WO2021033539A1 - チューブ、チューブの製造方法、および、チューブの保管方法 - Google Patents
チューブ、チューブの製造方法、および、チューブの保管方法 Download PDFInfo
- Publication number
- WO2021033539A1 WO2021033539A1 PCT/JP2020/029884 JP2020029884W WO2021033539A1 WO 2021033539 A1 WO2021033539 A1 WO 2021033539A1 JP 2020029884 W JP2020029884 W JP 2020029884W WO 2021033539 A1 WO2021033539 A1 WO 2021033539A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tube
- copolymer
- tfe
- vinyl ether
- die
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 23
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229920001577 copolymer Polymers 0.000 claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 230000003746 surface roughness Effects 0.000 claims abstract description 43
- 238000011156 evaluation Methods 0.000 claims abstract description 17
- 238000001125 extrusion Methods 0.000 claims description 27
- 239000004065 semiconductor Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical group FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims description 12
- -1 fluoroalkyl vinyl ether Chemical compound 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 25
- 125000000524 functional group Chemical group 0.000 description 23
- 239000000356 contaminant Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 239000008188 pellet Substances 0.000 description 14
- 229910021642 ultra pure water Inorganic materials 0.000 description 13
- 239000012498 ultrapure water Substances 0.000 description 13
- 238000000635 electron micrograph Methods 0.000 description 12
- 239000003344 environmental pollutant Substances 0.000 description 10
- 231100000719 pollutant Toxicity 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003608 radiolysis reaction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/06—Hoses, i.e. flexible pipes made of rubber or flexible plastics with homogeneous wall
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/27—Cleaning; Purging; Avoiding contamination
- B29C48/274—Cleaning; Purging; Avoiding contamination of the extruded articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/29—Feeding the extrusion material to the extruder in liquid form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/69—Filters or screens for the moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/86—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the nozzle zone
- B29C48/865—Heating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D23/00—Producing tubular articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- 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
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
- B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0085—Copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0072—Roughness, e.g. anti-slip
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2023/00—Tubular articles
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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
- 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
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
Definitions
- This disclosure relates to tubes, tube manufacturing methods, and tube storage methods.
- Patent Document 1 contains a melt-moldable tetrafluoroethylene / fluoroalkoxytrifluoroethylene copolymer containing polytetrafluoroethylene having a crystallization temperature of 305 ° C. or higher and a crystallization heat of 50 J / g or higher. The coalesced composition is described.
- the object of the present disclosure is to provide a tube having a smooth inner surface of the tube and a small amount of metal elution.
- a tube containing a tetrafluoroethylene / fluoroalkyl vinyl ether copolymer wherein the evaluation length is set to 3 ⁇ m and the inner surface of the tube is measured by an atomic force microscope (AFM).
- a tube having a surface roughness Ra of 5 nm or less and an amount of metal eluted from the inner surface of the tube of 0.30 ng / cm 2 or less is provided.
- the tube of the present disclosure preferably has an average spherulite diameter of 1 to 150 ⁇ m on the inner surface of the tube.
- the tube of the present disclosure preferably has an average spherulite diameter of more than 15 ⁇ m on the inner surface of the tube.
- the fluoroalkyl vinyl ether is preferably perfluoro (propyl vinyl ether).
- the tube of the present disclosure can be suitably used for transferring a high-purity chemical solution for manufacturing a semiconductor device.
- the tetrafluoroethylene / fluoroalkyl vinyl ether copolymer is passed through a hollow portion of a tube extruded from a die of an extruder while passing a gas having passed through a filter having a filtration accuracy of 5 nm or less. It is preferably obtained by extruding.
- the content of the fluoroalkyl vinyl ether unit in the tetrafluoroethylene / fluoroalkyl vinyl ether copolymer is preferably 1.0 to 8.0% by mass with respect to the total monomer unit. ..
- a filter having a filtration accuracy of 5 nm or less is formed in a hollow portion of a tube extruded from the tip of the die by using an extrusion polymer equipped with a die.
- a production method for obtaining the tube by extruding the tetrafluoroethylene / fluoroalkyl vinyl ether copolymer from the die while passing the gas through the die.
- the resin temperature of the tetrafluoroethylene / fluoroalkyl vinyl ether copolymer at the tip of the die is 350 to 370 ° C.
- a storage method for storing the tube in a state in which a high-purity liquid is sealed in the tube is also provided.
- FIG. 1 is a schematic cross-sectional view showing an example of extrusion molding of a TFE / FAVE copolymer using an extrusion molding machine.
- FIG. 2 is an atomic force microscope (AFM) topography image (evaluation length 3 ⁇ m) on the inner surface of the tube produced in Example 1.
- FIG. 3 is a roughness curve of the inner surface of the tube produced in Example 1 calculated from measurement data by an atomic force microscope (AFM).
- FIG. 4 is an electron micrograph of the inner surface of the tube produced in Example 1.
- FIG. 4A is an enlarged electron micrograph of the region 4A including the boundary between the spherulite and the spherulite in the electron micrograph of FIG.
- FIG. 1 is a schematic cross-sectional view showing an example of extrusion molding of a TFE / FAVE copolymer using an extrusion molding machine.
- FIG. 2 is an atomic force microscope (AFM) topography image (evaluation length 3 ⁇ m) on
- FIG. 5 shows the surface roughness Ra data measured according to the JIS standard (B0601) using a contact type surface roughness measuring machine manufactured by Mitutoyo Co., Ltd., and the average spherical crystal diameter calculated from the electron micrograph.
- It is an image diagram of the roughness curve drawn by enlarging the Y-axis to 10 times (vertical magnification) of the X-axis by the roughness curve of the inner surface of the tube produced in Example 1.
- FIG. 6 is an electron micrograph of the inner surface of the tube produced in Example 2.
- FIG. 6A is an enlarged electron micrograph of the region 6A including the boundary between spherulites in the electron micrograph of FIG. FIG.
- FIG. 7 shows the surface roughness Ra data measured according to the JIS standard (B0601) using a contact type surface roughness measuring machine manufactured by Mitutoyo Co., Ltd. and the average spherical crystal diameter calculated from the electron micrograph.
- FIG. 5 is an image diagram of a roughness curve drawn by enlarging the Y-axis to 10 times the X-axis (vertical magnification) of the roughness curve of the inner surface of the tube produced in Example 2.
- the tube of the present disclosure has an evaluation length set to 3 ⁇ m, and the surface roughness Ra of the inner surface of the tube measured by an atomic force microscope (AFM) is 5 nm or less.
- AFM atomic force microscope
- FIG. 1 is a schematic cross-sectional view showing an example of extrusion molding of a TFE / FAVE copolymer using an extrusion molding machine.
