CN110944920B - Tank and chemical liquid supply system - Google Patents
Tank and chemical liquid supply system Download PDFInfo
- Publication number
- CN110944920B CN110944920B CN201880048526.3A CN201880048526A CN110944920B CN 110944920 B CN110944920 B CN 110944920B CN 201880048526 A CN201880048526 A CN 201880048526A CN 110944920 B CN110944920 B CN 110944920B
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- CN
- China
- Prior art keywords
- composite resin
- fluororesin
- tank
- resin material
- tetrafluoroethylene
- Prior art date
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- 239000000126 substance Substances 0.000 title claims abstract description 235
- 239000007788 liquid Substances 0.000 title claims description 179
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- 239000000463 material Substances 0.000 claims abstract description 288
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 189
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 183
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 177
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 177
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 173
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 100
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229920001577 copolymer Polymers 0.000 claims abstract description 53
- 239000002033 PVDF binder Substances 0.000 claims abstract description 45
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 45
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims description 243
- 239000000243 solution Substances 0.000 claims description 153
- 239000003814 drug Substances 0.000 claims description 75
- 238000003756 stirring Methods 0.000 claims description 62
- 229940079593 drug Drugs 0.000 claims description 56
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 53
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 53
- 229920001780 ECTFE Polymers 0.000 claims description 23
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical group FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 claims description 21
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 21
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
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- 238000000034 method Methods 0.000 description 51
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 50
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- 230000000052 comparative effect Effects 0.000 description 31
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 22
- 239000002270 dispersing agent Substances 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 20
- 239000008188 pellet Substances 0.000 description 20
- 230000032258 transport Effects 0.000 description 20
- 238000000748 compression moulding Methods 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 17
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- 238000002844 melting Methods 0.000 description 16
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- 238000000465 moulding Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000011109 contamination Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000011268 mixed slurry Substances 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
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- 238000007599 discharging Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229960002050 hydrofluoric acid Drugs 0.000 description 4
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 4
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- 239000012498 ultrapure water Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
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- 239000005453 ketone based solvent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 241001089723 Metaphycus omega Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
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- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
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- 238000007561 laser diffraction method Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 2
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
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- 238000001241 arc-discharge method Methods 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 238000004299 exfoliation Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 238000000981 high-pressure carbon monoxide method Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
- B65D25/14—Linings or internal coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D90/00—Component parts, details or accessories for large containers
- B65D90/02—Wall construction
- B65D90/04—Linings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D90/00—Component parts, details or accessories for large containers
- B65D90/22—Safety features
- B65D90/46—Arrangements for carrying off, or preventing the formation of electrostatic charges
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
Abstract
The invention provides a tank for processing various chemical solutions, which can prevent the electrification of the contents in the tank and reduce the pollution of the contents in the tank. The tank of the present invention has an outer tank of the tank and a lining layer on the inner surface thereof, the lining layer containing, at least in part, a composite resin material containing a fluororesin A and a carbon nanotube, the fluororesin A being selected from the group consisting of polytetrafluoroethylene, modified polytetrafluoroethylene, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene/ethylene copolymer and polyvinyl fluoride.
Description
Technical Field
This patent application claims priority of paris treaty based on japanese patent application No. 2017-142264 (application 7/21/2017) and japanese patent application No. 2018-021649 (application 2/9/2018), the entire contents of which are incorporated herein by reference.
The present invention relates to a tank (tank) containing a composite resin material containing a fluororesin and carbon nanotubes in at least a part of a backing layer, and a chemical liquid supply system using the tank.
Background
Conventionally, in tanks for storing various chemical solutions and the like, a lining material made of a chemical-resistant material such as polyvinyl chloride, rubber, polyolefin resin, or fluororesin is bonded to the inner wall of a metal tank outer tank for the purpose of preventing corrosion of the tank inner wall due to the corrosiveness of the chemical solution and contamination of the chemical solution due to corrosion.
Various studies have been made on the chemical-resistant material contained in the lining material. For example, patent document 1 describes a fluorine resin lined tank lined with a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA). Patent document 2 describes a backing material including a sheet base material made of a polyolefin base material. Patent document 3 describes a backing sheet having a conductive tetrafluoroethylene resin layer formed of a tetrafluoroethylene resin and a conductive filler such as carbon black or graphite.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-170994
Patent document 2: japanese patent laid-open No. 2001 and 328209
Patent document 3: japanese laid-open patent publication No. H06-270353
Disclosure of Invention
Problems to be solved by the invention
Since a chemical-resistant material such as a fluororesin generally used as a lining material has an electrostatic property, when friction is generated between the chemical-resistant material and a chemical solution as a content, static electricity is generated, and the content may be ignited. Further, as described in patent document 3, for example, when a conductive material such as carbon black is added to a chemical-resistant material used as a lining material, it is necessary to add a large amount of the conductive material in order to achieve desired antistatic properties, and there is a possibility that a contaminant is mixed into the tank contents. Further, since these conductive materials and the like are present on the adhesion surface between the lining material and the inner wall of the groove, there is a problem that the lining material is easily peeled off.
The invention aims to provide a tank for processing various chemical solutions, which can prevent the electrification of the contents in the tank and reduce the pollution of the contents in the tank. It is another object of the present invention to provide a chemical liquid supply system using the tank.
Means for solving the problems
The present inventors have conducted intensive studies on a lining layer provided on the inner surface of a groove in order to solve the above problems. As a result, the present inventors have found that the above-described object can be achieved by providing a liner layer, at least a part of which is made of a composite resin material containing a fluororesin and carbon nanotubes, on the inner surface of a tank, and have completed the present invention.
That is, the present invention includes the following preferred embodiments.
[1] A tank having at least an outer tank and a lining layer provided on the inner surface of the outer tank,
the backing layer contains a composite resin material containing fluororesin A and carbon nanotubes in at least a part thereof,
the fluororesin a is selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
[2] The tank according to [1], wherein the liner layer provided at a portion where the chemical solution to be introduced first contacts the inner surface of the tank outer tank comprises a composite resin material containing a fluororesin A and carbon nanotubes.
[3] The tank as recited in the above [1] or [2], which has a drug solution tube connected to the inside and outside of the tank,
the drug solution tube has a lining layer on at least a part of the inner surface of the tube, the lining layer comprising a composite resin material containing fluororesin B and carbon nanotubes; and/or the liquid chemical tube is a molded body of a composite resin material containing fluororesin B and carbon nanotubes,
the fluororesin B is selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
[4] The tank according to any one of the above [1] to [3], which has a drug solution tube connected to the inside and outside of the tank,
the liquid medicine tube comprises a liquid medicine feeding tube for feeding liquid medicine into the groove,
the chemical liquid supply tube has a nozzle at its end (or tip),
the nozzle has a lining layer on at least a part of an inner surface of the nozzle, the lining layer comprising a composite resin material containing fluororesin B and carbon nanotubes; and/or the nozzle is a molded body of a composite resin material containing a fluororesin B and carbon nanotubes,
the fluororesin B is selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
[5] The tank according to the above [4], wherein the nozzle is selected from a spray nozzle, a rotary nozzle, a linear nozzle, and a shower nozzle.
[6] The tank according to any one of the above [1] to [5], further comprising a hollow spherical molded body at least partially comprising a composite resin material containing a fluororesin C and a carbon nanotube, the fluororesin C being selected from the group consisting of Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
[7] The tank according to any one of the above [1] to [6], further comprising a rod-like molded body at least partially comprising a composite resin material containing a fluororesin C and a carbon nanotube, the fluororesin C being selected from the group consisting of Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
[8] The tank according to any one of the above [1] to [7], further comprising a stirring bar at least partially comprising a composite resin material containing a fluororesin C selected from the group consisting of Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF) and a carbon nanotube.
[9] The tank as recited in the above [8], wherein the stirring rod has a propeller at least partially containing a composite resin material containing fluororesin C and carbon nanotubes.
[10] The tank according to any one of the above [1] to [9], wherein the chemical solution contains at least 1 selected from the group consisting of an organic solvent, a flammable liquid, an acidic liquid, an alkaline liquid, a neutral liquid, an aqueous solution, and a conductive liquid.
[11] The tank according to any one of the above [1] to [9], wherein the chemical solution contains an organic solvent.
[12] The tank according to any one of the above [1] to [9], wherein the chemical solution contains at least 1 selected from an acidic solution, an alkaline solution, and a conductive solution.
[13] The tank according to any one of the above [1] to [12], wherein the fluororesin A is a modified polytetrafluoroethylene.
[14] The tank according to any one of the above [1] to [13], wherein the modified polytetrafluoroethylene is a compound having a tetrafluoroethylene unit represented by the formula (I) and a perfluorovinyl ether unit represented by the formula (II),
-CF2-CF2- (I)
[ wherein X represents a C1-6 perfluoroalkyl group or a C4-9 perfluoroalkoxyalkyl group. ]
The amount of the perfluorovinyl ether unit represented by the formula (II) is 0.01 to 1% by mass based on the total mass of the modified polytetrafluoroethylene.
[15] The tank according to any one of the above [1] to [14], wherein the composite resin material is a compression-molded product of composite resin particles having an average particle diameter of 5 μm or more and 500 μm or less, the composite resin particles containing a carbon nanotube and any one of the fluororesins A to C.
[16] The tank according to any one of the above [1] to [15], which is a chemical liquid supply tank, a chemical liquid storage tank, and/or a chemical liquid transport tank.
[17] A chemical liquid supply system comprising the tank according to any one of [1] to [16] above for supplying a chemical liquid.
[18] A molded article for use in the tank according to any one of the above [1] to [16], the molded article comprising a carbon nanotube and any one of the fluororesins A to C.
[19] The molded article according to the above [18], which is selected from the group consisting of a lining sheet, a drug solution tube, a hollow molded article, a rod-shaped molded article holder, a stirring rod, a stirring blade and a stirring rod bushing.
[20] A compressed molded body of composite resin particles, wherein the composite resin particles contain carbon nanotubes and any resin of fluororesins A to C, and have an average particle diameter of 5 [ mu ] m or more and 500 [ mu ] m or less.
[21] The compression-molded article according to the above [20], which is selected from the group consisting of a lining sheet, a drug solution tube, a hollow-shaped molded article, a rod-shaped molded article holder, a stirring rod, a stirring blade and a stirring rod bushing.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a tank for processing various chemical solutions, which can prevent the contents in the tank from being charged and reduce the contamination of the contents in the tank, and a chemical solution supply system using the tank.
Drawings
Fig. 1A is a longitudinal sectional view of a groove according to a first embodiment a of the present invention.
Fig. 1B is a longitudinal sectional view of the groove according to the first embodiment B of the present invention.
Fig. 2 is a longitudinal sectional view of a groove according to a second embodiment of the present invention.
Fig. 3 is a schematic view of a chemical liquid supply system according to a third embodiment of the present invention.
Fig. 4 is a view showing a measurement sample for measuring the weld strength of the composite resin material.
Fig. 5 is a diagram for explaining a method of measuring the weld strength of the composite resin material.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the scope of the present invention.
The tank of the present invention has at least an outer tank and a lining layer provided on the inner surface of the outer tank.
< tank outside >
The material of the outer tank is not particularly limited as long as it is excellent in corrosion resistance, heat resistance and mechanical strength, and is usually a metal, and examples thereof include stainless steel, iron, carbon steel, titanium and the like. The shape, size, thickness, and the like of the tank outside the tank are not particularly limited, and may be appropriately selected according to the use of the tank of the present invention.
< backing layer >
A lining layer is arranged on the inner surface of the tank outside the tank. Examples of the resin contained in the backing layer include fluororesin, vinyl chloride resin, and polyolefin resin. From the viewpoint of chemical resistance and heat resistance, the backing layer preferably contains a fluororesin. Examples of the fluororesin include Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
The thickness of the backing layer is preferably 1.3 to 8mm, more preferably 1.8 to 4mm, and still more preferably 2 to 4mm, from the viewpoint of easily suppressing the elution of metal. The thickness of the backing layer can be measured using a micrometer. In a preferred embodiment of the present invention, the backing layer is a laminate of a glass cloth and a resin sheet, and in this case, the thickness of the glass cloth is preferably 0.3 to 3mm, more preferably 0.3 to 1mm, and even more preferably 0.5 to 1mm, and the thickness of the resin sheet is preferably 1 to 5mm, and even more preferably 1.5 to 3 mm.
In the tank of the present invention, the liner layer contains a composite resin material containing fluororesin a and carbon nanotubes in at least a part thereof. The lining layer including a composite resin material at least in part means that at least a part of the lining layer provided on the inner surface of the outer tank may be made of a composite resin material, or the whole lining layer may be made of a composite resin material. The composite resin material may be contained in a part of the lining layer provided on the inner surface of the outer tank, or may be contained in the entire lining layer provided on the inner surface of the outer tank. From the viewpoint of efficiently imparting antistatic properties and reducing the manufacturing cost of the tank, it is preferable that a part of the backing layer provided on the inner surface of the tank outside the tank is made of a composite resin material, or a part of the backing layer contains a composite resin material.
When a chemical liquid is charged into the tank of the present invention, static electricity is generated by friction at a portion where the charged chemical liquid first contacts the inner surface of the outer tank of the tank, and the chemical liquid is easily charged. Therefore, from the viewpoint of efficiently preventing the chemical solution from being charged, the liner layer provided at the portion where the chemical solution to be introduced first contacts the inner surface of the outer tank of the tank preferably includes a composite resin material containing fluororesin a and carbon nanotubes, and more preferably the liner layer is made of a composite resin material containing fluororesin a and carbon nanotubes. From the same viewpoint, the backing layer provided on the bottom portion of the inner surface of the tank outside the tank preferably includes a composite resin material containing fluororesin a and carbon nanotubes, and more preferably the backing layer is made of a composite resin material containing fluororesin a and carbon nanotubes.
