally employed in PVDF resin based paints is contemplated as suitable by the invention.
  • Other conventional paint components such as surfactants, dispersants, waxes, crosslinking agents, UV absorbers, flatting agents, thickeners and the like may also be included in the paint base or paint vehicle and the paint and varnish compositions of the invention.
  • Standard techniques well known to those of skill in the art, may be employed to mix the ingredients contained in the paint base or paint vehicle and the paint and varnish compositions contemplated by the present invention.
  • paint and varnish compositions of this invention may be applied to a wide variety of substrates including plastics, wood, metals, ceramics, glass and the like by conventional coating methods, such as spraying, brushing, dipping, casting, knife coating, coil coating, reverse roll coating, draw down and other methods known in the art .
  • solvent based paints and varnishes having the resins in solution are air-dried to remove the thinner, including the solvent, at ambient temperatures, 15° to 50°C, and other aqueous and non-aqueous solvent based paints and varnishes are baked or heated to evaporate the thinner, including the solvent, and coalesce the coating.
  • the heating temperatures will range from about 125° to about 300°C, preferably from about 175° to about 275°C. Obviously for coating substrates sensitive to the higher temperature range, solvent based paints and varnishes having the resin totally dissolved should be employed.
  • a useful primer is a layer of pigmented acrylic acid ester polymer as described in U.S. Patent 3,234,039 and in U.S. Patent 3,037,881.
  • a preferred primer layer is described in U.S. Patent 3,111,426 that is an epoxy based primer. More generally, acrylic based primers such as described in U.S. Patent 3,526,532 and the primers of U.S.
  • Patent 4,179,542 based on mixtures of partially fluorinated halogenated ethylene polymers, epoxy resins, powdered metallic pigments and wet ground mica are also useful on metals'.
  • glass fibers or other flexible substrates woven or non-woven, known adhesion promoters may be used.
  • glass fiber may first be treated with a silane coupling agent as described by I.L. Fan and R. G. Shaw, Rubber World, June 1971, page 56.
  • Air drying of the solvent based paints and varnishes of the invention having the resins in solution on substrates such as paper, glass fiber, glass cloth, and non-woven textiles may be accomplished at ambient temperatures with drying periods of from about 3 to 24 hours. However, with forced air drying at about 50°C the films will dry in 10 to 15 minutes. At 60°C about 5 to 10 minutes are adequate using forced air drying.
  • other aqueous and non-aqueous based systems are subjected to heat to evaporate the thinner, including the solvent, and subject the polymers to coalescence. As stated above, the heating temperatures will range from about 125°C to about 300°C, preferably between about 175°C and 275° and most preferably between about 215°C and 250°C.
  • the paints and varnishes of the invention may be cast and subjected to heating to obtain a free film of the composition.
  • coatings are smooth, glossy, uniform and adhere tenaciously to the substrate.
  • the films and coatings are also hard, creep resistant (that is dimensionally stable) , flexible, chemically resistant and weather resistant. Smoke generation resistance and hydrophobicity are also provided by the films and coatings .
  • AMF resins provide coatings with higher gloss levels than -conventional PVDF/acrylic blended paint systems.
  • flexibility of the AMF coatings are improved over blended systems under certain formulation and baking conditions . Accelerated UV testing indicates that the AMF based coatings having improved UV resistance as shown by improved gloss retention as compared to blended systems.
  • Formulations A, B, and C were prepared containing components outlined in Table I. For each formulation, the components were charged into a grinding container and 4 mm glass beads were added to each formulation in the amount of 1.25 times the total formulation weight. The paint formulations were milled for one hour.
  • the base resin used in formulation A was an AMF containing a PVDF to acrylic weight ratio of 80/20, and formulations B and C used two different PVDF homopolymers . Secondary acrylic resin was added to each formulation such that all formulations were at a final fluoropolymer to acrylic weight ratio of 70/30. Note that toluene was added only to formulation A to account for toluene added into formulations B and C with the Acryloid B-44S.
  • a wire drawdown applicator was used to apply each paint to aluminum panels, and the coated panels were baked at 525°F for 90 seconds. After baking, panels were post treated either by immediate immersion in room temperature water, quenched, or a secondary bake at 140°C for 24 hours, annealed. Table II shows gloss and flexibility test results for these panels.