- the extrusion molding machine 10 shown in FIG. 1 includes a cylinder 11, an adapter 12, a die head 13, and a die chip 14. As shown in FIG.
- the TFE / FAVE copolymer 16 is melted in the cylinder 11 and extruded from the die head 13 and the die chip 14 by the rotation of the screw 15.
- the extruded tubular TFE / FAVE copolymer passes through the sizing die 17 to define its outer shape.
- the inner surface of the extruded tubular TFE / FAVE copolymer is naturally cooled without any contact with a member such as a die.
- irregularities of a hexagonal pattern due to spherulite formed by crystallization of the TFE / FAVE copolymer during cooling appear.
- the surface roughness Ra of the tube for transferring a high-purity chemical solution for manufacturing a semiconductor device has been measured according to standards such as JIS standard and SEMI standard.
- the evaluation length of the roughness curve when measuring the surface roughness Ra is larger than the size of the spherulite appearing on the inner surface of the tube.
- SEMI F57-0314 describes that the surface roughness Ra of the inner surface of the tube is Ra ⁇ 0.25 ⁇ m (250 nm).
- the evaluation length when measuring the surface roughness Ra is defined by the size of the surface roughness Ra. Journal of Precision Engineering, Vol. 78, No. As described in 4, 2012 (p301-304), the evaluation length according to the magnitude of the surface roughness Ra is as follows. 0.1 ⁇ Ra ⁇ 2 Evaluation length: 4 mm 0.02 ⁇ Ra ⁇ 0.1 Evaluation length: 1.25 mm (0.006) ⁇ Ra ⁇ 0.02 Evaluation length: 0.4 mm
- Patent Document 1 describes that the diameter of spherulites of a normal melt-extruded product is about 20 to 150 ⁇ m.
- Patent Document 1 proposes that the recrystallization average spherulite diameter of the molded product is 15 ⁇ m or less, and the recrystallization average spherulite diameter of the test piece produced in the example is 2 ⁇ m at the smallest. Is. Therefore, the surface roughness calculated when the evaluation length of the roughness curve is 0.4 to 4 mm (400 to 4000 nm) is greatly affected by the spherulite size. That is, the surface roughness calculated by the conventional measurement conditions is a hexagonal pattern swell caused by spherulites appearing on the inner surface of the tube. On the other hand, the line width of recent semiconductor electronic circuits is several nanometers, and it has been pointed out that nano-sized particles affect the product yield.
- the present inventors have found that the cause of the influence of nano-sized particles on the product yield is the extremely minute unevenness on the inner surface of the tube.
- the present inventors measured the surface roughness Ra with the evaluation length of the roughness curve set to 3 ⁇ m, it was found that the surface of the spherulite had irregularities much smaller than the size of the spherulite. These minute irregularities existing on the inner surface of the conventional tube are large enough for nano-sized particles to enter.
- the particle size that can be detected by the particle counter is about 20 to 30 nm.
- the studies by the present inventors have revealed that the surface roughness Ra measured with the evaluation length set to 3 ⁇ m correlates with the amount of eluted metal. It is presumed that some of the pollutants such as particles contain metal components. Therefore, by measuring the amount of metal eluted from the inner surface of the tube into the aqueous nitric acid solution, the amount of contaminants such as nano-sized particles adhering to the inner surface of the tube can be estimated.
- the tube of the present disclosure has an evaluation length set to 3 ⁇ m, and the surface roughness Ra of the inner surface of the tube measured by an atomic force microscope (AFM) is 5 nm or less.
- AFM atomic force microscope
- the surface roughness Ra of the inner surface of the tube is 5 nm or less, more preferably 4 nm or less, and further preferably 3 nm or less.
- the surface roughness Ra is preferably as small as possible from the viewpoint of further reducing the amount of eluted metal, and the lower limit is not particularly limited, but may be 0.1 nm or more, and may be 1 nm or more.
- the surface roughness Ra of the inner surface of the tube can be adjusted by a method of appropriately selecting the type of FAVE unit in the TFE / FAVE copolymer, a method of appropriately adjusting the content of FAVE unit, or the like. According to the findings of the present inventors, the spherulite size does not affect the surface roughness Ra of the inner surface of the tube in the present disclosure.
- the amount of metal eluted from the inner surface of the tube is 0.30 ng / cm 2 or less, preferably 0.25 ng / cm 2 or less, and more preferably 0.20 ng / cm 2 or less. Yes, more preferably 0.15 ng / cm 2 or less, for example 0.13 ng / cm 2 or less.
- Elution amount of metal from the inner surface of the tube is smaller preferably, the lower limit is not particularly limited, it may be at 0 ng / cm 2 or more, may be at 0.01 ng / cm 2 or more, 0.08 ng / cm 2 or more There may be.
- the tube of the present disclosure the elution amount of Ca from the tube inner surface, and at 0.15 ng / cm 2 or less, preferably 0.09ng / cm 2 or less, more preferably 0.08 ng / cm 2 or less Yes, more preferably 0.07 ng / cm 2 or less.
- the amount of metal eluted from the inner surface of the tube is determined by measuring the total content of Na, Mg, Al, K, Ca and Fe in the nitric acid aqueous solution by inductively coupled plasma mass spectrometry (ICP-MS). , Can be identified.
- ICP-MS inductively coupled plasma mass spectrometry
- an aqueous nitric acid solution obtained by enclosing a nitric acid aqueous solution having a concentration of 5% by mass in a tube whose inner surface has been washed with ultrapure water in advance and leaving it at room temperature for 4 hours is used.
- Na, Mg, Al, K and Ca are not components generated from the equipment used in the manufacturing process of the TFE / FAVE copolymer or the molding machine for molding the TFE / FAVE copolymer.
- it is a component contained in pollutants in the air (air).
- Fe is one of the main metals contained in the air. Therefore, the amount of contaminants attached to the inner surface of the tube can be evaluated by measuring the contents of Na, Mg, Al, K, Ca and Fe in the aqueous nitric acid solution. By setting the leaving time after enclosing the nitric acid aqueous solution in the tube to 4 hours, even if these metals are contained inside the tube (inside the resin), the detection can be avoided as much as possible.
- the amount of metal eluted from the inner surface of the tube was extruded from the die of the extrusion molding machine when the surface roughness Ra of the inner surface of the tube was appropriately adjusted and the TFE / FAVE copolymer was extruded to manufacture the tube. It can be reduced by passing a gas that has passed through a filter through the hollow portion of the tube. Further, the amount of metal eluted from the inner surface of the tube can be further easily reduced by adjusting the maximum height RpV of the inner surface of the tube in addition to adjusting the surface roughness Ra of the inner surface of the tube.
