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WO1996017019A1 - Thermoplastic fluoro resin composition and fiber - Google Patents

Thermoplastic fluoro resin composition and fiber Download PDF

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Publication number
WO1996017019A1
WO1996017019A1 PCT/EP1995/004695 EP9504695W WO9617019A1 WO 1996017019 A1 WO1996017019 A1 WO 1996017019A1 EP 9504695 W EP9504695 W EP 9504695W WO 9617019 A1 WO9617019 A1 WO 9617019A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic
fiber
acid
fluoro resin
composition
Prior art date
Application number
PCT/EP1995/004695
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
Priority claimed from JP29519294A external-priority patent/JPH08151496A/en
Priority claimed from JP7015099A external-priority patent/JPH08209437A/en
Priority claimed from JP1510095A external-priority patent/JPH08209438A/en
Priority claimed from JP11179795A external-priority patent/JPH08208927A/en
Application filed by Elf Atochem S.A. filed Critical Elf Atochem S.A.
Priority to AU41768/96A priority Critical patent/AU4176896A/en
Publication of WO1996017019A1 publication Critical patent/WO1996017019A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43835—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4318—Fluorine series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters

Definitions

  • thermoplastic fluoro resin compositions and fibers relate to those based on thermoplastic fluoro resin and thermoplastic polyamide elastomer (hereinafter, PAEs) and/or thermoplastic copolyester elastomers (hereinafter, TPEEs).
  • PAEs thermoplastic fluoro resin and thermoplastic polyamide elastomer
  • TPEEs thermoplastic copolyester elastomers
  • Thermoplastic fluoro resin possessing high weather- and chemical- resistances is utilised in many fields such as paint, electric or electronics parts, steel pipe liner, materials for chemical plants and staining and weather resisting film. This resin, however, is difficult to be combined with other material due to its poor adhesive property and its improvement is limited. Thermoplastic fluoro resin fibers are difficult to be stretched due to their viscosity and shows poor knot strength
  • thermoplastic fluoro resin In order to improve this resin, several ideas such as alloying with polymethylmethacrylate (PMMA)(JP-B-43-12012 et al) and combination with polycarbonate (JP-A-57-8244 et al), with polyethylene (JP-B-3-22901 et al), with functional denatured polyolefin (JP-A-62-57448 et al) and with polyimide (JP-A-2-308856) are proposed but are not satisfactory.
  • Known compositions of thermoplastic fluoro resin are classified into two types of complete solution type (PMMA) and macro-phase dispersion type (variety) but it was not yet found such a system in which mixed components disperse uniformly without compatibility-improving agent and properties of components become complementary.
  • JP-A-4-28760 discloses a composition of polyester block copolymer and fluoro resin. An object of this patent is to modify polyether elastomer with a small proportion of fluoro resin and
  • thermoplastic fluoro resin fiber In order to improve thermoplastic fluoro resin fiber, a variety of combinations with other polymers such as polymethylmethacrylate (PMMA)(JP- B-43-12012 et al), isobutylene copolymer (JP-A-54-106622 et al), acrylate (JP- B-56-20610 et al), blending with other fluoro polymers (JP-B-4-44012, JP-A-60- 104514 et al), plasticizer (JP-A-55-84413 et al), polyolefin (JP-A-62-57448 et al), metal soap (JP-A-61-174418 et al), fluorocarbon wax (JP-A-60-115652 et al) and their combination (JP-A-6-101114 et al) are proposed. Improvement in spinning and stretching is also proposed (JP-B-53-22574 et al).
  • PMMA polymethylmethacrylate
  • PAE possessing high shock-resistance at low temperatures, anti static property and light weightiness is widely used in tube, hose, industrial parts and shoes such as ski boots. PAE show rather poor chemical- and heat-resistances and hence its usage is limited.
  • PAE is combined with polyamide (PA) (JP-B-5-2150 et al), with polyester (JP-B-5-37179 et al), with polycarbonate (JP-A-60-141757 et al), with polyoxymethylene (JP-A-59-191752 et al), with polyphenylene ether (JP-A-60-186560 et al), with polyolefin (JP-A-57-147520 et al), with polystyrene (JP-A-60- 17064 et al), with polyvinylchloride (JP-B-3-2903 et al), ionomer (JP- B-1 -56096 et al) and with polyepoxide (JP-B-2-50955 et al).
  • PA polyamide
  • PA polyamide
  • polyester JP-B-5-37179 et al
  • polycarbonate JP-A-60-141757 et al
  • polyoxymethylene JP
  • An object of the present invention is to provide a thermoplastic resin composition
  • a thermoplastic resin composition comprising thermoplastic fluoro resin and PAE improved in adhesive and anti static properties and flexibility in the thermoplastic fluoro resin and improved in weather-, chemical- and heat-resistances in PAE.
  • Another object of the present invention is to provide semi-micro dispersed thermoplastic fluoro resin fiber improved in adhesive and anti static properties, which is neither complete solution type nor macro-phase dispersion type.
  • thermoplastic resin composition comprising (A) thermoplastic fluoro resin containing more than 50 % by weight of at least one unit selected from the group comprising tetrafluoroethylene, trifluoroethylene, chlorot ⁇ fluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene and perfluoro alkyl vinyl ethers, and (B) polyether- polyamide block copolymer, the ratio of (A/B) being 1 /99 to 99/1.
  • thermoplastic fluoro resin fiber comprising (A) 99 to 50 % by weight of thermoplastic fluoro resin containing more than 50 % by weight of at least one unit selected from the group comprising tetrafluoroethylene (TFE), trifluoroethylene, chlorotrifluoroethyle ⁇ e (CTFE), vinylidene fluoride (VF2), vinyl fluoride (VF), hexafluoropropylene (HFP) and perfluoro alkyl vinyl ethers, and (B) 1 to 50 % by weight of polyamide block copolymer.
  • TFE tetrafluoroethylene
  • CTFE chlorotrifluoroethyle ⁇ e
  • VF2 vinylidene fluoride
  • VF vinyl fluoride
  • HFP hexafluoropropylene
  • B 1 to 50 % by weight of polyamide block copolymer
  • Thermoplastic fluoro resin (A)" contains more than 50 % by weight of at least one unit selected from the group comprising tetrafluoroethylene (TFE), trifluoroethylene, chlorotrifluoroethylene (CTFE), vinylidene fluoride (VF2), vinyl fluoride (VF), hexafluoropropylene (HFP) and perfluoro alkyl vinyl ethers.
