CN101068682A - Laminated thermoplastic resin film and laminated thermoplastic resin film roll - Google Patents
Laminated thermoplastic resin film and laminated thermoplastic resin film roll Download PDFInfo
- Publication number
- CN101068682A CN101068682A CN 200580040981 CN200580040981A CN101068682A CN 101068682 A CN101068682 A CN 101068682A CN 200580040981 CN200580040981 CN 200580040981 CN 200580040981 A CN200580040981 A CN 200580040981A CN 101068682 A CN101068682 A CN 101068682A
- Authority
- CN
- China
- Prior art keywords
- film
- thermoplastic resin
- phase
- particle
- resin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 150
- 239000004814 polyurethane Substances 0.000 claims abstract description 170
- 229920005989 resin Polymers 0.000 claims abstract description 168
- 239000011347 resin Substances 0.000 claims abstract description 168
- 239000002245 particle Substances 0.000 claims description 219
- 238000000034 method Methods 0.000 claims description 195
- 239000010410 layer Substances 0.000 claims description 167
- 239000000463 material Substances 0.000 claims description 156
- 229920002635 polyurethane Polymers 0.000 claims description 143
- 229920006267 polyester film Polymers 0.000 claims description 116
- 229920001634 Copolyester Polymers 0.000 claims description 101
- 239000000203 mixture Substances 0.000 claims description 80
- 229920000728 polyester Polymers 0.000 claims description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000003431 cross linking reagent Substances 0.000 claims description 56
- 230000003287 optical effect Effects 0.000 claims description 49
- 239000012528 membrane Substances 0.000 claims description 46
- 239000002346 layers by function Substances 0.000 claims description 31
- 239000003595 mist Substances 0.000 claims description 27
- 238000004621 scanning probe microscopy Methods 0.000 claims description 20
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 14
- 239000004925 Acrylic resin Substances 0.000 claims description 13
- 229920000178 Acrylic resin Polymers 0.000 claims description 13
- 150000007974 melamines Chemical class 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- 238000003475 lamination Methods 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 238000005728 strengthening Methods 0.000 claims description 6
- 238000003556 assay Methods 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 claims 1
- 239000000523 sample Substances 0.000 abstract description 17
- 238000005259 measurement Methods 0.000 abstract description 3
- 229920005749 polyurethane resin Polymers 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 420
- 238000000576 coating method Methods 0.000 description 366
- 239000011248 coating agent Substances 0.000 description 364
- 239000012530 fluid Substances 0.000 description 244
- 230000000052 comparative effect Effects 0.000 description 143
- 238000001035 drying Methods 0.000 description 140
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 119
- 230000006978 adaptation Effects 0.000 description 105
- 239000004094 surface-active agent Substances 0.000 description 91
- 239000007864 aqueous solution Substances 0.000 description 78
- 238000005191 phase separation Methods 0.000 description 73
- 239000006185 dispersion Substances 0.000 description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 67
- 239000002585 base Substances 0.000 description 61
- 238000004519 manufacturing process Methods 0.000 description 61
- 238000001914 filtration Methods 0.000 description 56
- 238000011282 treatment Methods 0.000 description 54
- 238000002360 preparation method Methods 0.000 description 42
- 239000002904 solvent Substances 0.000 description 42
- -1 Merlon (PC) Chemical compound 0.000 description 40
- 239000007787 solid Substances 0.000 description 38
- 239000000126 substance Substances 0.000 description 36
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 33
- 230000008859 change Effects 0.000 description 33
- 229920000877 Melamine resin Polymers 0.000 description 32
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 29
- 239000000470 constituent Substances 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 26
- 239000003814 drug Substances 0.000 description 25
- 230000008569 process Effects 0.000 description 23
- 239000000377 silicon dioxide Substances 0.000 description 23
- 229920002799 BoPET Polymers 0.000 description 21
- 238000009792 diffusion process Methods 0.000 description 21
- 239000011164 primary particle Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 20
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000009998 heat setting Methods 0.000 description 19
- 239000012535 impurity Substances 0.000 description 19
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 16
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 16
- 235000017557 sodium bicarbonate Nutrition 0.000 description 16
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 15
- 238000010586 diagram Methods 0.000 description 15
- 229920001155 polypropylene Polymers 0.000 description 15
- 238000002203 pretreatment Methods 0.000 description 15
- 230000006870 function Effects 0.000 description 14
- 238000007792 addition Methods 0.000 description 13
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical group OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 239000002390 adhesive tape Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 239000008187 granular material Substances 0.000 description 11
- 230000008676 import Effects 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 238000010791 quenching Methods 0.000 description 11
- 230000000171 quenching effect Effects 0.000 description 11
- 239000002202 Polyethylene glycol Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 230000033228 biological regulation Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
- 230000007547 defect Effects 0.000 description 9
- 239000004645 polyester resin Substances 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 9
- 238000007639 printing Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000007859 condensation product Substances 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 230000033001 locomotion Effects 0.000 description 7
- 239000010813 municipal solid waste Substances 0.000 description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 7
- 150000002918 oxazolines Chemical class 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 230000003746 surface roughness Effects 0.000 description 7
- 230000010148 water-pollination Effects 0.000 description 7
- NEOGGGHDLGYATP-UHFFFAOYSA-N 1,6-dimethylimidazo[4,5-b]pyridin-2-amine Chemical compound CC1=CN=C2N=C(N)N(C)C2=C1 NEOGGGHDLGYATP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000010954 inorganic particle Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005204 segregation Methods 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229940051250 hexylene glycol Drugs 0.000 description 3
- 210000004276 hyalin Anatomy 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- UUABJBNMBCIBFA-UHFFFAOYSA-N 1-hydroxy-2-(2-hydroxyethoxy)ethanesulfonic acid Chemical compound OCCOCC(O)S(O)(=O)=O UUABJBNMBCIBFA-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 101000598921 Homo sapiens Orexin Proteins 0.000 description 2
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- IEBJZLRZRKTGFN-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C1=CC=CC=C1 Chemical compound N=NC=NN.N=NC=NN.C1=CC=CC=C1 IEBJZLRZRKTGFN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- LMHDQOWNISVSPD-UHFFFAOYSA-N fluorine(1+) Chemical compound [F+] LMHDQOWNISVSPD-UHFFFAOYSA-N 0.000 description 2
- MSYLJRIXVZCQHW-UHFFFAOYSA-N formaldehyde;6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound O=C.NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 MSYLJRIXVZCQHW-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000003703 image analysis method Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000007591 painting process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000011182 sodium carbonates Nutrition 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- VEGNIXCUDMQGFZ-UHFFFAOYSA-N 1-[3-[3-[2,3-bis(oxiran-2-ylmethoxy)propoxy]-2-hydroxypropoxy]-2-(oxiran-2-ylmethoxy)propoxy]-3-(oxiran-2-ylmethoxy)propan-2-ol Chemical compound C1OC1COCC(OCC1OC1)COCC(O)COCC(OCC1OC1)COCC(O)COCC1CO1 VEGNIXCUDMQGFZ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BEXMOORQHNTVJZ-UHFFFAOYSA-N amino(oxo)methanesulfonic acid Chemical group NC(=O)S(O)(=O)=O BEXMOORQHNTVJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000003938 benzyl alcohols Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Images
Landscapes
- Laminated Bodies (AREA)
Abstract
This invention provides a laminated thermoplastic resin film having excellent adhesion and antiblocking properties. The laminated thermoplastic resin film comprises a thermoplastic resin film and a covering layer provided on one side or both sides of the thermoplastic resin film and comprising an interpolyester resin and a polyurethane resin. The structure of the covering layer is that microphase separated or nano phase separated structure is observed in PEs phase A composed mainly of a copolyPEs resin and PU phase B composed mainly of a PU resin. The area ratio of PEs phase A (dark color phase in phase image) on the covering layer surface (PEs surface fraction) defined by formula (1) is not less than 35% and less than 90% in a measurement area of 5 m 5 m as observed in a phase measurement mode under a scanning probe microscope. PEs surface fraction (%) = (area of PEs phase A/measuring area) x 100 (1).
Description
Technical field
The present invention relates to a kind of laminated thermoplastic resin film and aforementioned lamination thermoplastic resin membrane is wound into the laminated thermoplastic resin film roll that the roller shape forms, described laminated thermoplastic resin film is mainly used in the antireflection film relevant with display, the light diffusing sheet material, the prism sheet material, infrared absorbing film, transparent and electrically conductive film, antiglare film etc., with various functional layer (hard conatings, light diffusion layer, layers of prisms, the infrared ray absorbing layer, transparency conducting layer, antiglare layer etc.) adaptation is good, and block resistance, the transparency is good, is formed with the cover layer with the special phase separation structure that becomes optical functional film or optical functional sheet material.
Background technology
In general, at the base material of the optical functional film of the member that is used for LCD (LCD), plasma scope displays such as (PDP), use the hyaline membrane that constitutes by PETG (PET), acrylate, Merlon (PC), cellulose triacetate (TAC), polyolefin etc. usually.When these base material films are used for various optically functional film, on the base material film upper strata at all according to the functional layer of various uses.For example, in LCD (LCD), can enumerate the layers of prisms that prevents the injured diaphragm (hard conating) in surface, prevents anti-reflection layer (AR layer), the optically focused that is used for light and diffusion that outer light is mirrored, the functional layers such as light diffusion layer of raising brightness.In these base materials, consider from aspects such as the good transparency, dimensional stability, resistances to chemical reagents, use the base material of double axial orientated polyester film especially widely as various optical functional films.
In general, the situation of the Biaxially oriented thermoplastic film of double axial orientated polyester film and Biaxially orientated polyamide film and so on has following shortcoming: because film apparent height crystalline orientation, therefore, with the adaptation shortcoming of various coating, adhesive, printing ink etc.Therefore, motion at present has the method for the Biaxially oriented thermoplastic resin film surface being given highly adhesive by the whole bag of tricks.
Also motion has following method: in the film that does not have polar group of polyolefin film and so on, owing to be short of very much with the adaptation of various coating, adhesive, printing ink etc., so after carrying out physical treatments such as Corona discharge Treatment, flame treatment and chemical treatment in advance, give highly adhesive to the film surface by the whole bag of tricks.
For example, well-known method is, surface the thermoplastic resin membrane of base material, with various resins such as polyester, acrylate, polyurethane, acrylic acid-grafted polyester is tectal main composition composition, utilize rubbing method that aforementioned cover layer is set on base material film, give highly adhesive to base material film thus.In this rubbing method, the following two kinds of methods of industrial extensive execution: after the thermoplastic resin membrane before crystalline orientation finished directly or as required implements Corona discharge Treatment, to contain the solution of aforementioned resin or the water-based coating fluid of the dispersion that resin dispersion forms will be coated on the base material film with dispersant, after the drying, at least stretch along uniaxial orientation, then, implement heat treatment, make the method (so-called online coating) of thermoplastic resin membrane's crystalline orientation end; And after making the thermoplastic resin membrane, behind the coating fluid of coating water system or solvent system on this film, carry out dry method (so-called off-machine coating method).
Display such as LCD, PDP maximizes and cost degradation every year, in the manufacturing process of optical functional film that uses as its member or optical functional sheet material, implements the high speed of speed of production usually.Follow the high speed of this manufacturing process, more be easy to generate the stress of following cure shrinkage in the functional layer of hard conating, diffusion layer, layers of prisms and so on and the interface of base material film.Therefore, when in order to make display optical functional film or optical functional sheet material being cut into specific size, following problem can take place, when the adaptation in the aforementioned interface was insufficient, peeled off especially easily the end.Along with the maximization of the film that is wound into the roller shape and the high speed of the speed of production in the manufacturing process, the interface peel that the impact when this tendency can cause by cutting causes is more remarkable, and present adaptation level is insufficient.
And, in order to form the processing agent that functional layers such as aforementioned layers of prisms and diffusion layer are used, consider from reducing the carrying capacity of environment aspect, scarcely directly on base material film, be coated with processing agent with organic solvent diluting.Therefore, owing to can not obtain sometimes improving effect by the tectal wetability that organic solvent brings, so require higher adaptation.On the other hand, in the purposes of as hard conating, paying attention to flatness, obtain the good flat effect that is coated with, use the organic solvent diluting processing agent mostly in order to reduce processing agent viscosity.At this moment, require the cover layer of laminated thermoplastic resin film to have suitable solvent resistance.
In order to improve the adaptation between functional layer and base material film, the general method of in constituting tectal resin, using the low resin of vitrification point of using.But, when using the low resin of vitrification point, symphysis continuously is wound into the roller shape, when roller shape film begins film rolled, the tendency that has block resistance to reduce.
In addition, in recent years,, advancing the maximization that is used for the processing machine of functional layer such as lamination hard conating and diffusion layer on base material film for cost degradation, and the maximization in the roller footpath of the highly adhesive film that uses as base material film.Accompany with it, in order to prevent weaving of roller, when reeling with high-tension, particularly the volume core by roller carries out crimping with high pressure, therefore more is easy to generate adhesion.
In order to improve block resistance, the general employing given concavo-convex, as to reduce contact area method to the film surface.Concavo-convex for the film surface is given, conventional method is: the method for the particle that the method for the inorganic particle that contains in increase cover layer or the base material film or the content of organic granular or use particle diameter are big.But, general different with the refractive index that is used for tectal resin by the refractive index of commercially available available particle, and owing to around particle, form the space along with the stretch processing of film, so in these methods, the light penetration reduction of generation film, mist degree rising etc.Particularly the transparency that is required by the base material film of optical functional film or optical functional sheet material reduces.That is, in existing method, because the new problem of following the maximization of the high speed of operation and film coil diameter to produce, so when keeping the transparency, improve with the adaptation and the block resistance of functional layer very difficult.
On the other hand, the chance at the outdoor application information terminal increases day by day as mobile phone, PDA, sports type computer.And, as be used for the touch panel of auto-navigation system etc., the material that uses in the higher car of summer temp also increases day by day.Therefore, even in this purposes, require at the also few film of the severe rugged environment low-grades qualitative changeization of so high temperature, high humidity, be the good film of the hot adaptation of moisture-proof.
Particularly, known double axial orientated polyester film is that the adaptation of coating agent of main component is poor with the acrylic resin with what be used for prism lens and hard conating etc.Therefore, for formed the tectal material that constitutes by polyurethanes resin etc. on the polyester film surface, various motions (for example, with reference to patent documentation 1) are arranged.But the problem of its existence is, in having formed the tectal material that is made of the polyurethanes resin, though improve with the closing force of functional layer such as hard conating, but insufficient with the closing force as the polyester film of base material, the result is insufficient in the interface of cover layer and functional layer adaptation.In addition, because the tectal cross-linkage of resin of formation is also low, the hot adaptation of moisture-proof is poor, so in the purposes of the hot adaptation of strong request moisture-proof, can't satisfy the aforementioned market demand fully sometimes.
Patent documentation 1: Japanese kokai publication hei 6-340049 communique
In addition, motion has following method: utilize online coating, on the base film that constitutes by the biaxial orientation polyethylene glycol terephthalate, be provided with polyester resin and polyurethanes resin is the resin combination layer of main composition composition, improve the adaptation (for example, with reference to patent documentation 2) of functional layers such as substrate polyester film and printing ink.Specifically, longitudinally carrying out on the polyester film of uniaxial tension, coating contains copolyester resinoid and polyurethanes resin (=20/80; Quality %) behind the water dispersible coating fluid, imports the tentering device, behind drying, the cross directional stretch, under 220 ℃, carry out heat setting, obtain the highly adhesive double axial orientated polyester film.
Patent documentation 2: Japanese Patent Publication 64-6025 communique
But, in patent documentation 2 described methods, though its adaptation improves, but, in recent years, can not satisfy simultaneously as being used for the desired base material film of base material film of optical functional film or optical functional sheet material and adaptation, block resistance, the transparency of functional layers such as hard conating and diffusion layer.In addition, because the tectal cross-linkage of resin of formation is also low, the hot adaptation of moisture-proof is poor, so in the purposes of the hot adaptation of strong request moisture-proof, can't fully satisfy aforementioned market demands sometimes.
The applicant's motion has a kind of layered polyester film, described layered polyester film is on the base film that is made of the biaxial orientation polyethylene glycol terephthalate, be provided with the resin combination layer that the inorganic particle that is added with polyester resin and polyurethanes resin and suitable particle diameter forms, and, keep on the one hand as the transparency of optics with the very important characteristic of base material film, can fully satisfy adaptation on the other hand from the market demands level, and, its optical defect few (for example, with reference to patent documentation 3,4).Specifically, disclose a kind of highly adhesive double axial orientated polyester film, described double axial orientated polyester film is to obtain by the following method: longitudinally carrying out on the polyester film of uniaxial tension, coating contains copolyester resinoid and polyurethanes resin (=20/80; Quality %) and behind the water dispersible coating fluid of the different silicon oxide particle of two kinds of average grain diameters, anionic surfactant, imports the tentering device, behind dry, the cross directional stretch, under 240 ℃, carry out heat setting.
The highly adhesive double axial orientated polyester film that is obtained by patent documentation 3 and 4 has good adaptation and block resistance, the transparency, and optical defects such as impurity, scratch are improved significantly, satisfies the characteristic that requires at present.But, as previously mentioned, follow cost degradation in recent years, the big pictureization of display, to the adaptation of functional layers such as the desired base material film of base material film used as optical functional film or optical functional sheet material and hard conating, diffusion layer, layers of prisms and block resistance require level more and more harsher, can not fully satisfy the quality of requirement in the market.In addition, because the tectal cross-linkage of resin of formation is also low, the hot adaptation of moisture-proof is poor, so in the purposes of the hot adaptation of strong request moisture-proof, can not fully satisfy aforementioned market demands sometimes.
Patent documentation 3: TOHKEMY 2000-323271 communique
Patent documentation 4: TOHKEMY 2000-246855 communique
In addition, in order to improve the uniformity of adaptation, the applicant's motion has a kind of invention (for example, with reference to patent documentation 5) that relates to the easy adhesive film volume of the change that reduces coating weight.In the embodiment of patent documentation 5, record a kind of highly adhesive double axial orientated polyester film, described highly adhesive double axial orientated polyester film obtains by the following method: longitudinally carrying out on the polyester film of uniaxial tension, coating contains copolyester resinoid and polyurethanes resin (=50/50; Quality %), after average grain diameter is the silicon oxide particle of 1.4 μ m and water dispersible coating fluid that fluorine is surfactant, after 120 ℃ of following dryings, carry out cross directional stretch, then, under 220 ℃, carry out heat setting with drying oven.The film that obtains twists in the film volume integral body has good adaptation equably, satisfies the level that requires from market.But, as previously mentioned, for desired block resistance in recent years, can't be fully satisfied.In addition, because the tectal cross-linkage of resin of formation is also low, the hot adaptation of moisture-proof is poor, so in the purposes of the hot adaptation of strong request moisture-proof, can not fully satisfy aforementioned market demands sometimes.
Patent documentation 5: TOHKEMY 2004-10669 communique
In addition, disclose a kind of biaxially-stretched film, described biaxially-stretched film obtains by the following method: will contain by sour composition is that terephthalic acid (TPA)/different phthalic acid/trimellitic acid/decanedioic acid, diol component are ethylene glycol/neopentyl glycol/1, the coating fluid of polyester 100 mass parts that the 4-butanediol constitutes, methylol type melamine class crosslinking agent 15 mass parts, particle 0.7 mass parts, be coated on the PETG film that has longitudinally carried out uniaxial tension, further carry out cross directional stretch, heat setting, relaxation processes (for example, with reference to patent documentation 6).But, in the method, though the hot adaptation of its moisture-proof improve,, the initial stage closing force of functional layer such as itself and hard conating is poor, can not fully satisfy the desired quality of optical film in recent years.
Patent documentation 6: TOHKEMY 2004-299101 communique
That is, prior art also can't fully satisfy following requirement: keep high transparent on the one hand, have the adaptation that can bear the high-speed cutting that requires in recent years, the block resistance that can adapt with the maximization of film coil diameter on the other hand.In addition, under the severe rugged environment of high temperature, high humidity, descending for few hot adaptation of moisture-proof for adaptation, also is inadequate.
Summary of the invention
The present invention finishes in order to solve aforementioned existing issue, and its 1st purpose is, provides a kind of adaptation and block resistance very good laminated thermoplastic resin film.In addition, the 2nd purpose of the present invention is, provide a kind of except adaptation and block resistance, laminated thermoplastic resin film that the hot adaptation of moisture-proof is also very good.In addition, the 3rd purpose of the present invention is, provide a kind of except adaptation and block resistance, laminated thermoplastic resin film that the transparency is also very good.And the 4th purpose of the present invention is, a kind of adaptation, block resistance, the hot adaptation of moisture-proof is very good and changes these qualities are few laminated thermoplastic resin film roll are provided.
Aforementioned problems can utilize following solution to finish.
Promptly, in the laminated thermoplastic resin film of the present invention the 1st invention is, a kind of laminated thermoplastic resin film, described laminated thermoplastic resin film has the copolyester of containing resinoid and the resinoid cover layer of polyurethane at thermoplastic resin membrane's one or both sides, it is characterized in that, aforementioned cover layer have to be the polyester phase A of main component with the copolyester resinoid with the polyurethanes resin be main component polyurethane mutually B carried out microphase-separated or received the structure that is separated, and, when observing scanning probe microscopy with the phase determination pattern, mensuration planimeter with 5 μ m * 5 μ m, area ratio (PEs surface branch rate) with the polyester phase A (showing darker shade in the phase place picture) of the aforementioned cover surface of following formula (1) definition is more than 35%, and is lower than 90%.
PEs surface branch rate (%)=(area of polyester phase A/mensuration area) * 100 ... (1)
The 2nd invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that the copolyester resinoid carries out crosslinked with at least a crosslinking agent that is selected from epoxies crosslinking agent, the melamine class crosslinking agent, oxazoline class crosslinking agent.
The 3rd invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that aforementioned thermoplastic resin film or thermoplastic resin membrane and cover layer contain particle.
The 4th invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that the aforementioned thermoplastic resin film is substantially devoid of particle, and only cover layer contains particle.
The 5th invention is the described laminated thermoplastic resin films of the 3rd or 4 inventions, it is characterized in that aforementioned particles is a silicon oxide particle.
The 6th invention is the described laminated thermoplastic resin films of the 3rd or 4 inventions, it is characterized in that the particle in the cover layer is stored among polyester phase A or the polyurethane phase B partially.
The 7th invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that the aforementioned thermoplastic resin film is double axial orientated polyester film or Biaxially orientated polyamide film.
The 8th invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that, the following of aforementioned PEs surface branch rate is limited to 40%.The 9th invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that, the following of aforementioned PEs surface branch rate is limited to 45%.
The 10th invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that, is limited to 80% on the branch rate of aforementioned PEs surface.The 11st invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that, is limited to 75% on the branch rate of aforementioned PEs surface.
The 12nd invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that, observe aforementioned tectal surface with the phase determination pattern of scanning probe microscopy, in the phase place picture of the interface profile of strengthening light colour phase and darker shade, with the mensuration planimeter of 5 μ m * 5 μ m, the fractal dimension that uses the box-counting method to obtain from the boundary line (profile at interface) of light colour phase and darker shade is 1.60～1.95.
The 13rd invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that the tectal stiffness of following definitions is 3.0～15.0nm.
Need to prove, so-called cover layer stiffness is meant: with the sapphire pin of the subsidiary radius 75 μ m of front end, apply loading 5gf, make tectal surface in spite of wound, the adjacent protuberance and the difference of height of recess when measuring the concaveconvex shape of measure hindering at 50 places with the non-contact three-dimensional surface profile measuring instrument are obtained the mean value of each measured value.
The 14th invention is the described laminated thermoplastic resin films of the 3rd or 4 inventions, it is characterized in that aforementioned lamination thermoplastic resin membrane's mist degree is below 1.5%.
The 15th invention is the described laminated thermoplastic resin film of the 14th invention, it is characterized in that it is as the base material film of optical functional film or optical functional sheet material.
The 16th invention is the described laminated thermoplastic resin film of the 15th invention, it is characterized in that described optical functional film or optical functional sheet material are any one of hard coat film, antireflection film, light diffusing sheet material, prism sheet material, transparent and electrically conductive film, near-infrared absorption film, electro-magnetic wave absorption film.
The 17th invention is the described laminated thermoplastic resin film of the 1st invention, it is characterized in that, and in aforementioned tectal one side at least, will be that the functional layer lamination of main composition composition forms with the acrylic resin.
The 18th invention is a kind of laminated thermoplastic resin film roll, for one or both sides the thermoplastic resin membrane, has resinoid tectal the 1st～the 17th each the described thermoplastic resin membrane of invention of the copolyester of containing resinoid and polyurethane, more than long 1000m, the above size continuous reeling of wide 50mm becomes the roller shape to form, it is characterized in that, during with the area ratio (PEs surface branch rate) of the polyester phase A (showing darker shade in the phase place picture) of the aforementioned cover surface of 100m measuring space, the maximum of the PEs surface branch rate in the cover surface of length direction and the difference of minimum of a value are below 15% at the length direction of film.
Need to prove, the assay method of the PEs surface branch rate in the above-mentioned cover surface is as follows: roll out aforementioned lamination thermoplastic resin membrane volume, length direction (MD) at this film, one end in the constant zone that the film rerum natura is stable is set at the 1st end, when the other end is set at the 2nd end, carries out the first time and measure below the inboard 2m of the 1st end, in addition, below the inboard 2m of the 2nd end, finally measure, simultaneously, carry out once since the 1st the every 100m in mensuration place.
The 19th invention is the described laminated thermoplastic resin film roll of the 18th invention, it is characterized in that, roll out aforementioned lamination thermoplastic resin membrane volume, at width film is divided into 4 equal portions, when central portion was separately measured the area ratio (PEs surface branch rate) of the polyester phase A (showing darker shade in the phase place picture) of cover surface, the maximum of the PEs surface branch rate in the cover surface of width and the difference of minimum of a value were below 10%.
For laminated thermoplastic resin film of the present invention, owing to constitute tectal two kinds of resins, be copolyester resinoid and polyurethanes resin, for be the polyester phase A of main component with the copolyester resinoid with the polyurethanes resin be main component polyurethane mutually B have special microphase-separated or receive the structure that is separated, and the area occupation ratio of the polyester phase A of cover surface (PEs surface branch rate) is specific scope, so good with the adaptation and the block resistance of functional layers such as hard conating, diffusion layer, layers of prisms.
In addition, in cover layer, with at least a crosslinking agent that is selected from epoxies crosslinking agent, the melamine class crosslinking agent, oxazoline class crosslinking agent, it is crosslinked that aforementioned copolymer polyester resin is carried out, and can improve the hot adaptation of moisture-proof thus.
And, since by only make cover layer contain the particle of specified quantitative specified particle diameter or make that particle is stored in the polyester phase A of cover surface or polyurethane phase B partially any mutually in, can when highly keeping the transparency, improve block resistance, handling, marresistance, therefore, be useful as the optical functional film of the requirement for height transparency or the base material film of optical functional sheet material.Particularly when cover layer contains silicon oxide particle and since can make silicon oxide particle be stored in partially polyurethane mutually in, therefore, can remedy the defective of the polyurethane of block resistance difference.
Description of drawings
Fig. 1 is a key diagram of observing the phase place picture of the cover surface in the laminated thermoplastic resin film of the present invention with the phase determination pattern of scanning probe microscopy,
Fig. 2 strengthens light colour mutually and the key diagram of the phase place picture of the interface profile of darker shade with image processing software in the phase place picture of Fig. 1.
Fig. 3 is in the light colour of strengthening Fig. 2 mutually and in the phase place picture of the interface profile of darker shade, the key diagram of the phase place picture that forms mutually with image processing software time scumbling.
Fig. 4 be the light colour of strengthening Fig. 2 mutually and represent in the phase place picture of the interface profile of darker shade light colour mutually with the key diagram of the boundary line of darker shade.
Fig. 5 is the key diagram that the difference of height of 3 D non-contacting type surface profile measuring instrument, the wound when having the surface configuration of wound with waveguide mode instrumentation cover surface is used in expression.
Fig. 6 is in embodiment 1-20 and comparative example 1,4-6,8-13, the PEs surface branch rate of expression cover surface and the not corresponding key diagram of PEs mass ratio in the tectal resinous principle.