< composite resin Material >
In the tank of the present invention, the liner layer contains a composite resin material containing fluororesin a and carbon nanotubes in at least a part thereof. The composite resin material containing the fluororesin a and the carbon nanotubes is a molded article of composite resin particles obtained by compositing the fluororesin a and the carbon nanotubes. The composite resin particles are a composite of particles of fluororesin a and carbon nanotubes, and the carbon nanotubes are present on at least the surface and/or the surface layer of the particles of fluororesin a. For example, at least a part of the carbon nanotubes is supported or embedded on the particle surface of the fluororesin a. The carbon nanotubes may be attached to the surface of the fluororesin a particles and supported, may be partially embedded and supported, or may be completely embedded in the surface layer of the fluororesin a particles. In the composite resin material as a molded product of such composite resin particles, at least a part of the composite resin particles may be contained while maintaining the particle shape, or the composite resin particles may be integrated to form the composite resin material.
The average particle diameter of the composite resin particles is preferably 500 μm or less, more preferably 300 μm or less, still more preferably 200 μm or less, particularly preferably 100 μm or less, most preferably 50 μm or less, and most preferably 30 μm or less. When the average particle diameter is not more than the upper limit,the carbon nanotubes are easily dispersed uniformly in the backing layer, and the volume resistivity of the backing layer can be sufficiently reduced particularly even when the thickness of the backing layer is small. The lower limit of the average particle diameter of the composite resin material is not particularly limited, but is usually 5 μm or more. By producing the composite resin material constituting at least a part of the backing layer from the composite resin particles having the average particle diameter in the above range, the volume resistivity of the backing layer can be easily and efficiently lowered. In the present invention, the average particle diameter of the composite resin particles constituting the composite resin material contained in the backing layer may be the average particle diameter of the composite resin particles used for producing the composite resin material, and the average particle diameter is the median diameter (D) indicating the particle diameter of 50% of the cumulative value in the particle size distribution obtained by the laser diffraction/scattering method50) The measurement was performed using a laser diffraction scattering particle size distribution apparatus. In the tank of the present invention, the backing layer and the like preferably contain a composite resin material as a molded article of composite resin particles having the above-described average particle diameter, the composite resin material in the backing layer and the like may be composite resin particles having a particle diameter in the above-described preferred range, and the composite resin particles may be integrated and formed into a composite resin material without maintaining the particle shape.
In the tank of the present invention, the backing layer contains at least a portion of a composite resin material obtained by compositing fluororesin a and carbon nanotubes, and thus the volume resistivity of the backing layer can be effectively reduced, and antistatic properties and/or electrical conductivity can be imparted to the backing layer. Therefore, the contents can be prevented from being charged, and ignition of the chemical liquid such as the organic solvent can be prevented. Further, since the volume resistivity can be effectively reduced by using a small amount of carbon nanotubes by using the composite resin material, contamination of the tank contents such as a chemical solution due to mixing of the conductive material contained in the backing layer into the contents can be suppressed, and the cleaning property is excellent.
The amount of the fluororesin a contained in the composite resin material is preferably 98.0 mass% or more, more preferably 99.0 mass% or more, and still more preferably 99.8 mass% or more, with respect to the total amount of the composite resin material. When the amount of the fluororesin a is not less than the above lower limit, the mechanical properties and moldability of the composite resin material are easily improved. The upper limit of the amount of the fluororesin a is not particularly limited, and is about 99.99 mass% or less. The amount of the fluororesin a contained in the composite resin material can be measured by a carbon component analysis method.
The amount of the carbon nanotubes contained in the composite resin material is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 0.5% by mass, and still more preferably 0.025 to 0.2% by mass, based on the total amount of the composite resin material. When the amount of the carbon nanotubes is equal to or more than the above lower limit, the volume resistivity is easily lowered in order to improve antistatic property or conductivity, which is preferable. When the amount of the carbon nanotubes is equal to or less than the upper limit, the volume resistivity is easily and efficiently lowered, which is preferable. The amount of carbon nanotubes contained in the composite resin material can be measured by a carbon component analysis method.
The composite resin material is a molded product of composite resin particles, and the specific surface area of the composite resin particles is measured according to JIS Z8830, and is preferably 0.5-9.0 m2A more preferable range is 0.8 to 4.0 m/g2A more preferable range is 1.0 to 3.0 m/g2(ii) in terms of/g. When the specific surface area is not less than the lower limit, it is preferable from the viewpoint of easiness of improving the adhesion between the fluororesin a and the carbon nanotubes, and when it is not more than the upper limit, it is preferable from the viewpoint of easiness of producing the composite resin material. By producing the composite resin material constituting at least a part of the backing layer from the composite resin particles having the specific surface area in the above range, the volume resistivity of the backing layer can be easily and efficiently reduced. In the present invention, the specific surface area of the composite resin particles constituting the composite resin material contained in the backing layer may be the average particle diameter of the composite resin particles used for producing the composite resin material, and specifically, the average particle diameter may be measured by the BET method which is a general method for measuring the specific surface area, using a specific surface area/pore distribution measuring apparatus (e.g., besorp-miniII, manufactured by beyer, japan) which is a constant volume gas adsorption method. In the tank of the present invention, the backing layer and the like preferably contain a composite resin material as a molded article of composite resin particles having the above-mentioned average particle diameter, and the composite resin material in the backing layer and the like may beThe composite resin particles having a particle diameter in the above-described preferred range may also be integrated and formed into a composite resin material without maintaining the particle shape.
From the viewpoint of antistatic properties, the volume resistivity of the composite resin material is measured according to JIS K6911, and is preferably 1.0 × 108Omega cm or less, more preferably 1.0X 107Omega cm or less, more preferably 1.0X 106Omega cm or less. When the volume resistivity is not more than the above upper limit, good antistatic property can be obtained. The lower limit of the volume resistivity of the composite resin material is not particularly limited, and may be 0 or more, and usually 10 Ω · cm or more. The volume resistivity of the composite resin material was measured by a resistivity meter (for example, "Loresta" or "Hiresta" manufactured by mitsubishi chemical Analytech) using a molding material or a cut test piece in accordance with JIS K6911. For example, in the case of using a material obtained by compression molding (extrusion molding)
When the test piece of (3) is measured, the composite resin material preferably exhibits the above volume resistivity.
When the backing layer contains a composite resin material, the backing layer of a portion containing the composite resin material preferably has the above antistatic property. The volume resistivity is also applicable to a composite resin material containing fluororesin B or fluororesin C described later.
Here, when the volume resistivity of the composite resin material is X Ω · cm and the amount of the carbon nanotubes contained in the composite resin material with respect to the total amount of the composite resin material is Y mass%, X and Y preferably satisfy the following formula (1):
X/Y-14≤4×10-12 (1)。
when the above relationship is satisfied, the volume resistivity of the composite resin material can be efficiently lowered. In addition, since the volume resistivity can be sufficiently reduced by a small amount of carbon nanotubes, the cleanability of the backing layer containing the composite resin material can be easily improved. Easily and efficiently making the volume resistivity of the composite resin materialFrom the viewpoint of reduction, the value (X/Y) calculated by the above formula (1)-14) More preferably 10-12Hereinafter, more preferably 10-13The following. Further, the value (X/Y) calculated by the above formula (1)-14) The lower limit of (2) is not particularly limited, but is usually 10-18Above, preferably 10-16The above. The above relationship can be achieved by producing a molded article by the production method described later, or by producing a composite resin material using preferred composite resin particles that efficiently reduce the volume resistivity. As described above, the amount of carbon nanotubes contained in the composite resin material can be measured by a carbon component analysis method.
The reason is not clear, and the groove of the present invention can achieve desired antistatic properties with a small amount of carbon nanotubes by using the backing layer containing the composite resin material. Therefore, the composite resin material of the present invention is excellent in cleanability. In addition, for example, even when a molded article made of the composite resin material of the present invention is used for welding as a part of a backing layer, since the amount of the conductive material present on the welded surface is small, it is possible to avoid a decrease in adhesion. Further, according to the composite resin material of the present invention, even when the volume resistivity is in the above-described preferable range, the mechanical strength originally possessed by the resin can be easily maintained.
(fluororesin A)
The fluororesin a contained in the composite resin material is selected from, for example, Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
The fluororesin a contained in the composite resin material is preferably selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), and tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA). The fluororesin a is more preferably selected from Polytetrafluoroethylene (PTFE) and modified polytetrafluoroethylene (modified PTFE) from the viewpoint of facilitating efficient improvement of conductivity, and further more preferably modified polytetrafluoroethylene (modified PTFE) from the viewpoint of facilitating efficient improvement of conductivity and from the viewpoint of bendability and weldability.
Polytetrafluoroethylene (PTFE) is a homopolymer of tetrafluoroethylene.
Examples of the modified polytetrafluoroethylene (modified PTFE) include the following modified polytetrafluoroethylene: the modified polytetrafluoroethylene is a compound containing a tetrafluoroethylene unit represented by the formula (I) derived from tetrafluoroethylene and a perfluorovinyl ether unit represented by the formula (II), for example, and the amount of the perfluorovinyl ether unit represented by the formula (II) is 0.01 to 1% by mass based on the total mass of the modified polytetrafluoroethylene.
-CF2-CF2- (I)
[ wherein X represents a C1-6 perfluoroalkyl group or a C4-9 perfluoroalkoxyalkyl group. ]
X in the formula (II) includes a C1-6 perfluoroalkyl group or a C4-9 perfluoroalkoxyalkyl group. Examples of the perfluoroalkyl group having 1 to 6 carbon atoms include a perfluoromethyl group, a perfluoroethyl group, a perfluorobutyl group, a perfluoropropyl group, and a perfluorobutyl group. Examples of the C4-9 perfluoroalkoxyalkyl group include a perfluoro 2-methoxypropyl group, a perfluoro 2-propoxypropyl group and the like. From the viewpoint of easily improving the thermal stability of the modified PTFE, X is preferably a perfluoropropyl group, a perfluoroethyl group, or a perfluoromethyl group, and more preferably a perfluoropropyl group. The modified PTFE may have 1 kind of perfluorovinyl ether unit represented by the formula (II), or may have 2 or more kinds of perfluorovinyl ether units represented by the formula (II).
The amount of the perfluorovinyl ether unit represented by the formula (II) contained in the modified PTFE is less than 1 mol%, preferably 0.001 mol% or more and less than 1 mol%, based on the total structural units contained in the modified PTFE. When the amount of the perfluorovinyl ether unit represented by the formula (II) is less than the upper limit, the physical properties of the resin tend to be close to those of PTFE resins.When the amount of the perfluorovinyl ether unit represented by the formula (II) is not less than the above lower limit, the improvement in bendability, weldability, and compressive creep property is superior to that of PTFE. The amount of the above-mentioned perfluorovinyl ether unit can be determined by, for example, characteristic absorption of 1040 to 890cm-1Is measured by infrared spectroscopic analysis. The amount of the perfluorovinyl ether unit represented by the formula (II) contained in the modified PTFE is 0.01 to 1% by mass, preferably 0.03 to 0.2% by mass, based on the total mass of the modified PTFE.
The melting point of the modified PTFE is preferably 300-380 ℃, more preferably 320-380 ℃, and further preferably 320-350 ℃. When the melting point is not less than the above lower limit, moldability is easily improved, and therefore, it is preferable that the melting point is not more than the above upper limit, because optimum mechanical properties of the resin are easily obtained. The melting point of the modified PTFE was determined as the temperature of the melting peak which can be measured in accordance with ASTM-D4591 using a Differential Scanning Calorimeter (DSC).
The crystallization heat of the modified PTFE is preferably 18.0 to 25.0J/g, more preferably 18.0 to 23.5J/g. The crystallization heat can be measured by a differential scanning calorimeter (for example, "DSC-50" manufactured by Shimadzu corporation). Specifically, about 3mg of the sample was heated to 250 ℃ at a rate of 50 ℃/min and held temporarily, and after the sample was further heated to 380 ℃ at a rate of 10 ℃/min to melt the crystals, the peak of the crystallization point measured when the temperature was reduced at a rate of 10 ℃/min was converted into heat for measurement.
Examples of tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA) include the following compounds: which is a compound containing, for example, a perfluorovinyl ether unit represented by the formula (II) in addition to a tetrafluoroethylene unit represented by the formula (I) derived from tetrafluoroethylene, and the amount of the perfluorovinyl ether unit represented by the formula (II) is more than 1% by mass relative to the total mass of the PFA.
-CF2-CF2- (I)
[ wherein X represents a C1-6 perfluoroalkyl group or a C4-9 perfluoroalkoxyalkyl group. ]
Examples of X in the formula (II) include the above-mentioned groups of modified PTFE, and preferred descriptions are similarly applicable. The PFA may have 1 kind of perfluorovinyl ether unit represented by the formula (II), or may have 2 or more kinds of perfluorovinyl ether units represented by the formula (II).
The amount of the perfluorovinyl ether unit represented by the formula (II) contained in the PFA is 1 mol% or more, preferably 1 to 3 mol% based on the total structural units contained in the PFA. When the amount of the perfluorovinyl ether unit represented by the formula (II) is within the above range, moldability of a molded article obtained from the composite resin material is easily improved. The amount of the above-mentioned perfluorovinyl ether unit can be determined by, for example, characteristic absorption of 1040 to 890cm-1Is measured by infrared spectroscopic analysis.
Particularly, when the fluororesin is modified PTFE, the melting point is preferably 300 to 380 ℃, more preferably 320 to 380 ℃, and still more preferably 320 to 350 ℃. When the melting point is not less than the above lower limit, moldability is easily improved, and therefore, it is preferable that the melting point is not more than the above upper limit, because optimum mechanical properties of the resin are easily obtained. The melting point of the modified PTFE was determined as the temperature of the melting peak which can be measured in accordance with ASTM-D4591 using a Differential Scanning Calorimeter (DSC).