  • TFE tetrafluoroethylene
  • CTFE chlorotrifluoroethylene
  • VF2 vinylidene fluoride
  • VF vinyl fluoride
  • HFP hexafluoropropylene
  • Thermoplastic fluoro resin (A) is not limited to homopolymer (except polytetrafluoroethylene) but can be copolymers containing less than 50 % by weight of other components, provided that thermoplastic properties are not spoiled.
  • Thermoplastic fluoro resin (A) may be polyvinylidene fluoride (PVDF) and its copolymers (examples of comonomers are TFE, CTFE, HFP or the like), polyvinyl fluoride (P F) and its copolymers, polychlorotrifluoroethylene (PCTFE) and its copolymers, TFE-HFP copolymer (FEP), TFE- perfluoroalkylvinyl ether copolymer (PFA), ethylene-TFE copolymer (ETFE), ethylene-CTFE copolymer (ECTFE), and their mixtures with other polymers (except PAEs and/or TPEEs) provided that the proportion of thermoplastic fluoro resin is higher than 50 % by weight.
  • PVDF polyvinylidene fluoride
  • PCTFE polychlorotrifluoroethylene
  • FEP polychlorotrifluoroethylene
  • FEP polychlorotrifluoroethylene
  • the PAEs (B) are segmented block copolymers -the hard blocks consisting of aliphatic polyamides, the soft segments of aliphatic polyethers. Both segments are linked by ester or amide groups.
  • the PAE (B) may be a combination of (a) poly(oxyalkylene) chain and (b) polyamide chain comprising a polymer of aminocarboxylic acid having a carbon number of higher than 6 or lactam or a polymer of a salt of diamine having a carbon number of higher than 6 and dicarboxylic acid.
  • a product in which (a) and (b) are bonded through (c) dicarboxylic acid having a carbon number of 4 to 20 is called "polyetherester amide (hereinafter, PEEA).
  • the poly(oxyalkylene) chain (a)" may be poly(oxyethylene), poly(oxy-1 , 2- or 1 , 3-propylene), poly(oxytetramethylene), poly(oxy hexamethylene), block or random copolymer of ethyleneoxide and propyleneoxide and block or random copolymer of ethyleneoxide and tetrahydrofuran, terminal groups being hydroxyl, carboxyl, amino or the like.
  • the number average molecular weight of the poly(oxyalkylene) chain (a) is 300 to 6,000, preferably 500 to 4,000.
  • the aminocarboxylic acid having a carbon number of higher than 6 or lactam or a salt of diamine having a carbon number of higher than 6 and dicarboxylic acid (b)" may be aminocarboxylic acids such as 6-aminocaproic acid, 8-aminocaprylic acid, ⁇ -aminopelargonic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid ; lactams may be caprolactam, enantholactam, capryllactam and laurolactam ; salts may salt of hexamethylenediamine and adipic acid, hexamethylenediamine and sebacic acid, hexamethylenediamine and isophthalic acid, undecamethylenediamine and adipic acid, 4, 4-diamino cyclohexylme
  • 11-aminoundecanoic acid, 12-aminododecanoic acid, caprolactam, laurolactam and salts of hexamethylenediamine and adipic acid or salts of hexamethylenediamine and sebacic acid are advantageously used.
  • the component (b) can be used in combination of more than two compounds.
  • the dicarboxylic acid (c) having a carbon number of 4 to 20" may be
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylsulfone dicarboxylic acid and sodium 3-sulfone isophthalate, * cycloaliphatic dicarboxylic acids such as cyclohexane dicarboxylic acid, dicyclohexyl dicarboxylic acid, decalin dicarboxylic acid, norbornane dicarboxylic acid and adamantane dicarboxylic acid and/or
  • aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecane diacid.
  • succinic acid, oxalic acid, adipic acid, sebacic acid and dodecane diacid are advantageously used.
  • adipic acid, sebacic acid and dodecane diacid are advantageously used.
  • polyethers with amino end groups are used.
  • Polymerisation of PAE (B) can be effected by known process described in JP-B-56-45419 and JP-1 -46528 but is not limited thereto.
  • a proportion of polyether in PAEs depends on application or use but is preferably 20 to 80 % by weight.
  • thermoplastic copolyester elastomer (B)" is a combination of (a) poly(oxyalkylene) chain and (b) polyester chain which is a polymer of oxycarboxylic acid having a carbon number of higher than 6 or dihydroxy compound having a carbon number of higher than 2 and dicarboxylic acid having a carbon number of higher than 6.
  • the poly(oxyalkylene) chain (a) may be poly(oxyethylene), poly(oxy-1 ,
  • the number average molecular weight of the polyoxyalkylene chain (a) is 300 to 6,000, preferably 500 to 4,000.
  • the polymer (b) of oxycarboxylic acid having a carbon number of higher than 6 or dihydroxy compound having a carbon number of higher than 2 and dicarboxylic acid having a carbon number of higher than 6 may be p- oxybenzoic acid, p-hydroxyethoxybenzoic acid, oxyenanththoic acid, 6/17019 PO7EP95/04695
  • butyleneterephthlate, butyleneterephtalate/ isophtalate, ethyleneterephtalate and butylene naphtalate are advantageously used.
  • the component (b) can be used in combination of more than two.
  • the ratio by weight of (A) / (B) is 1/99 to 99/1 and is selected according to purposes, uses or applications.
  • a ratio of 99/1 to 50/50, preferably 95/5 to 60/40 is used to improve adhesion so as to fluoro resin and a ratio of 60/40 to 1/99, preferably 50/50 to 10/90 is used so as to improve resistances to weather, chemicals and gasoline, gas barrier property and staining resistance property.
  • thei ratio by weight of (A) / (B) is 1/99 to
  • 50/50 preferably 95/5 to 60/40 and is selected according to purposes, uses or applications.
  • the resin composition and fiber according to the present invention can contain know additives such as antioxidant, anti-pyrolysis agent, UV absorbent, anti-hydrolysis agent, colorant (dye, pigment)m anti static agent, electric conductive agent, crystal nuclear forming or improving agent, plasticizer, anti ⁇ friction agent, lubricant, mould releasing agent, fire retardant, reinforcement, filler, adhesive and tackifier.
