WO1996026980A1 - Thermoplastic fluoro resin compositions and moulded articles produced therefrom - Google Patents

Thermoplastic fluoro resin compositions and moulded articles produced therefrom Download PDF

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Publication number
WO1996026980A1
WO1996026980A1 PCT/EP1996/000845 EP9600845W WO9626980A1 WO 1996026980 A1 WO1996026980 A1 WO 1996026980A1 EP 9600845 W EP9600845 W EP 9600845W WO 9626980 A1 WO9626980 A1 WO 9626980A1
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Prior art keywords
weight
fluoro resin
moulded articles
copolymer
thermoplastic fluoro
Prior art date
Application number
PCT/EP1996/000845
Other languages
French (fr)
Inventor
Takatoshi Kuratsuji
Yoshiyuki Miyaki
Kazuyoshi Ohashi
Jérôme MAILLET
Original Assignee
Elf Atochem S.A.
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 S.A. filed Critical Elf Atochem S.A.
Priority to AU48317/96A priority Critical patent/AU4831796A/en
Publication of WO1996026980A1 publication Critical patent/WO1996026980A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—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
    • 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

Definitions

  • thermoplastic fluoro resin compositions and moulded articles produced therefrom in particular to thermoplastic fluoro resin compositions and moulded articles improved in melt-mouldability which permit high-speed extrusion and high-shear molding.
  • Thermoplastic fluoro resin possessing high weather- and chemical resistance is utilized in many fields such as paint, electrical or electronics parts, steel pipe liner, materials for chemical plant and stain- and weather-resistant film.
  • This resin is difficult to combine with other material due to its poor adhesiveness and its improvement is limited. Fibres of this resin are difficult to stretch due to their viscosity and crystallinity and their knot strength is low.
  • the use of a polymer possessing a high degree of polymerization which is indispensable to guarantee the desired properties of moulded articles, results in increasing its viscosity, so that such polymer cannot be extruded at high speed or through a small orifice of narrow cross-section.
  • the melt temperature is raised so as to lower the viscosity, the polymer decomposes in dead spaces of the extruder, resulting in defects in the moulded articles.
  • thermoplastic fluoro resin composition comprising (A) polyvinylidene fluoride and (B) vinylidene fluoride copolymer containing, as comonomers, 5 to 50 parts by weight of tetrafluoroethylene and 0 to 30 parts by weight of third monomers, the total proportion of the comonomers being 5 to 50 % by weight, the ratio of (A/B) being 95/5 to 40/60, preferably the logarithmic viscosity number (inherent viscosity: ⁇ inh) of polyvinylidene fluoride (A) being 0.6 to 1.8 dl/g and the logarithmic viscosity number of vinylidene fluoride VF2 copolymer (B) being 0.3 to 1.5 dl/g, the logarithmic viscosity number of PVDF (A) being higher than the
  • polyvinylidene fluoride (A) (hereinafter, polyvinylidene fluoride is expressed by PVDF) comprises mainly units or sequences of vinylidene fluoride VF2 but includes copolymer containing less than 3 % by weight of other comonomers such as trifluoroethylene (VF3), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), hexafluoropropylene (HFP) and perfluoroalkyl vinyl ethers.
  • VF3 trifluoroethylene
  • CTFE chlorotrifluoroethylene
  • VF vinyl fluoride
  • HFP hexafluoropropylene
  • perfluoroalkyl vinyl ethers perfluoroalkyl vinyl ethers
  • the vinylidene fluoride copolymer (B) also called “copolymer VF2 (B)” is a copolymer of VF2 and tetrafluoroethylene (TFE), the proportion of TFE being 5 to 50 % by weight, preferably 10 to 40 % by weight.
  • the copolymer VF2 (B) may contain other comonomers.
  • the proportion of other comonomers is 0 to 30 % by weight, preferably 0 to 25 % by weight and the total proportion of comonomers (TFE and third monomer(s)) is 5 to 50 % by weight, preferably higher than 20 % by weight but lower than to 45 % by weight.
  • the comonomers may be VF3, CTFE, VF, HFP, perfluoroalkyl vinyl ether and/or ethylene.