Fig. 7 be the expression coating fluid pallet, circulation with jar circulation with jar, modulation with jar configuration and the key diagram of the circulating path of coating fluid.
Fig. 8 is the key diagram with the phase place picture of the cover surface in the laminated thermoplastic resin film of phase determination pattern observation other embodiment of the present invention of scanning probe microscopy.
Fig. 9 strengthens light colour mutually and the key diagram of the phase place picture of the interface profile of darker shade with image processing software in the phase place picture of Fig. 8.
Figure 10 is in the light colour of having strengthened Fig. 9 mutually and in the phase place picture of the interface profile of darker shade, the key diagram of the phase place picture that forms mutually with image processing software time scumbling.
Figure 11 be the light colour of having strengthened Fig. 9 mutually and represent in the phase place picture of the interface profile of darker shade light colour mutually with the key diagram of the boundary line of darker shade.
Figure 12 is that the 3 D non-contacting type surface profile measuring instrument is used in expression, the key diagram of the difference of height of the wound the during surface configuration of the wound different with Fig. 4 that has with waveguide mode instrumentation cover surface.
Figure 13 is in embodiment 21-43 and comparative example 14,17-19,21-26, the PEs surface branch rate of expression cover surface and the not corresponding key diagram of PEs mass ratio in the tectal resinous principle.
Label declaration
1: darker shade (is the polyester phase A of main component with the copolyester resinoid)
2: light colour phase (is the polyurethane phase B of main component with the polyurethanes resin)
3: the projection that causes by particle
4: the line of strengthening the interface profile of light colour phase and darker shade
5: the concavo-convex contour curve of cover surface
6: the bottom of wound
7: the top of wound
8: embodiment 1-20
9: comparative example 1,4-6,8-13
10: coating machine
11: the coating fluid pallet
12: mould
13: the circulation jar
14: preparing tank
15: base material film
16: pinch roll
17: embodiment 21-43
18: comparative example 14,17-19,21-26
The specific embodiment
In the present invention, at first the definition of the described adaptation of problem, block resistance, the transparency, the hot adaptation of moisture-proof is described.
So-called adaptation is meant among the present invention: on the cover layer face of film, form to utilize ultraviolet ray to make the photo-hardening acrylic resin of solvent cutback solidify the hard conating that forms, utilize adhesive tape that it is carried out the adaptation at the tectal interface of aforementioned acrylic compounds hard conating after 10 grid disbonded tests (100 components) and film respectively repeatedly.In the present invention, will be with the adaptation of following formula definition more than 80% be set at qualified.Preferred more than 85%, preferred especially more than 90%.
Adaptation (%)=(1-component peel off number/100) * 100
In addition, so-called block resistance is meant among the present invention: make between the cover layer face of 2 film samples overlappingly, it is applied 1kgf/cm under 50 ℃, the environment of 60%RH
2Pressure driving fit after 24 hours, peel off, it is qualified for " cover layer do not shift can peel off gently " is set at that it is peeled off state.
And the film that the transparency among the present invention is very good is meant that mist degree is the film below 1.5%.Preferred mist degree is below 1.0%.
In addition, the hot adaptation of so-called moisture-proof is meant among the present invention: use the film sample of laminated thermoplastic resin film after preserving 1000 hours under the environment of 60 ℃ of temperature, relative humidity 90%, on the cover layer face of film, form to utilize ultraviolet ray to make the photo-hardening acrylic resin of no-solvent type solidify the hard conating that forms, utilize adhesive tape to carry out the adaptation at the tectal interface of aforementioned acrylic compounds hard conating after the grid disbonded test (100 components) and film.In the present invention, will be with the adaptation of following formula definition more than 71% be set at qualified.
Adaptation (%)=(1-component peel off number/100) * 100
In the present invention, in order to obtain having the so good adaptation and the laminated thermoplastic resin film of block resistance, make tectal surface manifest special micro phase separation structure or the phase separation structure of receiving is important.This special phase separation structure can form by the following method: select to be used to form the kind of resin composition, surfactant of tectal coating fluid and concentration, coating weight, tectal drying condition and heat-setting condition etc. and these conditions are controlled.
In addition, in order to obtain having the laminated thermoplastic resin film of the hot adaptation of moisture-proof, it is important making the tectal resin-shaped of formation become cross-linked structure.In addition, become cross-linked structure, suitably select kind, amount and the heat-treat condition (condition of cure) of crosslinking agent in order to make the tectal resin-shaped of formation.
At first,, for typical example its summary is described, be not limited to this typical example certainly with PETG (below, slightly be called PET) for the preparation method of laminated thermoplastic resin film of the present invention.
With being substantially free of to give easy sliding is after the PET particle of the particle of purpose fully carries out vacuum drying, supplies with extruder, becomes sheet 280 ℃ of following melt extruded, makes its cooling curing, with non-oriented PET sheet material system film.At this moment, at any part that molten resin is maintained at about 280 ℃, carry out high accuracy in order to remove the field trash that contains in the resin and filter.The non-oriented sheet material that will obtain with the roller that is heated to 80～120 ℃ stretches 2.5～5.0 times along its length, obtains uniaxial orientation PET film.
Then, at the one or both sides of uniaxial orientation PET film, be coated with aforementioned copolyester and polyurethanes resin aqueous solution.The method that is coated with aforementioned water-based coating fluid for example has: oppositely rolling method, notch board rubbing method, touch rubbing method, the method for cleaning with water of rolling, spraying rubbing method, air-blade type rubbing method, metal thread bar are coated with method, tubular type is scraped the skill in using a kitchen knife in cookery, dip coated method and curtain formula rubbing method etc., these methods can be carried out separately or make up and carry out.
Then, control the end of film with clamp, import to the hot blast section that is heated to 80～180 ℃, dry back broad ways stretches 2.5～5.0 times.Continue to import to 220～240 ℃ heat treatment section, carry out 1～20 second heat treatment, crystalline orientation is finished.In this heat treatment step, broad ways or length direction are implemented 1～12% relaxation processes as required.
Below, the tectal phase separation structure that obtains among the present invention is described.Secondly, to raw material and the manufacture method that is used for laminated thermoplastic resin film of the present invention and the condition factor that is used to control aforementioned phase separation structure, be described in detail.
(1) tectal phase separation structure
In the present invention, cover layer have to the polyester phase A that with the copolyester resinoid is main component (below, sometimes slightly be designated as the PEs phase) with the polyurethanes resin be main component polyurethane mutually B (below, slightly be designated as the PU phase sometimes) carried out microphase-separated or received the structure that is separated.And has following feature: when observing with the phase determination pattern with scanning probe microscopy, mensuration planimeter with 5 μ m * 5 μ m, area ratio (PEs surface branch rate) with the polyester phase A (showing darker shade in the phase place picture) of the aforementioned cover surface of following formula (1) definition is more than 35%, and is lower than 90%.
PEs surface branch rate (%)=(area of polyester phase A/mensuration area) * 100 ... (1)
PEs surface branch rate in this cover surface has following described technical meaning.
If PEs surface branch rate is lower than 35%, be that the surface branch rate of the phase of main component becomes big relatively with the polyurethanes resin in the cover surface then, the frequency that block resistance reduces increases.On the other hand, if PEs surface branch rate is more than 90%, then the frequency of adaptation reduction increases, and particularly the adaptation of the hard paint of no-solvent type significantly reduces relatively.
For the lower limit of the PEs of cover surface surface branch rate, consider that from the block resistance aspect PEs surface branch rate is preferably 40%, more preferably 45%, be preferably 50% especially.On the other hand, the upper limit for PEs surface branch rate from considering with the adaptation aspect of the functional layer that is made of acrylic resin, is preferably 85%, and more preferably 80%, be preferably 75% especially.
Need to prove that in the present invention, the phase determination pattern (phase place mode) of utilizing scanning probe microscopy (SPM) is used in the evaluation of the phase separation structure of cover surface.The phase place mode is and utilizes common dynamic pressure mode (DFM mode; When using エ ス ア イ ア イ Na イ テ Network ノ ロ ジ one society to make SPM) carry out configuration of surface and observe the phase place hysteresis mensuration mode of carrying out simultaneously.
The measuring principle that relates to the tectal phase separation structure of phase determination pattern (phase place mode) evaluation that utilizes scanning probe microscopy (SPM) is simply described.
In the phase place mode, the phase place that detects the cantilever vibration when finishing the DFM operation lags behind.In the DFM operation, the distance between control probe-sample is so that the cantilever vibration amplitude constant of resonance is measured its shape.At this, in the time of will making the signal of bimorph (piezoelectric element) vibration be called " input signal " in order to make cantilever vibration, in the phase determination pattern, the phase place that detects simultaneously the effective cantilever vibration signal of this " input signal " with vibration amplitude lags behind.Phase place lags behind and responds to the influence of surface physical property sensitively, and specimen surface is soft more, and it is big more to lag behind.By the sized imagesization that this phase place is lagged behind, can observe the distribution (being called phase place picture or phase place picture etc.) of surface physical property.Therefore, when the different resin of a plurality of rerum naturas is present in the surface mutually, utilize this determination method can estimate phase separation structure.
But, evaluation for tectal phase separation structure, so long as utilize the surface physical property distribution evaluation method of scanning probe microscopy, except that the phase determination pattern, also can be alternate manners such as frictional force measuring mode and determination of viscoelasticity mode, the most important thing is to select can the sensitivity highland to estimate the view mode of phase separation structure.Need to prove, in the phase determination pattern, not only can detect the phase place that causes by tectal viscoplasticity difference and lag behind, and can detect the phase place that the surface physical property difference of size by absorption affinity and so on causes and lag behind.
For the tectal phase separation structure among the present invention, consider from big or small aspect, be equivalent to micro phase separation structure or receive phase separation structure.When regarding PEs as with major axis and minor axis continuous structure mutually, the continuous structure that the length that is the width of short-axis direction to the maximum 1 μ m, long axis direction surpasses 1 μ m is set at main body.That is, with respect to the total area of PEs phase, the area with part of aforementioned continuous structure is more than 80%, is preferably more than 85%, more preferably more than 90%.In addition, even be not the described continuous structure of aforementioned definitions but be dispersed into the PEs phase of island, the end that cover layer inside has the material of continuous structure also can be revealed in the surface.
For the size of the continuous structure of this PEs phase, the width of preferred short-axis direction is 1 μ m to the maximum, 0.8 μ m more preferably, and more preferably 0.6 μ m is preferably 0.4 μ m especially.The lower limit of the width of short-axis direction is not particularly limited, and in order to keep continuous structure, preferably its narrowest part is 0.01 μ m, is preferably 0.05 μ m especially.On the other hand, for the size of the continuous structure of this PEs phase, the length of preferred long axis direction is more than the 1 μ m, more preferably more than the 1.5 μ m, more preferably more than the 2.0 μ m, is preferably especially more than the 2.5 μ m.
By Fig. 1 and typical example shown in Figure 8 as can be known, the tectal phase separation structure among the present invention demonstrates the invisible labyrinth of occurring in nature, is difficult to merely define the form that is separated.Aforementioned phase separation structure also can multiaspect as described below manifest.
For example, when the form with aforementioned phase separation structure is that style is when manifesting, in document record, approach " dendritic structure " (" chemical voluminous dictionary ", the 226th page, clear and to publish (strain) development altogether on June 15th, 54, three capable), " wave structure " (" civilian sample ", the 168th～169 page, the wild ば ら of 2002.10.1 (strain) society development are capable), " camouflage color pattern ".
In addition, for the phase separation structure of the cover surface among the present invention, the morphology field in the polymeric blends class is similar to the structure that is revealed as common continuous structure.And, also can be revealed as by copolyester resinoid and self-crosslinking type polyurethane resinoid and twine the Box junction structure that forms mutually.
In addition, on form, also can use fractal dimension quantitatively to manifest self similitude of PEs phase.For example, as Fig. 3 and shown in Figure 10, phase determination pattern with scanning probe microscopy is observed tectal surface, in the phase place picture of the interface profile of strengthening light colour phase (polyester phase A) and darker shade (polyurethane is B mutually), as the expression light colour mutually and the index of the complexity of the boundary line (interface profile) of darker shade, the fractal dimension that can use box-counting method, use to be obtained by aforementioned interface profile quantitatively manifests.
Fractal dimension in the unit are be meant straight line (one dimension) at 1 o'clock, be to be meant β face (two dimension) at 2 o'clock.That is, fractal dimension approaches 2 more, and structure is fine and close more.Refer to that on the other hand fractal dimension approaches 1 more, structure is loose more.
Specifically, in the phase place picture of the interface profile of aforementioned reinforcement light colour phase (polyester phase A) and darker shade (polyurethane is B mutually), with the mensuration planimeter of 5 μ m * 5 μ m, the fractal dimension of the boundary line (profile at interface) of expression light colour phase and darker shade is preferably 1.60～1.95.The upper limit of aforementioned fractal dimension more preferably 1.93 is preferably 1.90 especially.On the other hand, the lower limit of aforementioned fractal dimension more preferably 1.65 is preferably 1.70 especially.
For example, the light colour in Fig. 4 and the cover surface shown in Figure 11 mutually the fractal dimension of the boundary line (interface profile) of (polyester phase A) and darker shade (polyurethane is B mutually) be respectively 1.89 and 1.90.Need to prove that Fig. 4 and Figure 11 are in the phase place picture of Fig. 1 of the phase separation structure of the cover surface representative of expression among the present invention and Fig. 8, strengthen light colour mutually and the interface profile of darker shade, the figure of the boundary line of expression light colour phase and darker shade.
In the present invention, become the function that the copolyester of cover layer raw material resinoid and polyurethanes resin are had in order to manifest to greatest extent, cover layer has micro phase separation structure or receives phase separation structure is important.Its reason is that when two resins mixed fully, the character of two resins offseted, and can not expect the resinoid good characteristic of copolyester resinoid or polyurethane generally.It has been generally acknowledged that, in cover layer of the present invention, reach other phase separation structure that PU can adopt mutually mutually, also adopt as the structure that is dispersed with the PU phase at PEs in mutually and at PU and be dispersed with the island structure of the so-called complex morphological representative of PES phase in mutually as PEs.Certainly, this island structure is under the immiscible state of resin, if increase wherein a kind of resin phase, then another kind must tail off, and forms so-called island.In the present invention, as long as create conditions, just can make the cover layer that constitutes mutually by the separation of taking this island structure.When utilizing this island structure to expect action effect of the present invention, need further consider its structure.
But,, might influence the character of the resin that constitutes extra large structure greatly owing to when the big or small inhomogeneous and distribution of considering the resin phase that forms island structure is inhomogeneous, can not ignore the influence of its shape, quantity and distribution to the island phase.It has been generally acknowledged that so, in order to ensure the uniformity of material, it is favourable adopting and being wound to the such phase separation structure in each corner mutually with PU phase separation structure mutually mutually as PEs of the present invention.Can enumerate once adopt PEs mutually and the phase separation structure of PU island structure mutually also as one of representative form of the present invention.
In addition, the tectal other phase separation structure as among the present invention also can adopt core-shell structure.For example, PU be enclosed in mutually the PEs phase around, PEs surround again mutually it and so on structure.But,, need very strict control in order to form this core-shell structure.In addition, can think,, show the excellent material movement so can not expect it owing to adopt its core-structure.And, also can adopt PEs mutually and PU alternate ground, laminar structure arranged side by side is as the form of phase separation structure regularly.But, respectively parallel ground, roughly equally spaced configuration is desirable, if but the width of phase becomes big, then be difficult to evenly distribute at tectal interface PEs mutually with PU mutually, reluctantly for it, then may influence the quality of laminated thermoplastic resin film.The delicate difference that utilization is created conditions though adopt the form of island structure, core-shell structure and laminar structure sometimes, becomes the type that is mixed in of these structures.But in cover layer, in order to ensure its quality, PEs has certain size mutually and evenly is mixed in everywhere with PU mutually is important.
With the copolyester resinoid be the polyester phase A of main component with the polyurethanes resin be main component polyurethane mutually B made irregular form respectively.And, these resins mutually irregular and densely common configuration on the base material that constitutes by the thermoplastic resin membrane, form complicated arrangement architecture.In addition, also can be a resin gos deep into the surface of another resin phase with the non-state that mixes structure.Need to prove that in Fig. 3, Figure 10, black part is divided expression polyester phase A, white portion is represented polyurethane phase B.
With respect to unit are (for example 5 * 5 μ m), when two kinds of resins are arranged equably with the state of separator well,, then can restrict the size of another resin phase if the size of a resin phase becomes greatly.Therefore, in the existence of resin phase, produce big deflection.Its result is difficult to keep that two resins are separated and the even state of dispersed arrangement, in tectal material, produce inhomogeneous, so not preferred in qualitative control.
For two resins being separated and being present in the cover layer with the state that evenly is mixed in, the length that the width that preferably form of PEs phase is set at short-axis direction is 1 μ m, long axis direction to the maximum is more than the 1 μ m.Certainly, to quality requirements when not high, also can be that the width of short-axis direction is to the maximum and relatively becomes big structure about 6 μ m.Phase separation structure for this continuous phase (PEs phase), the drying condition of the resin composition by selecting to be used to form tectal coating fluid, the kind of surfactant and concentration, coating weight, coating layer and heat-setting condition etc. are also controlled these conditions, can make it show the special micro phase separation structure or the phase separation structure of receiving at cover layer.In a word, as Fig. 1 and shown in Figure 8, the form of the phase separation structure of the polyester phase A of cover surface and polyurethane phase B is the representative model that is used to manifest the effect of laminated thermoplastic resin film of the present invention.
And, the importance of phase separation structure is at length described.
For the cover layer in the laminated thermoplastic resin film of the present invention, importantly, with copolyester composition and polyurethane composition is resinous principle, and, with the copolyester composition is that the PEs of main component is separated mutually with the PU that is main component mutually with the polyurethane composition, and PEs has continuous structure mutually at least.By making aforementioned two kinds of resins is not evenly to mix but it is separated, the characteristic separately of copolyester resinoid and polyurethane resin does not offset, fully effectively utilize the speciality of each resin, described copolyester resinoid has good adaptation and has better solvent resistance with respect to the base material film that is made of the thermoplastic resin membrane, though described polyurethane resin poor solvent resistance has good adaptation with respect to many resins such as hard conating and diffusion layer, acrylic resins.
Constitute tectal polyester phase A, preferably constitute by the copolyester resinoid separately, but also can contain the polyurethanes resin of 0.01～40 quality %.And, in polyester phase A, can contain the particle of 0.001～20 quality %.In addition, in polyester phase A, also in aforementioned resin, adhere to or contain surfactant sometimes.Similarly, polyurethane phase B preferably is made of the polyurethanes resin separately, can contain particle, surfactant etc. with the amount of the described degree of aforementioned copolyester resinoid.Particularly with the high particle of the resinoid compatibility of polyurethane, in tectal forming process, with polyester mutually A compare, can optionally be stored in partially mostly among the polyurethane phase B.
In general, in the composition that is made of copolyester resinoid and the resinoid mixture of polyurethane, both are chemically uniform material usually, in most cases show the chemical supplementary functions of the complementary character that has each other or function and so on.On the other hand, reach the cover layer that polyurethane constitutes mutually mutually by polyester of the present invention, as previously mentioned, polyester reaches polyurethane mutually and is separated respectively physically mutually, in the existence of resin phase, produce big deflection, keep that two resins are separated and the structure of the state that evenly dispersed arrangement is good.By each resin phase surface, the character that each resin is had is respectively shared function separately with the state that is separated, and for example, the copolyester resinoid is shared block resistance, the polyurethanes resin is shared adaptation.Can be described as manifesting of physics miscellaneous function, this function or principle be we can say and related to the new technique of not recognizing fully in the prior art.
The detailed generation mechanism of the tectal phase separation structure among the present invention is still indeterminate.But, the kind of the ratio of the dispersion liquid of copolyester resinoid and the resinoid ratio of components of polyurethane, water and alcohol, surfactant, the material of coating fluids such as pH, coating weight of impurity, water-based coating fluid in the surfactant are constituted and characteristic, utilize the equilibrium of delicate condition of time, temperature, the wind speed of drying and heat-set treatment, in cover layer, show the special micro phase separation structure or the phase separation structure of receiving, can easily understand by the contrast of each embodiment and comparative example.
And, can think that the NCO that the polyurethanes resin has also affects reacting initial temperature knifeedge.At this so-called phase separation structure, not so-called PEs has the physical boundary mutually with this two-phase of PU phase last the separating of distance, but the border not approaching with not occupying distance, can see the many segregations of copolyester in PEs mutually in, the many special collection of polyurethanes resin relatively PU mutually in, two-layer border clearly separates just, forms to separate such border in appearance.And in occasion of the present invention, on its border, the resinoid NCO of polyurethane also may react, and demonstrates complicated isolating construction.
Laminated thermoplastic resin film of the present invention has by PEs and reaches the cover layer that PU constitutes mutually mutually, it has the effect at the interface function of the two sides of so-called substrate surface and function face performance equivalent effect between functional layers such as the base material that for example is made of the thermoplastic resin membrane and hard conating and diffusion layer.So, PEs reaches the structure that PU takes both separator wells mutually mutually, with respect to tectal two sides (interface of base material and tectal interface, cover layer and functional layer), PEs becomes the state of the resinoid advantageous property of copolyester that performance to greatest extent had originally mutually.That is, PU becomes the state of bringing into play the resinoid advantageous property of polyurethane that had originally with respect to the two sides to greatest extent mutually.
Its reason is, in having tectal laminated thermoplastic resin film, because tectal surface has by PEs and reaches the micro phase separation structure or the phase separation structure of receiving that PU constitutes mutually mutually, so the copolyester resinoid of PEs phase exposes, bring into play resinoid character of this copolyester or function to greatest extent, similarly, the polyurethanes resin of PU phase exposes, and brings into play character or function that this polyurethanes resin had originally to greatest extent.Therefore, in particular range, distribute respectively mutually, just can bring into play the character or the function of both resins to greatest extent as long as the PEs in the cover surface reaches PU mutually.Its reason is, because it is the peculiar structure of layered product and so on, so reasonably play a role at the interface of base material and tectal interface, cover layer and functional layer.
And, for the purpose of the present invention, constitute when containing particle in the resin combination that PEs reaches the PU phase mutually making, for example, silicon oxide particle can be stored in partially PU mutually in.Its reason is estimated as: compare with PEs, the surface energy of PU phase approaches silicon oxide particle.By making silicon oxide particle be stored in the PU phase partially, can improve block resistance, and owing to can reduce the overall granule content of cover layer, therefore to keep the such function of the transparency be useful structure to finishing as the resinoid shortcoming of polyurethane.
Similarly, as long as select surface energy more near the particle of copolyester, just hint can make particle select to be stored in partially PEs mutually in.By mutually or the method that particle can't be expected in the prior art of changing and so on partially by PEs, can keep its transparent in, improve its sliding and adherence greatly.Therefore, on can enlarging micro phase separation structure or receiving the range of application this point of material design of phase separation structure, the present invention is significant.
(2) base material film
In the present invention, the thermoplastic resin membrane who becomes base material is the film that obtains by following operation, thermoplastic resin is carried out the non-oriented sheet material that the extruding of melt extruded or solution obtains, as required, along its length or the uniaxial orientation of width stretch, or carry out biaxial stretch-formed successively or carry out biaxial stretch-formedly simultaneously along biaxially oriented, implement heat-set treatment.
In addition, for the aforementioned thermoplastic resin film, in the scope that does not influence purpose of the present invention, can implement surface activations such as Corona discharge Treatment, light emitting discharge processing, flame treatment, ultraviolet treatment with irradiation, electron beam irradiation processing, ozone treatment to aforementioned films and handle.
As the thermoplastic resin membrane's of the base material of laminated thermoplastic resin film of the present invention thickness, in the scope of 30～300 μ m, can determine arbitrarily according to the specification of the purposes of using.The preferred 250 μ m of the upper limit of the thickness of aforementioned thermoplastic resin film, preferred especially 200 μ m.On the other hand, the preferred 50 μ m of the lower limit of film thickness, preferred especially 75 μ m.When film thickness was lower than 50 μ m, its rigidity and mechanical strength were insufficient easily.On the other hand, when film thickness surpasses 300 μ m, increase, raise so become the frequency of optical defect owing to be present in the absolute magnitude of the impurity in the film.In addition, the property cut apart when film is cut into the width of regulation also worsens, and manufacturing cost raises.And because its rigidity grow, therefore, becoming easily is difficult to the film of growing up is wound into the roller shape.
Thermoplastic resin for example has: polyethylene (PE), polypropylene (PP), polymethylpentene polyolefin such as (TPX); PETG (PET), poly-2,6-(ethylene naphthalate) (PEN), poly terephthalic acid 1,4-butanediol ester (PTT), polybutylene terephthalate (PBT) mylar such as (PBT); Polyamide (PA) resins such as nylon 6, nylon 4, nylon 66, nylon 12; Polyimides (PI), polyamidoimide (PAI), polyether sulfone (PES), polyether-ether-ketone (PEEK), Merlon (PC), polyene propyl ester (PAR), cellulose propionate, polyvinyl chloride (PVC), Vingon, polyvinyl alcohol (PVA), PEI (PEI), polyphenylene sulfides (PPS), polyphenylene oxide, polystyrene (PS), syndiotactic polytyrene, norbornene polymer etc.In addition, these polymer can use separately, in addition, also can be the copolymers that contains the minor amounts of copolymerized composition, can also mix other thermoplastic resin more than a kind.
In these thermoplastic resins, preferred PETG, PTT, poly-2,6-(ethylene naphthalate), syndiotactic polytyrene, norbornene polymer, Merlon, polyene propyl ester etc.In addition, from consider the resin with polar functional group of preferred polyester and polyamide and so on tectal adaptation aspect.
Wherein, more preferably PETG, poly-2,6-(ethylene naphthalate), polybutylene terephthalate (PBT), PTT or be the copolymer of main component, the especially especially preferably Biaxially oriented film that forms by PETG with the constituent of these resins.
For example, as the resin that forms the thermoplastic resin membrane, when using with PETG to the polyester copolymer of basic framework, the ratio of copolymer composition is preferably and is lower than 20 moles of %.When it is 20 moles of % when above, film-strength, the transparency, poor heat resistance sometimes.Can have as the dicarboxylic acids composition illustration of copolymer composition: aliphatic dicarboxylic acids such as adipic acid, decanedioic acid; Isophthalic acid, phthalic acid and 2, aromatic dicarboxylic acids such as 6-naphthalene dicarboxylic acids; Polyfunctional carboxylic acids such as trihemellitic acid and pyromellitic acid etc.In addition, can have as the diol component illustration of copolymer composition: diethylene glycol, 1, aliphatic acid glycol such as 4-butanediol, propane diols and neopentyl glycol; Aromatic diols such as paraxylene glycol; 1, alicyclic diols such as 4-cyclohexanedimethanol; Mean molecule quantity is 150～20000 a polyethylene glycol etc.
In addition, in the scope that does not influence effect of the present invention, aforementioned thermoplastic resin can contain the various additives outside the catalyst.Additive for example has: inorganic particle, hear resistance polymeric particles, alkali metal compound, alkaline earth metal compound, phosphorus compound, antistatic agent, ultra-violet absorber, photostabilizer, fire retardant, heat stabilizer, antioxidant, anti-gelation agent, surfactant etc.
When making the thermoplastic resin membrane, when being wound into the roller shape or handling (following the degassing of air etc. when sliding, mobility, adherence, the coiling) aspect in when rolling consider that aforementioned particles is used with suitable surperficial convexity in order to give the film surface.
Inorganic particle for example has: calcium carbonate, calcium phosphate, amorphism silica, crystallinity glass filler, kaolin, talcum, titanium dioxide, aluminium oxide, silica-alumina composite oxide particle, barium sulfate, calcirm-fluoride, lithium fluoride, zeolite, molybdenum sulfide, mica etc.In addition, the hear resistance polymeric particles for example has: crosslinked polystyrene particle, crosslink propylene acid resin particle, crosslinked methyl methacrylate class particle, benzo guanamine-formaldehyde condensation polymer composition granule, melamine-formaldehyde condensation products particle, polytetrafluoroethylgranule granule etc.
