US20030204020A1 - Weatherable fluoropolymer-acrylic composition - Google Patents

Weatherable fluoropolymer-acrylic composition Download PDF

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Publication number
US20030204020A1
US20030204020A1 US10/135,670 US13567002A US2003204020A1 US 20030204020 A1 US20030204020 A1 US 20030204020A1 US 13567002 A US13567002 A US 13567002A US 2003204020 A1 US2003204020 A1 US 2003204020A1
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composition
acrylate
fluoropolymer
acrylic
meth
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US10/135,670
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US6635714B1 (en
Inventor
Kurt Wood
Lotfi Hedhli
Silvia Vicini
Stephane Moyses
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Arkema Inc
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Atofina Chemicals Inc
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Assigned to ATOFINA CHEMICALS, INC. reassignment ATOFINA CHEMICALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: VICINI, SILVIA, MOYSES, STEPHANE, HEDHLI, LOTFI, WOOD, KURT A.
Priority to EP03290922A priority patent/EP1359193A1/en
Priority to JP2003123953A priority patent/JP2004002845A/en
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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
    • 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
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • This invention relates to an improved fluoropolymer-acrylic composition having enhanced weathering properties, particularly to such compositions wherein the fluoropolymer component is made by the polymerization of vinylidene fluoride and, optionally, other perhalogenated monomers and wherein the acrylic component is made by the polymerization of predominantly acrylate and/or methacrylate esters, the improvement residing in the use of (meth)acrylate esters containing 10-50 weight % of straight chain meth(acrylate) esters having at least 3 carbons in the side chain and 50-90 weight % of methyl and/or ethyl (meth)acrylate esters.
  • This composition is useful as a weatherable component of coatings, films and other manufactured articles.
  • Fluoropolymer-acrylic blends including those referred to in the art as acrylic-modified fluoropolymers or AMF, are described in the patent literature, but teach that the preferred acrylic component to achieve good weatherability is based on methyl or ethyl (meth)acrylate. Representative of such patent art is U.S. Pat. No. 5,646,201 and EP 960918. These lower alkyl (meth)acrylates are believed to enhance the compatibility of the fluoropolymer and acrylic components, whereas the higher chain esters are believed to result in incompatibility and poor weatherability.
  • An improved fluoropolymer-acrylic composition with enhanced weathering properties is provided in which the fluoropolymer component is made by the polymerization of vinylidene fluoride and, optionally, other perhalogenated monomers and in which the acrylic component is made by the polymerization of predominantly acrylate and/or methacrylate esters, the improvement comprising using acrylate and/or methacrylate esters containing 10 to 50 weight % of straight chain (meth)acrylate esters having at least 3 carbons in the side chain and 50 to 90 weight % of straight chain (meth)acrylate esters having 1 or 2 carbons in the side chain.
  • the acrylic component is made by the polymerization of predominantly (meth)acrylate esters which contain the foregoing C3 and higher linear esters, 50-90 weight % of methyl and/or ethyl (meth)acrylate, and 0-20 weight % of other monomers such as methacrylic or itaconic acid, hydroxyethyl acrylate or methacrylate, carbonyl or acetoacetate functional monomers, various alkoxysilane methacrylates or acrylates, vinyl esters, vinyl ethers and styrene.
  • An example of a preferred acrylic composition is 20-32% butyl acrylate, 65-80% methyl methacrylate and 2-10% of one of the other foregoing functional monomers.
  • Possible uses of the invention include coatings, paints, films, and extruded articles (including the outermost layer of a multilayer extruded object). Thus, for instance, it can be used as the principal component of a weatherable latex paint as shown in the examples below.
  • the composition of the invention can be made into paints, coatings, varnishes or films by various routes well known in the coatings industry, each of which is an embodiment of the invention.
  • the composition of the invention is made as a latex dispersion prepared by seeded emulsion polymerization. These methods are well known in the art such as is shown in U.S. Pat. No. 5,646,201.
  • the composition contains at least 30 weight % fluoropolymer, more preferably 50-90% fluoropolymer, most preferably 65-80% fluoropolymer.
  • the fluoropolymer is preferably a copolymer of vinylidene fluoride (VDF) and a perhalogenated monomer such as hexafluoropropylene (HFP), chlorotetrafluoroethylene (CTFE) or tetrafluoroethylene (TFE).
