WO2015046215A1 - 不織布、分離膜支持体、分離膜、流体分離素子および不織布の製造方法 - Google Patents
不織布、分離膜支持体、分離膜、流体分離素子および不織布の製造方法 Download PDFInfo
- Publication number
- WO2015046215A1 WO2015046215A1 PCT/JP2014/075220 JP2014075220W WO2015046215A1 WO 2015046215 A1 WO2015046215 A1 WO 2015046215A1 JP 2014075220 W JP2014075220 W JP 2014075220W WO 2015046215 A1 WO2015046215 A1 WO 2015046215A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nonwoven fabric
- separation membrane
- melting point
- less
- membrane
- Prior art date
Links
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 273
- 239000012528 membrane Substances 0.000 title claims abstract description 207
- 238000000926 separation method Methods 0.000 title claims abstract description 167
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- 239000012530 fluid Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000009835 boiling Methods 0.000 claims abstract description 34
- 239000000835 fiber Substances 0.000 claims description 105
- 238000002844 melting Methods 0.000 claims description 73
- 230000008018 melting Effects 0.000 claims description 72
- 229920000642 polymer Polymers 0.000 claims description 71
- 239000002131 composite material Substances 0.000 claims description 22
- 229920000728 polyester Polymers 0.000 claims description 13
- 239000000470 constituent Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 20
- 238000001223 reverse osmosis Methods 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 description 34
- 239000002184 metal Substances 0.000 description 34
- -1 aromatic carboxylic acids Chemical class 0.000 description 30
- 239000010410 layer Substances 0.000 description 28
- 229920002492 poly(sulfone) Polymers 0.000 description 26
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 229920000139 polyethylene terephthalate Polymers 0.000 description 20
- 239000005020 polyethylene terephthalate Substances 0.000 description 20
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- 238000009987 spinning Methods 0.000 description 11
- 239000012466 permeate Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008358 core component Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920000747 poly(lactic acid) Polymers 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000004750 melt-blown nonwoven Substances 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229920006167 biodegradable resin Polymers 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000118 poly(D-lactic acid) Polymers 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
- D04H3/147—Composite yarns or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
- D04H1/5412—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres sheath-core
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/542—Adhesive fibres
- D04H1/55—Polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
Definitions
- the present invention relates to a non-woven fabric having low asperity under high temperature conditions and having excellent dimensional stability while having asymmetry of two surfaces, and particularly for applications such as a separation membrane support such as a reverse osmosis membrane.
- the present invention relates to a nonwoven fabric that can be suitably used.
- the present invention also relates to a separation membrane support using the nonwoven fabric, a separation membrane using the separation membrane support, a fluid separation element using the separation membrane, and a method for producing the nonwoven fabric.
- Membrane technology is often applied to water treatment in recent years.
- microfiltration membranes and ultrafiltration membranes are used for water treatment at water purification plants, and reverse osmosis membranes are used for seawater desalination.
- reverse osmosis membranes and nanofiltration membranes are used for the treatment of semiconductor manufacturing water, boiler water, medical water, laboratory pure water, and the like.
- a membrane separation activated sludge method using a microfiltration membrane or an ultrafiltration membrane is also applied to the treatment of sewage wastewater.
- separation membranes are roughly classified into flat membranes and hollow fiber membranes according to their shapes.
- flat membranes formed mainly from synthetic polymers are generally used in combination with separation membrane supports such as nonwoven fabrics and woven fabrics because the membrane itself having a separation function is inferior in mechanical strength. Often done.
- a membrane having a separation function and a separation membrane support are a method in which a solution of a polymer as a raw material for a membrane having a separation function is cast and fixed on a separation membrane support such as a nonwoven fabric or a woven fabric.
- a separation membrane support such as a nonwoven fabric or a woven fabric.
- a semipermeable membrane such as a reverse osmosis membrane
- a polymer layer solution is cast on a separation membrane support such as a nonwoven fabric or a woven fabric to form a support layer, and then the semipermeable membrane is formed on the support layer.
- a separation membrane support such as a nonwoven fabric or a woven fabric to form a support layer
- the nonwoven fabric used as the separation membrane support when the polymer solution is cast, it penetrates due to excessive permeation, the membrane substance peels off, and further, the nonwoven fabric fluffs, etc.
- An excellent film forming property that does not cause defects such as non-uniform film formation and pinholes is required.
- the nonwoven fabric used as a support in the separation membrane production process has a back-up caused by excessive permeation when a polymer solution is cast. High dimensional stability is also required to prevent deformation due to heat and tension applied to the nonwoven fabric.
- examples of the form of the fluid separation element for facilitating the handling of the separation membrane include fluid separation elements such as a flat membrane plate frame type, a pleat type, and a spiral type.
- a plate frame type fluid separation element requires a process of attaching a separation membrane cut to a predetermined size to the frame, and a spiral type fluid separation element is cut to a predetermined size. The process of sticking the outer peripheral part of separation membranes, processing it into an envelope shape, and winding around a water collection pipe is required. Therefore, the nonwoven fabric used as the separation membrane support is required to have excellent processability so that the membrane is not bent or rounded in these steps.
- non-woven fabric made of synthetic resin fine fibers and binder fibers, which is manufactured by heat-pressing after paper making, and has a tensile strength ratio of 2: 1 to 1 in the paper flow direction and the width direction. : 1 has been proposed (see Patent Document 2). Also, in the separation membrane support made of nonwoven fabric, the separation membrane support made of nonwoven fabric in which the fibers arranged on the membrane-forming surface side of the separation membrane are laterally oriented than the fibers arranged on the non-membrane-forming surface side of the separation membrane A body has been proposed (see Patent Document 3).
- the object of the present invention is that when used as a separation membrane support such as a reverse osmosis membrane, in addition to having a stable processability with a high yield against heat received during membrane formation and fluid separation element production,
- An object of the present invention is to provide a nonwoven fabric having excellent mechanical strength.
- Another object of the present invention is to provide a separation membrane support using the above-mentioned nonwoven fabric, a separation membrane and a fluid separation element using the same.
- the present invention is to solve the above-mentioned problems, and the nonwoven fabric of the present invention has a difference in smoothness between two surfaces of 10 seconds to 50 seconds, and boiling after being treated in boiling water for 5 minutes.
- the nonwoven fabric is characterized in that the water curl height is 0 mm or more and 8.0 mm or less.
- the nonwoven fabric comprises a composite fiber in which a low melting point polymer having a melting point lower than the melting point of the high melting point polymer is arranged around the high melting point polymer, A non-woven fabric in which a difference in melting point between the high melting point polymer and the low melting point polymer is 10 ° C. or more and 140 ° C. or less, and the high melting point polymer is contained in the composite fiber in an amount of 50% by weight to 90% by weight. It is.
- the nonwoven fabric is a spunbonded nonwoven fabric.
- the separation membrane support of the present invention is a separation membrane support made of the above-mentioned nonwoven fabric.
- the separation membrane of the present invention is a separation membrane formed by forming a membrane having a separation function on the surface of the above-mentioned separation membrane support.
- the fluid separation element of the present invention is a fluid separation element including the separation membrane as a component.
- the non-woven fabric manufacturing method of the present invention is the above-described non-woven fabric manufacturing method, in which a non-woven fabric sheet made of polyester fibers having a movable amorphous amount of 10% to 70% is thermocompression bonded with a pair of flat rolls. It is a manufacturing method.
- the above-mentioned method for producing a nonwoven fabric has a movable amorphous amount of 40% to 70%.
- the nonwoven fabric sheet is a nonwoven fabric sheet having a filling density of 0.1 or more and 0.3 or less that is preliminarily thermocompression bonded between flat rolls.
- This is a method for producing a nonwoven fabric in which the difference between the temperature of the roll and the melting point of the fibers constituting the nonwoven fabric sheet is 30 ° C. or higher and 130 ° C. or lower.
- the cast polymer solution when used as a support for a separation membrane such as a reverse osmosis membrane, the cast polymer solution is broken through by permeation, the membrane substance is peeled off, and there are defects such as pinholes.
- separation A nonwoven fabric having excellent mechanical strength that does not deform or break due to pressure applied when used as a membrane or a fluid separation element can be obtained.
- the nonwoven fabric of the present invention is suitably used as a separation membrane support such as a reverse osmosis membrane.
- the nonwoven fabric of the present invention is a nonwoven fabric in which the difference in smoothness between the two surfaces is 10 seconds or more and 50 seconds or less, and the boiling water curl height after being treated in boiling water for 5 minutes is 0 mm or more and 8.0 mm or less.
- Examples of the polymer of fibers constituting the nonwoven fabric of the present invention include polyester polymers, polyamide polymers, polyolefin polymers, and mixtures and copolymers thereof.
- a polyester polymer is preferably used because a separation membrane support excellent in durability such as mechanical strength, heat resistance, water resistance and chemical resistance can be obtained.
- the polyester polymer is a polyester composed of an acid component and an alcohol component.
- the acid component include aromatic carboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanecarboxylic acid.
- the alcohol component ethylene glycol, diethylene glycol, polyethylene glycol, or the like can be used.
- polyester-based polymers include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polylactic acid and polybutylene succinate, and copolymers thereof, among which polyethylene terephthalate Is preferably used.
- a biodegradable polymer can be used as a polymer of fibers constituting the nonwoven fabric because it is easy to dispose of after use and has a low environmental impact.
- the biodegradable resin include polylactic acid, polybutylene succinate, polycaprolactone, polyethylene succinate, polyglycolic acid, and polyhydroxybutyrate.
- polylactic acid is a plant-derived resin that does not deplete petroleum resources, has relatively high mechanical properties and heat resistance, and is a biodegradable resin that is low in production cost and is preferably used.
- Polylactic acid that is particularly preferably used includes poly (D-lactic acid), poly (L-lactic acid), a copolymer of D-lactic acid and L-lactic acid, or a blend thereof.
- the fiber constituting the nonwoven fabric of the present invention may be a single component fiber, a composite fiber composed of a plurality of components, or a so-called mixed fiber in which a plurality of types of fibers are mixed.
- a composite fiber in which a low melting point polymer having a melting point lower than that of the high melting point polymer is arranged around the high melting point polymer is particularly preferably used.
- the fibers in the nonwoven fabric are firmly bonded to each other by thermocompression bonding during the production of the nonwoven fabric. Therefore, even when the difference in smoothness between the two surfaces of the nonwoven fabric is increased, the boiling water curl height is increased.
- the thickness can be set to 8.0 mm or less, and even when heat is applied during use of the nonwoven fabric, deformation of the nonwoven fabric that is bent or rounded can be suppressed.
- a nonwoven fabric is used as a separation membrane support, it is possible to suppress non-uniformity during casting of a polymer solution due to fluffing and membrane defects.
- the number of adhesion points is increased as compared with a mixed fiber type in which fibers made only of a high melting point polymer and fibers made only of a low melting point polymer are mixed, the mechanical strength is improved.
- the difference in melting point between the high melting point polymer and the low melting point polymer constituting the composite fiber is preferably 10 ° C. or higher and 140 ° C. or lower.
- the difference in melting point preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 30 ° C. or higher, it contributes to the improvement of mechanical strength without impairing the strength of the high melting point polymer disposed in the center. Thermal adhesiveness can be obtained.
- fever applied at the time of nonwoven fabric use can be suppressed.
- the difference in melting point is preferably 140 ° C. or less, more preferably 120 ° C. or less, and further preferably 100 ° C. or less, the low melting point polymer component is fused to the roll during thermocompression bonding using a hot roll. It can suppress that productivity falls.
- the melting point of the high melting point polymer is such that when the nonwoven fabric of the present invention is used as a separation membrane support, the separation membrane has good film-forming properties when the separation membrane is formed on the separation membrane support and has excellent durability. Is preferably 160 ° C. or higher and 320 ° C. or lower from the viewpoint of being able to obtain the above.
- the melting point of the high melting point polymer is preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and even more preferably 180 ° C. or higher, so that it is dimensionally stable even if it passes through a process of applying heat when manufacturing a separation membrane or fluid separation element Excellent in properties.
- the melting point of the high-melting polymer is preferably 320 ° C. or lower, more preferably 300 ° C. or lower, and further preferably 280 ° C. or lower. It can suppress that it falls.
- the melting point of the low melting point polymer is preferably 120 ° C. or higher and 250 ° C. or lower, more preferably 140 ° C. or higher and 240 ° C. or lower, and further preferably 230 ° C. or higher and 240 ° C. or lower.
- the high melting point polymer contained in the composite fiber in which a low melting point polymer having a melting point lower than the melting point of the high melting point polymer is arranged around the high melting point polymer is contained in an amount of 50% by mass to 90% by mass. It is preferable that The high melting point polymer contained in the composite fiber is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more, thereby suppressing deformation due to heat applied when using the nonwoven fabric. Can do. On the other hand, thermal bonding that contributes to the improvement of the mechanical strength of the nonwoven fabric by controlling the high melting point polymer contained in the composite fiber to 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less. Even when the difference in smoothness between the two surfaces of the nonwoven fabric is increased, the boiling water curl height can be reduced to 8.0 mm or less, even when the nonwoven fabric is heated. It is possible to suppress deformation in which the nonwoven fabric is bent or rounded.
- high melting point polymer / low melting point polymer examples include, for example, polyethylene terephthalate / polybutylene terephthalate, polyethylene terephthalate / polytrimethylene terephthalate, polyethylene terephthalate / polylactic acid, And combinations of polyethylene terephthalate / copolymerized polyethylene terephthalate and the like.
- copolymerization component of copolymerized polyethylene terephthalate isophthalic acid or the like is preferably used, and in particular, a combination of polyethylene terephthalate / isophthalic acid copolymerized polyethylene terephthalate is preferably used.
- Additives such as a crystal nucleating agent, a matting agent, a lubricant, a pigment, an antifungal agent, an antibacterial agent and a flame retardant can be added to the fibers constituting the nonwoven fabric as long as the effects of the present invention are not impaired.
- metal oxides such as titanium oxide improve the spinnability by reducing the surface friction of the fibers and preventing the fusion between the fibers, and increase the thermal conductivity during thermocompression molding with a non-woven hot roll. This has the effect of improving the adhesion of the nonwoven fabric.
- aliphatic bisamides such as ethylene bis-stearic acid amide and / or alkyl-substituted aliphatic monoamides have an effect of improving adhesion stability by increasing the releasability between the hot roll and the web.
- Examples of the composite form of the composite fiber include a composite form such as a concentric core-sheath type, an eccentric core-sheath type, and a sea-island type from the viewpoint of efficiently obtaining a thermal bonding point between fibers.
- examples of the cross-sectional shape of the fibers constituting the nonwoven fabric include a circular cross section, a flat cross section, a polygonal cross section, a multileaf cross section, and a hollow cross section.
- the concentric core-sheath type is preferably a circular cross section or a flat cross section as the cross-sectional shape of the fiber, and by using such a composite form, the fibers are firmly bonded by thermocompression bonding.
- the thickness of the nonwoven fabric can be reduced, and when used as a separation membrane support, the separation membrane area per fluid separation element unit can be increased.
- the average single fiber diameter of the fibers constituting the nonwoven fabric is preferably 3 ⁇ m or more and 30 ⁇ m or less.
- the average single fiber diameter of the fibers is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 7 ⁇ m or more, the spinnability is less likely to deteriorate during the production of the nonwoven fabric, and the nonwoven fabric is used as a separation membrane support.
- the polymer solution cast at the time of film formation can quickly permeate the inside of the separation membrane support, and excellent film forming properties can be obtained.
- the average single fiber diameter of the fibers is preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, and even more preferably 20 ⁇ m or less, a smoothness of at least one side is 10 seconds or more, and a nonwoven fabric excellent in uniformity is obtained. be able to.
- the nonwoven fabric can be firmly integrated by thermal bonding, and even when the difference in smoothness between the two surfaces of the nonwoven fabric is increased, the boiling water curl height can be reduced to 8.0 mm or less. Even when applied, it is possible to suppress deformation of the nonwoven fabric that is bent or rounded.
- the nonwoven fabric of the present invention is preferably a spunbond nonwoven fabric produced by a spunbond method.
- Spunbond nonwoven fabric which is a long-fiber nonwoven fabric composed of thermoplastic filaments, is non-uniform during casting of a polymer solution caused by fluff, which is likely to occur when using a short-fiber nonwoven fabric when used as a support for a separation membrane. And film defects can be suppressed.
- the spunbonded nonwoven fabric is also preferably used from the viewpoint that it is superior in mechanical strength and can provide a separation membrane having excellent durability when used as a separation membrane support.
- the nonwoven fabric of the present invention can be a laminated nonwoven fabric composed of a plurality of layers.
- the nonwoven fabric excellent in the uniformity can be obtained, and also the density distribution in the thickness direction of the nonwoven fabric and the smoothness of the two surfaces of the nonwoven fabric can be easily adjusted.
- nonwoven fabric laminate examples include, for example, a laminate of two layers of spunbond nonwoven and a laminate of a three-layer structure in which a meltblown nonwoven is disposed between two layers of spunbond nonwoven.
- at least 1 layer is a spunbond nonwoven fabric from the point which is excellent in mechanical strength, and it is a more preferable aspect that it consists only of a spunbond nonwoven fabric.
- the basis weight of the nonwoven fabric of the present invention is preferably 20 g / m 2 or more and 150 g / m 2 or less.
- the basis weight is preferably 20 g / m 2 or more, more preferably 30 g / m 2 or more, and even more preferably 40 g / m 2 or more. It is possible to obtain a good membrane-forming property with little over-permeation, etc., excellent dimensional stability, high membrane peel strength and mechanical strength, and excellent durability.
- the thickness of the separation membrane is preferably set to 150 g / m 2 or less, more preferably 120 g / m 2 or less, and even more preferably 90 g / m 2 or less.
- the separation membrane area per fluid separation element unit can be increased.
- the thickness of the nonwoven fabric of the present invention is preferably 0.03 mm or more and 0.20 mm or less.
- the thickness of the nonwoven fabric is preferably 0.03 mm or more, more preferably 0.04 mm or more, and even more preferably 0.05 mm or more.
- Good film-forming properties with little over-permeation, etc., and high dimensional stability, so there is little dimensional change during the separation membrane manufacturing process, and curling and bending after film formation are suppressed, and fluid separation elements are manufactured. Excellent processability can be obtained, and a separation membrane having high mechanical strength and excellent durability can be obtained.
- the thickness of the nonwoven fabric is preferably 0.20 mm or less, more preferably 0.16 mm or less, and even more preferably 0.12 mm or less.
- the separation membrane area per fluid separation element unit can be increased.
- the non-woven fabric of the present invention has a difference in smoothness between two surfaces measured by JIS P8119 (1998 edition) of 10 seconds to 50 seconds.
- a non-woven fabric as a separation membrane support (hereinafter sometimes referred to as a support)
- the smoothness value is large, that is, a smoother surface is used as the film-forming surface (surface).
- a separation membrane a polymer solution is cast on the support surface, and the polymer solution is solidified by infiltrating a coagulation liquid containing water as a main component from the back surface of the support, so that the membrane is integrated with the support. The law is widely applied.
- the difference in smoothness between the two surfaces is preferably 15 seconds or more, more preferably 20 seconds or more. Moreover, it is preferable that it is 40 seconds or less, More preferably, it is 30 seconds or less.
- the smoothness of the nonwoven fabric of the present invention is preferably 5 seconds or more and 80 seconds or less, more preferably 10 seconds or more, and further preferably 15 seconds or more. Moreover, it is more preferably 70 seconds or less, and still more preferably 60 seconds or less.
- the non-woven fabric when used as a separation membrane support by setting the smoothness of the non-woven fabric to preferably 80 seconds or less, a polymer solution or a coagulation solution produced by excessive smoothing of the support surface or the back surface of the support Insufficient penetration into the support can be suppressed.
- the non-woven fabric of the present invention has a boiling water curl height of 0 mm or more and 8.0 mm or less after being treated in boiling water for 5 minutes.
- a non-woven fabric is used as a separation membrane support, it is often subjected to heat during the production of the separation membrane, such as washing with hot water and drying during the process, and also during the fluid separation element production process due to drying. Therefore, when the boiling water curl height of the non-woven fabric is 8.0 mm or less, preferably 6.0 mm or less, more preferably 4.0 mm or less, the film may be bent or round when subjected to the heat. And excellent film forming property and workability can be obtained with excellent dimensional stability.
- the boiling water curl height as used in the present invention refers to taking 3 samples of 25 cm length x 25 cm width from any part of the nonwoven fabric, immersing it in boiling water for 5 minutes, taking it out, and smoothing the nonwoven fabric on a flat table. After naturally drying with the large surface facing up, the height (distance from the base) of the central part of each side of each of the three samples was measured in units of 0.5 mm, and these were averaged. is there.
- a composite fiber such as a core-sheath type is used as the fiber constituting the nonwoven fabric
- a normal composite method can be adopted for manufacturing the composite fiber.
- thermocompression bonding In the case of the spunbond method as a method for producing a nonwoven fabric, a molten thermoplastic polymer is extruded from a nozzle, sucked and stretched with a high-speed suction gas, spun, and then collected on a moving conveyor. It is possible to produce a long-fiber non-woven fabric by integrating it by forming a web and further continuously applying thermocompression bonding or the like. At this time, from the viewpoint that wrinkles and the like due to excessive shrinkage of fibers during thermocompression bonding can be prevented and good processability can be obtained, and the strength of the fibers contributing to the mechanical strength of the nonwoven fabric is also improved.
- the spinning speed is preferably 3000 m / min or more, the spinning speed is more preferably 3500 m / min or more, and further preferably 4000 m / min or more.
- the spinning speed is preferably 5500 m / min or less, more preferably 5000 m / min or less, and even more preferably 4500 m, because the deformation of the nonwoven fabric can be suppressed even when heated when using the nonwoven fabric. / Min or less.
- the temperature of the fiber before carrying out suction drawing with a high-speed suction gas shall be 40 degreeC or more and 80 degrees C or less, and shall be 50 degreeC or more and 70 degrees C or less. It is more preferable.
- the temperature of the fiber before suction drawing with a high-speed suction gas to 40 ° C. or higher, yarn breakage during spinning can be suppressed.
- seat before thermocompression bonding mentioned later can be made high enough by making the temperature of the fiber before attraction
- the thermoplastic polymer is stretched to ultrafine fibers by spraying a heated high-speed gas fluid on the molten thermoplastic polymer, and collected to collect the long-fiber nonwoven fabric. Can be manufactured.
- a method in which long fibers are cut into short fibers and then nonwoven fabrics by a dry method or a wet method is preferably used.
- the laminated body (laminated nonwoven fabric) of the nonwoven fabric mentioned above in the case of the manufacturing method of the laminated body which consists of two layers of nonwoven fabrics, for example, two layers of the temporarily bonded nonwoven fabric obtained with one pair of rolls are used.
- the method of integrating by thermocompression after superimposing can be preferably used.
- a separate line is provided between two layers of temporarily bonded spunbond nonwoven fabric obtained by a pair of rolls.
- melt blown nonwoven fabric manufactured in step 1 After the melt blown nonwoven fabric manufactured in step 1 is stacked, it is extruded from the spunbond nozzle, meltblown nozzle, and spunbond nozzle arranged on the top of the collection conveyor.
- a method of collecting, laminating and thermocompression bonding the fiberized webs in order can be preferably used.
- thermocompression bonding In the case of a dry short fiber nonwoven fabric or a papermaking nonwoven fabric, a method in which a plurality of wound nonwoven fabrics are overlapped and then integrated by thermocompression bonding can be preferably used.
- thermocompression bonding for integrating the non-woven fabric
- the entire surface of the non-woven fabric is uniformly thermocompressed and integrated with a pair of upper and lower flat rolls so that the smoothness of at least one side of the non-woven fabric is 10 seconds or more.
- the method can be preferably used.
- This flat roll is a metal roll or elastic roll with no irregularities on the surface of the roll, and a pair of metal roll and metal roll or a pair of metal roll and elastic roll is used.
- Can do in particular, by providing a temperature difference between a pair of upper and lower flat rolls, a nonwoven fabric in which the difference in smoothness between the two surfaces is 10 seconds or more and 50 seconds or less can be obtained, and fibers on the surface of the nonwoven fabric can be fused.
- the dimensional change during the separation membrane manufacturing process can be reduced when the nonwoven fabric is used as a separation membrane support, so that the nonwoven fabric is more surface than the metal roll and the metal roll.
- a method of thermocompression bonding with an elastic roll having a low temperature is more preferably used.
- the elastic roll is a roll made of a material having elasticity compared to a metal roll.
- elastic rolls include so-called paper rolls such as paper, cotton and aramid paper, urethane-based resins, epoxy-based resins, silicone-based resins, polyester-based resins and hard rubbers, and resin-made rolls made of a mixture thereof. It is done.
- the hardness (Shore D) of the elastic roll is preferably 70 or more and 91 or less.
- the smoothness of the surface of the nonwoven fabric in contact with the elastic roll can be 10 seconds or more.
- the hardness (Shore D) of the elastic roll is preferably 91 or less, more preferably 86 or less, and even more preferably 81 or less, the smoothness of the surface in contact with the elastic roll of the nonwoven fabric is excessively improved. It is possible to obtain a nonwoven fabric in which the difference in smoothness between the two surfaces is 10 seconds or more and 50 seconds or less.
- a combination of metal / elastic rolls in a manufacturing process is used continuously or discontinuously.
- a combination of a method and a three-roll method such as elasticity / metal / elasticity, elasticity / metal / metal, and metal / elasticity / metal can also be preferably used.
- the hardness (Shore D) of the non-woven fabric, the elastic roll contacting the first stage and the elastic roll contacting the second stage may be changed.
- the surface temperature of the metal roll used for thermocompression bonding is preferably lower than the melting point of the polymer constituting at least the surface of the fiber constituting the nonwoven fabric, and constitutes at least the surface of the fiber constituting the nonwoven fabric and the surface temperature of the metal roll.
- the difference from the melting point of the polymer to be polymerized is more preferably 20 ° C or higher and 80 ° C or lower. If the difference between the surface temperature of the metal roll and the melting point of the polymer constituting at least the surface of the fibers constituting the nonwoven fabric is 20 ° C. or more, excessive fusion of the nonwoven fabric surface fibers can be suppressed, and the nonwoven fabric When the is used as a separation membrane support, the polymer solution can easily permeate, and a separation membrane support excellent in membrane peel strength can be obtained.
- the nonwoven fabric is constituted by setting the difference between the surface temperature of the metal roll and the melting point of the polymer constituting at least the surface of the fibers constituting the nonwoven fabric to preferably 80 ° C. or lower, more preferably 40 ° C. or lower.
- the fibers can be firmly bonded to each other, and the boiling water curl height of the nonwoven fabric can be 8.0 mm or less.
- the smoothness of the surface which contacted the metal roll of the nonwoven fabric can be made into 20 seconds or more, and the nonwoven fabric excellent in mechanical strength can be obtained by densifying it.
- thermocompression bonding is performed with a metal roll obtained by heating a nonwoven fabric and an elastic roll having a surface temperature lower than that of the metal roll is more preferable. It is a more preferable embodiment that the difference between the surface temperature of the metal roll and the surface temperature of the elastic roll is 10 ° C. or more and 120 ° C. or less. The difference between the surface temperature of the metal roll and the surface temperature of the elastic roll is more preferably 20 ° C. or more and 100 ° C. or less, and further preferably 30 ° C. or more and 80 ° C. or less.
- an induction heat generation method, a heat medium circulation method, or the like can be preferably used, but since a separation membrane support excellent in uniformity can be obtained, the temperature difference in the nonwoven fabric width direction becomes a central value. On the other hand, it is preferably within ⁇ 3 ° C., more preferably within ⁇ 2 ° C.
- a heating method for the elastic roll As a heating method for the elastic roll, a contact heating method that is heated by contact with a metal roll heated during pressurization, or a non-contact heating method that uses an infrared heater or the like that can control the surface temperature of the elastic roll more strictly. Etc. can be preferably used.
- the temperature difference in the nonwoven fabric width direction of the elastic roll is preferably within ⁇ 10 ° C., more preferably within ⁇ 5 ° C. with respect to the center value.
- an infrared heater or the like can be divided and installed in the width direction, and the respective outputs can be adjusted.
- the linear pressure of the flat roll is preferably 196 N / cm or more and 4900 N / cm or less.
- the linear pressure of the flat roll is preferably 196 N / cm or more, more preferably 490 N / cm or more, and even more preferably 980 N / cm or more.
- the height can be 8.0 mm or less.
- the nonwoven fabric excellent in mechanical strength can be obtained by densifying.
- the linear pressure of the flat roll is preferably 4900 N / cm or less, excessive fusion of the nonwoven fabric surface fibers can be suppressed, and when the nonwoven fabric is used as a separation membrane support, a high molecular polymer A separation membrane support excellent in membrane forming property can be obtained without impeding the penetration of the solution into the nonwoven fabric.
- the temporarily bonded laminated nonwoven fabric layers in which 2 to 5 temporarily bonded nonwoven fabrics are laminated are integrated by lamination thermocompression bonding. If the number of laminated layers is two or more, the texture is improved as compared with a single layer, and sufficient uniformity can be obtained. Moreover, if the number of laminated layers is 5 or less, it is possible to suppress wrinkling during lamination and to suppress delamination between layers.
- thermocompression bonding method for a spunbonded nonwoven fabric a two-step adhesion method can be adopted in order to control the properties of the nonwoven fabric more precisely, rather than thermocompression bonding the nonwoven fabric with only a pair of flat rolls. . That is, the nonwoven fabric is temporarily bonded by preliminarily thermocompression bonding the fiber web between a pair of flat rolls or by preliminarily thermocompression bonding between one flat roll and a collecting conveyor used for collecting the fiber web.
- nonwoven fabric sheet (Hereinafter, it may be called a nonwoven fabric sheet.)
- the two-step adhesion method in which it is further thermocompression bonded between flat rolls. Can also be preferably used.
- the density of the nonwoven fabric (nonwoven fabric sheet) in the temporarily adhered state can be set to 0.1 because the nonwoven fabric can be densified at the time of the second-stage thermocompression bonding. It is preferable to set it to 0.3 or less.
- the temperature of the flat roll used for preliminary thermocompression at that time is preferably lower than the melting point of the fibers constituting the nonwoven sheet, and the temperature of the flat roll used for preliminary thermocompression and the melting point of the fibers constituting the nonwoven sheet The difference is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 60 ° C. or higher and 120 ° C. or lower, and further preferably 100 ° C. or higher and 110 ° C. or lower.
- the movable amorphous amount of the polyester fibers constituting the nonwoven fabric sheet before thermocompression bonding is sufficient Can be high.
- the linear pressure of the flat roll used for the first stage pre-thermocompression bonding is 49 N / cm or more and 686 N / cm or less.
- a nonwoven fabric sheet made of polyester fiber having a movable amorphous amount of 10% to 70% is thermocompression bonded with a pair of flat rolls.
- Thermocompression bonding is achieved by setting the movable amorphous amount of the polyester fiber constituting the nonwoven fabric sheet before thermocompression bonding with a pair of flat rolls to preferably 10% or more, more preferably 25% or more, and even more preferably 40% or more.
- the fibers constituting the nonwoven fabric are firmly bonded to each other, the boiling water curl height of the nonwoven fabric can be reduced to 8.0 mm or less, and a nonwoven fabric excellent in mechanical strength can be obtained by increasing the density. .
- the movable amorphous amount of the polyester fiber constituting the nonwoven fabric sheet before thermocompression bonding preferably 70% or less, more preferably 60% or less, more preferably 50% or less, Generation
- the separation membrane of the present invention is a separation membrane obtained by forming a membrane having a separation function on the above-described separation membrane support made of nonwoven fabric.
- separation membranes include microfiltration membranes, ultrafiltration membranes, semiconductor manufacturing water, boiler water, medical water, and laboratory pure water used for water treatment at water purification plants and industrial process water production, etc.
- semipermeable membranes such as nanofiltration membranes and reverse osmosis membranes used in seawater desalination treatment.
- the separation membrane As a method for producing a separation membrane, a method of forming a membrane having a separation function by casting a polymer solution on at least one surface of the above-mentioned separation membrane support is preferably used. At this time, it is preferable that the surface of the nonwoven fabric having a large smoothness is the film-forming surface.
- the membrane having a separation function may be a composite membrane including a support layer and a semipermeable membrane layer, and the composite membrane may be laminated on at least one surface of the separation membrane support. This is a preferred form.
- the polymer solution that is cast on the separation membrane support made of the nonwoven fabric of the present invention has a separation function when it becomes a membrane, for example, polyarylethersulfone such as polysulfone and polyethersulfone, A solution of polyimide, polyvinylidene fluoride, cellulose acetate or the like is preferably used. Among them, a solution of polysulfone and polyarylethersulfone is preferably used from the viewpoint of chemical, mechanical and thermal stability.
- the solvent can be appropriately selected according to the film-forming substance.
- the semipermeable membrane in the case where the separation membrane is a composite membrane comprising a separation membrane support layer and a semipermeable membrane layer, a crosslinked polyamide membrane obtained by polycondensation of a polyfunctional acid halide and a polyfunctional amine is preferred. Used.
- the fluid separation element of the present invention is, for example, a fluid separation element in which the above separation membrane is housed in a casing for easy handling when incorporated in a seawater desalination apparatus.
- a fluid separation element in which the above separation membrane is housed in a casing for easy handling when incorporated in a seawater desalination apparatus.
- Examples of the form include flat membrane plate frame type, pleated type and spiral type fluid separation elements.
- a spiral type fluid separation element is preferably used in which the separation membrane is spirally wound around the water collecting pipe together with the permeate flow path material and the supply liquid flow path material.
- a plurality of fluid separation elements can be connected in series or in parallel to form a separation membrane unit.
- Melting point (° C) The melting point of the polymer was measured using a differential scanning calorimeter DSC-2 manufactured by Perkin Elma Co. under the condition of a temperature rising rate of 20 ° C./min, and the melting point was the temperature giving an extreme value in the melting endotherm curve. . Further, in the differential scanning calorimeter, for a resin whose melting endotherm curve does not show an extreme value, the resin was heated on a hot plate, and the temperature at which the resin was completely melted by microscopic observation was taken as the melting point.
- Intrinsic viscosity (IV) The intrinsic viscosity (IV) of the polyethylene terephthalate resin was measured by the following method. 8 g of a sample was dissolved in 100 ml of orthochlorophenol, and the relative viscosity ⁇ r was determined by the following formula using an Ostwald viscometer at a temperature of 25 ° C.
- ⁇ viscosity of polymer solution
- ⁇ 0 viscosity of orthochlorophenol
- t drop time of solution (seconds)
- d density of the solution (g / cm 3 )
- t 0 Fall time of orthochlorophenol (seconds)
- d Orthochlorophenol density (g / cm 3 )
- IV 0.0242 ⁇ r +0.2634.
- Movable amorphous amount (%) of the temporarily bonded sheet The amount of movable amorphous material was determined by taking two samples at random from a temporarily bonded sheet before thermocompression integration and using temperature modulation DSC (TA Instruments Q1000) under the following conditions and formula: The amount of movable amorphous was calculated, and the average value was calculated. Moreover, the specific heat change amount at the time of complete amorphous was 0.4052 J / g ° C.
- Average single fiber diameter For the average single fiber diameter, 10 small sample samples were taken at random from the nonwoven fabric, photographed at 500 to 3000 times with a scanning electron microscope, and the diameter of 100 single fibers, 10 from each sample, was measured. The average value was calculated by rounding off the first decimal place.
- Nonwoven fabric thickness (mm) Thickness is based on JIS L1906 (2000 version) 5.1, using a 10 mm diameter pressurizer, with a load of 10 kPa and 10 points at equal intervals per 1 m in the width direction of the nonwoven fabric. The average value was rounded off to the second decimal place.
- Non-woven fabric packing density (-) The weight was calculated from the basis weight (g / m 2 ), thickness (mm), and polymer density obtained in the above (5) and (6), respectively, using the following formula and rounded off to the second decimal place.
- Packing density basis weight (g / m 2 ) ⁇ thickness (mm) ⁇ 10 3 ⁇ polymer density (g / cm 3 )
- the polymer density of the polyethylene terephthalate resin and copolymerized polyethylene terephthalate resin in the examples of the present invention was 1.38 g / cm 3 .
- Boiling water curl height of non-woven fabric For boiling water curl height, three samples of 25 cm in length (nonwoven length direction) x 25 cm in width (nonwoven width direction) were taken from any part of the non-woven fabric, immersed in boiling water for 5 minutes and then removed. On the table, the non-woven fabric is air-dried with the smooth side facing up. For each of the three samples, measure the height of the central part (distance from the platform) on both sides in units of 0.5 mm, average them, and round off the second decimal place to obtain the boiling water curl height. Calculated.
- Tensile strength of nonwoven fabric (N / 5cm) Tensile strength is 5 cm ⁇ 30 cm for a nonwoven fabric sample of 5 cm ⁇ 30 cm based on JIS L1913 (2010 edition), with a grip interval of 20 cm and a tensile speed of 10 cm / min. The strength at the point was measured, the strength at break was read, and the value rounded to the first decimal place was taken as the tensile strength in the longitudinal and transverse directions.
- Cast liquid drainage property during film formation Cast liquid drainage property is evaluated by visually observing the back surface of the produced polysulfone membrane and evaluating the cast liquid strikethrough property in the following five stages. The score was passed. 5 points: There is no see-through of cast liquid. 4 points: Slightly see-through of casting solution is observed (area ratio is less than 5%). 3 points: See-through of casting solution is observed (area ratio: 5 to 50%). 2 points: Most of the cast liquid is seen through (area ratio 51 to 80%). 1 point: The cast liquid can be seen through almost the entire surface.
- Membrane bendability at the time of film formation Membrane bendability is determined by visually observing the state of the separation membrane support and the membrane from unwinding to winding at the time of film formation. Evaluation was made with 3-5 points as acceptable. 5 points: No film bending is observed.
- a spiral-type fluid separation element having an effective membrane area of 40 m 2 using a supply liquid channel material made of a polypropylene net, a reverse osmosis membrane for seawater desalination, a pressure-resistant sheet, and the following permeate channel material Produced.
- Permeate channel material A polyester single tricot (double denby knitting) having a groove width of 200 ⁇ m, a groove depth of 150 ⁇ m, a groove density of 40 lines / inch, and a thickness of 200 ⁇ m was used.
- the manufactured fluid separation element was subjected to a durability test under conditions of a reverse osmosis pressure of 7 MPa, a seawater salt concentration of 3 wt%, and an operating temperature of 40 ° C., and the fluid separation element was disassembled after 1000 hours of operation. Then, the amount of the separation membrane dropped into the permeate channel material was measured. The amount of sagging is measured by taking 500-3000 times photographs with a scanning electron microscope (unit: ⁇ m) for any three cross sections of the separation membrane in one fluid separation element. Calculated by rounding to the first place. The direction in which the separation membrane support and the permeate flow path material overlap each other was such that the nonwoven fabric width direction (lateral direction) of the separation membrane support was orthogonal to the groove direction of the permeate flow path material.
- Example 1 (Core component) A core component of a polyethylene terephthalate resin having an intrinsic viscosity (IV) of 0.65, a melting point of 260 ° C., and a titanium oxide content of 0.3 mass% dried to a moisture content of 10 ppm was used.
- IV intrinsic viscosity
- Sheath component A copolymerized polyethylene terephthalate resin having an intrinsic viscosity (IV) of 0.66, an isophthalic acid copolymerization ratio of 11 mol%, a melting point of 230 ° C., and a titanium oxide content of 0.2 mass% was dried to a moisture content of 10 ppm. The thing was used as a sheath component.
- the core component and the sheath component are melted at temperatures of 295 ° C. and 290 ° C., respectively, the core temperature is 300 ° C., and the mass ratio of the core component and the sheath component is 80/20. ) And spun from the pores, and then spun by an ejector at a spinning speed of 4300 m / min, and collected as a fiber web on a moving net conveyor.
- Preliminary thermocompression bonding The collected fiber web is passed between a pair of upper and lower metal flat rolls, each flat roll surface temperature is 130 ° C., pre-thermocompression bonding is performed at a linear pressure of 490 N / cm, the fiber diameter is 10 ⁇ m, and the basis weight is 72 g. / M 2 , a thickness of 0.29 mm, and a temporarily bonded non-woven fabric (a) having a movable amorphous amount of 36% was obtained.
- the obtained spunbonded nonwoven fabric (a) in the temporarily bonded state is a resin elastic roll having a hardness (Shore D) 91 on the top, a metal roll on the inside, and a resin elasticity having a hardness (Shore D) 75 on the bottom.
- One set of three flat rolls is thermo-compressed between the middle and bottom, and the nonwoven fabric is folded and thermo-compressed through the top-middle, with a basis weight of 72 g / m 2 and a thickness of 0.08 mm.
- a spunbonded nonwoven fabric having a surface smoothness of 29 seconds, a back surface smoothness of 11 seconds and a boiling water curl height of 4.6 mm was produced.
- the surface temperature of the three flat rolls at this time was 130 ° C. on the top, 190 ° C. on the inside, 140 ° C. on the bottom, and the linear pressure was 1862 N / cm.
- Example 2 Except that the basis weight and thickness were changed as shown in the table, the fiber diameter was 10 ⁇ m, the basis weight was 36 g / m 2 , the thickness was 0.15 mm, and the movable amorphous amount was the same as in Example 1. A spunbonded nonwoven fabric (b) in a temporarily bonded state of 38% was obtained.
- the obtained two temporarily bonded spunbond nonwoven fabrics (b) are stacked, and the laminated nonwoven fabric is an elastic roll made of resin having a hardness (Shore D) of 91, a metal roll inside, and a hardness below ( Shore D) 75 pairs of elastic rolls made of resin, thermocompression-bonded between the middle and bottom of a set of three flat rolls, and the laminated nonwoven fabric was folded and thermocompression-bonded through the top-intermediate, with a basis weight of 72 g / m 2 to produce a spunbonded nonwoven fabric having a thickness of 0.08 mm, a surface smoothness of 35 seconds, a back surface smoothness of 13 seconds, and a boiling water curl height of 3.5 mm.
- the surface temperature of the three flat rolls at this time was 130 ° C. on the top, 190 ° C. on the inside, 140 ° C. on the bottom, and the linear pressure was 1862 N / cm.
- Example 3 Except that the surface temperature of each flat roll was 140 ° C., the fiber diameter was 10 ⁇ m, the basis weight was 36 g / m 2 , the thickness was 0.13 mm, and the movable amorphous amount was the same as in Example 2. A spunbonded non-woven fabric (c) of 32% temporarily bonded was obtained.
- Two layers of the obtained temporarily bonded spunbond nonwoven fabric (c) are overlapped, and laminated thermocompression bonding is performed under the same conditions as in Example 2.
- the basis weight is 72 g / m 2 and the thickness is 0.09 mm.
- a spunbonded nonwoven fabric having a surface smoothness of 24 seconds, a back surface smoothness of 8 seconds, and a boiling water curl height of 6.2 mm was produced.
- Example 4 The average fiber diameter was 10 ⁇ m in the same manner as in Example 2 except that the melting temperature of the core component resin was 290 ° C., the melting temperature of the sheath component resin was 270 ° C., and the spinning speed was 4500 m / min.
- Example 5 The surface temperature of the three flat rolls at the time of lamination thermocompression bonding was 72 g / m 2 in basis weight in the same manner as in Example 2 except that the top was 120 ° C., the inside was 180 ° C., and the bottom was 130 ° C.
- Example 6 Except that the mass ratio of the core component and the sheath component is 85/15, the fiber diameter is 10 ⁇ m, the basis weight is 36 g / m 2 , the thickness is 0.15 mm, A temporarily bonded spunbond nonwoven fabric (e) having a crystal content of 38% was obtained.
- Example 7 Except that the die temperature was 290 ° C. and the spinning speed was 4200 m / min, the fiber diameter was 10 ⁇ m, the basis weight was 36 g / m 2 , the thickness was 0.15 mm, A temporarily bonded spunbond nonwoven fabric (f) having a crystal content of 42% was obtained.
- Example 8 Except that the die temperature was 290 ° C. and the spinning speed was 4100 m / min, the fiber diameter was 10 ⁇ m, the basis weight was 36 g / m 2 , the thickness was 0.15 mm, A temporarily bonded spunbond nonwoven fabric (g) having a crystal content of 46% was obtained.
- the characteristics of the obtained nonwoven fabric are as shown in the table.
- the separation membrane was produced using the nonwoven fabrics of Examples 1 to 8 as the separation membrane support, the processability was good and the obtained separation membrane was further obtained.
- the workability was good.
- thermocompression bonding The obtained temporarily bonded spunbond nonwoven fabric (f) was subjected to thermocompression bonding under the same conditions as in Example 1, with a basis weight of 72 g / m 2 , a thickness of 0.10 mm, and a surface smoothness of 17 seconds. A spunbonded nonwoven fabric having a back surface smoothness of 6 seconds and a boiling water curl height of 8.3 mm was produced.
- a polyethylene terephthalate resin having an intrinsic viscosity (IV) of 0.65, a melting point of 260 ° C., and a titanium oxide content of 0.3 mass% is dried to a moisture content of 10 ppm, melted at a temperature of 295 ° C., and a die temperature of 300 After spinning from pores with a circular cross section at 0 ° C., it was spun by an ejector at a spinning speed of 4300 m / min, and collected as a fiber web on a moving net conveyor.
- IV intrinsic viscosity
- Preliminary thermocompression bonding The collected fiber web is passed between a pair of upper and lower metal flat rolls, each flat roll surface temperature is 170 ° C., pre-thermocompression bonding is performed at a linear pressure of 490 N / cm, the fiber diameter is 10 ⁇ m, and the basis weight is 36 g / A spunbonded nonwoven fabric (g) in a temporarily bonded state having a thickness of 0.16 mm and a movable amorphous amount of 36% at m 2 was obtained.
- the laminated nonwoven fabric was an elastic roll made of resin having a hardness (Shore D) of 91, a metal roll inside, and a hardness below ( Shore D) 75 pairs of elastic rolls made of resin, thermocompression-bonded between the middle and bottom of a set of three flat rolls, and the laminated nonwoven fabric was folded and thermocompression-bonded through the top-intermediate, with a basis weight of 72 g / m 2 , a spunbonded nonwoven fabric having a thickness of 0.12 mm, a surface smoothness of 12 seconds, a back surface smoothness of 3 seconds, and a boiling water curl height of 10.4 mm was produced.
- the surface temperature of the three flat rolls at this time was 130 ° C. on the top, 200 ° C. on the inside, 140 ° C. on the bottom, and the linear pressure was 1862 N / cm.
- Example 3 (Laminated thermocompression bonding) Two temporarily bonded spunbond nonwoven fabrics (b) obtained in the same manner as in Example 2 were superposed and thermocompression bonded between a pair of upper and lower metal flat rolls, with a basis weight of 72 g / m 2 and a thickness. A spunbonded nonwoven fabric having a thickness of 0.08 mm, a surface smoothness of 42 seconds, a back surface smoothness of 40 seconds, and a boiling water curl height of 2.9 mm was produced. At this time, the surface temperature of the metal flat roll was 180 ° C. both in the upper and lower directions, and the linear pressure was 686 N / cm.
- the properties of the obtained nonwoven fabric are as shown in the table.
- the separation membrane was produced using the nonwoven fabrics of Comparative Examples 1 to 3 as a separation membrane support, the processability was poor, and the separation membrane was further used.
- Comparative Examples 1 and 2 were bent and rounded during the manufacturing process, and the workability was poor.
- Comparative Example 3 was processed with a large amount of friction of the resin that was penetrated when the films were stacked. Sex was poor.
- PET Polyethylene terephthalate co-PET: Copolymerized polyethylene terephthalate
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Abstract
Description
(1)融点(℃)
ポリマーの融点は、パーキンエルマ社製示差走査型熱量計DSC-2型を用い、昇温速度20℃/分の条件で測定し、得られた融解吸熱曲線において極値を与える温度を融点とした。また、示差走査型熱量計において、融解吸熱曲線が極値を示さない樹脂については、ホットプレート上で加熱し、顕微鏡観察により樹脂が完全に溶融した温度を融点とした。
ポリエチレンテレフタレート樹脂の固有粘度(IV)は、次の方法で測定した。オルソクロロフェノール100mlに対し試料8gを溶解し、温度25℃においてオストワルド粘度計を用いて相対粘度ηrを、下記式により求めた。
・ηr=η/η0=(t×d)/(t0×d0)
ここで、η:ポリマー溶液の粘度
η0:オルソクロロフェノールの粘度
t:溶液の落下時間(秒)
d:溶液の密度(g/cm3)
t0:オルソクロロフェノールの落下時間(秒)
d0:オルソクロロフェノールの密度(g/cm3)
次いで、相対粘度ηrから下記式により、固有粘度(IV)を算出した。
・IV=0.0242ηr+0.2634。
可動非晶量は、熱圧着一体化する前の仮接着状態のシートからランダムに試料2点を採取し、温度変調DSC(TA Instruments社製Q1000)を用いて、次の条件と式で測定と可動非晶量を算出し、平均値を算出した。また、完全非晶時の比熱変化量を0.4052J/g℃とした。
・測定雰囲気:窒素流(50ml/分)
・温度範囲 :0~300℃
・昇温速度 :2℃/分
・試料量 :5mg
・可動非晶量[%]=(ガラス転移温度前後の比熱変化量[J/g℃])/完全非晶時の比熱変化量[J/g℃]×100。
平均単繊維直径は、不織布からランダムに小片サンプル10個を採取し、走査型電子顕微鏡で500~3000倍の写真を撮影し、各サンプルから10本ずつ、計100本の単繊維の直径を測定し、それらの平均値を、小数点以下第一位を四捨五入して求めた。
目付は、30cm×50cmの不織布を3個採取して、各試料の質量をそれぞれ測定し、得られた値の平均値を単位面積当たりに換算し、小数点以下第一位を四捨五入した。
厚さは、JIS L1906(2000年版)の5.1に基づいて、直径10mmの加圧子を使用し、荷重10kPaで不織布の幅方向1mあたり等間隔に10点を0.01mm単位で厚さを測定し、その平均値の小数点以下第三位を四捨五入した。
上記(5)、(6)でそれぞれ求めた目付(g/m2)、厚さ(mm)、およびポリマー密度から、下記式を用いて算出し、小数点以下第二位を四捨五入した。
なお、本発明の実施例におけるポリエチレンテレフタレート樹脂、共重合ポリエチレンテレフタレート樹脂のポリマー密度は1.38g/cm3とした。
平滑度は、ベック平滑度試験機を用い、JIS P8119(1998年版)に基づいて、不織布の表面、裏面についてそれぞれ5点の測定を実施した。5点の平均値の小数点以下第一位を四捨五入した値を表面と裏面の平滑度とした。ここで分離膜支持体として用いる際の、製膜面を表面、非製膜面を裏面とした。
沸騰水カール高さは、不織布の任意の部分から縦(不織布長さ方向)25cm×横(不織布幅方向)25cmのサンプルを3個採取し、沸騰水中に5分間浸漬してから取り出し、平らな台上で不織布の平滑度が大きい面を上にして自然乾燥する。3個のサンプルそれぞれについて、両側辺の中央部の高さ(台との距離)を0.5mm単位で測定し、それらを平均し、小数点以下第二位を四捨五入して沸騰水カール高さを算出した。
引張強力は、JIS L1913(2010年版)の6.3.1に基づいて、5cm×30cmの不織布サンプルについて、つかみ間隔が20cmで、引張速度10cm/minの条件で、縦方向および横方向それぞれ5点について強力を測定し、破断したときの強力を読み取り、少数点以下第一位を四捨五入した値を縦方向と横方向の引張強力とした。
キャスト液裏抜け性は、作製したポリスルホン膜の裏面を目視で観察し、キャスト液の裏抜け性について、次の5段階で評価し、4~5点を合格とした。
5点:キャスト液の裏抜けが全く見られない。
4点:わずかにキャスト液の裏抜けが見られる(面積比率5%未満)。
3点:キャスト液の裏抜けが見られる(面積比率5~50%)。
2点:大部分でキャスト液の裏抜けが見られる(面積比率51~80%)。
1点:ほぼ全面でキャスト液の裏抜けが見られる。
膜折れ曲がり性は、製膜時の巻き出しから巻き取りまでの分離膜支持体および膜の状態を目視で観察し、膜折れ曲がり性について、次の5段階で評価し、3~5点を合格とした。
5点:膜折れ曲がりは全く見られない。
1点:全長の50%以上に渡って膜が折れ曲がり、折れ曲がった状態で巻き取られる。
[流体分離素子]
ポリプロピレン製のネットからなる供給液流路材、海水淡水化用逆浸透膜、耐圧シート、および下記の透過液流路材を用い、有効膜面積40m2のスパイラル型の流体分離素子(エレメント)を作製した。
溝幅が200μmで、溝深さが150μmで、溝密度が40本/インチで、そして厚さが200μmのポリエステル製シングルトリコット(ダブルデンビー編)を用いた。
(芯成分)
固有粘度(IV)が0.65、融点が260℃、酸化チタンの含有量が0.3質量%のポリエチレンテレフタレート樹脂を、水分率10ppmに乾燥したものを芯成分として用いた。
固有粘度(IV)が0.66、イソフタル酸共重合率が11モル%、融点が230℃、酸化チタンの含有量が0.2質量%の共重合ポリエチレンテレフタレート樹脂を、水分率10ppmに乾燥したものを鞘成分として用いた。
上記の芯成分および鞘成分を、それぞれ295℃と290℃の温度で溶融し、口金温度が300℃条件で、芯成分と鞘成分の質量比率を80/20として、同心芯鞘型(断面円形)に複合して細孔から紡出した後、エジェクターにより紡糸速度4300m/分で紡糸して、移動するネットコンベアー上に繊維ウエブとして捕集した。
捕集された繊維ウエブを、上下1対の金属製フラットロール間に通し、各フラットロール表面温度が130℃で、線圧が490N/cmで予備熱圧着し、繊維径が10μm、目付が72g/m2で、厚さが0.29mmで、可動非晶量が36%の仮接着状態のスパンボンド不織布(a)を得た。
得られた仮接着状態のスパンボンド不織布(a)を、上が硬度(Shore D)91の樹脂製の弾性ロールで、中が金属ロールで、下が硬度(Shore D)75の樹脂製の弾性ロールの1組の3本フラットロールの中-下間に通して熱圧着し、さらにその不織布を折り返して上-中間を通し熱圧着し、目付が72g/m2で、厚さが0.08mmで、表面の平滑度が29秒で、裏面の平滑度が11秒で、沸騰水カール高さが4.6mmのスパンボンド不織布を製造した。このときの3本フラットロールの表面温度は、上が130℃、中が190℃、下が140℃とし、線圧は1862N/cmとした。
[ポリスルホン膜]
得られたスパンボンド不織布50cm幅×10m長を、12m/minの速度で巻き出し、その上にポリスルホン(ソルベイアドバンスドポリマーズ社製の“Udel”(登録商標)-P3500)の16質量%ジメチルホルムアミド溶液(キャスト液)を45μm厚みで、室温(20℃)でキャストし、ただちに純水中に室温(20℃)で10秒間浸漬した後、75℃の温度の純水中に120秒間浸漬し、続いて90℃の温度の純水中に120秒間浸漬し、100N/全幅の張力で巻き取り、ポリスルホン膜を作製した。このとき、キャスト液の裏抜けがわずかに見られ、また巻き出しから巻き取りの間に膜の折れ曲がりも無く、製膜性は良好であった。結果を表に示す。
目付と厚さを、表のとおり変更したこと以外は、実施例1と同様にして、繊維径が10μmで、目付が36g/m2で、厚さが0.15mmで、可動非晶量が38%の仮接着状態のスパンボンド不織布(b)を得た。
得られた仮接着状態のスパンボンド不織布(b)を2枚重ね合わせ、その積層不織布を、上が硬度(Shore D)91の樹脂製の弾性ロールで、中が金属ロールで、下が硬度(Shore D)75の樹脂製の弾性ロールの1組の3本フラットロールの中-下間に通し熱圧着し、さらにその積層不織布を折り返して上-中間を通し熱圧着し、目付が72g/m2で、厚さが0.08mmで、表面の平滑度が35秒で、裏面の平滑度が13秒で、沸騰水カール高さが3.5mmのスパンボンド不織布を製造した。このときの3本フラットロールの表面温度は、上が130℃、中が190℃、下が140℃とし、線圧は1862N/cmとした。
[ポリスルホン膜]
得られたスパンボンド不織布50cm幅×10m長を用い、実施例1と同様の条件でポリスルホン膜を作成した。このとき、キャスト液の裏抜けが全く見られず、また巻き出しから巻き取りの間に膜の折れ曲がりも無く、製膜性は良好であった。結果を表に示す。
各フラットロールの表面温度を140℃としたこと以外は、実施例2と同様にして、繊維径が10μmで、目付が36g/m2で、厚さが0.13mmで、可動非晶量が32%の仮接着状態のスパンボンド不織布(c)を得た。
得られた仮接着状態のスパンボンド不織布(c)を2枚重ね合わせ、実施例2と同様の条件で積層熱圧着を実施し、目付が72g/m2で、厚さが0.09mmで、表面の平滑度が24秒で、裏面の平滑度が8秒で、沸騰水カール高さが6.2mmのスパンボンド不織布を製造した。
[ポリスルホン膜]
得られたスパンボンド不織布50cm幅×10m長を用い、実施例1と同様の条件でポリスルホン膜を作成した。このとき、キャスト液の裏抜けが全く見られず、また90℃の温度の純水中に浸漬している間に全長の30%程度で膜の折れ曲がりが見られたものの、巻き取りまでに元に戻り製膜性は概ね良好であった。結果を表に示す。
芯成分樹脂の溶融温度を290℃とし、鞘成分樹脂の溶融温度を270℃とし、そして紡糸速度を4500m/minとしたこと以外は、実施例2と同様にして、平均繊維径が10μmで、目付が36g/m2で、厚さが0.15mmで、可動非晶量が35%の仮接着状態のスパンボンド不織布(d)を得た。
得られた仮接着状態のスパンボンド不織布(d)を2枚重ね合わせ、実施例2と同様の条件で積層熱圧着を実施し、目付が72g/m2で、厚さが0.09mmで、表面の平滑度が28秒で、裏面の平滑度が10秒で、沸騰水カール高さが4.9mmのスパンボンド不織布を製造した。
[ポリスルホン膜]
得られた不織布50cm幅×10m長を用い、実施例1と同様の条件でポリスルホン膜を作成した。このときキャスト液の裏抜けが全く見られず、また90℃の温度の純水中に浸漬している間に全長の5%程度で膜の折れ曲がりが見られたものの、巻き取りまでに元に戻り製膜性は概ね良好であった。結果を表に示す。
積層熱圧着時の3本フラットロールの表面温度を、上が120℃、中が180℃、下が130℃としたこと以外は、実施例2と同様にして、目付が72g/m2で、厚さが0.10mmで、表面の平滑度が21秒で、裏面の平滑度が7秒で、沸騰水カール高さが7.7mmのスパンボンド不織布を製造した。
[ポリスルホン膜]
得られた不織布50cm幅×10m長を用い、実施例1と同様の条件でポリスルホン膜を作成した。このときキャスト液の裏抜けが全く見られず、また90℃の温度の純水中に浸漬している間に全長の40%程度で膜の折れ曲がりが見られたものの、巻き取りまでに元に戻り製膜性は概ね良好であった。結果を表に示す。
芯成分と鞘成分の質量比率を85/15としたこと以外は、実施例2と同様にして、繊維径が10μmで、目付が36g/m2で、厚さが0.15mmで、可動非晶量が38%の仮接着状態のスパンボンド不織布(e)を得た。
得られた仮接着状態のスパンボンド不織布(e)を2枚重ね合わせ、実施例2と同様の条件で積層熱圧着を実施し、目付が72g/m2で、厚さが0.08mmで、表面の平滑度が30秒で、裏面の平滑度が12秒で、沸騰水カール高さが4.1mmのスパンボンド不織布を製造した。
[ポリスルホン膜]
得られた不織布50cm幅×10m長を用い、実施例1と同様の条件でポリスルホン膜を作成した。このときキャスト液の裏抜けが全く見られず、また90℃の温度の純水中に浸漬している間に全長の5%程度で膜の折れ曲がりが見られたものの、巻き取りまでに元に戻り製膜性は概ね良好であった。結果を表に示す。
口金温度を290℃、紡糸速度を4200m/minとしたこと以外は、実施例4と同様にして、繊維径が10μmで、目付が36g/m2で、厚さが0.15mmで、可動非晶量が42%の仮接着状態のスパンボンド不織布(f)を得た。
得られた仮接着状態のスパンボンド不織布(f)を2枚重ね合わせ、実施例2と同様の条件で積層熱圧着を実施し、目付が72g/m2で、厚さが0.08mmで、表面の平滑度が37秒で、裏面の平滑度が14秒で、沸騰水カール高さが2.8mmのスパンボンド不織布を製造した。
[ポリスルホン膜]
得られたスパンボンド不織布50cm幅×10m長を用い、実施例1と同様の条件でポリスルホン膜を作成した。このとき、キャスト液の裏抜けが全く見られず、また巻き出しから巻き取りの間に膜の折れ曲がりも無く、製膜性は良好であった。結果を表に示す。
口金温度を290℃、紡糸速度を4100m/minとしたこと以外は、実施例4と同様にして、繊維径が10μmで、目付が36g/m2で、厚さが0.15mmで、可動非晶量が46%の仮接着状態のスパンボンド不織布(g)を得た。
得られた仮接着状態のスパンボンド不織布(g)を2枚重ね合わせ、実施例2と同様の条件で積層熱圧着を実施し、目付が72g/m2で、厚さが0.08mmで、表面の平滑度が40秒で、裏面の平滑度が15秒で、沸騰水カール高さが2.1mmのスパンボンド不織布を製造した。
[ポリスルホン膜]
得られたスパンボンド不織布50cm幅×10m長を用い、実施例1と同様の条件でポリスルホン膜を作成した。このとき、キャスト液の裏抜けが全く見られず、また巻き出しから巻き取りの間に膜の折れ曲がりも無く、製膜性は良好であった。結果を表に示す。
各フラットロール表面温度を150℃としたこと以外は、実施例1と同様にして、繊維径10μm、目付が72g/m2で、厚さが0.22mmで、可動非晶量が29%の仮接着状態のスパンボンド不織布(f)を得た。
得られた仮接着状態のスパンボンド不織布(f)を、実施例1と同様の条件で熱圧着を実施し、目付が72g/m2、厚さが0.10mm、表面の平滑度が17秒、裏面の平滑度が6秒、沸騰水カール高さが8.3mmのスパンボンド不織布を製造した。
[ポリスルホン膜]
得られた不織布50cm幅×10m長を用い、実施例1と同様の条件でポリスルホン膜を作成した。このときキャスト液の裏抜けがわずかに見られ、また90℃の温度の純水中に浸漬している間に全長の70%程度で膜の折れ曲がりが見られ、折れ曲がった状態で巻き取られ製膜性は不良であった。結果を表に示す。
固有粘度(IV)が0.65、融点が260℃、酸化チタンの含有量が0.3質量%のポリエチレンテレフタレート樹脂を、水分率10ppmに乾燥し、295℃の温度で溶融し、口金温度300℃、断面円形にて細孔から紡出した後、エジェクターにより紡糸速度4300m/分で紡糸して、移動するネットコンベアー上に繊維ウエブとして捕集した。
捕集した繊維ウエブを、上下1対の金属製フラットロール間に通し、各フラットロール表面温度が170℃で、線圧が490N/cmで予備熱圧着し、繊維径が10μm、目付が36g/m2で、厚さが0.16mm、可動非晶量が36%の仮接着状態のスパンボンド不織布(g)を得た。
得られた仮接着状態のスパンボンド不織布(g)を2枚重ね合わせ、その積層不織布を、上が硬度(Shore D)91の樹脂製の弾性ロールで、中が金属ロールで、下が硬度(Shore D)75の樹脂製の弾性ロールの1組の3本フラットロールの中-下間に通し熱圧着し、さらにその積層不織布を折り返して上-中間を通し熱圧着し、目付が72g/m2で、厚さが0.12mmで、表面の平滑度が12秒で、裏面の平滑度が3秒で、沸騰水カール高さが10.4mmのスパンボンド不織布を製造した。このときの3本フラットロールの表面温度は、上が130℃、中が200℃、下が140℃とし、線圧は1862N/cmとした。
[ポリスルホン膜]
得られた不織布50cm幅×10m長を用い、実施例1と同様の条件でポリスルホン膜を作成した。このときキャスト液の裏抜けがわずかに見られ、また90℃の温度の純水中に浸漬している間にほぼ全長で膜の折れ曲がりが見られ、折れ曲がった状態で巻き取られ製膜性は不良であった。結果を表に示す。
(積層熱圧着)
実施例2と同様にして得た仮接着状態のスパンボンド不織布(b)を2枚重ね合わせ、上下1対の金属製フラットロールの間に通し熱圧着し、目付が72g/m2で、厚さが0.08mmで、表面の平滑度が42秒で、裏面の平滑度が40秒で、沸騰水カール高さが2.9mmのスパンボンド不織布を製造した。このときの金属製フラットロールの表面温度は、上下ともに180℃とし、線圧は686N/cmとした。
[ポリスルホン膜]
得られた不織布50cm幅×10m長を用い、実施例1と同様の条件でポリスルホン膜を作成した。このとき巻き出しから巻き取りの間に膜の折れ曲がりは無かったものの、大部分でキャスト液の裏抜けが見られ、製膜性は不良であった。結果を表に示す。
PET:ポリエチレンテレフタレート
co-PET:共重合ポリエチレンテレフタレート
Claims (9)
- 2つの面の平滑度の差が10秒以上50秒以下であり、沸騰水中で5分間処理した後の沸騰水カール高さが0mm以上8.0mm以下であることを特徴とする不織布。
- 高融点重合体の周りに、該高融点重合体の融点よりも低い融点を有する低融点重合体を配した複合型繊維からなり、該高融点重合体と該低融点重合体との融点差が10℃以上140℃以下であり、該複合型繊維中に該高融点重合体が50質量%以上90質量%以下含まれてなる請求項1記載の不織布。
- 前記不織布がスパンボンド不織布である、請求項1または2記載の不織布。
- 請求項1~3のいずれかに記載の不織布からなる分離膜支持体。
- 請求項4記載の分離膜支持体の表面上に、分離機能を有する膜を形成してなる分離膜。
- 請求項5記載の分離膜を構成要素として含む流体分離素子。
- 請求項1~3のいずれかに記載の不織布を製造する方法であって、可動非晶量が10%以上70%以下であるポリエステル繊維からなる不織布シートを、1対のフラットロールで熱圧着することを特徴とする不織布の製造方法。
- 前記可動非晶量が40%以上70%以下である、請求項7記載の不織布の製造方法。
- 不織布シートがフラットロールで予備熱圧着された充填密度0.1以上0.3以下の不織布シートであり、該予備熱圧着に用いられるフラットロールの温度は不織布シートを構成する繊維の融点よりも低く、予備熱圧着におけるフラットロールの温度と不織布シートを構成する繊維の融点との差が30℃以上130℃以下である請求項7または8記載の不織布の製造方法。
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ES14847466T ES2750575T3 (es) | 2013-09-26 | 2014-09-24 | Tejido no tejido, soporte de membrana de separación, membrana de separación, elemento de separación de fluido y método para la fabricación de tejido no tejido |
JP2014551450A JP6492662B2 (ja) | 2013-09-26 | 2014-09-24 | 不織布、分離膜支持体、分離膜、流体分離素子および不織布の製造方法 |
KR1020167007660A KR102137425B1 (ko) | 2013-09-26 | 2014-09-24 | 부직포, 분리막 지지체, 분리막, 유체 분리 소자 및 부직포의 제조 방법 |
EP14847466.1A EP3051014B1 (en) | 2013-09-26 | 2014-09-24 | Non-woven fabric, separation membrane support, separation membrane, fluid separation element, and method for manufacturing non-woven fabric |
CN201480053261.8A CN105593423B (zh) | 2013-09-26 | 2014-09-24 | 无纺布、分离膜支持体、分离膜、流体分离元件及无纺布的制造方法 |
US15/024,592 US20160228824A1 (en) | 2013-09-26 | 2014-09-24 | Non-woven fabric, separation membrane support, separation membrane, fluid separation element, and method of manufacturing non-woven fabric |
SA516370809A SA516370809B1 (ar) | 2013-09-26 | 2016-03-24 | قماش غير منسوج، وحامل غشاء فصل، وعنصر فصل مائع، وطريقة لتصنيع القماش غير المنسوج |
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JP2019093366A (ja) * | 2017-11-27 | 2019-06-20 | 東レ株式会社 | 分離膜 |
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EP3497145B1 (en) * | 2016-08-09 | 2021-07-07 | Solvay Specialty Polymers Italy S.p.A. | Composition comprising aromatic and fluorinated polymers and use thereof |
KR102313168B1 (ko) * | 2016-09-02 | 2021-10-15 | 도레이 카부시키가이샤 | 스판본드 부직포 및 그의 제조 방법 |
WO2018174224A1 (ja) * | 2017-03-24 | 2018-09-27 | 三菱製紙株式会社 | 半透膜支持体 |
EP3815772A4 (de) * | 2018-06-29 | 2022-04-06 | Mitsubishi Paper Mills Limited | Semipermeabler membranträger zur membranbioreaktorbehandlung |
JP7226555B2 (ja) * | 2020-03-11 | 2023-02-21 | Jfeスチール株式会社 | 容器用樹脂被覆金属板 |
CN111485453A (zh) * | 2020-04-10 | 2020-08-04 | 宝鸡科达特种纸业有限责任公司 | 一种分离膜支撑用无纺布的制造方法 |
CN111888947A (zh) * | 2020-09-09 | 2020-11-06 | 江苏久朗高科技股份有限公司 | 一种高透气量空气净化复合膜、覆合装置及其制备方法 |
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US20160228824A1 (en) | 2016-08-11 |
SA516370809B1 (ar) | 2019-10-03 |
JPWO2015046215A1 (ja) | 2017-03-09 |
KR102137425B1 (ko) | 2020-07-24 |
KR20160062008A (ko) | 2016-06-01 |
EP3051014B1 (en) | 2019-09-18 |
CN105593423A (zh) | 2016-05-18 |
EP3051014A1 (en) | 2016-08-03 |
ES2750575T3 (es) | 2020-03-26 |
CN105593423B (zh) | 2018-11-06 |
JP6492662B2 (ja) | 2019-04-03 |
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