In particular, when the fluororesin is a modified PTFE, the heat of crystallization is preferably 18.0 to 25.0J/g, more preferably 18.0 to 23.5J/g. The crystallization heat can be measured by a differential scanning calorimeter (for example, "DSC-50" manufactured by Shimadzu corporation). Specifically, about 3mg of the sample was heated to 250 ℃ at a rate of 50 ℃/min and held temporarily, and after the sample was further heated to 380 ℃ at a rate of 10 ℃/min to melt the crystals, the peak of the crystallization point measured when the temperature was reduced at a rate of 10 ℃/min was converted into heat for measurement.
(carbon nanotubes)
The carbon nanotube (hereinafter, also referred to as "CNT") contained in the composite resin material has a structure in which 1 or more graphene sheets composed of six-membered rings of carbon atoms are wound in a cylindrical shape. The CNT is a single-layer CNT (single-wall carbon nanotube) in which 1 graphene sheet is wound in a concentric shape, or a multilayer CNT (multilayer carbon nanotube) in which 2 or more graphene sheets are wound in a concentric shape. The carbon nanomaterial described above may be used alone, or these materials may be used in combination. The carbon nanotube is more preferably a multilayered carbon nanotube in terms of easy complexing with particles of modified PTFE and easy reduction in volume resistivity.
(method for producing composite resin Material)
The following describes a method for producing the composite resin material contained in the backing layer. The following description applies similarly to a composite resin material containing fluororesin B and carbon nanotubes contained in a drug solution tube or the like, or a composite resin material containing fluororesin C and carbon nanotubes contained in a hollow spherical molded article or the like, in which fluororesin a is replaced with fluororesin B or fluororesin C.
The composite resin material contained in the backing layer is a composite material of fluororesin a and carbon nanotubes. The method for producing the composite resin material is not particularly limited as long as the material obtained by compositing the fluororesin and the carbon nanotube, which preferably has the above-described physical properties, can be obtained. Preferably, the composite resin material contained in the backing layer is made of composite resin particles obtained by compositing fluororesin a and carbon nanotubes. Here, the method for producing the composite resin particles is not particularly limited as long as a composite resin material in which carbon nanotubes are present on at least the surface and/or the surface layer of the fluororesin a, the fluororesin B, or the fluororesin C can be obtained. For example, composite resin particles can be produced by compositing particles of fluororesin a, fluororesin B, or fluororesin C with carbon nanotubes using carbon dioxide in a subcritical or supercritical state by the method described in japanese patent application laid-open No. 2014-34591, or using a ketone-based solvent by the method described in japanese patent application laid-open No. 2015-30821.
The method for producing composite resin particles in which particles of fluororesin a and carbon nanotubes are combined with each other using carbon dioxide in a subcritical or supercritical state will be specifically described below. This method is also applicable to a method for producing composite resin particles using the fluororesin B or the fluororesin C.
First, in the first step, carbon nanotubes are dispersed in a solvent to prepare a carbon nanotube dispersion. Examples of the solvent include water, alcohol solvents (ethanol, n-butanol, isopropanol, ethylene glycol, etc.), ester solvents (ethyl acetate, etc.), ether solvents (diethyl ether, dimethyl ether, etc.), ketone solvents (methyl ethyl ketone, acetone, diethyl ketone, methyl acetone, cyclohexanone, etc.), aliphatic hydrocarbon solvents (hexane, heptane, etc.), aromatic hydrocarbon solvents (toluene, benzene, etc.), and chlorinated hydrocarbon solvents (dichloromethane, chloroform, chlorobenzene, etc.). 1 kind of solvent may be used, or 2 or more kinds of solvents may be used in combination. From the viewpoint of facilitating the composite formation of the fluororesin a and the carbon nanotubes, a solvent that readily swells the particle surface of the fluororesin a is preferably used, and specifically, a ketone-based solvent is preferably used.
The amount of the solvent contained in the carbon nanotube dispersion is preferably 20,000 to 1,000,000 parts by mass, more preferably 30,000 to 300,000 parts by mass, and still more preferably 50,000 to 200,000 parts by mass, relative to 100 parts by mass of the carbon nanotubes contained in the carbon nanotube dispersion, from the viewpoint of facilitating monodispersion of the carbon nanotubes in the solvent.
The carbon nanotubes used for producing the composite resin particles have an average length of preferably 50 to 600 μm, more preferably 50 to 300 μm, and still more preferably 100 to 200 μm. The average length of the carbon nanotubes can be measured by a scanning electron microscope (SEM, FE-SEM) or a Transmission Electron Microscope (TEM).
The carbon nanotube can be produced by a conventional production method. Specifically, there are a gas phase growth method such as a carbon dioxide contact hydrogen reduction method, an arc discharge method, a laser evaporation method, a CVD method, a gas phase flow method, a HiPco method in which carbon monoxide is grown in a gas phase by reacting with an iron catalyst at high temperature and high pressure, an oil furnace method, and the like. Commercially available carbon nanotubes, for example "NC 7000" manufactured by Nanocyl, can also be used.
When the carbon nanotubes are dispersed in a solvent, a dispersant may be used for the purpose of improving the dispersibility of the carbon nanotubes. Examples of the dispersant include acrylic dispersants, synthetic polymers such as polyvinylpyrrolidone and polyaniline sulfonic acid, DNA, peptides, and organic amine compounds. 1 dispersant may be used, or 2 or more dispersants may be used in combination. From the viewpoint of easily reducing the amount of the dispersant remaining in the finally obtained molded article, it is preferable that the dispersant has a boiling point lower than the molding temperature of the composite resin particles preferable in the present invention. When a dispersant is used, the amount of the dispersant contained in the carbon nanotube dispersion can be appropriately selected according to the kind or amount of the carbon nanotube, the solvent, and the dispersant. For example, the amount of the dispersant used is preferably 100 to 6,000 parts by mass, more preferably 200 to 3,000 parts by mass, and still more preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the carbon nanotube.
When water is used as the solvent in the first step, the carbon nanotube dispersion liquid is mixed with an alcohol solvent or the like before the second step described later. This is because the fluororesin a added in the second step next has low affinity with water, and it is difficult to disperse the particles of the fluororesin a in the carbon nanotube dispersion liquid using water as a solvent. Thus, the alcohol solvent is mixed, whereby the affinity between the particles of the fluororesin a and the carbon nanotube dispersion can be improved.
Next, in the second step, the particles of the fluororesin a are added to the carbon nanotube dispersion liquid and stirred to prepare a mixed slurry in which the carbon nanotubes and the particles of the fluororesin a are dispersed.
When the particles of the fluororesin a are added to the carbon nanotube dispersion, the carbon nanotubes in the dispersion gradually adsorb to the particle surfaces of the fluororesin a. Here, by appropriately adjusting the temperature of the solvent, the dispersion concentration of the carbon nanotubes and the fluororesin a, the addition rate of the fluororesin a, and the like, it is possible to adsorb the carbon nanotubes to the particle surface of the fluororesin a while maintaining a high dispersion state of the carbon nanotubes and the fluororesin a. By such a method, even at a low addition concentration, the carbon nanotubes can be uniformly dispersed on the particle surface of the fluororesin a. In addition, even when long carbon nanotubes are used, the carbon nanotubes can be uniformly dispersed on the particle surface of the fluororesin a without impairing the properties thereof. In the case of adding the fluororesin a, the particles of the fluororesin a may be added as they are, or may be added in a form of dispersing the particles of the fluororesin a in a dispersion liquid of a solvent in advance.
The fluororesin A particles used in the production of the composite resin particles preferred in the present invention have an average particle diameter of preferably 5 to 500. mu.m, more preferably 10 to 250. mu.m, still more preferably 10 to 100. mu.m, particularly preferably 10 to 50 μm, and most preferably 15 to 30 μm. The average particle diameter of the fluororesin a is preferably not more than the upper limit described above because the dispersibility of the carbon nanotubes in the molded article (composite resin material) made of the composite resin particles is easily improved, and the antistatic property is easily and uniformly and efficiently improved. From the viewpoint of ease of production of the composite resin particles, the average particle diameter of the fluororesin a is preferably not less than the above-described lower limit. The average particle diameter of the fluororesin A is a median diameter (D) indicating a particle diameter of 50% of a cumulative value in a particle size distribution obtained by a laser diffraction/scattering method50) The measurement can be performed using a laser diffraction scattering particle size distribution apparatus.
The particles of the fluororesin A used for producing the composite resin particles are preferably 0.5 to 9.0m, as measured in accordance with JIS Z88302A specific ratio of 0.8 to 4.0m2A more preferable range is 1.0 to 3.0m2Specific surface area in g. The specific surface area is preferably not more than the upper limit from the viewpoint of easily improving the adhesion between the particles of the fluororesin a and the carbon nanotubes, and preferably not less than the lower limit from the viewpoint of easily producing the composite resin particles. The specific surface area of the particles of the fluororesin a can be measured by a BET method, which is a general method for measuring the specific surface area, specifically using a specific surface area/pore distribution measuring apparatus, which is a constant volume gas adsorption method.
The above description of the structure and melting point of the fluororesin a in the composite resin material contained in at least a part of the backing layer in the groove of the present invention is applicable to the pellets of the fluororesin a used for producing the composite resin pellets in the same manner since these are properties that do not change before and after the composite formation or before and after the production of the composite resin material. The same applies to the fluororesins B and C.
The method for producing the fluororesin a pellets having an average particle diameter or a specific surface area in the above-described preferred range is not particularly limited, and examples thereof include: a method of producing the fluororesin a by a conventionally known polymerization method, preferably by suspension polymerization, and spray-drying a dispersion liquid containing the reactive polymer obtained by the polymerization; a method of mechanically pulverizing the obtained fluororesin a by using a pulverizer such as a hammer mill, a turbo mill, a cutter mill, or a jet mill; and freeze-pulverizing the obtained fluororesin a at a temperature lower than room temperature by mechanical pulverization. From the viewpoint of easily obtaining fluororesin a pellet having a desired average particle diameter and specific surface area, it is preferable to produce the fluororesin a pellet by using a pulverizer such as a jet mill.
The fluororesin a pellets having an average particle diameter within the above-described preferred range can be produced by adjusting the average particle diameter by a sieve or a classification step using a gas flow.
Next, in the third step, the mixed slurry obtained in the second step is supplied to a pressure vessel, and carbon dioxide is supplied at a specific rate while maintaining the temperature and pressure at which carbon dioxide is in a subcritical or supercritical state in the pressure vessel, thereby filling the pressure vessel with carbon dioxide. As the carbon dioxide, any of liquefied carbon dioxide, gas-liquid mixed carbon dioxide, and gaseous carbon dioxide can be used. Here, the supercritical state of carbon dioxide means a state in which the carbon dioxide is at a temperature of not less than the critical point and a pressure of not less than the critical point, specifically, at a temperature of not less than 31.1 ℃ and a pressure of not less than 72.8 atm. The subcritical state is a state in which the pressure is equal to or higher than the critical point and the temperature is equal to or lower than the critical point.
In the third step, the solvent and the dispersant contained in the mixed slurry are dissolved in carbon dioxide, and the carbon nanotubes dispersed in the mixed slurry adhere to the particles of the fluororesin a.
From the viewpoint of suppressing aggregation of the carbon nanotubes and facilitating uniform adhesion of the carbon nanotubes to the particle surface of the fluororesin a, the supply rate of carbon dioxide is preferably 0.25 g/min or less, more preferably 0.07 g/min or less, and still more preferably 0.05 g/min or less, for example, with respect to 1mg of the dispersant contained in the mixed slurry.
In the next fourth step, the carbon dioxide is discharged from the pressure-resistant vessel together with the solvent and the dispersant dissolved in the carbon dioxide while maintaining the temperature and the pressure at which the carbon dioxide is in the subcritical or supercritical state for a predetermined period of time.
Next, in the fifth step, while maintaining the state of the fourth step, an entrainer having a high affinity for the dispersant is added to the pressure-resistant vessel. This enables the residual dispersant to be efficiently removed. As the entrainer, for example, a solvent used in the first step for preparing the carbon nanotube dispersion can be used. Specifically, when the organic solvent is used in the first step, the same organic solvent can be used as the entrainer. When water is used as the solvent in the first step, an alcohol solvent is preferably used as the entrainer. The fifth step is an arbitrary step for efficiently removing the dispersant, and is not an essential step. For example, the dispersant can be removed by maintaining the fourth step without adding the entrainer.
Next, in the sixth step, the pressure of the pressure-resistant container is reduced to remove carbon dioxide in the pressure-resistant container, thereby obtaining composite resin particles. Here, depending on the method of removing carbon dioxide, carbon dioxide or a solvent may remain in the composite resin particles. Therefore, by exposing the obtained composite resin particles to vacuum or heating, residual carbon dioxide or solvent can be efficiently removed.