  • the level of comonomer is adjusted such that the resulting copolymer preferably has an enthalpy of melting less than about 35 Joules per gram (J/g), most preferably 5-20 J/g.
  • the fluoropolymer has no detectable crystalline melting peak.
  • a coating or film is made using a solvent dispersion formulation.
  • the resin binder is comprised of about 20-90% fluoropolymer (preferably 40-80%, most preferably 50-75%), among the preferred fluoropolymers being a polyvinylidene fluoride (PVDF) homopolymer, most preferably a fine powder such as KYNAR® 301F (an air-milled powder form having a melting point of 160-170° C. available from Atofina Chemicals, Inc.), or a VDF-based copolymer, with the remainder being predominantly comprised of an acrylic resin of the invention composition, that is, with 10-50 wt. % of straight chain meth(acrylate) esters, preferably at least 80% of the remainder being an acrylic of this composition.
  • PVDF polyvinylidene fluoride
  • a coating or film is made using a waterborne dispersion formulation of similar composition to the second embodiment, formed by combining an acrylic latex of the inventive composition with a fluoropolymer in aqueous dispersion, the fluoropolymer being either in latex form or in the form of a redispersed powder.
  • a fluoropolymer being either in latex form or in the form of a redispersed powder.
  • preferable PVDF fluoropolymers for this embodiment include latex products such as LATEX 32 (melting point 160-170° C.) and air-milled powders such as KYNAR 741F (melting point 165-170° C.), both PVDF homopolymers being available from Atofina Chemicals, Inc.
  • a coating or film is made using a solvent-based solution formulation of similar composition to those described in the first and second embodiments.
  • This embodiment uses, preferably, a low crystallinity fluoropolymer, more preferably a terpolymer of VDF, TFE and HFP or CTFE.
  • a terpolymer of VDF, TFE and HFP or CTFE.
  • KYNAR 9301 melting point of 90° C.
  • a coating or film with the inventive composition as the principal resin component is applied as a powder coating.
  • Examples of some of the ways to produce PVDF powder coatings according to this embodiment are taught in U.S. Pat. Nos. 5,229,460; 4,770,939; 5,030,394; 5,739,202; 6,063,855 and 6,340,720, as well as in European Patents 659845 and 659851.
  • Preferred fluoropolymers for this embodiment are PVDF homopolymers or VDF-based copolymers with a melt viscosity below 20 kPs (100 sec ⁇ 1 at 230° C.), most preferably below 10 kPs.
  • An example of such a low melt viscosity homopolymer is KYNAR 710, available commercially from Atofina Chemicals, Inc.
  • Yet another embodiment is a solid material of the inventive composition, for example, a caulk, solid foam, or extruded or molded article of similar composition to the first embodiment.
  • the invention is illustrated in the following examples in which coatings were made from three fluoropolymer-acrylic compositions, each in aqueous latex form at 48 wt % solids, where the solids of the latex are comprised of a 70:30 ratio of fluoropolymer to acrylic in which the fluoropolymer is a copolymer of 75% VDF and 25% HFP. All parts and percentages are by weight unless otherwise indicated.
  • Examples 1 and 2 had an acrylic composition of 77 MMA/20 BA/3 MAA and 65 MMA/31 BA/4 MAA, while a Comparative Example had an acrylic composition of 67 MMA/26 EA/7 MAA, where MMA is methyl methacrylate, BA is butyl acrylate, MAA is methacrylic acid and EA is ethyl acrylate.
  • Coating formulations were then made by mixing the fluoropolymer-acrylic compositions with about 1 part per 100 of ammonia (7%) and about 10 parts per 100 of a mixture of about 84% dipropylene glycol methyl ether, 11% 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 5% of a hydrophobically modified ethoxylate urethane thickener. Coatings were applied on chromated aluminum test panels with a draw down bar (200 micron gap). The panels were air-dried overnight, then conditioned at 60° C. for 5 days in an oven before exposure to a QUV-B test unit equipped with UVB-313 lamps for accelerated weather testing according to ASTM G53-88.
  • the clear coats dry film thickness was about 30-40 microns.
  • the panels were cut to a size of approximately 15 cm ⁇ 8 cm.
  • the area exposed to radiation was roughly 9 cm ⁇ 6 cm.
  • the total exposure time for the samples was 2428 hours.
  • the acrylic weight loss for the clear coats made from the Example 1 and 2 compositions was only about 5-10%, while the weight loss for the clear coat made from the Comparative Example composition was greater than 30%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Weatherable fluoropolymer-acrylic compositions based on the use of C3 and higher straight chain (meth)acrylate esters are provided.