- the tube of the present disclosure has an average spherulite diameter on the inner surface of the tube, preferably 1 to 150 ⁇ m, and more preferably 2 to 120 ⁇ m.
- the tube of the present disclosure has an extremely small surface roughness Ra on the inner surface of the tube. Therefore, even if the average spherulite diameter on the inner surface of the tube is more than 15 ⁇ m, contaminants are less likely to adhere to the inner surface of the tube. Can be easily removed. In particular, it is presumed that, unlike conventional tubes, it is unlikely that fine-grained contaminants will enter the recesses existing on the rough inner surface of the tube, making it difficult to remove. Even if fine-grained contaminants enter the recesses, such contaminants are limited to extremely small ones, so it is thought that the effects of contaminants can be suppressed more than with conventional tubes.
- the tube of the present disclosure is a nucleating agent used to reduce the spherulite size of polytetrafluoroethylene (PTFE) or the like. May or may not be included.
- PTFE polytetrafluoroethylene
- the above-mentioned PTFE is not particularly limited.
- PTFE having a crystallization temperature of 305 ° C. or higher measured by a differential scanning calorimeter (DSC) can be mentioned, and the PTFE may have a crystallization heat of 50 J / g or higher.
- DSC differential scanning calorimeter
- the crystallization temperature is more preferably 310 ° C. or higher, still more preferably 312 ° C. or higher.
- PTFE may be undenatured or denatured.
- HFP hexafluoropropylene
- the molecular weight of PTFE is not particularly limited, but low molecular weight PTFE can be used.
- Such low molecular weight PTFE has a lower molecular weight than normal PTFE having a number average molecular weight of several million or more.
- the low molecular weight PTFE can be obtained by a known method such as polymerization of TFE in the presence of a chain transfer agent, thermal decomposition or radiolysis of molding powder or fine powder or a molded product thereof.
- the tubes of the present disclosure may contain the above PTFE in an amount that does not interfere with the effects of the present disclosure.
- the tubes of the present disclosure can contain, for example, 0.01% by weight or more and 10% by weight, preferably 0.01% by weight or more and 4% by weight or less of PTFE.
- the maximum spherulite diameter on the inner surface of the tube is preferably 2 to 160 ⁇ m, more preferably 3 to 130 ⁇ m.
- the tube of the present disclosure has an extremely small surface roughness Ra on the inner surface of the tube. Therefore, even if the maximum spherulite diameter of the inner surface of the tube is more than 20 ⁇ m, contaminants are less likely to adhere to the inner surface of the tube. Can be easily removed.
- the tube of the present disclosure contains a tetrafluoroethylene / fluoroalkyl vinyl ether copolymer.
- the tetrafluoroethylene (TFE) / fluoroalkyl vinyl ether (FAVE) copolymer (TFE / FAVE copolymer) is preferably a melt-processable fluororesin.
- the melt processability means that a polymer can be melted and processed by using conventional processing equipment such as an extruder and an injection molding machine. Therefore, in the melt processable fluororesin, the melt flow rate measured by the measuring method described later is usually 0.01 to 500 g / 10 minutes.
- the content of FAVE units in the TFE / FAVE copolymer is preferably 1.0 to 10% by mass, more preferably 2.0% by mass or more, still more preferably 2.0% by mass, based on all the monomer units. Is 3.0% by mass or more, particularly preferably 3.5% by mass or more, more preferably 8.0% by mass or less, still more preferably 7.0% by mass or less, and particularly preferably 6 It is 5.5% by mass or less, and most preferably 6.0% by mass or less.
- the content of the TFE unit in the TFE / FAVE copolymer is preferably 90 to 99.0% by mass, more preferably 92.0% by mass or more, still more preferably 92.0% by mass, based on all the monomer units.
- the amount of each monomer unit in the TFE / FAVE copolymer is measured by the 19 F-NMR method.
- CF 2 CFO (CF 2 CFY 1 O) p- (CF 2 CF 2 CF 2 O) q- R f (1)
- Y 1 represents F or CF 3
- R f represents a perfluoroalkyl group having 1 to 5 carbon atoms
- p represents an integer of 0 to 5
- q represents an integer of 0 to 5.
- CFX CXOCF 2 OR 1 (2)
- X represents the same or different, H, F or CF 3
- R 1 represents at least one atom selected from the group consisting of linear or branched H, Cl, Br and I.
- It may contain 1 to 2 fluoroalkyl groups having 1 to 6 carbon atoms, or 1 to 2 atoms of at least one selected from the group consisting of H, Cl, Br and I. It can be mentioned at least one selected from the group consisting of monomers represented by (representing a cyclic fluoroalkyl group having 5 or 6 carbon atoms).
- the FAVE is preferably a monomer represented by the general formula (1), and is composed of perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether) (PEVE) and perfluoro (propyl vinyl ether) (PPVE). At least one selected from the group is more preferred, and PPVE is even more preferred.
- PPVE perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether) (PEVE) and perfluoro (propyl vinyl ether) (PPVE).
- PEVE perfluoro (ethyl vinyl ether)
- PPVE perfluoro (propyl vinyl ether)
- At least one selected from the group is more preferred, and PPVE is even more preferred.
- the TFE / FAVE copolymer is not particularly limited, but a copolymer having a molar ratio of TFE units to FAVE units (TFE units / FAVE units) of 70/30 or more and less than 99/1 is preferable. A more preferable molar ratio is 70/30 or more and 98.9 / 1.1 or less, and a more preferable molar ratio is 80/20 or more and 98.9 / 1.1 or less. If the TFE unit is too small, the mechanical properties tend to deteriorate, and if it is too large, the melting point tends to be too high and the moldability tends to decrease.
- the TFE / FAVE copolymer contains 0.1 to 10 mol% of monomer units derived from TFE and a monomer copolymerizable with FAVE, and the total amount of TFE units and FAVE units is 90 to 99. It is also preferable that the copolymer is 9 mol%.
- TFE / FAVE copolymer at least one selected from the group consisting of only TFE units and FAVE units and the above TFE / HFP / FAVE copolymers is preferable, and TFE units and FAVE are preferable. Copolymers consisting only of units are more preferable.
- the melting point of the TFE / FAVE copolymer is preferably 280 to 322 ° C, more preferably 290 ° C or higher, further preferably 295 ° C or higher, particularly preferably 300 ° C or higher, and more preferably. It is 315 ° C or lower.
- the melting point can be measured using a differential scanning calorimeter [DSC].
- the glass transition temperature (Tg) of the TFE / FAVE copolymer is preferably 70 to 110 ° C., more preferably 80 ° C. or higher, and more preferably 100 ° C. or lower.
