WO2021118919A1 - Composition fluorée - Google Patents

Composition fluorée Download PDF

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Publication number
WO2021118919A1
WO2021118919A1 PCT/US2020/063568 US2020063568W WO2021118919A1 WO 2021118919 A1 WO2021118919 A1 WO 2021118919A1 US 2020063568 W US2020063568 W US 2020063568W WO 2021118919 A1 WO2021118919 A1 WO 2021118919A1
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Prior art keywords
fluorine
group
reactive functional
containing material
set forth
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PCT/US2020/063568
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English (en)
Inventor
Masatoshi Abe
Shigeru Aida
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Agc Chemicals Americas, Inc.
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Publication of WO2021118919A1 publication Critical patent/WO2021118919A1/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
    • 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
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the following disclosure relates to a fluorinated composition.
  • Conventional fluoropolymer compositions are used to form films suitable for lamination.
  • conventional fluoropolymer compositions include functional groups, which assist with achieving and maintaining lamination during and after lamination.
  • the inclusion of functional groups may result in yellowing of the film upon exposure to high temperatures that are realized during the lamination process.
  • there remains an opportunity to develop a fluorinated composition that has excellent adhesion to other materials yet is resistant to yellowing upon exposure to high temperatures.
  • the present disclosure provides a fluorinated composition.
  • the fluorinated composition includes a first fluorine-containing material having a melting point of at least 260°C and a reactive functional group content from 10 to 200 reactive functional groups for every 1,000,000 main chain carbon atoms.
  • the fluorinated composition further includes a second fluorine-containing material having a melting point of at least 260°C and a reactive functional group content greater than at least 700 reactive functional groups for every 1,000,000 main chain carbon atoms.
  • the reactive functional groups of the first and the second fluorine-containing materials are each independently selected from a group consisting of an anhydride group, a carbonyl group, a hydroxy group, an epoxy group, an isocyanate group, and combinations thereof.
  • the fluorinated composition includes the first fluorine-containing material and the second fluorine-containing material in a ratio of about 99/1 to about 20/80.
  • the fluorinated composition has a yellow index (YI) of less than 60 as measured in accordance with ASTM-E513-96
  • the present disclosure also provides a method of forming the fluorinated copolymer composition.
  • the method includes providing the first fluorine-containing material and providing the second fluorine-containing material.
  • the method further includes mixing the first and second fluorine-containing materials in a ratio of about 99/1 to about 20/80 to form the fluorinated composition.
  • the fluorinated composition of the present disclosure particularly due to the combination of the first and second fluorine-containing materials, has excellent adhesion to a variety of substrates and resists discoloration (e.g. yellowing) during high temperature processing, such as lamination.
  • a fluorinated composition includes a first fluorine-containing material and a second fluorine-containing material.
  • the polymeric portion of the fluorinated composition consists solely of the first and second fluorine-containing materials.
  • the fluorinated composition includes additional fluorine-containing materials in addition to the first and second fluorine-containing materials. Both the first and second fluorine- containing materials have a melting point of at least 260°C.
  • the first and second fluorine- containing materials are different, because the first fluorine-containing material has a reactive functional group content from 10 to 200 reactive functional groups for every 1,000,000 main chain carbon atoms, whereas the second fluorine-containing material has a reactive functional group content of at least 700 reactive functional groups for every 1,000,000 main chain carbon atoms.
  • the reactive functional groups of the first and second fluorine-containing materials are each independently selected from a group consisting of an anhydride group, a carbonyl group, a hydroxy group, an anhydride group, an epoxy group, an isocyanate group, and combinations thereof.
  • the first fluorine-containing material includes one or more fluorinated copolymers (hereinafter collectively referred to as fluorinated copolymer (A)).
  • the first fluorine-containing material may include one, two, three, four, five, or more fluorinated copolymers, with each fluorinated copolymer collectively referred to as fluorinated copolymer (A).
  • fluorinated copolymer (A) individually has a melting point of at least 260°C.
  • each fluorinated copolymer within fluorinated copolymer (A) also has a reactive functional group content from 10 to 200 reactive functional groups for every 1,000,000 main chain carbon atoms.
  • fluorinated copolymer included in fluorinated copolymer (A) has a melting point of at least 260°C and a reactive functional group content from 10 to 200 reactive functional groups for every 1,000,000 main chain carbon atoms
  • fluorinated copolymer (A) and the first fluorine- containing material also have these properties.
  • a detailed procedure setting forth the method for calculating the reactive functional group content is provided below.
  • Fluorinated copolymer (A) may include a fluorinated copolymer including units (i.e., monomers) derived from tetrafluoroethylene (TFE) and units derived from perfluoroalkyl vinyl ether (PAVE).
  • TFE tetrafluoroethylene
  • PAVE perfluoroalkyl vinyl ether
  • the phrase “including units derived from” means that the copolymer is formed from the reaction product of the units or a derivative of the unit(s).
  • fluorinated copolymer (A) is a copolymer of TFE and PAVE
  • fluorinated copolymer (A) is formed from the reaction product of TFE monomers and PAVE monomers.
  • R fl is a Ci-io perfluoroalkyl group which may have an oxygen atom between carbon atoms.
  • the perfluoroalkyl group (R fl ) length of the unit may be 2, 3, 4, 6, or 8 carbon atoms long.