Description

    BACKGROUND OF THE INVENTION
  • This invention relates to an improved fluoropolymer-acrylic composition having enhanced weathering properties, particularly to such compositions wherein the fluoropolymer component is made by the polymerization of vinylidene fluoride and, optionally, other perhalogenated monomers and wherein the acrylic component is made by the polymerization of predominantly acrylate and/or methacrylate esters, the improvement residing in the use of (meth)acrylate esters containing 10-50 weight % of straight chain meth(acrylate) esters having at least 3 carbons in the side chain and 50-90 weight % of methyl and/or ethyl (meth)acrylate esters. This composition is useful as a weatherable component of coatings, films and other manufactured articles. [0001]
  • Fluoropolymer-acrylic blends, including those referred to in the art as acrylic-modified fluoropolymers or AMF, are described in the patent literature, but teach that the preferred acrylic component to achieve good weatherability is based on methyl or ethyl (meth)acrylate. Representative of such patent art is U.S. Pat. No. 5,646,201 and EP 960918. These lower alkyl (meth)acrylates are believed to enhance the compatibility of the fluoropolymer and acrylic components, whereas the higher chain esters are believed to result in incompatibility and poor weatherability. [0002]
  • Testing of resistance to UV radiation is used herein as a measure of weatherability of the inventive compositions. Thus, in the examples below, the procedure of ASTM G53-88 was followed to measure the acrylic weight loss for coatings made from the inventive compositions and show that the amount of acrylic degradation is much lower than for a comparative example using (meth)acrylate esters having side chains with only 1-2 carbons. [0003]
    • BRIEF SUMMARY OF THE INVENTION
  • An improved fluoropolymer-acrylic composition with enhanced weathering properties is provided in which the fluoropolymer component is made by the polymerization of vinylidene fluoride and, optionally, other perhalogenated monomers and in which the acrylic component is made by the polymerization of predominantly acrylate and/or methacrylate esters, the improvement comprising using acrylate and/or methacrylate esters containing 10 to 50 weight % of straight chain (meth)acrylate esters having at least 3 carbons in the side chain and 50 to 90 weight % of straight chain (meth)acrylate esters having 1 or 2 carbons in the side chain. [0004]
    • DETAILED DESCRIPTION
  • As noted above, it has now been found that the key to improved weathering properties (as measured by resistance to UV radiation) is the use of 10-50 weight % of C3 and higher linear meth(acrylate) esters (preferably C3-C8 linear esters such as butyl or propyl acrylate or methacrylate) as part of the acrylic component of the inventive composition. Thus, the acrylic component is made by the polymerization of predominantly (meth)acrylate esters which contain the foregoing C3 and higher linear esters, 50-90 weight % of methyl and/or ethyl (meth)acrylate, and 0-20 weight % of other monomers such as methacrylic or itaconic acid, hydroxyethyl acrylate or methacrylate, carbonyl or acetoacetate functional monomers, various alkoxysilane methacrylates or acrylates, vinyl esters, vinyl ethers and styrene. An example of a preferred acrylic composition is 20-32% butyl acrylate, 65-80% methyl methacrylate and 2-10% of one of the other foregoing functional monomers. [0005]
  • While applicant does not wish to be bound by any mechanism responsible for the improved weatherability resulting from use of C3 and higher linear (meth)acrylates, it is possible that the degradation mechanism is different for the lower, C1 and C2 (meth)acrylates as compared to the longer chain materials. The former materials are believed to degrade by chain scission, the latter by crosslinking. [0006]
  • Possible uses of the invention include coatings, paints, films, and extruded articles (including the outermost layer of a multilayer extruded object). Thus, for instance, it can be used as the principal component of a weatherable latex paint as shown in the examples below. The composition of the invention can be made into paints, coatings, varnishes or films by various routes well known in the coatings industry, each of which is an embodiment of the invention. [0007]
  • In a first embodiment, the composition of the invention is made as a latex dispersion prepared by seeded emulsion polymerization. These methods are well known in the art such as is shown in U.S. Pat. No. 5,646,201. Preferably the composition contains at least 30 weight % fluoropolymer, more preferably 50-90% fluoropolymer, most preferably 65-80% fluoropolymer. The fluoropolymer is preferably a copolymer of vinylidene fluoride (VDF) and a perhalogenated monomer such as hexafluoropropylene (HFP), chlorotetrafluoroethylene (CTFE) or tetrafluoroethylene (TFE). The level of comonomer is adjusted such that the resulting copolymer preferably has an enthalpy of melting less than about 35 Joules per gram (J/g), most preferably 5-20 J/g. In another preferred latex dispersion embodiment, the fluoropolymer has no detectable crystalline melting peak. [0008]
  • In a second embodiment of the invention, a coating or film is made using a solvent dispersion formulation. In this embodiment, the resin binder is comprised of about 20-90% fluoropolymer (preferably 40-80%, most preferably 50-75%), among the preferred fluoropolymers being a polyvinylidene fluoride (PVDF) homopolymer, most preferably a fine powder such as KYNAR® 301F (an air-milled powder form having a melting point of 160-170° C. available from Atofina Chemicals, Inc.), or a VDF-based copolymer, with the remainder being predominantly comprised of an acrylic resin of the invention composition, that is, with 10-50 wt. % of straight chain meth(acrylate) esters, preferably at least 80% of the remainder being an acrylic of this composition. [0009]
  • In a third embodiment of the invention, a coating or film is made using a waterborne dispersion formulation of similar composition to the second embodiment, formed by combining an acrylic latex of the inventive composition with a fluoropolymer in aqueous dispersion, the fluoropolymer being either in latex form or in the form of a redispersed powder. Examples of preferable PVDF fluoropolymers for this embodiment include latex products such as LATEX 32 (melting point 160-170° C.) and air-milled powders such as KYNAR 741F (melting point 165-170° C.), both PVDF homopolymers being available from Atofina Chemicals, Inc. [0010]
  • In a fourth embodiment, a coating or film is made using a solvent-based solution formulation of similar composition to those described in the first and second embodiments. This embodiment uses, preferably, a low crystallinity fluoropolymer, more preferably a terpolymer of VDF, TFE and HFP or CTFE. One example of such a terpolymer is KYNAR 9301 (melting point of 90° C.), available commercially from Atofina Chemicals, Inc. [0011]
  • In a fifth embodiment, a coating or film with the inventive composition as the principal resin component is applied as a powder coating. Examples of some of the ways to produce PVDF powder coatings according to this embodiment are taught in U.S. Pat. Nos. 5,229,460; 4,770,939; 5,030,394; 5,739,202; 6,063,855 and 6,340,720, as well as in European Patents 659845 and 659851. Preferred fluoropolymers for this embodiment are PVDF homopolymers or VDF-based copolymers with a melt viscosity below 20 kPs (100 sec[0012] −1 at 230° C.), most preferably below 10 kPs. An example of such a low melt viscosity homopolymer is KYNAR 710, available commercially from Atofina Chemicals, Inc.
  • Yet another embodiment is a solid material of the inventive composition, for example, a caulk, solid foam, or extruded or molded article of similar composition to the first embodiment. [0013]
  • The invention is illustrated in the following examples in which coatings were made from three fluoropolymer-acrylic compositions, each in aqueous latex form at 48 wt % solids, where the solids of the latex are comprised of a 70:30 ratio of fluoropolymer to acrylic in which the fluoropolymer is a copolymer of 75% VDF and 25% HFP. All parts and percentages are by weight unless otherwise indicated. Examples 1 and 2 had an acrylic composition of 77 MMA/20 BA/3 MAA and 65 MMA/31 BA/4 MAA, while a Comparative Example had an acrylic composition of 67 MMA/26 EA/7 MAA, where MMA is methyl methacrylate, BA is butyl acrylate, MAA is methacrylic acid and EA is ethyl acrylate. Coating formulations were then made by mixing the fluoropolymer-acrylic compositions with about 1 part per 100 of ammonia (7%) and about 10 parts per 100 of a mixture of about 84% dipropylene glycol methyl ether, 11% 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 5% of a hydrophobically modified ethoxylate urethane thickener. Coatings were applied on chromated aluminum test panels with a draw down bar (200 micron gap). The panels were air-dried overnight, then conditioned at 60° C. for 5 days in an oven before exposure to a QUV-B test unit equipped with UVB-313 lamps for accelerated weather testing according to ASTM G53-88. The clear coats dry film thickness was about 30-40 microns. The panels were cut to a size of approximately 15 cm×8 cm. The area exposed to radiation was roughly 9 cm×6 cm. The total exposure time for the samples was 2428 hours. The acrylic weight loss for the clear coats made from the Example 1 and 2 compositions was only about 5-10%, while the weight loss for the clear coat made from the Comparative Example composition was greater than 30%. [0014]