  • TFE is an indispensable component in the copolymer.
  • high ⁇ speed moulding or high-shear moulding which is another object of the present invention, cannot be improved by an other comonomer such as HFP and CFE alone
  • HFP and CFE alone
  • thermal stability is assured if TFE is incorporated in the copolymer when the third comonomer(s) is (are) incorporated so as to lower the melting point.
  • the weight ratio of (A/B) is 95/5 to 40/60, preferably 95/5 to 60/40. and depends on application.
  • the degrees of polymerization according to the present invention are such that the logarithmic viscosity number of PVDF (A) is 0.6 to 1.8 dl/g and the logarithmic viscosity number of copolymer VF2 (B) is 0.3 to 1.5 dl/g.
  • the logarithmic viscosity number ( ⁇ inh) is measured in N.N'-dimethylformamide solution at a polymer concentration of 0.4 g/dl.
  • the composition according to the present invention can be extruded directly from a dry blend of components or from two separate components.
  • Kneading and extrusion can be done by any known technique such as a Banbury mixer, rubber rolls and a single- or twin-screw extruder.
  • the resin composition is melt-kneaded at 100 to 300 °C, preferably 150 to 260 °C.
  • composition according to the present invention may contain known additives such as antioxidants, antipyrolysis agents, UV absorbents, antihydrolysis agents, colorants (dyes, pigments), antistatic agents, electrically conductive agents, crystal nucleating or improving agents, plasticizers, slip agents, lubricants, mould release agents, flame retardants, reinforcements, fillers, adhesives and tackifiers.
  • additives such as antioxidants, antipyrolysis agents, UV absorbents, antihydrolysis agents, colorants (dyes, pigments), antistatic agents, electrically conductive agents, crystal nucleating or improving agents, plasticizers, slip agents, lubricants, mould release agents, flame retardants, reinforcements, fillers, adhesives and tackifiers.
  • the articles moulded from the composition according to the present invention are not limited to special products but include those produced by injection, moulding, extrusion, rotational moulding and compression moulding, such as films, sheets, tubes and pipes.
  • the composition according to the present invention is not limited to injection and extrusion moulding in which the composition is subjected to high shear but is also useful as material for rotational moulding or for paint or coating.
  • Thermal decomposition of the composition according to the present invention does not occur under high shear even if the composition is heated for a long time, so that the products moulded therefrom possess improved heat-resistance and flexibility.
  • PVDF-A2 100 % PVDF homopolymer
  • ⁇ inh 0.8 PVDF-B0 100 % PVDF homopolymer
  • ⁇ inh 0.3 copolymer VF2-B1 : copolymer of VF2 and TFE (30 %)
  • ⁇ inh 0.6 copolymer VF2-B2: copolymer of VF2, TFE (20 %) and HFP (15 %)
  • ⁇ inh 0.6 copolymer VF2-C2: copolymer of VF2 and CTFE (30 %)
  • ⁇ inh 0.7
  • PVDF-A1 and copolymer VF2-B2 were blended in a proportion of 80/20 an the resulting blend was extruded from an extruder equipped with a flat die having slit of 500 ⁇ m and a width of 100 mm to produce a sheet.
  • the resin temperature wa 280 °C and the shear rate was about 1 ,000/s and the head pressure was 4 MPa
  • the resulting sheet showed good appearance. The same sheet was obtaine continuously even if the screw rotation speed was increased so that the hea pressure was raised to 7 MPa. Comparative Example 6
  • PVDF-A2 and copolymer VF2-B2 were blended in a proportion of 90/10.
  • a test sample 80 x 10 x 4 mm was produced from the resulting material by injection moulding.
  • the flexural modulus of this sample was measured according to ISO 178 and was 1 ,000 MPa.
  • compositions according to the present invention show neither decomposition nor fluctuation in high-shear and high-speed melt moulding and the moulded articles obtained therefrom show improved heat resistance and flexibility.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Artificial Filaments (AREA)

Abstract

The objective of the present invention is to provide a thermoplastic fluoro resin composition improved in melt-mouldability at high shear and high speed and in flexibility and heat resistance, and moulded articles obtained therefrom. The thermoplastic fluoro resin composition comprises: (A) polyvinylidene fluoride and (B) vinylidene fluoride copolymer containing, as comonomers, 5 to 50 parts by weight of tetrafluoroethylene and 0 to 30 parts by weight of third monomers, the total proportion of the comonomers being 5 to 50 % by weight, the weight ratio of (A/B) being 95/5 to 40/60, and moulded articles obtained therefrom.

Description

SPECIFICATION
THERMOPLASTIC FLUORO RESIN COMPOSITIONS AND MOULDED ARTICLES
PRODUCED THEREFROM
TECHNICAL FIELD
This invention relates to thermoplastic fluoro resin compositions and moulded articles produced therefrom, in particular to thermoplastic fluoro resin compositions and moulded articles improved in melt-mouldability which permit high-speed extrusion and high-shear molding. PRIOR ART
Thermoplastic fluoro resin possessing high weather- and chemical resistance is utilized in many fields such as paint, electrical or electronics parts, steel pipe liner, materials for chemical plant and stain- and weather-resistant film. This resin, however, is difficult to combine with other material due to its poor adhesiveness and its improvement is limited. Fibres of this resin are difficult to stretch due to their viscosity and crystallinity and their knot strength is low. In particular, the use of a polymer possessing a high degree of polymerization, which is indispensable to guarantee the desired properties of moulded articles, results in increasing its viscosity, so that such polymer cannot be extruded at high speed or through a small orifice of narrow cross-section. On the other hand, if the melt temperature is raised so as to lower the viscosity, the polymer decomposes in dead spaces of the extruder, resulting in defects in the moulded articles.
Several ideas have been proposed to facilitate melt-moulding of this resin at usual temperatures, such as a polymer possessing high flowability (JP-A-61-41318), a polymer possessing a low degree of polymerization (JP-B-58-29922), blending with a copolymer possessing a low degree of polymerization (JP-B-4-61087) and addition of plasticizer (JP-A-55-84413), polyolefin (JP-A-62-268811 ) or fluorocarbon wax (JP-A-60-115652). Known techniques improve the flowability of resin but flexibility of the moulded articles cannot be obtained. This prior art is silent with regard to thermal stability of the resin. It was confirmed that thermal stability of the resin described in the prior art is poor. DISCLOSURE OF THE INVENTION
An objective of the present invention is to provide a thermoplastic fluoro resin composition improved in mouldability and flexibility without spoiling thermal stability. The present invention provides a thermoplastic fluoro resin composition comprising (A) polyvinylidene fluoride and (B) vinylidene fluoride copolymer containing, as comonomers, 5 to 50 parts by weight of tetrafluoroethylene and 0 to 30 parts by weight of third monomers, the total proportion of the comonomers being 5 to 50 % by weight, the ratio of (A/B) being 95/5 to 40/60, preferably the logarithmic viscosity number (inherent viscosity: η inh) of polyvinylidene fluoride (A) being 0.6 to 1.8 dl/g and the logarithmic viscosity number of vinylidene fluoride VF2 copolymer (B) being 0.3 to 1.5 dl/g, the logarithmic viscosity number of PVDF (A) being higher than the logarithmic viscosity number of copolymer VF2 (B), and moulded articles produced therefrom.
"The polyvinylidene fluoride (A)" (hereinafter, polyvinylidene fluoride is expressed by PVDF) comprises mainly units or sequences of vinylidene fluoride VF2 but includes copolymer containing less than 3 % by weight of other comonomers such as trifluoroethylene (VF3), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), hexafluoropropylene (HFP) and perfluoroalkyl vinyl ethers.
"The vinylidene fluoride copolymer (B)" also called "copolymer VF2 (B)" is a copolymer of VF2 and tetrafluoroethylene (TFE), the proportion of TFE being 5 to 50 % by weight, preferably 10 to 40 % by weight. The copolymer VF2 (B) may contain other comonomers. The proportion of other comonomers is 0 to 30 % by weight, preferably 0 to 25 % by weight and the total proportion of comonomers (TFE and third monomer(s)) is 5 to 50 % by weight, preferably higher than 20 % by weight but lower than to 45 % by weight. The comonomers may be VF3, CTFE, VF, HFP, perfluoroalkyl vinyl ether and/or ethylene. TFE is an indispensable component in the copolymer. In other words, high¬ speed moulding or high-shear moulding, which is another object of the present invention, cannot be improved by an other comonomer such as HFP and CFE alone The reason for this cannot be given theoretically, but incompatibility of TFE- containing copolymer VF2 with PVDF homopolymer in addition to high strength contributed to TFE structure may play some part. Surprisingly, thermal stability is assured if TFE is incorporated in the copolymer when the third comonomer(s) is (are) incorporated so as to lower the melting point.
The weight ratio of (A/B) is 95/5 to 40/60, preferably 95/5 to 60/40. and depends on application. The degrees of polymerization according to the present invention are such that the logarithmic viscosity number of PVDF (A) is 0.6 to 1.8 dl/g and the logarithmic viscosity number of copolymer VF2 (B) is 0.3 to 1.5 dl/g. The logarithmic viscosity number (η inh) is measured in N.N'-dimethylformamide solution at a polymer concentration of 0.4 g/dl. The composition according to the present invention can be extruded directly from a dry blend of components or from two separate components. Kneading and extrusion can be done by any known technique such as a Banbury mixer, rubber rolls and a single- or twin-screw extruder. The resin composition is melt-kneaded at 100 to 300 °C, preferably 150 to 260 °C.
The composition according to the present invention may contain known additives such as antioxidants, antipyrolysis agents, UV absorbents, antihydrolysis agents, colorants (dyes, pigments), antistatic agents, electrically conductive agents, crystal nucleating or improving agents, plasticizers, slip agents, lubricants, mould release agents, flame retardants, reinforcements, fillers, adhesives and tackifiers.
The articles moulded from the composition according to the present invention are not limited to special products but include those produced by injection, moulding, extrusion, rotational moulding and compression moulding, such as films, sheets, tubes and pipes. The composition according to the present invention is not limited to injection and extrusion moulding in which the composition is subjected to high shear but is also useful as material for rotational moulding or for paint or coating.
Thermal decomposition of the composition according to the present invention does not occur under high shear even if the composition is heated for a long time, so that the products moulded therefrom possess improved heat-resistance and flexibility.
WAYS OF CARRYING OUT THE INVENTION EXAMPLES Nonlimitative Examples of the present invention will now be described.
The following test methods were used in evaluation: 1) Logarithmic viscosity number (η inh)
The logarithmic viscosity number (η inh) is measured in N.N - dimethylformamide solution at a polymer concentration of 0.4 g/dl. 2) Preparation of compositions
Pellets of PVDF (A) and of copolymer VF2 (B) are mixed in a blender and extruded from a single-screw extruder to prepare pellets for fibre and film. Barrel temperatures are set to 160 to 260 °C. 3) Thermal stability (Td) A thermobalance is charged with a sample of about 30 mg and is heated at a rate of 20 °C/min with air flow of 30 ml/min. Thermal stability (Td) is determined when weight loss becomes 5 %. The proportions and ratios indicated below are expressed by weight. The following polymers were used in Examples: PVDF-A1 100 % PVDF homopolymer , η inh = 1.3
PVDF-A2 100 % PVDF homopolymer , η inh = 0.8 PVDF-B0 100 % PVDF homopolymer , η inh = 0.3 copolymer VF2-B1 : copolymer of VF2 and TFE (30 %), η inh = 0.6 copolymer VF2-B2: copolymer of VF2, TFE (20 %) and HFP (15 %), η inh = 0.7 copolymer VF2-C1 : copolymer of VF2 and HFP (20 %), η inh = 0.6 copolymer VF2-C2: copolymer of VF2 and CTFE (30 %), η inh = 0.7
Examples 1 to 4. Comparative Examples 1 to 5
Polymers were blended as shown in Table 1 and the resulting blends wer extruded from an extruder equipped with a die having an orifice of 0.3 mm at 270 ° to produce fibre. The shear rate at this die was about 10,000/s and the resi temperature was 290 °C. The results of mouldability are summarized in Table 1 which reveals that the composition according to the present invention can be used high speed for a long time run.
Table 1
Examples polymers ratio test results
Comp.1 A1/B1 100/0 fluctuated
Comp.2 A1/B1 99/1 fluctuated
Ex. 1 A1/B1 70/30 stable extrusion and uniform filament
Ex. 2 A1/B2 90/10 stable extrusion and uniform filament
Ex. 3 A1/B2 70/30 stable extrusion and uniform filament
Ex. 4 A2/B2 80/20 stable extrusion and uniform filament
Comp.3 A1/C1 37/63 viscosity is too low, unstable
Comp.4 A1/C1 70/30 a little coloured after 72 hours
Comp.5 A1/C2 70/30 a little coloured after 60 hours
Example 5
PVDF-A1 and copolymer VF2-B2 were blended in a proportion of 80/20 an the resulting blend was extruded from an extruder equipped with a flat die having slit of 500 μm and a width of 100 mm to produce a sheet. The resin temperature wa 280 °C and the shear rate was about 1 ,000/s and the head pressure was 4 MPa The resulting sheet showed good appearance. The same sheet was obtaine continuously even if the screw rotation speed was increased so that the hea pressure was raised to 7 MPa. Comparative Example 6
For comparison, the same test was effected with PVDF-A1 alone. The head pressure was initially 8 MPa and exceeded 15 MPa when the screw rotation speed was increased and varied.
Example 6
PVDF-A2 and copolymer VF2-B2 were blended in a proportion of 90/10. A test sample (80 x 10 x 4 mm) was produced from the resulting material by injection moulding. The flexural modulus of this sample was measured according to ISO 178 and was 1 ,000 MPa.
Comparative Example 7
For comparison, the same test sample was produced from a blend of PVDF- A2 and copolymer PVDF-BO (proportion of 90/10). Injection mouldability was not changed but the flexural modulus was 1 ,800 MPa and the product showed poor flexibility. Simple blending with a polymer possessing a low degree of polymerization did not show a good result.
The compositions according to the present invention show neither decomposition nor fluctuation in high-shear and high-speed melt moulding and the moulded articles obtained therefrom show improved heat resistance and flexibility.

Claims

1. Thermoplastic fluoro resin composition characterized in that it comprises (A) polyvinylidene fluoride and (B) vinylidene fluoride copolymer containing, as comonomers, 5 to 50 parts by weight of tetrafluoroethylene and 0 to 30 parts by weight of third monomers, the total proportion of said comonomers (TFE and third monomer(s)) being 5 to 50 % by weight.
2. Composition according to claim 1 , wherein the logarithmic viscosity number (inherent viscosity: η inh) of polyvinylidene fluoride (A) is 0.6 to 1.8 dl/g and the logarithmic viscosity number of vinylidene fluoride copolymer (B) is 0.3 to 1.5 dl/g.
3. Composition according to claim 1 or 2, wherein the weight ratio of (A/B) is in the range 95/5 to 40/60, and preferably 95/5 to 60/40.
4. Composition according to any one of claims 1 to 3, wherein the weight proportion of tetrafluoroethylene is in the range 10 to 40 %.
5. Composition according to any one of claims 1 to 4, wherein the weight proportion of third monomer(s) is 0 to 25 parts by weight.
6. Composition according to any one of claims 1 to 5, wherein the total proportion is in the range 20 to 45 % by weight.
7. Moulded articles made of and/or based on and/or comprising a thermo¬ plastic fluoro resin composition as defined in any one of claims 1 to 6.
8. Extruded articles, such as fibres, films or sheets, made of and/or based on and/or comprising a thermoplastic fluoro resin composition as defined in any one of claims 1 to 6.
9. Paints and coatings made of and/or based on and/or comprising a thermoplastic fluoro resin composition as defined in any one of claims 1 to 6
PCT/EP1996/000845 1995-03-01 1996-02-28 Thermoplastic fluoro resin compositions and moulded articles produced therefrom WO1996026980A1 (en)

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Application Number Priority Date Filing Date Title
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Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7/41766 1995-03-01
JP4176695A JPH08239537A (en) 1995-03-01 1995-03-01 Thermoplastic fluorine-based resin composition and molding produced therefrom

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EP1342752A1 (en) * 2002-03-07 2003-09-10 Atofina Compositions based on polyvinylidene fluoride
EP1454954A1 (en) * 2001-10-15 2004-09-08 Kureha Chemical Industry Company, Limited Wire coating polymer composition
FR2877009A1 (en) * 2004-10-21 2006-04-28 Solvay POLYMERIC COMPOSITION BASED ON HOMOPOLYMER PVDF AND THERMOPLASTIC COPOLYMER FLUORINE
EP1715087A1 (en) * 2005-04-20 2006-10-25 Kureha Corporation Polyvinylidenefluoride resin monofilament and method for manufacturing thereof
US8252398B2 (en) 2007-12-27 2012-08-28 Kureha Corporation Adhesive vinylidene fluoride resin sheet
WO2013128142A1 (en) * 2012-03-01 2013-09-06 Arkema France Vinylidene polyfluoride composition
FR2999590A1 (en) * 2012-12-13 2014-06-20 Arkema France FORMULATION OF A POROUS FLUORINATED MEMBRANE IMPLEMENTED BY A STRETCHING METHOD
US20150041118A1 (en) * 2012-03-01 2015-02-12 Alain Chalumeau Method for Installing a self-supporting tower for Extracting Hydrocarbons
CN107922702A (en) * 2015-07-09 2018-04-17 阿科玛股份有限公司 It is used to prepare the composition based on hypocrystalline fluorinated polymer and nucleator of hard-gloss paint

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JPH11152366A (en) * 1997-11-19 1999-06-08 Asahi Chem Ind Co Ltd Porous membrane of vinylidene fluoride-based resin
JP6090683B1 (en) * 2016-11-09 2017-03-08 株式会社デュエル Polyvinylidene fluoride monofilament and method for producing polyvinylidene fluoride monofilament

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JPS616307A (en) * 1984-06-18 1986-01-13 Unitika Ltd Polyvinylidene fluoride monofilament
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FR2877009A1 (en) * 2004-10-21 2006-04-28 Solvay POLYMERIC COMPOSITION BASED ON HOMOPOLYMER PVDF AND THERMOPLASTIC COPOLYMER FLUORINE
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US8609756B2 (en) 2004-10-21 2013-12-17 Solvay (Societe Anonyme) Polymeric composition based on a PVDF homopolymer and a thermoplastic fluorocopolymer
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US8252398B2 (en) 2007-12-27 2012-08-28 Kureha Corporation Adhesive vinylidene fluoride resin sheet
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