  • the first fluorine-containing material includes a fluorinated copolymer derived from units of TFE and units of PPVE.
  • the fluorinated copolymer (A) is or includes a fluorinated copolymer derived from TFE, PAVE and an additional unit.
  • fluorinated copolymer (A) is or includes a fluorinated copolymer formed from units derived from TFE, units derived from PAVE (e.g. PPVE), and units derived from HFP.
  • the fluorinated copolymer (A) is or includes a fluorinated copolymer derived from an adhesive functional group-containing monomer (AM monomer).
  • the AM monomer may be, for example, an unsaturated hydrocarbon monomer having a functional group such as an anhydride group, an amido group, a hydroxy group, an amino group, a carbonyl group-containing group, an epoxy group, or an isocyanate group.
  • a dicarboxylic acid such as itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid or maleic acid or an acid anhydride such as itaconic acid anhydride, citraconic acid anhydride, 5-norbomene-2,3-di carboxylic acid anhydride or maleic acid anhydride may be mentioned.
  • the reactive functional group content of from 10 to 200 reactive functional groups of the first fluorine-containing material is a result of fluorinated copolymer (A) being derived from the AM monomer unit in combination with additional units described above.
  • fluorinated copolymer (A) includes a fluorinated copolymer derived from TFE units, PAVE units, and an AM monomer.
  • the reactive functional group content of the first fluorine-containing material is not required to be established via the inclusion of the AM monomer.
  • fluorinated copolymer (A) may be free of the copolymers derived from the AM monomer, with the reactive functional group content being established by grafting a carbonyl group, a hydroxy group, an anhydride group, an epoxy group, an isocyanate group reactive functional group on the main chain of fluorinated copolymer (A).
  • the reactive functional group content per 1,000,000 main chain carbon atoms of the first fluorine-containing material is from 10 to 190, 10 to 180, 10 to 170, 10 to 160, 10 to 150, 20 to 190, 30 to 190, 40 to 190, 50 to 190, 20 to 180, 30 to 170, 40 to 160, 50 to 150, 60 to 140, or 70 to 130. It should be appreciated that when the first fluorine-containing material includes more than one type of reactive functional group, the reactive functional group content is the total of each individual functional group.
  • the first fluorine-containing material includes 40 anhydride groups, 60 isocyanate groups, and 5 carbonyl groups per 1,000,000 main chain carbon atoms
  • the first fluorine-containing material includes 105 reactive functional groups per 1,000,000 main chain carbon atoms.
  • “main chain” carbon atoms are carbon atoms in the backbone (i.e., longest segment) of the polymer. Main chain carbon atoms are not carbon atoms in pendant chains connected to the backbone because the carbon atoms of any potential pendant chain do not form a portion of the longest segment (i.e., the backbone) of the polymer.
  • the functional group content is the amount of carbonyl groups, hydroxy groups, anhydride groups, epoxy groups, isocyanate groups, and combinations thereof.
  • other reactive functional groups e.g. an amine group
  • these other reactive functional groups are not included in the functional group calculation.
  • the method may vary dependent on the particular reactive functional group.
  • the reactive functional group is an anhydride
  • its content is measured by preparing a film with a thickness of 200 ⁇ 10 pm by press molding.
  • the film is formed by preheating for 8 minutes at 340°C followed by 2 minutes of pressing at 340°C with a pressure of lOMpa.
  • an IR spectra is collected on the film. From the IR spectra, the intensity at 1,800 cm l and 2,300 cm l is determined. The intensity at 1,800 cm l is then divided by the intensity at 2,300 cm l. The resulting value is then multiplied by a correction factor (e.g. constant) of 6.5. This calculated value is the reactive functional group content of the anhydride group per 1,000,000 main chain carbon atoms.
  • a correction factor e.g. constant
  • the reactive functional group is a hydroxyl group
  • its content is measured by preparing a film with a thickness of 200 ⁇ 10 pm by press molding.
  • the film is formed by preheating for 8 minutes at 340°C followed by 2 minutes of pressing at 340°C with a pressure of lOMpa.
  • an IR spectra is collected on the film. From the IR spectra, the intensity at 3,636 cm l is determined. The intensity is then multiplied by a correction factor of 2,200 and divided by the sample thickness in pm. This calculated value is the reactive functional group content of the hydroxyl group per 1,000,000 main chain carbon atoms.
  • the reactive functional group is a carbonyl group
  • its content is measured by preparing a film with a thickness of 200 ⁇ 10 pm by press molding.
  • the film is formed by preheating for 8 minutes at 340°C followed by 2 minutes of pressing at 340°C with a pressure of lOMpa.
  • an IR spectra is collected on the film. From the IR spectra, the intensity at 1,883 cm l is determined. The intensity is then multiplied by a correction factor of 406 and then divided by the sample thickness in pm. This calculated value is the reactive functional group content of the hydroxyl group per 1,000,000 main chain carbon atoms.
  • the weight average molecular weight of fluorinated copolymer (A) is not particularly limited.
  • the weight average molecular weight of fluorinated copolymer (A) is from 2,000 to 1,000,000 g/mol.
  • the weight average molecular weight of the first fluorinated copolymer is from 2,000 to 900,000, from 2,000 to 800,000, from 2,000 to 700,000, from 100,000 to 900,000, from 200,000 to 900,000, from 300,000 to 900,000, from 100,000 to 800,000, or from 300,000 to 700,000, g/mol.