(method of manufacturing a cell of the present invention)
The lining layer provided on the inner surface of the groove of the present invention contains a composite resin material containing fluororesin a and carbon nanotubes at least in part. The backing layer containing a composite resin material may be composed of, for example, a backing sheet containing the composite resin material, or may be a laminate of a backing sheet containing the composite resin material and another sheet (e.g., glass cloth). The liner sheet containing the composite resin material may be produced, for example, by melting the composite resin particles and molding the composite resin particles into a sheet shape, or by subjecting the composite resin particles to, for example, compression molding (extrusion molding) to obtain a sheet-shaped molded body, or by cutting the molded body obtained by the compression molding into, for example, a sheet shape. From the viewpoint of facilitating efficient improvement of the conductivity of the backing sheet, it is preferable to produce the backing sheet containing the composite resin material by compression molding the composite resin particles to obtain a sheet-shaped molded body, or by cutting the molded body obtained by the compression molding into, for example, a sheet shape. The reason why the conductivity of the backing sheet is easily and efficiently improved by the above-described preferred production method is not clear, and it is considered that the following mechanism is obtained. The groove of the present invention is not limited to the mechanism described below. In the composite resin particles, as described above, it is considered that carbon nanotubes are present on at least the surface and/or the surface layer of the fluororesin, and these carbon nanotubes form a conductive network. It is considered that the carbon nanotubes are cut or aggregated by an external force applied to the composite resin particles, and the conductive network of the carbon nanotubes is easily cut. Therefore, it is considered that, when the liner sheet is produced from the composite resin particles, the conductivity of the liner sheet can be easily and efficiently improved by using a method in which the network is not cut as much as possible. It is considered that, in the method of obtaining a sheet-like molded article by compression molding composite resin particles and the method of producing a lining sheet by cutting the composite resin material obtained by the compression molding into, for example, a sheet shape, the cutting of the network of carbon nanotubes is easily suppressed as compared with the method of producing a lining sheet by melt-extruding composite resin particles, and as a result, the electrical conductivity of the lining sheet is easily and efficiently improved.
Accordingly, the present invention can provide a tank including, in at least a part of the backing layer, a composite resin material obtained by compression molding composite resin particles (for example, composite resin particles having an average particle diameter of 5 μm or more and 500 μm or less) containing a fluororesin a and carbon nanotubes.
Further, the tank of the embodiment can be provided in which the composite resin material included in at least a part of the backing layer is a compression-molded body obtained by compression-molding composite resin particles containing the fluororesin a and the carbon nanotubes (for example, composite resin particles having an average particle diameter of 5 μm to 500 μm).
From the viewpoint of facilitating the production of the backing sheet by compression molding of the composite resin particles and facilitating the efficient improvement of the electrical conductivity of the backing sheet, the fluororesin contained in the composite resin material may be selected from, for example, Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF). As the fluororesin contained in the composite resin material, a fluororesin selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), and tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA) is preferably used.
In addition, the above-described production method is described by taking the case of producing a sheet from a composite resin material as an example, but in the production of a drug solution tube, a hollow spherical molded article, or the like, these molded articles may be produced by melt extrusion molding of composite resin particles, may be obtained by compression molding of composite resin particles, or may be produced by cutting from a molded article obtained by the compression molding. Here, as described above, it is preferable to produce the drug solution tube or the hollow spherical molded body by compression molding the composite resin particles from the viewpoint that the network of the carbon nanotubes is easily inhibited from being cut off, and as a result, the electrical conductivity of the drug solution tube or the like is easily and efficiently improved.
From the viewpoint of being suitable for such a production method, the fluororesin B and/or C contained in the composite resin material can be selected from, for example, Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF). The fluororesin B and/or C contained in the composite resin material is preferably selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), and tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA).
When the fluororesin is a PTFE resin or a modified PTFE resin, a method of subjecting a preform obtained by compressing composite resin particles to a firing treatment can be mentioned as a method of producing a composite resin material by compression molding the composite resin particles. The preform before firing is produced by subjecting the composite resin particles to appropriate pretreatment (e.g., predrying, granulation, etc.) as needed, and then placing the composite resin particles in a mold and compressing the composite resin particles. The pressurization for compression for producing the preform before firing is preferably 0.1 to 100MPa, more preferably 1 to 80MPa, and still more preferably 5 to 50 MPa.
The preform obtained as described above is fired at a temperature equal to or higher than the melting point of the resin contained in the composite resin particles, for example, to produce a molded body. The firing temperature depends on the size of the preform before firing, the firing time, and the like, and is preferably 345 to 400 ℃, and more preferably 360 to 390 ℃. The preform before firing is placed in a firing furnace, and preferably fired at the above firing temperature to produce a molded body.
The obtained molded article may be used as a backing sheet or the like as it is (for example, a rod-shaped molded article, a stirring rod or the like described later), or a backing sheet or the like (for example, a nozzle, a hollow spherical molded article, a rod-shaped molded article, a stirring rod or the like described later) may be produced by subjecting the molded article to cutting or the like.
When the fluororesin is a PCTFE resin, a PFA resin, an FEP resin, an ETFE resin, an ECTFE resin, a PVDF resin, or a PVF resin (other than a PTFE resin and a modified PTFE resin), as a method for producing a composite resin material by compression molding composite resin particles, after performing an appropriate pretreatment such as preliminary drying according to the size of a molded article, a mold is heated in a hot air circulation type electric furnace set at 200 ℃ or higher, preferably 200 to 400 ℃, more preferably 210 to 380 ℃ for 2 hours or longer, preferably 2 to 12 hours, to melt the resin. After heating for a predetermined time, the mold was taken out of the electric furnace and pressed with a hydraulic press at a pressure of 25kg/cm2Above, preferably 50kg/cm2The mold is cooled to normal temperature while the above surface pressure is applied and the compression is performedAfter the completion of the treatment, a molded article (resin material) of the composite resin particles was obtained.
The obtained molded article may be used as a backing sheet or the like as it is (for example, a rod-shaped molded article, a stirring rod or the like described later), or a backing sheet or the like (for example, a nozzle, a hollow spherical molded article, a rod-shaped molded article, a stirring rod or the like described later) may be produced by subjecting the molded article to cutting or the like.
As a method for providing the lining layer on the inner surface of the outer tank, the following methods can be mentioned: a sheet obtained by etching one surface of a fluororesin sheet or a sheet in which a glass cloth is laminated on one surface of a fluororesin sheet is cut out in conformity with the shape of the inner surface of the outer tank, and the cut-out sheet is bonded to the inner surface of the tank using an epoxy adhesive or the like. The gaps between the sheets adhered to the inner surface of the groove may be welded using, for example, a rod-shaped welding material, preferably a PFA material, having a circular or triangular cross section with a diameter of 2 to 5 mm.
< liquid medicine tube >
The tank of the present invention can have drug solution tubes connected to the inside and outside of the tank. The drug solution tube includes a drug solution inlet tube for introducing a drug solution and a drug solution outlet tube for discharging a drug solution. When the liquid medicine passes through the liquid medicine tube, friction occurs between the inner surface of the liquid medicine tube and the liquid medicine, static electricity is generated, and therefore the liquid medicine is easy to charge. Therefore, from the viewpoint of efficiently preventing the electrification of the chemical solution, the chemical solution tube preferably has a liner layer made of a composite resin material containing fluororesin B and carbon nanotubes on at least a part of the inner surface of the chemical solution tube; and/or the drug solution tube is a molded body of a composite resin material containing fluororesin B and carbon nanotubes. Here, the fluororesin B can be selected from, for example, Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF). The fluororesin B is preferably selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), and tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA). The fluororesin B is more preferably selected from Polytetrafluoroethylene (PTFE) and modified polytetrafluoroethylene (modified PTFE) from the viewpoint of facilitating efficient improvement of conductivity, and is still more preferably modified polytetrafluoroethylene (modified PTFE) from the viewpoint of facilitating efficient improvement of conductivity and from the viewpoint of bendability and weldability.
The composite resin material constituting the drug solution tube or the composite resin material contained in the liner layer provided on the inner surface of the drug solution tube is a molded product of composite resin particles obtained by compositing fluororesin B and carbon nanotubes. The composite resin particles are a material obtained by compositing particles of fluororesin B with carbon nanotubes, and carbon nanotubes are present on at least the surface and/or the surface layer of the particles of fluororesin B. For example, at least a part of the carbon nanotubes is supported or embedded on the particle surface of the fluororesin B. The carbon nanotubes may be attached to the surface of the particles of the fluororesin B and supported, may be partially embedded and supported, or may be completely embedded in the surface layer of the particles of the fluororesin B. In the composite resin material as a molded product of such composite resin particles, at least a part of the composite resin particles may be contained while maintaining the particle shape, or the composite resin particles may be integrated to form the composite resin material.
The same applies to the composite resin material containing the fluororesin a and the carbon nanotubes, as described above, with respect to the composite resin material constituting the drug solution tube or the composite resin material contained in the liner layer provided on the inner surface of the drug solution tube. The same applies to the fluororesin B as described above for the fluororesin a, and the same applies to the carbon nanotubes as described above for the carbon nanotubes. The fluororesin B may be the same resin as the fluororesin a or a different resin.
Examples of a method for providing a lining layer comprising a composite resin material containing fluororesin B and carbon nanotubes on at least a part of the inner surface of the drug solution tube include: a method of producing a sheet of a composite resin material by melt-extruding or compression-molding composite resin particles and attaching the sheet to the inner surface of a drug solution tube; a method of cutting a molded product of composite resin particles into a tubular shape and bonding the tubular molded product to the inner surface of a drug solution tube. The above-mentioned description of the method for producing the liner sheet is also applied to the method for producing the sheet of composite resin material. As a method of bonding, in the case where the drug solution tube is made of metal, a method of bonding the drug solution tube to the inner surface thereof using an adhesive or the like, or in the case where the drug solution tube is made of resin, a method of welding the drug solution tube to the inner surface thereof may be mentioned.
< nozzle >
The present invention can provide a tank having a drug solution pipe connected to the inside and outside of the tank, the drug solution pipe including a drug solution inlet pipe for introducing drug solution into the tank,
the chemical liquid supply tube has a nozzle at its end (or tip),
the nozzle has a lining layer comprising a composite resin material containing fluororesin B and carbon nanotubes on at least a part of the inner surface of the nozzle, and/or the nozzle is a molded body of a composite resin material containing fluororesin B and carbon nanotubes,
the fluororesin B is selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE) tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
The "nozzle" in the present specification means a tubular mechanical member for determining the direction of the flow of the fluid, and is not particularly limited as long as it is a member for controlling the characteristics of the fluid such as the flow rate, flow velocity, direction, and pressure of the flowing substance, and is generally understood as a nozzle.
The nozzles can be selected, for example, from spray nozzles, rotary nozzles, linear nozzles, shower nozzles.
For the liner layer of the nozzle, the fluororesin B, and the like, reference may be made to the descriptions of the chemical liquid tube.
< hollow spherical molded body >
The tank of the present invention may have a hollow spherical molded body at least partially containing a composite resin material containing fluororesin C and carbon nanotubes. Such a hollow spherical molded article is usually floated on the liquid surface of the chemical solution to be introduced in the tank of the present invention, and is used for removing static electricity charged to the chemical solution from the liquid surface. In particular, when the chemical liquid is transported in a state of being stored in the tank of the present invention, friction with the inner surface of the tank occurs due to vibration of the chemical liquid, static electricity is generated, and the chemical liquid is easily charged. By using the hollow spherical molded body at least partially containing the composite resin material, static electricity generated by friction during transportation or the like can be efficiently removed. The fluororesin C is preferably selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF), and more preferably selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), and tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA). The fluororesin C is preferably selected from modified PTFE, PTFE and PFA from the viewpoint of moldability, more preferably selected from PTFE and modified PTFE from the viewpoint of facilitating efficient improvement of conductivity, and further preferably selected from modified PTFE from the viewpoint of facilitating efficient improvement of conductivity, and bendability and weldability.
The composite resin material at least partially contained in the hollow spherical molded body is a molded body of composite resin particles obtained by compositing fluororesin C and carbon nanotubes. The composite resin particles are a material obtained by compositing particles of fluororesin C with carbon nanotubes, and the carbon nanotubes are present on at least the surface and/or the surface layer of the particles of fluororesin C. For example, at least a part of the carbon nanotubes is supported or embedded on the particle surface of the fluororesin C. The carbon nanotubes may be attached to the surface of the fluororesin C and supported, may be partially embedded and supported, or may be completely embedded in the surface layer of the fluororesin C.
The composite resin material contained in at least a part of the hollow spherical molded article is similarly applicable to the composite resin material containing the fluororesin a and the carbon nanotubes described above. The fluororesin C is similarly applicable to the fluororesin a described above. The fluororesin C may be the same resin as the fluororesin a or B, or may be a different resin. The same applies to the carbon nanotubes as described above.
The hollow spherical molded body may be formed by at least partially containing a composite resin material, as long as the composite resin material containing fluororesin C and carbon nanotubes is contained in at least a part of the hollow spherical molded body, and the hollow spherical molded body may include, for example: a mode in which a lining material containing the composite resin material is lined in at least a part of the surface of a hollow spherical molded body made of a resin; the hollow spherical molded article may be a molded article made of a composite resin material containing fluororesin C and carbon nanotubes.
< shaped articles in stick form >
In an embodiment of the present invention, there is provided a tank further comprising a rod-shaped molded body at least partially containing a composite resin material containing a fluororesin C and carbon nanotubes.
Such a rod-shaped molded article generally enters the interior of the chemical solution from the surface of the chemical solution charged into the tank of the present invention, and is used for removing static electricity charged in the chemical solution from the liquid. In particular, when the chemical liquid is transported in a state of being stored in the tank of the present invention, friction with the inner surface of the tank occurs due to vibration of the chemical liquid, static electricity is generated, and the chemical liquid is easily charged. By using a rod-shaped molded body at least partially containing a composite resin material, static electricity generated by friction during transportation or the like can be efficiently removed. The size (diameter and length), the shape of the cross section (circular, hexagonal, etc.), the conductivity, and the like of the rod-shaped molded article can be appropriately selected.
The fluororesin C is preferably selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
The above description can be referred to as appropriate for "fluororesin C", "carbon nanotube", and "composite resin material", and the like.
The rod-shaped molded body can be connected to a ground wire. The rod-shaped molded body is connected to a ground line, and thus the electricity can be removed more efficiently.