  • additives such as antioxidant, anti-pyrolysis agent, UV absorbent, anti-hydrolysis agent, colorant (dye, pigment)m anti static agent, electric conductive agent, crystal nuclear forming or improving agent, plasticizer, anti ⁇ friction agent, lubricant, mould releasing agent, fire retardant, reinforcement, filler, adhesive and tackifier.
  • the resin composition according to the present invention is prepared preferably by melt-mixing of know technique without using any compatibility improving agent in any known kneader such as Banbury mixer, rollers, single- or double-screw extruder at 100 to 300 °C, preferably 150 to 260 °C. It is useful as thermoplastic fluoro resin or PAE and/or TPEE resin possessing improved properties and can be used in a form of molded articles produced by any known technique such as injection moulding, extrusion moulding, blow moulding and rotary moulding, including industrial parts, film, sheet, tube, hollow container, fiber and material for non-woven web.
  • any known kneader such as Banbury mixer, rollers, single- or double-screw extruder at 100 to 300 °C, preferably 150 to 260 °C.
  • thermoplastic fluoro resin or PAE and/or TPEE resin possessing improved properties and can be used in a form of molded articles produced by any known technique such as injection moulding, extrusion
  • thermoplastic resin composition according to the present invention show no phase separation but improve the resistance to alkali and anti-static property of thermoplastic fluoro resin and chemical-resistances of thermoplastic polyamide and/or copolyester elastomer as well as adhesion to other materials and can be utilised in molded articles prepared by a variety technique including injection and extrusion moulding.
  • the fiber according to the present invention can be spun directly from a dry blend of two components but is preferably prepared after melt-kneading. Kneading can be done by any know technique without using any compatibility improving agent to realise semi-micro dispersion.
  • the resin composition can be prepared in any known kneader such as Banbury mixer, rollers, single- or double-screw extruder at 100 to 300 °C, preferably 150 to 260°C.
  • the fiber can be spun by usual technique of melt spinning and stretching.
  • the fiber can be in any form including multifilament, mono-filament, staple, textile, knitted article and non woven web.
  • a mixed non woven web can be manufactured with the fiber according to the present invention because the fiber possesses improved adhesive property.
  • thermoplastic fluoro resin fiber according to the present invention is useful as a material for textile, knitted article and non woven web.
  • the fiber according to the present invention show no phase separation but improve the resistance to alkali and anti-static property of thermoplastic fluoro resin and adhesion to other materials and can be utilised in textile, knitted article and non woven web.
  • MFR Melt Flow Rate
  • test samples Composition
  • Predetermined amounts of pellets of fluoro resin and of PAE or TPEE were blended in a blender.
  • the resulting mixture was fed to a single screw extruder having a cylinder temperature of 160 to 240 °C for PAEs and 280 °C for TPEEs to prepare a film of 1 mm thick.
  • a square sample (5 x 5 cm) for anti static test was cut from this film.
  • a macro dumbbell shaped specimen according to ASTM 1708 for chemical-resistance test was prepared from the film.
  • a specimen for shock resistance (30 x 20 x 4 mm for PAEs ; 80 x 10 x 4 mm for TPEEs) was prepared by an injection moulding machine (clamping force is 80 ton) from pellets which was prepared by blending predetermined amounts of pellets in a blender and extruding the resulting mixture out of a single screw extruder.
  • the film was rubbed with polyester cloth for 30 seconds and then was supported by a stand at a level of 10 cm from a table on which ash of cigarette was placed for 10 min.
  • Anti-static property was determined by the degree of adhesion of cigarette ash. Following is criteria of evaluations:
  • the same macro dumbbell shaped specimen was immersed, at a curvature of 5 mm, in 50 % caustic soda solution (resistance to alkali), fumaric acid (resistance to acid) and gasoline respectively at ambient temperature for one month and surface conditions were observed by naked eyes. Following is criteria of evaluations:
  • PVDF1 homopolymer of PVDF 100 %
  • MFR 20 PVDF2 copolymer of PVDF and HFP (5%)
  • MFR 8 PVDF3 copolymer of PVDF and TFE (20%)
  • MFR 10 PVDF4 copolymer of PVDF and CTFE (9%)
  • MFR 7 PVDF5 homopolymer of PVDF 100 %
  • MFR 12 PVDF6 copolymer of PVDF and HFP (10%)
  • MFR 55 PVDF7 copolymer of PVDF and TFE (25%)
  • MFR 5 PEEA1 : a product between PA-6 having carboxylic acid groups at opposite terminals derived from adipic acid and polyoxyethyleneglycol having the number average molecular weight of 2,000 (proportions of 1/1 ).
  • Relative viscosity 1.8
  • a film of Comparative Example 1 did not adhere to polypropylene film, while a film of Example 2 well adhered to polypropylene film.
  • Example 12 Improved anti-static property was observed also in such cases that PVDF-1 of Example 1 was replaced by FEP (Examples 12) and by ECTFE (Example 13).
  • Acid resistance to acid gas.: resistance to gasoline
  • compositions according to the present invention No phase separation was observed in the compositions according to the present invention. Observation by a microscope reveal that the compositions according to the present invention were finely dispersed although their compatibility was not complete.
  • shock resistance (kg. cm/cm)
  • Alkali resistance to alkali
  • Example 14 When PVDF-5 of Example 14 was replaced by FEP (Example 19) and by ECTFE (Example 20) respectively, improved surface specific resistances of in the order of 1 ⁇ 11 were observed and no surface change were observed after immersion in alkali solution.
  • Pellets of fluoro resin/TPEE and/or PAE were mixed in a blender and fed to an extruder of single screw (cylinder temperature of 160 to 260 °C) to produce pellets. After the pellets were dried, pellets were extruded out of an extruder through a die having 10 holes of the diameter of which is 0.5 mm to produce fiber of about 150 de/10 filaments. Filaments were stretched on a hot roller at the maximum elongation of 80 %. The fibers were knitted to prepare a sample for anti static test. 3) Spinning property
  • Filament was stretched at ambient temperature and evaluated by following criteria : 1 : filament can be stretched at more then 3 times without fibrillation.