  • AMF formulation A has a higher gloss than both PVDF formulations B and C when quenched or annealed. Also, the high flexibility of the quenched coatings is maintained only by formulation A. Formulations B and C both loose some degree of flexibility upon annealing. Surface SEM photos of quenched coatings prepared from formulations A and C were examined. The SEM photos clearly show that the AMF coating has a
  • 6UBSmUTESHEET(RUUI ⁇ ) significantly smoother surface than the PVDF/acrylic blended coating. This is also in agreement with the higher gloss of the AMF coating.
  • Example 2 White coatin ⁇ s at 80/20 PVDF/acrylic ratio
  • Formulations D and E were prepared containing components outlined in Table III. For each formulation, the components were charged into a grinding container and 4 mm glass beads were added to each formulation in the amount of 1.25 times the total formulation weight. The paint formulations were milled for one hour.
  • the base resin used in formulation D was an AMF containing a PVDF to acrylic weight ratio of 80/20
  • formulation E base resin was PVDF homopolymer. Secondary acrylic resin was added to formulation E such that both 'formulations were at a final fluoropolymer to acrylic weight ratio of 80/20. Note that toluene was added into formulation D only to account for toluene added into
  • a wire wound drawdown applicator was used to apply each paint to aluminum panels, and the coated panels were baked at 525°F for 90 seconds. After baking, panels were post treated either by immediate immersion in room temperature water, quenched, or a secondary bake at 140°C for 24 hours, annealed. Table IV shows gloss and flexibility test results for these panels .
  • AMF formulation D has a higher gloss than PVDF formulation E when quenched or annealed. In this case, the high flexibility of the coatings is maintained for both formulations under- both post treatment conditions.
  • Formulations F and G were prepared containing components outlined in Table V. For each formulation, the components were charged into a grinding container and 4 mm glass beads were added to each formulation in the amount of 1.25 times the total formulation weight. The paint formulations were milled for one hour.
  • the base resin used in formulation F was an AMF containing PVDF to acrylic weight ratio of 70/30
  • formulation G base resin was PVDF homopolymer. Secondary acrylic resin was added to formulation G such that both formulations were at a final fluoropolymer to acrylic weight ratio of 70/30.
  • a wire wound drawdown applicator was used to apply each paint to aluminum panels, and the coated panels were baked at 550°F for 90 seconds and immediately quenched into room temperature water. As shown in Table V, AMF formulation F gives a higher original gloss than PVDF formulation G. After 15,000 hours of fluorescent UV-B exposure, the AMF coating also maintains a higher percentage of the original gloss .
  • Example 4 Water Based Dispersion Coating of VDF-HFP based AMF
  • a 100 g paint batch was prepared from Formulation
  • 8UBSnTUTESHEET(RULE26) H by charging components 1 to 6, in the ratios shown in Table VI, into a grinding container with 100 g of 4 mm glass milling beads. The mixture was milled for 2 hours and strained through a coarse filter to remove the milling media. Component 7 and 8 were added to the strained mixture, and the mixture was rolled slowly for approximately 2 hours . The paint was applied to aluminum panels with a wire wound drawdown applicator chosen to produce 20-25 micron dry coatings. Coated panels baked at 450°F for 10 minutes produced smooth continuous coatings. The coatings passed 0-T flexibility testing, 100% Crosshatch adhesion, and 60 inch-pounds (the maximum load which does not produce substrate rupture) of direct or reverse impact without cracking.
  • T-Bend formability was determined according to ASTM D 4145-83 (Reapproved 1990) a Standard Test
  • SUBST ⁇ 7UTESHEEr(RULE26) removed by rubbing and the specimen is allowed to set to return to room temperature (but no more than 10 minutes) .
  • the tape is removed with a quick pull at right angles to the test surface.
  • BYK 182 is a dispersant from BYK-Chemie
  • the vinylidene fluoride polymer and the acrylic modified fluoropolymers employed in formulating the paint vehicles employed are identified as follows:
  • PVDF polymers were all commercially available VDF homopolymers sold by Elf Atochem North America, Inc., under the KYNAR ⁇ trademark. PVDF 1 was KYNAR 500+
  • PVDF 2 was KYNAR 500
  • PVDF 3 was KYNAR 500
  • AMF polymers were all based on PVDF polymer latices synthesized in accordance with procedures used for commercially available PVDF polymers sold by Elf Atochem North America, Inc., under the KYNAR trademark.
  • the AMF polymers were made as described in the specification.
  • the PVDF type polymer in the seed polymer latices and the acrylic monomers and their relative percentages by weight are as follows:
  • MMA methyl methacrylate
  • EA ethylacrylate
  • EMA ethyl methacrylate
  • MAA methacrylic acid