A holder for placing the rod-shaped molded article in the groove (also referred to as a "rod-shaped molded article holder") can be used. The rod-shaped molded body holder is generally cylindrical, and has an outer shape corresponding to the size of the hole of the groove and an inner shape corresponding to the outer shape of the rod-shaped molded body. The size of the rod-shaped molded body holder can be appropriately selected depending on the size of the rod-shaped molded body and the size of the hole of the groove.
< stirring rod >
In an embodiment of the present invention, there is provided a tank further having a stirring rod at least partially containing a composite resin material containing fluororesin C and carbon nanotubes.
Such a stirring rod is generally inserted into the chemical solution from the liquid surface of the chemical solution charged into the tank of the present invention, and is used for stirring the chemical solution, and is used for removing static electricity generated in the chemical solution from the liquid during the stirring. The size (diameter and length) of the stirring rod, the shape of the cross section (circular, hexagonal, etc.), the conductivity, and the like can be appropriately selected.
The fluororesin C is preferably selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
The above description can be referred to as appropriate for "fluororesin C", "carbon nanotube", and "composite resin material", and the like.
The stirring rod can have a propeller (or stirring blade) at least partially including a composite resin material containing fluororesin C and carbon nanotubes. The stirring rod and the propeller can be integrated, and the stirring rod can also be separated from the propeller. When the stirring rod has a propeller, the liquid medicine can be stirred more efficiently. The size (size) and shape (crescent shape, etc.) of the stirring rod, conductivity, and the like can be appropriately selected.
As for the "fluororesin C", "carbon nanotube" and "composite resin material" related to the propeller, the above description can be appropriately referred to.
When the stirring rod has a propeller, both the stirring rod and the propeller may exhibit the intended static elimination property.
The stirring rod can be suitably connected to the ground. The stirring rod is connected with the ground wire, so that electricity can be removed more efficiently.
A bush (also referred to as a "stir bar bush") for installing a stir bar in a tank can be used. The stir bar insert is generally cylindrical with an outer shape corresponding to the size of the bore of the tank and an inner shape corresponding to the outer shape of the stir bar. The size of the stirring rod bush can be appropriately selected according to the size of the stirring rod and the size of the hole of the tank.
< groove >
The use of the tank of the present invention is not particularly limited, and examples thereof include a tank containing a chemical as a content, specifically, a chemical supply tank, a chemical storage tank, and/or a chemical transport tank. The chemical liquid supply tank is, for example, a tank used in a system for supplying a chemical liquid described later. The chemical liquid supply tank is used for supplying the chemical liquid to another tank through the tank. Therefore, the chemical liquid supply tank can be provided with a chemical liquid inlet pipe and a chemical liquid outlet pipe, and can supply and discharge the chemical liquid at the same time. The chemical liquid storage tank is a tank for storing chemical liquid therein. Therefore, the chemical storage tank may have at least 1 opening. The chemical liquid transport tank is a tank for transporting a chemical liquid as a content in a stored state. When the chemical liquid is transported, static electricity is likely to be generated due to vibration of the chemical liquid, but the static electricity can be removed by using the tank of the present invention. The tank of the present invention may be a tank for the purpose of supplying, storing, or transporting a chemical solution, or may be a tank having 2 or more of these purposes in combination.
< medicinal liquid >
Examples of the chemical solution to be contained in the tank of the present invention include aqueous solutions such as hydrochloric acid, nitric acid, hydrofluoric acid, hydrogen peroxide water, and sulfuric acid, organic solvents such as isopropyl alcohol (IPA), ethanol, acetone, Tetrahydrofuran (THF), and Methyl Ethyl Ketone (MEK), and water. The chemical liquid contained in the tank is preferably an organic solvent. The organic solvent is a chemical solution used in, for example, semiconductor production, and in the use of semiconductor production, contamination due to static charge of the chemical solution or contamination due to a trace amount of mixed substances also becomes a problem, and therefore, the advantages of the tank of the present invention can be more easily exhibited.
< medicinal liquid >
The chemical solution stored in the tank according to the embodiment of the present invention is not particularly limited as long as it can be stored. The chemical solution may contain at least 1 selected from the group consisting of an organic solvent, a flammable liquid, an acidic liquid, a basic liquid, a neutral liquid, an aqueous solution, and a conductive liquid.
Examples of the organic solvent include isopropyl alcohol (IPA), ethanol, acetone, Tetrahydrofuran (THF), Methyl Ethyl Ketone (MEK), and the like.
The flammable liquid includes, for example, isopropyl alcohol (IPA), ethanol, acetone, Tetrahydrofuran (THF), Methyl Ethyl Ketone (MEK), and the like.
The acidic liquid contains, for example, hydrochloric acid, nitric acid, fluoric acid, sulfuric acid, hydrogen peroxide water, and the like.
The alkaline liquid includes, for example, ammonia water and the like.
The neutral liquid includes, for example, ozone water, so-called water, ultrapure water, pure water, deionized water, ion-exchanged water, distilled water, and the like.
The aqueous solution includes, for example, hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, ammonia water, hydrogen peroxide water, ozone water, and the like.
The conductive liquid includes, for example, hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, hydrogen peroxide water, ammonia water, so-called water, ion-exchanged water, deionized water, pure water, and the like.
The chemical liquid contained in the tank may be, for example, an organic solvent. The organic solvent is a chemical solution used in, for example, semiconductor production, and in the use of semiconductor production, contamination due to static electricity or trace impurities carried by the chemical solution also becomes a problem, and therefore, the advantages of the tank of the present invention can be more easily exhibited.
Even if the chemical liquid contained in the tank is a conductive liquid, it can be used.
< chemical liquid supply System >
The present invention also provides a chemical liquid supply system including a tank of the present invention for supplying a chemical liquid. The application of the chemical liquid supply system of the present invention is not particularly limited, and the chemical liquid supply system used in semiconductor manufacturing is preferable from the viewpoint of making it easy to utilize the advantages of the chemical liquid supply system of the present invention, such as reduction in contamination of the chemical liquid as a content and high cleanability, to the maximum extent. In a preferred embodiment of the present invention, the chemical supply system of the present invention includes a chemical transport tank, a chemical storage tank of a semiconductor factory line, a pump for pumping a chemical from the chemical transport tank to the chemical storage tank, and a pump for pumping a chemical from the chemical storage tank to each line, and the tank of the present invention can be used as the chemical transport tank and/or the chemical storage tank. In a preferred chemical liquid supply system according to the present invention of this aspect, specifically, the following series of chemical liquid supplies can be performed: a chemical liquid transport tank (for example, ISO tank) is transported to a semiconductor factory by a tank car, and a chemical liquid is pumped from the chemical liquid transport tank to a chemical liquid storage tank in a semiconductor factory line by a pump, and the chemical liquid is sent from the chemical liquid storage tank to each line. The chemical liquid supply system of the present invention may include, in addition to the tank of the present invention, a device for supplying the contents of the tank of the present invention, a compressed gas source or a chemical liquid supply pump for transporting an inert gas such as nitrogen gas under high pressure, and a filter or the like for filtering the chemical liquid and removing impurities.
< shaped body >
The present invention can provide a molded article which comprises,
it can be used in a tank for processing a chemical solution.
The trough may have a layer of liner sheet.
The molded body may be a compression molded body obtained by compression molding composite resin particles containing a fluororesin and carbon nanotubes. The fluororesin may be any of the fluororesins a to C described in the present specification. The description of the present specification with respect to the composite resin particles, any of the fluororesins a to C, and the carbon nanotubes may refer to the composite resin particles, any of the fluororesins a to C, and the carbon nanotubes in the molded article, respectively.
Examples of the molded article that can be used in the tank include the above-mentioned lining sheet, drug solution tube, hollow molded article, rod-shaped molded article holder, stirring rod, stirring blade, and stirring rod bushing.
< embodiment >
The present invention will be described in detail with reference to the following embodiments. In the following description, terms indicating directions such as "up", "down", "left", "right", and the like, and other terms including these are used in order to explain the configuration shown in the drawings, and these terms are used for the purpose of making the embodiments easier to understand through the drawings. Therefore, these terms are not intended to limit the direction in which the embodiments of the present invention are actually used, and the technical scope of the invention described in the claims is not intended to be limited by these terms at all.
(first embodiment)
The groove according to the first embodiment of the present invention includes the grooves according to the first embodiment a and the first embodiment B.
As shown in fig. 1A, a groove according to a first embodiment a of the present invention includes: an outer tank 1, a lining layer 2 provided on the inner surface of the outer tank 1, a chemical liquid feed pipe 3 for feeding a chemical liquid into the tank, a chemical liquid discharge pipe 4 for discharging the chemical liquid to the outside of the tank, and a hollow spherical molded body 5 floating on the surface of the chemical liquid and removing static electricity charged in the chemical liquid, wherein the chemical liquid 6 is stored in the tank. As a method for providing the lining layer 2 on the inner surface of the outer tank 1, the following method can be mentioned: a lining sheet obtained by etching one surface of a fluororesin sheet or a lining sheet in which a glass cloth is laminated on one surface of a fluororesin sheet is cut out in conformity with the shape of the inner surface of the outer tank 1, and the cut-out sheet is bonded to the inner surface of the tank using an epoxy adhesive or the like. For example, a rod-shaped welding material having a circular or triangular cross section with a diameter of 2 to 5mm, preferably a PFA material, may be used to weld the gaps between the sheets adhered to the inner surface of the groove. The tank in the first embodiment a includes the chemical solution inlet pipe 3, the chemical solution outlet pipe 4, and the hollow spherical molded body 5, but these are not essential to the tank of the present invention, and at least 1 of these may be provided or none of these may be provided.
In the tank according to the first embodiment a of the present invention, from the viewpoint of efficiently removing static electricity, the lining layer including at least the lining sheet 8 provided at a portion (the liquid contact portion 7 in fig. 1A) where the chemical solution to be injected first contacts the inner surface of the tank outer tank when the chemical solution is injected into the tank preferably includes a composite resin material containing fluororesin a and carbon nanotubes, and more preferably the lining sheet is a molded body made of a composite resin material containing fluororesin a and carbon nanotubes. From the viewpoint of further improving the antistatic property, the backing layer including the backing sheet 10 (including the backing sheet 8) provided on the groove bottom portion 9 preferably includes a composite resin material containing fluororesin a and carbon nanotubes, and the backing sheet is more preferably a molded body made of a composite resin material containing fluororesin a and carbon nanotubes. The ground line 11 is connected to the lining sheet 8 or the lining sheet 10, and static electricity that flows from the chemical solution into the lining sheet 8 or 10 having a low volume resistivity flows into the ground via the ground line 11 and is removed. The liner sheet comprising the composite resin material containing the fluororesin a and the carbon nanotubes is produced by, for example, thinly cutting out the molded body of the composite resin particles produced as described above to produce a sheet, or extrusion molding the composite resin particles into a sheet. The thus obtained lining sheet comprising a composite resin material is lined on the tank inner surface in the liquid contact portion 7 or the tank bottom portion 9 in the same manner as the method for providing the lining layer 2, whereby the static electricity of the chemical solution 6 can be efficiently removed.
As shown in fig. 1A, the tank according to the first embodiment a of the present invention includes a chemical solution inlet pipe 3 and a chemical solution outlet pipe 4 provided at an upper portion of the tank. The discharge port of the chemical liquid inlet pipe 3 is provided at a position higher than the liquid surface 12 of the chemical liquid 6, and the suction port of the chemical liquid outlet pipe 4 is provided at a position close to the bottom of the tank. In the case where the tank of the first embodiment a has the chemical liquid inlet pipe 3 and the chemical liquid outlet pipe 4 at the above-mentioned positions and the tank has the chemical liquid inlet pipe 3 and/or the chemical liquid outlet pipe 4, these positions are not particularly limited, and the tank may have the chemical liquid inlet pipe at the upper portion and the chemical liquid outlet pipe at the bottom portion, or these pipes may be positioned on the side surface of the tank. The position of the discharge port of the chemical solution inlet pipe or the suction port of the chemical solution outlet pipe may be set as appropriate. Although not shown in fig. 1A, the tank of the first embodiment a may have other structures that are common in the tank, such as a drug solution tube, a safety valve, and an air vent provided at any position such as an upper portion, a side portion, and a lower portion.
Lining layers 31 and 41 made of a composite resin material containing fluororesin B and carbon nanotubes are provided on the inner surfaces of the chemical solution inlet pipe 3 and the chemical solution outlet pipe 4, respectively. The chemical solution inlet pipe 3 and the chemical solution outlet pipe 4, in which the lining layers 31 and 41 of the composite resin material are provided on the inner surfaces of the pipes, can be manufactured by, for example, a method of cutting a molded body of composite resin particles into a pipe shape and joining the pipe to the inner surface of a metal pipe or a method of welding the pipe to the inner surface of a resin pipe. The lining layers 31 and 41 of the chemical liquid introduction tube 3 and the chemical liquid discharge tube 4 are electrically connected to the ground line 11, respectively, and static electricity charged when passing through the chemical liquid introduction tube 3 and the chemical liquid discharge tube 4 is finally removed via the ground line 11. Further, the backing layers 31 and 41 may also have ground lines different from the ground line 11, respectively. Further, although the chemical liquid inlet tube 3 and the chemical liquid outlet tube 4 shown in fig. 1A are provided with a lining layer made of a composite resin material containing fluororesin B and carbon nanotubes at a part of the inner surface, these tubes may be molded bodies made of a composite resin material containing fluororesin B and carbon nanotubes, or tubes obtained by cutting a molded body of composite resin particles into a tubular shape may be used as the chemical liquid inlet tube and the chemical liquid outlet tube as they are.