Claims (7)

We claim:
1. An improved fluoropolymer-acrylic composition with enhanced weathering properties in which the fluoropolymer component is made by the polymerization of vinylidene fluoride and, optionally, other perhalogenated monomers and in which the acrylic component is made by the polymerization of predominantly acrylate and/or methacrylate esters, the improvement comprising using acrylate and/or methacrylate esters containing 10 to 50 weight % of straight chain (meth)acrylate esters having at least 3 carbons in the side chain and 50 to 90 weight % of straight chain (meth)acrylate esters having 1 or 2 carbons in the side chain.
2. A coating made from a latex dispersion of the composition of claim 1.
3. A coating made from a solvent dispersion of the composition of claim 1.
4. A coating made from a waterborne dispersion of the composition of claim 1.
5. A coating made from a solvent-based solution of the composition of claim 1.
6. A powder coating made using the composition of claim 1 as the principal resin component.
7. A solid material of the composition of claim 1 in the form of a caulk, solid foam, or extruded or molded article.
US10/135,670 2002-04-30 2002-04-30 Weatherable fluoropolymer-acrylic composition Expired - Lifetime US6635714B1 (en)

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US10/135,670 US6635714B1 (en) 2002-04-30 2002-04-30 Weatherable fluoropolymer-acrylic composition
EP03290922A EP1359193A1 (en) 2002-04-30 2003-04-14 Weatherable composition of fluoropolymer and acrylic polymer
JP2003123953A JP2004002845A (en) 2002-04-30 2003-04-28 Weatherable fluoropolymer-acrylic composition

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060264563A1 (en) * 2005-05-19 2006-11-23 Kevin Hanrahan Highly weatherable roof coatings containing aqueous fluoropolymer dispersions
US20100000601A1 (en) * 2006-08-04 2010-01-07 Arkema France Photovoltaic modules having a polyvinylidene fluoride surface
US20100175742A1 (en) * 2007-06-15 2010-07-15 Arkema Inc. Photovoltaic modules having a polyvinylidene fluoride backsheet
WO2020263937A1 (en) * 2019-06-25 2020-12-30 Arkema Inc. Hybrid functional fluoropolymers
WO2022232530A1 (en) * 2021-04-29 2022-11-03 Trinseo Europe Gmbh High heat acrylic copolymers containing a functional comonomer as binders for batteries

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1454955B1 (en) * 2003-03-07 2006-06-21 Rohm and Haas Electronic Materials, L.L.C. Levelling agents for cast ferroelectric polymer films
JP4492057B2 (en) * 2003-07-25 2010-06-30 ダイキン工業株式会社 Vinylidene fluoride copolymer resin film
US7267865B2 (en) * 2004-02-20 2007-09-11 Saint-Gobain Performance Plastics Corporation Draw resonant resistant multilayer films
US7297391B2 (en) * 2004-02-20 2007-11-20 Saint-Gobain Performance Plastics Corporation Draw resonance resistant multilayer films
US7901778B2 (en) * 2006-01-13 2011-03-08 Saint-Gobain Performance Plastics Corporation Weatherable multilayer film
US20100069488A1 (en) * 2008-09-17 2010-03-18 Michael John Mabey Fire retardant composition
US8344055B1 (en) 2009-07-01 2013-01-01 No-Burn Investments, L.L.C. Ammonium phosphate fire retardant with water resistance
WO2012036297A1 (en) * 2010-09-17 2012-03-22 ダイキン工業株式会社 Acryl-fluorine composite polymer particles, and aqueous dispersant
US8742004B1 (en) 2013-03-14 2014-06-03 Donald D. Sloan Coating system having long-term durability and chemical resistance
US10533109B2 (en) * 2014-07-01 2020-01-14 Arkema Inc. Stable aqueous fluoropolymer coating composition
EP3580288A4 (en) * 2017-02-08 2020-09-30 Akzo Nobel Coatings International B.V. A coating composition, the preparation method therefore and use thereof
CN110591472A (en) * 2019-08-26 2019-12-20 佛山科学技术学院 Modified water-based fluorocarbon coating and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5322899A (en) * 1992-07-21 1994-06-21 Ppg Industries, Inc. Fluoropolymer blend for coextrusion onto thermoplastic substrates
US5599873A (en) * 1993-12-23 1997-02-04 Fina Research, S.A. Fluorinated powder coatings for galvanized steel

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53146752A (en) * 1977-05-27 1978-12-20 Dainippon Ink & Chem Inc Polymer composition
US4383075A (en) * 1981-05-08 1983-05-10 Scm Corporation Thermosetting acrylic polyvinylidene fluorine composition
KR100333577B1 (en) * 1993-09-22 2002-10-18 다이낑 고오교 가부시키가이샤 Fluorinated Copolymer Aqueous Dispersion
JP3941128B2 (en) * 1995-12-18 2007-07-04 ダイキン工業株式会社 Powder coating composition
DE69918607T2 (en) 1998-03-05 2005-07-21 Solvay Solexis, Inc., Wilmington Weather resistant coating compositions of polyvinylidene fluoride containing polymethylmethacrylate
JP3289700B2 (en) * 1999-04-09 2002-06-10 ダイキン工業株式会社 Resin composition for water-based paint
JP2001001478A (en) * 1999-06-22 2001-01-09 Nakae Bussan Kk Molded article of polycarbonate or polyethylene terephthalate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5322899A (en) * 1992-07-21 1994-06-21 Ppg Industries, Inc. Fluoropolymer blend for coextrusion onto thermoplastic substrates
US5599873A (en) * 1993-12-23 1997-02-04 Fina Research, S.A. Fluorinated powder coatings for galvanized steel

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060264563A1 (en) * 2005-05-19 2006-11-23 Kevin Hanrahan Highly weatherable roof coatings containing aqueous fluoropolymer dispersions
WO2007030152A3 (en) * 2005-05-19 2007-10-18 Arkema Inc Highly weatherable roof coatings containing aqueous fluoropolymer dispersions
US7803867B2 (en) 2005-05-19 2010-09-28 Arkema Inc. Highly weatherable roof coatings containing aqueous fluoropolymer dispersions
CN101175814B (en) * 2005-05-19 2013-01-02 阿科玛股份有限公司 Highly weatherable roof coatings containing aqueous fluoropolymer dispersions
US20100000601A1 (en) * 2006-08-04 2010-01-07 Arkema France Photovoltaic modules having a polyvinylidene fluoride surface
US20100175742A1 (en) * 2007-06-15 2010-07-15 Arkema Inc. Photovoltaic modules having a polyvinylidene fluoride backsheet
US10050164B2 (en) * 2007-06-15 2018-08-14 Arkema Inc. Photovoltaic modules having a polyvinylidene fluoride backsheet
WO2020263937A1 (en) * 2019-06-25 2020-12-30 Arkema Inc. Hybrid functional fluoropolymers
WO2022232530A1 (en) * 2021-04-29 2022-11-03 Trinseo Europe Gmbh High heat acrylic copolymers containing a functional comonomer as binders for batteries

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