When using polyester film as base material film, in aforementioned particles since the refractive index ratio of silicon oxide particle and mylar near and obtain the high transparency easily, so in the purposes of the strong request transparency most preferably.On the other hand, in requiring concealed purposes, be fit to the Chinese white of titanium oxide and so on.In addition, the particle that contains among the thermoplastic resin membrane can be a kind, also can use multiple simultaneously.
For kind, average grain diameter, the addition of aforementioned particles, consider from the transparency and handling balanced aspect, be that granule content in 0.01～2 μ m, the film is in the scope of 0.01～5.0 quality % in average grain diameter, get final product according to the purposes of film is definite.In addition, when laminated thermoplastic resin film of the present invention is used for the purposes of the requirement for height transparency, in the thermoplastic resin membrane of base material, preferably is substantially devoid of and causes the particle that the transparency reduces and make cover layer contain the formation of particle.
Aforementioned what is called " is substantially devoid of particle " and is meant in the thermoplastic resin membrane of base material: for example, occasion at inorganic particle, with xrf analysis inorganic elements is being carried out when quantitative, it is following for 50ppm, be preferably 10ppm following, most preferably be and detect the following content of boundary detectability.Its reason is, even do not have a mind to add particle in the base material film, peels off from the dirt that is attached to pipeline and device in the pollutant component of foreign impurity and material resin or the film manufacturing process, also can sneak in the film sometimes.
In addition, it can be individual layer that the thermoplastic resin membrane's who uses as base material among the present invention layer constitutes, and also can make the laminar structure of having given the function that can't obtain in the individual layer.When being set at laminar structure, preferred co-extrusion platen press.
Below, be typical example to use polyester as the situation of thermoplastic resin membrane's raw material, the manufacture method of base material film is described in detail.
The inherent viscosity that is used as the polyester granulate of pleurodiaphragmatic in terspace material is preferably the scope of 0.45～0.70dl/g.When inherent viscosity is lower than 0.45dl/g, when making film, often rupture easily.On the other hand, when inherent viscosity surpassed 0.70dl/g, filter pressed and rises greatlyyer, is difficult to carry out high accuracy and filters, and productivity reduces easily.
In addition, when being used for optical functional film or optical functional sheet material, preferably remove the field trash that contains in the raw material polyester that causes optical defect.In order to remove the field trash in the polyester, molten resin is maintained at about 280 ℃ any part and carries out high accuracy and filter when melt extruded.Be used for the filtering material that the high accuracy of molten resin filters and be not particularly limited, when filtering material was the stainless steel sintered body, removing with Si, Ti, Sb, Ge, Cu was the condensation product of main component and the organic function admirable of high-melting-point and preferred.
Be used for below the preferred 15 μ m of filtering particle size (initial stage filter efficiency 95%) of the filtering material that the high accuracy of molten resin filters.When the filtering particle size of filtering material surpasses 15 μ m, make removing of the above field trash of 20 μ m insufficient easily.By using filtering particle size (initial stage filter efficiency 95%) is that the high accuracy that the following filtering material of 15 μ m carries out molten resin is filtered, and productivity reduces sometimes, but is very important for obtaining the few film of optical defect.
Extruding in the operation of molten resin, even microinclusions by filtering material, in the refrigerating work procedure of sheet fused mass, around being mingled with material, carry out crystallization, it causes the inhomogeneities of orientation in orientation procedure, produce small difference in thickness, become the position of lens state.At this, when having lens, refraction or scattering take place in light, can see that when detecting by an unaided eye its field trash than reality is big.This small thickness difference can be used as the height of protuberance and the difference of concave depth is observed, when the height of protuberance is more than the 1 μ m, the concave depth adjacent with protuberance is that 0.5 μ m is when above, utilize lens effect, even size is the object of the shape of 20 μ m, naked eyes also are identified as the above size of 50 μ m, and, also be identified as the above big or small optical defect of 100 μ m sometimes.
In order to obtain high hyaline membrane, do not contain particle in the preferred substrates film, it is high more to tend to the few more transparency of granule content, distincter by the small concavo-convex optical defect that causes.In addition, owing to exist the thin film of thick film surface ratio to be difficult to quenching, and tend to carry out crystallization, so when making non-oriented sheet material, film integral body need be carried out quenching.Method as making non-oriented sheet cools is preferably as follows method: the breach portion from the plastic film squeeze film on rotation cooling rotating cylinder is squeezed into sheet with molten resin, and on one side with sheet fused mass and the driving fit of rotation cooling rotating cylinder, carrying out quenching makes sheet material on one side.Method with the air surface (opposing face of the face that contacts with the cooling rotating cylinder) of this non-oriented sheet material is cooled off effectively is blown into the method that high velocity air cools off.
(3) cover layer
For laminated thermoplastic resin film of the present invention, its manufacture method comprises following operation: will be applied to the painting process of mobile thermoplastic resin membrane's one or both sides continuously to contain the resinoid resin of copolyester resinoid and polyurethane, water and to contain the dispersant of ethanol, the water-based coating fluid that surfactant is the main composition composition; Coating layer (cover layer) is carried out dry drying process; Then, the stretching process that stretches along uniaxial orientation at least; Further the coated film that will stretch is carried out the heat-set treatment operation of heat-set treatment; Form the laminated thermoplastic resin film that obtains continuously through these operations and be provided with the cover layer that has micro phase separation structure or receive phase separation structure.In addition, be that at least a crosslinking agent in oxygen class crosslinking agent, the melamine class crosslinking agent, oxazoline class crosslinking agent is blended in the coating fluid by being selected from epoxy, heat-treat, can in the copolyester resinoid, form cross-linked structure.
Be provided with in the method for the tectal laminated thermoplastic resin film that has this micro phase separation structure or receive phase separation structure in manufacturing, the mass ratio (A/B) of preferred aforementioned copolyester resinoid A and polyurethanes resin B is 30/70～70/30, satisfies following (i)～(condition vi).In addition, the situation that contains crosslinking agent in the coating fluid too.
(i) film to the inlet of drying process is lower than 2 seconds by the time after the coating coating fluid
(ii) in drying process, temperature is that 120～150 ℃, drying time are 0.1～5 second
(iii) the wind speed of dry wind is that 30m/ is more than second in drying process
(iv) the heat-set treatment operation separates, so that strengthen being a plurality of heat-set section continuously, and each section can carry out temperature control independently, the temperature in the 1st heat setting zone that film passes through is 190～200 ℃, the temperature that is set at the heat-set section of maximum temperature is 210～240 ℃, the time of passing through of film that is set at the heat-set section (need to prove that most cases is the heat-set section of first entrance side) of maximum temperature from being exported to of the 1st heat-set section is below 10 seconds
(v) nonionic surface active agent or cationic surface active agent are mixed 0.01～0.18 quality % with respect to coating fluid
(vi) tectal final coating weight is 0.005～0.20g/m
2
In addition, in aforementioned lamination thermoplastic resin membrane's manufacturing, further preferably satisfy following (condition vii)～(ix).
(vii) the film to the inlet of drying process is lower than 1.5 seconds by the time after the coating coating fluid
(viii) in drying process, temperature is that 130～150 ℃, drying time are 0.5～3 second
(ix) in the heat-set treatment operation, the temperature that is set at the heat-set section of maximum temperature is 225～235 ℃, the film that is set at the heat-set section (need to prove, in most cases be the heat-set section of first entrance side) of maximum temperature from being exported to of the 1st heat-set section is below 5 seconds by the time.
In addition, by in the cover layer that utilizes aforementioned online coating to be laminated into, containing the particulate of suitable particle diameter, form suitable concavo-convexly on tectal surface, can give sliding, coiling, marresistance.Therefore, do not need to make and contain particulate among the thermoplastic resin membrane, can keep high transparent.
When laminated thermoplastic resin film of the present invention was used as optical functional film or optical functional sheet material, preferred 0.002～0.010 μ m of the three-dimensional center face average surface roughness (SRa) of cover surface was level and smooth.Consider that from transparent aspect the upper limit of SRa is 0.0080 μ m more preferably, be preferably 0.0060 μ m especially.On the other hand,, marresistance aspect handling from sliding and coiling etc. considers that the lower limit of SRa is 0.0025 μ m more preferably, preferred especially 0.0030 μ m.
Tectal SRa is lower than handling, the marresistance reduction such as block resistance, sliding and coiling of the smooth surface of 0.002 μ m, and is not preferred.On the other hand, when tectal SRa surpasses 0.010 μ m because mist degree rises, transparency deterioration, pretend into the base material film of optical functional film or optical functional sheet material not preferred.
In preferred implementation of the present invention, cover layer has following feature 4 forms, structure, can obtain by the following method.
(a) polyester mutually and polyurethane carry out microphase-separated or receive being separated in mutually, polyester has specific area mutually than (the surperficial branch rate of PEs)
(b) can be at surface and the inner ratio of components that changes tectal resinous principle
(c) cover layer has cross-linked structure
When (d) cover layer contains particle, particle be stored in partially polyester mutually or polyurethane mutually in
With the copolyester resinoid is the polyester phase of main component, preferably has width and is the continuous structure that 1 μ m, length surpass 1 μ m to the maximum, and more preferably copolyester has the structure of common continuous structure mutually with polyurethane mutually.In the scope of the PEs surface of the present invention regulation branch rate, be the polyester phase of main component with the copolyester resinoid, have width and be the fine continuous structure that 1 μ m, length surpass 1 μ m to the maximum, obtain uniform adaptation thus microcosmic.
With the copolyester resinoid be main component polyester mutually in, be to the maximum in the phase separation structure that the position that surpasses 1 μ m scatters at width, with respect to the functional layer of hard conating, diffusion layer, layers of prisms and so on, the local position that produces the adaptation difference.When there is the position of adaptation difference in cover surface, be that starting point initiation macroscopic view is peeled off with this part sometimes.For the width with aforementioned polyester phase makes the fine continuous structure that is 1 μ m to the maximum, arrive time, the heat-setting condition that maximum temperature needs importantly suitably selecting from the cross directional stretch section to heat-set section.Particularly when to heat-set section, arriving the overlong time of maximum temperature needs from the cross directional stretch section, tectal being separated excessively carried out, consequently, be that the width of polyester phase of main component surpasses 1 μ m at the narrowest position position is dispersed in the copolyester resinoid.Concrete heat-setting condition when aftermentioned is made laminated thermoplastic resin film of the present invention.
In order to control the phase separation structure of final cover surface, evaporation rate of solvent in the drying process described later and subsequent heat treated are very important.By the evaporation rate of solvent of control in the drying process, can change the polyester composition in the cover surface and the ratio of components of polyurethane composition.
For example, when making water/isopropyl alcohol mixed solvent, under weak drying condition, remain in the later stage of drying process in the solvent on surface, the ratio that water accounts for increases.Therefore, compare when making cover layer dry under capable and experienced dry condition, hydrophily increases than the ratio that higher polyurethanes resin is present in cover surface.In addition, change coating weight and have equal effect with the control evaporation rate of solvent.That is, when increasing coating weight, dried floral is time-consuming, and for being present in the remaining solvent of coated face before the drying, the ratio that water accounts for increases.That is, compare after a little while, can improve the ratio of the polyurethane composition in the surface with coating weight.
In stretching process and heat-set treatment operation, polyester composition and polyurethane composition are separated, and when either party began heat cross-linking, the motility of each phase reduced greatly, suppress the carrying out that is separated.That is,, can control phase separation structure by the heating condition in control stretching process and the heat-set treatment operation.
As mentioned above, there be the carrying out that is separated in ratio and control stretching process, the heat-set treatment operation in the surface by the polyester/polyurethane of control in the drying process, can strict control surface phase separation structure and each phase have a ratio.In addition, the surface energy of the particle that contains in the cover layer by control, can make particle select to be dispersed in the copolyester resinoid is that the polyester of main component is among either party of polyurethane phase of main component mutually or with the polyurethanes resin.
The cover layer of laminated thermoplastic resin film of the present invention contains copolyester resinoid and the main resinous principle of polyurethanes resin conduct.The adaptation of copolyester resinoid and polyesters base material film is abundant separately, but its adaptation with the acrylic resin that is used for prism lens and hard conating is poor.In addition, owing to be more crisp resin, so the impact when cutting off relatively takes place by cohesion destruction easily.On the other hand, the adaptation of polyurethanes resin and hard conating and diffusion layer, acrylic resin is better separately, but poor with the adaptation of polyesters base material film, and block resistance is poor.Therefore, need make it contain particle a large amount of or that particle diameter is big, or increase the content of particle.Its result is because the mist degree of film rises, so particularly not preferred as the base material film of the optical functional film of the strong request transparency or optical functional sheet material.
(3-1) coating fluid preparation process
In the present invention, use rubbing method to form cover layer.The material that is used for coating fluid is resin and dispersant or solvent.In the present invention, be used to form tectal coating fluid and be preferably water-based.In addition, in the present invention, except that resinous principle, using particle and surfactant simultaneously is preferred implementation.And, as required, can use additives such as antistatic agent, ultra-violet absorber, organic lubricant, antiseptic, photooxidation catalyst.In addition,, catalyst can be added in the coating fluid, for example, various chemical substances such as inorganic substances, salt, organic substance, alkaline matter, acidic materials and containing metal organic compound can be used in order to promote the heat cross-linking reaction of resin.In addition, in order to regulate the pH of the aqueous solution, can add alkaline matter or acidic materials.The method that is mixed with of coating fluid is as follows, in dispersant or solvent, under agitation with resin dispersionization or dissolving, then, outside particle-removing, the surfactant, uses various additives as required simultaneously, is diluted to desirable solid component concentration.
In addition, in laminated film of the present invention, disperse,, preferably coating fluid is carried out secondary filter in order further to remove field trashes such as thick particle aggregation thing and in-process dirt for the resinous principle and the uniform particles that make coating fluid.
Be used for the type of the filtering material of secondary filter coating fluid,, just be not particularly limited, for example have: long filament type, felt type, grid type as long as have aforementioned properties.Be used for the material of the filtering material of secondary filter coating fluid,, just be not particularly limited, for example have: stainless steel, polyethylene, polypropylene, nylon etc. as long as have aforementioned properties and coating fluid is not had harmful effect.
The filtering material that is used for the secondary filter coating fluid, preferred filtering particle size (initial stage filter efficiency: 95%) be the following filtering materials of 25 μ m, further preferred strainability is the following filtering materials of 5 μ m, and preferred especially strainability is the following filtering material of 1 μ m.The method that the different film of strainability is used in combination.When using the filtering particle size to surpass the filtering material of 25 μ m, removing of thick condensation product is insufficient easily.Therefore, by filtering the thick condensation product that can't remove, the orientation stress in dried uniaxial orientation of coating or biaxial orientation operation is wideer, is identified as the above condensation product of 100 μ m, causes optical defect easily.
Below, the raw material that is used for coating fluid is described in detail.
(a) resin
The composition of the tectal resinous principle that on the base material that constitutes by the thermoplastic resin membrane, forms, when preparation contains the coating fluid of copolyester resinoid (A) and polyurethanes resin (B), the mass ratio (A)/(B)=70/30～30/70 of the solid constituent standard of preferred resin (A) and resin (B) is preferably 60/40～40/60 scope especially.In the present invention, constitute tectal resin and also can use aforementioned copolyester resinoid and polyurethanes resin the 3rd resin in addition simultaneously.In addition, also can use crosslinking agent simultaneously.
Need to prove that in the present invention, as Fig. 6 and shown in Figure 13, the PEs mass ratio in the PEs of cover surface surface branch rate and the tectal resinous principle is not corresponding.In Fig. 6,, show clearly that also the PEs surface branch rate of cover surface is changed to 30～91% even the PEs mass ratio in the tectal resinous principle is 50%.In addition, in Figure 13,, show clearly that also the PEs surface branch rate of cover surface is changed to 26～86% even the PEs mass ratio in the tectal resinous principle is 45%.This fact hint, in tectal surface and inside, the copolyester resinoid is different with the resinoid constituent ratio of polyurethane.That is, be meant in the present invention, can control copolyester resinoid and the resinoid constituent ratio of polyurethane arbitrarily at tectal thickness direction.
In addition, be set at aforementioned range, the stiffness of cover surface can be set at 3.0～15.0nm by ratio with copolyester resinoid (A) in the cover layer and polyurethanes resin (B).When the stiffness of cover surface was lower than 3.0nm, cover layer became fragile.Therefore, form with the acrylic resin be the functional layers such as hard conating, diffusion layer, layers of prisms of constituent after, carrying out with given size in the manufacturing procedure of high-speed cutting, the shearing force during with respect to high-speed cutting is difficult to obtain sufficient adaptation.In addition, when the stiffness of cover surface surpassed 15.0nm, its block resistance reduced easily.And, might become insufficient to coating, adaptation, the solvent resistance of base material film.
The forming process of the water-dispersion type copolyester composition among the present invention and the phase separation structure of hydrophilic polyurethane composition is presumed as follows.Two resinous principles that mix with general solvent are the state that evenly disperses or dissolves in coating fluid.After coating on the PET film, the coated face of process drying process is not for having the uniform state of clear and definite phase separation structure.Then, utilize the heat treated in stretching process and the heat-set treatment operation, manifest phase separation structure.That is, to being the phase of main component with the copolyester and be separating mutually of main component with polyurethane.And it has been generally acknowledged that along with the carrying out that is separated, the surface with copolyester composition of lower surface energy exists ratio to raise.
(copolyester resinoid)
Being used for tectal copolyester resinoid of the present invention, is constituent with the aromatic dicarboxylic acid composition with as the ethylene glycol of diol component and the glycol of side chain preferably.The diol component of aforementioned side chain for example has: 2,2-dimethyl-1, ammediol, 2-methyl-2-ethyl-1, ammediol, 2-methyl-2-butyl-1, ammediol, 2-methyl-2-propyl group-1, ammediol, 2-methyl-2-isopropyl-1, ammediol, 2-methyl-2-n-hexyl-1, ammediol, 2,2-diethyl-1, ammediol, 2-ethyl-2-normal-butyl-1, ammediol, 2-ethyl-2-n-hexyl-1, ammediol, 2,2-di-n-butyl-1, ammediol, 2-normal-butyl-2-propyl group-1, ammediol and 2,2-di-n-hexyl-1, ammediol etc.
With respect to whole diol components, the lower limit of the mol ratio of the diol component of aforementioned side chain is preferably 10 moles of %, is preferably 20 moles of % especially.On the other hand, its upper limit is preferably 80 moles of %, and more preferably 70 moles of % are preferably 60 moles of % especially.In addition, as required, can use diethylene glycol, propane diols, butanediol, hexylene glycol or 1 simultaneously, 4-cyclohexanedimethanol etc.
The aromatic dicarboxylic acid composition is terephthalic acid (TPA) and M-phthalic acid most preferably.With respect to whole dicarboxylic acids compositions, can in 10 moles of scopes below the %, add other aromatic dicarboxylic acid, particularly diphenyl carboxylic acid and 2, aromatic dicarboxylic acids such as 6-naphthalene dicarboxylic acids make its copolymerization.
Be used as the copolyester resinoid of tectal resinous principle among the present invention, preferably use the water-soluble resin that maybe can carry out aqueous dispersion.Therefore, except that aforementioned dicarboxylic acids composition, in order to give water dispersible to polyester, preferably in the scope of 1～10 mole of %, use 5-sulfoisophthalic acid or its alkali metal salt, for example can enumerate: sulfo group terephthalic acid (TPA), 5-sulfoisophthalic acid, 4-sulfo group naphthalene M-phthalic acid-2,7-dicarboxylic acids and 5-(4-sulfophenoxy) M-phthalic acid or its alkali metal salt.
(polyurethanes resin)
The tectal polyurethanes resin that is used for laminated thermoplastic resin film of the present invention preferably uses resin water-soluble or can aqueous dispersion.For example, contain the resin of NCO, terminal isocyanate group is blocked water-soluble urethane of thermal-reactive that (below, slightly be designated as end-blocking) form etc. with the hydrophily base as end-sealed type.
The end-capping reagent of aforementioned NCO for example has: bisulfite salt and contain sulfonic phenols, alcohols, lactams, oximes or activity methene compound class etc.The NCO of end-blocking carries out hydrophiling or water-solubleization with urethane prepolymer.In the drying process or heat-set treatment operation when making film, when giving with thermal energy to aforementioned resin, because end-capping reagent comes off from NCO, so the water dispersible copolyester resinoid that aforementioned resin will be mixed in the tissue that self-crosslinking crosses carries out immobilization, simultaneously, also with the reactions such as end group of aforementioned resin.Because the resin of coating fluid in being mixed with is hydrophily, thus its poor water resistance, but when be coated with, when dry, heat fixation and thermal response end, owing to the hydrophilic group of urethane resin, be that end-capping reagent comes off, so obtain good the filming of resistance to water.
In aforementioned end-capping reagent, aspect the heat treatment temperature film manufacturing process, heat treatment time end-capping reagent come off from NCO and the industrial aspect that can obtain consider bisulfite salt most preferably.The chemical composition of the urethane prepolymer that uses in aforementioned resin is: have the molecular weight that has 2 active hydrogen atoms in organic PIC of 2 above active hydrogen atoms or the molecule at least in (1) molecule and be 200～20,000 compound; (2) has organic PIC of 2 above NCOs in the molecule; Or (3) make the chain elongation agent that has 2 active hydrogen atoms in the molecule at least react the compound with terminal isocyanate group that obtains.
Well-known as the compound of aforementioned (1) is to contain the compound of hydroxyl, carboxyl, amino or sulfydryl more than 2 in end or the molecule.Particularly preferred compound for example has: PPG and polyester ether polylol etc.In addition, PPG for example has: the compound that epoxides such as oxirane and expoxy propane or phenyl ethylene oxide and chloropropylene oxide etc. are polymerized; Or these materials carry out atactic polymerization, block polymerization or multivalence alcohol are carried out the compound that addition polymerization obtains.
PPG and polyester ether polylol are mainly enumerated the compound of a direct-connected shape or a chain.Can obtain by the following method: with the saturated or unsaturated carboxylic acid of multivalence such as butanedioic acid, adipic acid, phthalic acid and maleic anhydride or this carboxylic acid anhydrides etc. and ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1, the mixture of polyalkylene ether glycols class such as the polyethylene glycol that the saturated and unsaturated alcohols of multivalence such as 6-hexylene glycol and trimethylolpropane, molecular weight ratio are lower and polypropylene glycol or these alcohols carries out condensation.
And PEPA can exemplify the polyesters that is obtained by lactone and hydroxy acid.In addition, polyester ether polylol can use the polyether ester class that addition of ethylene oxide or expoxy propane etc. form in making good polyesters in advance.
Organic PIC of aforementioned (2) for example has: the isomer class of toluene di-isocyanate(TDI), 4, aromatic diisocyanate classes such as 4-methyl diphenylene diisocyanate, aromatic series aliphatic diisocyanate classes such as xyxylene vulcabond, IPDI and 4, ester ring type diisocyanates such as 4-dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate and 2,2, aliphatic diisocyanate classes such as 4-trimethyl hexamethylene diisocyanate, or the PIC class that these compounds are formed with additions in advance such as single or multiple and trimethylolpropanes.
At least the chain elongation agent that has 2 reactive hydrogens of aforementioned (3) for example has: ethylene glycol, diethylene glycol, 1,4-butanediol, and 1, glycols such as 6-hexylene glycol; Multivalence alcohols such as glycerine, trimethylolpropane and pentaerythrite; Ethylenediamine, 1, two amines such as 6-hexamethylene diamine and piperazine; Alkamine such as monoethanolamine and diethanol amine; Sulfo-diethylene glycol (DEG) classes such as thio-diethylene glycol; Or water.
When synthetic urethane prepolymer, utilize usually and use one-part form or the multisection type isocyanates addition polymerization process that aforementioned chain elongation agent is arranged,, and be lower than under 150 ℃, preferred 70～120 ℃ temperature reaction 5 minutes to a few hours.As long as the ratio of NCO relative activity hydrogen atom is more than 1, just can freely select, but must remaining free NCO in the urethane prepolymer that obtains.And to be that 10 quality % are following get final product the content of free NCO, but when the urethane prepolymer aqueous solution behind the consideration end-blocking stable, its content is preferably below the 7 quality %.
For the aforementioned urethane prepolymer that obtains, preferably use bisulfites to carry out end-blocking.With the bisulfites aqueous solution, Yi Bian fully stir, Yi Bian it was reacted about 5 minutes～1 hour.Reaction temperature is preferably set to below 60 ℃.Then, be diluted with water to suitable concentration, make the water-soluble urethane composition of thermal-reactive.Said composition has following character: be mixed with suitable concentration and viscosity in use, but usually when being heated to 80～200 ℃ of left and right sides, because end-capping reagent bisulfites disassociation, the regeneration of active isocyanate base, so the sudden reaction of or intermolecular generation interior by the prepolymer molecule generates polyether polyols with reduced unsaturation, or the addition to other functional group takes place.
As 1 example of the resin (B) of the blocked isocyanate base that contains above stated specification, the trade name エ ラ ス ト ロ Application (Elastron) made of illustration the one worker industry System medicine (strain) typically.Because エ ラ ス ト ロ Application utilizes sodium hydrogensulfite that NCO is carried out end-blocking to form, there is the carbamoyl sulfonate group with strongly hydrophilic in molecular end, so that it becomes is water-soluble.
(b) crosslinking agent
In the present invention,,, heat-treat then, form the cover layer that comprises resin with cross-linked structure by in coating fluid, adding crosslinking agent in order to improve tectal humidity resistance.Crosslinking agent uses and to be selected from least a in epoxies crosslinking agent, the melamine class crosslinking agent, oxazoline class crosslinking agent.Crosslinking agent can be selected when considering to carry out with the compatibility of the copolymer polyester resin that is used for coating fluid and the hot adaptation of the desired moisture-proof of cover layer.
Particularly when requiring to have the hot adaptation of moisture-proof of height, in aforementioned crosslinking agent, preferred epoxies crosslinking agent or melamine class crosslinking agent.The epoxies crosslinking agent is not particularly limited, and for example, Na ガ セ changes into soluble epoxide crosslinking agent (the デ コ Na one Le series that Industrial Co., Ltd makes; EX-521, EX-512, EX-421, EX-810, EX-811, EX-851 etc.) can obtain as commercially available product.As the melamine class crosslinking agent, for example, the methylated melamine resin (MW-22, MX-706 etc.) of Sumitomo Chemical society manufacturing ス ミ テ Star Network ス resin series (M-3, MK, M-6, MC etc.) and Co., Ltd. three and the manufacturing of ケ ミ カ Le society can obtain as commercially available product.In addition, make to be oxazoline class crosslinking agent, the NX Linker FX that the エ Port Network ロ ス series (WS-700) that Nippon Shokubai Co., Ltd makes, Xin Zhong village chemical industry society make etc. can obtain as commercially available product.
Preferred cover layer forms with containing above-mentioned crosslinking agent in the coating fluid, and with respect to the total amount (100 quality %) of copolymer polyester resin in the cover layer and crosslinking agent, its content is preferably 5～40 quality %, more preferably 10～30 quality %.When the content of crosslinking agent surpassed 40 quality %, cover layer became fragile, and in the manufacturing procedure after forming functional layers such as the hard conating that is made of acrylic resin and diffusion layer, can't fully obtain sometimes only tolerating the high-speed cutting adaptation.On the other hand, when the content of crosslinking agent is lower than 5 quality %, be difficult to the durability that is required in recent years sometimes.Need to prove, crosslinked in order to promote in coating fluid, can add catalyst as required.
(c) solvent
In the present invention, so-called solvent is not only the liquid of dissolving resin, also broadly comprises the dispersant that uses in order to make resin dispersion become graininess.In order to implement the present invention, can be with an organic solvent, all kinds of solvents such as aqueous solvent.
The solvent that is used for coating fluid is the composite mixed liquor of scope of 30～50 quality % with the ratio that accounts for total coating fluid with alcohols such as water and ethanol, isopropyl alcohol, benzylalcohols preferably.And, if it is lower than 10 quality %, then mix getting final product in the scope of the organic solvent beyond can dissolving alcohols.But in coating fluid, the total amount of alcohols and other organic solvent is set at and is lower than 50 quality %.