As shown in fig. 1A, the groove of the first embodiment a of the present invention has a hollow spherical molded body 5. The number of the hollow spherical molded bodies 5 is not particularly limited, and may be appropriately selected depending on the size of each molded body 5 and the desired charging effect. The molded bodies 5 are connected to ground wires 13, which extend from the lid body 14 to the outside of the tank and are connected to the ground. The static electricity charged in the chemical solution 6 flows into the molded body 5 having a low volume resistivity and is removed through the ground 13. The hollow sphere-shaped molded body 5 can be produced by thinly cutting out a molded body of a composite resin material containing fluororesin C and carbon nanotubes, or by laminating a sheet produced by extrusion molding a composite resin material into a sheet shape to a hollow sphere. The tank of the present embodiment has a lid 14, but the lid 14 is not essential. In addition, although ground wire 13 extends from cover 14 in first embodiment a, ground wire 13 may be electrically connected to ground wire 11.
The groove of the first embodiment B of the present invention is similar in shape to the groove of the first embodiment a, and as shown in fig. 1B, has: the chemical solution 6 is stored in the tank by an outer tank 1, a lining layer 2 provided on the inner surface of the outer tank 1, a chemical solution feed pipe 3 for feeding a chemical solution into the tank, a nozzle 36 provided at an end of the chemical solution feed pipe 3, a chemical solution discharge pipe 4 for discharging the chemical solution to the outside of the tank, a rod-shaped molded body 52 for removing static electricity of the chemical solution and inserted into the chemical solution, and a stirring rod 56 for stirring the chemical solution.
As a method for providing the lining layer 2 on the inner surface of the outer tank 1, the same method as that described in the tank of the first embodiment a can be used.
The groove of the first embodiment B has: the chemical solution inlet pipe 3, the chemical solution outlet pipe 4, the rod-shaped molded body 52, and the stirring rod 56 are not essential to the tank of the present invention, and at least 1 of these may be provided or none of these may be provided.
The groove according to the first embodiment B of the present invention also includes: the liquid contact part 7, the backing layer comprising the backing sheet 8, the backing layer comprising the backing sheet 10 (comprising the backing sheet 8) arranged at the cell bottom 9, and the ground line 11. With respect to these, the electrostatic charge of the chemical solution 6 can be efficiently removed with reference to the description of the tank of the first embodiment a.
As shown in fig. 1B, the tank according to the first embodiment B of the present invention also includes a chemical solution inlet pipe 3 and a chemical solution outlet pipe 4 provided at an upper portion of the tank. The chemical solution inlet tube 3 and the chemical solution outlet tube 4 can refer to the description of the tank of the first embodiment a.
Although not shown in fig. 1B, the tank of the first embodiment B may have other structures in the tank, such as a drug solution tube, a safety valve, and an air vent provided at any position, such as an upper portion, a side portion, and a lower portion.
As shown in fig. 1B, the tank according to the first embodiment B of the present invention includes a nozzle 36 provided at an end of the chemical solution inlet pipe 3. The size of the nozzle 36 is not particularly limited, and the length, thickness, cross-sectional shape, and the like may be appropriately selected in accordance with the desired charging effect. The nozzle 36 may be connected to a ground, but the chemical liquid inlet pipe 3 may function as a ground. It is preferable to reduce static electricity of the chemical solution passing through the nozzle before entering the tank.
The nozzle 36 can be manufactured by cutting a molded body of a composite resin material containing the fluororesin B and the carbon nanotubes into a cylindrical shape, or by extrusion molding the composite resin material into a cylindrical shape.
As shown in fig. 1B, the groove according to the first embodiment B of the present invention may have a rod-shaped molded body 52. The size of the rod-shaped molded article 52 is not particularly limited, and the length, thickness, cross-sectional shape, and the like can be appropriately selected according to the desired charging effect. The rod-shaped molded body 52 is connected to a ground line 53 and to the ground. Static electricity of the chemical solution 6 flows into the rod-shaped molded body 52 having a low volume resistivity, and is removed through the ground line 53.
The rod-shaped molded body 52 can be produced by cutting a molded body of a composite resin material containing the fluororesin C and the carbon nanotubes into a rod shape, or by extrusion molding the composite resin material into a rod shape.
The groove of embodiment B of the present invention has a rod-shaped molded body holder 54 (hereinafter also referred to as a "rod-shaped molded body holder"), and preferably holds the rod-shaped molded body 52 by the holder 54, but the "rod-shaped molded body holder 54" is not essential. The size of the outer side of the rod-like shaped body holder 54 can be appropriately selected in consideration of the size of the hole provided in the groove.
As shown in fig. 1B, the tank according to the first embodiment B of the present invention may have a stirring bar 56. The size of the stirring rod 56 is not particularly limited, and the length, thickness, cross-sectional shape, and the like can be appropriately selected according to the desired charging effect and stirring effect. The stirring rod 56 can be provided with a propeller (or stirring wing) 57 at its end. The stirring rod 56 and the propeller 57 may be integrated or separate. The stirring rod 56 can be in contact with a ground wire (not shown) and connected to the ground. Static electricity of the chemical solution 6 can flow into the stirring rod 56 having a low volume resistivity and be removed through the ground.
The stirring rod 56 can be produced by cutting a molded article of a composite resin material containing the fluororesin C and the carbon nanotubes into a rod shape, or by extrusion molding the composite resin material into a rod shape.
The propeller 57 can be produced by cutting a molded body of a composite resin material containing fluororesin C and carbon nanotubes into a propeller shape, the composite resin material containing fluororesin C and carbon nanotubes at least partially.
The tank according to embodiment B of the present invention includes a stirring rod bush 58 (hereinafter also referred to as "stirring rod bush"), and preferably holds the stirring rod 56 by the bush 58, but the "stirring rod bush 58" is not essential. The size of the outer side of the stirring rod bush 58 can be appropriately selected in consideration of the size of the hole provided in the groove.
The stirring rod bush can be produced by cutting a molded body of a composite resin material containing the fluororesin C and the carbon nanotubes into a cylindrical shape, or by extrusion molding the composite resin material into a cylindrical shape. Further, a ground wire may be connected to the stirring rod bushing.
(second embodiment)
As shown in fig. 2, a groove according to a second embodiment of the present invention includes: the chemical solution 6 is stored in the tank by an outer tank 1, a lining layer 2 provided on the inner surface of the outer tank 1, a chemical solution pipe 15 for introducing or discharging the chemical solution in the tank, and a hollow spherical molded body 5 floating on the liquid surface of the chemical solution and removing static electricity charged in the chemical solution. As a method for providing the lining layer 2 on the inner surface of the outer tank 1, the following method can be mentioned: a lining sheet obtained by etching one surface of a fluororesin sheet or a lining sheet in which a glass cloth is laminated on one surface of a fluororesin sheet is cut out in conformity with the shape of the inner surface of the outer tank 1, and the cut-out sheet is bonded to the inner surface of the tank using an epoxy adhesive or the like. For example, a rod-shaped welding material having a circular or triangular cross section with a diameter of 2 to 5mm, preferably a PFA material, may be used to weld the gaps between the sheets adhered to the inner surface of the groove. The tank in the present embodiment includes the drug solution tube 15 and the hollow sphere-shaped molded body 5, but these are not essential to the tank of the present invention, and at least 1 of these may be provided, or none of these may be provided.
In the tank according to the second embodiment of the present invention, from the viewpoint of efficiently removing static electricity, the lining layer including at least the lining sheet 8 provided at a portion (liquid contact portion 7 in fig. 2) where the chemical solution to be introduced first contacts the inner surface of the tank outer tank when the chemical solution is introduced into the tank preferably includes a composite resin material containing fluororesin a and carbon nanotubes, and more preferably the lining sheet is a molded body of the composite resin material containing fluororesin a and carbon nanotubes. From the viewpoint of further improving the antistatic property, the backing layer including the backing sheet 10 (including the backing sheet 8) provided on the groove bottom portion 9 preferably includes a composite resin material including fluororesin a and carbon nanotubes, and the backing sheet is more preferably a molded article of the composite resin material including fluororesin a and carbon nanotubes. The ground line 11 is connected to the lining sheet 8 or the lining sheet 10, and static electricity that flows from the chemical solution into the lining sheet 8 or 10 having a low volume resistivity flows into the ground via the ground line 11 and is removed. The liner sheet comprising the composite resin material containing the fluororesin a and the carbon nanotubes is produced by, for example, thinly cutting out the molded body of the composite resin material produced as described above to produce a sheet, or extruding the composite resin material to form a sheet. The thus obtained lining sheet comprising a composite resin material is lined on the tank inner surface in the liquid contact portion 7 or the tank bottom portion 9 in the same manner as the method for providing the lining layer 2, whereby the static electricity of the chemical solution 6 can be efficiently removed.
As shown in fig. 2, the well of the second embodiment of the present invention has a drug solution tube 15. A liner layer 151 made of a composite resin material containing fluororesin B and carbon nanotubes is provided on the inner surface of the drug solution tube 15. The chemical liquid tube 15 having the lining layer 151 made of the composite resin material provided on the inner surface thereof is manufactured by, for example, a method of cutting a molded body made of the composite resin material into a tubular shape and joining the same to the inner surface of a metal pipe or a method of welding the same to the inner surface of a resin pipe. The liner layer 151 of the drug solution tube 15 is electrically connected to the ground wire 11, and static electricity charged when passing through the drug solution tube 15 is finally removed via the ground wire 11. Further, the backing layer 151 may also have a ground line different from the ground line 11. Further, although the drug solution tube 15 shown in fig. 2 is provided with a liner layer made of a composite resin material containing fluororesin B and carbon nanotubes at a part of the inner surface, the drug solution tube may be a molded product made of a composite resin material containing fluororesin B and carbon nanotubes, or a tube obtained by cutting the molded product made of the composite resin material into a tubular shape may be used as it is as a drug solution tube.
As shown in fig. 2, the groove of the second embodiment of the present invention has a hollow spherical molded body 5. The number of the hollow spherical molded bodies 5 is not particularly limited, and may be appropriately selected depending on the size of each molded body 5 and the desired charging effect. The molded bodies 5 are connected to ground wires 13, which extend from the lid 14 to the outside of the groove and are connected to the outside. The static electricity charged in the chemical solution 6 flows into the molded body 5 having a low volume resistivity and is removed through the ground 13. The hollow spherical molded body 5 can be produced by thinly cutting out a molded body of a composite resin material containing the fluororesin C and the carbon nanotubes, or by laminating a sheet produced by extrusion-molding the composite resin material into a sheet shape to the hollow spheres. The tank of the present embodiment has a lid 14, but the lid 14 is not essential. In the present embodiment, ground wire 13 extends from cover 14, but ground wire 13 may be electrically connected to ground wire 11.
The tank according to the second embodiment of the present invention has a shape shown in fig. 2, and can be used as a tank for transporting a chemical solution, for example. Specifically, it may be a tank container known as an ISO tank. A tank container is a container used when cargo is liquid in cargo transportation such as ships, railways, and automobiles. In particular, when a chemical liquid is transported in a tank container, the liquid in the tank vibrates due to the vibration during transportation, and friction is generated by the vibration, which may cause the chemical liquid to be charged. The tank of the present embodiment can efficiently remove static electricity generated in the chemical solution. Although not shown in fig. 2, the tank of the present embodiment may have other structures that are common in the tank, such as a drug solution tube, a safety valve, and an air vent provided at any position such as an upper portion, a side portion, and a lower portion. The transport means of the tank of the present embodiment is not particularly limited, and the tank may be transported by a transport vehicle such as a tank car or a freight train, or a ship.
(third embodiment)
Next, fig. 3 shows an embodiment of the supply system of the present invention as a third embodiment. As shown in fig. 3, the supply system of the present invention in this embodiment includes a chemical liquid transport tank 16 and a chemical liquid supply tank 22, and is a system for supplying a chemical liquid to each point of use 18(POU, point of use). At least one of the chemical liquid transport tank 16 and the chemical liquid supply tank 22 may be the tank of the present invention, or may be the tank of the present invention. The chemical liquid transport tank 16 may be, for example, the tank of the embodiment shown in fig. 2. The chemical liquid transport tank 16 stores and transports the chemical liquid as a content in a transport vehicle 17. The chemical liquid transported in the chemical liquid transport tank 16 is transported to the final use points 28 by the operation of the pump 24. First, the chemical solution transport tank 16 is connected to a chemical solution supply tank 22 via a coupler 20 and connection pipes 18 and 21 in a transfer box 19, for example, in a semiconductor manufacturing plant. The chemical liquid in the chemical liquid transport tank 16 is connected by a coupler 20 via a connection pipe 18, and is transferred to a chemical liquid supply tank 22 via a connection pipe 21. A pump 24 is connected to the chemical liquid supply tank 22, and the chemical liquid transferred from the chemical liquid supply tank 22 through the connection pipes 23 and 25 passes through a filter 26, thereby removing fine contaminants contained in the chemical liquid, and the chemical liquid is transferred to each use point 28 through a connection pipe 27. In the third embodiment shown in fig. 3, the liquid is supplied by using the pump 24, but the position of the pump 24 is not limited to the illustrated position. In addition, a plurality of pumps 24 may be used. Alternatively, the chemical liquid may be supplied by a pressurizing system or the like without using a supply pump.
Examples
The present invention will be described in further detail below with reference to examples, but these do not limit the scope of the present invention.
< average particle diameter D50Measurement of
The average particle diameters of the fluororesin particles and the composite resin particles used for producing the composite resin particles were measured by a laser diffraction scattering particle size distribution apparatus (MT 3300II manufactured by japanese unexamined patent publication (r)), to obtain an average particle diameter D50。
< determination of specific surface area >
The specific surface areas of the fluororesin pellets and the composite resin pellets used for producing the composite resin pellets were measured in accordance with JIS Z8830 using a specific surface area/pore distribution measuring apparatus (bessel orp-miniII, japan).