  • Stretched fibers were mixed with propylene fibers at a proportion of 1 : 1 and the resulting mixture was compressed by an electric iron. Adhesion after 30 seconds was evaluated.
  • Polymers were blended as shown in Table 3 and the resulting blends were spun to fibers.
  • a fiber of Comparative Example 6 did not adhere to polypropylene fiber, while a fiber of Example 22 well adhered to polypropylene fiber. Improved anti-static property was observed also in such cases that PVDF-1 of Example 21 was replaced by FEP (Examples 32) and by ECTFE (Example 33).
  • Anti-s anti static property alkali : resistance to alkali acid : resistance to acid
  • a fiber made of PVDF-1 alone did not adhere to polypropylene fiber, while a fiber of invention well adhered to polypropylene fiber.
  • Example 34 Improved anti-static property without spoiling spinning and stretching properties was observed also in such cases that PVDF-1 of Example 34 was replaced by FEP (Examples 42) and by ECTFE (Example 43).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The object of the present invention is to provide a composition and a fiber of thermoplastic fluoro resin/TPEE(s) and/or PAE (improved in chemical-resistances, anti static property and shock-resistance). The thermoplastic composition and fiber comprise (A) thermoplastic fluoro resin(s) and (B) thermoplastic copolyester elastomer(s) and/or thermoplastic polyamide elastomer(s), the ratio of (A/B) being 1/99 to 99/1 in the claimed composition and 99/1 to 50/50.

Description

Specification Thermoplastic fluoro resin composition and fiber Technical field of Invention]
This invention relates to thermoplastic fluoro resin compositions and fibers and particularly to those based on thermoplastic fluoro resin and thermoplastic polyamide elastomer (hereinafter, PAEs) and/or thermoplastic copolyester elastomers (hereinafter, TPEEs). Prior Art
Thermoplastic fluoro resin possessing high weather- and chemical- resistances is utilised in many fields such as paint, electric or electronics parts, steel pipe liner, materials for chemical plants and staining and weather resisting film. This resin, however, is difficult to be combined with other material due to its poor adhesive property and its improvement is limited. Thermoplastic fluoro resin fibers are difficult to be stretched due to their viscosity and shows poor knot strength
In order to improve this resin, several ideas such as alloying with polymethylmethacrylate (PMMA)(JP-B-43-12012 et al) and combination with polycarbonate (JP-A-57-8244 et al), with polyethylene (JP-B-3-22901 et al), with functional denatured polyolefin (JP-A-62-57448 et al) and with polyimide (JP-A-2-308856) are proposed but are not satisfactory. Known compositions of thermoplastic fluoro resin are classified into two types of complete solution type (PMMA) and macro-phase dispersion type (variety) but it was not yet found such a system in which mixed components disperse uniformly without compatibility-improving agent and properties of components become complementary. JP-A-4-28760 discloses a composition of polyester block copolymer and fluoro resin. An object of this patent is to modify polyether elastomer with a small proportion of fluoro resin and hence this patent is not relevant to the present invention.
In order to improve thermoplastic fluoro resin fiber, a variety of combinations with other polymers such as polymethylmethacrylate (PMMA)(JP- B-43-12012 et al), isobutylene copolymer (JP-A-54-106622 et al), acrylate (JP- B-56-20610 et al), blending with other fluoro polymers (JP-B-4-44012, JP-A-60- 104514 et al), plasticizer (JP-A-55-84413 et al), polyolefin (JP-A-62-57448 et al), metal soap (JP-A-61-174418 et al), fluorocarbon wax (JP-A-60-115652 et al) and their combination (JP-A-6-101114 et al) are proposed. Improvement in spinning and stretching is also proposed (JP-B-53-22574 et al).
PAE possessing high shock-resistance at low temperatures, anti static property and light weightiness is widely used in tube, hose, industrial parts and shoes such as ski boots. PAE show rather poor chemical- and heat-resistances and hence its usage is limited.
In order to improve these problems, a variety of combination with other polymers are proposed. PAE is combined with polyamide (PA) (JP-B-5-2150 et al), with polyester (JP-B-5-37179 et al), with polycarbonate (JP-A-60-141757 et al), with polyoxymethylene (JP-A-59-191752 et al), with polyphenylene ether (JP-A-60-186560 et al), with polyolefin (JP-A-57-147520 et al), with polystyrene (JP-A-60- 17064 et al), with polyvinylchloride (JP-B-3-2903 et al), ionomer (JP- B-1 -56096 et al) and with polyepoxide (JP-B-2-50955 et al). These combinations, however, are not satisfactory to improve resistances to weather, chemicals and stain.
Problems to be solved by the Invention
An object of the present invention is to provide a thermoplastic resin composition comprising thermoplastic fluoro resin and PAE improved in adhesive and anti static properties and flexibility in the thermoplastic fluoro resin and improved in weather-, chemical- and heat-resistances in PAE.
Another object of the present invention is to provide semi-micro dispersed thermoplastic fluoro resin fiber improved in adhesive and anti static properties, which is neither complete solution type nor macro-phase dispersion type.
Means to solve the Problems
The present invention provides a thermoplastic resin composition comprising (A) thermoplastic fluoro resin containing more than 50 % by weight of at least one unit selected from the group comprising tetrafluoroethylene, trifluoroethylene, chlorotπfluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene and perfluoro alkyl vinyl ethers, and (B) polyether- polyamide block copolymer, the ratio of (A/B) being 1 /99 to 99/1.