When the addition of organic solvent is lower than 50 quality % with respect to total solvent, have following advantage: drying property improves when coating is dry, simultaneously, compares with the situation of independent water, and the outward appearance of coating layer is improved.When the addition of organic solvent is 50 quality % when above with respect to total solvent, the evaporation rate of solvent is accelerated, and causes the change in concentration of coating fluid in coating easily.Its result, because the viscosity of coating fluid rises, coating reduces, so cause the bad order of coated film sometimes.And, because of the danger of volatilization initiation fire of organic solvent etc. also raises.In addition, when the addition of organic solvent is lower than 30 quality % with respect to total solvent, the ratio of water increases relatively, the high polyurethane component segregation of hydrophily is in cover surface, in the laminated thermoplastic resin film that finally obtains, be difficult to the PEs surface branch rate of cover surface is controlled to be in the scope of the present invention's regulation.
(d) pH of coating fluid adjusts
In the present invention, the coating fluid that uses in order to form cover layer, its pH is preferably more than 5, and is lower than 8 scope.When the pH of coating fluid is lower than 5, may make easily then that PEs surface branch rate is bigger than the scope of the present invention's regulation, adaptation is poor.On the other hand, when the pH of coating fluid be 8 when above, because because of significant cohesion takes place the kind of particle, so mist degree rising transparency deterioration is not preferred.The pH conditioning agent only otherwise adaptation, block resistance, coating are brought baneful influence maybe can be ignored, and just is not particularly limited.Can use sodium acid carbonate or sodium carbonate when for example, improving pH; Can use acetic acid etc. when reducing pH.
(e) surfactant also uses
When aforementioned water-based coating fluid being coated the base material film surface, in order to improve wetability, be coated with coating fluid equably to this film, generally use surfactant.In the present invention, in addition,, can use surfactant as being used to one of method of controlling the specific PEs surface branch rate of cover surface.
For surfactant, as long as can obtain good coating, and can obtain the PEs surface branch rate that the present invention stipulates, its kind just is not particularly limited.In surfactant, for the interpolation with trace obtains good coating, preferred fluorine is a surfactant.And in order to obtain the PEs surface branch rate of the present invention's regulation, preferred coating fluid relatively cooperates cationic surface active agent or the nonionic surface active agent of 0.01～0.18 quality %.
When using anionic surfactant, can improve sometimes with aforementioned shown in copolyester and the intermiscibility of polyurethane, be difficult to obtain the phase separation structure of the present invention's regulation.For the addition of surfactant, so long as do not influence adaptation with functional layers such as hard conating and diffusion layers, can obtain the scope of good coating, just can suitably select.For example, be the occasion of surfactant at fluorine, preferably its addition be from respect to the critical micelle concentration of pure water to its below 30 times.Since when its be critical micelle concentration more than 30 times the time, the particle that contains in the coating fluid condenses easily, so the mist degree of the laminated film that obtains rising is particularly not preferred as the base material film of optical functional film or optical functional sheet material.In addition, surfactant component oozes out in cover surface, also adaptation is brought harmful effect sometimes.On the other hand, when it is critical micelle concentration when following, can not obtain good coating.In addition, be difficult to control the scope of the PEs surface branch rate of the present invention's regulation.
(making with extra care of surfactant)
Be used for surfactant of the present invention, the preferred surfactant that refines that uses.The surfactant of listing contains the impurity of trace usually mostly.Particularly, obtain good phase separation structure because of its content influence sometimes as the polyethylene glycol of impurity.In order to prevent this situation, preferably carry out from surfactant, removing the pre-treatment of impurity, use the surfactant that refines.
As the pretreatment procedure of removing impurity, so long as being gone bad, surfactant can not remove impurity, its method is not particularly limited.Can exemplify following method.
For example, be dissolved in the organic solvent that can dissolve to major general's surfactant and polyethylene glycol, leave standstill at low temperatures, make surfactant carry out saturated precipitation, filter then, take out the method for the surfactant that has improved purity as main component.In the occasion of perfluoroalkyl ethylene oxide adduct class surfactant, in 30 ℃ water-bath, isopropyl alcohol is carried out heating for dissolving, after leaving standstill about 24 hours under 0 ℃, filter and take out sediment, the surfactant of the purity that has been improved thus.
(f) particle
The mist degree of laminated thermoplastic resin film of the present invention is below 1.5%, is important when using as the base material film that requires high optical functional film of the transparency or optical functional sheet material.Further preferred aforementioned mist degree is below 1.0%.When mist degree surpasses 1.5%, when film being used for lens coating that LCD uses and backlight, because the definition of picture reduces, so not preferred with base material film etc.
For the mist degree that makes laminated thermoplastic resin film of the present invention is below 1.5%, do not contain particle in the preferred substrates film.When in base material film, not containing particle, in order to improve tectal marresistance and to be wound into the roller shape and handling (the following the degassing of air etc. when sliding, mobility, adherence, coiling) in when rolling, the particle that contains the suitable size of specified quantitative in the preferred cover layer, it is suitable concavo-convex that cover surface is formed.
As particle, preferably with copolymerization polyester resin or the high particle of polyurethanes resin compatibility, there is the difference that is stored in any degree in mutually partially in the compatibility of preferred these two kinds of resins relatively.By particle is stored in partially particle has been carried out among the side of the resin that is separated, particle is suitably concentrated, even add fewer particle, promptly mist degree is risen significantly, also can obtain good block resistance.
The particle that cover layer contains for example has: inorganic particles such as calcium carbonate, calcium phosphate, amorphism silica, crystalline glass filler, kaolin, talcum, titanium dioxide, aluminium oxide, silica-alumina composite oxide particle, barium sulfate, calcirm-fluoride, lithium fluoride, zeolite, molybdenum sulfide, mica; Hear resistance polymeric particles such as crosslinked polystyrene particle, crosslink propylene acid resin particle, crosslinked methyl methacrylate class particle, benzo guanamine formaldehyde condensation composition granule, carbamide condensation product particle, polytetrafluoroethylgranule granule.
In these particles, consider the preferred oxygen silicon carbide particle from the following aspect.
The 1st advantage: because it is more approaching with the refractive index ratio of tectal resinous principle, so obtain the transparent film of height easily.The 2nd advantage: silicon oxide particle has and is stored in easily the polyurethanes resin that the is separated feature in mutually partially, and the block resistance of polyurethanes resin phase that is present in cover surface is poor, can replenish the intrinsic character of polyurethanes resin.Its reason is, it has been generally acknowledged that, the resinoid surface energy of silicon oxide particle and polyurethane is more close than polyester resin, the compatibility height.
In addition, coating of particles is not particularly limited, but considers from giving easy sliding aspect, preferably near spherical particle.
With respect to cover layer, the granule content in the cover layer is preferably below the 20 quality %, more preferably below the 15 quality %, is preferably especially below the 10 quality %.When the granule content in the cover layer surpasses 20 quality %, make the adaptation of transparency deterioration, film also insufficient easily.On the other hand, with respect to cover layer, the lower limit of granule content is preferably set to 0.1 quality %, further preferred 1 quality %, preferred especially 3 quality %.
In addition, can contain the different particle of average grain diameter more than 2 kinds in the cover layer.In addition, also can contain the different particle of the same race of average grain diameter.In a word, as long as the average grain diameter and the total content of particle are aforementioned range.In coating during aforementioned coating fluid, in order to remove the thick condensation product of particle in the coating fluid, preferred configurating filtered material before coating is so that its secondary filter coating fluid.
In addition, the average grain diameter of particle is preferably 20～150nm, more preferably 40～60nm.When average grain diameter was lower than 20nm, except being difficult to obtain the sufficient block resistance, its marresistance might deterioration.On the other hand, when the average grain diameter of particle surpassed 150nm, because its mist degree rises, and particle came off easily, so not preferred.
In the present invention, be the particle A of 20～150nm only with average grain diameter, can not obtain sufficient block resistance and marresistance sometimes.Therefore, in order further to improve block resistance and marresistance, further preferred a small amount of and with the big particle B of average grain diameter.The average grain diameter of the particle B that average grain diameter is big is preferably 160～1000nm, is preferably 200～800nm especially.When the average grain diameter of particle B is lower than 160nm, its marresistance, sliding, crimpiness deterioration sometimes.On the other hand, when the average grain diameter of particle B surpassed 1000nm, its mist degree might raise.In addition, particle B is preferably the agglomerate particle that primary particle cohesion forms, and considers from the marresistance aspect, and the ratio that preferably uses the average grain diameter of average grain diameter under the state of aggregation and primary particle is the particle more than 4 times.
When using two kinds of particles, for example with the particle A in the cover layer (average grain diameter: 20～150nm) with particle B (average grain diameter: 160～1000nm) content is set at 5～30 than (P1/P2), and, with respect to tectal solid constituent, the content of particle B is set at 0.1～1 quality %.Preferably the content with the particle of two kinds of specified particle diameters is controlled to be aforementioned range, thus the three-dimensional center face average surface roughness of cover surface is suitably changed, and makes the transparency, handling and block resistance is balanced.When the content with respect to tectal particle B surpassed 1 quality %, mist degree might significantly rise.
Utilize following method to measure the average primary particle diameter and the average grain diameter of aforementioned particles.
With electron microscope particle is taken pictures,, its mean value is set at average primary particle diameter or average grain diameter so that the size of 1 minimum particle is the maximum gauge of 300～500 particles of magnifying power mensuration of 2～5mm.In addition, during the average grain diameter of the particle in asking the cover layer of laminated film, use transmission electron microscope (TEM),, can obtain the maximum gauge of the particle that is present in tectal section with 120,000 times of sections of taking laminated film of magnifying power.The assay method of the average grain diameter of the particle B that is made of agglomerate is as follows: use light microscope with 200 times of tectal sections of taking 300～500 laminated films of magnifying power, measure its maximum gauge.
(3-2) painting process
Be coated with the online rubbing method that the operation of aforementioned water-based coating fluid preferably is coated with in the manufacturing process of this film.Further preferably be coated on the base material film before crystalline orientation finishes.Solid component concentration in the water-based coating fluid is preferably below the 30 quality %, is preferably especially below the 10 quality %.The lower limit of solid component concentration is preferably 1 quality %, 3 quality % more preferably, be preferably 5 quality % especially, be coated with the film of this water-based coating fluid with the coating weight of this water-based coating fluid, in order to be orientated and heat setting, be imported in the jar, be heated at this, utilize the heat cross-linking reaction to form stable tunicle, become the polyesters laminated film.
(coating weight)
Coating weight when dry (below, slightly be designated as wet coating weight) is preferably 2g/m
2Above 10g/m
2Below.When wet coating weight is lower than 2g/m
2The time, when the dry-coated amount of wanting to obtain designing (final tectal coating weight), must improve the solid component concentration of coating fluid.Because when improving the solid component concentration of coating fluid, the viscosity of coating fluid raises, so be easy to generate the coating spot of striated.On the other hand, when wet coating weight be 10g/m
2When above, be subjected to the influence of the dry wind in the drying oven easily, be easy to generate the coating spot.Need to prove,, preferably under with the cleaning ambient of cleannes classification below 5000, be coated with coating fluid for the defective that prevents to cause by adhering to of dust.
In addition, final tectal coating weight (the solid constituent quality of film per unit area) preferably is controlled to be 0.005～0.20g/m
2Prior art is lower than 0.05g/m in coating weight
2The time be difficult to obtain sufficient adaptation.But, because cover layer has specific phase separation structure, therefore, even coating weight is lower than 0.05g/m
2, also can obtain the laminated film that relative functional layer and base material have good adaptation.When coating weight is lower than 0.005g/m
2The time, adaptation is insufficient.In addition, be lower than 0.05g/m when coating weight
2The time, the particle of its use preferably uses average grain diameter to be the particle below the 60nm.When the average grain diameter of particle surpassed 60nm, particle came off from cover layer easily.Be stored in the polyurethane phase time partially at particle, as long as coating weight is 0.005g/m
2More than, particle just is difficult to come off.On the other hand, surpass 0.20g/m when coating weight
2The time, segregation becomes many in the polyurethanes resinous principle of cover surface, and block resistance reduces.
In addition, can measure tectal thickness, but when cover layer is soft, when cutting off, deform sometimes by cutting off tectal section with slicer and observing with electron microscope.Short-cut method is, if coating weight is known, then can carry out thickness conversion by tectal density.For example, be 1g/m in tectal density
3The time, if coating weight is 1g/m
2, then thickness is equivalent to 1 μ m.The estimation method of tectal density is as follows: obtain the density of various materials by the kind that constitutes tectal resin, particle, multiply by the mass ratio of material with the density of each material, ask itself and, can infer tectal thickness thus.
(3-3) drying process
In the manufacture method of laminated thermoplastic resin film of the present invention, behind coating coating fluid on the base material film, carry out drying with being coated with filming of forming thinly.Generally speaking, when behind the coating coating fluid, making dried coating film, utilize the preheating section of jar to make its drying mostly.At this moment, the size of membrane equipment also depends on the translational speed of film, but generally spends at least about 5 seconds from being applied to the dry time that begins.During this period, as the water and the pure disequilibrium of the solvent of coating fluid, the high easy segregation of polyurethane composition of hydrophily is in cover surface.Therefore, in the laminated thermoplastic resin film that finally obtains, be difficult to the PEs surface branch rate of cover surface is controlled in the specific scope.Important part of the present invention is that the film direct of travel that the drying oven (pre-drier) that is specifically designed to dry coating is configured in from apparatus for coating exports very near place, after coating fluid is coated polyester film, makes its drying immediately.
In drying oven, the temperature of the dry wind of contact coated face is preferably more than 120 ℃, and is lower than 150 ℃.In addition, wind speed is preferably 30m/ more than second.Further preferred baking temperature is more than 130 ℃, and is lower than 150 ℃.Be lower than 30m/ during second when this baking temperature is lower than 120 ℃ or wind speed, rate of drying is slack-off, and as the water and the pure disequilibrium of the solvent of coating fluid, the relative ratios of water increases easily.Therefore, the high polyurethane component segregation of hydrophily in the laminated thermoplastic resin film that finally obtains, is difficult to obtain the PEs surface branch rate of the present invention's regulation in cover surface.On the other hand, when baking temperature is more than 150 ℃ the time, the crystallization of base material film takes place easily, the frequency that fracture takes place when cross directional stretch increases.
In addition, in aforementioned drying oven, preferred on one side with temperature maintenance more than 120 ℃, and be lower than 150 ℃, Yi Bian make its drying 0.1～5 second.More preferably 0.5～3 second drying time.When be lower than 0.1 second drying time, that films was dry insufficient, when being configured in the roller of drying process between the cross directional stretch operation, this roller was polluted because of the inadequate coated face of drying.On the other hand, when surpass 5 seconds drying time, the crystallization of base material film takes place easily, the frequency that fracture takes place when cross directional stretch increases.
Preferably use aforementioned drying oven inherent more than 120 ℃, and be lower than will film under 150 ℃ the temperature carry out drying after, will have tectal laminated film and be cooled near the room temperature immediately.During near the roller surface temperature of aforementioned laminated film is the drying oven of the high temperature more than the 100 ℃ room temperature of coming out of laminated film contact, because of the contraction of film is easy to generate scar.
When the wind speed in the drying oven being set at usually 30m/ second when above, because strong dry wind contacts the not coated face of drying regime in drying oven, so be easy to generate uneven drying.But, in the present invention,, can carry out with the wind speed of 30m/ more than second by being discharged to outside the drying oven with amount or the air quantity more than it with the blowing amount.In addition, importantly, this exhaust wind direction and coating machine opposition side are flowed, prevent from inequality to take place because coating machine causes the coated face that exhaust wind is formed.
Importantly, will from the coating after to the film that enters drying oven by time set for being lower than 2 seconds, preferably being lower than 1.5 seconds.When being more than 2 seconds the time from being applied to the time that enters drying oven, during this period as the water and the pure disequilibrium of the solvent of coating fluid, thus, the high easy segregation of polyurethane composition of hydrophily is in cover surface.Therefore, the laminated thermoplastic resin film that finally obtains is difficult to the PEs surface branch rate of cover surface is set at particular range.
To be lower than 2 seconds in order will after coating, being held in by time dimension, need the translational speed of suitable selective membrane, but preferred coating machine and drying oven to enter the mouth approaching as much as possible to the film that enters drying oven.Need to prove, in drying oven, in order to prevent to sneak into the preferred air of crossing with the HEPA filter cleaning that uses from the dust of dry wind.The HEPA filter that use this moment, the preferred use has the filter that cutting 95% above nominal filtering accuracy is the performance of the above dust of 0.5 μ m.
Drying process preferably change successively conditions such as baking temperature and drying time, constitute by the so-called dry section that is divided into 2～8 sections.The preferred especially multistage drying device that is divided into 3～6 sections that adopts.For example, at uniaxial orientation thermoplastic resin membrane's one or both sides coating coating fluid, with being configured in multistage drying oven directly over the coating machine when coating fluid is carried out drying, preferred following method.
For example, when carrying out drying, carry out drying with the drying oven that is divided into 4 dry sections with 4 stages.Can exemplify following method:, under 125～140 ℃ of temperature, make its drying 0.1～4 second at the 1st dry section; At the 2nd dry section, under 55～100 ℃ of temperature, make its drying 0.1～4 second; At the 3rd dry section, under 35～55 ℃ of temperature, make its drying 0.1～4 second; At the 4th dry section, under 25～35 ℃ of temperature, make its drying 0.1～4 second.
The number range of aforementioned drying condition has a little change according to the solid component concentration of coating fluid, is not limited to the condition of above-mentioned representative.And importantly, when carrying out heated-air drying, air quantity also changes to some extent in each stage.
For example, be preferably as follows method.
In the 1st dry section, the wind speed of dry wind is set at 20～50m/ second, the air feed air quantity of dry wind is set at 100～150m
3/ second, the exhaust air quantity is set at 150～200m
3/ second.From the 2nd dry section to the 4 dry sections, the air feed air quantity is set at 60～140m
3/ second, the exhaust air quantity is set at 100～180m
3/ second.In any dry section section, set dry wind and do not flow at the coating pusher side, continue to control the end of film with clamp, import wind speed 10～20m/ hot blast section of second down for 100 ℃～140 ℃ in temperature, broad ways is stretched to 2～6 times.
In addition, with temperature maintenance in 120 ℃～150 ℃, in 0.1～5 second, preferred 0.5 second～3 seconds time, suitably adjust and get final product baking temperature and total drying time.Determining of each section in this drying process (section) can be considered the various conditions such as temperature, wind speed, air quantity of translational speed, the hot blast of the concentration, coating weight of dispersion liquid, coated moving film, making on-the-spot determine suitable, exact value.
(3-4) heat-set treatment operation
In the manufacture method of laminated thermoplastic resin film of the present invention, cross directional stretch operation, heat-set treatment operation, refrigerating work procedure separate, so that its to strengthen continuously be 10～30 sections, and each section can carry out temperature control independently, and, with temperature mode jumpy not taking place designs between each section.Particularly set section from the cross directional stretch section second half section to the heat setting maximum temperature,, can suppress the rapid variations in temperature between adjacent section by heat up interimly.In the present invention, when the manufacturing cover surface had the laminated thermoplastic resin film of special phase separation structure, particularly in drying process and heat-set treatment operation, the control temperature was very important.In addition, in order to form cross-linked structure in constituting tectal resin, the temperature in the heat-set treatment operation is very important, and this temperature has influence on cross-linking reaction speed widely.Below, describe this embodiment in detail.
As previously mentioned, in heat-set treatment operation of the present invention, the tectal phase-separated state in the heat-treat condition left and right sides.That is, importantly, suitably set maximum temperature in the heat-set treatment operation, reach time that aforementioned maximum temperature needs, and the temperature that begins significantly to be separated from cover layer to time that the maximum temperature that reaches the heat-set treatment operation needs.
Temperature in each heat-set section in the heat-set treatment operation has a little difference because of the kind of the thermoplastic resin membrane's of base material formation resin is different, but as long as suitably sets in 100～260 ℃ temperature range.Below, will be as the thermoplastic resin of representative be that the situation of base material film describes for example with the PETG.
Maximum temperature in the heat-set treatment operation preferably is controlled to be 210～240 ℃, and further preferred lower limit is 225 ℃, on be limited to 235 ℃.In general, in the initial stage of heat-set treatment, mostly 210～240 ℃ and than higher temperature under carry out heat setting, along with having arrived after-stage, be 100～200 ℃, temperature reduces successively.
If the maximum temperature in the heat-set treatment operation is lower than 210 ℃, then in cover layer, be difficult to form micro phase separation structure or receive phase separation structure.Therefore, be difficult to the base material of the interface peel that required in recent years fully, the impact in the time of restraining oneself by high-speed cutting causes and the adaptation of functional layer.And it is big, not preferred that the percent thermal shrinkage of the laminated film that obtains becomes.
In addition, when the maximum temperature in the heat-set treatment operation surpasses 240 ℃, the PEs of cover surface surface branch rate becomes big, and the adaptation of hard conating, diffusion layer, layers of prisms, the functional layers such as printed layers that form with the ultraviolet curable ink printing reduces easily relatively.And, because the temperature that begins to be separated significantly from cover layer is elongated to the time that the maximum temperature that reaches heat-set treatment needs, so be that the width at the thinnest place of the polyester phase of main component is spread state above the position of 1 μ m with the copolyester resinoid.Its result, the functional layers such as printed layers that form with respect to hard conating, diffusion layer, layers of prisms, with the ultraviolet curable ink printing, the position that produces the adaptation difference partly is that starting point causes macroscopic view and peels off with this part sometimes.
Specifically the temperature that begins to be separated significantly from cover layer, was preferably as follows and sets to the time that the maximum temperature that reaches heat-set treatment needs.
In the present invention, the temperature that begins to be separated significantly from cover layer is set section sets the segment entry to the maximum temperature that reaches the heat-set treatment operation film by the time, and is preferred more than 3 seconds below 20 seconds, preferred especially more than 4 seconds below 15 seconds.
If aforementionedly be lower than 3 seconds by the time, be used to manifest the deficiency of time of the phase separation structure of the present invention's regulation sometimes.On the other hand, if aforementioned by the time be more than 20 seconds, then be separated and excessively carry out, be that the position that the width at the thinnest place of the polyester phase of main component surpasses 1 μ m is spread state easily with the copolyester resinoid.Its result produces relative hard conating, diffusion layer, layers of prisms, partly with the position of the adaptation difference of the functional layers such as printed layers of ultraviolet curable ink printing, is that starting point causes macroscopic view and peels off with this part sometimes.
In the present invention, the temperature that so-called cover layer begins to be separated significantly in the scope that the coating fluid shown in the embodiments of the invention is formed, is speculated as about 200 ℃.But, though this temperature is natural and since because of the difference of tectal resinous principle different, so be not limited to this temperature.
The heat-set treatment operation is further described particularly.
In general,,, in jar, be divided into 10～30 sections, carry out temperature control independently at each section for the temperature that suppresses adjacent each section sharply changes for cross directional stretch operation, heat-set treatment operation, refrigerating work procedure.Particularly from second half section of cross directional stretch section to the section of the maximum temperature that is set at the heat-set treatment operation, preferably the temperature of each section is heated up, so that rapid variation does not take place the temperature between each heat-set section with respect to the film direct of travel.
In the present invention, importantly, make from the beginning temperature of carrying out significantly that is separated and set section sets the segment entry to the maximum temperature that reaches the heat-set treatment operation film, heat up fast and equably by the time.For temperature is risen, the method that improve the method for heat transference efficiency in each heat-set section, for example improves the wind speed of the hot blast that blows to film is effective.But, in the method, owing to generally be easy to generate the temperature inequality, so produce uneven sometimes in tectal phase-separated state, sometimes the impurity such as oligomer that only are attached in heat-set section in the device float, and the impurity that floats is attached to film, cause optical defect.
On the other hand, cross when low, can not obtain sufficient programming rate when wind speed.Therefore, in the present invention, preferably wind speed is set at 10m/ second above 20m/ below second.For laminated film is heated up, the interval that will be used for the nozzle of blowing hot-air is effective with the method that the relatively shorter interval below the 500mm is configured.In the arranged spaced of the nozzle that will be used for blowing hot-air is 500mm when following, for example unfavorable in the corrective maintenance when nozzle arranged spaced becomes 300mm, 350mm, 400mm, but is important for finishing the present invention.If whenever being equivalent to the nozzle number of one section 1 section is about 6～10, then considers the state of nozzle interval, ventilation, ventilation time and determine its radical.Need to prove that wind speed of the present invention is meant the wind speed in the film surface that blows out hot-blast spray nozzle outlet, use hot type airspeedometer (Japanese カ ノ マ Star Network ス makes, ア ネ モ マ ス one モ デ Le 6161) to measure.
Below, represent a preferred implementation of heat-set treatment operation of the present invention.
Aforementioned hot setting treatment process separates, so that strengthen continuously being a plurality of heat-set section, and each section can carry out temperature control independently.Heat-set section preferably is arranged with the operation of 2～10 sections heat-set section continuously, preferably is divided into 4～8 sections operation, carries out the temperature control and management of laminated film in the heat-set section that is divided into this multistage.
Can exemplify following method: have the occasion of tectal polyester film, make it by the heat-set section that is divided into 6 sections successively continuously as described below, keep delicate temperature difference in each stage, carry out heat-set treatment, the coating layer portion that do not have at film two ends is repaired.Aforesaid heat-set treatment temperature is set at: 200 ℃ of the 1st heat-set section, 225 ℃ of the 2nd heat-set section, 230 ℃ of the 3rd heat-set section, 230 ℃ of the 4th heat-set section, 210 ℃ of the 5th heat-set section, 170 ℃ of the 6th heat-set section, the 7th heat-set section are 120 ℃.In addition, carry out 3% relaxation processes in the 6th heat-set section broad ways.
Aforesaid section is equivalent to 1 heat-set section.Preferred keep delicate temperature difference in the temperature of the heat-set section of each section as mentioned above, promptly keep the temperature difference about 5～40 ℃.The setting of this temperature difference is considered to have tectal thermoplastic resin membrane's various principal elements such as translational speed, air quantity and tectal thickness and is at random determined.
As the base material film of optical functional film such as lens coating and diffuser plate or optical functional sheet material the time, even film thickness is the above thicker films of 100 μ m, generally, be at least more than the 1000m, be to be wound into the form supply lamination layers of prisms of roller shape and the manufacturing procedure of diffusion layer more than the 2000m sometimes with film length.
In the present invention, along the length direction of film during with the area ratio (PEs surface branch rate) of the polyester phase A (showing darker shade in the phase place picture) of 100m measuring space cover surface, the maximum of the PEs surface branch rate of the cover surface of preferred length direction and the difference of minimum of a value are set at below 15%, more preferably below 10%.By the maximum of the PEs surface branch rate of the cover surface of this length direction and the difference of minimum of a value are set at below 15%, obtain having the laminated thermoplastic resin film roll of stable adaptation and block resistance.
For the maximum of the PEs surface branch rate of the cover surface of length direction and the difference of minimum of a value are controlled to be below 15%, importantly when making laminated thermoplastic resin film roll of the present invention, remain film forming conditions such as the composition of coating fluid, coating condition, drying condition etc. and heat-setting condition constant.But the ratio that is used for the mixed solvent of coating fluid changes especially easily, and the ratio of this mixed solvent is remained constant method, is being important aspect the change of the PEs surface of the length direction that reduces film volume branch rate.In the present invention, for example, can be controlled at below 15% by the amplitude of fluctuation of the method shown in following with PEs surface branch rate.Need to prove that the ratio of mixed solvent remains constant method, be not limited to following method.
With respect to the capacity of the pallet of coating fluid (Fig. 7 11), increase the capacity of circulation with jar (Fig. 7 13), be effective making aspect the concentration ratio stabilisation of mixed solvent.Specifically, as shown in Figure 7, be set at 1 o'clock, be set at circulation preferred more than 10, preferred more than 50 especially with the ratio of the capacity of jar at capacity with the pallet of coating fluid.Be lower than 10 in Capacity Ratio (circulation with jar the capacity of pallet of capacity/coating fluid), i.e. circulation with jar capacity when too small, the change of the concentration ratio of mixed solvent becomes greatly easily.