< measurement of crystallization Heat >
The heat of crystallization of the fluororesin pellets used for producing the composite resin pellets was measured using a differential scanning calorimeter ("DSC-50" manufactured by shimadzu corporation). After a 3mg measurement sample was heated to 250 ℃ at a rate of 50 ℃/min and held temporarily, and further heated to 380 ℃ at a rate of 10 ℃/min to melt the crystals, the peak of the crystallization point measured at the time of cooling at a rate of 10 ℃/min was converted into heat for measurement.
< determination of melting Point >
The melting point of the fluororesin pellets used for producing the composite resin pellets was measured as the temperature of the melting heat peak which can be measured by a Differential Scanning Calorimeter (DSC) in accordance with ASTM-D4591.
< preparation of composite resin Material >
The composite resin particles obtained in the production examples described later are subjected to pretreatment (e.g., predrying, granulation, etc.) as necessary, and then uniformly filled in a certain amount into a molding die. The production steps after filling differ depending on the type of fluororesin.
When the fluororesin is a PTFE resin or a modified PTFE resin, the composite resin particles are compressed by pressurizing at 15MPa and holding for a certain period of time, thereby obtaining a preform. The preform thus obtained was taken out of the mold, fired in a hot air circulation type electric furnace set at 345 ℃ or higher for 2 hours or longer, slowly cooled, and then taken out of the electric furnace to obtain a molded article of composite resin particles (composite resin material).
When the fluororesin is a PCTFE resin, a PFA resin, an FEP resin, an ETFE resin, an ECTFE resin, a PVDF resin, or a PVF resin (other than a PTFE resin or a modified PTFE resin), the resin is melted by heating the mold in a hot air circulation electric furnace set at 200 ℃ or higher for 2 hours or more. After heating for a predetermined time, the material is discharged from an electric furnaceThe mold was removed, and the pressure was controlled at 25kg/cm using an oil press2The mold is cooled to around room temperature while the surface pressure is increased and compressed, thereby obtaining a molded article (resin material) of composite resin particles.
< determination of volume resistivity >
Production from composite resin Material (molded body) obtained from composite resin particles by the above-described operation
The test piece of (3) is used as a measurement sample. The volume resistivity was measured according to JIS K6911 using a resistivity meter ("Loresta" or "Hiresta" manufactured by Mitsubishi chemical Analyticch).
< measurement of weld Strength of composite resin Material >
From the composite resin material (molded article) obtained by the above-described operation from the composite resin pellets, a test piece having a thickness of 10mm, a width of 30mm and a length of 100mm was prepared, and a V-shaped groove having a length of 50mm and a depth of about 1mm was cut out from the test piece. Next, a PFA welding rod having a diameter of 3mm was welded to the groove portion using a hot air welding machine so that the length of the welded portion became 50mm, thereby producing a test piece for measuring welding strength shown in fig. 4. Next, as shown in fig. 5, the test piece for measuring the welding strength was set in a tensile tester so that the folded portion of the welded PFA welding rod was positioned on the lower side, and the remaining portion of the welding rod, which was not welded, was fixed to the chuck plate of the tensile tester. The resultant was drawn at a speed of 10 mm/min using a tensile tester ("Tesilon Universal Material testing machine" manufactured by A & D), and the maximum stress was measured to obtain the weld strength.
< measurement of Metal elution amount of composite resin Material >
The degree of metal contamination in the molded article due to the addition of carbon nanotubes was evaluated by measuring the amount of metal elution of the metal-based 17 element using an ICP mass spectrometer ("ELAN DRCII", PerkinElmer). Specifically, a test piece of 10mm × 20mm × 50mm obtained by cutting the composite resin material obtained as described above was immersed in 0.5L of 3.6% hydrochloric acid (EL-UM grade manufactured by Kanto chemical Co., Ltd.) for about 1 hour, taken out after 1 hour of immersion, rinsed with ultrapure water (specific resistance value:. gtoreq.18.0 M.OMEGA.cm), washed, and the whole test piece was immersed in 0.1L of 3.6% hydrochloric acid and stored at room temperature for 24 hours and 168 hours. After a predetermined time, the whole amount of the impregnation solution was recovered, and the concentration of metal impurities in the impregnation solution was analyzed.
< determination of carbon exfoliation of composite resin Material >
The degree of detachment of the carbon nanotubes from the composite resin material was evaluated by measuring TOC using a total organic carbon analyzer ("TOCvwp" manufactured by shimadzu corporation). Specifically, a test piece of 10mm × 20mm × 50mm obtained by cutting the composite resin material obtained as described above was immersed in 0.5L of 3.6% hydrochloric acid (EL-UM grade manufactured by Kanto chemical Co., Ltd.) for about 1 hour, taken out after 1 hour of immersion, rinsed with ultrapure water (specific resistance value:. gtoreq.18.0 M.OMEGA.cm), washed, and the whole test piece was immersed in ultrapure water and stored at room temperature for 24 hours and 168 hours. After a predetermined time had elapsed, the whole amount of the impregnation solution was recovered, and the total organic carbon analysis was performed on the impregnation solution.
< evaluation of chemical resistance of composite resin Material >
Using an electronic balance (A)&Electronic balance "BM-252" for analysis manufactured by D corporation) was used to measure the weight of a test piece of 10 mm. times.20 mm. times.50 mm cut from the composite resin material obtained by the above-described operation. Next, the test piece was immersed in SPM (H)2SO4︰H2O21: 2 (mass ratio)), FPM (HF: H)2O21: 2 (mass ratio)), APM (SC-1) (NH4OH ︰H2O2︰H2O1: 5 (mass ratio)), and ozone water (50ppm) were added to each solution for 168 hours and dried, and the weight of the test piece after immersion was measured using an electronic balance as before immersion. The change in weight before and after immersion was calculated by the following formula and used as an index of chemical resistance.
Weight change (%) [ (weight after impregnation-weight before impregnation)/weight before impregnation ] × 100
[ production of composite resin particles ]
In the following examples and comparative examples, modified PTFE particles or Polytetrafluoroethylene (PTFE) particles shown in table 1 below were used. In addition, it was confirmed that X in the above formula (II) in the modified PTFE particles 1 and 2 shown in table 1 is a perfluoropropyl group, and the amount of a perfluorovinyl ether unit was 0.01 to 1% by mass based on the total mass of the modified polytetrafluoroethylene.
[ Table 1]
Production example 1
To 500g of a carbon nanotube dispersion (0.15 mass% dispersant and 0.025 mass% carbon nanotube) using water as a solvent, 3,500g of ethanol was added and diluted. Subsequently, 1,000g of modified PTFE particles 1 was added to prepare a mixed slurry.
Then, the obtained mixed slurry was supplied to a pressure vessel, liquefied carbon dioxide was supplied at a supply rate of 0.03 g/min to 1mg of the dispersant contained in the mixed slurry in the pressure vessel, the pressure in the pressure vessel was increased to 20MPa, and the temperature was increased to 50 ℃. While maintaining the above pressure and temperature for 3 hours, carbon dioxide was discharged from the pressure-resistant vessel together with the solvent (water, ethanol) into which carbon dioxide was dissolved and the dispersant.
Next, the pressure and temperature in the pressure-resistant container were reduced to atmospheric pressure and room temperature, and carbon dioxide in the pressure-resistant container was removed to obtain CNT composite resin particles 1.
Production example 2
CNT composite resin particles 2 were obtained in the same manner as in production example 1-1, except that the amount of CNTs was 0.05 mass% with respect to the total amount of the composite resin particles obtained.
Production example 3
CNT composite resin particles 3 were obtained in the same manner as in production example 1-1, except that the total amount of the composite resin particles obtained was changed to 0.1 mass% of CNTs.
Production example 4
CNT composite resin particles 4 were obtained in the same manner as in production example 1, except that modified PTFE2 was used instead of modified PTFE 1.
Production example 5
A CNT composite resin material 5 was obtained in the same manner as in production example 2, except that modified PTFE2 was used instead of modified PTFE 1.
Comparative resin pellets 6 (production example 6)
Modified PTFE1 in which CNTs were not composited was used as comparative resin particles 6.
Comparative resin particles 7 (production example 7)
Modified PTFE2 in which CNTs were not composited was used as comparative resin particles 7.
Comparative resin pellets 8 (production example 8)
PTFE particles in which CNTs were not combined were used as comparative resin particles 8.
The average particle diameter and specific surface area of the resin particles obtained in production examples 1 to 8 were measured by the above-described measurement methods. The results are shown in Table 2. Further, the molded articles obtained by the above-described methods using the resin pellets obtained in production examples 1 to 8 were measured, and the volume resistivity and weld strength obtained are shown in table 2, and the results of chemical resistance evaluation are shown in table 3. Further, table 2 also shows a value a obtained from the amount of CNT and the volume resistivity of the resin material by the following formula:
A＝X/Y-14。
in the above formula, X is the volume resistivity [ Ω · cm ] of the resin material, and Y is the amount [ mass% ] of the CNT contained in the resin material (equal to the amount of the CNT used in the production of the resin material).
Hereinafter, the composite resin materials obtained from the composite resin particles 1 to 5 by the above-described method are also referred to as composite resin materials 1 to 5, respectively, and the resin materials obtained from the comparative resin particles 6 to 8 by the above-described method are also referred to as comparative resin materials 6 to 8, respectively. In addition, the amount of CNTs in the composite resin particles or resin particles is equal to the amount of CNTs in the composite resin material or resin material obtained from these.
The resin materials obtained from the composite resin materials 1 and 2 and the comparative resin material 6 were evaluated for the amount of metal elution and carbon shedding. The obtained results are shown in table 4. In addition, the metal elution amounts of elements other than the elements described in the column of the metal elution amounts in table 4 (Ag, Cd, Co, Cr, K, Li, Mn, Na, Ni, Pb, Ti, Zn) were measured, but the results are not described in table 4 because they are the device detection limit (ND). The results in table 4 are all the results after 24 hours of immersion.
[ Table 4]
A test piece of 10 mm. times.10 mm. times.2 mm in thickness was obtained from the composite resin material 2 prepared in accordance with the above-mentioned method for producing a composite resin material and using the composite resin particles obtained in production example 2. The test piece was immersed in each of the chemical solutions shown in table 5, and the weight change between before immersion and after immersion for about 1 week (1W) and about 1 month (1M) was measured. The obtained results are shown in table 5. The immersion test of APM in table 5 was performed at 80 ℃, and the immersion test of other chemical solutions was performed at room temperature. The details of each chemical solution in table 5 are shown in table 6.
Production example 9 and composite resin Material 9
PCTFE (average particle diameter 10 μm, specific surface area 2.9, volume resistivity 10) was used2Ω · cm) was used instead of modified PTFE1, and CNT composite resin particles 9 were obtained in the same manner as in production example 2. Using the obtained CNT composite resin particles 9, a composite resin material 9 was produced according to the above-described method for producing a composite resin material, and a test piece of 10mm × 10mm × 2mm in thickness was obtained. The test piece was also subjected to immersion tests of various chemical solutions shown in table 5. The obtained results are shown in table 5.
[ comparative resin materials 10 to 12]
A commercially available molded product obtained by adding 15 wt% of graphite to PTFE was used as comparative resin material 10, and a commercially available molded product obtained by adding 15 wt% of carbon fiber to PTFE was used as comparative resin material 11. A commercially available composite material (composite material of PFA resin and carbon fiber) was used as the comparative resin material 12. The test pieces of these materials having the above dimensions were subjected to the immersion tests of various chemicals shown in table 5 in the same manner. The obtained results are shown in table 5.
[ Table 5]
[ Table 6]
[ production of composite resin Particles (PCTFE) ]
The Polychlorotetrafluoroethylene (PCTFE) pellets shown in table 7 below were used to produce composite resin pellets.
[ Table 7]
Production example 13: production of CNT composite resin particles 13
CNT composite resin particles 13 were obtained in the same manner as in production example 1, except that PCTFE particles 2 were used instead of modified PTFE particles 1.
Production example 14 production of CNT composite resin particles 14
CNT composite resin particles 14 were obtained in the same manner as in production example 2, except that PCTFE particles 2 were used instead of modified PTFE particles 1.
Production example 15 production of CNT composite resin particles 15
CNT composite resin particles 15 were obtained in the same manner as in production example 14, except that the amount of CNTs was 0.1 mass% with respect to the total amount of the composite resin particles obtained.
Production example 16 production of CNT composite resin particles 16
CNT composite resin particles 16 were obtained in the same manner as in production example 14, except that the amount of CNTs was 0.125 mass% with respect to the total amount of the composite resin particles obtained.
Production example 17 production of CNT composite resin particles 17
CNT composite resin particles 17 were obtained in the same manner as in production example 14, except that the amount of CNTs was 0.15 mass% with respect to the total amount of the composite resin particles obtained.
Production example 18 production of CNT composite resin particles 18
CNT composite resin particles 18 were obtained in the same manner as in production example 15, except that PCTFE particles 3 were used instead of PCTFE particles 2.
Production example 19 production of CNT composite resin particles 19
CNT composite resin particles 19 were obtained in the same manner as in production example 15, except that PCTFE particles 1 were used instead of PCTFE particles 2.
Production example 20 comparative resin pellets 20
PCTFE2 without CNT composite was used as the comparative resin particles 20.
The average particle diameter and specific surface area of the composite resin particles obtained in production examples 13 to 20 and the comparative resin particles were measured by the above-described measurement methods. The results are shown in Table 8. The volume resistivities of the composite resin materials (molded articles) 13 to 19 and the comparative resin material (molded article) 20 prepared by the above method using the above resin particles are also shown in table 8. Further, table 8 also shows a value a obtained from the amount of CNT and the volume resistivity of the resin material by the following formula:
A＝X/Y-14。
in the above formula, X is the volume resistivity [ Ω · cm ] of the resin material, and Y is the amount [ mass% ] of the CNT contained in the resin material (equal to the amount of the CNT used in the production of the resin material). The composite resin materials obtained from the composite resin particles 13 to 19 by the above-described method are also referred to as composite resin materials 13 to 19, respectively, and the composite resin material obtained from the comparative resin particles 20 by the above-described method is also referred to as comparative resin material 20.
[ Table 8]
The composite resin materials 14 and 15 and the comparative resin material 20 were evaluated for the amount of metal elution and carbon shedding. The obtained results are shown in table 9. In addition, the metal elution amounts of elements other than the elements described in the column of the metal elution amounts in table 9 (Ag, Cd, Co, Cr, K, Li, Mn, Na, Ni, Pb, Ti, Zn) were measured, but the results are not described in table 9 because they are the device detection limit (ND). The results in table 9 are all the results after 24 hours of immersion.
[ Table 9]
The composite resin materials 14 and 15 and the comparative resin material 20 were evaluated for chemical resistance by the above-described method. The obtained results are shown in table 10.
[ Table 10]
The composite resin materials 14 and 15 were subjected to a hydrogen peroxide sulfate mixed solution impregnation treatment (SPM treatment) under the above conditions, and the volume resistivity after the treatment was measured. As a result, as shown in table 11 below, it was confirmed that the volume resistivity of the composite resin materials 14 and 15 did not increase even when the SPM treatment was performed.
[ Table 11]
[ production of liner sheet 1 comprising composite resin Material ]
A method for manufacturing a lining sheet 1 containing a composite resin material from the composite resin particles obtained by the operation described above is set forth. The production method differs depending on the fluororesin used. When the fluororesin is Polytetrafluoroethylene (PTFE) or modified polytetrafluoroethylene (modified PTFE), the composite resin particles obtained in production example 2 are subjected to pretreatment (e.g., predrying, granulation, etc.) as necessary, and then uniformly filled in a molding die in a certain amount, and the composite resin material is compressed by holding the composite resin particles under a pressure of 15MPa for a certain period of time, thereby obtaining a preform. The preform obtained was taken out from the mold, fired in a hot air circulation type electric furnace set at 345 ℃ or higher for 2 hours or longer, slowly cooled, and then taken out from the electric furnace to obtain a block-shaped molded article of the composite resin material. (examples and comparative examples do not describe, and in the case where the fluororesin is a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), there are compression molding, press molding, sheet extrusion molding, etc., and in the case of the compression molding, the CNT composite resin particles are subjected to pretreatment (e.g., predrying, granulation, etc.) as needed, and then uniformly filled in a molding die in a predetermined amount, and then fired in an electric furnace set at 300 ℃ or higher for 2 hours or more, and then taken out of the electric furnace, and pressure-cooled by a hydraulic press at 5MPa or more to obtain a block-shaped composite resin material molding.) the molding is subjected to cutting (rotary cutting) to produce a sheet having a thickness of 2.4 mm. The obtained sheet was laminated with a glass cloth having a thickness of 0.5mm and heat-welded to obtain a backing sheet 1. The resulting backing sheet 1 had a volume resistivity of 102Ω·cm。
[ production of liner sheet 2 not containing composite resin Material ]
A liner sheet 2 was obtained in the same manner as in the production of the liner sheet 1, except that the composite resin particles obtained in production example 2 were replaced with the comparative resin particles 6 (production example 6).
[ production of drug solution tube 1 comprising composite resin Material ]
A method for manufacturing a drug solution tube 1 containing a composite resin material from the composite resin particles obtained by the operation as described above is set forth. The composite resin particles obtained in production example 2 were subjected to pretreatment (e.g., predrying, granulation, etc.) as necessary, and then uniformly filled in a certain amount into a molding die, and the composite resin material was compressed by pressurizing at 15MPa for a certain period of time to obtain a preform. The preform obtained was taken out from the mold, fired in a hot air circulation type electric furnace set at 345 ℃ or higher for 2 hours or longer, slowly cooled, and then taken out from the electric furnace to obtain a block-shaped molded article of the composite resin material. The obtained molded body was subjected to cutting processing using a CNC common rotary disk ("TAC-510" by greens corporation) to manufacture a 2-inch diameter drug solution tube. The volume resistivity of the obtained drug solution tube 1 was 5.0X 102Ω· cm。
[ production of drug solution tube 2 comprising composite resin Material ]
A drug solution tube 2 was obtained in the same manner as in the production of the drug solution tube 1 except that the composite resin particles obtained in production example 2 were replaced with the comparative resin particles 6 (production example 6).
[ production of hollow sphere 1 comprising composite resin Material ]
A method for manufacturing a drug solution tube 1 containing a composite resin material from the composite resin particles obtained by the operation as described above is set forth. The composite resin particles obtained in production example 2 were subjected to pretreatment (e.g., predrying, granulation, etc.) as necessary, and then uniformly filled in a certain amount into a molding die, and the composite resin material was compressed by pressurizing at 15MPa and holding for a certain period of time, thereby obtaining a preform. The preform obtained was taken out from the mold, fired in a hot air circulation type electric furnace set at 345 ℃ or higher for 2 hours or longer, slowly cooled, and then taken out from the electric furnace to obtain a block-shaped molded article of the composite resin material. The obtained molded article was subjected to cutting or welding using a machining center, thereby producing a hollow spherical molded article having a diameter of 50 mm.The volume resistivity of the resulting hollow spherical molded article was 5.0X 102Ω· cm。
[ production of hollow sphere 2 comprising composite resin Material ]
Example 1
The lining sheet 1 is bonded to the inner surface of the tank having a capacity of 50L using an adhesive (for example, an epoxy-based adhesive). Use of
The PFA welding bar of (3) seals the gap between the sheets. A drug solution tube 1 is attached to the tank, and a plurality of hollow spheres 1 are arranged inside the tank.
Comparative example 1
Comparative example 1 was obtained in the same manner as in the production of example 1 except that the lining sheet 2, the drug solution tube 2, and the hollow sphere 2 were used instead of the lining sheet 1, the drug solution tube 1, and the hollow sphere 1.
Evaluation of antistatic Property
Antistatic properties of the organic solvent were evaluated by placing 10L of a diluent (NTX eco diluent, manufactured by Sanko chemical Co., Ltd.) in the tank obtained in example 1 and comparative example 1, stirring the mixture at 285r.p.m for 10 minutes with a stirrer having a stirring blade made of PTFE, and measuring the charging potential of the lining sheet with a potentiometer (FMX-003, manufactured by SIMCO). As a result, in comparative example 1, the charging was rapidly accelerated by the stirring, and the charging potential tended to increase with the passage of time (about 1.5kV in about 5 minutes). On the other hand, example 1 is a value not more than the measurement limit (-0.01kV), and it was confirmed that the tank of example 1 is superior in antistatic property to the tank of comparative example 1.
Description of the symbols
1 tank outer tank
2 liner layer
3 liquid medicine feeding pipe
31 backing layer
4 liquid medicine discharge pipe
41 backing layer
5 hollow spherical molded body
6 medicinal liquid
7 liquid contact part
8 lining sheet
9 groove bottom
10 liner sheet
11 ground wire
12 liquid level
13 ground wire
14 cover body
15 liquid medicine tube
151 liner layer
16 liquid medicine conveying tank
17 transport vehicle
18 connecting pipe
19 transfer box
20 coupler
21 connecting pipe
22 chemical liquid supply tank
24 circulation pump
25 connecting pipe
26 Filter
27 connecting pipe
28 points of use
29 PFA fusion bar
30 test piece
31 groove
32 lower chuck
33 chuck
36 spray nozzle
52 rod-shaped molded article
53 ground wire
54 support
56 stirring rod
57 propeller
58 bush.
Claims (20)
1. A tank, characterized by:
at least comprises an outer tank and a lining layer arranged on the inner surface of the outer tank,
the backing layer contains a composite resin material containing fluororesin A and carbon nanotubes in at least a part thereof,
the fluororesin A is selected from the group consisting of Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF),
the amount of the carbon nanotubes contained in the composite resin material is 0.01 to 0.2 mass% based on the total amount of the composite resin material,
the backing layer is provided at least partially with a backing sheet containing a composite resin material layer, and the gap between the backing sheets is welded with a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA) material.
2. The cell of claim 1, wherein:
the lining layer provided at a portion where the chemical solution to be introduced first contacts the inner surface of the outer tank includes a composite resin material containing fluororesin a and carbon nanotubes.
3. The cell of claim 1, wherein:
has a medicine liquid tube connected to the inside and outside of the tank,
the drug solution tube has a lining layer on at least a part of an inner surface of the drug solution tube, the lining layer comprising a composite resin material containing fluororesin B and carbon nanotubes; and/or the liquid chemical tube is a molded body of a composite resin material containing fluororesin B and carbon nanotubes,
the fluororesin B is selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
4. The cell of claim 1, wherein:
has a medicine liquid tube connected to the inside and outside of the tank,
the liquid medicine tube comprises a liquid medicine feeding tube for feeding liquid medicine into the groove,
the chemical liquid pouring pipe has a nozzle at an end thereof,
the nozzle has a lining layer on at least a part of an inner surface of the nozzle, the lining layer comprising a composite resin material containing fluororesin B and carbon nanotubes; and/or the nozzle is a molded body of a composite resin material containing a fluororesin B and carbon nanotubes,
the fluororesin B is selected from Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
5. The cell of claim 4, wherein:
the nozzle is selected from spray nozzle, rotary nozzle, linear nozzle, and shower nozzle.
6. The cell of claim 1, wherein:
also provided is a hollow spherical molded body at least partially comprising a composite resin material containing a fluororesin C and a carbon nanotube, the fluororesin C being selected from the group consisting of Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
7. The cell of claim 1, wherein:
and a rod-shaped molded body at least partially comprising a composite resin material containing a fluororesin C and a carbon nanotube, the fluororesin C being selected from the group consisting of Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
8. The cell of claim 1, wherein:
also provided is a stir bar comprising at least in part a composite resin material comprising a fluororesin C and carbon nanotubes, the fluororesin C being selected from the group consisting of Polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/Ethylene Copolymer (ECTFE), and polyvinyl fluoride (PVF).
9. The cell of claim 8, wherein:
the stirring rod has a propeller at least partially including a composite resin material containing fluororesin C and carbon nanotubes.
10. The cell of any one of claims 1 to 9, wherein:
the chemical solution contains at least 1 selected from organic solvent, flammable liquid, acidic liquid, alkaline liquid, neutral liquid, aqueous solution, and conductive liquid.
11. The cell of any one of claims 1 to 9, wherein:
the fluororesin A is modified polytetrafluoroethylene.
12. The cell of any one of claims 1 to 9, wherein:
the modified polytetrafluoroethylene is a compound having a tetrafluoroethylene unit represented by formula (I) and a perfluorovinyl ether unit represented by formula (II),
in the formula (II), X represents a C1-6 perfluoroalkyl group or a C4-9 perfluoroalkoxyalkyl group,
the amount of the perfluorovinyl ether unit represented by the formula (II) is 0.01 to 1% by mass based on the total mass of the modified polytetrafluoroethylene.
13. The cell of any one of claims 1 to 9, wherein:
the composite resin material is a compression-molded product of composite resin particles having an average particle diameter of 5 [ mu ] m or more and 500 [ mu ] m or less, the composite resin particles containing a fluororesin A and carbon nanotubes.
14. The cell of claim 3 or 4, wherein:
the composite resin material is a compression-molded product of composite resin particles having an average particle diameter of 5 [ mu ] m or more and 500 [ mu ] m or less, the composite resin particles containing a fluororesin B and carbon nanotubes.
15. The cell of any one of claims 6 to 8, wherein:
the composite resin material is a compression-molded product of composite resin particles having an average particle diameter of 5 [ mu ] m or more and 500 [ mu ] m or less, the composite resin particles containing a fluororesin C and carbon nanotubes.
16. The cell of any one of claims 1 to 9, wherein:
which is a chemical liquid supply tank, a chemical liquid storage tank, and/or a chemical liquid transport tank.
17. A chemical liquid supply system, characterized in that:
comprising supplying a chemical solution by using the tank according to any one of claims 1 to 16.
18. A molded body, characterized in that:
for a cell according to any one of claims 1 to 16,
the molded body contains a fluororesin A and carbon nanotubes.
19. A molded body, characterized in that:
a tank for use as claimed in any one of claims 3 to 5 or 14,
the molded body contains fluororesin B and carbon nanotubes.
20. A molded body, characterized in that:
for a cell according to any one of claims 6 to 8 or 15,
the molded body contains fluororesin C and carbon nanotubes.
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| JP2017142264 | 2017-07-21 | ||
| JP2017-142264 | 2017-07-21 | ||
| JP2018021649 | 2018-02-09 | ||
| JP2018-021649 | 2018-02-09 | ||
| PCT/JP2018/027359 WO2019017488A1 (en) | 2017-07-21 | 2018-07-20 | Tank, and chemical solution supply system |
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| CN110944920A CN110944920A (en) | 2020-03-31 |
| CN110944920B true CN110944920B (en) | 2022-04-12 |
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| JP (1) | JP6571304B2 (en) |
| KR (1) | KR102616116B1 (en) |
| CN (1) | CN110944920B (en) |
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| JPWO2021166743A1 (en) * | 2020-02-17 | 2021-08-26 | ||
| CN113525943B (en) * | 2020-04-15 | 2022-11-15 | 何建智 | Liquid storage container and method for manufacturing the same |
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- 2018-07-20 CN CN201880048526.3A patent/CN110944920B/en active Active
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| KR102616116B1 (en) | 2023-12-21 |
| TW201908208A (en) | 2019-03-01 |
| JPWO2019017488A1 (en) | 2019-11-07 |
| JP6571304B2 (en) | 2019-09-04 |
| WO2019017488A1 (en) | 2019-01-24 |
| TWI772468B (en) | 2022-08-01 |
| KR20200034761A (en) | 2020-03-31 |
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