- the glass transition temperature can be measured by dynamic viscoelasticity measurement.
- the melt flow rate (MFR) of the TFE / FAVE copolymer at 372 ° C. is preferably 0.1 to 100 g / 10 minutes, more preferably 0.5 g / 10 minutes or more, still more preferably 1 g / 10 minutes. It is 10 minutes or more, more preferably 80 g / 10 minutes or less, further preferably 40 g / 10 minutes or less, and particularly preferably 30 g / 10 minutes or less.
- ASTM D1238 the mass of the polymer (g) flowing out from a nozzle having an inner diameter of 2.1 mm and a length of 8 mm per 10 minutes under a load of 372 ° C. and 5 kg using a melt indexer (manufactured by Yasuda Seiki Seisakusho). It is a value obtained as / 10 minutes).
- TFE / FAVE copolymer since the tube elution amount of metal is further reduced can be obtained, smaller copolymer having functional groups are preferred, 0 carbon atoms 10 6 per functional group in total to 50 It is preferable to have one.
- the number of functional groups per 10 to 6 carbon atoms is more preferably 0 to 30, and even more preferably 0 to 15.
- the functional group is a functional group existing at the main chain end or the side chain end of the TFE / FAVE copolymer, and a functional group existing in the main chain or the side chain.
- Infrared spectroscopy can be used to identify the type of functional group and measure the number of functional groups.
- the number of functional groups is measured by the following method.
- the TFE / FAVE copolymer is melted at 330 to 340 ° C. for 30 minutes and compression molded to prepare a film having a thickness of 0.25 to 0.3 mm.
- This film is analyzed by Fourier transform infrared spectroscopic analysis to obtain an infrared absorption spectrum of the above TFE / FAVE copolymer, and a difference spectrum from a base spectrum which is completely fluorinated and has no functional group. From the absorption peak of a specific functional group appearing in this difference spectrum, the number N of functional groups per 1 ⁇ 10 6 carbon atoms in the TFE / FAVE copolymer is calculated according to the following formula (A).
- N I ⁇ K / t (A)
- Table 1 shows the absorption frequency, molar absorption coefficient, and correction coefficient for the functional groups in the present disclosure.
- the molar extinction coefficient was determined from the FT-IR measurement data of the low molecular weight model compound.
- the absorption frequencies of -CH 2 CF 2 H, -CH 2 COF, -CH 2 COOH, -CH 2 COOCH 3 , and -CH 2 CONH 2 are shown in the table, respectively, -CF 2 H, -COF, and -COOH free. It is several tens of Kaiser (cm -1 ) lower than the absorption frequency of -COOH bounded, -COOCH 3 , and -CONH 2. Therefore, for example, the number of functional groups of -COF is derived from the number of functional groups obtained from the absorption peak of absorption frequency 1883 cm -1 caused by -CF 2 COF and the absorption peak of absorption frequency 1840 cm -1 caused by -CH 2 COF. It is the total with the obtained number of functional groups.
- the functional group is introduced into the TFE / FAVE copolymer by, for example, a chain transfer agent or a polymerization initiator used in producing the TFE / FAVE copolymer.
- a chain transfer agent or a polymerization initiator used in producing the TFE / FAVE copolymer.
- a chain transfer agent or a polymerization initiator used in producing the TFE / FAVE copolymer.
- -CH 2 OH end of the main chain of the TFE / FAVE copolymer Is introduced.
- the functional group is introduced into the side chain terminal of the TFE / FAVE copolymer.
- the TFE / FAVE copolymer having the number of functional groups within the above range can be obtained. That is, the TFE / FAVE copolymer is preferably fluorinated. It is also preferable that the TFE / FAVE copolymer has a -CF 3-terminal group.
- the above fluorination treatment can be performed by contacting a non-fluorinated TFE / FAVE copolymer with a fluorine-containing compound.
- the fluorine-containing compound is not particularly limited, and examples thereof include a fluorine radical source that generates fluorine radicals under fluorination treatment conditions.
- a fluorine radical source that generates fluorine radicals under fluorination treatment conditions.
- the fluorine radical source include F 2 gas, CoF 3 , AgF 2 , UF 6 , OF 2 , N 2 F 2 , CF 3 OF, halogen fluoride (for example, IF 5 , ClF 3 ) and the like.
- the fluorine radical source such as the F 2 gas may have a concentration of 100%, but from the viewpoint of safety, it is preferably mixed with an inert gas and diluted to 5 to 50% by mass before use. It is more preferable to dilute it to about 30% by mass before use.
- the inert gas include nitrogen gas, helium gas, argon gas and the like, but nitrogen gas is preferable from the economical point of view.
- the conditions for the fluorination treatment are not particularly limited, and the melted TFE / FAVE copolymer may be brought into contact with the fluorine-containing compound, but usually, it is preferably below the melting point of the TFE / FAVE copolymer. Can be carried out at a temperature of 20 to 220 ° C., more preferably 100 to 200 ° C.
- the fluorination treatment is generally carried out for 1 to 30 hours, preferably 5 to 25 hours.
- the fluorination treatment is preferably such that the non-fluorinated TFE / FAVE copolymer is brought into contact with a fluorine gas (F 2 gas).
- the TFE / FAVE copolymer is produced by a conventionally known method such as emulsion polymerization or suspension polymerization by appropriately mixing a monomer as a constituent unit thereof or an additive such as a polymerization initiator. Can be done.
- the tube of the present disclosure is obtained by extruding a TFE / FAVE copolymer through a hollow portion of a tube extruded from a die of an extruder while passing a gas that has passed through a filter having a filtration accuracy of 5 nm or less. It is preferable that it is a thing.
- the present disclosure is a method for manufacturing a tube, in which a gas having a filtration accuracy of 5 nm or less is passed through a hollow portion of a tube extruded from the tip of the die by using an extrusion molding machine provided with a die. It also relates to a production method for obtaining the tube by extruding the TFE / FAVE copolymer from the die while circulating.
- the method of circulating the gas passed through the filter through the hollow part of the tube will be described in a little more detail with reference to FIG.
- the melted TFE / FAVE copolymer 16 in the cylinder 11 is extruded from the die head 13 and the die chip 14 of the extrusion molding machine 10.
- the die chip 14 is provided with a gas introduction port 23 so that the gas 21 can be introduced into the hollow portion 19 of the tubular TFE / FAVE copolymer 16.
- the gas (outside air) 21 passes through the filter 22 and is introduced into the hollow portion 19 from the gas introduction port 23. Since the gas introduced into the hollow portion in this way does not contain contaminants having a relatively large particle size, adhesion of the relatively large contaminants to the inner surface 18 of the tube is prevented.
- the filtration accuracy of the filter 22 is preferably 1 nm. That is all.
- a gas that has passed through a plurality of filters connected in series may be used, or a gas that has passed through a plurality of filters having different filtration accuracy may be used.
- Filters may be installed in parallel to reduce gas resistance.
- the gas pressurized by means such as an air pump may be passed through the filter, or the gas contained in the high-pressure gas cylinder may be controlled to an appropriate pressure before being passed through the filter.
- FIG. 1 is a gas that has passed through a plurality of filters connected in series
- a gas that has passed through a plurality of filters having different filtration accuracy may be used.
- Filters may be installed in parallel to reduce gas resistance.
- the gas pressurized by means such as an air pump may be passed through the filter, or the gas contained in the high-pressure gas cylinder may be controlled to an appropriate pressure before being passed through the filter.
- the gas is introduced from the extrusion molding machine 10 into the hollow portion 19, but the gas that has passed through the filter is introduced from the tip of the tube that has passed through the sizing die 17, and the extrusion molding machine 10 is optional. You may exhaust from the place of.
- a single-screw extruder is used, but a twin-screw extruder can also be used, and the extrusion molding machine is not limited to that shown in FIG.
- the temperatures of the cylinder 11, the adapter 12, the die head 13 and the die tip 14 of the extrusion molding machine 10 are adjusted so that the resin temperature at the die tip 24 of the extrusion molding machine 10 becomes 350 to 370 ° C. It is also preferable to set it.
- the resin temperature at the die tip 24 By lowering the resin temperature at the die tip 24 to a relatively low temperature, the amount of the component (polymer fume) volatilized from the TFE / FAVE copolymer can be suppressed, and the contamination of the inner surface of the tube can be further suppressed. it can.
- pellets of TFE / FAVE copolymer When pellets of TFE / FAVE copolymer are used as a molding material, they are volatilized from the TFE / FAVE copolymer by lowering the resin temperature at the die tip 24 than the molding temperature at the time of producing the pellets. The amount of the component can be further suppressed, and the contamination of the inner surface of the tube can be further suppressed. If the resin temperature at the tip portion 24 of the die is too low, molding defects may occur, the appearance of the tube may be impaired, or the surface roughness of the inner surface of the tube may be increased.
- the inner surface of the tube may be contaminated by contaminants in the gas during storage after manufacturing, so that the tube is stored.
- Appropriate selection of the method is also suitable. For example, by storing the tube with a high-purity liquid sealed in the tube, contamination after production can be suppressed. Ultrapure water is preferable as the high-purity liquid to be sealed in the tube.
- the outer diameter of the tube is not particularly limited, but may be 2 to 100 mm, or 5 to 50 mm.
- the thickness of the tube may be 0.1 to 10 mm and may be 0.3 to 5 mm.
- the tube of the present disclosure can be suitably used as a tube for chemical solution piping for distributing chemical solutions, and can be particularly preferably used as a tube for chemical solution piping used for transferring high-purity chemical solutions for manufacturing semiconductor devices.
- the inner surface of the tube may be contaminated with contaminants such as fine particles present in the air and polymer fume generated during melt molding of the TFE / FAVE copolymer.
- contaminants such as fine particles present in the air and polymer fume generated during melt molding of the TFE / FAVE copolymer.
- nano-sized pollutants adhere to the inner surface of the polymer due to van der Waals force, electrostatic force, etc., and are difficult to remove with washing water such as pure water. Therefore, when a new tube is used in a semiconductor factory, a large amount of ultrapure water or a chemical solution is required to clean the inside of the tube (flushing), or a long-time cleaning is required. There is.
- the tube of the present disclosure Since the tube of the present disclosure has the above configuration, almost no contaminants adhere to the inner surface, and it is difficult to contaminate ultrapure water or high-purity chemicals used for manufacturing semiconductor devices. Since the tube of the present disclosure exhibits such an effect, it is preferable that the tube is a tube for piping the chemical solution for circulating the chemical solution.
- the chemical solution include chemical solutions used for semiconductor production, and examples thereof include chemical solutions such as ammonia water, ozone water, hydrogen peroxide solution, hydrochloric acid, sulfuric acid, resist solution, thinner solution, and developer solution.
- the tube of the present disclosure can be used, for example, as a tube used in a semiconductor manufacturing facility such as a semiconductor manufacturing chemical supply line, a semiconductor manufacturing chemical supply facility, a semiconductor cleaning device, a coater developer, or a semiconductor manufacturing device.
- a semiconductor manufacturing facility such as a semiconductor manufacturing chemical supply line, a semiconductor manufacturing chemical supply facility, a semiconductor cleaning device, a coater developer, or a semiconductor manufacturing device.
- a high-purity chemical solution can be reliably supplied to a use point.
- a semiconductor device having a line width of 5 nm or less is manufactured, defect defects due to particles and metal pollutants of the semiconductor device are reduced, and the yield in manufacturing the semiconductor device is improved. Can be expected.
- MFR Melt flow rate
- TS tensile breaking strength
- EL tensile elongation
- the pellets used in Examples and Comparative Examples were heat-pressed to prepare a sheet having a thickness of 1.5 mm.
- the obtained sheet was cut out using an ASTM V-type dumbbell to prepare a dumbbell-shaped test piece.
- ASTM V-type dumbbell to prepare a dumbbell-shaped test piece.
- the breaking strength and tensile elongation were measured at 25 ° C. under the condition of 50 mm / min using an autograph (AGS-J 5 kN manufactured by Shimadzu Corporation) according to ASTM D638. ..
- test pieces having a width of 12.5 mm, a length of 130 mm, and a thickness of 0.25 mm were prepared.
- the MIT value of the prepared test piece was measured according to ASTM D2176. Specifically, the test piece was mounted on a MIT tester (model number 12176, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) and tested under the conditions of a load of 1.25 kg, left and right bending angles of 135 degrees each, and the number of bendings of 175 times / minute. The piece was bent and the number of times (MIT value) until the test piece was cut was measured.
- a tube obtained by extrusion molding was cut to a length of about 2 cm and then cut in the length direction to prepare a test piece having a length of about 5 mm and a width of 5 mm. Images were taken with a scanning electron microscope (SEM) at a magnification of 1000x. The diameter of the spherulite was measured from the image. A total of 15 spherulites were measured, and the arithmetic mean value was taken as the average spherulite diameter. The largest diameter among the 15 pieces was defined as the maximum spherulite diameter. Since the spherulite is observed as a distorted polygon due to collision with the adjacent spherulite, its major axis diameter is taken as the diameter.
- the surface roughness Ra is obtained by extracting only the reference length L from the roughness curve in the direction of the average line, summing the absolute values of the deviations from the average line of the extracted portion to the measurement curve, and averaging the average value (arithmetic average roughness). It is).
- the calculation formula of the surface roughness Ra is as follows. ..
- the surface roughness Ra was calculated by performing an automatic tilt correction process on the AFM topography images of the inner surface of the tubes obtained in Examples and Comparative Examples.
- the maximum height (Rpv) was calculated by performing an automatic tilt correction process on the AFM topography images of the inner surface of the tubes obtained in Examples and Comparative Examples.
- ⁇ Amount of eluted metal> The tubes obtained in Examples and Comparative Examples were cut to a length of 60 cm. A tube having a length of 60 cm was bent in an arc shape and fixed. The inner surface of the tube was cleaned by injecting the same amount of ultrapure water as the content of the tube into the arcuate tube and immediately discarding the ultrapure water. Next, from one end of the tube, gently prepare a 5 mass% HNO 3 aqueous solution (prepared by diluting "Tamapure" (68 mass% HNO 3) manufactured by Kanto Chemical Co., Inc. with ultrapure water) using a washed dropper. 34 ml was injected. After leaving at room temperature for 4 hours, the aqueous nitric acid solution was recovered.
- a 5 mass% HNO 3 aqueous solution prepared by diluting "Tamapure" (68 mass% HNO 3) manufactured by Kanto Chemical Co., Inc. with ultrapure water
- the metal content of the metal component in the recovered aqueous nitrate solution was measured by inductively coupled plasma mass spectrometry (ICP-MS).
- the metal content of the chemical solution used was used as a blank value, and the value obtained by subtracting the metal content of the chemical solution used from the detected value was adopted as the measured value.
- the temperatures of the cylinders (C1, C2, C3), adapter (A), die head (D1) and die chip (D2) of the extruder were set to 330 to 370 ° C.
- the resin temperature of the copolymer at the tip of the die (the tip of the die tip) was 370 ° C.
- Table 2 shows the composition of the pellets, the physical characteristics of the pellets, the physical characteristics of the tube, the amount of metal eluted from the inner surface of the tube, and the like.
- FIG. 2 shows an atomic force microscope (AFM) topography image (evaluation length 3 ⁇ m) on the inner surface of the tube.
- FIG. 3 shows the roughness curve of the inner surface of the tube calculated based on the data measured by the atomic force microscope (AFM).
- Example 2 Except for using pellets containing a TFE / PPVE copolymer (the content of PPVE units is 3.7% by mass based on all monomer units) and PTFE (manufactured by Daikin Industries, Ltd., trade name "Lubron L5"). Made a tube in the same manner as in Example 1. The results are shown in Table 2.
- Example 3 A tube was prepared in the same manner as in Example 1 except that pellets containing a TFE / PPVE copolymer (content of PPVE units was 3.6% by mass based on all monomer units) were used. The results are shown in Table 2.
- Comparative Example 1 Except for using pellets containing TFE / PEVE copolymer (content of PEVE unit is 8.3% by mass based on all monomer units) and PTFE (manufactured by Daikin Industries, Ltd., trade name "Lubron L5"). Made a tube in the same manner as in Example 1. The results are shown in Table 2.
- Comparative Example 2 A tube was prepared in the same manner as in Example 1 except that pellets containing a TFE / PEVE copolymer (content of PEVE units was 6.5% by mass based on all monomer units) were used. The results are shown in Table 2.
- Comparative Example 3 A tube was produced in the same manner as in Example 1 except that air (outside air) was directly introduced into the hollow portion of the tube without using a filter. The results are shown in Table 2.
- the tube of Example 1 has a larger average spherulite diameter than the tube of Example 2.
- the amount of metal eluted from the inner surface of the tube of Example 1 is equivalent to the amount of metal eluted from the inner surface of the tube of Example 2. The reason for this is presumed as follows. 4 to 7 are electron micrographs and roughness curves of the inner surfaces of the tubes of Examples 1 and 2.
- FIG. 4 is an electron micrograph of the inner surface of the tube produced in Example 1
- FIG. 6 is an electron micrograph of the inner surface of the tube produced in Example 2.
- the spherulite diameters on the inner surfaces of the tubes of Examples 1 and 2 are significantly different between the two.
- the roughness curves of FIGS. 5 and 7 even when the spherulite diameter is large as in Example 1 or when the spherulite diameter is small as in Example 2.
- there is no groove at the boundary between spherulites and they are flat and gentle. It is unlikely that contaminants with relatively small particle sizes will concentrate and adhere to the boundary between spherulites. Therefore, the spherulite diameter on the inner surface of the tube has little effect on the amount of eluted metal.
- the inner surface of each tube has irregularities much smaller than the size of the spherulite. ..
- the surface roughness Ra in the present disclosure is measured by AFM with the evaluation length set to 3 ⁇ m. Therefore, the surface roughness Ra in the present disclosure is not an index of roughness formed by spherulites on the inner surface of the tube, but an index of roughness formed by minute irregularities shown in the roughness curves of FIGS. 5 and 7. Is.
- the factor that affects the amount of eluted metal is not the size of the spherulite diameter, but the surface roughness Ra, which is much smaller than the spherulite diameter. Since the tubes of Examples 1 and 2 have the same surface roughness Ra, it is presumed that they showed the same amount of eluted metal.
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Abstract
Description
本開示のチューブは、前記チューブ内面の平均球晶径が、15μm超であることが好ましい。
本開示のチューブは、フルオロアルキルビニルエーテルが、パーフルオロ(プロピルビニルエーテル)であることが好ましい。
本開示のチューブは、半導体デバイス製造用高純度薬液を移送するために好適に用いることができる。
本開示のチューブは、押出成形機のダイから押し出されたチューブの中空部に、ろ過精度が5nm以下のフィルターを通過させた気体を流通させながら、前記テトラフルオロエチレン/フルオロアルキルビニルエーテル共重合体を押し出すことにより得られるものであることが好ましい。
本開示のチューブは、前記テトラフルオロエチレン/フルオロアルキルビニルエーテル共重合体におけるフルオロアルキルビニルエーテル単位の含有量が、全単量体単位に対して、1.0~8.0質量%であることが好ましい。
0.1<Ra≦2 評価長さ:4mm
0.02<Ra≦0.1 評価長さ:1.25mm
(0.006)<Ra≦0.02 評価長さ:0.4mm
また、本開示のチューブは、チューブ内面からの溶出Ca量が、0.15ng/cm2以下であり、好ましくは0.09ng/cm2以下であり、より好ましくは0.08ng/cm2以下であり、さらに好ましくは0.07ng/cm2以下である。
上記PTFEは特に限定されない。一例としては、示差走査熱量計(DSC)で測定した結晶化温度が305℃以上であるPTFEが挙げられ、該PTFEは結晶化熱が50J/g以上であってもよい。本開示のチューブがこのようなPTFEを含むことにより、チューブ内面をより平滑にすることができる。上記結晶化温度は、より好ましくは310℃以上、さらに好ましくは312℃以上である。
PTFEは未変性であっても、変性されていてもよい。例えば、テトラフルオロエチレン(TFE)のホモポリマー、又は1重量%未満の微量のヘキサフルオロプロピレン(HFP)、フルオロアルコキシトリフルオロエチレン、フルオロアルキルエチレン、クロロトリフルオロエチレン等の変性剤を含有する変性PTFEが挙げられる。
PTFEの分子量は特に限定されないが、低分子量PTFEを用いることができる。数百万以上の数平均分子量を有する通常のPTFEと比べて、かかる低分子量PTFEは低い分子量を有する。低分子量PTFEは、連鎖移動剤の存在下におけるTFEの重合や、モールディングパウダー若しくはファインパウダー又はこれらの成形物の熱分解又は放射線分解等の公知の方法で得ることができる。
本開示のチューブは、本開示の効果を妨げない範囲の量で上記PTFEを含むことができる。本開示のチューブは、例えば0.01重量%以上10重量%、好ましくは0.01重量%以上4重量%以下の量のPTFEを含むことができる。
上記TFE/FAVE共重合体におけるTFE単位の含有量は、全単量体単位に対して、好ましくは90~99.0質量%であり、より好ましくは92.0質量%以上であり、さらに好ましくは93.0質量%以上であり、特に好ましくは93.5質量%以上であり、最も好ましくは94.0質量%以上であり、より好ましくは98.0質量%以下であり、さらに好ましくは97.0質量%以下であり、特に好ましくは96.5質量%以下である。
TFE/FAVE共重合体における各単量体単位の量は、19F-NMR法により測定する。
CF2=CFO(CF2CFY1O)p-(CF2CF2CF2O)q-Rf (1)
(式中、Y1はFまたはCF3を表し、Rfは炭素数1~5のパーフルオロアルキル基を表す。pは0~5の整数を表し、qは0~5の整数を表す。)で表される単量体、および、一般式(2):
CFX=CXOCF2OR1 (2)
(式中、Xは、同一または異なり、H、FまたはCF3を表し、R1は、直鎖または分岐した、H、Cl、BrおよびIからなる群より選択される少なくとも1種の原子を1~2個含んでいてもよい炭素数が1~6のフルオロアルキル基、若しくは、H、Cl、BrおよびIからなる群より選択される少なくとも1種の原子を1~2個含んでいてもよい炭素数が5または6の環状フルオロアルキル基を表す。)で表される単量体からなる群より選択される少なくとも1種を挙げることができる。
N=I×K/t (A)
I:吸光度
K:補正係数
t:フィルムの厚さ(mm)
従って、たとえば、-COFの官能基数とは、-CF2COFに起因する吸収周波数1883cm-1の吸収ピークから求めた官能基数と、-CH2COFに起因する吸収周波数1840cm-1の吸収ピークから求めた官能基数との合計である。
共重合体中のテトラフルオロエチレン(TFE)単位およびフルオロアルキルビニルエーテル(FAVE)単位の含有量は、19F-NMR法により測定した。
実施例および比較例で用いたペレットのMFRを次の方法により求めた。ASTM D1238に従って、メルトインデクサー(安田精機製作所社製)を用いて、372℃、5kg荷重下で、内径2.1mm、長さ8mmのノズルから10分間あたりに流出する共重合体の質量(g/10分)を求めた。
実施例および比較例で用いたペレットの融点を、示差走査熱量計〔DSC〕を用いて、10℃/分の速度で昇温したときの融解熱曲線における極大値に対応する温度として求めた。
実施例および比較例で用いたペレットの比重を、水中置換法にて測定した。
実施例および比較例で用いたペレットを、ヒートプレスすることにより、1.5mm厚のシートを作製した。ASTM V型ダンベルを用いて、得られたシートを切り抜き、ダンベル状試験片を作製した。ダンベル状試験片を用いて、オートグラフ(島津製作所社製 AGS-J 5kN)を使用して、ASTM D638に準じて、50mm/分の条件下で、25℃で破断強度および引張伸びを測定した。
実施例および比較例で用いたペレットから、幅12.5mm、長さ130mm、厚さ0.25mmの試験片を作製した。作製した試験片のMIT値を、ASTM D2176に準じて測定した。具体的には、試験片を、MIT試験機(型番12176、安田精機製作所社製)に装着し、荷重1.25kg、左右の折り曲げ角度各135度、折り曲げ回数175回/分の条件下で試験片を屈曲させ、試験片が切断するまでの回数(MIT値)を測定した。
押出成形して得られたチューブを約2cmの長さにカットした後、長さ方向に裁断して、長さ約5mm、幅5mmの試験片を作製した。走査型電子顕微鏡(SEM)にて倍率1000倍で、画像を撮影した。画像から球晶の直径を測定した。総計15個の球晶を測定して、算術平均した数値を平均球晶径とした。15個の中で最大の直径を最大球晶径とした。球晶は隣接して成長した球晶との衝突によりいびつな多角形として観察されるので、その長軸径を直径とした。
表面粗度Raは、粗さ曲線からその平均線の方向に基準長さLだけを抜き取り、この抜き取り部分の平均線から測定曲線までの偏差の絶対値を合計し、平均した値(算術平均粗さ)である。抜き取り部分の平均線の方向にx軸を、縦倍率の方向にy軸を取り、粗さ曲線をy=f(x)で表したとき、表面粗度Raの計算式は次のとおりである。
最大高さ(Rp-v)は、粗さ曲線からその平均線の方向に基準長さLだけを抜き取り、この抜き取り部分の平均線から最も高い山頂までの間隔Ypと最も低い谷底までの間隔Yvとの和、つまりRp-v=Yp+Yvを表す。
最大高さ(Rp-v)は、実施例および比較例で得られたチューブの内面のAFMトポグラフィ像について、傾斜自動補正処理を行うことにより算出した。
AFMトポグラフィ像は、原子間力顕微鏡(AFM)として、高精度大型プローブ顕微鏡ユニットAFM5200S(HITACHI High-Tech社製)を使用し、ダイナミックフォースモードで、試料表面を、測定面積3×3μm角、走査速度1Hz、x-y方向256×256分割、カンチレバーSI-DF-20(Si、f=134kHz、C=16N/m)の条件で測定した。
実施例および比較例で得られたチューブを60cmの長さにカットした。60cmの長さのチューブを円弧状に曲げて固定した。円弧状のチューブに、チューブの内容量と同量の超純水を注入し、直ちに超純水を廃棄することにより、チューブ内面を洗浄した。次に、チューブの一端から、洗浄したスポイトを用いて、5質量%HNO3水溶液(関東化学社製「タマピュア」(68質量%HNO3)を超純水で希釈することにより調製)を静かに34ml注入した。室温で4時間放置した後、硝酸水溶液を回収した。誘導結合プラズマ質量分析法(ICP-MS)により、回収した硝酸水溶液中の金属成分の金属含有量を測定した。使用した薬液の金属含有量をブランク値として、検出値から使用した薬液の金属含有量を差し引いた値を、測定値として採用した。測定値(ng/ml)に、封入液量34mlを乗じ、チューブの接液面積160cm2で除して、溶出金属量(ng/cm2)を求めた。超純水および硝酸水溶液は、いずれも、ろ過精度5nmのフィルターを通過させてから測定に用いた。
TFE/PPVE共重合体(PPVE単位の含有量が全単量体単位に対して5.5質量%)を含有するペレットを、押出成形機(シリンダー軸径30mm、L/D=22)を用いて、引き取り速度0.5m/分で押出成形し、外径10.5mm、内径8.5mmのチューブを得た。押出成形機のスクリュー回転数を5~10rpmの範囲で調整することにより、チューブの肉厚を調整した。押出成形機のシリンダー(C1,C2,C3)、アダプター(A)、ダイヘッド(D1)およびダイチップ(D2)の温度は、330~370℃に設定した。ダイの先端部(ダイチップの先端部)での共重合体の樹脂温度は、370℃であった。
TFE/PPVE共重合体(PPVE単位の含有量が全単量体単位に対して3.7質量%)およびPTFE(ダイキン工業社製、商品名「ルブロンL5」)を含有するペレットを用いた以外は、実施例1と同様にして、チューブを作製した。結果を表2に示す。
TFE/PPVE共重合体(PPVE単位の含有量が全単量体単位に対して3.6質量%)を含有するペレットを用いた以外は、実施例1と同様にして、チューブを作製した。結果を表2に示す。
TFE/PEVE共重合体(PEVE単位の含有量が全単量体単位に対して8.3質量%)およびPTFE(ダイキン工業社製、商品名「ルブロンL5」)を含有するペレットを用いた以外は、実施例1と同様にして、チューブを作製した。結果を表2に示す。
TFE/PEVE共重合体(PEVE単位の含有量が全単量体単位に対して6.5質量%)を含有するペレットを用いた以外は、実施例1と同様にして、チューブを作製した。結果を表2に示す。
フィルターを用いることなく、チューブの中空部に空気(外気)をそのまま導入した以外は、実施例1と同様にして、チューブを作製した。結果を表2に示す。
11 シリンダー
12 アダプター
13 ダイヘッド
14 ダイチップ
15 スクリュー
16 TFE/FAVE共重合体
17 サイジングダイ
18 チューブ内面
19 中空部
21 気体(外気)
22 フィルター
23 気体導入口
24 ダイ先端部
Claims (10)
- テトラフルオロエチレン/フルオロアルキルビニルエーテル共重合体を含有するチューブであって、
評価長さを3μmに設定して、原子間力顕微鏡(AFM)により測定される、前記チューブ内面の表面粗度Raが、5nm以下であり、
前記チューブ内面からの溶出金属量が、0.30ng/cm2以下である
チューブ。 - 前記チューブ内面の平均球晶径が、1~150μmである請求項1に記載のチューブ。
- 前記チューブ内面の平均球晶径が、15μm超である請求項1または2に記載のチューブ。
- フルオロアルキルビニルエーテルが、パーフルオロ(プロピルビニルエーテル)である請求項1~3のいずれかに記載のチューブ。
- 半導体デバイス製造用高純度薬液を移送するために用いる請求項1~4のいずれかに記載のチューブ。
- 押出成形機のダイから押し出されたチューブの中空部に、ろ過精度が5nm以下のフィルターを通過させた気体を流通させながら、前記テトラフルオロエチレン/フルオロアルキルビニルエーテル共重合体を押し出すことにより得られる請求項1~5のいずれかに記載のチューブ。
- 前記テトラフルオロエチレン/フルオロアルキルビニルエーテル共重合体におけるフルオロアルキルビニルエーテル単位の含有量が、全単量体単位に対して、1.0~8.0質量%である、請求項1~6のいずれかに記載のチューブ。
- 請求項1~7のいずれかに記載のチューブの製造方法であって、
ダイを備える押出成形機を用いて、前記ダイの先端部から押し出されたチューブの中空部に、ろ過精度が5nm以下のフィルターを通過させた気体を流通させながら、前記テトラフルオロエチレン/フルオロアルキルビニルエーテル共重合体を、前記ダイから押し出すことにより、前記チューブを得る製造方法。 - 前記テトラフルオロエチレン/フルオロアルキルビニルエーテル共重合体の、前記ダイの先端部での樹脂温度が、350~370℃である請求項8に記載の製造方法。
- 請求項1~7のいずれかに記載のチューブの保管方法であって、前記チューブ中に高純度液体を封入した状態で、前記チューブを保管する保管方法。
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- 2020-08-04 EP EP20854340.5A patent/EP4019820A4/en active Pending
- 2020-08-04 JP JP2021540712A patent/JP7485964B2/ja active Active
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WO2023112525A1 (ja) * | 2021-12-17 | 2023-06-22 | 株式会社トヨックス | 可撓管 |
JP2023090196A (ja) * | 2021-12-17 | 2023-06-29 | 株式会社トヨックス | 可撓管の製造方法 |
JP7401927B2 (ja) | 2021-12-17 | 2023-12-20 | 株式会社トヨックス | 可撓管 |
WO2024053707A1 (ja) * | 2022-09-09 | 2024-03-14 | ダイキン工業株式会社 | チューブおよびチューブの製造方法 |
Also Published As
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TW202115134A (zh) | 2021-04-16 |
EP4019820A4 (en) | 2024-01-03 |
JP7485964B2 (ja) | 2024-05-17 |
EP4019820A1 (en) | 2022-06-29 |
TWI809296B (zh) | 2023-07-21 |
CN114206583A (zh) | 2022-03-18 |
US20220170573A1 (en) | 2022-06-02 |
KR20220041140A (ko) | 2022-03-31 |
JPWO2021033539A1 (ja) | 2021-02-25 |
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