And, will circulate with jar capacity be set at 1 o'clock, the ratio that preferably will prepare with the capacity of jar (Fig. 7 14) is set at more than 10, and is preferred especially more than 20.Therefore, with coating fluid from preparation with jar supply with circulation with jar the time, circulation with jar capacity when working, can often keep constant.
In addition, the precision of the dispenser roller in the rising apparatus for coating (circularity and cylindricity) also is effective aspect the change of the PEs surface branch rate in reducing the length direction of film volume.
The circularity of so-called aforementioned dispenser roller shown in JIS B 0621, is the index of representing with the difference of two concentrically ringed each radiuses that utilize the definite Minimum Area method of service recorder formula circularity analyzer to form.Need to prove that the unit of the circularity of roller is mm.In addition, the cylindricity of dispenser roller is the index of following mensuration: move along axis direction this roller is placed on band mircrometer gauge platform on the price fixing, on cylinder, under the state of measuring son, implement in the various mensuration plane in length range to measure, represent with 1/2 of the maximum difference that reads this moment.Need to prove that the unit of cylindricity is mm.
In the present invention, roller precision (circularity and cylindricity), can reduce the deviation of thickness of the coating layer of length direction by improving.Specifically, preferably roller precision (circularity and cylindricity) is set at below the 5/1000mm.
In addition, when the coating coating fluid, the Surface Finishing of each roller of duplex coater is set at below the 0.3S, and, be set at below the 5/1000mm, more than the 2/1000mm by precision (circularity and cylindricity) dispenser roller and measuring roller, can suppress the change of wet coating weight, and the deviation that can suppress to film.Can preferably use the applicator roll of the precision (circularity and cylindricity) of dispenser roller and measuring roller as 3/1000mm.
In addition, (blank width of film is 1～2m), can keep the flatness of film on commercial scale, and the transfer printing quantitative change of coating fluid gets evenly to be set at 4000～10000N/ blank width by the tension force with film.Need to prove that the tension force of film is different because of the thickness of film, relatively Bao film keeps flatness by applying lower tension force.
When the tension force of film surpasses the 10000N/ blank width, film blank deformation or fracture sometimes.On the other hand, if the tension force of film is lower than the 4000N/ blank width, the flatness of the film when being coated with sometimes is insufficient or produce the wrinkle of film.Its result, the transfer printing amount of coating fluid is inhomogeneous at the length direction of film, and the wet coating weight of film changes widely, and thus, it is bigger that the deviation of the thickness of coating layer also becomes.
In addition, for the maximum of the PEs surface branch rate of the width of film volume and the difference of minimum of a value are controlled to be below 10%, importantly reduce the deviation of thickness of coating layer of the width of relative film volume.The flatness of the width when therefore, improving coating is effective.Specifically, with after the two sides roller coat cloth, use pinch roll (Fig. 7 16) only to control the both ends of the surface of film.By control the both ends of the surface of film with pinch roll, on commercial scale, improve the flatness of the width of film, make the wet coating weight stabilisation of the width of film.Thus, can reduce the deviation of coating layer of the width of film volume.When controlling the two ends of film without pinch roll, the big cataclysm of wet coating weight of the width of film and length direction, it is big that the deviation of coating layer thickness also becomes more.
Embodiment
Below, to the formation of laminated thermoplastic resin film of the present invention and action effect, manufacture method, use embodiment and comparative example to describe, the present invention is not limited to these embodiment certainly.In addition, following method is used in the rerum natura of each film among the embodiment and evaluation.
(1) PEs surface branch rate
(1-1) evaluation of phase separation structure
Use scanning probe microscopy (エ ス ア イ ア Na ノ テ Network ノ ロ ジ Yi System, SPI3800N system/SPA300), carry out the evaluation of tectal phase separation structure with phase determination pattern (phase place mode).In the phase place picture, phase place is slow to be manifested bright more greatly more, and on the contrary, phase place is slow more little, manifests dark more.So-called phase place is slow little, be meant compare hard with other or attraction smaller.In the cover layer of laminated thermoplastic resin film of the present invention, darker shade is polyester phase A, and the light colour layer is a layer of polyurethane.
The measuring principle of the phase determination pattern in the scanning probe microscopy, be recorded in エ ス ア イ ア Na ノ テ Network ノ ロ ジ one Co., Ltd. website (http://www.siint.com/technology/probe_applications.html) " 1-2. uses the pdf document folder of " 1. the utilizing the phase determination of SPM " on the Phase hurdle in (alternate manner).
The cantilever that is used to measure mainly uses DF3 (spring fixed number: about 1.6N/m), for the sensitivity that prevents to be caused by the probe pollution and the reduction of resolution ratio, often use new product.Scanner uses FS-20A.In addition, overview setup is more than resolution ratio 512 * 512 pixels, and field of view is set at 5 μ m * 5 μ m.Location parameters such as the amplitude damping factor of the cantilever during mensuration and sweep speed, scan frequency are set with the condition of implementing line scanning, can sensitivity resolution ratio observe best.
Read by the aforementioned phase place mode image that obtains (bit flag form, 512 * 512 pixels) with image processing software (Adobe System, Photoshop ver7.0), it is presented on the display, so that its image size is 205mm * 205mm (with reference to Fig. 1, Fig. 8).Then, utilization is with the pencil tool (normal diameter: 3px), describe the line of black on the border of light colour phase and darker shade, the border of clear and definite two-phase (with reference to Fig. 2, Fig. 9) of software.And use with the darker shade painted black, with light colour phase painted white, is carried out 2 values (with reference to Fig. 3, Figure 10) with the full instrument of being coated with of software.At this moment, be positioned at dark-coloured portion below the light colour diameter 2mm mutually with the size of picture, be judged as the particle that is stored in the light colour phase partially, being coated with expires into white.For example, when using silicon oxide particle, as mentioned above, can confirm to be stored in partially the light colour layer.
(1-2) mensuration of PEs surface branch rate
(1-2-1) image analysis method
With with software with this 2 value image table be shown with brightness (black, white) be transverse axis, be the block diagram of the longitudinal axis, obtain the area ratio of black part, be set at the surperficial branch rate of PEs with the number of degrees.
(1-2-2) paper weight method
Except that the image analysis method, also can use the paper weight method to carry out the mensuration of aforementioned PEs surface branch rate.Determination step is as follows.
To preserve as the digital picture of bit flag form by the aforementioned phase place mode image that obtains.Then, this image is exported on matter paper on the A4 version with printer (Xerox System, DocuPrintC830) printing.(the light colour phase in the image of affirmation and the border of darker shade are clearly estimated in 200mm * 200mm), bright indoor under the illumination of 500 luxs with the 4B pencil to the image of output.At this moment, be to be stored in the particle that contains in the cover layer of light colour in mutually partially owing to confirm to be present in the following darker shade of diameter 0.1 μ m of light colour in mutually, so do not draw the boundary line, be set at and be contained in the light colour phase.Then, clear and definite light colour mutually and on the boundary line of darker shade by cutting apart with cutter, measure the quality of the paper of light colour phase (layer of polyurethane (B)) and darker shade (polyester is A mutually), unit with % obtains the ratio of the paper of light colour phase and darker shade with respect to the quality of the darker shade (polyester is A mutually) of gross mass, and being set is PEs surface branch rate.
(1-2-3) amplitude of fluctuation of PEs surface branch rate (maximum and minimum of a value poor)
(a) length direction of film volume
Roll out the laminated thermoplastic resin film roll that long 1000m is above, wide 50mm is above, length direction (MD) for this film, measure the area ratio (PEs surface branch rate) of the polyester phase A (showing darker shade in the phase place picture) of aforementioned cover surface at following position, obtain the poor of the maximum of the PEs surface branch rate that obtains and minimum of a value.
The assay method of the PEs surface branch rate of cover surface is as follows, one end in the constant zone that the film rerum natura is stable is set at the 1st end, when the other end is set at the 2nd end, carrying out the first time below the inboard 2m of the 1st end measures, in addition, below the inboard 2m of the 2nd end, finally measure, simultaneously, carry out once since the 1st the every 100m in mensuration place.
(b) width of film volume
Roll out the laminated thermoplastic resin film roll that long 1000m is above, wide 50mm is above, length direction (MD) for this film, roll out aforementioned lamination thermoplastic resin membrane volume, broad ways is divided into 4 equal portions with film, measure the area ratio (PEs surface branch rate) of the polyester phase A (showing darker shade in the phase place picture) of cover surface at separately central portion, obtain the poor of the maximum of PEs surface branch rate of cover surface of width and minimum of a value.The especially big roller that can be divided into the width with film before the small size size carries out this mensuration.
(2) the minimum position that surpasses 1 μ m of the width of polyester phase A has or not
In aforementioned phase place mode image, for the different positions of measuring, 10 places, research is having or not of the width of short-axis direction of the polyester phase A of the main component position that surpasses 1 μ m at the thinnest place with the copolyester resinoid.
(3) fractal dimension
(エ ス ア イ ア Na ノ テ Network ノ ロ ジ one makes, SPI3800N system/SPA300) to use aforementioned scanning probe microscopy, (Adobe manufacturing, Photoshopver7.0) reads the phase place mode image (bit flag form, 512 * 512 pixels) that is obtained by phase determination pattern (phase place mode) with image processing software, it is presented on the display, so that its image size is 205mm * 205mm (with reference to Fig. 1, Fig. 8).Then, utilization is with the pencil tool (normal diameter: 3px), describe the line of black on the border of light colour phase and darker shade, the border of clear and definite two-phase (with reference to Fig. 2, Fig. 9) of software.At this moment, be positioned at dark-coloured portion below the light colour diameter 2mm mutually, be judged as the particle that is stored in the light colour phase partially, do not draw the operation of boundary line with respect to this part with the size of picture.For example, when using silicon oxide particle, as mentioned above, can confirm to be stored in partially the light colour layer.
On the basis that the image of clear and definite boundary line is preserved as bit flag form image, utilize the box-counting method to carry out fractal dimension and resolve, the index of the complexity of the boundary line that the FRACTAL DIMENSION numerical value that obtains is separated as expression.In the parsing that utilizes the box-counting method, use software AT-Image Ver3.2.Specifically, the bit flag image of keeping is opened on image analysis software (AT-Image Ver3.2), the separation of images from the menu is utilized the binary conversion treatment (with reference to Fig. 6) of brightness block diagram.Need to prove that the threshold value during binaryzation is set at 8.With respect to the image that binary conversion treatment is crossed, the image measurement from menu is selected fractal dimension, obtains fractal dimension.At this moment, an edge lengths being used in the calculating of the fractal dimension that utilizes least square method is the count results of the box of 6 pixels～63 pixels.
Need to prove, the parsing that utilizes the fractal dimension of box-counting method is a known method, in dimension is resolved, use other image analysis software or program,, also can use other software with congenerous as long as can obtain the repeatability of analysis result fully.So-called other software for example has image analysis softwares such as " the system fractal dimension resolution system version 3 .33 of National Agricultural Research Organization livestock products Grassland Research Institute ", " デ ジ Le PVC one イ Application グ キ Star ズ company makes PopImaging Ver.3.40 ".
(4) mensuration of mist degree
According to JIS K7136, use haze meter (Japanese Electricity look manufacturing, NDH2000), different parts 3 places of film sample are measured mist degree, use its mean value.
(5) with the adaptation of light-cured type acrylic compounds hard conating
(5-1) with the adaptation of the light-cured type acrylic compounds hard conating of solvent cutback
On the cover layer face of film sample, hard paint (manufacturing, セ イ カ PVC one system EXF01 (B) refine big day) 50 mass parts, toluene 25 mass parts, butanone 25 mass parts are mixed, the smears that fully stirred is coated with method with metal thread bar to be coated with, 70 ℃ removed in dry 1 minute down desolvate after, with high-pressure mercury-vapor lamp at 200mJ/cm
2, irradiation distance 15cm, translational speed 5m/ minute condition under, obtain having the hard coat film of the hard conating of thick 3 μ m.
On the glass plate of the thick 5mm that is pasted with two-sided tape, paste the opposing face of the hard conating of the hard coat film that obtains.Then, the cutter with gapping interval 2mm forms 100 grid-like otch that run through hard conating and cover layer arrival base material film.Then, adhesive tape (ニ チ バ Application company makes, No. 405,24mm wide) is sticked on the grid-like cut sides.With rubber by being pressed in the air that residues in the interface when pasting, make its complete driving fit after, vertically peel off adhesive tape rapidly.New adhesive tape is heavily pasted in further same operation, vertically peels off rapidly equally.With the strip operation of this adhesive tape repeatedly 10 times altogether, obtain adaptation by following formula range estimation.Need to prove that what take place partly to peel off is also contained in the number of peeling off in 1 grid.
Adaptation (%)=(1-grid peel off number/100) * 100
(5-2) with the adaptation of the light-cured type acrylic compounds hard conating of no-solvent type
On the glass substrate of the peace and quiet thick 5mm of maintenance, load the about 5g of hard paint (manufacturing, セ イ カ PVC one system EXF01 (B) refine big day), make it overlapping, so that the cover layer face of film sample is connected with hard paint, carry out extrusion from film sample top with the hand loading rubber rollers of wide 10cm, diameter 4cm, so that hard paint elongates.Then, use high-pressure mercury-vapor lamp at 500mJ/cm from the face side
2, irradiation distance 15cm, translational speed 5m/ minute condition under irradiation ultraviolet radiation, hard conating is solidified.
Then, peel off film sample, obtain hard coat film with hard conating from glass substrate.On the glass plate of thick 5mm of adhesion two-sided tape, paste the opposing face of the hard conating of aforementioned hard coat film.Then, the cutter with gapping interval 2mm forms 100 grid-like otch that run through hard conating and cover layer arrival base material film.Then, adhesive tape (ニ チ バ Application company makes, No. 405,24mm wide) is sticked on the grid-like cut sides.With rubber by being pressed in the air that residues in the interface when pasting, make its complete driving fit after, vertically peel off adhesive tape rapidly.New adhesive tape is heavily pasted in further same operation, vertically peels off rapidly equally.With the strip operation of this adhesive tape repeatedly 10 times altogether, obtain adaptation by following formula utilization range estimation.Need to prove that what take place in 1 grid that part peels off also is set at the number of peeling off.
Adaptation (%)=(1-grid peel off number/100) * 100
(6) block resistance
Make between the cover layer face of 2 film samples overlappingly, it is applied 1kgf/cm under 50 ℃, the environment of 60%RH
2Pressure driving fit after 24 hours, peel off, it is peeled off the following standard determination of state.
Zero: cover layer does not shift, and can peel off lightly
△: produce and peel off sound, cover layer is partly transferred to the aspect
*: 2 bonding can not peeling off of film, although or can peel off, the substrate polyester film also ftractures
(7) tectal stiffness
Use that superficiality analyzer (Xin East Ami chemistry is made, HEIDON14), the cover layer that makes the film sample is in spite of wound.Make its pin in spite of wound this moment, use the sapphire pure pin of most advanced and sophisticated band radius 75 μ m.The translational speed of pin is 150mm/ minute, and loading is 5gf.
Use non-contact three-dimensional surface profile measuring instrument (マ イ Network ロ マ Star プ makes, Micromap550), measure under the following conditions cover layer with the surface configuration of wound, profile mode data are shown.Typical example is shown in Fig. 5 and Figure 12.Obtain the mean value of adjacent protruding and recessed difference of height 30 from the shape data of the wound that obtains, be set at tectal stiffness.At this moment, highly be the above projection of 30nm, be judged as the projection that causes by the particle that contains among cover layer or the thermoplastic resin membrane, except.In addition, owing to highly have the influence of nozzle for the following projection of 1nm, so except.
(condition determination)
Profile mode: fluctuation mode
Thing lens: 10 times
Definition: 160 * 160 pixels
Measured length: 207.1nm
(embodiment 1)
(1) preparation of coating fluid
Be used for coating fluid of the present invention according to following method preparation.With dimethyl terephthalate (DMT) 95 mass parts, DMIP 95 mass parts, ethylene glycol 35 mass parts, neopentyl glycol 145 mass parts, zinc acetate 0.1 mass parts and the antimony trioxide 0.1 mass parts reaction vessel of packing into, under 180 ℃, carried out ester exchange reaction 3 hours.Then, add M-phthalic acid 5-sodium sulfonate 6.0 mass parts, carrying out esterification under 240 ℃ after 1 hour, (10～0.2mmHg) carried out polycondensation reaction 2 hours under 250 ℃, decompression, obtain the copolyester resinoid of 60 ℃ of number-average molecular weights 19,500, softening point.
The 20 quality % aqueous solution of the self-crosslinking type polyurethane resinoid of crossing with 30 quality % aqueous dispersions, 7.5 mass parts of the copolyester resinoid (A) that obtains, with the sodium hydrogensulfite end-blocking (B) that contains NCO (worker industry System medicine is made, エ ラ ス ト ロ Application H-3), 11.3 mass parts, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 39.8 mass parts and isopropyl alcohol 37.4 mass parts respectively.Further add fluorine and be nonionic surface active agent (big Japanese イ Application キ chemical industry is made, メ ガ Off ア Star Network F142D) the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts.Then, the pH of coating fluid is adjusted into 6.2, with filtering particle size (initial stage filter efficiency: be that the felt type polypropylene filter made device of 10 μ m carries out secondary filter 95%), be mixed with coating fluid A with the sodium bicarbonate aqueous solution of 5 quality %.Need to prove that aforementioned surfactants is used the surfactant that has carried out pre-treatment with following method.
In aforementioned surfactants, add isopropyl alcohol (IPA), in 30 ℃ water-bath, carry out heating for dissolving, make the IPA solution of the surfactant of 15 quality %.This solution is filtered with quantitative filter paper (manufacturing of ア De バ Application テ ツ ク East ocean, No.5C), remove insoluble composition and rubbish in the solution.After aforementioned solution filtration, this solution is put into airtight glass container, in 0 ℃ freezer, left standstill 24 hours.After 24 hours, will contain the solution of the solid of separating out, use aforementioned quantitative filter paper to carry out suction filtration.Solid on the filter paper is carried out vacuum drying, obtain solid, be diluted with water to the 10 quality % aqueous solution, as the surfactant use of pre-treatment.
Need to prove that the surfactant that will be obtained by aforementioned pre-treatment is a solvent with methyl alcohol, analyze with the coated plastic sheet of TLC (メ Le Network is made, silica gel 60).It is painted that sample point utilizes iodine steam to carry out, and its result confirms not detect the suitable point of polyethylene glycol.
(2) manufacturing of layered polyester film
As raw polymer, PETG (PET) resin particle that with the inherent viscosity that does not contain particle is 0.62dl/g was 135 ℃ of following drying under reduced pressure (1Torr) 6 hours.Then, dried PET resin particle is supplied with extruder, become sheet, remain in surface temperature and carry out quenching on 20 ℃ the metallic roll and solidify, obtain cast film in about 285 ℃ of following melt extruded.At this moment, as the filtering material of removing the impurity in the molten resin, use filtering particle size (initial stage filter efficiency: 95%) be the stainless steel sintering filtering material of 15 μ m.
The cast film that obtains is heated to 95 ℃ with roller group that heated and infrared heater, then,, obtains uniaxial orientation PET film with existing the roller group of linear differential to stretch 3.5 times along its length.Then, with aforementioned coating fluid A with filtering particle size (initial stage filter efficiency: be that the felt type polypropylene filter made material of 10 μ m carries out secondary filter 95%), be coated on the one side of uniaxial orientation PET film with two sides roller method.Need to prove, at this moment,, use and to utilize superhard chromium to electroplate accurately machined surface to be made into the following and circularity of 0.2S and cylindricity roller as 3/1000mm for the dispenser roller and the measuring roller of coating machine.
Then, the drying oven that is divided into 4 sections with being configured in directly over the coating machine carries out drying by the 1st section (following 1.0 seconds at 135 ℃), the 2nd section (following 2.2 seconds at 65 ℃), the 3rd section (following 1.8 seconds at 40 ℃), the 4th section (following 1.8 seconds at 30 ℃) with coated face.In addition, be 0.08g/m with final solid constituent amount
2Set coating weight.Is 0.8 second from the film that is applied to the drying oven inlet to film by the time.In addition, at this moment, the wind speed of the dry wind of the 1st section is set at 30m/ second, and the air feed air quantity of dry wind is set at 130m
3/ second, the exhaust air quantity is set at 170m
3/ second, be set at 100m from the air feed air quantity of the 2nd section to the 4 sections
3/ second, the exhaust air quantity is set at 150m
3/ second, do not flow at coating pusher side dry wind.Need to prove that the tension force of film is the 7000N/ blank, control the two ends of film with pinch roll from being applied between the drying oven inlet.
And, in the coating at this moment, use the capacity of pallet of coating fluid and circulation with jar capacity and the preparation apparatus for coating that has following relation with the Capacity Ratio of jar.
(a) Capacity Ratio=1/50 of jar is used in the capacity of the pallet of coating fluid and circulation
(b) the circulation capacity and Capacity Ratio=1/40 of preparation of jar with jar
Next, with clamp control the end of film on one side, importing 120 ℃ of temperature, the wind speed 15m/ hot blast section of second on one side, broad ways is stretched to 4.3 times.Then, the width that remains untouched and keep broad ways to stretch is successively continuously by the 1st heat-set section (temperature: 200 ℃), the 2nd heat-set section (temperature: 225 ℃), the 3rd heat-set section (temperature: 230 ℃), the 4th heat-set section (temperature: 230 ℃), the 5th heat-set section (temperature: 210 ℃), the 6th heat-set section (temperature: 170 ℃), the 7th heat-set section (temperature: 120 ℃).Need to prove, carry out 3% relaxation processes in the 6th heat-set section broad ways.Then, finishing film two ends do not have the part of coating, reel with coiler device, and further broad ways is divided into 4 five equilibriums, and obtaining width is that 1000mm, film length are that 1000m, film thickness are the laminated polyester film volume of 125 μ m.Need to prove that the wind speed of the hot blast in the heat-set section all is 15m/ second, the time of passing through of each section is 4.5 seconds all, and the nozzle number that the nozzle that blows out hot blast is spaced apart 350mm, every section is 8.
Film rerum natura and characteristic are shown in table 4.In addition, with the maximum of the maximum of the length direction of the laminated polyester film that obtains volume and the surface of the PEs in width branch rate, minimum of a value, mist degree, minimum of a value, maximum, the minimum of a value of the adaptation of hard conating is shown in table 5.Need to prove that for block resistance, all measuring point all is zero.
(embodiment 2)
In embodiment 1, as the surfactant that is used for coating fluid, change to coating fluid B, this coating fluid B has used the 10 quality % aqueous solution that carried out the fluorine cation type surfactant (the ネ オ ス of Co., Ltd. manufacturing, Off one ジ エ Application ト 310) of pre-treatment with method similarly to Example 1, in addition, method with similarly to Example 1 obtains layered polyester film.
(embodiment 3)
In the heat-set treatment operation in embodiment 1, the temperature of each heat-set section is set at: 190 ℃ of the 1st heat-set section, 205 ℃ of the 2nd heat-set section, 220 ℃ of the 3rd heat-set section, 220 ℃ of the 4th heat-set section, in addition, use method similarly to Example 1 to obtain layered polyester film.
(embodiment 4)
In embodiment 1, coating fluid is changed to copolyester resinoid in the coating fluid and the resinoid mass ratio of polyurethane change to 60/40 following coating fluid C, in addition, obtain layered polyester film with similarly to Example 1 method.
(preparation of coating fluid C)
The 20 quality % aqueous solution, 9.0 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 9.0 mass parts of the copolyester resinoid (A) that embodiment 1 is used, embodiment 1 use, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 40.6 mass parts and isopropyl alcohol 37.3 mass parts respectively.Further add aqueous surfactant solution 0.6 mass parts that embodiment 1 uses, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, carry out pH with the sodium bicarbonate aqueous solution of 5 quality % and adjust, making it is the filter of 5 μ m and 1 μ m by strainability successively, makes coating fluid C.
(embodiment 5)
In embodiment 1, coating fluid is changed to copolyester resinoid in the coating fluid and the resinoid mass ratio of polyurethane change to 40/60 following coating fluid D, in addition, obtain layered polyester film with similarly to Example 1 method.
(preparation of coating fluid D)
The 20 quality % aqueous solution, 13.5 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 6.0 mass parts of the copolyester resinoid (A) that embodiment 1 is used, embodiment 1 use, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 38.9 mass parts and isopropyl alcohol 37.5 mass parts respectively.Further add the surfactant that embodiment 1 uses the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, with the sodium bicarbonate aqueous solution of 5 quality % pH is adjusted into 6.2, making it is the filter of 5 μ m and 1 μ m by strainability successively, makes coating fluid D.
(embodiment 6)
In embodiment 1, be 0.12g/m with final solid constituent amount
2Set coating weight, in addition, use method similarly to Example 1 to obtain layered polyester film.
(embodiment 7)
In embodiment 1, using has the following coating fluid E that the combined amount of the surfactant in the coating fluid is changed to 0.03 quality %, in addition, uses method similarly to Example 1 to obtain layered polyester film.
(preparation of coating fluid E)
In the preparation of the coating fluid of embodiment 1, with fluorine is that the 10 quality % aqueous solution of nonionic surface active agent (big Japanese イ Application キ chemical industry is made, メ ガ Off ア Star Network F142D) change to 0.3 mass parts, water is changed to 38.2 mass parts, and isopropyl alcohol is changed to 39.3 mass parts.
(embodiment 8)
In embodiment 1, using has the following coating fluid F that the combined amount of the surfactant in the coating fluid is changed to 0.10 quality %, in addition, uses method similarly to Example 1 to obtain layered polyester film.
(preparation of coating fluid F)
In the preparation of the coating fluid of embodiment 1, with fluorine is that the 10 quality % aqueous solution of non-ionic surface active agent (big Japanese イ Application キ chemical industry is made, メ ガ Off ア Star Network F142D) change to 1.0 mass parts, water is changed to 37.5 mass parts, and isopropyl alcohol is changed to 39.3 mass parts.
(embodiment 9)
In embodiment 1, to it be 0.7 second by time change from the film that is applied to the drying oven inlet, to change to drying time 0.8 second, further the time change of passing through with each section in the heat-set treatment operation is 3.5 seconds, film thickness is changed to 100 μ m, in addition, use method similarly to Example 1 to obtain layered polyester film.
(embodiment 10)
In embodiment 1, to it be 1.0 seconds from the time change of passing through of the film that is applied to drying oven inlet, to change to drying time 1.9 seconds, further the time change of passing through with each section in the heat-set treatment operation is 6.6 seconds, film thickness is changed to 188 μ m, in addition, use method similarly to Example 1 to obtain layered polyester film.
(embodiment 11)
In embodiment 1, change to the aqueous sodium carbonate that uses 5 quality % the pH of coating fluid is adjusted into 7.9 coating fluid G, in addition, obtain layered polyester film with similarly to Example 1 method.
(embodiment 12)
In embodiment 1,, in addition, use method similarly to Example 1 to obtain layered polyester film at the two sided coatings cover layer of uniaxial orientation polyester film.Need to prove that pass through the time from the film that is applied to the drying oven inlet to film, one side is 0.8 second, opposing face is 1.0 seconds.
(embodiment 13)
In embodiment 1, be 0.02g/m with final solid constituent amount
2Set coating weight, in addition, use method similarly to Example 1 to obtain layered polyester film.
(embodiment 14)
In embodiment 1, use the coating fluid H of the pre-treatment of not carrying out surfactant, in addition, use method similarly to Example 1 to obtain layered polyester film.In the tectal surface of the layered polyester film that obtains, utilize scanning probe microscopy (SPM) to observe and can differentiate copolyester resinoid and the resinoid phase separation structure of polyurethane, but indeterminate a little.
(embodiment 15)
In embodiment 1, use that (mass ratio of water/IPA) changes to 50/50 following coating fluid I, in addition, obtains layered polyester film with similarly to Example 1 method with the dispersant of coating fluid.
(preparation of coating fluid I)
In the preparation of the coating fluid of embodiment 1, the 20 quality % aqueous solution, 11.3 mass parts, the エ ラ ス ト ロ Application of the polyurethanes resin (B) that uses of 30 quality % aqueous dispersions, 7.5 mass parts of the polyester resin (A) that embodiment 1 is used, embodiment 1 mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 30.4 mass parts and isopropyl alcohol 46.8 mass parts respectively.Further add the surfactant that embodiment 1 uses the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, with the sodium bicarbonate aqueous solution of 5 quality % pH is adjusted into 6.2, making it is the filter of 5 μ m and 1 μ m by strainability successively, makes coating fluid I.