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Laminated Bodies (AREA)
PCT/US1998/013734 1997-07-02 1998-07-02 Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins WO1999001505A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002264719A CA2264719A1 (en) 1997-07-02 1998-07-02 Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins
JP50735699A JP2002513442A (ja) 1997-07-02 1998-07-02 変性熱可塑性弗化ビニリデンを基材とする樹脂からのフルオロポリマー分散塗料
BR9806106-2A BR9806106A (pt) 1997-07-02 1998-07-02 Base de tinta para revestimento de dispersão, tinta, revestimento, e, artigo de fabricação
EP98933065A EP0932645A4 (en) 1997-07-02 1998-07-02 FLUOROPOLYMERIC DISPERSION COATINGS MADE FROM VINYLIDENE POLYFLUORIDE RESINS
AU82817/98A AU735801B2 (en) 1997-07-02 1998-07-02 Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins
EA199900181A EA001802B1 (ru) 1997-07-02 1998-07-02 Дисперсионные покрытия на основе (со)полимеров винилиденфторида, модифицированных акриловыми полимерами

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US5164297P 1997-07-02 1997-07-02
US60/051,642 1997-07-02
US10876498A 1998-07-01 1998-07-01
US09/108,764 1998-07-01

Publications (1)

Publication Number Publication Date
WO1999001505A1 true WO1999001505A1 (en) 1999-01-14

Family

ID=26729669

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/013734 WO1999001505A1 (en) 1997-07-02 1998-07-02 Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins

Country Status (10)

Country Link
EP (1) EP0932645A4 (zh)
JP (1) JP2002513442A (zh)
KR (1) KR20000068392A (zh)
CN (1) CN1278285A (zh)
AU (1) AU735801B2 (zh)
BR (1) BR9806106A (zh)
CA (1) CA2264719A1 (zh)
EA (1) EA001802B1 (zh)
NZ (1) NZ335012A (zh)
WO (1) WO1999001505A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001019883A1 (fr) * 1999-09-14 2001-03-22 Atofina Latex fluores en minidispersion dans l'eau
EP1108761A2 (en) 1999-12-13 2001-06-20 Canon Kabushiki Kaisha Polymer film, and polymeric compound for the production thereof
US6340720B1 (en) 2000-02-14 2002-01-22 Ausimont Usa, Inc. Process for making polyvinylidene fluoride power coatings and coating formulations
EP1888836A2 (en) 2005-05-19 2008-02-20 Arkema Inc. Highly weatherable roof coatings containing aqueous fluoropolymer dispersions
US20130089671A1 (en) * 2011-10-05 2013-04-11 Honeywell International Inc. Polymers formed from 2,3,3,3-tetrafluoropropene and articles and uses thereof
WO2022055472A1 (en) * 2020-09-08 2022-03-17 Hewlett-Packard Development Company, L.P. Housings for electronic devices

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2635691C (en) * 2006-01-17 2013-10-29 Abbott Laboratories Combination therapy with parp inhibitors
CN100393826C (zh) * 2006-06-01 2008-06-11 江苏兰陵化工集团有限公司 水性氟碳乳胶涂料及其制备方法
EP3580288A4 (en) * 2017-02-08 2020-09-30 Akzo Nobel Coatings International B.V. COATING COMPOSITION, MANUFACTURING METHOD FOR IT AND USE OF IT

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5439980A (en) * 1990-11-29 1995-08-08 Daikin Industries Process for preparing polymer
US5646201A (en) * 1993-09-22 1997-07-08 Daikin Industries, Ltd. Aqueous dispersion of fluorine-containing copolymer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5439980A (en) * 1990-11-29 1995-08-08 Daikin Industries Process for preparing polymer
US5646201A (en) * 1993-09-22 1997-07-08 Daikin Industries, Ltd. Aqueous dispersion of fluorine-containing copolymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0932645A4 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001019883A1 (fr) * 1999-09-14 2001-03-22 Atofina Latex fluores en minidispersion dans l'eau
FR2804440A1 (fr) * 1999-09-14 2001-08-03 Atofina Latex fluores en minidispersion dans l'eau sans tensioactif ni solvant organique
EP1108761A2 (en) 1999-12-13 2001-06-20 Canon Kabushiki Kaisha Polymer film, and polymeric compound for the production thereof
EP1108761A3 (en) * 1999-12-13 2001-07-18 Canon Kabushiki Kaisha Polymer film, and polymeric compound for the production thereof
US6761431B2 (en) 1999-12-13 2004-07-13 Canon Kabushiki Kaisha Polymer film, polymeric compound for forming the same, method of manufacturing such polymeric compound, liquid-repellency treatment solution using such polymeric compound, surface-modifying method using such treatment solution and surface-modified article
US6340720B1 (en) 2000-02-14 2002-01-22 Ausimont Usa, Inc. Process for making polyvinylidene fluoride power coatings and coating formulations
EP1888836A2 (en) 2005-05-19 2008-02-20 Arkema Inc. Highly weatherable roof coatings containing aqueous fluoropolymer dispersions
US20130089671A1 (en) * 2011-10-05 2013-04-11 Honeywell International Inc. Polymers formed from 2,3,3,3-tetrafluoropropene and articles and uses thereof
EP3219770A1 (en) * 2011-10-05 2017-09-20 Honeywell International Inc. Coating compositions comprising a polymer of 2,3,3,3-tetrafluoropropene and a film-forming polymer
WO2022055472A1 (en) * 2020-09-08 2022-03-17 Hewlett-Packard Development Company, L.P. Housings for electronic devices

Also Published As

Publication number Publication date
CN1278285A (zh) 2000-12-27
JP2002513442A (ja) 2002-05-08
BR9806106A (pt) 1999-08-31
EA199900181A1 (ru) 1999-12-29
EA001802B1 (ru) 2001-08-27
NZ335012A (en) 2000-01-28
EP0932645A4 (en) 2000-09-13
AU735801B2 (en) 2001-07-12
AU8281798A (en) 1999-01-25
KR20000068392A (ko) 2000-11-25
CA2264719A1 (en) 1999-01-14
EP0932645A1 (en) 1999-08-04

Similar Documents

Publication Publication Date Title
US6362295B2 (en) Fluoropolymer powder coatings from modified thermoplastic vinylidene fluoride based resins
US5349003A (en) Aqueous fluorine-containing polymer dispersion and aqueous dispersion containing fluorine-containing polymer and water-soluble resin and/or water dispersible resin
EP3164436B1 (en) Stable aqueous fluoropolymer coating composition
EP2297215B1 (en) Fluoropolymer aqueous hybrid compositions with improved film formation
EP0360575B1 (en) Aqueous fluorine-containing polymer dispersion and aqueous dispersion containing fluorine-containing polymer and water-soluble resin and/or water dispersible resin
JP3941128B2 (ja) 粉体塗料用組成物
JP2001072725A (ja) 架橋可能なフルオロポリマー基材水性分散液
JPH04227743A (ja) 弗化ビニリデン／ヘキサフルオルプロピレン共重合体の粉末被覆
AU735801B2 (en) Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins
JPH0692566B2 (ja) 分散型塗料樹脂組成物
MXPA99002007A (en) Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins
JP2966480B2 (ja) 水希釈可能な含フッ素重合体及び該重合体水性液の製造方法
CA2225579A1 (en) Vehicles for paints and varnishes formulated with vinylidene fluoride-hexafluoropropylene copolymers
EP0857769A1 (en) Vehicles for paints and varnishes formulated with vinylidene fluoride-hexafluoropropylene copolymers
MXPA99002578A (en) Fluoropolymer powder coatings from modified thermoplastic vinylidene fluoride based resins
JP3953924B2 (ja) アクリル系重合体凝固組成物およびそれを用いたアクリルゾル
JPH037784A (ja) フッ素系重合体水性分散液およびフッ素系重合体含有水性分散液
NO830070L (no) Vandig, herdbart belegningspreparat

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 98800901.3

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN JP KR MX NZ

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): 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

WWE Wipo information: entry into national phase

Ref document number: 82817/98

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2264719

Country of ref document: CA

Ref document number: 2264719

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/a/1999/002007

Country of ref document: MX

Ref document number: 199900181

Country of ref document: EA

WWE Wipo information: entry into national phase

Ref document number: 1019997001699

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1998933065

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 335012

Country of ref document: NZ

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWP Wipo information: published in national office

Ref document number: 1998933065

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019997001699

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 82817/98

Country of ref document: AU

WWW Wipo information: withdrawn in national office

Ref document number: 1019997001699

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1998933065

Country of ref document: EP