The present invention provides also a thermoplastic fluoro resin fiber comprising (A) 99 to 50 % by weight of thermoplastic fluoro resin containing more than 50 % by weight of at least one unit selected from the group comprising tetrafluoroethylene (TFE), trifluoroethylene, chlorotrifluoroethyleπe (CTFE), vinylidene fluoride (VF2), vinyl fluoride (VF), hexafluoropropylene (HFP) and perfluoro alkyl vinyl ethers, and (B) 1 to 50 % by weight of polyamide block copolymer. 'Thermoplastic fluoro resin (A)" according to the present invention contains more than 50 % by weight of at least one unit selected from the group comprising tetrafluoroethylene (TFE), trifluoroethylene, chlorotrifluoroethylene (CTFE), vinylidene fluoride (VF2), vinyl fluoride (VF), hexafluoropropylene (HFP) and perfluoro alkyl vinyl ethers. Thermoplastic fluoro resin (A) is not limited to homopolymer (except polytetrafluoroethylene) but can be copolymers containing less than 50 % by weight of other components, provided that thermoplastic properties are not spoiled. Thermoplastic fluoro resin (A) may be polyvinylidene fluoride (PVDF) and its copolymers (examples of comonomers are TFE, CTFE, HFP or the like), polyvinyl fluoride (P F) and its copolymers, polychlorotrifluoroethylene (PCTFE) and its copolymers, TFE-HFP copolymer (FEP), TFE- perfluoroalkylvinyl ether copolymer (PFA), ethylene-TFE copolymer (ETFE), ethylene-CTFE copolymer (ECTFE), and their mixtures with other polymers (except PAEs and/or TPEEs) provided that the proportion of thermoplastic fluoro resin is higher than 50 % by weight.
"The PAEs (B)" according to the present invention according to the present invention are segmented block copolymers -the hard blocks consisting of aliphatic polyamides, the soft segments of aliphatic polyethers. Both segments are linked by ester or amide groups. The PAE (B) may be a combination of (a) poly(oxyalkylene) chain and (b) polyamide chain comprising a polymer of aminocarboxylic acid having a carbon number of higher than 6 or lactam or a polymer of a salt of diamine having a carbon number of higher than 6 and dicarboxylic acid. A product in which (a) and (b) are bonded through (c) dicarboxylic acid having a carbon number of 4 to 20 is called "polyetherester amide (hereinafter, PEEA).
'The poly(oxyalkylene) chain (a)" may be poly(oxyethylene), poly(oxy-1 , 2- or 1 , 3-propylene), poly(oxytetramethylene), poly(oxy hexamethylene), block or random copolymer of ethyleneoxide and propyleneoxide and block or random copolymer of ethyleneoxide and tetrahydrofuran, terminal groups being hydroxyl, carboxyl, amino or the like.
The number average molecular weight of the poly(oxyalkylene) chain (a) is 300 to 6,000, preferably 500 to 4,000. 'The aminocarboxylic acid having a carbon number of higher than 6 or lactam or a salt of diamine having a carbon number of higher than 6 and dicarboxylic acid (b)" may be aminocarboxylic acids such as 6-aminocaproic acid, 8-aminocaprylic acid, ω-aminopelargonic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid ; lactams may be caprolactam, enantholactam, capryllactam and laurolactam ; salts may salt of hexamethylenediamine and adipic acid, hexamethylenediamine and sebacic acid, hexamethylenediamine and isophthalic acid, undecamethylenediamine and adipic acid, 4, 4-diamino cyclohexylmethane and dodecanedioic acid or the like. Among them, 11-aminoundecanoic acid, 12-aminododecanoic acid, caprolactam, laurolactam and salts of hexamethylenediamine and adipic acid or salts of hexamethylenediamine and sebacic acid are advantageously used. The component (b) can be used in combination of more than two compounds. "The dicarboxylic acid (c) having a carbon number of 4 to 20" may be
* aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylsulfone dicarboxylic acid and sodium 3-sulfone isophthalate, * cycloaliphatic dicarboxylic acids such as cyclohexane dicarboxylic acid, dicyclohexyl dicarboxylic acid, decalin dicarboxylic acid, norbornane dicarboxylic acid and adamantane dicarboxylic acid and/or
* aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecane diacid. Among these acids, adipic acid, sebacic acid and dodecane diacid are advantageously used.
When the link between the polyamide and the polyether moieties is an amide group, polyethers with amino end groups are used.
Polymerisation of PAE (B) can be effected by known process described in JP-B-56-45419 and JP-1 -46528 but is not limited thereto. For the fibers, a proportion of polyether in PAEs depends on application or use but is preferably 20 to 80 % by weight.
'The thermoplastic copolyester elastomer (B)" according to the present invention is a combination of (a) poly(oxyalkylene) chain and (b) polyester chain which is a polymer of oxycarboxylic acid having a carbon number of higher than 6 or dihydroxy compound having a carbon number of higher than 2 and dicarboxylic acid having a carbon number of higher than 6.
'The poly(oxyalkylene) chain (a)" may be poly(oxyethylene), poly(oxy-1 ,
2- or 1 , 3-propyl), poly(oxytetramethylene), poly(oxy hexamethylene), block or random copolymer of ethyleneoxide and propyleneoxide and block or random copolymer of ethyleneoxide and tetrahydrofuran. Their alkyl possess preferably carbon number of 2 to 4.
The number average molecular weight of the polyoxyalkylene chain (a) is 300 to 6,000, preferably 500 to 4,000. 'The polymer (b) of oxycarboxylic acid having a carbon number of higher than 6 or dihydroxy compound having a carbon number of higher than 2 and dicarboxylic acid having a carbon number of higher than 6" may be p- oxybenzoic acid, p-hydroxyethoxybenzoic acid, oxyenanththoic acid, 6/17019 PO7EP95/04695
5 hydroxyethoxynaphthoic acid, ethyleneglycol, trimethyleneglycol, tetramethyleneglycol, hexamethyleneglycol, cyclohexanedimethanol, terephtalic acid, isophtalic acid, diphenyl dicarboxylic acid, diphenyl ketone dicarboxylic acid, diphenoxyethane dicarboxylic acid, naphthalene dicarboxylic acid or their combinations
Among them, butyleneterephthlate, butyleneterephtalate/ isophtalate, ethyleneterephtalate and butylene naphtalate are advantageously used. The component (b) can be used in combination of more than two.
As far as compositions are involved, the ratio by weight of (A) / (B) is 1/99 to 99/1 and is selected according to purposes, uses or applications. For example, a ratio of 99/1 to 50/50, preferably 95/5 to 60/40 is used to improve adhesion so as to fluoro resin and a ratio of 60/40 to 1/99, preferably 50/50 to 10/90 is used so as to improve resistances to weather, chemicals and gasoline, gas barrier property and staining resistance property. As far as fibers are involved, thei ratio by weight of (A) / (B) is 1/99 to
50/50, preferably 95/5 to 60/40 and is selected according to purposes, uses or applications.
The resin composition and fiber according to the present invention can contain know additives such as antioxidant, anti-pyrolysis agent, UV absorbent, anti-hydrolysis agent, colorant (dye, pigment)m anti static agent, electric conductive agent, crystal nuclear forming or improving agent, plasticizer, anti¬ friction agent, lubricant, mould releasing agent, fire retardant, reinforcement, filler, adhesive and tackifier.
The resin composition according to the present invention is prepared preferably by melt-mixing of know technique without using any compatibility improving agent in any known kneader such as Banbury mixer, rollers, single- or double-screw extruder at 100 to 300 °C, preferably 150 to 260 °C. It is useful as thermoplastic fluoro resin or PAE and/or TPEE resin possessing improved properties and can be used in a form of molded articles produced by any known technique such as injection moulding, extrusion moulding, blow moulding and rotary moulding, including industrial parts, film, sheet, tube, hollow container, fiber and material for non-woven web.
The claimed thermoplastic resin composition according to the present invention show no phase separation but improve the resistance to alkali and anti-static property of thermoplastic fluoro resin and chemical-resistances of thermoplastic polyamide and/or copolyester elastomer as well as adhesion to other materials and can be utilised in molded articles prepared by a variety technique including injection and extrusion moulding. The fiber according to the present invention can be spun directly from a dry blend of two components but is preferably prepared after melt-kneading. Kneading can be done by any know technique without using any compatibility improving agent to realise semi-micro dispersion. For example, the resin composition can be prepared in any known kneader such as Banbury mixer, rollers, single- or double-screw extruder at 100 to 300 °C, preferably 150 to 260°C.
It can be spun by usual technique of melt spinning and stretching. The fiber can be in any form including multifilament, mono-filament, staple, textile, knitted article and non woven web. A mixed non woven web can be manufactured with the fiber according to the present invention because the fiber possesses improved adhesive property.
The claimed thermoplastic fluoro resin fiber according to the present invention is useful as a material for textile, knitted article and non woven web. The fiber according to the present invention show no phase separation but improve the resistance to alkali and anti-static property of thermoplastic fluoro resin and adhesion to other materials and can be utilised in textile, knitted article and non woven web.
Now, non limitative Examples of the present invention will be described. Parts used in Examples mean parts by weight if not mentioned specially. EXAMPLES RELATING TO COMPOSITIONS Following test methods were used in evaluation :
1 ) Melt Flow Rate (MFR) of fluoro resin determined by ISO 1 133, at 230 °C under a load of 2.16 kg and expressed in term of g/10 min.
2) Relative viscosity of PAE and TPEE calculated from a solution viscosity of 0.5 % o-chlorophenol solution of polymer at 25 °C
3) Preparation of test samples (composition) Predetermined amounts of pellets of fluoro resin and of PAE or TPEE were blended in a blender. The resulting mixture was fed to a single screw extruder having a cylinder temperature of 160 to 240 °C for PAEs and 280 °C for TPEEs to prepare a film of 1 mm thick. A square sample (5 x 5 cm) for anti static test was cut from this film. A macro dumbbell shaped specimen according to ASTM 1708 for chemical-resistance test was prepared from the film. A specimen for shock resistance (30 x 20 x 4 mm for PAEs ; 80 x 10 x 4 mm for TPEEs) was prepared by an injection moulding machine (clamping force is 80 ton) from pellets which was prepared by blending predetermined amounts of pellets in a blender and extruding the resulting mixture out of a single screw extruder.
4) Anti-static property
The film was rubbed with polyester cloth for 30 seconds and then was supported by a stand at a level of 10 cm from a table on which ash of cigarette was placed for 10 min. Anti-static property was determined by the degree of adhesion of cigarette ash. Following is criteria of evaluations:
1 : no adhesion
2: little adhesion
3: some adhesion
4: manyadhesion
5) Resistance to chemicals
The same macro dumbbell shaped specimen was immersed, at a curvature of 5 mm, in 50 % caustic soda solution (resistance to alkali), fumaric acid (resistance to acid) and gasoline respectively at ambient temperature for one month and surface conditions were observed by naked eyes. Following is criteria of evaluations:
1 : no change
2: intermediate of 1 and 3
3: seriously swelled or cracked
6) Shock-resistance
Sharpy strength was determined in the specimen for shock resistance with a A-type notch according to ISO 179 for the PAEs and according to ISO 180 for the TPEEs. Following polymers were used in Examples:
PVDF1 homopolymer of PVDF 100 %, MFR = 20 PVDF2 copolymer of PVDF and HFP (5%), MFR = 8 PVDF3 copolymer of PVDF and TFE (20%), MFR = 10 PVDF4 copolymer of PVDF and CTFE (9%), MFR = 7 PVDF5 homopolymer of PVDF 100 %, MFR = 12 PVDF6 copolymer of PVDF and HFP (10%), MFR = 55 PVDF7 copolymer of PVDF and TFE (25%), MFR = 5 PEEA1 : a product between PA-6 having carboxylic acid groups at opposite terminals derived from adipic acid and polyoxyethyleneglycol having the number average molecular weight of 2,000 (proportions of 1/1 ). Relative viscosity = 1.8
PEEA2 : a product between the same PA-6 as above and polyoxyteramethyleneglycol having the number average molecular weight of 2,000 (proportions of 1/1 ). Relative viscosity = 1.9
PEEA3 : a product between PA-12 having carboxylic acid groups at opposite terminals with dodecanoic diacid and polyoxyethyleneglycol having the number average molecular weight of 2,000 (proportions of 1/1). Relative viscosity = 2.0 PEEA4 : a product between the same PA 12 as above and polyoxyteramethyleneglycol having the number average molecular weight of 1 ,000 (proportions of 2/1 ). Relative viscosity = 1.9
TPEE1 : a reaction product between butyleneterephtalate and polyoxytetramethyleneglycol having the number average molecular weight of 2,000 (proportions of 1/3). Viscosity =
1.7 TPEE-2 : a reaction product between butyleneterephtalate/ isophtalate (75/25) and polyoxy tetramethyleneglycol having the number average molecular weight of 2,000 (proportions of 1/1 ). Viscosity = 2.2 Polymers were blended as shown in Table 1. No phase separation was observed in the compositions according to the present invention. Observation by a microscope reveal that the compositions according to the present invention were finely dispersed although their compatibility was not complete.
The results of evaluation including Comparative Examples are also shown in Table 1. From Table 1 , it is clear that the compositions according to the present invention posses balanced properties.
A film of Comparative Example 1 did not adhere to polypropylene film, while a film of Example 2 well adhered to polypropylene film.
Improved anti-static property was observed also in such cases that PVDF-1 of Example 1 was replaced by FEP (Examples 12) and by ECTFE (Example 13).
Symbols used in Tables 1 and 2 have following meanings : AS : Anti static property Alkali : resistance to alkali
Acid : resistance to acid gas.: resistance to gasoline
NB : not broken
Shock : shock resistance (kg. cm/cm)
SR : surface specific resistance (! )
Table 1
polymer ratio AS Alkali Acid gas. Shock
Comp.1 PVDF1/PEEA-1 100/0 4 2 1 1 5
Ex. 1 PVDF1/PEEA-1 90/10 2 1 1 1 10
Ex. 2 PVDF1/PEEA-1 70/30 2 1 1 1 8
Ex. 3 PVDF1/PEEA-1 20/80 1 1 1 1 NB
Comp.2 PVDF1/PEEA1 0/100 1 3 3 3 NB
Ex. 4 PVDF1/PEEA2 70/30 2 1 1 1 7
Comp.3 PVDF1/PEEA2 0/100 1 3 3 3 NB
Ex. 5 PVDF1/PEEA3 80/20 2 1 1 1 8
Ex. 6 PVDF1/PEEA3 30/70 1 1 2 2 NB
Ex. 7 PVDF1/PEEA4 90/10 3 1 1 1 8
Ex. 8 PVDF1/PEEA1 70/30 2 1 1 1 NB
Ex. 9 PVDF3/PEEA1 70/30 2 1 1 1 NB
Ex. 10 PVDF4/PEEA1 70/30 2 1 1 1 NB
Ex. 11 PVDF2/PEEA3 70/30 2 1 1 1 NB
Other polymers were blended as shown in Table 2.
No phase separation was observed in the compositions according to the present invention. Observation by a microscope reveal that the compositions according to the present invention were finely dispersed although their compatibility was not complete.
A film made of PVDF-5 alone of Comparative Example 4 did not adhere to polypropylene film, while a film of Example 14 adhered to polypropylene film. The results of evaluation including Comparative Examples are also shown in Table 2. From Table 2, it is clear that the compositions according to the present invention posses balanced properties.
Table 2
N° Ex polymer ratio SR 1 ) shock 2) alkali acid
Comp.4 PVDF5/TPEE1 100/0 1014 5 2 1
Ex. 14 PVDF5/TPEE1 70/30 10*10 10 1
Ex. 15 PVDF5/TPEE1 95/5 1011 7 1
Comp.5 PVDF5/TPEE1 40/60 1010 10 2
Ex. 16 PVDF6/TPEE2 80/20 1011 9 1
Ex. 17 PVDF7/TPEE1 80/20 ion 8 1
Ex. 18 PVDF8/TPEE1 80/20 ion 10 1
SR : surface specific resistance (Ω)
Shock: shock resistance (kg. cm/cm)
Alkali: resistance to alkali
Acid: resistance to acid
When PVDF-5 of Example 14 was replaced by FEP (Example 19) and by ECTFE (Example 20) respectively, improved surface specific resistances of in the order of 1θ11 were observed and no surface change were observed after immersion in alkali solution.
EXAMPLES RELATING TO FIBERS
1 ) The polymers used those described above
2) Preparation of fiber
Pellets of fluoro resin/TPEE and/or PAE were mixed in a blender and fed to an extruder of single screw (cylinder temperature of 160 to 260 °C) to produce pellets. After the pellets were dried, pellets were extruded out of an extruder through a die having 10 holes of the diameter of which is 0.5 mm to produce fiber of about 150 de/10 filaments. Filaments were stretched on a hot roller at the maximum elongation of 80 %. The fibers were knitted to prepare a sample for anti static test. 3) Spinning property
Filaments extruded out of the die were observed and evaluated by following criteria :
1 : smooth surface and no bending 2 : intermediate of 1 and 3
3 : fractured and shark skin surface
4) Stretching property
Filament was stretched at ambient temperature and evaluated by following criteria : 1 : filament can be stretched at more then 3 times without fibrillation.
2 : intermediate of 1 and 3
3 : filament can not be stretched over 1.5 times. 6) Anti-static property The knitted sample was rubbed with polyester cloth for 30 seconds and then was supported by a stand at a level of 10 cm from a table on which ash of cigarette was placed for 10 min. Anti-static property was determined by the degree of adhesion of cigarette ash. Following is criteria of evaluations : 1 : no adhesion 2 : little adhesion
3 : some adhesion
4 : many adhesion 6) Adhesive property
Stretched fibers were mixed with propylene fibers at a proportion of 1 : 1 and the resulting mixture was compressed by an electric iron. Adhesion after 30 seconds was evaluated.
Polymers were blended as shown in Table 3 and the resulting blends were spun to fibers.
No phase separation was observed in the fibers according to the present invention. Observation by a microscope reveal that the fibers according to the present invention were finely dispersed in a form of intermesh although their compatibility was not complete.
The results of evaluation including Comparative Examples are also shown in Table 3. From Table 3, it is clear that the fiber according to the present invention posses balanced properties.
A fiber of Comparative Example 6 did not adhere to polypropylene fiber, while a fiber of Example 22 well adhered to polypropylene fiber. Improved anti-static property was observed also in such cases that PVDF-1 of Example 21 was replaced by FEP (Examples 32) and by ECTFE (Example 33).
Table 3
polymer ratio Spin. Stret. Anti-s. alkali acid
Comp.6 PVDF1/PEEA1 100/0 4 2 1
Ex. 21 PVDF1/PEEA1 90/10 2 1 1
Ex. 22 PVDF1/PEEA1 70/30 2 1 1
Ex. 23 PVDF1/PEEA1 60/40 2 1 1
Comp.7 PVDF1/PEEA1 0/100 1 3 3
Ex. 24 PVDF1/PEEA2 70/30 2 1 1
Comp.8 PVDF1/PEEA2 0/100 1 3 3
Ex. 25 PVDF1/PEEA3 80/20 2 1 1
Ex. 26 PVDF1/PEEA3 60/40 2 1 1
Ex. 27 PVDF1/PEEA4 90/10 3 1 1
Ex. 28 PVDF2/PEEA1 70/30 2 1 1
Ex. 29 PVDF3/PEEA1 70/30 2 1 1
Ex. 30 PVDF4/PEEA1 70/30 2 1 1
Ex. 31 PVDF2/PEEA3 70/30 2 1 1 note
Symbols used in Tables 3 and 4 have following meanings :
Spin. : spinning property
Stre.: stretching property
Anti-s : anti static property alkali : resistance to alkali acid : resistance to acid
Other polymers were blended as are shown in Table 4 and the resulting blends were spun to fibers. No phase separation was observed in the fibers according to the present invention. Observation by a microscope reveal that the fibers according to the present invention were finely dispersed in a form of intermesh although their compatibility was not complete.
The results of evaluation including Comparative Examples are also shown in Table 4. From Table 4, it is clear that the fibers according to the present invention posses balanced properties.
A fiber made of PVDF-1 alone (Comparative Example 9) did not adhere to polypropylene fiber, while a fiber of invention well adhered to polypropylene fiber.
Table 4
polymer ratio Spin. Stret. Anti- ■s. alkali acid
Comp.9 PVDF1/TPEE1 100/0 2 2 4 2 1
Ex. 34 PVDF1/TPEE1 90/10 2 1 1
Ex. 35 PVDF1/TPEE1 70/30 2 1 1
Ex. 36 PVDF1/TPEE1 20/80 2 1 1
Comp.10 PVDF1/TPEE1 0/100 1 3 3
Ex. 37 PVDF 1 /TPEE 2 70/30 2 1 1
Comp.1 1 PVDF 1 /TPEE 2 0/100 1 3 3
Ex. 38 PVDF1/TPEE3 80/20 2 1 1
Ex. 39 PVDF1/TPEE3 30/70 2 1 1
Ex. 40 PVDF1/TPEE4 90/10 3 1 1
Ex. 41 PVDF2/TPEE1 70/30 2 1 1
Improved anti-static property without spoiling spinning and stretching properties was observed also in such cases that PVDF-1 of Example 34 was replaced by FEP (Examples 42) and by ECTFE (Example 43).

Claims

Claims 1. Thermoplastic resin composition, characterised in that it comprises (A) at least a thermoplastic fluoro resin containing more than 50 % by weight of at least one unit selected from the group comprising tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene and perfluoro alkyl vinyl ethers, and (B) at least a thermoplastic polyamide elastomer and/or a thermoplastic copolyester elastomer, the ratio of (A/B) being 1 /99 to 99/1 , and preferably 95/5 to 60/40.
2. Thermoplastic resin fiber, characterised in that it comprises (A) at least a thermoplastic fluoro resin containing more than 50 % by weight of at least one unit selected from the group comprising tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene and perfluoro alkyl vinyl ethers, and (B) at least a thermoplastic polyamide elastomer and/or a thermoplastic copolyester elastomer, the ratio of (A/B) being 99 /1 to 50/50, and preferably 95/5 to 60/40.
3. Thermoplastic composition or fiber according to claim 1 or 2, characterised in that said thermoplastic fluoro resin is polyvinylidenefluoride or copolymer containing more than 50 % by weight of vinylidene fluoride.
4. Thermoplastic composition or fiber according to claim 1 to 3, characterised in that said thermoplastic polyamide elastomer is polyether-ester amide.
5. Thermoplastic composition or fiber according to claim 1 to 4, characterised in that said thermoplastic copolyester elastomer is polyoxybutylene terephtalate copolymer.
6. Thermoplastic composition or fiber according to claim 1 to 5, characterised in that said thermoplastic fluoro resin is ethylene/chlorotrifluoroethylene or tetrafluoroetylene/hexafluoropropylene copolymer.
7. Moulded articles comprising compositions of claim 1 to 6.
8. Textiles, knitted articles and non woven webs comprising fibers of claim 1 to 6.
9. Process for making compositions such as defined in claims 1 to 6 in dry-blending its components and/or preferably melt-mixing them.
10. Process for making fibers such as defined in claims 1 to 6 in spinning its components and/or preferably melt-kneading them and stretching the fiber.
RECTIFIED SHEET (RULE 81)
PCT/EP1995/004695 1994-11-29 1995-11-28 Thermoplastic fluoro resin composition and fiber WO1996017019A1 (en)

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JP7015099A JPH08209437A (en) 1994-11-29 1995-02-01 Thermoplastic fluorine-based resin fiber
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EP1086151A4 (en) * 1998-05-13 2001-09-19 Radu Olimpiu Gherghel Polymers containing nylon and halogenated polymer
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EP0908542A3 (en) * 1997-10-07 1999-09-22 Asten, Inc. Yarns and industrial fabrics made from a fluoropolymer blend
US6136437A (en) * 1997-10-07 2000-10-24 Astenjohson, Inc. Industrial fabric and yarn made from an improved fluoropolymer blend
EP1086151A4 (en) * 1998-05-13 2001-09-19 Radu Olimpiu Gherghel Polymers containing nylon and halogenated polymer
WO1999061527A1 (en) * 1998-05-27 1999-12-02 Institut Für Polymerforschung E.V. Dresden Compounds made of polyamide and perfluoroalkyl substance(s) and mixtures of these compounds with additional polymer substances, a method for the production thereof, and their use
US6770378B1 (en) 1998-05-27 2004-08-03 Institut Fur Polymerforschung E.V. Dresden Compounds made of polyamide substance(s) and perfluoroalkyl substance(s) and mixtures of these compounds with additional polymer substance(s), methods for their production and use
DE10082051B3 (en) * 1999-06-23 2017-06-08 Polyplastics Co. Ltd. Molded article of thermoplastic polyester resin composition
US9332802B2 (en) 2011-12-30 2016-05-10 Ticona Llc Molded polymer articles for use in low temperatures having a low rigidity factor
US9328229B2 (en) 2012-05-09 2016-05-03 Ticona Llc Polymer composition and articles for use in low temperature environments that are wear resistant
WO2014015111A1 (en) * 2012-07-18 2014-01-23 Ticona Llc Wear resistant thermoplastic copolyester elastomer

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