(embodiment 16)
In embodiment 1, use with acetic acid the coating fluid J that the pH of coating fluid changes to 4.6, in addition, obtain the layered polyester film of thick 125 μ m with method similarly to Example 1.
(embodiment 17)
In embodiment 1, use polyurethanes resin (B) is changed to the resinoid coating fluid K of following polyurethane, in addition, use method similarly to Example 1 to obtain layered polyester film.The polyurethanes resin obtains by following method.
(the resinoid preparation of polyurethane)
Will be by adipic acid // 1,6-hexylene glycol/neopentyl glycol (mol ratio: mix by polyester-diol (OHV:111.8eq/ton, AV:1.1eq/ton) 93 mass parts, benzene diformazan vulcabond 22 mass parts that composition 4/3/2) constitutes, flow down, under 95～100 ℃, make its reaction 1 hour at nitrogen, obtain urethane prepolymer (NCO/OH ratio: 1.50, free isocyanate groups: theoretical value 3.29 quality %, actual value 3.16 quality %).
Then, the urethane prepolymer that obtains is cooled to 60 ℃, adds diacetylmonoxime 4.5 mass parts, under 60 ℃, make its reaction obtained in 50 minutes containing free isocyanate 1.3 quality % and partly end-blocking urethane prepolymer.Continuation is cooled to 55 ℃ with aforementioned urethane prepolymer, adds the mixed solvent that is made of isopropyl alcohol 9 mass parts and methyl alcohol 140 mass parts, mixes equably.Then, add aqueous solution of sodium bisulfite 9.3 mass parts of 50 quality % and the 30 quality % aqueous solution, 5.4 mass parts of N methyl taurine, stir tempestuously.The water-soluble beginning manifests after about 30 minutes, and sodium hydrogensulfite free after 2 hours is almost nil, and reaction finishes.Add entry therein, obtain the aqueous solution of 20 quality % of muddiness and thickness.
(comparative example 1)
(1) preparation of coating fluid L
Dimethyl terephthalate (DMT) 33.7 mass parts, DMIP 20.0 mass parts, DMIP 5-sodium sulfonate 9.1 mass parts, ethylene glycol 40.0 mass parts, diethylene glycol 10.0 mass parts, a water acetic acid calcium 0.049 mass parts are mixed, under 200～230 ℃, carry out ester exchange to the methyl alcohol of theoretical amount and distillate.Then, add orthophosphoric acid 0.09 mass parts, under reduced pressure, 280 ℃ carry out polymerization, obtain the copolyester resinoid.
The polyethers that will contain the oxirane that useful sodium metabisulfite will obtain by allyl alcohol has carried out the polyethers (SO of the sulfonate group of sulfonation
3Content: 8.3 quality %, PEO content: 83 quality %) 192 mass parts, poly adipate succinic acid ester (number-average molecular weight: 2,250) (number-average molecular weight: 550) 248 mass parts are mixed, and dewater under 100 ℃ under vacuum for 1013 mass parts, the PPOX polyethers that caused by bisphenol-A.
This mixture is set at 70 ℃, add IPDI 178 mass parts and hexa-methylene-1 therein, the mixture of 6-vulcabond 244 mass parts, then, stir in 80 ℃～90 ℃ scope generating mixture, to isocyanate content be 5.6 quality %.This prepolymer is cooled to 60 ℃, add successively by 3 moles of hexamethylene diisocyanates and 1 mole of biuret PIC 56 mass parts that obtain of water with by PVC ス ケ ミ チ Application 175 mass parts that IPD and acetone obtain, obtain polyurethane aqueous dispersion.
Aforementioned copolyester resinoid and polyurethane aqueous dispersion are mixed,, be mixed with the aqueous dispersions that solid component concentration is 10 quality %, make coating fluid L so that its solid constituent is respectively 20 mass parts, 80 mass parts.Need to prove in coating fluid, do not have hybrid particles and surfactant.
(2) manufacturing of layered polyester film
As raw polymer, be that the pet resin particle of 0.66dl/g is at 135 ℃ of following drying under reduced pressure (1Torr) after 6 hours with the inherent viscosity that does not contain particle, supply with extruder, become sheet in about 285 ℃ of following melt extruded, remain in surface temperature and to carry out quenching on 60 ℃ the metallic roll and solidify, obtain cast film.At this moment, as the filtering material of the impurity of removing molten resin similarly to Example 1, use filtering particle size (initial stage filter efficiency: 95%) be the stainless steel sintering filtering material of 15 μ m.
Then, this cast film is heated to 95 ℃ with roller group that heated and infrared heater, then,, obtains uniaxial orientation PET film with existing the roller group of linear differential to stretch 3.5 times along its length.Then, with aforementioned coating fluid L with filtering particle size (initial stage filter efficiency: be that the felt type polypropylene filter made material of 10 μ m carries out secondary filter 95%), be coated on the one side of uniaxial orientation PET film with two sides roller method.Next, control the end of film with clamp, import to the hot blast section that is heated to 110 ℃, after the drying, broad ways is stretched to 3.5 times.Wind speed in the jar of this moment is 15m/ second, and be 20 seconds drying time.From the time that is applied to jar inlet to film be 10.0 seconds.In addition, be 0.15g/m with final solid constituent amount
2Set coating weight.
Then, the width of the film that the maintenance broad ways that remains untouched stretched is successively continuously by the 1st heat-set section (200 ℃), the 2nd heat-set section (205 ℃), the 3rd heat-set section and the 4th heat-set section (210 ℃), the 5th heat-set section (215 ℃), the 6th heat-set section (220 ℃), the 7th heat-set section (170 ℃).And, carry out 3% relaxation processes in the 7th heat-set section broad ways after, finishing film two ends do not have the part of coating, obtain the layered polyester film of thickness 125 μ m.Need to prove that the wind speed of the hot blast in the heat-set section all is 15m/ second, the time of passing through of each section is 4.5 seconds all, and the nozzle number that the nozzle that blows out hot blast is spaced apart 700mm, every section is 4.
In the cover surface of the layered polyester film that obtains, the resinoid phase separation structure of copolyester resinoid and polyurethane is indeterminate.
(comparative example 2)
(1) preparation of coating fluid M
The 20 quality % aqueous solution, 18.0 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 3.0 mass parts of the copolyester resinoid (A) that embodiment 1 is used, embodiment 1 use, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 70.7 mass parts and isopropyl alcohol 4.7 mass parts respectively.Further add the 10 quality % aqueous solution, 0.6 mass parts as the dodecyl benzene sulfonic acid of surfactant, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, make coating fluid M adjust because the pH of coating fluid M carries out pH, so be 4.8.
(2) manufacturing of layered polyester film
As raw polymer, the inherent viscosity that does not contain particle that embodiment 1 is used as the pet resin particle of 0.62dl/g at 135 ℃ of following drying under reduced pressure (1Torr) after 6 hours, supply with extruder, become sheet in about 285 ℃ of following melt extruded, remain in surface temperature and to carry out quenching on 20 ℃ the metallic roll and solidify, obtain cast film.At this moment, as the filtering material of the impurity of removing molten resin, use filtering particle size (initial stage filter efficiency: 95%) be the stainless steel sintering filtering material of 15 μ m.
The cast film that obtains is heated to 95 ℃ with roller group that heated and infrared heater, then,, obtains uniaxial orientation PET film with existing the roller group of linear differential to stretch 3.5 times along its length.Then, with aforementioned coating fluid M with filtering particle size (initial stage filter efficiency: be that the felt type polypropylene filter made material of 10 μ m carries out secondary filter 95%), be coated on the one side of uniaxial orientation PET film with two sides roller method.
Next, Yi Bian control the end of film with clamp, Yi Bian import to the hot blast section that is heated to 80 ℃, after the coated face drying, broad ways is stretched to 4.0 times.Wind speed in the jar of this moment is 15m/ second, and be 20 seconds drying time.From being applied to jar time of inlet is 10.0 seconds.In addition, be 0.10g/m with final solid constituent amount
2Set coating weight.And, temperature in each heat-set treatment operation is set at: 200 ℃ of the 1st heat-set section, 210 ℃ of the 2nd heat-set section, 220 ℃ of the 3rd heat-set section, 225 ℃ of the 4th heat-set section, 230 ℃ of the 5th heat-set section, 235 ℃ of the 6th heat-set section, 240 ℃ of the 7th heat-set section, no longer carry out the relaxation processes of width, in addition, use with the same method of comparative example 1 and obtain the layered polyester film that film thickness is 125 μ m.
In the cover surface of the layered polyester film that obtains, can't observe the resinoid phase separation structure of copolyester resinoid and polyurethane.
(comparative example 3)
(1) preparation of coating fluid N
The 20 quality % aqueous solution, 11.3 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 7.5 mass parts of the copolyester resinoid (A) that embodiment 1 is used, embodiment 1 use, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 40.5 mass parts and isopropyl alcohol 39.5 mass parts respectively.Further interpolation is not carried out the 10 quality % aqueous solution, 0.6 mass parts that the fluorine of pre-treatment is a nonionic surface active agent (big Japanese イ Application キ chemical industry is made, メ ガ Off ア Star Network F142D), is not used particle B, (the シ リ シ ア of Fuji chemistry is made, サ イ リ シ ア 310 as the agglomerate silica of particle A; Average grain diameter 1.4 μ m) the 3.5 quality % aqueous solution, 0.03 mass parts is made coating fluid N.Need to prove that the pH that does not carry out coating fluid N adjusts.The pH of coating fluid N is 4.6.
(2) manufacturing of layered polyester film
As raw polymer, the inherent viscosity that does not contain particle that embodiment 1 is used is the pet resin pellet supply extruder of 0.62dl/g, become sheet in about 285 ℃ of following melt extruded, remain in surface temperature and to carry out quenching on 20 ℃ the metallic roll and solidify, obtain cast film.At this moment, as the filtering material of the impurity of removing molten resin, use filtering particle size (initial stage filter efficiency: 95%) be the stainless steel sintering filtering material of 15 μ m.
The cast film that obtains is heated to 95 ℃ with roller group that heated and infrared heater, then,, obtains uniaxial orientation PET film with existing the roller group of linear differential to stretch 3.5 times along its length.Then, with aforementioned coating fluid L with filtering particle size (initial stage filter efficiency: be that the felt type polypropylene filter made material of 10 μ m carries out secondary filter 95%), be coated on the one side of uniaxial orientation PET film with two sides roller method.
After the coating, import drying oven, following dry 3.2 seconds 120 ℃ of temperature.In addition, be 0.08g/m with final solid constituent amount
2Set coating weight.Is 3.2 seconds from the film that is applied to the drying oven inlet by the time.In addition, the wind speed of the 1st section of drying oven is 15m/ second, and the wind speed of the 2nd section to the 4 sections all is set at 70m with the air feed air quantity of the dry wind of the 1st dry section to the 4 dry sections similarly to Example 1
3/ second, exhaust wind is set at from the drying oven natural exhaust in front and back.
Next, the cross directional stretch multiplying power is set at 4.0 times, in addition, carries out cross directional stretch with method similarly to Example 1, with with the same method heat setting of comparative example 1, carry out the relaxation processes of width, obtain the layered polyester film that film thickness is 125 μ m.In the cover surface of the layered polyester film that obtains, can not observe the resinoid phase separation structure of copolyester resinoid and polyurethane.
(comparative example 4)
In embodiment 1, be 3.2 seconds from coating fluid A being coated the film that enters the mouth to drying oven behind the film by time set, in addition, use method similarly to Example 1 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 5)
The 20 quality % aqueous solution, 18.0 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 3.0 mass parts of the copolyester resinoid (A) that embodiment 1 is used, embodiment 1 use, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 37.3 mass parts and isopropyl alcohol 37.8 mass parts respectively.Further add the surfactant that embodiment 1 uses the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, with the sodium bicarbonate aqueous solution of 5 quality % pH is adjusted into 6.2, make coating fluid O.Use aforementioned coating fluid O as coating fluid, in addition, use method similarly to Example 1 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 6)
The 20 quality % aqueous solution, 4.5 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 12.0 mass parts of the copolyester resinoid (A) that embodiment 1 is used, embodiment 1 use, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 42.3 mass parts and isopropyl alcohol 37.2 mass parts respectively.Further add the surfactant that embodiment 1 uses the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, with the sodium bicarbonate aqueous solution of 5 quality % pH is adjusted into 6.2, make coating fluid P.Use aforementioned coating fluid P as coating fluid, in addition, use method similarly to Example 1 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 7)
In embodiment 1, temperature in each heat-set treatment operation is set at: 190 ℃ of the 1st heat-set section, 195 ℃ of the 2nd heat-set section, 200 ℃ of the 3rd heat-set section to the 5 heat-set section, in addition, use method similarly to Example 1 to obtain the layered polyester film that film thickness is 125 μ m.In the cover surface of the layered polyester film that obtains, can not observe the resinoid phase separation structure of copolyester resinoid and polyurethane.
(comparative example 8)
In embodiment 1, the wind speed in the drying oven is set at 15m/ second, in addition, use method similarly to Example 1 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 9)
In embodiment 1, be 0.20g/m with final solid constituent amount
2Set coating weight, in addition, use method similarly to Example 1 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 10)
In embodiment 1, use with 5 quality % aqueous sodium carbonates the pH of coating fluid is adjusted into 9.0 coating fluid Q, in addition, usefulness method similarly to Example 1 obtains the layered polyester film that film thickness is 125 μ m.
(comparative example 11)
In embodiment 1, use in coating fluid the not formulated coating fluid R of mixed surfactant, in addition, obtain the layered polyester film that film thickness is 125 μ m with similarly to Example 1 method.
(embodiment 18)
The 20 quality % aqueous solution, 11.3 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 7.5 mass parts of the copolyester resinoid (A) that embodiment 1 is used, embodiment 1 use, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 40.5 mass parts and isopropyl alcohol 39.5 mass parts respectively.And, further add the surfactant that embodiment 1 uses the 10 quality % aqueous solution, 0.6 mass parts, (the シ リ シ ア of Fuji chemistry is made, サ イ リ シ ア 310 as the agglomerate silica of particle A; Average grain diameter 1.4 μ m) the 3.5 quality % aqueous solution, 4.3 mass parts are adjusted into 6.2 with 5 quality % sodium bicarbonate aqueous solutions with pH, and making it is the filter of 5 μ m and 1 μ m by strainability successively, makes coating fluid S.Need to prove that particle B is not blended in the coating fluid.Except that using aforementioned coating fluid S, use method similarly to Example 1 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 12)
In embodiment 1, using and only making the amount of the surfactant in the coating fluid is the formulated coating fluid T of 0.60 quality % by the solid constituent amount, in addition, uses method similarly to Example 1 to obtain the layered polyester film that film thickness is 125 μ m.
(embodiment 19)
In embodiment 1, temperature in each heat-set treatment operation is set at: 200 ℃ of the 1st heat-set section, 210 ℃ of the 2nd heat-set section, 215 ℃ of the 3rd heat-set section, 220 ℃ of the 4th heat-set section, 225 ℃ of the 5th heat-set section, 230 ℃ of the 6th heat-set section, 170 ℃ of the 7th heat-set section, and carry out 3% relaxation processes in the 7th heat-set section broad ways, in addition, with method similarly to Example 1, the film thickness that does not have coating layer portion that obtains repairing the film two ends is the layered polyester film of 125 μ m.
(comparative example 13)
In embodiment 1, the 20 quality % aqueous solution, 11.3 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 7.5 mass parts of the copolyester resinoid (A) that embodiment 1 is used, embodiment 1 use, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 51.0 mass parts and isopropyl alcohol 26.2 mass parts respectively.Further add the surfactant that embodiment 1 uses the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, with 5 quality % sodium bicarbonate aqueous solutions pH is adjusted into 6.2, make coating fluid U.Use coating fluid U as coating fluid, in addition, use method similarly to Example 1 to obtain layered polyester film.
(embodiment 20)
In embodiment 1, as apparatus for coating, the capacity, circulation that uses the pallet of coating fluid with jar capacity and the preparation apparatus for coating that has following condition with the ratio of the capacity of jar, in addition, obtaining film length with similarly to Example 1 method is that 2000m, width are that 1000mm, thickness are the laminated polyester film volume of 125 μ m.
(a) capacity=1/5 of jar is used in the capacity of the pallet of coating fluid/circulation
(b) capacity=1/50 of jar is used in circulation with capacity/preparation of jar
(c) circularity of dispenser roller and measuring roller and cylindricity: 6/1000mm
(d) from coating machine to pinch roll is not set between the drying oven
In embodiment 1～20, comparative example 1～13, the composition and the characteristic of coating fluid is shown in table 1, will be coated with drying condition and be shown in table 2, heat-setting condition is shown in table 3, film rerum natura and characteristic are shown in table 4.In addition, maximum, the minimum of a value of the adaptation of the maximum of the maximum of length direction that the laminated polyester film that obtains is rolled up and the surface of the PEs in width branch rate, minimum of a value, mist degree, minimum of a value, relative hard conating are shown in table 5.Need to prove that for block resistance, all measuring point all is zero.
[table 1]
| Coating fluid is formed | Coating fluid | ||||||||||
| Resin | Particle A | Particle B | Solvent | Surfactant | pH | Solid component concentration | |||||
| The mass ratio of copolymerization PEs/PU | Average grain diameter | Addition | Average grain diameter | Addition | Water/IPA mass ratio | Kind | Having or not of pre-treatment | Combined amount | |||
| μm | Quality % | μm | Quality % | Quality % | Quality % | ||||||
| Embodiment 1 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 2 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Cation | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 3 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 4 | 60/40 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 5 | 40/60 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 6 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 7 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.03 | 6.2 | 5.30 |
| Embodiment 8 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.10 | 6.2 | 5.30 |
| Embodiment 9 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 10 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 11 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 7.9 | 5.30 |
| Embodiment 12 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 13 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 14 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Do not have | 0.06 | 6.2 | 5.30 |
| Embodiment 15 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 50/50 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 16 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 4.6 | 5.30 |
| Embodiment 17 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 18 | 50/50 | 1.4 | 3.0 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 19 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 20 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 1 | 20/80 | - | - | - | - | 100/0 | Nonionic | - | - | - | 10.00 |
| Comparative example 2 | 20/80 | 0.04 | 0.36 | 0.20 | 0.04 | 95/5 | Anion | Do not have | 0.06 | 4.8 | 10.93 |
| Comparative example 3 | 50/50 | 1.4 | 0.02 | - | - | 60/40 | Nonionic | Do not have | 0.06 | 4.6 | 4.87 |
| Comparative example 4 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 5 | 20/80 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 6 | 80/20 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 7 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 8 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 9 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 10 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 9.0 | 5.30 |
| Comparative example 11 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | - | - | - | 6.2 | 5.30 |
| Comparative example 12 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.60 | 6.2 | 5.30 |
| Comparative example 13 | 50/50 | 0.04 | 0.45 | 0.20 | 0.02 | 72/28 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
[table 2]
| The coating drying condition | |||||
| Passing through the time (second) after coating to the drying process inlet | Baking temperature (℃) | Drying time (second) | Wind speed (m/s) | Final coating weight (g/m 2) | |
| Embodiment 1 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 2 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 3 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 4 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 5 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 6 | 0.8 | 135 | 1.0 | 30 | 0.12 |
| Embodiment 7 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 8 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 9 | 0.7 | 135 | 0.8 | 30 | 0.08 |
| Embodiment 10 | 1.0 | 135 | 1.9 | 30 | 0.08 |
| Embodiment 11 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 12 | 0.8/1.0 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 13 | 0.8 | 135 | 1.0 | 30 | 0.02 |
| Embodiment 14 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 15 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 16 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 17 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 18 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 19 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 20 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 1 | 10 | 110 | 20 | 15 | 0.15 |
| Comparative example 2 | 10 | 80 | 20 | 20 | 0.10 |
| Comparative example 3 | 3.2 | 120 | 1.0 | 15 | 0.08 |
| Comparative example 4 | 3.2 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 5 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 6 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 7 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 8 | 0.8 | 135 | 1.0 | 15 | 0.08 |
| Comparative example 9 | 0.8 | 135 | 1.0 | 30 | 0.20 |
| Comparative example 10 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 11 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 12 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 13 | 0.8 | 135 | 1.0 | 30 | 0.08 |
[table 3]
| Heat-setting condition | ||||||||
| Heat-set temperature (℃) | Passing through the time (second) of each section | |||||||
| The #1 section | The #2 section | The #3 section | The #4 section | The #5 section | The #6 section | The #7 section | ||
| Embodiment 1 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 2 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 3 | 190 | 205 | 220 | 220 | 210 | 170 | 120 | 4.5 |
| Embodiment 4 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 5 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 6 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 7 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 8 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 9 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 3.5 |
| Embodiment 10 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 6.6 |
| Embodiment 11 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 12 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 13 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 14 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 15 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 16 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 17 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 18 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 19 | 200 | 210 | 215 | 220 | 225 | 230 | 170 | 4.5 |
| Embodiment 20 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 1 | 200 | 205 | 210 | 213 | 215 | 220 | 170 | 4.5 |
| Comparative example 2 | 200 | 210 | 220 | 225 | 230 | 235 | 240 | 4.5 |
| Comparative example 3 | 200 | 205 | 210 | 213 | 215 | 220 | 170 | 4.5 |
| Comparative example 4 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 5 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 6 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 7 | 190 | 195 | 200 | 200 | 200 | 170 | 120 | 4.5 |
| Comparative example 8 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 9 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 10 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 11 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 12 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 13 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
[table 4]
| The phase separation structure of PEs phase | The film rerum natura | Film is estimated | |||||||
| PEs surface branch rate (%) | Width surpasses the having or not of PEs phase (A) of 1 μ m | Fractal dimension | Film thickness (μ m) | Tectal stiffness (nm) | Mist degree (%) | Adaptation (%) with the HC layer | Block resistance | ||
| No-solvent type HC layer/cover layer | Solvent cutback HC layer/cover layer | ||||||||
| Embodiment 1 | 68 | Do not have | 1.86 | 125 | 5.1 | 0.58 | 95 | 100 | ○ |
| Embodiment 2 | 65 | Do not have | 125 | 5.3 | 0.65 | 100 | 100 | ○ | |
| Embodiment 3 | 52 | Do not have | 1.75 | 125 | 7.0 | 0.45 | 100 | 100 | ○ |
| Embodiment 4 | 76 | Do not have | 1.70 | 125 | 3.5 | 0.41 | 95 | 97 | ○ |
| Embodiment 5 | 48 | Do not have | 125 | 12.5 | 0.85 | 100 | 95 | ○ | |
| Embodiment 6 | 52 | Do not have | 125 | 7.3 | 0.65 | 100 | 100 | ○ | |
| Embodiment 7 | 75 | Do not have | 125 | 6.5 | 0.61 | 92 | 95 | ○ | |
| Embodiment 8 | 64 | Do not have | 125 | 5.5 | 0.85 | 100 | 100 | ○ | |
| Embodiment 9 | 70 | Do not have | 1.89 | 100 | 5.3 | 0.55 | 100 | 100 | ○ |
| Embodiment 10 | 51 | Do not have | 1.85 | 188 | 8.0 | 0.46 | 100 | 100 | ○ |
| Embodiment 11 | 61 | Do not have | 125 | 5.3 | 0.73 | 100 | 100 | ○ | |
| Embodiment 12 | 68 | Do not have | 125 | 5.3 | 0.78 | 96 | 100 | ○ | |
| Embodiment 13 | 79 | Do not have | 125 | 4.3 | 0.78 | 91 | 93 | ○ | |
| Embodiment 14 | 66 | Do not have | 125 | 5.5 | 0.54 | 85 | 86 | ○ | |
| Embodiment 15 | 70 | Do not have | 125 | 5.2 | 0.56 | 85 | 86 | ○ | |
| Embodiment 16 | 87 | Do not have | 125 | 4.0 | 0.47 | 50 | 80 | ○ | |
| Embodiment 17 | 69 | Do not have | 125 | 5.0 | 0.57 | 96 | 100 | ○ | |
| Embodiment 18 | 69 | Have | 125 | 5.3 | 3.40 | 100 | 100 | ○ | |
| Embodiment 19 | 50 | Have | 125 | 7.9 | 0.47 | 83 | 95 | ○ | |
| Embodiment 20 | 68 | Do not have | 125 | 5.1 | 0.58 | 95 | 100 | ○ | |
| Comparative example 1 | 8 | Do not have | 1.25 | 125 | 15.5 | 1.05 | 75 | 50 | × |
| Comparative example 2 | - | Do not have | 125 | 15.3 | 0.75 | 84 | 60 | × | |
| Comparative example 3 | - | Do not have | 125 | 5.5 | 0.41 | 100 | 95 | × | |
| Comparative example 4 | 30 | Do not have | 1.58 | 125 | 15.1 | 0.73 | 93 | 79 | × |
| Comparative example 5 | 15 | Do not have | 125 | 15.7 | 0.98 | 95 | 60 | × | |
| Comparative example 6 | 93 | Have | 1.40 | 125 | 2.8 | 0.47 | 30 | 70 | ○ |
| Comparative example 7 | - | Do not have | 125 | 4.1 | 0.62 | 78 | 65 | × | |
| Comparative example 8 | 34 | Do not have | 125 | 6.0 | 0.70 | 100 | 98 | × | |
| Comparative example 9 | 32 | Do not have | 125 | 6.5 | 0.54 | 100 | 92 | × | |
| Comparative example 10 | 33 | Do not have | 125 | 6.0 | 1.55 | 100 | 90 | △ | |
| Comparative example 11 | 91 | Do not have | 125 | 3.5 | 0.38 | 25 | 70 | ○ | |
| Comparative example 12 | 34 | Do not have | 125 | 5.9 | 1.53 | 98 | 87 | △ | |
| Comparative example 13 | 32 | Do not have | 125 | 6.8 | 2.20 | 95 | 88 | × | |
[table 5]
| PEs surface branch rate (%) | Mist degree (%) | Adaptation (%) with the HC layer | |||||||
| No-solvent type HC layer/cover layer | Solvent cutback HC layer/cover layer | ||||||||
| Max | Min | Max | Min | Max | Min | | Min | ||
| Embodiment | |||||||||
| 1 | Length direction | 73 | 63 | 0.59 | 0.56 | 100 | 94 | 100 | 96 |
| Width | 72 | 64 | 0.59 | 0.56 | 100 | 96 | 100 | 97 | |
| | Length direction | 77 | 60 | 0.60 | 0.56 | 100 | 93 | 100 | 95 |
| Width | 75 | 61 | 0.60 | 0.56 | 100 | 91 | 100 | 94 | |
The following examples represent that cover layer contains the useful at least a crosslinking agent that is selected from epoxies crosslinking agent, melamine class crosslinking agent, the oxazoline class crosslinking agent and carries out the resinoid embodiment of crosslinked copolyester.Need to prove that the hot adaptation of the moisture-proof of Shi Yonging is used following evaluation method in this embodiment.
(8) the hot adaptation of moisture-proof
To under the environment of 60 ℃ of temperature, relative humidity 90%, preserve 1000 hours by the film sample that embodiment and comparative example obtain.Then, on the glass plate of the thick 5mm that keeps clean, loading is as the about 5g of hard paint (manufacturing, セ イ カ PVC one system EXF01 (B) refine big day) of the photo-curable acrylic resin of no-solvent type, make it overlapping, so that the cover layer face of above-mentioned film sample is connected with hard paint, carry out extrusion from the top of film sample with the hand loading rubber rollers of wide 10cm, diameter 4cm, so that hard paint elongates.Then, use high-pressure mercury-vapor lamp at exposure 500mJ/cm from the face side
2, irradiation distance 15cm, translational speed 5m/ minute condition under irradiation ultraviolet radiation, hard conating is solidified.
Then, peel off film sample, obtain hard coat film with hard conating from glass plate.On the glass plate of the thick 5mm that is pasted with two-sided tape, paste the face of opposition side of the hard conating of aforementioned hard coat film.Then, the cutter with gapping interval 2mm forms 100 grid-like otch that run through hard conating and cover layer arrival base material film.