  • the TFE units typically comprise from 90.0 to 99.9 mol % of fluorinated copolymer (A).
  • the TFE units may comprise from 95.0 to 99.9 mol % of fluorinated copolymer (A). This particular range of TFE is associated with excellent heat resistance, which may be compromised if the content of TFE is below the range set forth above.
  • the fluorinated copolymer (A) is derived from units derived from PAVE
  • the PAVE units typically comprise from 0.1 to 1.9 mol % of fluorinated copolymer (A). If the content of the units derived from PAVE is higher than the upper limit value, the crystallinity of the fluorinated copolymer (A) deteriorates, and the abrasion property and the mechanical strength thereby deteriorate.
  • fluorinated copolymer (A) is derived from TFE and PAVE units
  • the collective mol % of these units is typically from 90 to 100 mol %, or from 95 to 100 mol %, of fluorinated copolymer (A). If the total content is lower than the above lower limit value, the heat resistance is poor.
  • the melt flow rate (MFR) of fluorinated copolymer (A) is typically at least 0.1 and less than 15 g/lOmin. If the MFR is lower than the above lower limit value, the molding processability deteriorates, and thereby it is difficult to mold an insulating layer having a low surface roughness. On the other hand, if the MFR is higher than the above upper limit value, the binding force among molecules becomes low due to high molecular weight of the fluorinated copolymer (A), and the abrasion resistance of the insulating layer deteriorates.
  • the MFR may be at least 1 and less than 14, at least 2 and less than 13, or at least 3 and less than 12, g/lOMin.
  • the MFR falls within the above range, the abrasion resistance of the insulating layer is excellent. If the MFR is lower than the above lower limit value, the viscosity of the fluorinated copolymer (A) is too high, the melting workability is poor, melt fraction occurs, and an insulating layer having a high surface roughness is formed. On the other hand, if the MFR is higher than the above upper limit value, the abrasion resistance of the insulating layer deteriorates.
  • any reference to the MFR is a value measured by the method in accordance with ASTM D-3307.
  • the MFR of this disclosure is a value obtained by measuring a mass (g) of the fluorinated copolymer (A) flowing out for 10 minutes from a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 49 N at a measuring temperature of 372°C by using a melt indexer (for example, manufactured by Takara Thermistor Ltd.).
  • the melting point of the first fluorine-containing material is at least 260°C.
  • the melting point may be from 260 to 330, from 280 to 320, or from 290 to 315, °C.
  • the melting point is at least the above lower limit value, mechanical properties such as the abrasion resistance, the tensile strength, the tensile elongation and the elastic coefficient are excellent, and when the melting point is at most the above upper limit value, the molding property is excellent.
  • the second fluorine-containing material includes one or more fluorinated copolymers (hereinafter collectively referred to as fluorinated copolymer (B)).
  • the first fluorine-containing material may include one, two, three, four, five, or more fluorinated copolymers, with each fluorinated copolymer collectively referred to as fluorinated copolymer (B).
  • fluorinated copolymer (B) individually has a melting point of at least 260°C.
  • each fluorinated copolymer within fluorinated copolymer (B) also has a reactive functional group content of at least 700 reactive functional groups for every 1,000,000 main chain carbon atoms.
  • fluorinated copolymer included in fluorinated copolymer (B) has a melting point melting point of at least 260°C and a reactive functional group content of at least 700 for every 1,000,000 main chain carbon atoms, fluorinated copolymer (B) and the second fluorine-containing material also have these properties.
  • a detailed procedure setting forth the method for calculating the reactive functional group content is provided above.
  • Fluorinated copolymer (B) typically includes fluorocopolymer (XI) as the main component in an amount of at least 80 wt. % based on the total weight of fluorinated copolymer (B). In certain embodiments, fluorocopolymer (XI) is present in an amount of 85, 90, or even 100, wt.% based on the total weight of fluorinated copolymer (B).
  • the proportion of the fluorocopolymer (XI) to the total amount (100 mass %) of the material (X) may be at least 85 mass %, at least 90 mass %, or 100 mass %.
  • the fluorocopolymer (XI) is derived from at least unit (1) and unit (2), both of which are described in detail below. In certain embodiments, fluorocopolymer (XI) may also be derived from another unit(s) in addition to unit (1) and unit (2).
  • the unit (1) is a unit containing at least one type of functional group selected from the group consisting of a carbonyl group, a hydroxy group, an epoxy group, an isocyanate group, or an anhydride group (hereinafter referred to also as “functional group (i)”).
  • the carbonyl group is not particularly limited so long as it is a structure containing a carbonyl group, and, for example, a group having a carbonyl group between carbon atoms in a hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride residue group, a polyfluoroalkoxycarbonyl group, a fatty acid residue group, etc. may be mentioned.
  • a carboxy group and an acid anhydride residue group are used.
  • the hydrocarbon group may, for example, be an alkylene group having from 2 to 8 carbon atoms.
  • the number of carbon atoms in the alkylene group is the number of carbon atoms not containing (i.e. not bonded to) the carbonyl group.
  • the alkylene group may be linear or branched.
  • halogen atom in the haloformyl group a fluorine atom or a chlorine atom may, for example, be mentioned, and a fluorine atom is typical. That is, as the haloformyl group, a fluoroformyl group (referred to also as a carbonyl fluoride group) is typical.
  • the alkoxy group in the alkoxycarbonyl group may be linear or branched, and is typically an alkoxy group having from 1 to 8 carbon atoms, or a methoxy group or an ethoxy group.
  • a unit may be derived from a monomer (hereinafter referred to also as “monomer (ml)”) containing a functional group (i).
  • the functional group (i) in the monomer (ml) may be one, or two or more.
  • the monomer has two or more functional groups (i)
  • such two or more functional groups (i) may be respectively the same or different.
  • the monomer (ml) a compound having one functional group (i) and having one polymerizable double bond, is typical.
  • a cyclic hydrocarbon compound hereinafter referred to also as “monomer (m 1 -2)
  • the monomer (ml-1) may, for example, be an acid anhydride of an unsaturated dicarboxylic acid.
  • the acid anhydride of an unsaturated dicarboxylic acid may, for example, be itaconic anhydride (hereinafter referred to also as “IAH”), citraconic anhydride (hereinafter referred to also as “CAH”), 5-norbornene-2, 3 -dicarboxylic acid anhydride (another name: anhydrous high mix acid, hereinafter referred to also as “NAH”), maleic anhydride, etc.
  • the monomer (ml -2) may, for example, be an unsaturated dicarboxylic acid such as itaconic acid, citraconic acid, 5-norbornene-2, 3 -dicarboxylic acid, maleic acid, etc.; an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, etc.
  • the vinyl ester may, for example, be vinyl acetate, vinyl chloroacetate, vinyl butanoate, vinyl pivalate, vinyl benzoate, vinyl crotonate, etc.
  • the (meth)acrylate may, for example, be a (polyfluoroalkyl) acrylate, a (polyfluoroalkyl) methacrylate, etc.
  • the monomer containing a hydroxy group may, for example, be a vinyl ester, a vinyl ether, an allyl ether or a (meth)acrylate compound, and one having one or more hydroxy groups at its terminal or in its side chain, a crotonic acid-modified compound such as hydroxyethyl crotonate, or allyl alcohol, may, for example, be mentioned.
  • the monomer containing an epoxy group may, for example, be an unsaturated glycidyl ether (e.g. allyl glycidyl ether, 2-methyl allyl glycidyl ether, vinyl glycidyl ether, etc.), an unsaturated glycidyl ester (e.g. glycidyl acrylate, glycidyl methacrylate, etc.), etc.
  • unsaturated glycidyl ether e.g. allyl glycidyl ether, 2-methyl allyl glycidyl ether, vinyl glycidyl ether, etc.
  • an unsaturated glycidyl ester e.g. glycidyl acrylate, glycidyl methacrylate, etc.
  • the monomer containing an isocyanate group may, for example, be an unsaturated monomer having an isocyanate group, such as 2-(meth)acryloyloxyethyl isocyanate, 2-(2- (meth)acryloyloxyethoxy)ethyl isocyanate, l,l-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc.
  • the monomer (ml) one type may be used alone, or two or more types may be used in combination.
  • typically unit (1) has at least a carbonyl group-containing group as a functional group (i). Therefore, the monomer (ml) typically includes a monomer containing a carbonyl group-containing group.
  • the monomer (m 1-1) is typically selected for this property.
  • at least one member selected from the group consisting of IAH, CAH and NAH may be used.
  • IAH, CAH and NAH it is possible to easily produce a fluorocopolymer having an acid anhydride residue group, without necessity of using a special polymerization method (see JP-A- 11-193312) which is required when maleic anhydride is used.
  • Unit (2) is typically a unit derived from tetrafluoroethylene (hereinafter referred to also as “TFE”). Other units other than unit (1) and unit (2) may, for example, be a unit (3-1), a unit (3- 2), a unit (4), etc.
  • TFE tetrafluoroethylene
  • Other units other than unit (1) and unit (2) may, for example, be a unit (3-1), a unit (3- 2), a unit (4), etc.
  • the fluorocopolymer (XI) specific examples include, but are not limited to, a tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer (PFA), a tetrafluoroethylene/hexafluoropropylene copolymer (FEP), and their modified products.
  • fluorocopolymer (XI) may be further defined as fluorocopolymer (Xl-1) or fluorocopolymer (Xl-2).
  • Fluorocopolymer (Xl-1) has unit (1), unit (2) described above, but also includes unit (3- 1) and may further include unit (3-2) and/or unit (4).
  • Unit (3-1) is a unit derived from a PAVE or more specifically PPVE as described above.
  • Unit (3-2) is a unit derived from hexafluoropropylene (hereinafter referred to also as “HFP”).
  • Unit (4) is a unit other than units (1), (2), (3-1) and (3-2) and may, for example, be a unit derived from a monomer other than the monomer (ml), TFE, PAVE and HFP.
  • Such other monomer may, for example, be a fluorinated monomer (but excluding the monomer (ml), TFE, PAVE and HFP) (hereinafter referred to also as “monomer (m4-l)”), a non- fluorinated monomer (but excluding the monomer (ml)) (hereinafter referred to also as “monomer (m4-2)”), etc.
  • a fluorinated compound having one polymerizable double bond and, for example, a fluoroolefm (but excluding TFE and HFP) such as vinyl fluoride, vinylidene fluoride (hereinafter referred to also as “VdF”), trifluoroethylene, chlorotrifluoroethylene (hereinafter referred to also as “CTFE”), etc.
  • CF 2 CF0R n S0 2 X
  • R n is a Ci-io perfluoroalkylene group, or a C2-10 perfluoroalkylene group containing an etheric oxygen atom, and X 3 is a halogen atom or a hydroxy group
  • monomer (m4-2) a non-fluorinated compound having one polymerizable double bond is typical, and, for example, an olefin having at most 3 carbon atoms, such as ethylene or propylene. One of them may be used alone, or two or more of them may be used in combination. [0065] In certain embodiments, monomer (m4-2) may be ethylene or propylene.
  • one type may be used alone, or two or more types may be used in combination.
  • two or more monomers (m4-l) may be used in combination, or two or more monomers (m4-2) may be used in combination, or at least one monomer (m4-l) and at least one monomer (m4-2) may be used in combination.
  • the fluorocopolymer (Xl-1) may be one composed of unit (1), unit (2) and unit (3-1), or one composed of unit (1), unit (2), unit (3-1) and unit (3-2), or one composed of unit (1), unit (2), unit (3-1) and unit (4), or one composed of unit (1), unit (2), unit (3-1), unit (3-2) and unit (4).
  • fluorocopolymer (Xl-1) is a copolymer having the unit derived from a monomer containing a carbonyl group-containing group, unit (2) and unit (3-1).
  • fluorocopolymer (Xl-1) is a copolymer having the unit derived from the monomer (ml-1), unit (2) and unit (3-1).
  • the fluorocopolymer (Xl-1) may, for example, be a TFE/PPVE/NAH copolymer, a TFE/PPVE/IAH copolymer, a TFE/PPVE/CAH copolymer, etc.
  • the fluorocopolymer (Xl-1) may have a functional group (i) as a main chain terminal group.
  • a functional group (i) as a main chain terminal group an alkoxycarbonyl group, a carbonate group, a carboxy group, a fluoroformyl group, an acid anhydride residue group, a hydroxy group, may be included.
  • Such a functional group may be introduced by suitably selecting a radical polymerization initiator, a chain transfer agent or the like to be used at the time of producing the fluorocopolymer (Xl-1).
  • the proportion of (1) to the total (100 mol %) of all units constituting the fluorocopolymer (Xl-1) may be from 0.01 to 3 mol %, from 0.03 to 2 mol %, or from 0.05 to 1 mol %.
  • the proportion of unit (2) to the total of all units constituting the fluorocopolymer (XI- 1) is from 90 to 99.89 mol %, from 95 to 99.47 mol %, or from 96 to 98.95 mol %.
  • the fluorocopolymer (Xl-1) will be excellent in electrical characteristics (low relative dielectric constant, etc.), heat resistance, chemical resistance, etc.
  • the fluorocopolymer (Xl-1) will be excellent in melt moldability, stress cracking resistance, etc.
  • the proportion of unit (3-1) to the total of all units constituting the fluorocopolymer (Xl-1) is typically from 0.1 to 9.99 mol %, from 0.5 to 9.97 mol %, or from 1 to 9.95 mol %. When the content of unit (3-1) is within the above range, the fluorocopolymer (Xl-1) will be excellent in moldability.
  • the total proportion of units (1), (2) and (3-1) to the total of all units in the fluorocopolymer (Xl-1) is typically at least 90 mol %, at least 95 mol %, or at least 98 mol %.
  • the upper limit of such a total proportion is not particularly limited and may be 100 mol %.
  • the content of each unit in the fluorocopolymer (Xl-1) can be measured by a NMR analysis such as a molten nuclear magnetic resonance (NMR) analysis, a fluorine content analysis, an infrared absorption spectrum analysis, etc.
  • NMR molten nuclear magnetic resonance
  • fluorine content analysis a fluorine content analysis
  • infrared absorption spectrum analysis etc.
  • the fluorocopolymer (XI -2) has unit (1), unit (2) and unit (3-2). As the case requires, it may further contain unit (3-1) and/or unit (4).
  • the fluorocopolymer (XI -2) may include unit (1), unit (2) and unit (3-2), or one composed of unit (1), unit (2), unit (3-2) and unit (3-1), or one composed of unit (1), unit (2), unit (3-2) and unit (4), or one composed of unit (1), unit (2), unit (3-2), unit (3-1) and unit (4).
  • fluorocopolymer (XI -2) is a copolymer having the unit derived from the monomer containing a carbonyl group-containing group, unit (2) and unit (3-2), or is a copolymer having the unit derived from the monomer (ml-1), unit (2) and unit (3-2).
  • fluorocopolymer (XI -2) may, for example, be a TFE/HFP/NAH copolymer, a TFE/HFP/IAH copolymer, a TFE/HFP/CAH copolymer, etc.
  • the fluorocopolymer (XI -2) may have a functional group (i) as a main chain terminal group.
  • the functional group (i) may be the same as described above.
  • the proportion of unit (1) to the total (100 mol %) of all units constituting the fluorocopolymer (Xl-2) is from 0.01 to 3 mol %, from 0.02 to 2 mol %, or from 0.05 to 1.5 mol %.
  • the proportion of unit (2) to the total of all units constituting the fluorocopolymer (XI- 2) is from 90 to 99.89 mol %, from 91 to 98 mol %, or from 92 to 96 mol %.
  • the fluorocopolymer (Xl-2) will be excellent in electrical characteristics (low relative dielectric constant, etc.), heat resistance, chemical resistance, etc.
  • the fluorocopolymer (Xl-2) will be excellent in melt moldability, stress cracking resistance, etc.
  • the proportion of unit (3-2) to the total of all units constituting the fluorocopolymer (Xl-2) is from 0.1 to 9.99 mol %, from 1 to 9 mol %, or from 2 to 8 mol %. When the content of unit (3-2) is within the above range, the fluorocopolymer (Xl-2) will be excellent in moldability.
  • the total proportion of units (1), (2) and (3-2) to the total of all units in the fluorocopolymer (Xl-2) is typically at least 90 mol %, at least 95 mol %, or at least 98 mol %. The upper limit for such a total proportion is not particularly limited and may be 100 mol %.
  • the reactive functional group content per 1,000,000 main chain carbon atoms of the second fluorine-containing material is at least 700 reactive functional groups for every 1,000,000 main chain carbon atoms.
  • the reactive functional group content for every 1,000,000 main chain carbon atoms may be from 700 to 2,500, from 700 to 2,300, from 700 to 2,100, from 700 to 1,900, from 700 to 1,700, from 700 to 1,500, from 700 to 1,300, from 800 to 2,500, from 900 to 2,500, from 1,000 to 2,500, from 700 to 1,300, from 750 to 1,250, from 800 to 1,200, or from 850 to 1,150.
  • the melting point of the second fluorine-containing material is at least 260°C.
  • the melting point of the second fluorine-containing material is from 260 to 320, 280 to 320, 295 to 315, or 295 to 310, °C.
  • the heat resistance will be excellent, and when it is at most the upper limit value in the above range, the melt moldability will be excellent.
  • the fluorinated composition may include the first fluorine-containing material and the second fluorine-containing material in a ratio of from about 99/1 to about 20/80. In certain embodiments, the ratio of the first fluorine-containing material to the second fluorine-containing material is from 95/5 to 20/80, 90/10 to 20/80, or 90/10 to 40/60.
  • the average particle size of the first and second fluorine- containing materials is individually less than 600 pm.
  • the average particle size may be from 0.1 to 600, 0.1 to 500, 0.1 to 400, 0.1 to 300, 0.1 to 200, 0.1 to 100, 0.1 to 50, 0.1 to 10, pm.
  • the average particle size of the first and second fluorine-containing materials is less than 10 pm.
  • the first fluorine-containing material and second fluorine- containing material may be in the form of a powder.
  • the first fluorine-containing material has an average particle size (D50) from 25 to 35 microns, alternatively from 26 to 33, or from 28 to 31 microns.
  • the second fluorine-containing material has an average particle size (D50) from 30 to 40 microns, alternatively from 33 to 37, or from 34 to 36 microns.
  • the average particle size is measured by using a 2.000 mesh sieve (mesh opening 2.400 mm), a 1.410 mesh sieve (mesh opening 1.705 mm), a 1.000 mesh sieve (mesh 1.205 mm), a 0.710 mesh sieve (mesh opening 0.855 mm), a 0.500 mesh sieve (mesh opening 0.605 mm), a 0.250 mesh sieve (mesh opening 0.375 mm), a 0.149 mesh sieve (mesh opening 0.100 mm) and a receiving tray, stacked in this order.
  • a sample is placed thereon and sieved by a shaker for 30 minutes. Thereafter, the mass of the sample remaining on each sieve is measured, and the cumulative transit mass for each opening is represented in a graph, whereby a particle size at the time when the cumulative transit mass becomes 50% is adopted as the average particle size of the sample.
  • the fluorinated composition may have a reactive functional group content of from 200 to 1000 reactive functional groups for every 1,000,000 main chain carbon atoms based on the weight average of the first and the second fluorine-containing materials.
  • the fluorinated composition may have a reactive functional group content of from 200 to 900, from 200 to 800, from 200 to 700, from 200 to 600, from 200 to 500, from 300 to 900, from 400 to 900, from 500 to 900, from 600 to 900, from 300 to 800, or from 400 to 700, reactive functional groups for every 1,000,000 main chain carbon atoms based on the weight average of the first and the second fluorine-containing materials.
  • the fluorinated composition may include additives such as a reinforcing filler, a plasticizer, a flame retardant, etc. If included, the additives are typically included in at most 50% of the volume of the fluorinated composition. Alternatively, the total volumes of the additives may be from 1 to 40 vol % or from 3 to 30 vol %.
  • the reinforcing filler may include carbon black, carbon nanofiber, carbon fiber, carbon milled fiber, graphite, graphene or nano-diamond.
  • the reinforcing filler may be particulate filler comprising a central carbon-based core having an average size in the range of about 350 to 1000 microns selected from the group consisting of natural graphite, synthetic graphite, carbon black and mixtures thereof.
  • the reinforcing filler may be a conductive metal coating of one or more metals selected from the group consisting of nickel, copper, aluminum, tin, cobalt, zinc, gold, silver, platinum, palladium, rhodium, iridium, indium and their alloys encapsulating said central carbon-based core.
  • the conductive metal, composite metals or alloys thereof comprise about 20 to 90 weight % of the coated particles, or about 40 to 90 weight % of the coated particles.
  • the conductive metal preferably is nickel and the central carbon-based core typically is natural graphite or synthetic graphite having an average particle size of about 600 microns, the nickel comprising about 40 to 80 weight %, or about 60 weight %, of the coated particles.
  • a noble metal such as gold or silver forming a coating on a non-noble metal coating such as nickel encapsulating the central carbon- based core may comprise 1 to 40 weight % of the coated particle.
  • Plasticizers and flame retardants for use in the fluorinated composition are not particularly limited, and known plasticizers and flame retardants may be employed.
  • plasticizers phthalic acid esters, adipic acid esters, etc. may be used.
  • flame retardants aluminum hydroxide, magnesium hydroxide, magnesium carbonate, antimony trioxide, sodium antimonate, antimony pentoxide, phosphazene compounds, phosphoric acid esters, ammonium polyphosphate, melamine polyphosphate, melam, melem, red phosphorus, molybdenum compounds, borate compounds, PTFE, etc.
  • the fluorinated composition also has excellent resistance to yellowing as shown by its Yellow Index (YI).
  • the fluorinated composition typically has a YI of less than 60 as measured in accordance with ASTM-E513-96 with a film specimen having a thickness of 0.2 ⁇ 0.02mm prepared by pressure molding with a mold temperature 340°C, a mold time of 10 minutes including a 8 minute preheating, and a pressure of 10 Mpa.
  • the YI of the fluorinated composition may be from 5 to 60, 5 to 50, or 5 to 40.
  • the fluorinated composition may consist essentially of the first and second fluorine-containing materials.
  • the term “consists essentially of’ with respect to the fluorinated composition means that the fluorinated composition may include additional components up to 5 wt.% based on the total weight of the fluorinated composition, provided that the additional components do not negatively impact the resistance to yellowing or adhesive properties of the fluorinated composition.
  • the fluorinated composition may consist essentially of the first and second fluorine-containing materials and still include up to a combined total amount of 5 wt.% of the reinforcing fillers, flame retarders, and plasticizers described above.
  • the fluorinated composition when the fluorinated composition consists essentially of the first and second fluorine-containing materials, the fluorinated composition includes the first and second fluorine-containing materials in an amount of at least 95 parts by weight and further include up to 5 parts by weight of additional components that do not negatively impact the resistance to yellowing or adhesive properties of the fluorinated composition, with each weight based on 100 parts by weight of the fluorinated composition.
  • the only polymeric portion of the fluorinated composition is the first and second fluorine-containing materials.
  • the fluorinated composition does not include polymers other than the first and second fluorine-containing materials.
  • the fluorinated composition consists of the first and second fluorine-containing materials, such that the fluorinated composition includes no additional polymers, additives, components, etc.
  • the fluorinated composition consists of the first and second fluorine-containing materials, the first and second fluorine-containing materials are present in a combined total amount of 100 parts by weight, based on 100 parts by weight of the fluorinated composition.
  • the fluorinated composition does not include a polyimide, which would be expected to decrease the yellowing resistance of the fluorinated composition.
  • the fluorinated composition only includes polymers that are fluorine-containing polymers.
  • the fluorinated composition may include fluorine-containing polymers other than the first and second fluorine-containing materials but may not include polymers which do not include fluorine.
  • Uses for the fluorinated composition are not particularly limited.
  • One particular advantageous use is a film.
  • the thickness of the film is typically from 10 pm to 5 mm, from 20 pm to 1 mm, or from 20 to 500 pm. Once the film is formed, the film may then be laminated to a substrate to form a coated article.
  • a method for forming a film from the fluorinated composition a known method such as a spin coating method, a cast method, a press method or a melt extrusion method may be used. Among them, since a film having high uniformity of the film thickness, an excellent optical transparency and few contaminates can be obtained, the cast method is typically used. Suitable film forming processes are also disclosed in U.S. 2014/0187728, which is hereby incorporated by reference in its entirety.
  • the fluorinated composition may also be used to coat an article (i.e., substrate). For example, the film produced from the fluorinated composition may be laminated to a substrate.
  • the fluorinated composition may also be used to coat PTC materials.
  • PTC materials are materials whose resistivity increases sharply with temperature over a relatively small temperature range.
  • the fluorinated composition that may be used to coat PTC materials which have been used or proposed for use in such electrical devices are certain ceramics and certain conductive polymers, the term "conductive polymer” being used herein to denote a composition which comprises an organic polymer (this term being used to include polysiloxanes) and, dispersed or otherwise distributed in the organic polymer, a particulate conductive filler.
  • Suitable ceramic materials include doped barium titanates, and suitable conductive polymers include crystalline polymers having carbon black dispersed therein.
  • PTC ceramics generally exhibit a sharp change in resistivity at the Curie point of the material, and PTC conductive polymers generally exhibit a sharp change in resistivity over a temperature range just below the crystalline melting point of the polymeric matrix.
  • the PTC ceramics which are used in commercial practice generally show a sharper rate of increase in resistivity than do the PTC conductive polymers.
  • PTC ceramics generally have a resistivity of at least 30 ohm-cm at 23° C, whereas PTC conductive polymers can have a lower resistivity at 23° C, e.g. down to about 1 ohm-cm or lower.
  • PTC ceramics tend to crack and thus to fail suddenly if exposed to excessive electrical stress, whereas PTC conductive polymers tend to degrade relatively slowly.
  • the fluorinated composition is particularly useful for coating PTC materials because of its relatively high melting point and excellent heat resistance. These properties lend themselves to the longer term and wide range of temperatures that PTC materials are often exposed to. Moreover, because the fluorinated composition has a relatively high resistivity, even under high temperatures, the fluorinated composition assists in controlling current flow through the circuit.
  • the present disclosure also provides a method of forming the fluorinated composition.
  • the method includes providing the first fluorine-containing material and providing the second fluorine-containing material.
  • the method also includes mixing the first and second fluorine-containing materials to form the fluorinated composition.
  • the first and second fluorine-containing materials are in the form of a powder prior to mixing.
  • Samples 1-5 and Comparative Examples 1-4 were formed and evaluated for adhesion and yellowing. Compositions for Samples 1-5 and Comparative Examples 1-4 are provided below in Table I.
  • Copolymer 1 is a PFA copolymer including PPVE at 1.5 mol % of the total structural units, with 94 reactive hydroxyl groups and 64 reactive carbonyl groups per 1,000,000 main chain carbon atoms (total of 154 reactive functional groups per 1,000,000 main chain carbon atoms). Copolymer 1 is in powder form and has an average particle size (D50) of 28.65 pm. Copolymer 1 is commercially available from AGC Inc. under the tradename Fluon PFA.
  • Copolymer 2 is a PFA copolymer including PPVE at 1.5 mol % of the total structural units, with 73 reactive hydroxyl groups per 1,000,000 main chain carbon atoms (total of 73 reactive functional groups per 1,000,000 main chain carbon atoms). Copolymer 2 also has a melting point of 310°C and an MFR of 13.5. Copolymer 2 is in powder form and has an average particle size (D50) of 30.15 pm. Copolymer 2 is commercially available from AGC Inc. under the tradename Fluon PFA.
  • Copolymer 3 is formed from NAH:TFE:PPVE (0.1:97.9:2.0 molar ratio), with 144 reactive carbonyl groups and 989 reactive anhydride groups per 1,000,000 main chain carbon atoms (total of 1,133 reactive functional groups per 1,000,000 main chain carbon atoms). Copolymer 3 also have a melting point of 310°C. Copolymer 3 is in powder form and has an average particle size (D50) of 35.75 pm. Copolymer 3 is commercially available from AGC Inc. under the tradename Fluon Adhesive.
  • any ranges and subranges relied upon in describing various embodiments of the present disclosure independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein.
  • One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present disclosure, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one example, a range “of from 0.1 to 0.9” may be further delineated into a lower third, i.e.
  • a range of “at least 10” inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
  • an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
  • a range “of from 1 to 9” includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

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Abstract

Composition fluorée comprenant un premier matériau contenant du fluor ayant un point de fusion d'au moins 260 °C et une teneur en groupe fonctionnel réactif de 10 à 200 groupes fonctionnels réactifs pour tous les 1 000 000 atomes de carbone de chaîne principale. La composition fluorée comprend en outre un second matériau contenant du fluor ayant un point de fusion d'au moins 260 °C et une teneur en groupe fonctionnel réactif supérieure à au moins 700 groupes fonctionnels réactifs pour tous les 1 000 000 atomes de carbone de chaîne principale. Les groupes fonctionnels réactifs des premier et second matériaux contenant du fluor sont chacun indépendamment choisis dans un groupe constitué d'un groupe anhydride, d'un groupe hydroxyle, d'un groupe époxy, d'un groupe isocyanate et de combinaisons de ceux-ci. Un rapport du premier matériau contenant du fluor au second matériau contenant du fluor est d'environ 99/1 à environ 20/80. La composition fluorée présente un indice de jaune (YI) inférieur à 60 tel que mesuré conformément à ASTM-E513-96.
PCT/US2020/063568 2019-12-12 2020-12-07 Composition fluorée WO2021118919A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11193312A (ja) 1997-10-15 1999-07-21 E I Du Pont De Nemours & Co 無水マレイン酸またはマレイン酸とフッ素化されたオレフィンとの共重合体
JP2007314720A (ja) 2006-05-29 2007-12-06 Asahi Glass Co Ltd ガラス繊維強化複合材料、その製造方法およびプリント回路基板
JP2012112448A (ja) * 2010-11-24 2012-06-14 Asahi Glass Co Ltd 自動車用シールリング、産業ガス圧縮機用シールリング及び摺動部品
US20140187728A1 (en) 2011-10-05 2014-07-03 Asahi Glass Company, Limited Process for producing fluorinated olefin/vinyl alcohol copolymer and film made by forming a composition containing the copolymer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11193312A (ja) 1997-10-15 1999-07-21 E I Du Pont De Nemours & Co 無水マレイン酸またはマレイン酸とフッ素化されたオレフィンとの共重合体
JP2007314720A (ja) 2006-05-29 2007-12-06 Asahi Glass Co Ltd ガラス繊維強化複合材料、その製造方法およびプリント回路基板
JP2012112448A (ja) * 2010-11-24 2012-06-14 Asahi Glass Co Ltd 自動車用シールリング、産業ガス圧縮機用シールリング及び摺動部品
US20140187728A1 (en) 2011-10-05 2014-07-03 Asahi Glass Company, Limited Process for producing fluorinated olefin/vinyl alcohol copolymer and film made by forming a composition containing the copolymer

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