Then, adhesive tape (ニ チ バ Application company makes, No. 405,24mm wide) is sticked on the grid-like cut sides.With rubber by being pressed in the air that residues in the interface when pasting, make its complete driving fit after, vertically peel off adhesive tape rapidly.Utilize range estimation to count the number of the grid of peeling off, obtain adaptation by following formula.It is carried out at 3 places, obtain the mean value of adaptation, judge humidity resistance according to following criterion.Need to prove that what part was peeled off in 1 grid also is set at the number of peeling off.
Adaptation (%)=(number of the grid that 1-peels off/100) * 100
○：71～100％
△：51～70％
×：0～50％
(embodiment 21)
(1) preparation of coating fluid
Be used for coating fluid of the present invention according to following method preparation.With dimethyl terephthalate (DMT) 95 mass parts, DMIP 95 mass parts, ethylene glycol 35 mass parts, neopentyl glycol 145 mass parts, zinc acetate 0.1 mass parts and the antimony trioxide 0.1 mass parts reaction vessel of packing into, under 180 ℃, carried out ester exchange reaction 3 hours.Then, add M-phthalic acid 5-sodium sulfonate 6.0 mass parts, carrying out esterification under 240 ℃ after 1 hour, (10～0.2mmHg) carried out polycondensation reaction 2 hours under 250 ℃, decompression, obtain the copolyester resinoid of 60 ℃ of number-average molecular weights 19,500, softening point.
Respectively with 30 quality % aqueous dispersions, 12.8 mass parts of the copolyester resinoid (A) that obtains, the self-crosslinking type polyurethane resinoid of crossing with the sodium sulfite end-blocking (B) that contains NCO (make by worker industry System medicine, エ ラ ス ト ロ Application H-3) the 20 quality % aqueous solution, 10.1 mass parts, (the sumitomo chemical company manufacturing of methylated melamine class crosslinking agent, ス ミ マ one Le M-100) aqueous dispersions 2.3 mass parts of solid constituent 20 quality %, (make by worker industry System medicine with catalyst for エ ラ ス ト ロ Application, Cat64) 0.3 mass parts, water 39.4 mass parts and isopropyl alcohol 37.5 mass parts are mixed.Further add fluorine and be nonionic surface active agent (big Japanese イ Application キ chemical industry is made, メ ガ Off ア Star Network F142D) the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts.Then, the pH of coating fluid is adjusted into 6.2, with filtering particle size (initial stage filter efficiency: be that the felt type polypropylene filter made device of 10 μ m carries out secondary filter 95%), be mixed with coating fluid AA with the sodium bicarbonate aqueous solution of 5 quality %.Need to prove that aforementioned surfactants is used the surfactant that has carried out pre-treatment with following method.
In aforementioned surfactants, add isopropyl alcohol (IPA), in 30 ℃ water-bath, carry out heating for dissolving, make the IPA solution of the surfactant of 15 quality %.This solution is filtered with quantitative filter paper (manufacturing of ア De バ Application テ ツ ク East ocean, No.5C), remove insoluble composition and rubbish in the solution.After aforementioned solution filtration, this solution is put into airtight glass container, in 0 ℃ freezer, left standstill 24 hours.After 24 hours, will contain the solution of the solid of separating out, use aforementioned quantitative filter paper to carry out suction filtration.Solid on the filter paper is carried out vacuum drying, obtain solid, be diluted with water to the 10 quality % aqueous solution, as the surfactant use of pre-treatment.
Need to prove that the surfactant that will be obtained by aforementioned pre-treatment is a solvent with methyl alcohol, analyze with the coated plastic sheet of TLC (メ Le Network is made, silica gel 60).It is painted that sample point utilizes iodine steam to carry out, its results verification do not detect the suitable point of polyethylene glycol.
(2) manufacturing of layered polyester film
As raw polymer, PETG (PET) resin particle that with the inherent viscosity that does not contain particle is 0.62dl/g was 135 ℃ of following drying under reduced pressure (1Torr) 6 hours.Then, dried PET resin particle is supplied with extruder, become sheet, remain in surface temperature and carry out quenching on 20 ℃ the metallic roll and solidify, obtain cast film in about 285 ℃ of following melt extruded.At this moment, as the filtering material of removing the impurity in the molten resin, use filtering particle size (initial stage filter efficiency: 95%) be the stainless steel sintering filtering material of 15 μ m.
The cast film that obtains is heated to 95 ℃ with roller group that heated and infrared heater, then,, obtains uniaxial orientation PET film with existing the roller group of linear differential to stretch 3.5 times along its length.Then, with aforementioned coating fluid AA with filtering particle size (initial stage filter efficiency: be that the felt type polypropylene filter made material of 10 μ m carries out secondary filter 95%), be coated on the one side of uniaxial orientation PET film with two sides roller method.Need to prove, at this moment,, use and to utilize superhard chromium to electroplate accurately machined surface to be made into the following and circularity of 0.2S and cylindricity roller as 3/1000mm for the dispenser roller and the measuring roller of coating machine.
Then, with the drying oven that is divided into 4 sections that is configured in directly over the coating machine, with 135 ℃ of the 1st zone temperatures, 1.0 seconds; The 2nd dry section 65 ℃, 2.2 seconds; The 3rd dry zone temperatures 40 ℃, 1.8 seconds; The 4th zone temperatures 30 ℃, 1.8 seconds is carried out drying with coated face.In addition, be 0.08g/m with final solid constituent amount
2Set coating weight.Is 0.8 second from the film that is applied to the drying oven inlet to film by the time.In addition, at this moment, the wind speed of the dry wind of the 1st section is set at 30m/ second, and the air feed air quantity of dry wind is set at 130m
3/ second, the exhaust air quantity is set at 170m
3/ second, be set at 100m from the air feed air quantity of the 2nd section to the 4 sections
3/ second, the exhaust air quantity is set at 150m
3/ second, do not flow at coating pusher side dry wind.Need to prove that the tension force of film is the 7000N/ blank, control the two ends of film with pinch roll from being applied between the drying oven inlet.
And, in the coating at this moment, use the capacity of pallet of coating fluid and circulation with jar capacity and the preparation apparatus for coating that has following relation with the Capacity Ratio of jar.
(a) Capacity Ratio=1/50 of jar is used in the capacity of the pallet of coating fluid and circulation
(b) the circulation capacity and Capacity Ratio=1/40 of preparation of jar with jar
Next, with clamp control the end of film on one side, importing 120 ℃ of temperature, the wind speed 15m/ hot blast section of second on one side, broad ways is stretched to 4.3 times.Then, the width that remains untouched and keep broad ways to stretch is successively continuously by the 1st heat-set section (temperature: 200 ℃), the 2nd heat-set section (temperature: 225 ℃), the 3rd heat-set section (temperature: 230 ℃), the 4th heat-set section (temperature: 230 ℃), the 5th heat-set section (temperature: 210 ℃), the 6th heat-set section (temperature: 170 ℃), the 7th heat-set section (temperature: 120 ℃).Need to prove, carry out 3% relaxation processes in the 6th heat-set section broad ways.Then, finishing film two ends do not have the part of coating, reel with coiler device, and further broad ways is divided into 4 five equilibriums, and obtaining width is that 1000mm, film length are that 1000m, film thickness are the laminated polyester film volume of 125 μ m.Need to prove that the wind speed of the hot blast in the heat-set section all is 15m/ second, the time of passing through of each section is 4.5 seconds all, and the nozzle number that the nozzle that blows out hot blast is spaced apart 350mm, every section is 8.
Film rerum natura and characteristic are shown in table 9.In addition, maximum, the minimum of a value of the adaptation of the maximum of the maximum of length direction that the laminated polyester film that obtains is rolled up and the surface of the PEs in width branch rate, minimum of a value, mist degree, minimum of a value, relative hard conating are shown in table 10.Need to prove that for block resistance, all measuring point all is zero.
(embodiment 22)
In embodiment 21, as the surfactant that is used for coating fluid, change to and use useful method similarly to Example 21 to carry out the coating fluid BB of the 10 quality % aqueous solution of the fluorine cation type surfactant of pre-treatment (the ネ オ ス of Co., Ltd. manufacturing, Off one ジ エ Application ト 310), in addition, method with similarly to Example 21 obtains layered polyester film.
(embodiment 23)
In the heat-set treatment operation of embodiment 21, the temperature of each heat-set section is set at: 190 ℃ of the 1st heat-set section, 205 ℃ of the 2nd heat-set section, 220 ℃ of the 3rd heat-set section, 220 ℃ of the 4th heat-set section, in addition, method with similarly to Example 21 obtains layered polyester film.
(embodiment 24)
In embodiment 21, the mass ratio that coating fluid is changed to copolyester resinoid, polyurethanes resin and crosslinking agent in the coating fluid changes to 55/35/10 following coating fluid CC, in addition, obtains layered polyester film with similarly to Example 21 method.
(preparation of coating fluid CC)
The 20 quality % aqueous solution, 7.9 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 8.3 mass parts of the copolyester resinoid (A) that embodiment 21 is used, embodiment 21 uses, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 40.2 mass parts and isopropyl alcohol 37.4 mass parts respectively.Further add aqueous surfactant solution 0.6 mass parts that embodiment 21 uses, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, carry out pH with the sodium bicarbonate aqueous solution of 5 quality % and adjust, making it is the filter of 5 μ m and 1 μ m by strainability successively, makes coating fluid CC.
(embodiment 25)
In embodiment 21, the mass ratio that coating fluid is changed to copolyester resinoid, polyurethanes resin and crosslinking agent in the coating fluid changes to 35/55/10 following coating fluid DD, in addition, obtains layered polyester film with similarly to Example 21 method.
(preparation of coating fluid DD)
Crosslinking agent 2.3 mass parts of the 20 quality % aqueous solution, 12.4 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 5.3 mass parts of the copolyester resinoid (A) that embodiment 21 is used, embodiment 21 uses, embodiment 21 uses, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 38.5 mass parts and isopropyl alcohol 37.6 mass parts respectively.Further add the surfactant that embodiment 21 uses the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, with the sodium bicarbonate aqueous solution of 5 quality % pH is adjusted into 6.2, making it is the filter of 5 μ m and 1 μ m by strainability successively, makes coating fluid DD.
(embodiment 26)
In embodiment 21, be 0.12g/m with final solid constituent amount
2Set coating weight, in addition, use method similarly to Example 21 to obtain layered polyester film.
(embodiment 27)
In embodiment 21, use the following coating fluid EE that the combined amount of the surfactant in the coating fluid is changed to 0.03 quality %, in addition, use method similarly to Example 21 to obtain layered polyester film.
(preparation of coating fluid EE)
In the preparation of the coating fluid of embodiment 21, with fluorine is that the 10 quality % aqueous solution of nonionic surface active agent (big Japanese イ Application キ chemical industry is made, メ ガ Off ア Star Network F142D) change to 0.3 mass parts, water is changed to 39.4 mass parts, and isopropyl alcohol is changed to 37.5 mass parts.
(embodiment 28)
In embodiment 21, use the following coating fluid FF that the combined amount of the surfactant in the coating fluid is changed to 0.10 quality %, in addition, use method similarly to Example 21 to obtain layered polyester film.
(preparation of coating fluid FF)
In the preparation of the coating fluid of embodiment 21, with fluorine is that the 10 quality % aqueous solution of non-ionic surface active agent (big Japanese イ Application キ chemical industry is made, メ ガ Off ア Star Network F142D) change to 1.0 mass parts, water is changed to 39.0 mass parts, and isopropyl alcohol is changed to 37.5 mass parts.
(embodiment 29)
In embodiment 21, to it be 0.7 second by time change from the film that is applied to the drying oven inlet, to change to drying time 0.8 second, further the time change of passing through with each section in the heat-set treatment operation is 3.5 seconds, film thickness is changed to 100 μ m, in addition, use method similarly to Example 21 to obtain layered polyester film.
(embodiment 30)
In embodiment 21, to it be 1.0 seconds from the time change of passing through of the film that is applied to drying oven inlet, to change to drying time 1.9 seconds, further the time change of passing through with each section in the heat-set treatment operation is 6.6 seconds, film thickness is changed to 188 μ m, in addition, use method similarly to Example 21 to obtain layered polyester film.
(embodiment 31)
In embodiment 21, change to the aqueous sodium carbonate that uses 5 quality % the pH of coating fluid is adjusted into 7.9 coating fluid GG, in addition, obtain layered polyester film with similarly to Example 21 method.
(embodiment 32)
In embodiment 21,, in addition, use method similarly to Example 21 to obtain layered polyester film at the two sided coatings cover layer of uniaxial orientation polyester film.Need to prove that pass through the time from the film that is applied to the drying oven inlet to film, one side is 0.8 second, opposing face is 1.0 seconds.
(embodiment 33)
In embodiment 21, be 0.02g/m with final solid constituent amount
2Set coating weight, in addition, use method similarly to Example 21 to obtain layered polyester film.
(embodiment 34)
In embodiment 21, use the coating fluid HH of the pre-treatment of not carrying out surfactant, in addition, use method similarly to Example 21 to obtain layered polyester film.On the tectal surface of the layered polyester film that obtains, can differentiate the resinoid phase separation structure of copolyester resinoid and polyurethane, but indeterminate a little.
(embodiment 35)
In embodiment 21, use that (mass ratio of water/IPA) changes to 50/50 following coating fluid II, in addition, obtains layered polyester film with similarly to Example 21 method with the dispersant of coating fluid.
(preparation of coating fluid II)
In the preparation of the coating fluid of embodiment 21, the 20 quality % aqueous solution, 10.1 mass parts of the polyurethanes resin (B) that uses of 30 quality % aqueous dispersions, 6.8 mass parts of the polyester resin (A) that embodiment 21 is used, embodiment 21, crosslinking agent 2.3 mass parts, the エ ラ ス ト ロ Application that embodiment 21 uses mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 30.0 mass parts and isopropyl alcohol 46.8 mass parts respectively.Further add the surfactant that embodiment 1 uses the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, with the sodium bicarbonate aqueous solution of 5 quality % pH is adjusted into 6.2, making it is the filter of 5 μ m and 1 μ m by strainability successively, makes coating fluid II.
(embodiment 36)
In embodiment 21, use with acetic acid the coating fluid JJ that the pH of coating fluid changes to 4.6, in addition, obtain the layered polyester film of thick 125 μ m with method similarly to Example 21.
(embodiment 37)
In embodiment 21, use polyurethanes resin (B) is changed to the resinoid coating fluid KK of following polyurethane, in addition, use method similarly to Example 21 to obtain layered polyester film.The polyurethanes resin obtains by following method.
(the resinoid preparation of polyurethane)
Will be by adipic acid // 1,6-hexylene glycol/neopentyl glycol (mol ratio: mix by polyester-diol (OHV:111.8eq/ton, AV:1.1eq/ton) 93 mass parts, benzene diformazan vulcabond 22 mass parts that composition 4/3/2) constitutes, flow down, under 95～100 ℃, make its reaction 1 hour at nitrogen, obtain urethane prepolymer (NCO/OH ratio: 1.50, free isocyanate groups: theoretical value 3.29 quality %, actual value 3.16 quality %).
Then, the urethane prepolymer that obtains is cooled to 60 ℃, adds diacetylmonoxime 4.5 mass parts, under 60 ℃, make its reaction obtain containing the free isocyanate 1.3 quality % and the urethane prepolymer of end-blocking partly in 50 minutes.Continuation is cooled to 55 ℃ with aforementioned urethane prepolymer, adds the mixed solvent that is made of isopropyl alcohol 9 mass parts and methyl alcohol 140 mass parts, mixes equably.Then, add aqueous solution of sodium bisulfite 9.3 mass parts of 50 quality % and the 30 quality % aqueous solution, 5.4 mass parts of N methyl taurine, stir tempestuously.The water-soluble beginning manifests after about 30 minutes, and sodium hydrogensulfite free after 2 hours is almost nil, and reaction finishes.Add entry therein, obtain the aqueous solution of 20 quality % of muddiness and thickness.
(comparative example 14)
(1) preparation of coating fluid LL
Dimethyl terephthalate (DMT) 33.7 mass parts, DMIP 20.0 mass parts, DMIP 5-sodium sulfonate 9.1 mass parts, ethylene glycol 40.0 mass parts, diethylene glycol 10.0 mass parts, a water acetic acid calcium 0.049 mass parts are mixed, under 200～230 ℃, carry out ester exchange to the methyl alcohol of theoretical amount and distillate.Then, add orthophosphoric acid 0.09 mass parts, under reduced pressure, 280 ℃ carry out polymerization, obtain the copolyester resinoid.
The polyethers that will contain the oxirane that useful sodium metabisulfite will obtain by allyl alcohol has carried out the polyethers (SO of the sulfonate group of sulfonation
3Content: 8.3 quality %, PEO content: 83 quality %) 192 mass parts, poly adipate succinic acid ester (number-average molecular weight: 2,250) (number-average molecular weight: 550) 248 mass parts are mixed, and dewater under 100 ℃ under vacuum for 1013 mass parts, the PPOX polyester that caused by bisphenol-A.
This mixture is set at 70 ℃, add IPDI 178 mass parts and hexa-methylene-1 therein, the mixture of 6-vulcabond 244 mass parts, then, stir in 80 ℃～90 ℃ scope generating mixture, to isocyanate content be 5.6 quality %.The fruit thing is cooled to 60 ℃ in advance, add successively by 3 moles of hexamethylene diisocyanates and 1 mole of biuret PIC 56 mass parts that obtain of water with by PVC ス ケ ミ チ Application 175 mass parts that IPD and acetone obtain, obtain polyurethane aqueous dispersion.
Aforementioned copolyester resinoid and polyurethane aqueous dispersion are mixed,, be mixed with the aqueous dispersions that solid component concentration is 10 quality %, make coating fluid LL so that it is respectively 20 mass parts, 80 mass parts in solid constituent.Need to prove in coating fluid, do not have hybrid particles and surfactant.
(2) manufacturing of layered polyester film
As raw polymer, be that the pet resin particle of 0.66dl/g is at 135 ℃ of following drying under reduced pressure (1Torr) after 6 hours with the inherent viscosity that does not contain particle, supply with extruder, become sheet in about 285 ℃ of following melt extruded, remain in surface temperature and to carry out quenching on 60 ℃ the metallic roll and solidify, obtain cast film.At this moment, as the filtering material of the impurity of removing molten resin similarly to Example 21, use filtering particle size (initial stage filter efficiency: 95%) be the stainless steel sintering filtering material of 15 μ m.
Then, this cast film is heated to 95 ℃ with roller group that heated and infrared heater, then,, obtains uniaxial orientation PET film with existing the roller group of linear differential to stretch 3.5 times along its length.Then, with aforementioned coating fluid LL with filtering particle size (initial stage filter efficiency: be that the felt type polypropylene filter made material of 10 μ m carries out secondary filter 95%), be coated on the one side of uniaxial orientation PET film with two sides roller method.Next, control the end of film with clamp, import to the hot blast section that is heated to 110 ℃, after the drying, broad ways is stretched to 3.5 times.Wind speed in the jar of this moment is 15m/ second, and be 20 seconds drying time.From the time that is applied to jar inlet to film be 10.0 seconds.In addition, be 0.15g/m with final solid constituent amount
2Set coating weight.
Then, the width of the film that the maintenance broad ways that remains untouched stretched is successively continuously by the 1st heat-set section (200 ℃), the 2nd heat-set section (205 ℃), the 3rd heat-set section and the 4th heat-set section (210 ℃), the 5th heat-set section (215 ℃), the 6th heat-set section (220 ℃), the 7th heat-set section (170 ℃).And, carry out 3% relaxation processes in the 7th heat-set section broad ways after, finishing film two ends do not have the part of coating, obtain the layered polyester film of thickness 125 μ m.Need to prove that the wind speed of the hot blast in the heat-set section all is 15m/ second, the time of passing through of each section is 4.5 seconds all, and the nozzle number that the nozzle that blows out hot blast is spaced apart 700mm, per 1 section is 4.
In the cover surface of the layered polyester film that obtains, the resinoid phase separation structure of copolyester resinoid and polyurethane is indeterminate.
(comparative example 15)
(1) preparation of coating fluid MM
The 20 quality % aqueous solution, 18.0 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 3.0 mass parts of the copolyester resinoid (A) that embodiment 21 is used, embodiment 21 uses, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 70.7 mass parts and isopropyl alcohol 4.7 mass parts respectively.Further add the 10 quality % aqueous solution, 0.6 mass parts as the dodecyl benzene sulfonic acid of surfactant, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, make coating fluid MM adjust because the pH of coating fluid M carries out pH, so be 4.8.
(2) manufacturing of layered polyester film
As raw polymer, the inherent viscosity that does not contain particle that embodiment 21 is used as the pet resin particle of 0.62dl/g at 135 ℃ of following drying under reduced pressure (1Torr) after 6 hours, supply with extruder, become sheet in about 285 ℃ of following melt extruded, remain in surface temperature and to carry out quenching on 20 ℃ the metallic roll and solidify, obtain cast film.At this moment, as the filtering material of the impurity of removing molten resin, use filtering particle size (initial stage filter efficiency: 95%) be the stainless steel sintering filtering material of 15 μ m.
The cast film that obtains is heated to 95 ℃ with roller group that heated and infrared heater, then,, obtains uniaxial orientation PET film with existing the roller group of linear differential to stretch 3.5 times along its length.Then, with aforementioned coating fluid MM with filtering particle size (initial stage filter efficiency: be that the felt type polypropylene filter made material of 10 μ m carries out secondary filter 95%), be coated on the one side of uniaxial orientation PET film with two sides roller method.
Next, Yi Bian control the end of film with clamp, Yi Bian import to the hot blast section that is heated to 80 ℃, after the coated face drying, broad ways is stretched to 4.0 times.Wind speed in the jar of this moment is 15m/ second, and be 20 seconds drying time.From being applied to jar time of inlet is 10.0 seconds.In addition, be 0.10g/m with final solid constituent amount
2Set coating weight.And, temperature in each heat-set treatment operation is set at: 200 ℃ of the 1st heat-set section, 210 ℃ of the 2nd heat-set section, 220 ℃ of the 3rd heat-set section, 225 ℃ of the 4th heat-set section, 230 ℃ of the 5th heat-set section, 235 ℃ of the 6th heat-set section, 240 ℃ of the 7th heat-set section, and no longer carry out the relaxation processes of width, in addition, use with the same method of comparative example 14 and obtain the layered polyester film that film thickness is 125 μ m.
In the cover surface of the layered polyester film that obtains, can not observe the resinoid phase separation structure of copolyester resinoid and polyurethane.
(comparative example 16)
(1) preparation of coating fluid NN
The 20 quality % aqueous solution, 11.3 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 7.5 mass parts of the copolyester resinoid (A) that embodiment 21 is used, embodiment 21 uses, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 40.5 mass parts and isopropyl alcohol 39.5 mass parts respectively.Further interpolation is not carried out the 10 quality % aqueous solution, 0.6 mass parts that the fluorine of pre-treatment is a nonionic surface active agent (big Japanese イ Application キ chemical industry is made, メ ガ Off ア Star Network F142D), is not used particle B, (the シ リ シ ア of Fuji chemistry is made, サ イ リ シ ア 310 as the agglomerate silica of particle A; Average grain diameter 1.4 μ m) the 3.5 quality % aqueous solution, 0.03 mass parts is made coating fluid NN.Need to prove that the pH that does not carry out coating fluid NN adjusts.The pH of coating fluid NN is 4.6.
(2) manufacturing of layered polyester film
As raw polymer, the inherent viscosity that does not contain particle that embodiment 1 is used is the pet resin pellet supply extruder of 0.62dl/g, become sheet in about 285 ℃ of following melt extruded, remain in surface temperature and to carry out quenching on 20 ℃ the metallic roll and solidify, obtain cast film.At this moment, as the filtering material of the impurity of removing molten resin, use filtering particle size (initial stage filter efficiency: 95%) be the stainless steel sintering filtering material of 15 μ m.
The cast film that obtains is heated to 95 ℃ with roller group that heated and infrared heater, then,, obtains uniaxial orientation PET film with existing the roller group of linear differential to stretch 3.5 times along its length.Then, with aforementioned coating fluid NN with filtering particle size (initial stage filter efficiency: be that the felt type polypropylene filter made material of 10 μ m carries out secondary filter 95%), be coated on the one side of uniaxial orientation PET film with two sides roller method.
After the coating, import drying oven, following dry 3.2 seconds 120 ℃ of temperature.In addition, be 0.08g/m with final solid constituent amount
2Set coating weight.Is 3.2 seconds from the film that is applied to the drying oven inlet by the time.In addition, the wind speed of the 1st section of drying oven is 15m/ second, and the wind speed of the 2nd section to the 4 sections all is set at 70m with the air feed air quantity of the dry wind of the 1st dry section to the 4 dry sections similarly to Example 21
3/ second, exhaust wind is set at from the drying oven natural exhaust in front and back.
Next, the cross directional stretch multiplying power is set at 4.0 times, in addition, carries out cross directional stretch with method similarly to Example 21, with with the same method heat setting of comparative example 15, carry out the relaxation processes of width, obtain the layered polyester film that film thickness is 125 μ m.In the cover surface of the layered polyester film that obtains, can not observe the resinoid phase separation structure of copolyester resinoid and polyurethane.
(comparative example 17)
In embodiment 21, be 3.2 seconds from coating fluid AA being coated the film that enters the mouth to drying oven behind the film by time set, in addition, use method similarly to Example 21 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 18)
Crosslinking agent 2.3 mass parts of the 20 quality % aqueous solution, 16.9 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 2.3 mass parts of the copolyester resinoid (A) that embodiment 21 is used, embodiment 21 uses, embodiment 21 uses, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 36.9 mass parts and isopropyl alcohol 37.7 mass parts respectively.Further add the surfactant that embodiment 21 uses the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, with the sodium bicarbonate aqueous solution of 5 quality % pH is adjusted into 6.2, make coating fluid OO.Use aforementioned coating fluid OO as coating fluid, in addition, use method similarly to Example 21 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 19)
30 quality % aqueous dispersions, 11.3 mass parts of the copolyester resinoid (A) that embodiment 21 is used respectively, the 20 quality % aqueous solution, 3.4 mass parts of the polyurethanes resin (B) that embodiment 21 uses, crosslinking agent 2.3 mass parts that embodiment 21 uses, (make by worker industry System medicine with catalyst for エ ラ ス ト ロ Application, Cat64) 0.3 mass parts, water 41.9 mass parts and isopropyl alcohol 37.2 mass parts are mixed, and further add the 10 quality % aqueous solution, 0.6 mass parts of the surfactant of embodiment 21 uses, cabosil (Ri Productivity chemical industry as particle A is made, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, with the sodium bicarbonate aqueous solution of 5 quality % pH is adjusted into 6.2, make coating fluid PP.Use aforementioned coating fluid PP as coating fluid, in addition, use method similarly to Example 21 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 20)
In embodiment 21, temperature in each heat-set treatment operation is set: 190 ℃ of the 1st heat-set section, 195 ℃ of the 2nd heat-set section: 200 ℃ of the 3rd heat-set section to the 5 heat-set section, in addition, use method similarly to Example 21 to obtain the layered polyester film that film thickness is 125 μ m.In the cover surface of the layered polyester film that obtains, can not observe the resinoid phase separation structure of copolyester resinoid and polyurethane.
(comparative example 21)
In embodiment 21, the wind speed in the drying oven is set at 15m/ second, in addition, use method similarly to Example 21 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 22)
In embodiment 21, be 0.20g/m with final solid constituent amount
2Set coating weight, in addition, use method similarly to Example 21 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 23)
In embodiment 21, use with 5 quality % aqueous sodium carbonates the pH of coating fluid is adjusted into 9.0 coating fluid QQ, in addition, usefulness method similarly to Example 21 obtains the layered polyester film that film thickness is 125 μ m.
(comparative example 24)
In embodiment 21, in addition the coating fluid RR that uses in coating fluid mixed surfactant not to be mixed with, obtains the layered polyester film that film thickness is 125 μ m with similarly to Example 21 method.
(embodiment 38)
Crosslinking agent 2.3 mass parts of the 20 quality % aqueous solution, 11.3 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 7.5 mass parts of the copolyester resinoid (A) that embodiment 21 is used, embodiment 21 uses, embodiment 21 uses, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 40.5 mass parts and isopropyl alcohol 39.5 mass parts respectively.And, further add the surfactant that embodiment 21 uses the 10 quality % aqueous solution, 0.6 mass parts, (the シ リ シ ア of Fuji chemistry is made, サ イ リ シ ア 310 as the agglomerate silica of particle A; Average grain diameter 1.4 μ m) the 3.5 quality % aqueous solution, 4.3 mass parts are adjusted into 6.2 with 5 quality % sodium bicarbonate aqueous solutions with pH, and making it is the filter of 5 μ m and 1 μ m by strainability successively, makes coating fluid SS.Need to prove that particle B is not blended in the coating fluid.Except that using aforementioned coating fluid SS, use method similarly to Example 21 to obtain the layered polyester film that film thickness is 125 μ m.
(comparative example 25)
In embodiment 21, using and only making the amount of the surfactant in the coating fluid is the coating fluid TT that 0.60 quality % prepares by the solid constituent amount, in addition, uses method similarly to Example 21 to obtain the layered polyester film that film thickness is 125 μ m.
(embodiment 39)
In embodiment 21, temperature in each heat-set treatment operation is set: 200 ℃ of the 1st heat-set section, 210 ℃ of the 2nd heat-set section, 215 ℃ of the 3rd heat-set section, 220 ℃ of the 4th heat-set section, 225 ℃ of the 5th heat-set section, 230 ℃ of the 6th heat-set section, 170 ℃ of the 7th heat-set section, and carry out 3% relaxation processes in the 7th heat-set section broad ways, in addition, with method similarly to Example 21, the film thickness that does not have coating layer portion that obtains repairing the film two ends is the layered polyester film of 125 μ m.
(comparative example 26)
In embodiment 1, the 20 quality % aqueous solution, 10.1 mass parts of the polyurethanes resin (B) of 30 quality % aqueous dispersions, 6.8 mass parts of the copolyester resinoid (A) that embodiment 21 is used, embodiment 21 uses, エ ラ ス ト ロ Application mix with catalyst (manufacturing of worker industry System medicine, Cat64) 0.3 mass parts, water 50.6 mass parts and isopropyl alcohol 26.2 mass parts respectively.Further add the surfactant that embodiment 21 uses the 10 quality % aqueous solution, 0.6 mass parts, as the cabosil (Ri Productivity chemical industry of particle A make, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, with 5 quality % sodium bicarbonate aqueous solutions pH is adjusted into 6.2, make coating fluid UU.Use coating fluid UU as coating fluid, in addition, use method similarly to Example 21 to obtain layered polyester film.
(embodiment 40)
In embodiment 21, as apparatus for coating, the capacity, circulation that uses the pallet of coating fluid with jar capacity and the preparation apparatus for coating that has following condition with the ratio of the capacity of jar, in addition, with method similarly to Example 1, obtaining film length is that 2000m, width are that 1000mm, thickness are the laminated polyester film volume of 125 μ m.
(a) capacity=1/5 of jar is used in the capacity of the pallet of coating fluid/circulation
(b) capacity=1/50 of jar is used in circulation with capacity/preparation of jar
(c) circularity of dispenser roller and measuring roller and cylindricity: 6/1000mm
(d) from coating machine to pinch roll is not set between the drying oven
(embodiment 41)
In embodiment 21,20 quality % aqueous dispersions, 2.9 mass parts of using epoxies crosslinking agent (Na ガ セ changes into industry manufacturing, デ Na コ one Le EX-810) are made coating fluid VV as the crosslinking agent that is used for the preparation of coating fluid.Use coating fluid VV as coating fluid, in addition, the method with similarly to Example 21 obtains layered polyester film.
(embodiment 42)
In embodiment 21, Shi Yong oxazoline class crosslinking agent (Japanese catalyst manufacturing, エ Port Network ロ ス series, WS-700) 2.3 mass parts are made coating fluid WW as the crosslinking agent that is used for the preparation of coating fluid.Use coating fluid WW as coating fluid, in addition, the method with similarly to Example 21 obtains layered polyester film.
(embodiment 43)
In embodiment 21, respectively with 30 quality % aqueous dispersions, 7.5 mass parts of copolyester resinoid (A), the 20 quality % aqueous solution of the self-crosslinking type polyurethane resinoid of crossing with the sodium hydrogensulfite end-blocking (B) that contains NCO (make by worker industry System medicine, trade name エ ラ ス ト ロ Application (registration mark) H-3) 11.3 mass parts, (make by worker industry System medicine with catalyst for エ ラ ス ト ロ Application, trade name Cat64) 0.3 mass parts, water 39.8 mass parts and isopropyl alcohol 37.4 mass parts are mixed, and further adding fluorine is that nonionic surface active agent (make by big Japanese イ Application キ chemical industry, メ ガ Off ア Star Network F142D) the 10 quality % aqueous solution, 0.6 mass parts, cabosil (Ri Productivity chemical industry as particle A is made, ス ノ one テ Star Network ス OL; Average grain diameter 40nm) 20 quality % aqueous dispersions, 2.3 mass parts, (Japanese ア エ ロ ジ Le is made, ア エ ロ ジ Le OX50 as the dry process silica of particle B; Average grain diameter 200nm, average primary particle diameter 40nm) 3.5 quality % aqueous dispersions, 0.5 mass parts, make coating fluid XX.Use coating fluid XX as coating fluid, in addition, use method similarly to Example 21 to obtain layered polyester film.
In embodiment 21～43, comparative example 14～26, the composition and the characteristic of coating fluid is shown in table 6, will be coated with drying condition and be shown in table 7, heat-setting condition is shown in table 8, film rerum natura and characteristic are shown in table 9.In addition, maximum, the minimum of a value of the adaptation of the maximum of the maximum of length direction that the laminated polyester film that obtains is rolled up and the surface of the PEs in width branch rate, minimum of a value, mist degree, minimum of a value, relative hard conating are shown in table 10.Need to prove that for block resistance, all measuring point all is zero.
[table 6]
| Coating fluid is formed | Coating fluid | |||||||||||
| Resin | Crosslinking agent | Particle | Particle B | Solvent | Surfactant | pH | Solid component concentration | |||||
| Overlap PEs/PU/ crosslinking agent (mass ratio) altogether | Kind | Average grain diameter | Addition | Average grain diameter | Addition | Water/IPA mass ratio | Kind | Having or not of pre-treatment | Combined amount | |||
| μm | Quality % | μm | Quality % | Quality % | Quality % | |||||||
| Embodiment 21 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 22 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Cation | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 23 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 24 | 55/35/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 25 | 35/55/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 26 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 27 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.03 | 6.2 | 5.30 |
| Embodiment 28 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.10 | 6.2 | 5.30 |
| Embodiment 29 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 30 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 31 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 7.9 | 5.30 |
| Embodiment 32 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 33 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 34 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | No | 0.06 | 6.2 | 5.30 |
| Embodiment 35 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 50/50 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 36 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 4.6 | 5.30 |
| Embodiment 37 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 38 | 45/45/10 | Melamine | 1.4 | 3.0 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 39 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 40 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 41 | 45/45/10 | Epoxy | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 42 | 45/45/10 | Oxazoline | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Embodiment 43 | 50/50/0 | - | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 14 | 20/80/0 | - | - | - | - | - | 100/0 | - | - | - | 6.2 | 10.00 |
| Comparative example 15 | 20/80/0 | - | 0.04 | 0.36 | 0.20 | 0.04 | 95/5 | Anion | No | 0.06 | 4.8 | 10.93 |
| Comparative example 16 | 50/50/0 | - | 1.4 | 0.02 | - | - | 60/40 | Nonionic | No | 0.06 | 4.6 | 4.87 |
| Comparative example 17 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 18 | 15/75/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 19 | 75/15/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 20 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 21 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 22 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
| Comparative example 23 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.06 | 9.0 | 5.30 |
| Comparative example 24 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | - | - | - | 6.2 | 5.30 |
| Comparative example 25 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 60/40 | Nonionic | Have | 0.60 | 6.2 | 5.30 |
| Comparative example 26 | 45/45/10 | Melamine | 0.04 | 0.45 | 0.20 | 0.02 | 72/28 | Nonionic | Have | 0.06 | 6.2 | 5.30 |
[table 7]
| The coating drying condition | |||||
| Passing through the time (second) after coating to the drying process inlet | Baking temperature (℃) | Drying time (second) | Wind speed (m/s) | Final coating weight (g/m 2) | |
| Embodiment 21 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Embodiment 22 | 0.8 | 0.8 | 0.8 | 30 | 0.08 |
| Embodiment 23 | 0.8 | 0.8 | 0.8 | 30 | 0.08 |
| Embodiment 24 | 0.8 | 0.8 | 0.8 | 30 | 0.08 |
| Embodiment 25 | 0.8 | 0.8 | 0.8 | 30 | 0.08 |
| Embodiment 26 | 0.8 | 0.8 | 0.8 | 30 | 0.12 |
| Embodiment 27 | 0.8 | 0.8 | 0.8 | 30 | 0.08 |
| Embodiment 28 | 0.8 | 0.8 | 0.8 | 30 | 0.08 |
| Embodiment 29 | 0.7 | 0.8 | 0.8 | 30 | 0.08 |
| Embodiment 30 | 1.0 | 0.8 | 1.9 | 30 | 0.08 |
| Embodiment 31 | 0.8 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 32 | 0.8/1.0 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 33 | 0.8 | 0.8 | 1.0 | 30 | 0.02 |
| Embodiment 34 | 0.8 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 35 | 0.8 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 36 | 0.8 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 37 | 0.8 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 38 | 0.8 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 39 | 0.8 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 40 | 0.8 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 41 | 0.8 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 42 | 0.8 | 0.8 | 1.0 | 30 | 0.08 |
| Embodiment 43 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 14 | 10 | 110 | 20 | 15 | 0.15 |
| Comparative example 15 | 10 | 80 | 20 | 20 | 0.10 |
| Comparative example 16 | 3.2 | 120 | 1.0 | 15 | 0.08 |
| Comparative example 17 | 3.2 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 18 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 19 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 20 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 21 | 0.8 | 135 | 1.0 | 15 | 0.08 |
| Comparative example 22 | 0.8 | 135 | 1.0 | 30 | 0.20 |
| Comparative example 23 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 24 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 25 | 0.8 | 135 | 1.0 | 30 | 0.08 |
| Comparative example 26 | 0.8 | 135 | 1.0 | 30 | 0.08 |
[table 8]
| Heat-setting condition | ||||||||
| Heat-set temperature (℃) | Passing through the time (second) of each section | |||||||
| The #1 section | The #2 section | The #3 section | The #4 section | The #5 section | The #6 section | The #7 section | ||
| Embodiment 21 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 22 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 23 | 190 | 205 | 220 | 220 | 210 | 170 | 120 | 4.5 |
| Embodiment 24 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 25 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 26 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 27 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 28 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 29 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 3.5 |
| Embodiment 30 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 6.6 |
| Embodiment 31 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 32 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 33 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 34 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 35 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 36 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 37 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 38 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 39 | 200 | 210 | 215 | 220 | 225 | 230 | 170 | 4.5 |
| Embodiment 40 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 41 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 42 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Embodiment 43 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 14 | 200 | 205 | 210 | 213 | 215 | 220 | 170 | 4.5 |
| Comparative example 15 | 200 | 210 | 220 | 225 | 230 | 235 | 240 | 4.5 |
| Comparative example 16 | 200 | 205 | 210 | 213 | 215 | 220 | 170 | 4.5 |
| Comparative example 17 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 18 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 19 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 20 | 190 | 195 | 200 | 200 | 200 | 170 | 120 | 4.5 |
| Comparative example 21 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 22 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 23 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 24 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 25 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
| Comparative example 26 | 200 | 225 | 230 | 230 | 210 | 170 | 120 | 4.5 |
Table 9
| The phase separation structure of PEs phase | The film rerum natura | Film is estimated | |||||||
| PEs surface branch rate (%) | Width surpasses the having or not of PEs phase (A) of 1 μ m | Fractal dimension | Film thickness (μ m) | Tectal stiffness (nm) | Mist degree (%) | Adaptation (%) with the HC layer | Anti-adhesive | ||
| No-solvent type HC layer cover layer | Solvent cutback HC layer/cover layer | ||||||||
| Embodiment 21 | 65 | Do not have | 1.90 | 125 | 4.2 | 0.59 | 92 | 98 | ○ |
| Embodiment 22 | 63 | Do not have | 125 | 4.5 | 0.65 | 99 | 99 | ○ | |
| Embodiment 23 | 51 | Do not have | 1.77 | 125 | 6.0 | 0.47 | 99 | 99 | ○ |
| Embodiment 24 | 72 | Do not have | 1.72 | 125 | 2.8 | 0.42 | 92 | 95 | ○ |
| Embodiment 25 | 44 | Do not have | 125 | 12.8 | 0.87 | 98 | 94 | ○ | |
| Embodiment 26 | 50 | Do not have | 125 | 6.1 | 0.66 | 98 | 99 | ○ | |
| Embodiment 27 | 73 | Do not have | 125 | 5.6 | 0.62 | 91 | 94 | ○ | |
| Embodiment 28 | 63 | Do not have | 125 | 4.6 | 0.86 | 98 | 99 | ○ | |
| Embodiment 29 | 68 | Do not have | 1.93 | 100 | 4.4 | 0.56 | 97 | 98 | ○ |
| Embodiment 30 | 49 | Do not have | 1.87 | 188 | 7.0 | 0.48 | 97 | 98 | ○ |
| Embodiment 31 | 59 | Do not have | 125 | 4.4 | 0.74 | 98 | 99 | ○ | |
| Embodiment 32 | 66 | Do not have | 125 | 4.6 | 0.8 | 94 | 98 | ○ | |
| Embodiment 33 | 75 | Do not have | 125 | 3.4 | 0.79 | 88 | 92 | ○ | |
| Embodiment 34 | 63 | Do not have | 125 | 4.8 | 0.53 | 84 | 86 | ○ | |
| Embodiment 35 | 67 | Do not have | 125 | 4.3 | 0.57 | 84 | 85 | ○ | |
| Embodiment 36 | 82 | Do not have | 125 | 3.5 | 0.45 | 50 | 78 | ○ | |
| Embodiment 37 | 66 | Do not have | 125 | 4.1 | 0.58 | 95 | 98 | ○ | |
| Embodiment 38 | 65 | Have | 125 | 4.7 | 3.43 | 99 | 99 | ○ | |
| Embodiment 39 | 45 | Have | 125 | 7.0 | 0.48 | 76 | 93 | ○ | |
| | 67 | Do not have | 125 | 4.2 | 0.59 | 94 | 97 | ○ | |
| Embodiment 41 | 66 | Do not have | 125 | 4.1 | 0.73 | 91 | 96 | ○ | |
| Embodiment 42 | 65 | Do not have | 125 | 4.0 | 0.71 | 91 | 97 | ○ | |
| Embodiment 43 | 68 | Do not have | 125 | 5.1 | 0.58 | 95 | 100 | × | |
| Comparative example 14 | 8 | Do not have | 1.25 | 125 | 16.6 | 1.05 | 75 | 50 | × |
| Comparative example 15 | - | Do not have | 125 | 16.4 | 0.75 | 84 | 60 | × | |
| Comparative example 16 | - | Do not have | 125 | 6.6 | 0.41 | 100 | 95 | × | |
| Comparative example 17 | 26 | Do not have | 1.60 | 125 | 14.2 | 0.74 | 91 | 76 | ○ |
| Comparative example 18 | 13 | Do not have | 125 | 14.8 | 0.99 | 93 | 55 | ○ | |
| Comparative example 19 | 90 | Have | 1.45 | 125 | 1.9 | 0.48 | 27 | 68 | ○ |
| Comparative example 20 | - | Do not have | 125 | 3.2 | 0.63 | 70 | 63 | ○ | |
| Comparative example 21 | 30 | Do not have | 125 | 5.1 | 0.71 | 90 | 92 | ○ | |
| Comparative example 22 | 28 | Do not have | 125 | 5.6 | 0.57 | 90 | 83 | ○ | |
| Comparative example 23 | 30 | Do not have | 125 | 5.1 | 1.56 | 95 | 85 | ○ | |
| Comparative example 24 | 86 | Do not have | 125 | 2.6 | 0.39 | 22 | 65 | ○ | |
| Comparative example 25 | 32 | Do not have | 125 | 5.0 | 1.56 | 92 | 83 | ○ | |
| Comparative example 26 | 29 | Do not have | 125 | 5.9 | 2.21 | 90 | 84 | ○ | |
[table 10]
| PEs surface branch rate (%) | Mist degree (%) | Adaptation (%) with the HC layer | ||||||||
| No-solvent type HC layer/cover layer | Solvent cutback HC layer/cover layer | The hot adaptation of moisture-proof | ||||||||
| Max | Min | Max | Min | Max | Min | Max | Min | |||
| Embodiment 21 | Length direction | 70 | 60 | 0.6 | 0.57 | 100 | 90 | 100 | 97 | ○ |
| Width | 71 | 61 | 0.6 | 0.57 | 100 | 91 | 100 | 97 | ○ | |
| | Length direction | 72 | 55 | 0.6 | 0.57 | 100 | 90 | 100 | 97 | ○ |
| Width | 70 | 55 | 0.6 | 0.57 | 100 | 91 | 100 | 97 | ○ | |
| Embodiment 41 | Length direction | 71 | 61 | 0.75 | 0.70 | 95 | 87 | 100 | 93 | ○ |
| Width | 70 | 62 | 0.75 | 0.69 | 95 | 88 | 100 | 94 | ○ | |
| Embodiment 42 | Length direction | 70 | 60 | 0.72 | 0.71 | 97 | 88 | 100 | 94 | ○ |
| Width | 69 | 61 | 0.72 | 0.70 | 95 | 90 | 100 | 95 | ○ | |
The possibility of industrial utilization
The laminated thermoplastic resin film of the present invention that obtains as mentioned above, because the adaptation of the functional layers such as itself and hard conating, diffusion layer, anti-reflection layer is good, and, block resistance and the transparency are also good, so be suitable as the base material film of the optical functional films such as hard coat film, antireflection (AR) film, prismatic lens sheet material, transparent and electrically conductive film, infrared absorbing film, electro-magnetic wave absorption film or optical functional sheet material. In addition, also can be as using with the printing film of acrylic resin as the UV ink printing of resinous principle. At this moment, the thermoplastic resin membrane as base material except hyaline membrane, also can use opaque coating.
Claims (19)
1. laminated thermoplastic resin film has the copolyester of containing resinoid and the resinoid cover layer of polyurethane at thermoplastic resin membrane's one or both sides, it is characterized in that,
Described cover layer, have to be the polyester phase A of main component with the copolyester resinoid with the polyurethanes resin be main component polyurethane mutually B carried out microphase-separated or received the structure that is separated, and, when observing with the phase determination pattern with scanning probe microscopy, mensuration planimeter with 5 μ m * 5 μ m, area ratio (PEs surface branch rate) with the polyester phase A (showing darker shade in the phase place picture) of the described cover surface of following formula (1) definition is more than 35%, and is lower than 90%
PEs surface branch rate (%)=(area of polyester phase A/mensuration area) * 100 (1).
2. laminated thermoplastic resin film as claimed in claim 1 is characterized in that, the copolyester resinoid carries out crosslinked with at least a crosslinking agent that is selected from epoxies crosslinking agent, the melamine class crosslinking agent, oxazoline class crosslinking agent.
3. laminated thermoplastic resin film as claimed in claim 1 is characterized in that the two contains particle described thermoplastic resin membrane or thermoplastic resin membrane and cover layer.
4. laminated thermoplastic resin film as claimed in claim 1 is characterized in that described thermoplastic resin membrane is substantially devoid of particle, only contains particle in cover layer.
5. as claim 3 or 4 described laminated thermoplastic resin films, it is characterized in that described particle is a silicon oxide particle.
6. as claim 3 or 4 described laminated thermoplastic resin films, it is characterized in that the particle in the cover layer is stored among polyester phase A or the polyurethane phase B partially.
7. laminated thermoplastic resin film as claimed in claim 1 is characterized in that, described thermoplastic resin membrane is double axial orientated polyester film or Biaxially orientated polyamide film.
8. laminated thermoplastic resin film as claimed in claim 1 is characterized in that, the following of described PEs surface branch rate is limited to 40%.
9. laminated thermoplastic resin film as claimed in claim 1 is characterized in that, the following of described PEs surface branch rate is limited to 45%.
10. laminated thermoplastic resin film as claimed in claim 1 is characterized in that, is limited to 80% on the branch rate of described PEs surface.
11. laminated thermoplastic resin film as claimed in claim 1 is characterized in that, is limited to 75% on the branch rate of described PEs surface.
12. laminated thermoplastic resin film as claimed in claim 1, it is characterized in that, observe described tectal surface with the phase determination pattern of scanning probe microscopy, in the phase place picture of the interface profile of strengthening light colour phase and darker shade, with the mensuration planimeter of 5 μ m * 5 μ m, the fractal dimension that uses the box-counting method to obtain from the boundary line (interface profile) of light colour phase and darker shade is 1.60～1.95.
13. laminated thermoplastic resin film as claimed in claim 1 is characterized in that, the tectal stiffness of following definitions is 3.0～15.0nm,
So-called cover layer stiffness is meant: the sapphire pin with the subsidiary radius 75 μ m of front end applies loading 5gf, make tectal surface in spite of wound, the adjacent protuberance and the difference of height of recess when measuring the concaveconvex shape of measure hindering at 50 places with the non-contact three-dimensional surface profile measuring instrument, the mean value of each measured value of obtaining.
14., it is characterized in that the mist degree of described laminated thermoplastic resin film is below 1.5% as claim 3 or 4 described laminated thermoplastic resin films.
15. laminated thermoplastic resin film as claimed in claim 14 is characterized in that, it is as the base material film of optical functional film or optical functional sheet material.
16. laminated thermoplastic resin film as claimed in claim 15, it is characterized in that described optical functional film or optical functional sheet material are any one in hard coat film, antireflection film, light diffusing sheet material, prism sheet material, transparent and electrically conductive film, near-infrared absorption film, the electro-magnetic wave absorption film.
17. laminated thermoplastic resin film as claimed in claim 1 is characterized in that, in described tectal one side at least, lamination is that the functional layer of main composition composition forms with the acrylic resin.
18. laminated thermoplastic resin film roll, for one or both sides the thermoplastic resin membrane, has each the described thermoplastic resin membrane who contains in copolyester resinoid and the resinoid tectal claim 1～17 of polyurethane, more than long 1000m, the above size of wide 50mm is rolled into the roller shape continuously and forms, it is characterized in that, at the length direction of film during with the area ratio (PEs surface branch rate) of the polyester phase A (showing darker shade in the phase place picture) of the described cover surface of 100m measuring space, the maximum of the PEs surface branch rate in the cover surface of length direction and the difference of minimum of a value are below 15%
The assay method of the PEs surface branch rate in the above-mentioned cover surface is as follows: roll out described laminated thermoplastic resin film roll, length direction (MD) at this film, one end in the constant zone that the film rerum natura is stable is set at the 1st end, when the other end is set at the 2nd end, below the inboard 2m of the 1st end, carry out the first time and measure, in addition, below the inboard 2m of the 2nd end, finally measure, simultaneously, measure once since the 1st the every 100m in mensuration place.
19. laminated thermoplastic resin film roll as claimed in claim 18, it is characterized in that, roll out described laminated thermoplastic resin film roll, at width film is divided into 4 equal portions, when central portion was separately measured the area ratio (PEs surface branch rate) of the polyester phase A (showing darker shade in the phase place picture) of cover surface, the maximum of the PEs surface branch rate in the cover surface of width and the difference of minimum of a value were below 10%.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP343223/2004 | 2004-11-29 | ||
| JP2004343223 | 2004-11-29 | ||
| JP219694/2005 | 2005-07-28 | ||
| JP221426/2005 | 2005-07-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101068682A true CN101068682A (en) | 2007-11-07 |
| CN100532093C CN100532093C (en) | 2009-08-26 |
Family
ID=38880885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800409811A Active CN100532093C (en) | 2004-11-29 | 2005-11-28 | Laminated thermoplastic resin film and laminated thermoplastic resin film roll |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100532093C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102076498A (en) * | 2008-04-30 | 2011-05-25 | 东洋纺织株式会社 | Substrate film with modified adhesiveness and hard coat film |
| CN102427943A (en) * | 2009-05-25 | 2012-04-25 | 三菱树脂株式会社 | laminated polyester film |
| CN103733312A (en) * | 2011-09-16 | 2014-04-16 | 琳得科株式会社 | Dicing sheet substrate film and dicing sheet |
| CN103833994A (en) * | 2012-11-22 | 2014-06-04 | 东丽纤维研究所（中国）有限公司 | Alkali-soluble copolyester and its production method and use |
| CN114059210A (en) * | 2020-07-30 | 2022-02-18 | 湖南科力嘉纺织股份有限公司 | High-hygroscopicity yarn and preparation method thereof |
-
2005
- 2005-11-28 CN CNB2005800409811A patent/CN100532093C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102076498A (en) * | 2008-04-30 | 2011-05-25 | 东洋纺织株式会社 | Substrate film with modified adhesiveness and hard coat film |
| CN102076498B (en) * | 2008-04-30 | 2014-12-17 | 东洋纺织株式会社 | Substrate film with modified adhesiveness and hard coat film |
| CN102427943A (en) * | 2009-05-25 | 2012-04-25 | 三菱树脂株式会社 | laminated polyester film |
| CN102427943B (en) * | 2009-05-25 | 2015-04-01 | 三菱树脂株式会社 | Laminated polyester film |
| CN103733312A (en) * | 2011-09-16 | 2014-04-16 | 琳得科株式会社 | Dicing sheet substrate film and dicing sheet |
| CN103833994A (en) * | 2012-11-22 | 2014-06-04 | 东丽纤维研究所（中国）有限公司 | Alkali-soluble copolyester and its production method and use |
| CN114059210A (en) * | 2020-07-30 | 2022-02-18 | 湖南科力嘉纺织股份有限公司 | High-hygroscopicity yarn and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100532093C (en) | 2009-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1178075C (en) | Infrared absorbing filter | |
| CN1253311C (en) | Laminated polyester film | |
| TWI450820B (en) | Adhesive modified base film and hard-coated film | |
| CN1106263C (en) | Double-axle oriented polyester film and making method thereof | |
| TWI317324B (en) | Laminated polyester film and laminated polyester film roll | |
| CN1236913C (en) | Optical coated film | |
| CN1097065C (en) | Reactive two-part polyurethane compositions and optionally self-healable and scratch-resistant coatings prepared therefrom | |
| CN1246366C (en) | Block polymer and antistatic agent comprising the same | |
| CN1126668C (en) | Record material | |
| CN1512934A (en) | Adhesive polyester film for optics | |
| CN101460308B (en) | Hard coat film and optically functional film | |
| CN1649734A (en) | Optical Lamination Films | |
| CN1295076C (en) | Polyester film and recording medium using same | |
| CN1553857A (en) | Glass protecting film | |
| CN1655927A (en) | peel film | |
| CN1772825A (en) | Material for forming antiglare hard coat layer and antiglare hard coat film | |
| CN1611533A (en) | Antistatic resin composition | |
| CN1649744A (en) | Information recording display card, and image processing method and image processing device using the card | |
| CN1922029A (en) | Biaxially oriented white film for thermal transfer recording and receptive sheet for thermal transfer recording comprising this biaxially oriented white film | |
| CN101065849A (en) | Easily adhesive polyester film for solar cell back surface-protecting film and solar cell back surface-protecting film obtained using the same | |
| CN1934464A (en) | Method for manufacturing antireflection film, antireflection film, polarizing plate and image display device | |
| CN1759137A (en) | Biaxially oriented polyester film and release film | |
| CN1900830A (en) | Image transfer sheet for electrophotography, and image recorded medium, as well as method for manufacturing the same | |
| JP2009269174A (en) | Substrate film having modified adhesiveness and hard coat film | |
| CN101068682A (en) | Laminated thermoplastic resin film and laminated thermoplastic resin film roll |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |