WO2012176829A1 - Method for improving adhesion between polyester film and aqueous dispersion and process for manufacturing polyester film - Google Patents
Method for improving adhesion between polyester film and aqueous dispersion and process for manufacturing polyester film Download PDFInfo
- Publication number
- WO2012176829A1 WO2012176829A1 PCT/JP2012/065823 JP2012065823W WO2012176829A1 WO 2012176829 A1 WO2012176829 A1 WO 2012176829A1 JP 2012065823 W JP2012065823 W JP 2012065823W WO 2012176829 A1 WO2012176829 A1 WO 2012176829A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- corona treatment
- resin film
- polyester
- polyester film
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 97
- 229920006267 polyester film Polymers 0.000 title claims abstract description 92
- 239000006185 dispersion Substances 0.000 title claims description 18
- 230000008569 process Effects 0.000 title abstract description 22
- 238000003851 corona treatment Methods 0.000 claims abstract description 188
- 229920005989 resin Polymers 0.000 claims abstract description 136
- 239000011347 resin Substances 0.000 claims abstract description 136
- 238000010438 heat treatment Methods 0.000 claims abstract description 132
- 239000000758 substrate Substances 0.000 claims abstract description 104
- 229920000642 polymer Polymers 0.000 claims abstract description 84
- 229920000728 polyester Polymers 0.000 claims abstract description 59
- 230000009477 glass transition Effects 0.000 claims abstract description 11
- 238000000113 differential scanning calorimetry Methods 0.000 claims abstract description 8
- -1 polyethylene terephthalate Polymers 0.000 claims description 233
- 239000000463 material Substances 0.000 claims description 73
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 30
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 30
- 230000001681 protective effect Effects 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 abstract description 32
- 239000010410 layer Substances 0.000 description 194
- 239000010408 film Substances 0.000 description 174
- 238000000576 coating method Methods 0.000 description 110
- 239000011248 coating agent Substances 0.000 description 96
- 239000000243 solution Substances 0.000 description 65
- 125000004432 carbon atom Chemical group C* 0.000 description 63
- 125000003118 aryl group Chemical group 0.000 description 33
- 229920001296 polysiloxane Polymers 0.000 description 33
- 239000011230 binding agent Substances 0.000 description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 239000003431 cross linking reagent Substances 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 28
- 239000002131 composite material Substances 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 125000004122 cyclic group Chemical group 0.000 description 26
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- 108010010803 Gelatin Proteins 0.000 description 20
- 229920000159 gelatin Polymers 0.000 description 20
- 235000019322 gelatine Nutrition 0.000 description 20
- 235000011852 gelatine desserts Nutrition 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 125000001931 aliphatic group Chemical group 0.000 description 19
- 125000005647 linker group Chemical group 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 125000002723 alicyclic group Chemical group 0.000 description 18
- 239000004332 silver Substances 0.000 description 18
- 229910052709 silver Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000008273 gelatin Substances 0.000 description 17
- 125000001424 substituent group Chemical group 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- 239000012463 white pigment Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 125000005842 heteroatom Chemical group 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 229920001225 polyester resin Polymers 0.000 description 15
- 239000007790 solid phase Substances 0.000 description 15
- 238000011282 treatment Methods 0.000 description 15
- 239000012790 adhesive layer Substances 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000000945 filler Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 239000004645 polyester resin Substances 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 13
- 125000005843 halogen group Chemical group 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- 125000003368 amide group Chemical group 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 239000004925 Acrylic resin Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 10
- 125000003172 aldehyde group Chemical group 0.000 description 10
- 125000000732 arylene group Chemical group 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 150000002009 diols Chemical class 0.000 description 10
- 125000001033 ether group Chemical group 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 239000004816 latex Substances 0.000 description 10
- 229920000126 latex Polymers 0.000 description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 9
- 125000004185 ester group Chemical group 0.000 description 9
- 229910052809 inorganic oxide Inorganic materials 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 229920000058 polyacrylate Polymers 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 125000002993 cycloalkylene group Chemical group 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000002346 layers by function Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000006224 matting agent Substances 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 5
- 239000011112 polyethylene naphthalate Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 150000001718 carbodiimides Chemical class 0.000 description 4
- 239000000805 composite resin Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 238000007767 slide coating Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 125000004976 cyclobutylene group Chemical group 0.000 description 3
- 125000004977 cycloheptylene group Chemical group 0.000 description 3
- 125000004956 cyclohexylene group Chemical group 0.000 description 3
- 125000004978 cyclooctylene group Chemical group 0.000 description 3
- 125000004979 cyclopentylene group Chemical group 0.000 description 3
- 125000004980 cyclopropylene group Chemical group 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000007765 extrusion coating Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 235000012245 magnesium oxide Nutrition 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 125000003327 methanetetrayl group Chemical group *C(*)(*)* 0.000 description 3
- 125000001800 methanetriyl group Chemical group C(*)(*)* 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000012788 optical film Substances 0.000 description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 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
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000001142 dicarboxylic acid group Chemical class 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229960002479 isosorbide Drugs 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical class CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- BEQDKWKSUMQVMX-UHFFFAOYSA-N 2,4-dimethyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(C)=N1 BEQDKWKSUMQVMX-UHFFFAOYSA-N 0.000 description 1
- KKKKCPPTESQGQH-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-yl)-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=NCCO1 KKKKCPPTESQGQH-UHFFFAOYSA-N 0.000 description 1
- QEEZSWGDNCHFKC-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-ylmethyl)-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CC1=NCCO1 QEEZSWGDNCHFKC-UHFFFAOYSA-N 0.000 description 1
- VJIADJVPBWWZEC-UHFFFAOYSA-N 2-(4-bicyclo[2.2.1]heptanyl)-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1(C2)CCC2CC1 VJIADJVPBWWZEC-UHFFFAOYSA-N 0.000 description 1
- VHOJALQDYQKSMT-UHFFFAOYSA-N 2-(4-carboxyphenyl)-9H-fluorene-1-carboxylic acid Chemical compound C(=O)(O)C1=CC=C(C=C1)C1=C(C=2CC3=CC=CC=C3C=2C=C1)C(=O)O VHOJALQDYQKSMT-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- KFNAHVKJFHDCSK-UHFFFAOYSA-N 2-[2-(4,5-dihydro-1,3-oxazol-2-yl)ethyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCC1=NCCO1 KFNAHVKJFHDCSK-UHFFFAOYSA-N 0.000 description 1
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 description 1
- XRMPKRMBDKCXII-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)propyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCC1=NCCO1 XRMPKRMBDKCXII-UHFFFAOYSA-N 0.000 description 1
- GZQKJQLFIGBEIE-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)butyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCC1=NCCO1 GZQKJQLFIGBEIE-UHFFFAOYSA-N 0.000 description 1
- ZDNUPMSZKVCETJ-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=C(C=2OCCN=2)C=C1 ZDNUPMSZKVCETJ-UHFFFAOYSA-N 0.000 description 1
- LDXQWLJXDIZULP-UHFFFAOYSA-N 2-[6-(4,5-dihydro-1,3-oxazol-2-yl)hexyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCCCC1=NCCO1 LDXQWLJXDIZULP-UHFFFAOYSA-N 0.000 description 1
- MPPNPBNSYXFIBF-UHFFFAOYSA-N 2-[8-(4,5-dihydro-1,3-oxazol-2-yl)octyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCCCCCC1=NCCO1 MPPNPBNSYXFIBF-UHFFFAOYSA-N 0.000 description 1
- ZKTPGXSTOJXHIG-UHFFFAOYSA-N 2-cyclohexyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1CCCCC1 ZKTPGXSTOJXHIG-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- PBYIFPWEHGSUEY-UHFFFAOYSA-N 2-ethenyl-4-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(C=C)=N1 PBYIFPWEHGSUEY-UHFFFAOYSA-N 0.000 description 1
- HMEVYZZCEGUONQ-UHFFFAOYSA-N 2-ethenyl-5-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1CN=C(C=C)O1 HMEVYZZCEGUONQ-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- XFEGRFIENDJTCK-UHFFFAOYSA-N 2-phenyl-2,3-dihydroindene-1,1-dicarboxylic acid Chemical compound C1C2=CC=CC=C2C(C(=O)O)(C(O)=O)C1C1=CC=CC=C1 XFEGRFIENDJTCK-UHFFFAOYSA-N 0.000 description 1
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- MBLQIMSKMPEILU-UHFFFAOYSA-N 4-methyl-2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(C(C)=C)=N1 MBLQIMSKMPEILU-UHFFFAOYSA-N 0.000 description 1
- IRHWINGBSHBXAD-UHFFFAOYSA-N 5-ethyl-2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CCC1CN=C(C(C)=C)O1 IRHWINGBSHBXAD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- JJOJFIHJIRWASH-UHFFFAOYSA-N Eicosanedioic acid Natural products OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 101150010777 SUS5 gene Proteins 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- LBVBDLCCWCJXFA-UHFFFAOYSA-N adamantane-1,2-dicarboxylic acid Chemical compound C1C(C2)CC3CC1C(C(=O)O)C2(C(O)=O)C3 LBVBDLCCWCJXFA-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- FNGGVJIEWDRLFV-UHFFFAOYSA-N anthracene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=CC3=C(C(O)=O)C(C(=O)O)=CC=C3C=C21 FNGGVJIEWDRLFV-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- IHWUGQBRUYYZNM-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)=CC1C2 IHWUGQBRUYYZNM-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- RPPBZEBXAAZZJH-UHFFFAOYSA-N cadmium telluride Chemical compound [Te]=[Cd] RPPBZEBXAAZZJH-UHFFFAOYSA-N 0.000 description 1
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 1
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 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 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- AJDJKHROQJQURF-UHFFFAOYSA-N phenanthrene-1,2-dicarboxylic acid Chemical compound C1=CC=C2C3=CC=C(C(=O)O)C(C(O)=O)=C3C=CC2=C1 AJDJKHROQJQURF-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
- G03C1/7954—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
- G03C1/915—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means using mechanical or physical means therefor, e.g. corona
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a method for improving the adhesion between a polyester film and an aqueous dispersion and a method for producing a polyester film.
- a method for producing a polyester film coated with a silver halide photosensitive material, various optical films, or production of a polyester film for a solar cell back surface protection sheet provided on the side opposite to the sunlight incident side of a solar cell element The present invention relates to a method and a polyester film obtained by the production method.
- Polyester films especially biaxially stretched films of polyethylene terephthalate and polyethylene naphthalate, are excellent in mechanical strength characteristics, dimensional stability, transparency, optical characteristics, heat resistance, electrical insulation, chemical resistance, etc., and cost-effective.
- it has been used for medical films, magnetic tapes, photographic films, printing plate making films, etc., but in recent years, prism sheets, light diffusion sheets, reflectors for LCD members have been used.
- prism sheets, light diffusion sheets, reflectors for LCD members have been used.
- it is used as a protective sheet for solar cell modules as an alternative to conventional glass and fluororesins. It is a material that will become even more important in the future.
- polyester films are nonpolar, they have low wettability, and it is generally known that there are problems with interfacial adhesion when other polymer layers are laminated by coating. In fields where long-term storage and long-term operation are required, improvement in adhesion has been strongly demanded.
- corona treatment is a total of effect and cost. This method is widely adopted from the viewpoint of balance.
- Corona treatment is carried out using a corona treatment electrode, preferably while the film to be treated is conveyed by an electrode facing roll, and the surface is modified by generating functional groups such as hydroxyl groups and carboxyl groups on the film surface. is there.
- functional groups such as hydroxyl groups and carboxyl groups on the film surface.
- a technique for improving functional group imparting by corona treatment a technique for heating the substrate before the corona treatment, a technique for changing the corona treatment atmosphere to nitrogen gas or other inert gas, and the like are known.
- Patent Document 1 when a polypropylene film is pre-heated and subjected to a corona discharge treatment, a treatment atmosphere of 60 ° C. or more is maintained, so that the atmosphere gas on the surface of the film to be treated is kept highly active and the ink adheres. Describes a method for improving the surface adhesion of the film, such as the property and the vapor deposition of metals.
- Patent Document 2 a thermoplastic resin film is conveyed by a preheating roll heated to 60 to 130 ° C., and one surface of the film is subjected to corona treatment while being conveyed by an electrode facing roll heated to 70 to 130 ° C. Wrinkles and homogeneity compared to the film obtained by the method described in Patent Document 1 by corona-treating the other surface (back surface) of the film while being conveyed by an electrode facing roll heated to 70 to 130 ° C. It is described that can be.
- Patent Document 3 describes a method for improving paintability, printability, and adhesiveness by performing corona treatment at a temperature equal to or higher than the melting point of the crystalline resin or higher than the softening point of the amorphous resin.
- Patent Document 4 describes a method of removing a WBL layer formed by applying a physical mechanical force in a state wetted with water or an organic solvent after corona treatment. Further, in claims 3 and 4 of Patent Document 5, as a method for removing the WBL layer formed after the plasma treatment, functionalities formed in the case of O 2 or CO 2 plasma and in the case of N 2 or NH 3 plasma, respectively. A method for defining the optimum range of the composition of the group is described, and it is described that the adhesion between the film surface and the coating layer can be improved.
- the present inventors examined a method for improving the corona treatment effect by heating the film in advance as described in Patent Documents 1 to 3, but a sufficient adhesion improvement effect was not obtained.
- the reason is considered to be that the WBL layer that decreases the adhesion could not be removed even if heating was performed before the corona treatment.
- the method of patent document 2 was examined, when the electrode facing roll itself is used as a heating roll, the heating temperature is restricted depending on the material of the surface resin, and sufficient heating cannot be performed. In addition to this, it was found that there are other problems in the film forming suitability such as deterioration of the surface material and deformation of the roll.
- the present invention has been made in view of the above, and the problem to be solved by the present invention is to improve the adhesion with the coating layer of the resin film base material containing polyester as a main component, and polyester having good film forming suitability It is providing the manufacturing method of a film.
- the present inventors heated the corona treatment of the resin film substrate and formed the coating layer after the film surface temperature dropped to room temperature, the resin film base was compared with the case where the corona treatment was performed by heating in advance. It was found that the adhesion between the material and the coating layer was improved.
- the inventors of the present invention scraped the surface of the film that had been subjected to the corona treatment alone and the film that had been subjected to the heat treatment after the corona treatment.
- the Tc ′ of the film surface subjected to the treatment alone shifted to a higher temperature side (faster crystallization, that is, lower molecular weight) than in the case of the untreated film, and the film subjected to the heat treatment after the corona treatment.
- the surface Tc ′ did not show a shift to the high temperature side (equivalent to untreated or shifted to the low temperature side), and it was found that the low molecular weight was suppressed (or increased in polymer).
- the present invention also has a feature that the functional groups can be increased without roughening and the generation of the WBL layer can be suppressed.
- the heat treatment was performed before the corona treatment and the coating was performed, it was estimated that the WBL layer could not be removed because there was no effect of improving the adhesion, and the coating was performed after the corona treatment by the methods described in Patent Documents 1 to 3. Since it is estimated that the WBL layer remains without being removed even after drying, the inventors have found that it is necessary to perform a heat treatment after the corona treatment and before the coating step.
- Production method (where Tg represents a glass transition temperature, and Tmeta represents a minute endothermic peak (unit: ° C.) determined by differential scanning calorimetry).
- the resin film substrate is a monolayer film of polyethylene terephthalate or poly (1,4-cyclohexylenedimethylene terephthalate), or a laminate including one or two of them.
- the manufacturing method of the polyester film as described in [1].
- It includes a pre-corona treatment heating step for heating the resin film substrate before the corona treatment step, and the pre-corona treatment heating step and the post-corona treatment heating step are performed by different heat treatment apparatuses.
- a method for producing a photosensitive material comprising the method for producing a polyester film according to any one of [1] to [10].
- a polyester film produced by the method for producing a polyester film according to any one of [1] to [10].
- the present invention it is possible to provide a method for producing a polyester film that can improve the adhesion to a coating layer of a resin film base material containing polyester as a main component and has good film forming suitability.
- a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the method for producing a polyester film of the present invention comprises a step of corona treating the surface of a resin film substrate comprising polyester as a main component, and the resin film substrate after the corona treatment.
- the corona treatment On the surface of the resin film substrate on the side subjected to the corona treatment after the corona treatment heating step after the corona treatment.
- Tg represents a glass transition temperature
- Tmeta represents a minute endothermic peak (unit: ° C.) determined by differential scanning calorimetry).
- Tmeta is synonymous with Tmeta described in WO2010 / 110119 etc., for example,
- the measuring method of Tmeta can also be performed by the method as described in the literature. With such a configuration, it is possible to improve the adhesion with the coating layer of the resin film substrate, and to provide a method for producing a polyester film with good film forming suitability. Although not bound by any theory, the following mechanism is presumed.
- radicals are generated on the surface of the resin film substrate, and a part of the radicals react with oxygen atoms to generate functional groups (—OH, —COOH, etc.), contributing to the improvement of adhesion.
- the radicals generated by the corona treatment are recombined (crosslinked) so that the radicals contributing to the formation of the WBL layer do not remain on the surface of the resin film substrate. It is estimated that the polyester molecular chain is not broken, and as a result, the generation of the WBL layer can be suppressed and the adhesion decrease can be prevented.
- the production method of the present invention will be described.
- the polymer species used as the main component for the resin film substrate is polyester.
- the main component in this invention means the component which comprises 50 mass% or more of a resin film base material.
- the component constituting 80% by mass or more of the resin film substrate is preferably polyester, and the component constituting 90% by mass or more is more preferably polyester.
- the resin film base material is preferably polyester from the viewpoint of cost, mechanical strength, and the like.
- the polyester used as the resin film substrate (support) is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
- Specific examples of such polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate and the like. Polyethylene terephthalate is more preferred.
- the polyester may be a homopolymer or a copolymer. Furthermore, the polyester may be a blend of a small amount of other types of resin, such as polyimide, and may be blended with a plasticizer such as trimellitic acid ester. It may be added before the polymerization.
- the polyester in the present invention is polymerized, it is preferable to use an Sb-based, Ge-based, or Ti-based compound as a catalyst from the viewpoint of keeping the carboxyl group content below a predetermined range.
- the Sb catalyst is a heavy metal, which is not preferable from the viewpoint of environmental influences, and has a problem of forming foreign matter in the film forming process because metal Sb particles precipitated in the course of the polymerization reaction are included in the PET.
- the Ge catalyst is expensive and inevitably increases in cost, has low solubility in ethylene glycol, and has a problem that minute insoluble matter remains in the PET and causes die lip contamination in the extrusion process.
- a Ti catalyst system is preferable, and a PET resin polymerized with a Ti catalyst tends to have lower terminal COOH groups than Sb and Ge. For example, when used for a solar cell protective sheet requiring hydrolysis resistance. Is preferred.
- Examples of the synthesis of polyester using a Ti compound include Japanese Patent Publication No. 8-301198, Japanese Patent No. 2543624, Japanese Patent No. 3335683, Japanese Patent No. 3717380, Japanese Patent No. 3897756, Japanese Patent No. 396226, and Japanese Patent No. 39786666. , Patent No. 3996871, Patent No. 40000867, Patent No. 4053837, Patent No. 4127119, Patent No. 4134710, Patent No. 4159154, Patent No. 4269704, Patent No. 4135538, etc. it can.
- the resin film substrate contains a polyester-based resin
- the carboxyl group content in the polyester is preferably 35 equivalents / t or less. Preferably it is 20 equivalent / t or less.
- the lower limit of the carboxyl group content is preferably 2 equivalents / t in terms of maintaining adhesion between the layer formed on the polyester (for example, a colored layer).
- the content of carboxyl groups in the polyester resin is particularly preferably 2 to 20 equivalent / t.
- the carboxyl group content in the polyester can be adjusted by polymerization conditions (catalyst type, polymerization temperature, tank pressure) and film formation conditions (film formation temperature and time).
- Solid phase polymerization After the polycondensation step is completed, the obtained polyester resin may be processed into a pellet and the like, and solid phase polymerization may be performed using this.
- Solid-phase polymerization may be a continuous method (a method in which a tower is filled with a resin, which is slowly heated for a predetermined time while being heated, and then sent out sequentially), or a batch method (a resin is charged into a container). , A method of heating for a predetermined time).
- the temperature of the solid phase polymerization is preferably 170 ° C. or higher and 240 ° C. or lower, more preferably 180 ° C. or higher and 230 ° C. or lower, and further preferably 190 ° C. or higher and 220 ° C. or lower. When the temperature is within the above range, it is preferable for achieving hydrolysis resistance.
- the solid phase polymerization time is preferably 5 hours to 100 hours, more preferably 10 hours to 75 hours, and still more preferably 15 hours to 50 hours. When the time is within the above range, it is preferable for achieving hydrolysis resistance.
- the solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
- IV of the polyester resin composition after solid-phase polymerization the range of 0.65 or more is preferable, More preferably, the range of 0.70 or more is more preferable.
- the polyester is polyethylene terephthalate
- the IV of the polyester resin composition after solid phase polymerization is preferably 0.90 or less, and more preferably 0.85 or less.
- the polyester is poly (1,4-cyclohexylenedimethylene terephthalate)
- the upper limit of the preferred range of IV of the polyester resin composition after solid phase polymerization is 1.2, more preferably 1.15, and even more preferably 1.1.
- Such heat treatment is preferably performed in a low oxygen atmosphere, for example, in a nitrogen atmosphere or in a vacuum.
- Solid-phase polymerization may be carried out in a batch mode (a method in which a resin is placed in a container and stirred while applying heat for a predetermined time), or a continuous mode (a resin is placed in a heated cylinder and this is stirred). It may be carried out by a system in which the gas is passed through the cylinder while being kept flowing for a predetermined time while being heated, and sequentially fed out.
- the carbodiimide compound is intended to seal the terminal group of the polyester to improve the hydrolysis resistance of the polyester film and is not directly related to the effect of improving the adhesion with the coating layer of the resin film substrate of the present invention.
- the resin film substrate preferably contains a carbodiimide compound.
- the carbodiimide compounds cyclic carbodiimide is preferable.
- the said resin film base material used for the manufacturing method of the polyester film of this invention contains the compound which has one carbodiimide group and the cyclic structure by which the 1st nitrogen and the 2nd nitrogen are couple
- a compound having a cyclic structure in which one carbodiimide group and the first nitrogen and the second nitrogen are bonded by a linking group is used to seal the terminal carboxyl group of the polyester as a so-called terminal blocking agent.
- the wet heat durability of the polyester film can be improved.
- the said resin film base material used for the manufacturing method of the polyester film of this invention has one said carbodiimide group with respect to 100 mass parts of said polyester, The 1st nitrogen and the 2nd nitrogen couple
- the said resin film base material used for the manufacturing method of the polyester film of this invention has one carbodiimide group, The compound containing the cyclic structure with which the 1st nitrogen and the 2nd nitrogen are couple
- the molecular weight is preferably 400 or more, more preferably 500 to 1500.
- the compound having a cyclic structure in which one carbodiimide group is included and the first nitrogen and the second nitrogen are bonded to each other through a bonding group may have a plurality of cyclic structures.
- the cyclic structure has one carbodiimide group (—N ⁇ C ⁇ N—), and the first nitrogen and the second nitrogen are bonded by a bonding group.
- One cyclic structure has only one carbodiimide group.
- the compound may have a plurality of carbodiimide groups as long as it has a carbodiimide group.
- the number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and particularly preferably 10 to 15.
- the number of atoms in the cyclic structure means the number of atoms directly constituting the cyclic structure, and is, for example, 8 for an 8-membered ring and 50 for a 50-membered ring. This is because if the number of atoms in the cyclic structure is smaller than 8, the stability of the cyclic carbodiimide compound is lowered, and it may be difficult to store and use. From the viewpoint of reactivity, there is no particular restriction on the upper limit of the number of ring members, but cyclic carbodiimide compounds having more than 50 atoms are difficult to synthesize, and the cost may increase significantly. From this viewpoint, the number of atoms in the cyclic structure is preferably selected in the range of 10 to 30, more preferably 10 to 20, and particularly preferably 10 to 15.
- the ring structure is preferably a structure represented by the following formula (1).
- Q is a divalent to tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, each of which may contain a hetero atom and a substituent.
- a heteroatom in this case refers to O, N, S, P.
- Two of the valences of this linking group are used to form a cyclic structure.
- Q is a trivalent or tetravalent linking group, it is bonded to a polymer or other cyclic structure via a single bond, a double bond, an atom, or an atomic group.
- the linking group may contain a heteroatom and a substituent, respectively, a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent carbon group having 3 to 20 alicyclic groups, 2 to
- a linking group which is a tetravalent aromatic group having 5 to 15 carbon atoms or a combination thereof and has a necessary number of carbon atoms to form the cyclic structure defined above is selected. Examples of the combination include an alkylene-arylene group structure in which an alkylene group and an arylene group are bonded.
- the linking group (Q) is preferably a divalent to tetravalent linking group represented by the following formula (1-1), (1-2) or (1-3).
- Ar 1 and Ar 2 are each independently a divalent to tetravalent aromatic group having 5 to 15 carbon atoms which may contain a hetero atom and a substituent.
- an aromatic group each of which may contain a hetero atom and have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetra having 5 to 15 carbon atoms Yl group.
- the arylene group (divalent) include a phenylene group and a naphthalenediyl group.
- examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group.
- Examples of the arenetetrayl group include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted.
- Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
- R 1 and R 2 are each independently a heteroatom and a substituent, and may be a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, or a divalent to tetravalent carbon atom having 3 to 20 carbon atoms.
- Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms.
- Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group.
- alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group
- alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group.
- Examples include a hexadecantriyl group.
- alkanetetrayl group methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like.
- These aliphatic groups may be substituted.
- substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
- Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms.
- Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group.
- alkanetriyl group cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like.
- alkanetetrayl group cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like.
- These alicyclic groups may be substituted.
- substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
- an aromatic group each of which may contain a hetero atom and have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetra having 5 to 15 carbon atoms Yl group.
- the arylene group include a phenylene group and a naphthalenediyl group.
- the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group.
- the arenetetrayl group tetravalent
- aromatic groups may be substituted.
- substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
- X 1 and X 2 are each independently a divalent to tetravalent C 1-20 aliphatic optionally containing a hetero atom and a substituent.
- Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms.
- Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group.
- alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group
- alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group.
- Examples include a hexadecantriyl group.
- alkanetetrayl group methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like.
- These aliphatic groups may be substituted.
- substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
- Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms.
- Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group.
- alkanetriyl group cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like.
- alkanetetrayl group cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like.
- These alicyclic groups may be substituted.
- substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
- an aromatic group each of which may contain a hetero atom and have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetra having 5 to 15 carbon atoms Yl group.
- the arylene group include a phenylene group and a naphthalenediyl group.
- the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group.
- the arenetetrayl group tetravalent
- aromatic groups may be substituted.
- substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
- s and k are integers of 0 to 10, preferably integers of 0 to 3, and more preferably integers of 0 to 1. If s and k exceed 10, the cyclic carbodiimide compound is difficult to synthesize, and the cost may increase significantly. From this viewpoint, the integer is preferably in the range of 0 to 3. When s or k is 2 or more, X 1 or X 2 as a repeating unit may be different from other X 1 or X 2 .
- X 3 may contain a heteroatom and a substituent, respectively, a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, and a divalent to tetravalent carbon number of 3 to 20 Or a combination thereof.
- Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms.
- Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group.
- alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group
- alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group.
- Examples include a hexadecantriyl group.
- alkanetetrayl group methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like.
- These aliphatic groups may contain a substituent.
- substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, and an ester group. , Ether group, aldehyde group and the like.
- Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms.
- Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group.
- alkanetriyl group cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like.
- alkanetetrayl group cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like.
- These alicyclic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester.
- a substituent such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester.
- a substituent such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester.
- Group, ether group, aldehyde group and the like such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a
- an aromatic group each of which may contain a hetero atom and have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetra having 5 to 15 carbon atoms Yl group.
- the arylene group include a phenylene group and a naphthalenediyl group.
- the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group.
- the arenetetrayl group tetravalent
- aromatic groups may be substituted.
- substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
- Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 and X 3 may contain a hetero atom, and when Q is a divalent linking group, Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 and X 3 are all divalent groups.
- Q is a trivalent linking group, one of Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 and X 3 is a trivalent group.
- Q is a tetravalent linking group
- one of Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 and X 3 is a tetravalent group, or two are trivalent It is a group.
- Examples of the cyclic carbodiimide compound used in the present invention include compounds represented by the following (a) to (c).
- cyclic carbodiimide compound (a) examples include a compound represented by the following formula (2) (hereinafter sometimes referred to as “cyclic carbodiimide compound (a)”).
- Q a is an aliphatic group, an alicyclic group, an aromatic group or a divalent linking group which is a combination of these, it may contain a heteroatom.
- the aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of the formula (2), the aliphatic group, alicyclic group, and aromatic group are all divalent.
- Q a is preferably a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).
- Ar a 1 , Ar a 2 , R a 1 , R a 2 , X a 1 , X a 2 , X a 3 , s, and k are respectively in the formulas (1-1) to (1-3) Are the same as Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k. However, these are all divalent.
- Examples of the cyclic carbodiimide compound (a) include the following compounds.
- cyclic carbodiimide compound (b) examples include a compound represented by the following formula (3) (hereinafter sometimes referred to as “cyclic carbodiimide compound (b)”).
- Q b is an aliphatic group, an alicyclic group, an aromatic group or a trivalent linking group combinations thereof, and may contain a hetero atom.
- Y is a carrier supporting a cyclic structure.
- the aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1).
- the inner one of the group constituting the Q b is trivalent.
- Q b is preferably a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3).
- Ar b 1 , Ar b 2 , R b 1 , R b 2 , X b 1 , X b 2 , X b 3 , s and k are respectively represented by the formulas (1-1) to (1-3) The same as Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k. However, one of these is a trivalent group.
- Y is preferably a single bond, a double bond, an atom, an atomic group or a polymer.
- Y is a bonding portion, and a plurality of cyclic structures are bonded via Y to form a structure represented by the formula (3).
- Examples of the cyclic carbodiimide compound (b) include the following compounds.
- cyclic carbodiimide compound (c) examples include a compound represented by the following formula (4) (hereinafter sometimes referred to as “cyclic carbodiimide compound (c)”).
- Q c is a tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may have a hetero atom.
- Z 1 and Z 2 are carriers that support a cyclic structure. Z 1 and Z 2 may be bonded to each other to form a cyclic structure.
- the aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1).
- Q c is tetravalent. Accordingly, one of these groups is a tetravalent group or two are trivalent groups.
- Q c is preferably a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3).
- Ar c 1 , Ar c 2 , R c 1 , R c 2 , X c 1 , X c 2 , X c 3 , s and k are each Ar 1 in formulas (1-1) to (1-3).
- Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k are the same.
- Ar c 1 , Ar c 2 , R c 1 , R c 2 , X c 1 , X c 2 and X c 3 are one of which is a tetravalent group or two of which are trivalent It is a group.
- Z 1 and Z 2 are preferably each independently a single bond, a double bond, an atom, an atomic group or a polymer.
- Z 1 and Z 2 are bonding portions, and a plurality of cyclic structures are bonded via Z 1 and Z 2 to form a structure represented by the formula (4).
- Examples of the cyclic carbodiimide compound (c) include the following compounds.
- the cyclic carbodiimide compound can be synthesized based on the method described in JP2011-256337A.
- a polyester film can be obtained by molding the obtained polyester resin composition of the present invention into a film or sheet.
- the polyester resin can be melt-kneaded using, for example, a melt extruder such as a single-screw kneading extruder provided with a screw inside a cylinder, and extruded from a die.
- a preferable molding temperature is in a range of 250 ° C. or higher and 300 ° C. or lower, more preferably in a range of 260 ° C. or higher and 290 ° C. or lower.
- the extruder may be uniaxial or biaxial, but when the carbodiimide compound is added, when the carbodiimide compound is added, the master batch containing the raw material polyester resin and the carbodiimide compound is extruded in a hopper. It is preferable to extrude the master batch from a side feeder when mixing with a twin screw extruder, and mix and extrude in a molten state. Biaxial is preferable in that thermal decomposition due to shear heat generation can be suppressed and increase in terminal COOH can be suppressed, and it is more preferable to perform the nitrogen substitution inside the extruder.
- the molten resin (melt) of the polyester resin is preferably extruded from an extrusion die through a gear pump, a filter or the like. At this time, it may be extruded as a single layer or may be extruded as a multilayer.
- the resin film substrate may have at least one layer containing a CHDM polyester containing a structure derived from 1,4-cyclohexanedimethanol (CHDM) as a diol component.
- CHDM polyester refers to a polyester containing a structure derived from 1,4-cyclohexanedimethanol (CHDM) as a diol component.
- the CHDM polyester preferably contains a structure derived from 1,4-cyclohexanedimethanol in a diol component (in all diols) in an amount of 0.1 to 20 mol% or 80 to 100 mol%, more preferably It is more preferably 5 mol% or more and 16 mol% or less or 83 to 100 mol%, and particularly preferably 1 mol% or more and 12 mol% or less or 86 to 100 mol%.
- a region having a low CHDM-derived structure 0.1 to 20 mol%) and a region having a high structure (80 to 100 mol%). In this region, the polyester has a crystalline structure. This is because it is easy to exhibit high mechanical strength and heat resistance.
- Materials for forming units other than the structure derived from 1,4-cyclohexanedimethanol of the CHDM polyester include 1,2-propanediol, 1,3-propanediol, 1,4-butane as diol components.
- Representative examples include diols such as aromatic diols such as dimethanol and 9,9′-bis (4-hydroxyphenyl) fluorene, but are not limited thereto. Among these, it is preferable to use ethylene glycol.
- a dicarboxylic acid component malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, Aliphatic dicarboxylic acids such as dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, Such as alicyclic dicarboxylic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
- a typical example is dicarboxylic acid or an ester derivative thereof, but it is not limited thereto.
- the dicarboxylic component of the CHDM polyester preferably includes at least a structure derived from terephthalic acid.
- isophthalic acid (IPA) may be added to the dicarboxylic acid component of the CHDM polyester in addition to terephthalic acid.
- the amount of IPA is preferably 0 mol% or more and 15 mol% or less, more preferably 0 mol% or more and 12 mol% or less, and still more preferably 0 mol% or more and 9 mol% or less in the total dicarboxylic acid.
- the resin film substrate may or may not have a layer containing the CHDM-based polyester. You may do it. That is, you may laminate
- the structure derived from CHDM is 80 to 100 mol%, a laminated structure is preferable.
- the weather resistance hydrolysis resistance
- PET polyethylene terephthalate
- PET mechanical strength
- the polyester film of the present invention preferably has an aspect in which a layer containing the CHDM polyester (referred to as P1 layer) and a layer containing a polyester containing polyethylene terephthalate as a main component (referred to as P2 layer) are laminated.
- P1 layer a layer containing the CHDM polyester
- P2 layer a layer containing a polyester containing polyethylene terephthalate as a main component
- the P2 layer refers to a layer having 95% or more of terephthalic acid units in dicarboxylic acid units and 95 mol% or more of ethylene glycol units in diol units.
- the IV of the P2 layer is preferably 0.7 or more and 0.9 or less, more preferably 0.72 or more and 0.85 or less, and still more preferably 0.74 or more and 0.82 or less.
- 2 or more layers are preferable, as for the sum of the number of layers of P1 layer and P2 layer, More preferably, they are 2 layers or more and 5 layers or less, More preferably, 2 There are 4 or more layers.
- a three-layer structure in which both sides of the P2 layer are sandwiched by P1 layers a three-layer structure in which both sides of the P1 layer are sandwiched by P2 layers, or a two-layer structure in which the P2 layers and the P1 layers are stacked are preferable.
- the total thickness of the P1 layers is preferably 5% to 40%, more preferably 7% to 38% of the total thickness. As mentioned above, More preferably, they are 10% or more and 35% or less. High weather resistance can be expressed by setting this lower limit value or more, and high mechanical strength is easily expressed by setting this lower limit value or less.
- Such a laminated structure can be prepared by an ordinary method, and can be achieved by laminating and extruding melt (resin melt) supplied from a plurality of extruders using a multi-manifold die and a feed block die. The thickness of each layer of the polyester film can be determined by measuring the cross section of the film using SIMS and imaging with the characteristic fragment of the P1 layer and the characteristic fragment of the P2 layer.
- the melt-extruded melt is cooled on a casting drum, solidified, and formed into a film. Further, as a system other than the casting drum, a touch roll system in which the melt is sandwiched with a uniform pressure may be used.
- the temperature of the cooling roll itself is preferably 10 ° C. to 80 ° C., more preferably 15 ° C. to 70 ° C., and further preferably 20 ° C. to 60 ° C.
- the thickness of the molten resin (melt) discharged in a band after solidification (before stretching) is in the range of 2600 ⁇ m to 6000 ⁇ m, and a polyester film having a desired thickness can be obtained through subsequent stretching.
- the thickness of the melt after solidification is preferably in the range of 3100 ⁇ m to 6000 ⁇ m, more preferably in the range of 3300 ⁇ m to 5000 ⁇ m, and still more preferably in the range of 3500 ⁇ m to 4500 ⁇ m.
- the thickness after solidification and before stretching is 6000 ⁇ m or less, wrinkles are unlikely to occur during melt extrusion, and unevenness is suppressed.
- the thickness before stretching after solidification is 2600 ⁇ m or more suppresses uneven adhesion to the chill roll (cooling roll for solidification) generated due to weak melt, and is preferable from the viewpoint of reducing unevenness of the film.
- the produced extruded film (unstretched film) is stretched in the longitudinal direction and the transverse direction, and then subjected to heat setting and thermal relaxation in a heat treatment zone in the tenter and cooled. It is preferable to include a winding step.
- the thickness of the film after stretching in the longitudinal and transverse directions is preferably 50 to 300 ⁇ m, and preferably 100 to 250 ⁇ m. It is more preferable that the thickness is 150 to 200 ⁇ m.
- the thickness of the film after stretching in the longitudinal direction and the transverse direction is preferably 100 to 400 ⁇ m, More preferably, it is 150 to 350 ⁇ m, and particularly preferably 200 to 300 ⁇ m.
- the manufacturing method of this invention includes the process of corona-treating the surface of the resin film base material which has polyester as a main component.
- the surface treatment may be performed only on one surface of the base material, or the surface treatment may be performed on both surfaces of the base material.
- other functional layers described later on the resin film base material Is preferably applied to both surfaces by applying the surface treatment.
- a preferred embodiment of the corona treatment, the resin film substrate particularly preferably from 0.1 ⁇ 2.0kJ / m 2, more preferably 0.15 ⁇ 1.0kJ / m 2.
- the manufacturing method of the present invention includes a post-corona treatment heating step in which the resin film substrate after the corona treatment is heated to Tmeta or less exceeding the Tg of the resin film substrate (where Tg is a glass transition). Temperature (unit: ° C)).
- Tmeta the resin film substrate after the corona treatment
- Temperature unit: ° C
- the adhesiveness can be greatly improved by heat treatment exceeding the Tg of the resin film substrate.
- a resin film base material does not adhere to heating apparatuses, such as a heating roll, or it adheres to a conveyance roll, and film forming suitability becomes favorable.
- heating after the corona treatment step means not including an aspect in which the electrode facing roll is heated simultaneously with the corona treatment.
- the heating after the corona treatment is not performed by the electrode facing roll for performing the corona treatment on the surface opposite to the side subjected to the corona treatment, and a heating device independent of the corona treatment device may be used. From the viewpoint of production suitability, it is preferable.
- by performing heating after the corona treatment step in such a temperature range formation of the WBL layer can be suppressed.
- the surface of the film that has not been subjected to the corona treatment, the film that has been subjected to the corona treatment alone, and the film that has been subjected to the heat treatment after the corona treatment is scraped, and the crystallization temperature by DSC (cooling crystallization; Tc ′) is measured, and the Tc ′ of the film surface that has been subjected to corona treatment alone is shifted to a higher temperature side (faster crystallization, that is, lower molecular weight) than when untreated, and heat treatment is performed after corona treatment.
- the presence or absence of suppression can be determined by confirming that no shift to the high temperature side is observed at Tc ′ of the film surface subjected to.
- the heating temperature after the corona treatment step is preferably Tg to Tmeta, more preferably Tg + 30 ° C. to Tg + 120, and particularly preferably Tg + 60 ° C. to Tg + 90 ° C.
- the heating temperature after the corona treatment step is preferably 70 to 200 ° C., more preferably 100 to 180 ° C., and particularly preferably 130 to 160 ° C. .
- Heating after the corona treatment step is preferably performed within 30 seconds, more preferably within 20 seconds, and even more preferably within 10 seconds after the corona treatment.
- the corona effect is hardly attenuated (radical disappearance), and the adhesion improving effect by heating after the corona treatment step is easily obtained.
- the heat treatment method and the heat treatment apparatus used there is no particular limitation on the heat treatment method and the heat treatment apparatus used.
- the heat treatment is air blowing of heated gas (heated air), infrared irradiation or contact with a heating roll, but controllability of film heating temperature, foreign matter adhesion due to air, infrared irradiation From the standpoint that the problem of bulk physical property change due to is less likely to occur, contact with a heating roll is more preferable.
- the corona treatment may be performed again on the surface of the resin film substrate on which the corona treatment has been performed after the post-corona treatment heating step.
- the preferable range of the output in the second corona treatment is the same.
- the corona treatment and the re-corona treatment may be performed by different corona treatment apparatuses. Further, it is possible to carry out the re-corona treatment online without taking up the resin film base material between the corona treatment and the re-corona treatment, which may cause scratches or the like during winding or feeding. It is preferable from the viewpoint of reducing the possibility. Furthermore, it is more preferable that the resin film base material is carried out online without taking up the resin film substrate until all the corona treatment and all the heat treatments included in the production method of the present invention are completed.
- the corona treatment step when the corona treatment step is performed a plurality of times, the corona treatment step is not performed continuously, and the heating step is performed between the plurality of corona treatments from the viewpoint of suppressing the formation of the WBL layer. preferable. Furthermore, when both the corona treatment and the heat treatment are performed a plurality of times, it is preferable to perform the corona treatment and the heat treatment alternately. That is, it is preferable to perform the corona treatment and the subsequent heat treatment as a set of combined treatments.
- count of a heating process may not be the same, and the application process mentioned later is not performed after the corona treatment of the 2nd time or later. You may do it.
- positioned continuously, and the aspect using a some heater are not denied.
- this composite treatment may be performed a plurality of times.
- the contact angle is reduced by the corona treatment. Although it decreases, it increases by heating. For example, the contact angle after performing a plurality of treatments of corona ⁇ heating ⁇ corona ⁇ heating is increased as compared with the case of no treatment. As for Tc ′, the result of the same treatment shifted to a lower temperature side than the case of no treatment. From this, it is possible to increase the functional groups by repeating the combined treatment of corona treatment and subsequent heat treatment, and not only suppress the formation of the WBL layer, but also promote radical crosslinking and strengthen the surface.
- the combined treatment of the corona treatment and the subsequent heat treatment is preferably 1 to 3 times as the combined treatment, and more preferably 1 to 2 times.
- the preferable aspect of the heat processing after the 2nd time it is the same as that of the said post-corona-processing heating process.
- a resin film base material is unwound from an unwinding roll 10, and is composed of a corona treatment electrode 1, an electrode facing roll 12, and the like.
- a corona treatment is preferably applied to at least one surface of the resin film substrate by a treatment device while being conveyed. After the corona treatment, the resin film substrate is brought into contact with the heating roll 2 shown in FIG. 1 and FIG. 4, or the heated gas is blown in the heated gas blowing zone 3 shown in FIG.
- the infrared heater 4 carbon heater or the like
- the surface of the resin film substrate is heated so as to be within the temperature range defined in the present invention.
- the manufacturing method of this invention includes the process of apply
- the manufacturing method of the present invention may or may not include other steps between the post-corona treatment heating step and the coating step when the coating step is performed after the post-corona treatment heating step. That is, the coating process may be performed immediately after the heating process after the corona treatment, or the coating process may be performed after performing the corona treatment again after the heating process after the corona treatment. Furthermore, the coating process may be performed after the heat treatment after the re-corona treatment.
- the coating layer formed from the polymer solution in the coating step is not particularly limited in function, and can be used as an arbitrary functional layer.
- the said application layer is a layer arrange
- the coating layer formed on the surface of the resin film substrate on the side subjected to the corona treatment by the coating step can be applied to any layer constituting the polyester film.
- the polymer layer can be applied as, for example, an undercoat layer described later or other functional layers. Among them, it is particularly preferable to use it as an undercoat layer.
- coating process includes the process of apply
- the production method of the present invention may further include a step of laminating other layers on the coating layer as the undercoat layer.
- other functional layers may be provided by coating.
- the photosensitive material shown in FIG. 5 is preferably formed by the following steps.
- a latex base coating solution is applied to the surface side of the support 24 (resin film substrate such as polyester film) (step S1) and dried (step S2). ), And the latex base coat layer 23 is preferably formed.
- the photosensitive material coating liquid is applied to the surface side of the gelatin-based undercoat layer (step S4) and dried (step). S5), the photosensitive material coating layer 21 is formed.
- the corona treatment step and the post-corona treatment heating step method in the production method of the present invention can be applied, for example, when the undercoat layer is formed in the above steps S1 and S2.
- the adhesion between the latex undercoat layer and the resin film substrate can be improved.
- the coating solution for the undercoat layer contains a hydrophilic colloid.
- the hydrophilic colloid include acylated gelatin such as gelatin, phthalated gelatin, and maleated gelatin: cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose: acrylic acid, Grafted gelatin obtained by grafting methacrylic acid or amide (such as acrylamide) onto gelatin: polyvinyl alcohol: polyhydroxyalkyl acrylate: polyvinyl pyrrolidone: vinyl pyrrolidone / vinyl acetate copolymer: gazein: agarose: albumin: sodium alginate: polysaccharide : Agar: Starch: Grafted starch: Polyacrylamide: Polyethyleneimine acylated product: Synthetic or natural hydrophilic polymer such as partial hydrolyzate: etc.
- an acrylic resin, polyester resin, polyurethane resin, polystyrene resin, SBR, PVDC resin, or the like can be used in combination as a binder.
- the undercoat layer coating solution is preferably maintained at a temperature of 50 to 80 ° C. for 10 minutes to 5 hours, more preferably at a temperature of 60 to 70 ° C. for 30 minutes to 3 hours, before forming the undercoat layer. More preferably, the temperature is 60 to 70 ° C. for 1 to 2 hours.
- the pH of the coating solution for the undercoat layer is preferably 4 to 8 from the viewpoint of the stability of the coating solution, more preferably 5 to 8, and still more preferably 6 to 7. .
- the undercoat layer coating solution preferably contains a monovalent saturated alcohol having 3 or less carbon atoms from the viewpoint of suppressing repelling failure during coating.
- the monovalent saturated alcohol include methanol, ethanol, propanol, and isopropanol. These monovalent saturated alcohols may be used alone or in combination of two or more. In addition, these monovalent saturated alcohols are intentionally added for the above-mentioned purpose. For example, they may be added also as a solvent as described later. When used as a solvent, a solvent used in the synthesis of a material, a purification process, or the like, or as a cleaning solvent for a chemical storage tank, piping, etc., it may be mixed with the coating solution. However, the alcohol content in the coating solution is preferably 20% by weight or less, more preferably 1 to 10% by weight.
- the undercoat layer coating solution may contain a crosslinking agent, a matting agent, a dye, a filler, a surfactant, and the like.
- a crosslinking agent known compounds such as epoxy, isocyanate, and melamine are used. Further, active halogen crosslinking agents described in JP-A No. 51-114120 are also preferred.
- the matting agent is preferably used for the purpose of improving high-speed transportability in production.
- fine particles such as styrene, polymethyl methacrylate and silica having an average particle diameter of 0.1 to 8 ⁇ m, preferably about 0.2 to 5 ⁇ m are used.
- the amount of the matting agent used is preferably 1 to 200 mg, more preferably 2 to 100 mg, per 1 m 2 of the photothermographic material.
- colloidal silica or the like can be used.
- surfactant an anionic, nonionic or cationic surfactant can be used.
- dye antihalation, a color tone adjusting dye, and the like can be used.
- the undercoat layer coating solution may be either aqueous or organic solvent, but is preferably an aqueous dispersion from the viewpoint of cost and environment.
- the “aqueous dispersion” refers to a coating liquid in which 30% by mass or more, more preferably 50% by mass or more, of the solvent (dispersion medium) of the coating liquid is water.
- the undercoat layer is formed by applying and drying the above undercoat layer coating solution.
- a bar coater is used as a coating method.
- Wet coating amount of 7.0 ml / m 2 or more 30 ml / m 2 or less is preferably set to less than 8.0 ml / m 2 or more 10 ml / m 2. That's Wet coating weight less than 7.0 ml / m 2, but soon planar failure occurs when the aggregate in the coating solution is generated by a 7.0 ml / m 2 or more, aggregation occurs Can also prevent the occurrence of surface failure. Further, when the wet coating amount exceeds 30 ml / m 2 , a surface failure such as coating unevenness occurs, but this can be prevented by setting the wet coating amount to 30 ml / m 2 or less.
- the undercoat layer may be provided alone or in two or more layers. However, in the case of providing a plurality of subbing layers, each subbing layer together sequentially applied by a bar coater, its Wet coating amount at the time of each coating 7.0 ml / m 2 or more 30 ml / m 2 or less, preferably 8.0 ml / m 2 or more 10 ml / m 2 set below. Thereby, the occurrence of planar failure can be prevented in each undercoat layer.
- the thickness of each undercoat layer is preferably about 0.05 to 5 ⁇ m, more preferably about 0.1 to 3 ⁇ m per layer.
- the drying method after application of the undercoat layer is not particularly limited.
- the drying method may be performed at a temperature of about 25 to 200 ° C. for about 0.5 to 20 minutes, and can be dried under these conditions.
- the above is an example applied to the undercoating of the silver halide photosensitive material, but it can also be suitably used for the undercoating of other photosensitive materials and optical film materials.
- the same effect can be obtained when an undercoat material such as water-dispersed latex, gelatin, PVA, or the like, a polyester resin binder, a polyurethane resin binder, a UV effect resin, a graft polymerization material, or the like is used.
- the other functional layers are: Examples thereof include a photosensitive layer (photosensitive material coating layer) and an image forming layer.
- the photosensitive layer and the organic silver salt-containing layer will be described.
- the photosensitive layer preferably contains a photosensitive silver halide.
- the image forming layer is an organic silver salt-containing layer containing an organic silver salt.
- the image forming layer is also a photosensitive layer (emulsion layer) containing a photosensitive silver halide which is a photosensitive silver salt.
- the photosensitive layer and the image forming layer are used without distinction. There is a case.
- the embodiments described in JP-A-2007-270066 can be preferably used.
- gelatin contained in the photosensitive silver halide emulsion used for the photosensitive layer various gelatins can be used.
- low molecular weight gelatin having a molecular weight of 500 to 60,000.
- These low molecular weight gelatins may be used at the time of particle formation or dispersion after desalting, but are preferably used at the time of dispersion after desalting.
- the binder of the organic silver salt-containing layer as the image forming layer may be any polymer. Suitable binders are transparent or translucent and generally colorless. Natural resins and polymers and copolymers, synthetic resins and polymers and Copolymers and other film-forming media such as gelatins, rubbers, poly (vinyl alcohol) s, hydroxyethylcelluloses, cellulose acetates, cellulose acetate butyrates, poly (vinylpyrrolidone) s, casein, starch, poly (Acrylic acid) s, poly (methyl methacrylic acid) s, poly (vinyl chloride) s, poly (methacrylic acid) s, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymer Polymers, poly (vinyl acetal) s (eg, (Vinyl formal) and poly (viny
- the binder may be formed from water or an organic solvent or an emulsion.
- the polymer used as a binder may be used alone or in combination of two or more as required. Further, a glass transition temperature of 20 ° C. or higher and a glass transition temperature of less than 20 ° C. may be used in combination. When two or more kinds of polymers having different Tg are blended and used, the weight average Tg is preferably within the above range.
- the binder of the organic silver salt-containing layer coating solution is particularly preferably a polymer that can be dispersed in an aqueous solvent.
- Preferred embodiments of the polymer dispersible in the aqueous solvent include acrylic polymers, poly (esters), rubbers (eg, SBR resin), poly (urethanes), poly (vinyl chloride) s, poly (vinyl acetate) , Hydrophobic polymers such as poly (vinylidene chloride) s and poly (olefins) can be preferably used.
- These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more types of monomers. In the case of a copolymer, it may be a random copolymer or a block copolymer.
- the polymer latex is particularly preferably a styrene-butadiene copolymer
- a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose may be added to the organic silver salt-containing layer coating solution.
- the organic silver salt-containing layer coating solution is preferably a so-called thixotropic fluid.
- a crosslinking agent for crosslinking In the image forming layer, a crosslinking agent for crosslinking, a surfactant for improving coating properties, and the like may be added.
- the respective layers may be applied by any method.
- various coating operations including extrusion coating, slide coating, curtain coating, dip coating, knife coating, flow coating, or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294.
- Is used, and Stephen F. Kistler, Peter M. Extrusion coating or slide coating described in pages 399 to 536 of “LIQUID FILM COATING” (CHAPMAN & HALL, 1997) by Schweizer is preferably used, and slide coating is particularly preferably used.
- An example of the shape of the slide coater used for the slide coating is shown in FIG. 11b. 1
- two or more layers may be simultaneously coated by the method described on pages 399 to 536 of the same document, the method described in US Pat. No. 2,761,791 and British Patent No. 837,095. can do.
- each layer includes the embodiments described in JP-A-2007-270066.
- a non-photosensitive layer described in JP-A-2007-270066 can be used, and examples thereof include a surface protective layer, a back layer, and an antihalation layer.
- the described embodiment can be preferably used.
- a method for applying the undercoat layer There is no particular limitation on the solvent of the coating solution to be used, and for example, materials having a structure described in JP2011-29397A can be used, but the present invention is not limited thereto.
- the coating method for example, a known coating method such as a gravure coater or a bar coater can be used.
- the solvent used for the coating solution for the undercoat layer may be water or an organic solvent such as toluene or methyl ethyl ketone.
- a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
- the coating may be applied to the resin film substrate after biaxial stretching, or may be a method of stretching in a direction different from the initial stretching after coating to the resin film substrate after uniaxial stretching. Furthermore, you may extend
- the coating amount of the coating solution for the undercoat layer is preferably changed according to the desired thickness of the undercoat layer, preferably 2 g / m 2 or less, more preferably 0.05 g / m 2 to 2 g / m. 2 , more preferably 0.1 g / m 2 to 1.5 g / m 2 .
- the coating amount is preferably from 0.005 ⁇ 0.05g / m 2, is 0.005 ⁇ 0.03g / m 2 Is more preferable, and 0.005 to 0.02 g / m 2 is particularly preferable.
- the thickness of the undercoat layer coating solution is preferably 0.05 ⁇ m to 2 ⁇ m, more preferably 0.1 ⁇ m to 1.5 ⁇ m. When the thickness is 0.05 ⁇ m or more, it is easy to ensure necessary adhesiveness.
- the undercoat layer coating solution (preferably, a polymer layer coating solution containing a composite polymer described later) may be an aqueous system using water as a coating solvent, or a solvent system using an organic solvent such as toluene or methyl ethyl ketone. Good. Among these, from the viewpoint of environmental burden, it is preferable to use water as a solvent.
- a coating solvent may be used individually by 1 type, and may mix and use 2 or more types.
- the undercoat layer coating liquid is preferably an aqueous dispersion in which 50% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more of the solvent contained therein is water.
- the aqueous dispersion is preferable in terms of environmental load, and is advantageous in that the environmental load is particularly reduced when the ratio of water is 50% by mass or more.
- a binder such as a crosslinking agent, a surfactant, a filler, and a composite polymer may be added as necessary.
- the undercoat layer coating solution contains a crosslinking agent from the viewpoint of improving the wet heat durability by making the resulting polyester film coating layer into a crosslinked structure.
- a crosslinking agent it is preferable to add a crosslinking agent to the undercoat layer coating solution so that the polymer layer to be described later has a crosslinked structure.
- the crosslinking agent include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents.
- an oxazoline-based crosslinking agent in the present invention.
- oxazoline-based crosslinking agent examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2,2'-bis- (2-oxazoline), 2,2'-methylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline), 2,2′-trimethylene-bis- (2-oxazoline), 2,2′-tetramethylene-bis- (2-oxazoline) ), 2,2′-hexamethylene-bis- (2-oxazoline), 2,2′-octamethylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4 ′) Dimethyl-2-oxazoline), 2,2'-p-pheny
- (co) polymers of these compounds are also preferably used.
- a compound having an oxazoline group Epocros K2010E, K2020E, K2030E, WS-500, WS-700 (all manufactured by Nippon Shokubai Chemical Co., Ltd.) and the like can be used.
- carbodiimide-based crosslinking agent examples include carbodilite V-02-L2 (manufactured by Nisshinbo Chemical Co., Ltd.) and the following compounds.
- Carbodilite SV-02 (Nisshinbo Chemical Co., Ltd.), Carbodilite E-01 (Nisshinbo Chemical Co., Ltd.).
- the coating solution for the undercoat layer preferably contains 5 to 50% by mass of a crosslinking agent, and more preferably contains 10 to 40% by mass of the crosslinking agent with respect to the binder. Preferably, it contains 20 to 40% by mass of a crosslinking agent.
- the addition amount of the crosslinking agent is 5% by mass or more, a sufficient crosslinking effect is obtained while maintaining the strength and adhesion of the coating layer, and when it is 50% by mass or less, the pot life of the coating solution is kept long. Can do.
- the surfactant a known surfactant such as an anionic or nonionic surfactant can be used.
- the addition amount is preferably 0.1 to 15 mg / m 2 , more preferably 0.5 to 5 mg / m 2 .
- the addition amount of the surfactant is 0.1 mg / m 2 or more, generation of a repellency is suppressed and a favorable layer formation is obtained, and when it is 15 mg / m 2 or less, adhesion can be performed satisfactorily. .
- a filler may be further added to the undercoat layer coating solution.
- the inorganic oxide filler include silica, calcium carbonate, magnesium oxide, magnesium carbonate, and tin oxide. Among these, tin oxide and silica fine particles are preferable, and silica is more preferable in that the decrease in adhesiveness when exposed to a humid heat atmosphere is small.
- the particle size of the inorganic oxide filler is preferably about 10 to 700 nm, more preferably about 20 to 300 nm in terms of volume average particle size. When the particle size is within this range, better easy adhesion can be obtained.
- the particle size is a value measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 (manufactured by Horiba, Ltd.).
- the shape of the inorganic oxide filler is not particularly limited, and any shape such as a spherical shape, an irregular shape, or a needle shape can be used.
- the content of the inorganic oxide filler is preferably in the range of 5 to 400% by mass with respect to the binder in the undercoat layer coating solution. If the content of the inorganic fine particles is 5% by mass or more, good adhesiveness can be maintained when exposed to a humid heat atmosphere, and if it is 400% by mass or less, the surface of the white content layer laminated on the undercoat layer. The condition becomes difficult to deteriorate.
- the content of the inorganic oxide filler is more preferably in the range of 50 to 300% by mass.
- the undercoat layer coating solution may contain a binder.
- the undercoat layer contains at least one resin selected from the group consisting of a composite polymer, a polyolefin resin, a polyurethane resin, a polyvinyl alcohol resin, a polyacrylic resin, and a polyester resin, which will be described later, as a binder. It is more preferable to use a composite polymer, polyester, polyurethane, acrylic resin, polyolefin or the like described later. These binders may be used alone or in combination of two or more.
- the undercoat layer coating solution preferably contains at least one of the composite polymers including a polysiloxane structural unit represented by the following general formula (I) and a non-polysiloxane structural unit in the molecule.
- R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and n represents an integer of 1 or more.
- R 1 and R 2 may be the same or different from each other.
- a plurality of R 1 may be the same or different from each other, and a plurality of R 2 may be the same or different from each other.
- the composite polymer is a copolymer in which a polysiloxane structural unit represented by the following general formula (I) and a non-polysiloxane structural unit are copolymerized, and even if it is a block copolymer, a random copolymer It may be.
- the composite polymer is preferably a block copolymer.
- Each of the polysiloxane structural unit represented by the general formula (I) and the non-polysiloxane structural unit to be copolymerized may be one kind or two or more kinds.
- the polysiloxane structural unit represented by the general formula (I) is preferably a polysiloxane segment derived from various polysiloxanes having a linear, branched or cyclic structure.
- R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group.
- Examples of the halogen atom represented by R 1 and R 2 include a fluorine atom, a chlorine atom, and an iodine atom.
- the monovalent organic group preferably represents a monovalent organic group that can be covalently bonded to a Si atom.
- the above-mentioned “monovalent organic group capable of covalent bonding with Si atom” represented by R 1 and R 2 may be unsubstituted or substituted, for example, an alkyl group (eg, methyl group, ethyl group) Etc.), aryl groups (eg: phenyl groups, etc.), aralkyl groups (eg: benzyl groups, phenylethyl etc.), alkoxy groups (eg: methoxy groups, ethoxy groups, propoxy groups etc.), aryloxy groups (eg: phenoxy groups) Etc.), mercapto group, amino group (eg, amino group, diethylamino group, etc.), amide group and the like.
- an alkyl group eg, methyl group, ethyl group
- aryl groups eg: pheny
- the R 1 and R 2 are each independently a hydrogen atom, a chlorine atom, a bromine atom, an unsubstituted or substituted, in terms of adhesion to a resin film substrate and durability in a wet heat environment.
- Alkyl groups having 1 to 4 carbon atoms particularly methyl and ethyl groups
- unsubstituted or substituted phenyl groups mercapto groups
- unsubstituted amino groups and amide groups are preferred.
- R 1 and R 2 are each independently more preferably an unsubstituted or substituted alkoxy group, and more preferably an unsubstituted alkoxy group having 1 to 4 carbon atoms, from the viewpoint of durability in a moist heat environment. is there.
- the n is preferably 1 to 5000, particularly preferably 1 to 1000.
- the polysiloxane structural unit represented by the general formula (I) is preferably 15 to 85% by mass with respect to the entire composite polymer molecule.
- the adhesiveness with the resin film substrate and the wet heat environment are preferable. From the viewpoint of durability, the range of 20 to 80% by mass is more preferable. If the ratio of the polysiloxane structural unit is 15% by mass or more, the adhesion with the resin film substrate and the adhesion durability when exposed to a moist heat environment are improved. become stable.
- the non-polysiloxane structural unit portion copolymerized with the polysiloxane structural unit portion represented by the general formula (I) is a non-polysiloxane structural unit copolymerized as a repeating unit.
- the polymer segment is not particularly limited except that it may be any polymer segment derived from any polymer.
- the polymer (precursor polymer) that is a precursor of the polymer segment for example, various polymers such as a vinyl polymer, a polyester polymer, and a polyurethane polymer are preferably exemplified.
- the non-polysiloxane structural unit is preferably at least one of a vinyl structural unit, a polyester structural unit, and a polyurethane structural unit. That is, in the present invention, the non-polysiloxane structural unit of the composite polymer is preferably at least one of a vinyl structural unit, a polyester structural unit, and a polyurethane structural unit. From the viewpoint of easy preparation and excellent hydrolysis resistance, a vinyl polymer and a polyurethane polymer are more preferable.
- the vinyl polymer include various polymers such as an acrylic polymer, a carboxylic acid vinyl ester polymer, an aromatic vinyl polymer, and a fluoroolefin polymer.
- acrylic polymers are particularly preferable from the viewpoint of design freedom.
- the polymer which comprises a nonpolysiloxane type structural unit may be single 1 type, and 2 or more types of combined use may be sufficient as it.
- the precursor polymer constituting the non-polysiloxane structural unit preferably contains at least one of an acid group and a neutralized acid group and / or a hydrolyzable silyl group.
- the vinyl polymer includes, for example, (a) a vinyl monomer containing an acid group and a vinyl monomer containing a hydrolyzable silyl group and / or a silanol group.
- the undercoat layer coating solution may be used alone or in combination with another polymer as a binder.
- the ratio of the composite polymer is preferably 30% by mass or more, more preferably 60% by mass or more of the total binder.
- the ratio of the composite polymer is 30% by mass or more, the adhesiveness with the resin film substrate and the durability under a wet heat environment are more excellent.
- the molecular weight of the composite polymer is preferably 5000 to 100,000, more preferably 10,000 to 50,000.
- a method of hydrolyzing and condensing a compound can be used.
- Examples of the silane compound used in the method (ii) include various silane compounds, and alkoxysilane compounds are particularly preferable.
- the temperature is about 20 to 150 ° C. for about 30 minutes to 30 hours ( (Preferably, the reaction can be performed at 50 to 130 ° C. for 1 to 20 hours).
- various silanol condensation catalysts such as an acidic compound, a basic compound, and a metal containing compound, can be added.
- water and a silanol condensation catalyst are added to the mixture of the precursor polymer and the alkoxysilane compound, and the temperature is about 20 to 150 ° C. for 30 minutes to 30 minutes. It can be prepared by performing hydrolysis condensation for about an hour (preferably at 50 to 130 ° C. for 1 to 20 hours).
- the other functional layer may be white.
- a pigment layer, an easily adhesive layer, a back layer and the like can be mentioned.
- the white pigment layer can be formed by a method in which a polymer sheet containing a pigment is bonded to a substrate, a method in which the white pigment layer is coextruded when forming the substrate, a method by coating, or the like.
- the white pigment layer can be formed by bonding, co-extrusion, coating, or the like directly on the surface of the resin film substrate or through an undercoat layer having a thickness of 2 ⁇ m or less.
- the formed white pigment layer may be in a state of being in direct contact with the surface of the resin film substrate or may be in a state of being laminated via an undercoat layer.
- the method by coating is preferable because it is simple and can be formed in a thin film with uniformity.
- the coating solution may be an aqueous system using water as an application solvent, or a solvent system using an organic solvent such as toluene or methyl ethyl ketone. Especially, it is preferable to use water as a solvent from a viewpoint of environmental impact.
- a coating solvent may be used individually by 1 type, and may mix and use 2 or more types. It is preferable to apply the white pigment layer coating solution onto the undercoat layer.
- the function of the white pigment layer in the present invention is to generate power of the solar cell module by reflecting the light that has passed through the solar cell and has reached the back sheet without being used for power generation, and returns it to the solar cell. It is to increase efficiency.
- the white pigment layer contains at least one kind of white pigment.
- the white pigment include inorganic pigments such as titanium oxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc, ultramarine blue, bitumen, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green. Can be appropriately selected and contained.
- the binder suitable for the white pigment layer is polyester, polyurethane, acrylic resin, polyolefin or the like, and acrylic resin or polyolefin is preferable from the viewpoint of durability.
- acrylic resin a composite resin of acrylic and silicone is also preferable.
- preferred binders include Chemipearl S-120 and S-75N (both manufactured by Mitsui Chemicals, Inc.) as polyolefins, and Julimer ET-410 and SEK-301 (both Nippon Pure Chemical Industries, Ltd.) as examples of acrylic resins.
- Examples of the composite resin of acrylic and silicone include Ceranate WSA1060, WSA1070 (both manufactured by DIC Corporation), H7620, H7630, H7650 (both manufactured by Asahi Kasei Chemicals Corporation), and the like.
- additives such as a crosslinking agent, a surfactant, and a filler may be further added to the white pigment layer in the present invention as necessary.
- crosslinking agent examples include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents.
- an oxazoline-based crosslinking agent is preferable, and specifically, an oxazoline-based crosslinking agent that can be used for an easily-adhesive layer described later can be suitably used.
- the addition amount is preferably 5 to 50% by mass, more preferably 10 to 40% by mass with respect to the binder in the white pigment layer.
- the addition amount of the crosslinking agent is 5% by mass or more, a sufficient crosslinking effect is obtained while maintaining the strength and adhesiveness of the white pigment layer, and when it is 50% by mass or less, the pot life of the coating liquid is prolonged. I can keep it.
- the surfactant examples include known surfactants such as anionic and nonionic surfactants.
- the addition amount is preferably 0.1 to 15 mg / m 2 , more preferably 0.5 to 5 mg / m 2 .
- the addition amount of the surfactant is 0.1 mg / m 2 or more, generation of repellency can be suppressed and good layer formation can be obtained, and when it is 15 mg / m 2 or less, adhesion can be performed satisfactorily. .
- an inorganic oxide filler such as silica may be added to the white pigment layer.
- the addition amount is preferably 20% by mass or less, more preferably 15% by mass or less, with respect to the binder in the white pigment layer.
- the added amount of the inorganic oxide filler is 20% by mass or less, a necessary reflectance can be obtained while suppressing a decrease in the ratio of the pigment.
- the easy-adhesion layer is a layer for firmly bonding the back sheet to a sealing material that seals a solar cell element (hereinafter also referred to as a power generation element) of the battery side substrate (battery body).
- the easy-adhesion layer can be formed using a binder and inorganic fine particles, and may further include other components such as additives as necessary.
- the easy-adhesion layer is 10 N / cm or more (preferably 20 N / cm or more) with respect to an ethylene-vinyl acetate (EVA: ethylene-vinyl acetate copolymer) -based sealing material that seals the power generation element of the battery side substrate. It is preferable that it is comprised so that it may have the adhesive force of (). When the adhesive force is 10 N / cm or more, it is easy to obtain wet heat resistance capable of maintaining adhesion.
- EVA ethylene-vinyl acetate copolymer
- the adhesive strength can be adjusted by adjusting the amount of the binder and inorganic fine particles in the easy-adhesive layer, or applying a corona treatment to the surface of the back sheet that is bonded to the sealing material.
- the easy-adhesion layer can contain at least one binder.
- the binder suitable for the easy-adhesive layer include polyester, polyurethane, acrylic resin, polyolefin, and the like. Among these, acrylic resin and polyolefin are preferable from the viewpoint of durability. As the acrylic resin, a composite resin of acrylic and silicone is also preferable.
- binders examples include Chemipearl S-120 and S-75N (both manufactured by Mitsui Chemicals) as specific examples of polyolefins, and Jurimer ET-410 and SEK-301 (both Nippon Pure Chemical (both manufactured by Mitsui Chemicals, Inc.)).
- Jurimer ET-410 and SEK-301 both Nippon Pure Chemical (both manufactured by Mitsui Chemicals, Inc.)
- Ceranate WSA1060, WSA1070 both manufactured by DIC Corporation
- H7620, H7630, H7650 both manufactured by Asahi Kasei Chemicals Corporation
- the content of the binder in the easy-adhesive layer is in the range of 0.05 to 5 g / m 2 . Of these, the range of 0.08 to 3 g / m 2 is preferable.
- the content of the binder is not adhesive strength is obtained and desired to be less than 0.05 g / m 2, not exceeding 5 g / m 2 good surface state is obtained.
- the easily adhesive layer can contain at least one kind of inorganic fine particles.
- the inorganic fine particles include silica, calcium carbonate, magnesium oxide, magnesium carbonate, and tin oxide.
- fine particles of tin oxide and silica are preferable in that the decrease in adhesion when exposed to a humid heat atmosphere is small.
- the particle size of the inorganic fine particles is preferably about 10 to 700 nm, more preferably about 20 to 300 nm in terms of volume average particle size. When the particle size is within this range, better easy adhesion can be obtained.
- the particle size is a value measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 (manufactured by Horiba, Ltd.).
- the shape of the inorganic fine particles is not particularly limited, and any shape such as a spherical shape, an irregular shape, or a needle shape can be used.
- the content of the inorganic fine particles is in the range of 5 to 400% by mass with respect to the binder in the easy-adhesive layer.
- the content of the inorganic fine particles is less than 5% by mass, good adhesiveness cannot be maintained when exposed to a moist heat atmosphere, and when it exceeds 400% by mass, the surface state of the easily adhesive layer is deteriorated.
- the content of inorganic fine particles is preferably in the range of 50 to 300% by mass.
- the easily adhesive layer can contain at least one crosslinking agent.
- the crosslinking agent suitable for the easily adhesive layer include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents.
- an oxazoline-based cross-linking agent is particularly preferable from the viewpoint of ensuring adhesion after wet heat aging.
- the content of the crosslinking agent in the easy-adhesive layer is preferably 5 to 50% by mass, more preferably 20 to 40% by mass, based on the binder in the easy-adhesive layer.
- the content of the crosslinking agent is 5% by mass or more, a good crosslinking effect can be obtained, and the strength and adhesion of the colored layer can be maintained.
- the content is 50% by mass or less, the pot life of the coating liquid Can be kept long.
- the easily adhesive layer in the present invention may further contain a known matting agent such as polystyrene, polymethylmethacrylate, or silica, or a known surfactant such as anionic or nonionic. .
- the formation of the easy-adhesion layer includes a method of bonding a polymer sheet having easy adhesion to a substrate and a method by coating. Especially, the method by application
- a coating method for example, a known coating method such as a gravure coater or a bar coater can be used.
- the coating solvent used for preparing the coating solution may be water or an organic solvent such as toluene or methyl ethyl ketone.
- a coating solvent may be used individually by 1 type, and may mix and use 2 or more types.
- the thickness of the easy-adhesion layer is not particularly limited, but is usually preferably 0.05 to 8 ⁇ m, more preferably 0.1 to 5 ⁇ m. When the thickness of the easy-adhesion layer is 0.05 ⁇ m or more, necessary easy adhesion can be suitably obtained, and when it is 8 ⁇ m or less, the surface shape becomes better.
- the easy-adhesion layer is preferably transparent so as not to reduce the effect of the colored layer.
- the solar cell module includes a transparent substrate on which sunlight is incident, a solar cell element, and a solar cell back surface protection sheet.
- a solar cell element for converting light energy of sunlight into electric energy is disposed between a transparent substrate on which sunlight is incident and a solar cell back surface protective sheet including the polyester film of the present invention.
- the substrate and the back sheet are preferably sealed with an ethylene-vinyl acetate sealing material.
- the transparent substrate only needs to have a light-transmitting property through which sunlight can be transmitted, and can be appropriately selected from base materials that transmit light. From the viewpoint of power generation efficiency, the higher the light transmittance, the better.
- a transparent resin such as an acrylic resin, or the like can be suitably used.
- solar cell elements examples include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenide, and II.
- silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon
- III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenide, and II.
- Various known solar cell elements such as -VI group compound semiconductor systems can be applied.
- Example 1 Examination of adhesiveness with coating solution for photosensitive material The adhesiveness with coating layer coating solution for photosensitive material described below was examined for the resin film substrate prepared below. .
- a polyester resin was obtained using a direct esterification method in which terephthalic acid and ethylene glycol were directly reacted to distill off water and esterify, followed by polycondensation under reduced pressure.
- (1) Esterification reaction In a first esterification reactor, 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol are mixed over 90 minutes to form a slurry, and continuously at a flow rate of 3800 kg / h. It supplied to the 1st esterification reaction tank.
- the inside of the second esterification reaction tank is partitioned into three zones, and an ethylene glycol solution of magnesium acetate is continuously supplied from the second zone so that the amount of Mg added is 75 ppm in terms of element, From the third zone, an ethylene glycol solution of trimethyl phosphate was continuously supplied so that the added amount of P was 65 ppm in terms of element.
- the temperature in the reaction tank was 278 ° C.
- the pressure in the reaction tank was 1.0 torr (1.33 ⁇ 10 ⁇ 4 MPa)
- the residence time was 1.5 hours.
- the reaction (polycondensation) was carried out under the following conditions to obtain polyethylene terephthalate (PET).
- PET polyethylene terephthalate
- Example 1 A schematic diagram of the apparatus used is shown in FIGS.
- the obtained PET base material was unwound from the unwinding roll 10 and conveyed by the electrode facing roll 12, and the corona treatment was performed by the corona treatment electrode 1 under the following conditions. That is, a corona treatment was performed at an output of 20 W ⁇ min / m 2 on one surface of the PET base material before applying a coating liquid described later.
- the production order, the number of corona treatments and the output are shown in Table 1 below.
- the PET base material which performed the corona treatment with respect to one surface above it heated on the following conditions, conveying using the heating roll 2.
- the PET base after the heat treatment step The material was taken up on a take-up roll 11. The presence / absence, method, and temperature of the heat treatment step are shown in Table 1 below.
- the time from the corona treatment to the start of heating after the corona treatment step was 3 seconds. This time is the same in other examples.
- ⁇ Application process> Preparation of coating solution for photosensitive material, application to pre-coated surface of resin film substrate
- a latex undercoat layer and a gelatin undercoat layer having the following composition are coated by hand (bar coater). It formed in order and dried with the thermostat.
- a styrene butadiene rubber (SBR) solution containing a triazine-based hardener was applied as a coating solution for the latex undercoat layer so as to have a thickness of 0.3 ⁇ m after drying.
- the gelatin solution was dried to a thickness of 0.1 ⁇ m.
- a gelatin dispersion (emulsion layer) containing a silver halide salt was further applied thereon.
- the obtained film was used as the polyester film of Example 1.
- Example 1 polyester film films of Examples and Comparative Examples were produced in the same manner as Example 1 except that the film production method was changed as shown in Table 1 below.
- the coating process was performed on the resin film substrate that had been subjected to corona treatment once or twice using the equipment from which the heating roll was removed.
- the corona treatment was performed after the heat treatment using the heating roll, and no heating was performed after the corona treatment.
- the corona treatment and the heat treatment were performed simultaneously.
- the heat treatment after the corona treatment was performed at a temperature lower than Tg of the resin film substrate.
- the resin film base material was directly conveyed as shown in FIG. 4 after the heat treatment, and the second and subsequent corona treatments and the second and subsequent heat treatments were performed online.
- Example 7 the resin film substrate was changed to PEN produced by the following method.
- (Manufacturing method of PEN) 0.005 part (0.2 mol) of cobalt acetate tetrahydrate and 0.014 part of calcium acetate monohydrate (100 parts of 2,6-naphthalenedicarboxylic acid dimethyl ester and 51 parts of ethylene glycol (abbreviated as EG)) 0.02 mol) and 0.036 parts (1.7 mol) of magnesium acetate tetrahydrate as a transesterification catalyst were subjected to a transesterification according to a conventional method to obtain 0.98 parts of an EG 1% solution of antimony trioxide (1.
- Example 8 the resin film substrate was changed to poly (1,4-cyclohexylenedimethylene terephthalate) (hereinafter also referred to as PCDMT) produced by the following method.
- PCDMT poly (1,4-cyclohexylenedimethylene terephthalate)
- TPA terephthalic acid
- CHDM 1,4-cyclohexanedimethanol
- magnesium acetate magnesium acetate
- antimony trioxide as a catalyst
- Second step After completion of the transesterification reaction, an ethylene glycol solution in which phosphoric acid was dissolved in ethylene glycol was added.
- Third step The polymerization reaction was performed at a final temperature of 285 ° C. and a vacuum of 0.1 Torr to obtain a polyester, which was pelletized.
- Fourth step The polyester pellets obtained above were subjected to solid phase polymerization in a nitrogen stream at 210 ° C. for 24 hours. After drying the resin, it was melted at 285 ° C. under vacuum with a twin screw extruder, extruded onto a cast drum, peeled off with a peeling roll, and then stretched 3.5 times in the longitudinal direction and 4 times in the transverse direction. The temperature during stretching is 90 ° C.
- Example 9 the resin film substrate was changed to a laminate of PCDMT and PET produced by the following method.
- the PET resin obtained in Example 1 and the PCDMT resin obtained in Example 8 were melt-extruded at 285 ° C. under vacuum with a twin-screw extruder, and extruded onto a cast drum using a feed block die.
- a laminated film having a structure was prepared.
- This was stretched 3.5 times in the longitudinal direction and 4 times in the transverse direction.
- the stretching temperature is 100 ° C. for longitudinal stretching and 130 ° C. for lateral stretching.
- After heat setting at 210 ° C. it was relaxed by 5% in each of the longitudinal and lateral directions at 205 ° C. to obtain a biaxially stretched polyester film having a thickness of 250 ⁇ m.
- Example 10 the corona treatment was performed using the manufacturing apparatus shown in FIG. 3, and then the heat treatment was performed after the corona treatment using an infrared heater.
- Example 11 after the corona treatment was performed using the manufacturing apparatus illustrated in FIG. 2, the heat treatment after the corona treatment was performed by blowing the heated gas in the heated gas blowing zone.
- a coating layer coating solution for a solar battery backsheet having the following composition is applied to the surface of the PET substrate on the side subjected to the corona treatment after the heating step after the corona treatment, and the adhesion is examined. went.
- an aqueous dispersion P-1 of a composite polymer containing a polysiloxane structural unit having a solid content concentration of 42% by mass and an average particle diameter of 110 nm and a structural unit derived from a carboxyl group-containing acrylic polymer was obtained.
- the aqueous dispersion P-1 has a polysiloxane structural unit of about 25% and an acrylic polymer structural unit of about 75%.
- the obtained coating solution for a solar battery backsheet was applied to the surface of the PET substrate on the side subjected to the corona treatment after the post-corona treatment heating step of the PET, with a binder amount of 3.0 g /
- the coating layer was applied to m 2 and dried at 180 ° C. for 1 minute to form a coating layer containing a composite polymer containing a polysiloxane structural unit having a dry thickness of 3 ⁇ m.
- the obtained polyester films were used as polyester films of Examples 12 to 22 and Comparative Examples 7 to 12.
- SYMBOLS 1 Electrode for corona treatment 2 Heating roll 3 Heated gas ventilation zone 4 Infrared heater 10 Unwinding roll 11 Winding roll 12 Electrode facing roll 21 Photosensitive layer (photosensitive agent layer) 22 Gelatin-based undercoat layer 23 Latex-based undercoat layer 24 Support 25 Antistatic agent layer (back layer) 26 Protective layer (back layer) 31 Back sheet (solar cell protection sheet) 32 Support 33 Application Layer (Composite Polymer Layer) 34 Back layer 35 Sealing material 36 Solar cell element 37 Transparent front substrate 38 Solar cell module
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
A process for manufacturing a polyester film, characterized by comprising: a step of subjecting a surface of a resin film substrate comprising a polyester as the main component to corona treatment; a post-heating step of subjecting the corona-treated resin film substrate to heat treatment at a temperature that exceeds the Tg of the resin film substrate and is up to the Tmeta thereof; and a step of applying a polymer solution onto the corona-treated surface of the resin film substrate. In the process, Tg is glass transition temperature, and Tmeta is a minute endothermic peak (unit: °C) as observed in differential scanning calorimetry). The process can improve the adhesion between a resin film comprising a polyester as the main component and a coating layer, and achieves excellent film production.
Description
本発明は、ポリエステルフィルムと水系分散液との密着性向上方法、ポリエステルフィルムの製造方法に関する。特に好ましくは、ハロゲン化銀感光材料を塗布したポリエステルフィルムの製造方法、各種光学用フィルム、または、太陽電池素子の太陽光入射側の反対側に設けられる太陽電池裏面保護シート用のポリエステルフィルムの製造方法、並びにそれらの製造方法で得られるポリエステルフィルムに関する。
The present invention relates to a method for improving the adhesion between a polyester film and an aqueous dispersion and a method for producing a polyester film. Particularly preferably, a method for producing a polyester film coated with a silver halide photosensitive material, various optical films, or production of a polyester film for a solar cell back surface protection sheet provided on the side opposite to the sunlight incident side of a solar cell element The present invention relates to a method and a polyester film obtained by the production method.
ポリエステルフィルム、特にポリエチレンテレフタレートやポリエチレンナフタレートの二軸延伸フィルムは、機械的強度特性、寸法安定性、透明性、光学特性、耐熱性、電気絶縁性、耐薬品性等の特性に優れ、コスト的にもバランスのとれたフィルムであることから、従来医療用フィルムや磁気テープ、写真フィルム、印刷製版用フィルム等に用いられてきたが、近年では、LCD部材のプリズムシート、光拡散シート、反射板、タッチパネル用フィルム、反射防止用フィルム、PDPフィルター用フィルム等の各種光学用フィルムに多く用いられるようになった他、太陽電池モジュールの保護シートとして従来のガラスやフッ素樹脂の代替として注目、使用されており、今後より一層重要性が増す材料である。
Polyester films, especially biaxially stretched films of polyethylene terephthalate and polyethylene naphthalate, are excellent in mechanical strength characteristics, dimensional stability, transparency, optical characteristics, heat resistance, electrical insulation, chemical resistance, etc., and cost-effective. In recent years, it has been used for medical films, magnetic tapes, photographic films, printing plate making films, etc., but in recent years, prism sheets, light diffusion sheets, reflectors for LCD members have been used. In addition to being widely used for various types of optical films such as touch panel films, antireflection films, and PDP filter films, it is used as a protective sheet for solar cell modules as an alternative to conventional glass and fluororesins. It is a material that will become even more important in the future.
しかしながら、ポリエステルフィルムは非極性であるため濡れ性が低く、他のポリマー層を塗布により積層したときの界面の密着性に問題があることが一般に知られており、感光材料や太陽電池保護シートの分野などの長期保存や長期運転が求められる分野ではその密着性の改善が強く求められていた。
However, since polyester films are nonpolar, they have low wettability, and it is generally known that there are problems with interfacial adhesion when other polymer layers are laminated by coating. In fields where long-term storage and long-term operation are required, improvement in adhesion has been strongly demanded.
ポリエステルフィルムと塗布層との密着力を向上させる方法としては、コロナ処理や低圧プラズマ処理、大気圧プラズマ処理、火炎処理等の各種表面処理方法があり、その中でもコロナ処理は効果とコストとのトータルバランスの点から広く採用されている手法である。コロナ処理はコロナ処理用電極を用いて、処理するフィルムを好ましくは電極対向ロールで搬送しながら実施し、フィルム表面に水酸基やカルボキシル基等の官能基を生成することで表面を改質するものである。ただし、コロナ処理については、表面処理後の官能基の生成量が他の表面処理方法に比べて小さいことや、生成した官能基の減衰が早いといったことが知られており、樹脂フィルム基材と塗布層との密着力が不十分となることがあった。そこで、更なる樹脂フィルム基材の表面改質を高め、塗布層との密着性の向上を課題として様々な改良がなされていた。
There are various surface treatment methods such as corona treatment, low-pressure plasma treatment, atmospheric pressure plasma treatment, and flame treatment as a method for improving the adhesion between the polyester film and the coating layer. Among them, the corona treatment is a total of effect and cost. This method is widely adopted from the viewpoint of balance. Corona treatment is carried out using a corona treatment electrode, preferably while the film to be treated is conveyed by an electrode facing roll, and the surface is modified by generating functional groups such as hydroxyl groups and carboxyl groups on the film surface. is there. However, for corona treatment, it is known that the amount of functional groups generated after surface treatment is small compared to other surface treatment methods and that the generated functional groups decay quickly. Adhesion with the coating layer may be insufficient. Thus, various improvements have been made with the aim of further improving the surface modification of the resin film substrate and improving the adhesion with the coating layer.
コロナ処理による官能基付与を改善する技術としては、コロナ処理前に基材を加熱する技術や、コロナ処理の雰囲気を窒素ガスやその他の不活性ガスに変える技術等が知られている。例えば、特許文献1には、ポリプロピレンフィルムを予熱処理し、コロナ放電処理するときに60℃以上の処理雰囲気とすることで、被処理フィルム表面での雰囲気ガスを高活性に維持し、インキの付着性や金属の蒸着性などのフィルムの表面接着性を改善する方法が記載されている。
特許文献2には、熱可塑性樹脂フィルムを60~130℃に加熱した予備加熱ロールで搬送し、70~130℃に加熱した電極対向ロールで搬送しながらフィルムの一方の表面をコロナ処理し、その後70~130℃に加熱した電極対向ロールで搬送しながらフィルムのもう一方の表面(裏面)をコロナ処理することによって、特許文献1に記載の方法で得られるフィルムよりもシワや均質性などの品質ができることが記載されている。
特許文献3には、結晶性樹脂の融点以上または非結晶性樹脂の軟化点以上の温度でコロナ処理を行うことで、塗装性、印刷性および接着性を改善する方法が記載されている。 As a technique for improving functional group imparting by corona treatment, a technique for heating the substrate before the corona treatment, a technique for changing the corona treatment atmosphere to nitrogen gas or other inert gas, and the like are known. For example, inPatent Document 1, when a polypropylene film is pre-heated and subjected to a corona discharge treatment, a treatment atmosphere of 60 ° C. or more is maintained, so that the atmosphere gas on the surface of the film to be treated is kept highly active and the ink adheres. Describes a method for improving the surface adhesion of the film, such as the property and the vapor deposition of metals.
InPatent Document 2, a thermoplastic resin film is conveyed by a preheating roll heated to 60 to 130 ° C., and one surface of the film is subjected to corona treatment while being conveyed by an electrode facing roll heated to 70 to 130 ° C. Wrinkles and homogeneity compared to the film obtained by the method described in Patent Document 1 by corona-treating the other surface (back surface) of the film while being conveyed by an electrode facing roll heated to 70 to 130 ° C. It is described that can be.
Patent Document 3 describes a method for improving paintability, printability, and adhesiveness by performing corona treatment at a temperature equal to or higher than the melting point of the crystalline resin or higher than the softening point of the amorphous resin.
特許文献2には、熱可塑性樹脂フィルムを60~130℃に加熱した予備加熱ロールで搬送し、70~130℃に加熱した電極対向ロールで搬送しながらフィルムの一方の表面をコロナ処理し、その後70~130℃に加熱した電極対向ロールで搬送しながらフィルムのもう一方の表面(裏面)をコロナ処理することによって、特許文献1に記載の方法で得られるフィルムよりもシワや均質性などの品質ができることが記載されている。
特許文献3には、結晶性樹脂の融点以上または非結晶性樹脂の軟化点以上の温度でコロナ処理を行うことで、塗装性、印刷性および接着性を改善する方法が記載されている。 As a technique for improving functional group imparting by corona treatment, a technique for heating the substrate before the corona treatment, a technique for changing the corona treatment atmosphere to nitrogen gas or other inert gas, and the like are known. For example, in
In
一方、ポリエステルフィルムでは、コロナ処理によってカルボキシル基等の官能基を生成すると同時に、フィルム表面に脆弱層(WBL層、Weak Boundary Layer)が形成され、それが密着を低下させる一因となっていることが特許文献4などに記載されている。特許文献4ではコロナ処理後に水や有機溶媒でぬらした状態で物理的機械力を加えることによって形成したWBL層を除去する方法が記載されている。
また、特許文献5の請求項3および4には、プラズマ処理後に形成したWBL層を除去する方法として、O2またはCO2プラズマの場合とN2またはNH3プラズマの場合においてそれぞれ形成される官能基の組成の最適範囲を規定する方法が記載されており、フィルム表面と塗布層との密着性を向上させることができると記載されている。 On the other hand, in a polyester film, a functional group such as a carboxyl group is generated by corona treatment, and at the same time, a fragile layer (WBL layer, Weak Boundary Layer) is formed on the film surface, which contributes to a decrease in adhesion. Is described inPatent Document 4 and the like. Patent Document 4 describes a method of removing a WBL layer formed by applying a physical mechanical force in a state wetted with water or an organic solvent after corona treatment.
Further, in claims 3 and 4 of Patent Document 5, as a method for removing the WBL layer formed after the plasma treatment, functionalities formed in the case of O 2 or CO 2 plasma and in the case of N 2 or NH 3 plasma, respectively. A method for defining the optimum range of the composition of the group is described, and it is described that the adhesion between the film surface and the coating layer can be improved.
また、特許文献5の請求項3および4には、プラズマ処理後に形成したWBL層を除去する方法として、O2またはCO2プラズマの場合とN2またはNH3プラズマの場合においてそれぞれ形成される官能基の組成の最適範囲を規定する方法が記載されており、フィルム表面と塗布層との密着性を向上させることができると記載されている。 On the other hand, in a polyester film, a functional group such as a carboxyl group is generated by corona treatment, and at the same time, a fragile layer (WBL layer, Weak Boundary Layer) is formed on the film surface, which contributes to a decrease in adhesion. Is described in
Further, in
本発明者らが特許文献1~3に記載の事前にフィルムを加熱することでコロナ処理効果を向上させる方法を検討したが、十分な密着性向上効果は得られなかった。その理由としては、コロナ処理前に加熱を行っても密着を低下させるWBL層を除去することができなかったためと考えられる。また、特許文献2に記載の方法を検討したが、電極対向ロール自体を加熱ロールとする場合、表面樹脂の材質によっては加熱温度に制約が発生し、十分な加熱が出来ないために密着向上効果が得られず、それ以外にも、表面材質の劣化やロールの変形といった製膜適性上の問題があることがわかった。
本発明者らが特許文献4に記載の方法を検討したところ、フィルムにキズが付くなどの観点から、製膜適性に問題があることがわかった。
また、特許文献5に記載のリモートプラズマでは、気流の影響を受けやすく、高速時などエアー同伴によって処理効率が落ちるという問題がある他、CO2、NH3等のガスが必要であり、ランニングコストが高くなるといった問題があることが分かった。 The present inventors examined a method for improving the corona treatment effect by heating the film in advance as described inPatent Documents 1 to 3, but a sufficient adhesion improvement effect was not obtained. The reason is considered to be that the WBL layer that decreases the adhesion could not be removed even if heating was performed before the corona treatment. Moreover, although the method of patent document 2 was examined, when the electrode facing roll itself is used as a heating roll, the heating temperature is restricted depending on the material of the surface resin, and sufficient heating cannot be performed. In addition to this, it was found that there are other problems in the film forming suitability such as deterioration of the surface material and deformation of the roll.
When the present inventors examined the method ofpatent document 4, it turned out that there exists a problem in film forming ability from viewpoints, such as a film being damaged.
In addition, the remote plasma described in Patent Document 5 is susceptible to airflow, and there is a problem that the processing efficiency is lowered due to air entrainment such as at high speeds. In addition, gas such as CO 2 and NH 3 is required, and the running cost is low. It turned out that there was a problem that became high.
本発明者らが特許文献4に記載の方法を検討したところ、フィルムにキズが付くなどの観点から、製膜適性に問題があることがわかった。
また、特許文献5に記載のリモートプラズマでは、気流の影響を受けやすく、高速時などエアー同伴によって処理効率が落ちるという問題がある他、CO2、NH3等のガスが必要であり、ランニングコストが高くなるといった問題があることが分かった。 The present inventors examined a method for improving the corona treatment effect by heating the film in advance as described in
When the present inventors examined the method of
In addition, the remote plasma described in Patent Document 5 is susceptible to airflow, and there is a problem that the processing efficiency is lowered due to air entrainment such as at high speeds. In addition, gas such as CO 2 and NH 3 is required, and the running cost is low. It turned out that there was a problem that became high.
本発明は上記に鑑みなされたものであり、本発明が解決しようとする課題は、ポリエステルを主成分とする樹脂フィルム基材の塗布層との密着性を改善でき、製膜適性が良好なポリエステルフィルムの製造方法を提供することにある。
The present invention has been made in view of the above, and the problem to be solved by the present invention is to improve the adhesion with the coating layer of the resin film base material containing polyester as a main component, and polyester having good film forming suitability It is providing the manufacturing method of a film.
本発明者らが、樹脂フィルム基材をコロナ処理した後に加熱し、フィルム表面温度が常温に下がった後に塗布層を形成したところ、事前に加熱してコロナ処理した場合に比べて、樹脂フィルム基材と塗布層の間の密着力が向上することがわかった。本発明者らにて、コロナ処理だけを行ったフィルム、および、コロナ処理後に加熱処理を行ったフィルムの表面を削り取り、DSCによる結晶化温度(降温結晶化;Tc’)を測定した結果、コロナ処理だけを行ったフィルム表面のTc’は、未処理の場合よりも高温側(結晶化が早い、すなわち低分子化)にシフトすることが判明し、また、コロナ処理後に加熱処理を行ったフィルム表面のTc’では高温側へのシフトは見られず(未処理と同等または低温側にシフト)、低分子化が抑制(または高分子化)されていることが分かった。いかなる理論に拘泥するものでもないが、コロナ処理による樹脂フィルム基材の表面のポリマーの低分子化を抑制できたことにより、これが密着低下を抑え、結果として密着向上に繋がっていると推定している。
また、コロナ処理によって粗面化するのは表面分子の切断(コロナ処理で生じたラジカルのうち、COOH、OH等の官能基に変化しなかったものが残存し、結果としてポリエステル分子鎖が切断(すなわちWBL層の生成)されると推測)が原因であるが、本発明者らによる検討結果では、コロナ処理後に熱処理した場合は、未処理時に比べて表面粗さに顕著な変化は見られなかった。いかなる理論に拘泥するものでもないが、コロナ処理後に加熱することでラジカルが再結合(架橋)し、表面に残存しない(すなわち分子鎖の切断がなく、結果としてWBL層の生成を抑制される)ことが原因であると推定している。このように本発明では、粗面化せずに官能基を増やし、かつWBL層の生成を抑制することができるという特徴も持っている。
また、コロナ処理前に加熱処理を行い、塗布を行った場合は密着向上効果が無かったことからWBL層の除去ができないと推測され、特許文献1~3に記載の方法でコロナ処理後に塗布を行った後に乾燥してもWBL層が除去されずに残ると推測されるため、コロナ処理後から塗布工程の前までの間に加熱処理を行う必要があることを見出すに至った。
さらに、このような樹脂フィルム基材をコロナ処理した後に加熱し、加熱後に塗布層を形成する方法は、特許文献2や4に記載の方法と比べて製膜適性も良好であることがわかった。
すなわち、以下の構成により、前記課題を解決できることを見出し、本発明の完成に至った。 When the present inventors heated the corona treatment of the resin film substrate and formed the coating layer after the film surface temperature dropped to room temperature, the resin film base was compared with the case where the corona treatment was performed by heating in advance. It was found that the adhesion between the material and the coating layer was improved. As a result of measuring the crystallization temperature (cooling crystallization; Tc ′) by DSC, the inventors of the present invention scraped the surface of the film that had been subjected to the corona treatment alone and the film that had been subjected to the heat treatment after the corona treatment. It was found that the Tc ′ of the film surface subjected to the treatment alone shifted to a higher temperature side (faster crystallization, that is, lower molecular weight) than in the case of the untreated film, and the film subjected to the heat treatment after the corona treatment. The surface Tc ′ did not show a shift to the high temperature side (equivalent to untreated or shifted to the low temperature side), and it was found that the low molecular weight was suppressed (or increased in polymer). Although not bound by any theory, it is estimated that the reduction in the molecular weight of the polymer on the surface of the resin film substrate due to the corona treatment can be suppressed, which suppresses the decrease in adhesion and as a result, improves adhesion. Yes.
Also, roughening by corona treatment is the cutting of surface molecules (of radicals generated by corona treatment, those that have not changed to functional groups such as COOH and OH remain, and as a result, the polyester molecular chain is cut ( That is, it is estimated that the generation of the WBL layer is caused). However, according to the examination results by the present inventors, when the heat treatment is performed after the corona treatment, the surface roughness is not significantly changed as compared with the untreated case. It was. Although not bound by any theory, by heating after corona treatment, radicals recombine (crosslink) and do not remain on the surface (ie, there is no molecular chain scission, resulting in the suppression of WBL layer formation). It is estimated that this is the cause. As described above, the present invention also has a feature that the functional groups can be increased without roughening and the generation of the WBL layer can be suppressed.
In addition, when the heat treatment was performed before the corona treatment and the coating was performed, it was estimated that the WBL layer could not be removed because there was no effect of improving the adhesion, and the coating was performed after the corona treatment by the methods described inPatent Documents 1 to 3. Since it is estimated that the WBL layer remains without being removed even after drying, the inventors have found that it is necessary to perform a heat treatment after the corona treatment and before the coating step.
Furthermore, it was found that the method of heating the resin film substrate after corona treatment and forming the coating layer after the heating have better film forming suitability than the methods described in Patent Documents 2 and 4. .
That is, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.
また、コロナ処理によって粗面化するのは表面分子の切断(コロナ処理で生じたラジカルのうち、COOH、OH等の官能基に変化しなかったものが残存し、結果としてポリエステル分子鎖が切断(すなわちWBL層の生成)されると推測)が原因であるが、本発明者らによる検討結果では、コロナ処理後に熱処理した場合は、未処理時に比べて表面粗さに顕著な変化は見られなかった。いかなる理論に拘泥するものでもないが、コロナ処理後に加熱することでラジカルが再結合(架橋)し、表面に残存しない(すなわち分子鎖の切断がなく、結果としてWBL層の生成を抑制される)ことが原因であると推定している。このように本発明では、粗面化せずに官能基を増やし、かつWBL層の生成を抑制することができるという特徴も持っている。
また、コロナ処理前に加熱処理を行い、塗布を行った場合は密着向上効果が無かったことからWBL層の除去ができないと推測され、特許文献1~3に記載の方法でコロナ処理後に塗布を行った後に乾燥してもWBL層が除去されずに残ると推測されるため、コロナ処理後から塗布工程の前までの間に加熱処理を行う必要があることを見出すに至った。
さらに、このような樹脂フィルム基材をコロナ処理した後に加熱し、加熱後に塗布層を形成する方法は、特許文献2や4に記載の方法と比べて製膜適性も良好であることがわかった。
すなわち、以下の構成により、前記課題を解決できることを見出し、本発明の完成に至った。 When the present inventors heated the corona treatment of the resin film substrate and formed the coating layer after the film surface temperature dropped to room temperature, the resin film base was compared with the case where the corona treatment was performed by heating in advance. It was found that the adhesion between the material and the coating layer was improved. As a result of measuring the crystallization temperature (cooling crystallization; Tc ′) by DSC, the inventors of the present invention scraped the surface of the film that had been subjected to the corona treatment alone and the film that had been subjected to the heat treatment after the corona treatment. It was found that the Tc ′ of the film surface subjected to the treatment alone shifted to a higher temperature side (faster crystallization, that is, lower molecular weight) than in the case of the untreated film, and the film subjected to the heat treatment after the corona treatment. The surface Tc ′ did not show a shift to the high temperature side (equivalent to untreated or shifted to the low temperature side), and it was found that the low molecular weight was suppressed (or increased in polymer). Although not bound by any theory, it is estimated that the reduction in the molecular weight of the polymer on the surface of the resin film substrate due to the corona treatment can be suppressed, which suppresses the decrease in adhesion and as a result, improves adhesion. Yes.
Also, roughening by corona treatment is the cutting of surface molecules (of radicals generated by corona treatment, those that have not changed to functional groups such as COOH and OH remain, and as a result, the polyester molecular chain is cut ( That is, it is estimated that the generation of the WBL layer is caused). However, according to the examination results by the present inventors, when the heat treatment is performed after the corona treatment, the surface roughness is not significantly changed as compared with the untreated case. It was. Although not bound by any theory, by heating after corona treatment, radicals recombine (crosslink) and do not remain on the surface (ie, there is no molecular chain scission, resulting in the suppression of WBL layer formation). It is estimated that this is the cause. As described above, the present invention also has a feature that the functional groups can be increased without roughening and the generation of the WBL layer can be suppressed.
In addition, when the heat treatment was performed before the corona treatment and the coating was performed, it was estimated that the WBL layer could not be removed because there was no effect of improving the adhesion, and the coating was performed after the corona treatment by the methods described in
Furthermore, it was found that the method of heating the resin film substrate after corona treatment and forming the coating layer after the heating have better film forming suitability than the methods described in
That is, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.
上記課題を解決するための具体的な手段は以下の通りである。
[1] ポリエステルを主成分とする樹脂フィルム基材の表面をコロナ処理する工程と、前記コロナ処理後の前記樹脂フィルム基材を該樹脂フィルム基材のTgを超えて、Tmeta以下に加熱処理するコロナ処理後加熱工程と、前記コロナ処理後加熱工程の後に前記樹脂フィルム基材の前記コロナ処理を施された側の表面上にポリマー溶液を塗布する工程とを含むことを特徴とするポリエステルフィルムの製造方法(ここで、Tgはガラス転移温度、Tmetaは示差走査熱量測定にて求められる微小吸熱ピーク(単位:℃)を表す)。
[2] 前記樹脂フィルム基材がポリエチレンテレフタレートまたはポリ(1,4-シクロヘキシレンジメチレンテレフタレート)の単層フィルム、あるいは、それらのうち1種または2種を含む積層体であることを特徴とする[1]に記載のポリエステルフィルムの製造方法。
[3] 前記コロナ処理後加熱工程における前記樹脂フィルム基材の表面温度が70~220℃であることを特徴とする[1]または[2]に記載のポリエステルフィルムの製造方法。
[4] 前記コロナ処理工程の前に前記樹脂フィルム基材を加熱するコロナ処理前加熱工程を含み、前記コロナ処理前加熱工程と、前記コロナ処理後加熱工程を、異なる加熱処理装置によって行うことを特徴とする[1]~[3]のいずれか一項に記載のポリエステルフィルムの製造方法。
[5] 前記コロナ処理後加熱工程の後に、前記樹脂フィルム基材の前記コロナ処理を施された側の表面に再度のコロナ処理を行うことを特徴とする[1]~[4]のいずれか一項に記載のポリエステルフィルムの製造方法。
[6] 前記コロナ処理と、前記再度のコロナ処理を、異なるコロナ処理装置によって行うことを特徴とする[5]に記載のポリエステルフィルムの製造方法。
[7] 前記加熱処理が、加熱気体の送風、赤外線の照射または加熱ロールとの接触であることを特徴とする[1]~[6]のいずれか一項に記載のポリエステルフィルムの製造方法。
[8] 前記加熱ロールが、前記コロナ処理における電極対向ロールとは異なるロールであることを特徴とする[7]に記載のポリエステルフィルムの製造方法。
[9] 前記コロナ処理工程および前記加熱処理を、いずれも前記樹脂フィルム基材を搬送しながら行うことを特徴とする[1]~[8]のいずれか一項に記載のポリエステルフィルムの製造方法。
[10] 前記コロナ処理工程の前に、前記樹脂フィルム基材を二軸延伸する工程を含むことを特徴とする[1]~[9]のいずれか一項に記載のポリエステルフィルムの製造方法。
[11] [1]~[10]のいずれか一項に記載のポリエステルフィルムの製造方法を含むことを特徴とする太陽電池保護シートの製造方法。
[12] [1]~[10]のいずれか一項に記載のポリエステルフィルムの製造方法を含むことを特徴とする感光材料の製造方法。
[13] [1]~[10]のいずれか一項に記載のポリエステルフィルムの製造方法によって製造されたことを特徴とするポリエステルフィルム。
[14] ポリエステルを主成分とする樹脂フィルム基材の表面をコロナ処理する工程と、前記コロナ処理後の前記樹脂フィルム基材を該樹脂フィルム基材のTgを超えて、Tmeta以下に加熱処理するコロナ処理後加熱工程と、前記コロナ処理後加熱工程の後に前記樹脂フィルム基材の前記コロナ処理を施された側の表面上にポリマー溶液を塗布する工程を含み、前記ポリマー溶液が水系分散液であることを特徴とするポリエステルフィルムと水系分散液との密着性向上方法(ここで、Tgはガラス転移温度、Tmetaは示差走査熱量測定にて求められる微小吸熱ピーク(単位:℃)を表す)。 Specific means for solving the above problems are as follows.
[1] A step of corona-treating the surface of a resin film substrate containing polyester as a main component, and heat-treating the resin film substrate after the corona treatment to a Tmeta or less exceeding the Tg of the resin film substrate. A heating step after corona treatment, and a step of applying a polymer solution onto the surface of the resin film substrate on the side subjected to the corona treatment after the heating step after the corona treatment. Production method (where Tg represents a glass transition temperature, and Tmeta represents a minute endothermic peak (unit: ° C.) determined by differential scanning calorimetry).
[2] The resin film substrate is a monolayer film of polyethylene terephthalate or poly (1,4-cyclohexylenedimethylene terephthalate), or a laminate including one or two of them. The manufacturing method of the polyester film as described in [1].
[3] The method for producing a polyester film according to [1] or [2], wherein the surface temperature of the resin film substrate in the heating step after the corona treatment is 70 to 220 ° C.
[4] It includes a pre-corona treatment heating step for heating the resin film substrate before the corona treatment step, and the pre-corona treatment heating step and the post-corona treatment heating step are performed by different heat treatment apparatuses. The method for producing a polyester film according to any one of [1] to [3], which is characterized in that
[5] Any one of [1] to [4], wherein the corona treatment is performed again on the surface of the resin film base on which the corona treatment has been performed after the post-corona treatment heating step. The manufacturing method of the polyester film of one term.
[6] The method for producing a polyester film according to [5], wherein the corona treatment and the re-corona treatment are performed by different corona treatment apparatuses.
[7] The method for producing a polyester film according to any one of [1] to [6], wherein the heat treatment is blowing of heated gas, irradiation with infrared rays, or contact with a heating roll.
[8] The method for producing a polyester film according to [7], wherein the heating roll is a roll different from the electrode facing roll in the corona treatment.
[9] The method for producing a polyester film according to any one of [1] to [8], wherein the corona treatment step and the heat treatment are both carried out while the resin film substrate is conveyed. .
[10] The method for producing a polyester film according to any one of [1] to [9], further including a step of biaxially stretching the resin film substrate before the corona treatment step.
[11] A method for producing a solar cell protective sheet, comprising the method for producing a polyester film according to any one of [1] to [10].
[12] A method for producing a photosensitive material, comprising the method for producing a polyester film according to any one of [1] to [10].
[13] A polyester film produced by the method for producing a polyester film according to any one of [1] to [10].
[14] A step of corona-treating the surface of the resin film base material containing polyester as a main component, and heat-treating the resin film base material after the corona treatment to Tmeta or less exceeding Tg of the resin film base material. A heating step after corona treatment, and a step of applying a polymer solution on the surface of the resin film substrate on the side subjected to the corona treatment after the heating step after the corona treatment, wherein the polymer solution is an aqueous dispersion. A method for improving adhesion between a polyester film and an aqueous dispersion, wherein Tg is a glass transition temperature and Tmeta is a minute endothermic peak (unit: ° C.) determined by differential scanning calorimetry.
[1] ポリエステルを主成分とする樹脂フィルム基材の表面をコロナ処理する工程と、前記コロナ処理後の前記樹脂フィルム基材を該樹脂フィルム基材のTgを超えて、Tmeta以下に加熱処理するコロナ処理後加熱工程と、前記コロナ処理後加熱工程の後に前記樹脂フィルム基材の前記コロナ処理を施された側の表面上にポリマー溶液を塗布する工程とを含むことを特徴とするポリエステルフィルムの製造方法(ここで、Tgはガラス転移温度、Tmetaは示差走査熱量測定にて求められる微小吸熱ピーク(単位:℃)を表す)。
[2] 前記樹脂フィルム基材がポリエチレンテレフタレートまたはポリ(1,4-シクロヘキシレンジメチレンテレフタレート)の単層フィルム、あるいは、それらのうち1種または2種を含む積層体であることを特徴とする[1]に記載のポリエステルフィルムの製造方法。
[3] 前記コロナ処理後加熱工程における前記樹脂フィルム基材の表面温度が70~220℃であることを特徴とする[1]または[2]に記載のポリエステルフィルムの製造方法。
[4] 前記コロナ処理工程の前に前記樹脂フィルム基材を加熱するコロナ処理前加熱工程を含み、前記コロナ処理前加熱工程と、前記コロナ処理後加熱工程を、異なる加熱処理装置によって行うことを特徴とする[1]~[3]のいずれか一項に記載のポリエステルフィルムの製造方法。
[5] 前記コロナ処理後加熱工程の後に、前記樹脂フィルム基材の前記コロナ処理を施された側の表面に再度のコロナ処理を行うことを特徴とする[1]~[4]のいずれか一項に記載のポリエステルフィルムの製造方法。
[6] 前記コロナ処理と、前記再度のコロナ処理を、異なるコロナ処理装置によって行うことを特徴とする[5]に記載のポリエステルフィルムの製造方法。
[7] 前記加熱処理が、加熱気体の送風、赤外線の照射または加熱ロールとの接触であることを特徴とする[1]~[6]のいずれか一項に記載のポリエステルフィルムの製造方法。
[8] 前記加熱ロールが、前記コロナ処理における電極対向ロールとは異なるロールであることを特徴とする[7]に記載のポリエステルフィルムの製造方法。
[9] 前記コロナ処理工程および前記加熱処理を、いずれも前記樹脂フィルム基材を搬送しながら行うことを特徴とする[1]~[8]のいずれか一項に記載のポリエステルフィルムの製造方法。
[10] 前記コロナ処理工程の前に、前記樹脂フィルム基材を二軸延伸する工程を含むことを特徴とする[1]~[9]のいずれか一項に記載のポリエステルフィルムの製造方法。
[11] [1]~[10]のいずれか一項に記載のポリエステルフィルムの製造方法を含むことを特徴とする太陽電池保護シートの製造方法。
[12] [1]~[10]のいずれか一項に記載のポリエステルフィルムの製造方法を含むことを特徴とする感光材料の製造方法。
[13] [1]~[10]のいずれか一項に記載のポリエステルフィルムの製造方法によって製造されたことを特徴とするポリエステルフィルム。
[14] ポリエステルを主成分とする樹脂フィルム基材の表面をコロナ処理する工程と、前記コロナ処理後の前記樹脂フィルム基材を該樹脂フィルム基材のTgを超えて、Tmeta以下に加熱処理するコロナ処理後加熱工程と、前記コロナ処理後加熱工程の後に前記樹脂フィルム基材の前記コロナ処理を施された側の表面上にポリマー溶液を塗布する工程を含み、前記ポリマー溶液が水系分散液であることを特徴とするポリエステルフィルムと水系分散液との密着性向上方法(ここで、Tgはガラス転移温度、Tmetaは示差走査熱量測定にて求められる微小吸熱ピーク(単位:℃)を表す)。 Specific means for solving the above problems are as follows.
[1] A step of corona-treating the surface of a resin film substrate containing polyester as a main component, and heat-treating the resin film substrate after the corona treatment to a Tmeta or less exceeding the Tg of the resin film substrate. A heating step after corona treatment, and a step of applying a polymer solution onto the surface of the resin film substrate on the side subjected to the corona treatment after the heating step after the corona treatment. Production method (where Tg represents a glass transition temperature, and Tmeta represents a minute endothermic peak (unit: ° C.) determined by differential scanning calorimetry).
[2] The resin film substrate is a monolayer film of polyethylene terephthalate or poly (1,4-cyclohexylenedimethylene terephthalate), or a laminate including one or two of them. The manufacturing method of the polyester film as described in [1].
[3] The method for producing a polyester film according to [1] or [2], wherein the surface temperature of the resin film substrate in the heating step after the corona treatment is 70 to 220 ° C.
[4] It includes a pre-corona treatment heating step for heating the resin film substrate before the corona treatment step, and the pre-corona treatment heating step and the post-corona treatment heating step are performed by different heat treatment apparatuses. The method for producing a polyester film according to any one of [1] to [3], which is characterized in that
[5] Any one of [1] to [4], wherein the corona treatment is performed again on the surface of the resin film base on which the corona treatment has been performed after the post-corona treatment heating step. The manufacturing method of the polyester film of one term.
[6] The method for producing a polyester film according to [5], wherein the corona treatment and the re-corona treatment are performed by different corona treatment apparatuses.
[7] The method for producing a polyester film according to any one of [1] to [6], wherein the heat treatment is blowing of heated gas, irradiation with infrared rays, or contact with a heating roll.
[8] The method for producing a polyester film according to [7], wherein the heating roll is a roll different from the electrode facing roll in the corona treatment.
[9] The method for producing a polyester film according to any one of [1] to [8], wherein the corona treatment step and the heat treatment are both carried out while the resin film substrate is conveyed. .
[10] The method for producing a polyester film according to any one of [1] to [9], further including a step of biaxially stretching the resin film substrate before the corona treatment step.
[11] A method for producing a solar cell protective sheet, comprising the method for producing a polyester film according to any one of [1] to [10].
[12] A method for producing a photosensitive material, comprising the method for producing a polyester film according to any one of [1] to [10].
[13] A polyester film produced by the method for producing a polyester film according to any one of [1] to [10].
[14] A step of corona-treating the surface of the resin film base material containing polyester as a main component, and heat-treating the resin film base material after the corona treatment to Tmeta or less exceeding Tg of the resin film base material. A heating step after corona treatment, and a step of applying a polymer solution on the surface of the resin film substrate on the side subjected to the corona treatment after the heating step after the corona treatment, wherein the polymer solution is an aqueous dispersion. A method for improving adhesion between a polyester film and an aqueous dispersion, wherein Tg is a glass transition temperature and Tmeta is a minute endothermic peak (unit: ° C.) determined by differential scanning calorimetry.
本発明によれば、ポリエステルを主成分とする樹脂フィルム基材の塗布層との密着性を改善でき、製膜適性が良好なポリエステルフィルムの製造方法を提供することができる。
According to the present invention, it is possible to provide a method for producing a polyester film that can improve the adhesion to a coating layer of a resin film base material containing polyester as a main component and has good film forming suitability.
以下、本発明のポリエステルフィルムおよびその製造方法について詳細に説明する。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。なお、本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 Hereinafter, the polyester film of the present invention and the production method thereof will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。なお、本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 Hereinafter, the polyester film of the present invention and the production method thereof will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
[ポリエステルフィルムの製造方法]
本発明のポリエステルフィルムの製造方法(以下、本発明の製造方法とも言う)は、ポリエステルを主成分とする樹脂フィルム基材の表面をコロナ処理する工程と、前記コロナ処理後の前記樹脂フィルム基材を該樹脂フィルム基材のTgを超えて、Tmeta以下に加熱処理するコロナ処理後加熱工程と、前記コロナ処理後加熱工程の後に前記樹脂フィルム基材の前記コロナ処理を施された側の表面上にポリマー溶液を塗布する工程とを含むことを特徴とする(ここで、Tgはガラス転移温度、Tmetaは示差走査熱量測定にて求められる微小吸熱ピーク(単位:℃)を表す)。また、Tmetaは例えばWO2010/110119号公報等に記載されているTmetaと同義であり、Tmetaの測定方法も同文献に記載の方法で行うことができる。
このような構成により、樹脂フィルム基材の塗布層との密着性を改善でき、製膜適性が良好なポリエステルフィルムの製造方法を提供することができる。いかなる理論に拘泥するものでもないが、以下のメカニズムを推定している。コロナ処理によって樹脂フィルム基材の表面にラジカルが生成され、そのラジカルの一部は酸素原子と反応し官能基(-OH、-COOH等)を生成し、密着性の向上に寄与する。一方、ラジカルの一部は酸素原子と結合せず、樹脂フィルム基材を構成する表層の樹脂自体を低分子化してWBL層を形成させ、樹脂フィルム基材と塗布層との密着性が低下する原因となる。従来の方法ではコロナ処理で生じたラジカルのうち、COOH、OH等の官能基に変化しなかったものが多く残存し、結果としてポリエステル分子鎖が切断(すなわちWBL層が生成)される。これに対し、本発明では、コロナ処理後に加熱することで、コロナ処理で生じたラジカルを再結合(架橋)させ、WBL層形成に寄与するラジカルが樹脂フィルム基材の表面に残存しないようにする(ポリエステル分子鎖の切断がなく、結果としてWBL層の生成を抑制し、密着低下を防ぐ)ことができると推定している。
以下、本発明の製造方法について説明する。 [Production method of polyester film]
The method for producing a polyester film of the present invention (hereinafter also referred to as the production method of the present invention) comprises a step of corona treating the surface of a resin film substrate comprising polyester as a main component, and the resin film substrate after the corona treatment. On the surface of the resin film substrate on the side subjected to the corona treatment after the corona treatment heating step after the corona treatment. (Wherein Tg represents a glass transition temperature and Tmeta represents a minute endothermic peak (unit: ° C.) determined by differential scanning calorimetry). Moreover, Tmeta is synonymous with Tmeta described in WO2010 / 110119 etc., for example, The measuring method of Tmeta can also be performed by the method as described in the literature.
With such a configuration, it is possible to improve the adhesion with the coating layer of the resin film substrate, and to provide a method for producing a polyester film with good film forming suitability. Although not bound by any theory, the following mechanism is presumed. By the corona treatment, radicals are generated on the surface of the resin film substrate, and a part of the radicals react with oxygen atoms to generate functional groups (—OH, —COOH, etc.), contributing to the improvement of adhesion. On the other hand, some of the radicals are not bonded to oxygen atoms, and the surface of the resin film constituting the resin film substrate itself is reduced in molecular weight to form a WBL layer, which decreases the adhesion between the resin film substrate and the coating layer. Cause. In the conventional method, among radicals generated by corona treatment, many radicals that have not changed to functional groups such as COOH and OH remain, and as a result, the polyester molecular chain is cleaved (that is, a WBL layer is generated). On the other hand, in the present invention, by heating after the corona treatment, the radicals generated by the corona treatment are recombined (crosslinked) so that the radicals contributing to the formation of the WBL layer do not remain on the surface of the resin film substrate. It is estimated that the polyester molecular chain is not broken, and as a result, the generation of the WBL layer can be suppressed and the adhesion decrease can be prevented.
Hereinafter, the production method of the present invention will be described.
本発明のポリエステルフィルムの製造方法(以下、本発明の製造方法とも言う)は、ポリエステルを主成分とする樹脂フィルム基材の表面をコロナ処理する工程と、前記コロナ処理後の前記樹脂フィルム基材を該樹脂フィルム基材のTgを超えて、Tmeta以下に加熱処理するコロナ処理後加熱工程と、前記コロナ処理後加熱工程の後に前記樹脂フィルム基材の前記コロナ処理を施された側の表面上にポリマー溶液を塗布する工程とを含むことを特徴とする(ここで、Tgはガラス転移温度、Tmetaは示差走査熱量測定にて求められる微小吸熱ピーク(単位:℃)を表す)。また、Tmetaは例えばWO2010/110119号公報等に記載されているTmetaと同義であり、Tmetaの測定方法も同文献に記載の方法で行うことができる。
このような構成により、樹脂フィルム基材の塗布層との密着性を改善でき、製膜適性が良好なポリエステルフィルムの製造方法を提供することができる。いかなる理論に拘泥するものでもないが、以下のメカニズムを推定している。コロナ処理によって樹脂フィルム基材の表面にラジカルが生成され、そのラジカルの一部は酸素原子と反応し官能基(-OH、-COOH等)を生成し、密着性の向上に寄与する。一方、ラジカルの一部は酸素原子と結合せず、樹脂フィルム基材を構成する表層の樹脂自体を低分子化してWBL層を形成させ、樹脂フィルム基材と塗布層との密着性が低下する原因となる。従来の方法ではコロナ処理で生じたラジカルのうち、COOH、OH等の官能基に変化しなかったものが多く残存し、結果としてポリエステル分子鎖が切断(すなわちWBL層が生成)される。これに対し、本発明では、コロナ処理後に加熱することで、コロナ処理で生じたラジカルを再結合(架橋)させ、WBL層形成に寄与するラジカルが樹脂フィルム基材の表面に残存しないようにする(ポリエステル分子鎖の切断がなく、結果としてWBL層の生成を抑制し、密着低下を防ぐ)ことができると推定している。
以下、本発明の製造方法について説明する。 [Production method of polyester film]
The method for producing a polyester film of the present invention (hereinafter also referred to as the production method of the present invention) comprises a step of corona treating the surface of a resin film substrate comprising polyester as a main component, and the resin film substrate after the corona treatment. On the surface of the resin film substrate on the side subjected to the corona treatment after the corona treatment heating step after the corona treatment. (Wherein Tg represents a glass transition temperature and Tmeta represents a minute endothermic peak (unit: ° C.) determined by differential scanning calorimetry). Moreover, Tmeta is synonymous with Tmeta described in WO2010 / 110119 etc., for example, The measuring method of Tmeta can also be performed by the method as described in the literature.
With such a configuration, it is possible to improve the adhesion with the coating layer of the resin film substrate, and to provide a method for producing a polyester film with good film forming suitability. Although not bound by any theory, the following mechanism is presumed. By the corona treatment, radicals are generated on the surface of the resin film substrate, and a part of the radicals react with oxygen atoms to generate functional groups (—OH, —COOH, etc.), contributing to the improvement of adhesion. On the other hand, some of the radicals are not bonded to oxygen atoms, and the surface of the resin film constituting the resin film substrate itself is reduced in molecular weight to form a WBL layer, which decreases the adhesion between the resin film substrate and the coating layer. Cause. In the conventional method, among radicals generated by corona treatment, many radicals that have not changed to functional groups such as COOH and OH remain, and as a result, the polyester molecular chain is cleaved (that is, a WBL layer is generated). On the other hand, in the present invention, by heating after the corona treatment, the radicals generated by the corona treatment are recombined (crosslinked) so that the radicals contributing to the formation of the WBL layer do not remain on the surface of the resin film substrate. It is estimated that the polyester molecular chain is not broken, and as a result, the generation of the WBL layer can be suppressed and the adhesion decrease can be prevented.
Hereinafter, the production method of the present invention will be described.
<樹脂フィルム基材の調製>
(ポリマー種)
樹脂フィルム基材に主成分として用いられるポリマー種としては、ポリエステルである。ここで、本発明における主成分とは、樹脂フィルム基材の50質量%以上を構成する成分のことをいう。前記樹脂フィルム基材は、樹脂フィルム基材の80質量%以上を構成する成分がポリエステルであることが好ましく、90質量%以上を構成する成分がポリエステルであることがより好ましい。
本発明の製造方法では、これらの中では、コストや機械強度などの点から、前記樹脂フィルム基材がポリエステルであることが好ましい。 <Preparation of resin film substrate>
(Polymer type)
The polymer species used as the main component for the resin film substrate is polyester. Here, the main component in this invention means the component which comprises 50 mass% or more of a resin film base material. In the resin film substrate, the component constituting 80% by mass or more of the resin film substrate is preferably polyester, and the component constituting 90% by mass or more is more preferably polyester.
In the production method of the present invention, among these, the resin film base material is preferably polyester from the viewpoint of cost, mechanical strength, and the like.
(ポリマー種)
樹脂フィルム基材に主成分として用いられるポリマー種としては、ポリエステルである。ここで、本発明における主成分とは、樹脂フィルム基材の50質量%以上を構成する成分のことをいう。前記樹脂フィルム基材は、樹脂フィルム基材の80質量%以上を構成する成分がポリエステルであることが好ましく、90質量%以上を構成する成分がポリエステルであることがより好ましい。
本発明の製造方法では、これらの中では、コストや機械強度などの点から、前記樹脂フィルム基材がポリエステルであることが好ましい。 <Preparation of resin film substrate>
(Polymer type)
The polymer species used as the main component for the resin film substrate is polyester. Here, the main component in this invention means the component which comprises 50 mass% or more of a resin film base material. In the resin film substrate, the component constituting 80% by mass or more of the resin film substrate is preferably polyester, and the component constituting 90% by mass or more is more preferably polyester.
In the production method of the present invention, among these, the resin film base material is preferably polyester from the viewpoint of cost, mechanical strength, and the like.
前記樹脂フィルム基材(支持体)として用いられるポリエステルとしては、芳香族二塩基酸又はそのエステル形成性誘導体とジオール又はそのエステル形成性誘導体とから合成される線状飽和ポリエステルである。かかるポリエステルの具体例としては、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリブチレンテレフタレート、ポリ(1,4-シクロヘキシレンジメチレンテレフタレート)、ポリエチレン-2,6-ナフタレートなどを挙げることができる。ポリエチレンテレフタレートがより好ましい。
The polyester used as the resin film substrate (support) is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. Specific examples of such polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate and the like. Polyethylene terephthalate is more preferred.
前記ポリエステルは、単独重合体であってもよいし、共重合体であってもよい。更に、前記ポリエステルに他の種類の樹脂、例えばポリイミド等を少量ブレンドしたものであってもよく、また、例えばトリメリット酸エステルのような可塑剤を配合してもよく、トリメリット酸エステルはポリエステルの重合前に添加してもよい。
The polyester may be a homopolymer or a copolymer. Furthermore, the polyester may be a blend of a small amount of other types of resin, such as polyimide, and may be blended with a plasticizer such as trimellitic acid ester. It may be added before the polymerization.
(ポリマーの合成)
本発明におけるポリエステルを重合する際には、カルボキシル基含量を所定の範囲以下に抑える観点から、Sb系、Ge系、Ti系の化合物を触媒として用いることが好ましい。ただし、Sb触媒は重金属であり、環境影響の点で好ましくない他、重合反応の過程で析出する金属Sb粒子がPET中に含まれるため、製膜工程において異物化する問題がある。また、Ge触媒は高価であり、コストアップが避けられない他、エチレングリコールへの溶解性が低く、微小不溶物がPET中に残存し、押出工程においてダイリップ汚れを引き起こすといった問題がある。その点でTi触媒系が好ましく、また、Ti触媒で重合したPET樹脂はSbやGeに比べて末端COOH基が低い傾向があり、例えば、耐加水分解性を要する太陽電池保護シートに用いる場合に好適である。 (Polymer synthesis)
When the polyester in the present invention is polymerized, it is preferable to use an Sb-based, Ge-based, or Ti-based compound as a catalyst from the viewpoint of keeping the carboxyl group content below a predetermined range. However, the Sb catalyst is a heavy metal, which is not preferable from the viewpoint of environmental influences, and has a problem of forming foreign matter in the film forming process because metal Sb particles precipitated in the course of the polymerization reaction are included in the PET. In addition, the Ge catalyst is expensive and inevitably increases in cost, has low solubility in ethylene glycol, and has a problem that minute insoluble matter remains in the PET and causes die lip contamination in the extrusion process. In this respect, a Ti catalyst system is preferable, and a PET resin polymerized with a Ti catalyst tends to have lower terminal COOH groups than Sb and Ge. For example, when used for a solar cell protective sheet requiring hydrolysis resistance. Is preferred.
本発明におけるポリエステルを重合する際には、カルボキシル基含量を所定の範囲以下に抑える観点から、Sb系、Ge系、Ti系の化合物を触媒として用いることが好ましい。ただし、Sb触媒は重金属であり、環境影響の点で好ましくない他、重合反応の過程で析出する金属Sb粒子がPET中に含まれるため、製膜工程において異物化する問題がある。また、Ge触媒は高価であり、コストアップが避けられない他、エチレングリコールへの溶解性が低く、微小不溶物がPET中に残存し、押出工程においてダイリップ汚れを引き起こすといった問題がある。その点でTi触媒系が好ましく、また、Ti触媒で重合したPET樹脂はSbやGeに比べて末端COOH基が低い傾向があり、例えば、耐加水分解性を要する太陽電池保護シートに用いる場合に好適である。 (Polymer synthesis)
When the polyester in the present invention is polymerized, it is preferable to use an Sb-based, Ge-based, or Ti-based compound as a catalyst from the viewpoint of keeping the carboxyl group content below a predetermined range. However, the Sb catalyst is a heavy metal, which is not preferable from the viewpoint of environmental influences, and has a problem of forming foreign matter in the film forming process because metal Sb particles precipitated in the course of the polymerization reaction are included in the PET. In addition, the Ge catalyst is expensive and inevitably increases in cost, has low solubility in ethylene glycol, and has a problem that minute insoluble matter remains in the PET and causes die lip contamination in the extrusion process. In this respect, a Ti catalyst system is preferable, and a PET resin polymerized with a Ti catalyst tends to have lower terminal COOH groups than Sb and Ge. For example, when used for a solar cell protective sheet requiring hydrolysis resistance. Is preferred.
Ti系化合物を用いたポリエステルの合成には、例えば、特公平8-301198号公報、特許第2543624号、特許第3335683号、特許第3717380号、特許第3897756号、特許第3962226号、特許第3979866号、特許第3996871号、特許第4000867号、特許第4053837号、特許第4127119号、特許第4134710号、特許第4159154号、特許第4269704号、特許第4313538号各公報等に記載の方法を適用できる。
Examples of the synthesis of polyester using a Ti compound include Japanese Patent Publication No. 8-301198, Japanese Patent No. 2543624, Japanese Patent No. 3335683, Japanese Patent No. 3717380, Japanese Patent No. 3897756, Japanese Patent No. 396226, and Japanese Patent No. 39786666. , Patent No. 3996871, Patent No. 40000867, Patent No. 4053837, Patent No. 4127119, Patent No. 4134710, Patent No. 4159154, Patent No. 4269704, Patent No. 4135538, etc. it can.
本発明の製造方法で得られたポリエステルフィルムを太陽電池保護シートに用いる場合では、前記樹脂フィルム基材がポリエステル系樹脂を含み、前記ポリエステル中のカルボキシル基含量は35当量/t以下が好ましく、より好ましくは20当量/t以下である。カルボキシル基含量が35当量/t以下であると、耐加水分解性を保持し、湿熱経時したときの強度低下を小さく抑制することができる。カルボキシル基含量の下限は、ポリエステルに形成される層(例えば着色層)との間の密着性を保持する点で、2当量/tが望ましい。すなわち、本発明では、前記ポリエステル樹脂のカルボキシル基の含量が2~20当量/tであることが特に好ましい。
ポリエステル中のカルボキシル基含量は、重合条件(触媒種類や重合温度、槽内圧力)、製膜条件(製膜温度や時間)により調整することが可能である。 In the case where the polyester film obtained by the production method of the present invention is used for a solar cell protective sheet, the resin film substrate contains a polyester-based resin, and the carboxyl group content in the polyester is preferably 35 equivalents / t or less. Preferably it is 20 equivalent / t or less. When the carboxyl group content is 35 equivalents / t or less, hydrolysis resistance can be maintained, and a decrease in strength when subjected to wet heat aging can be suppressed to be small. The lower limit of the carboxyl group content is preferably 2 equivalents / t in terms of maintaining adhesion between the layer formed on the polyester (for example, a colored layer). That is, in the present invention, the content of carboxyl groups in the polyester resin is particularly preferably 2 to 20 equivalent / t.
The carboxyl group content in the polyester can be adjusted by polymerization conditions (catalyst type, polymerization temperature, tank pressure) and film formation conditions (film formation temperature and time).
ポリエステル中のカルボキシル基含量は、重合条件(触媒種類や重合温度、槽内圧力)、製膜条件(製膜温度や時間)により調整することが可能である。 In the case where the polyester film obtained by the production method of the present invention is used for a solar cell protective sheet, the resin film substrate contains a polyester-based resin, and the carboxyl group content in the polyester is preferably 35 equivalents / t or less. Preferably it is 20 equivalent / t or less. When the carboxyl group content is 35 equivalents / t or less, hydrolysis resistance can be maintained, and a decrease in strength when subjected to wet heat aging can be suppressed to be small. The lower limit of the carboxyl group content is preferably 2 equivalents / t in terms of maintaining adhesion between the layer formed on the polyester (for example, a colored layer). That is, in the present invention, the content of carboxyl groups in the polyester resin is particularly preferably 2 to 20 equivalent / t.
The carboxyl group content in the polyester can be adjusted by polymerization conditions (catalyst type, polymerization temperature, tank pressure) and film formation conditions (film formation temperature and time).
(固相重合)
上記の重縮合工程を終了した後には、得られたポリエステル樹脂をペレット状等に加工し、これを用いて固相重合を行なってもよい。
固相重合は、連続法(タワーの中に樹脂を充満させ、これを加熱しながらゆっくり所定の時間滞流させた後、順次送り出す方法)でもよく、バッチ法(容器の中に樹脂を投入し、所定の時間加熱する方法)でもよい。具体的には、固相重合として、特許第2621563号、特許第3121876号、特許第3136774号、特許第3603585号、特許第3616522号、特許第3617340号、特許第3680523号、特許第3717392号、特許第4167159号等に記載の方法を用いることができる。
固相重合の温度は、170℃以上240℃以下が好ましく、より好ましくは180℃以上230℃以下であり、さらに好ましくは190℃以上220℃以下である。温度が上記範囲内であると、耐加水分解性を達成する上で好ましい。また、固相重合時間は、5時間以上100時間以下が好ましく、より好ましくは10時間以上75時間以下であり、さらに好ましくは15時間以上50時間以下である。時間が上記範囲内であると、耐加水分解性を達成する上で好ましい。固相重合は、真空中あるいは窒素雰囲気下で行なうことが好ましい。
固相重合後のポリエステル樹脂組成物のIVとしては、0.65以上の範囲が好ましく、より好ましくは0.70以上の範囲がより好ましい。
ポリエステルがポリエチレンテレフタレートであれば固相重合後のポリエステル樹脂組成物のIVは、0.90以下が好ましく、0.85以下がより好ましい。また、ポリエステルがポリ(1,4-シクロヘキシレンジメチレンテレフタレート)であれば固相重合後のポリエステル樹脂組成物のIVの好ましい範囲の上限は1.2、より好ましくは1.15、さらに好ましくは1.1である。
このような熱処理は低酸素雰囲気下で行うのが好ましく、例えば窒素雰囲気下または真空中で行うことが好ましい。 (Solid phase polymerization)
After the polycondensation step is completed, the obtained polyester resin may be processed into a pellet and the like, and solid phase polymerization may be performed using this.
Solid-phase polymerization may be a continuous method (a method in which a tower is filled with a resin, which is slowly heated for a predetermined time while being heated, and then sent out sequentially), or a batch method (a resin is charged into a container). , A method of heating for a predetermined time). Specifically, as solid phase polymerization, Japanese Patent No. 2621563, Japanese Patent No. 3121876, Japanese Patent No. 3136774, Japanese Patent No. 3603585, Japanese Patent No. 3616522, Japanese Patent No. 3617340, Japanese Patent No. 3680523, Japanese Patent No. 3717392, The method described in Japanese Patent No. 4167159 can be used.
The temperature of the solid phase polymerization is preferably 170 ° C. or higher and 240 ° C. or lower, more preferably 180 ° C. or higher and 230 ° C. or lower, and further preferably 190 ° C. or higher and 220 ° C. or lower. When the temperature is within the above range, it is preferable for achieving hydrolysis resistance. The solid phase polymerization time is preferably 5 hours to 100 hours, more preferably 10 hours to 75 hours, and still more preferably 15 hours to 50 hours. When the time is within the above range, it is preferable for achieving hydrolysis resistance. The solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
As IV of the polyester resin composition after solid-phase polymerization, the range of 0.65 or more is preferable, More preferably, the range of 0.70 or more is more preferable.
If the polyester is polyethylene terephthalate, the IV of the polyester resin composition after solid phase polymerization is preferably 0.90 or less, and more preferably 0.85 or less. If the polyester is poly (1,4-cyclohexylenedimethylene terephthalate), the upper limit of the preferred range of IV of the polyester resin composition after solid phase polymerization is 1.2, more preferably 1.15, and even more preferably 1.1.
Such heat treatment is preferably performed in a low oxygen atmosphere, for example, in a nitrogen atmosphere or in a vacuum.
上記の重縮合工程を終了した後には、得られたポリエステル樹脂をペレット状等に加工し、これを用いて固相重合を行なってもよい。
固相重合は、連続法(タワーの中に樹脂を充満させ、これを加熱しながらゆっくり所定の時間滞流させた後、順次送り出す方法)でもよく、バッチ法(容器の中に樹脂を投入し、所定の時間加熱する方法)でもよい。具体的には、固相重合として、特許第2621563号、特許第3121876号、特許第3136774号、特許第3603585号、特許第3616522号、特許第3617340号、特許第3680523号、特許第3717392号、特許第4167159号等に記載の方法を用いることができる。
固相重合の温度は、170℃以上240℃以下が好ましく、より好ましくは180℃以上230℃以下であり、さらに好ましくは190℃以上220℃以下である。温度が上記範囲内であると、耐加水分解性を達成する上で好ましい。また、固相重合時間は、5時間以上100時間以下が好ましく、より好ましくは10時間以上75時間以下であり、さらに好ましくは15時間以上50時間以下である。時間が上記範囲内であると、耐加水分解性を達成する上で好ましい。固相重合は、真空中あるいは窒素雰囲気下で行なうことが好ましい。
固相重合後のポリエステル樹脂組成物のIVとしては、0.65以上の範囲が好ましく、より好ましくは0.70以上の範囲がより好ましい。
ポリエステルがポリエチレンテレフタレートであれば固相重合後のポリエステル樹脂組成物のIVは、0.90以下が好ましく、0.85以下がより好ましい。また、ポリエステルがポリ(1,4-シクロヘキシレンジメチレンテレフタレート)であれば固相重合後のポリエステル樹脂組成物のIVの好ましい範囲の上限は1.2、より好ましくは1.15、さらに好ましくは1.1である。
このような熱処理は低酸素雰囲気下で行うのが好ましく、例えば窒素雰囲気下または真空中で行うことが好ましい。 (Solid phase polymerization)
After the polycondensation step is completed, the obtained polyester resin may be processed into a pellet and the like, and solid phase polymerization may be performed using this.
Solid-phase polymerization may be a continuous method (a method in which a tower is filled with a resin, which is slowly heated for a predetermined time while being heated, and then sent out sequentially), or a batch method (a resin is charged into a container). , A method of heating for a predetermined time). Specifically, as solid phase polymerization, Japanese Patent No. 2621563, Japanese Patent No. 3121876, Japanese Patent No. 3136774, Japanese Patent No. 3603585, Japanese Patent No. 3616522, Japanese Patent No. 3617340, Japanese Patent No. 3680523, Japanese Patent No. 3717392, The method described in Japanese Patent No. 4167159 can be used.
The temperature of the solid phase polymerization is preferably 170 ° C. or higher and 240 ° C. or lower, more preferably 180 ° C. or higher and 230 ° C. or lower, and further preferably 190 ° C. or higher and 220 ° C. or lower. When the temperature is within the above range, it is preferable for achieving hydrolysis resistance. The solid phase polymerization time is preferably 5 hours to 100 hours, more preferably 10 hours to 75 hours, and still more preferably 15 hours to 50 hours. When the time is within the above range, it is preferable for achieving hydrolysis resistance. The solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
As IV of the polyester resin composition after solid-phase polymerization, the range of 0.65 or more is preferable, More preferably, the range of 0.70 or more is more preferable.
If the polyester is polyethylene terephthalate, the IV of the polyester resin composition after solid phase polymerization is preferably 0.90 or less, and more preferably 0.85 or less. If the polyester is poly (1,4-cyclohexylenedimethylene terephthalate), the upper limit of the preferred range of IV of the polyester resin composition after solid phase polymerization is 1.2, more preferably 1.15, and even more preferably 1.1.
Such heat treatment is preferably performed in a low oxygen atmosphere, for example, in a nitrogen atmosphere or in a vacuum.
固相重合は、バッチ式(容器内に樹脂を入れ、この中で所定の時間熱を与えながら撹拌する方式)で実施してもよく、連続式(加熱した筒の中に樹脂を入れ、これを加熱しながら所定の時間滞流させながら筒中を通過させて、順次送り出す方式)で実施してもよい。
Solid-phase polymerization may be carried out in a batch mode (a method in which a resin is placed in a container and stirred while applying heat for a predetermined time), or a continuous mode (a resin is placed in a heated cylinder and this is stirred). It may be carried out by a system in which the gas is passed through the cylinder while being kept flowing for a predetermined time while being heated, and sequentially fed out.
(カルボジイミド化合物)
カルボジイミド化合物はポリエステルの末端基を封止してポリエステルフィルムの耐加水分解性を向上させるものであり、本発明の樹脂フィルム基材の塗布層との密着改良効果には直接関係しないものの、本発明のポリエステルフィルムを太陽電池バックシート用に使用する場合は前記樹脂フィルム基材がカルボジイミド化合物を含むことが好ましい。
前記カルボジイミド化合物の中でも、環状カルボジイミドが好ましい。 (Carbodiimide compound)
The carbodiimide compound is intended to seal the terminal group of the polyester to improve the hydrolysis resistance of the polyester film and is not directly related to the effect of improving the adhesion with the coating layer of the resin film substrate of the present invention. When the polyester film is used for a solar battery back sheet, the resin film substrate preferably contains a carbodiimide compound.
Among the carbodiimide compounds, cyclic carbodiimide is preferable.
カルボジイミド化合物はポリエステルの末端基を封止してポリエステルフィルムの耐加水分解性を向上させるものであり、本発明の樹脂フィルム基材の塗布層との密着改良効果には直接関係しないものの、本発明のポリエステルフィルムを太陽電池バックシート用に使用する場合は前記樹脂フィルム基材がカルボジイミド化合物を含むことが好ましい。
前記カルボジイミド化合物の中でも、環状カルボジイミドが好ましい。 (Carbodiimide compound)
The carbodiimide compound is intended to seal the terminal group of the polyester to improve the hydrolysis resistance of the polyester film and is not directly related to the effect of improving the adhesion with the coating layer of the resin film substrate of the present invention. When the polyester film is used for a solar battery back sheet, the resin film substrate preferably contains a carbodiimide compound.
Among the carbodiimide compounds, cyclic carbodiimide is preferable.
-環状カルボジイミド-
本発明のポリエステルフィルムの製造方法に用いられる前記樹脂フィルム基材は、カルボジイミド基を1個有し、その第一窒素と第二窒素とが結合基により結合されている環状構造を含む化合物を含むことが好ましい。前記カルボジイミド基を1個有し、その第一窒素と第二窒素とが結合基により結合されている環状構造を含む化合物は、いわゆる末端封止剤として前記ポリエステルの末端カルボキシル基を封止して、ポリエステルフィルムの湿熱耐久性を改善することができる。 -Cyclic carbodiimide-
The said resin film base material used for the manufacturing method of the polyester film of this invention contains the compound which has one carbodiimide group and the cyclic structure by which the 1st nitrogen and the 2nd nitrogen are couple | bonded by the coupling group. It is preferable. A compound having a cyclic structure in which one carbodiimide group and the first nitrogen and the second nitrogen are bonded by a linking group is used to seal the terminal carboxyl group of the polyester as a so-called terminal blocking agent. The wet heat durability of the polyester film can be improved.
本発明のポリエステルフィルムの製造方法に用いられる前記樹脂フィルム基材は、カルボジイミド基を1個有し、その第一窒素と第二窒素とが結合基により結合されている環状構造を含む化合物を含むことが好ましい。前記カルボジイミド基を1個有し、その第一窒素と第二窒素とが結合基により結合されている環状構造を含む化合物は、いわゆる末端封止剤として前記ポリエステルの末端カルボキシル基を封止して、ポリエステルフィルムの湿熱耐久性を改善することができる。 -Cyclic carbodiimide-
The said resin film base material used for the manufacturing method of the polyester film of this invention contains the compound which has one carbodiimide group and the cyclic structure by which the 1st nitrogen and the 2nd nitrogen are couple | bonded by the coupling group. It is preferable. A compound having a cyclic structure in which one carbodiimide group and the first nitrogen and the second nitrogen are bonded by a linking group is used to seal the terminal carboxyl group of the polyester as a so-called terminal blocking agent. The wet heat durability of the polyester film can be improved.
本発明のポリエステルフィルムの製造方法に用いられる前記樹脂フィルム基材は、前記ポリエステル100質量部に対して、前記カルボジイミド基を1個有し、その第一窒素と第二窒素とが結合基により結合されている環状構造を含む化合物を0.05~20質量部含むことが好ましい。
The said resin film base material used for the manufacturing method of the polyester film of this invention has one said carbodiimide group with respect to 100 mass parts of said polyester, The 1st nitrogen and the 2nd nitrogen couple | bond together by a coupling group. It is preferable to contain 0.05 to 20 parts by mass of the compound having a cyclic structure.
本発明のポリエステルフィルムの製造方法に用いられる前記樹脂フィルム基材は、前記カルボジイミド基を1個有し、その第一窒素と第二窒素とが結合基により結合されている環状構造を含む化合物の分子量が400以上であることが好ましく、500~1500であることがより好ましい。
The said resin film base material used for the manufacturing method of the polyester film of this invention has one carbodiimide group, The compound containing the cyclic structure with which the 1st nitrogen and the 2nd nitrogen are couple | bonded by the coupling group. The molecular weight is preferably 400 or more, more preferably 500 to 1500.
前記カルボジイミド基を1個有し、その第一窒素と第二窒素とが結合基により結合されている環状構造を含む化合物は、環状構造を複数有していてもよい。
The compound having a cyclic structure in which one carbodiimide group is included and the first nitrogen and the second nitrogen are bonded to each other through a bonding group may have a plurality of cyclic structures.
環状構造は、カルボジイミド基(-N=C=N-)を1個有しその第一窒素と第二窒素とが結合基により結合されている。一つの環状構造中には、1個のカルボジイミド基のみを有するが、例えば、スピロ環など、分子中に複数の環状構造を有する場合にはスピロ原子に結合するそれぞれの環状構造中に1個のカルボジイミド基を有していれば、化合物として複数のカルボジイミド基を有していてよいことはいうまでもない。環状構造中の原子数は、好ましくは8~50、より好ましくは10~30、さらに好ましくは10~20、特に、10~15が好ましい。
The cyclic structure has one carbodiimide group (—N═C═N—), and the first nitrogen and the second nitrogen are bonded by a bonding group. One cyclic structure has only one carbodiimide group. For example, when there are a plurality of cyclic structures in the molecule, such as a spiro ring, one cyclic structure bonded to a spiro atom is included in each cyclic structure. Needless to say, the compound may have a plurality of carbodiimide groups as long as it has a carbodiimide group. The number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and particularly preferably 10 to 15.
ここで、環状構造中の原子数とは、環状構造を直接構成する原子の数を意味し、例えば、8員環であれば8、50員環であれば50である。環状構造中の原子数が8より小さいと、環状カルボジイミド化合物の安定性が低下して、保管、使用が困難となる場合があるためである。また反応性の観点よりは環員数の上限値に関しては特別の制限はないが、50を超える原子数の環状カルボジイミド化合物は合成上困難となり、コストが大きく上昇する場合が発生するためである。かかる観点より環状構造中の原子数は好ましくは、10~30、より好ましくは10~20、特に好ましくは10~15の範囲が選択される。
Here, the number of atoms in the cyclic structure means the number of atoms directly constituting the cyclic structure, and is, for example, 8 for an 8-membered ring and 50 for a 50-membered ring. This is because if the number of atoms in the cyclic structure is smaller than 8, the stability of the cyclic carbodiimide compound is lowered, and it may be difficult to store and use. From the viewpoint of reactivity, there is no particular restriction on the upper limit of the number of ring members, but cyclic carbodiimide compounds having more than 50 atoms are difficult to synthesize, and the cost may increase significantly. From this viewpoint, the number of atoms in the cyclic structure is preferably selected in the range of 10 to 30, more preferably 10 to 20, and particularly preferably 10 to 15.
環状構造は、下記式(1)で表される構造であることが好ましい。
The ring structure is preferably a structure represented by the following formula (1).
式中、Qは、それぞれヘテロ原子ならびに置換基を含んでいてもよい、脂肪族基、脂環族基、芳香族基またはこれらの組み合わせである2~4価の結合基である。ヘテロ原子とはこの場合、O、N、S、Pを指す。この結合基の価のうち2つの価は環状構造を形成するために使用される。Qが3価あるいは4価の結合基である場合、単結合、二重結合、原子、原子団を介して、ポリマーあるいは他の環状構造と結合している。
In the formula, Q is a divalent to tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, each of which may contain a hetero atom and a substituent. A heteroatom in this case refers to O, N, S, P. Two of the valences of this linking group are used to form a cyclic structure. When Q is a trivalent or tetravalent linking group, it is bonded to a polymer or other cyclic structure via a single bond, a double bond, an atom, or an atomic group.
結合基は、それぞれヘテロ原子ならびに置換基を含んでいてもよい、2~4価の炭素数1~20の脂肪族基、2~4価の炭素数3~20の脂環族基、2~4価の炭素数5~15の芳香族基またはこれらの組み合わせであり、上記で規定される環状構造を形成するための必要炭素数を有する結合基が選択される。組み合わせの例としては、アルキレン基とアリーレン基が結合した、アルキレン-アリーレン基のような構造などが挙げられる。
結合基(Q)は、下記式(1-1)、(1-2)または(1-3)で表される2~4価の結合基であることが好ましい。 The linking group may contain a heteroatom and a substituent, respectively, a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent carbon group having 3 to 20 alicyclic groups, 2 to A linking group which is a tetravalent aromatic group having 5 to 15 carbon atoms or a combination thereof and has a necessary number of carbon atoms to form the cyclic structure defined above is selected. Examples of the combination include an alkylene-arylene group structure in which an alkylene group and an arylene group are bonded.
The linking group (Q) is preferably a divalent to tetravalent linking group represented by the following formula (1-1), (1-2) or (1-3).
結合基(Q)は、下記式(1-1)、(1-2)または(1-3)で表される2~4価の結合基であることが好ましい。 The linking group may contain a heteroatom and a substituent, respectively, a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent carbon group having 3 to 20 alicyclic groups, 2 to A linking group which is a tetravalent aromatic group having 5 to 15 carbon atoms or a combination thereof and has a necessary number of carbon atoms to form the cyclic structure defined above is selected. Examples of the combination include an alkylene-arylene group structure in which an alkylene group and an arylene group are bonded.
The linking group (Q) is preferably a divalent to tetravalent linking group represented by the following formula (1-1), (1-2) or (1-3).
式中、Ar1およびAr2は各々独立に、それぞれヘテロ原子ならびに置換基を含んでいてもよい、2~4価の炭素数5~15の芳香族基である。
芳香族基として、それぞれへテロ原子を含んで複素環構造を持っていてもよい、炭素数5~15のアリーレン基、炭素数5~15のアレーントリイル基、炭素数5~15のアレーンテトライル基が挙げられる。アリーレン基(2価)として、フェニレン基、ナフタレンジイル基などが挙げられる。アレーントリイル基(3価)として、ベンゼントリイル基、ナフタレントリイル基などが挙げられる。アレーンテトライル基(4価)として、ベンゼンテトライル基、ナフタレンテトライル基などが挙げられる。これらの芳香族基は置換されていても良い。置換基として、炭素数1~20のアルキル基、炭素数6~15のアリール基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。 In the formula, Ar 1 and Ar 2 are each independently a divalent to tetravalent aromatic group having 5 to 15 carbon atoms which may contain a hetero atom and a substituent.
As an aromatic group, each of which may contain a hetero atom and have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group (divalent) include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
芳香族基として、それぞれへテロ原子を含んで複素環構造を持っていてもよい、炭素数5~15のアリーレン基、炭素数5~15のアレーントリイル基、炭素数5~15のアレーンテトライル基が挙げられる。アリーレン基(2価)として、フェニレン基、ナフタレンジイル基などが挙げられる。アレーントリイル基(3価)として、ベンゼントリイル基、ナフタレントリイル基などが挙げられる。アレーンテトライル基(4価)として、ベンゼンテトライル基、ナフタレンテトライル基などが挙げられる。これらの芳香族基は置換されていても良い。置換基として、炭素数1~20のアルキル基、炭素数6~15のアリール基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。 In the formula, Ar 1 and Ar 2 are each independently a divalent to tetravalent aromatic group having 5 to 15 carbon atoms which may contain a hetero atom and a substituent.
As an aromatic group, each of which may contain a hetero atom and have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group (divalent) include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
R1およびR2は各々独立に、それぞれヘテロ原子ならびに置換基を含んでいてもよい、2~4価の炭素数1~20の脂肪族基、2~4価の炭素数3~20の脂環族基、およびこれらの組み合わせ、またはこれら脂肪族基、脂環族基と2~4価の炭素数5~15の芳香族基の組み合わせである。
R 1 and R 2 are each independently a heteroatom and a substituent, and may be a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, or a divalent to tetravalent carbon atom having 3 to 20 carbon atoms. A cyclic group, and a combination thereof, or a combination of the aliphatic group, the alicyclic group, and a divalent to tetravalent aromatic group having 5 to 15 carbon atoms.
脂肪族基として、炭素数1~20のアルキレン基、炭素数1~20のアルカントリイル基、炭素数1~20のアルカンテトライル基などが挙げられる。アルキレン基として、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、へプチレン基、オクチレン基、ノニレン基、デシレン基、ドデシレン基、へキサデシレン基などが挙げられる。アルカントリイル基として、メタントリイル基、エタントリイル基、プロパントリイル基、ブタントリイル基、ペンタントリイル基、ヘキサントリイル基、ヘプタントリイル基、オクタントリイル基、ノナントリイル基、デカントリイル基、ドデカントリイル基、ヘキサデカントリイル基などが挙げられる。アルカンテトライル基として、メタンテトライル基、エタンテトライル基、プロパンテトライル基、ブタンテトライル基、ペンタンテトライル基、ヘキサンテトライル基、ヘプタンテトライル基、オクタンテトライル基、ノナンテトライル基、デカンテトライル基、ドデカンテトライル基、ヘキサデカンテトライル基などが挙げられる。これらの脂肪族基は置換されていても良い。置換基として、炭素数1~20のアルキル基、炭素数6~15のアリール基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。
Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
脂環族基として、炭素数3~20のシクロアルキレン基、炭素数3~20のシクロアルカントリイル基、炭素数3~20のシクロアルカンテトライル基が挙げられる。シクロアルキレン基として、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、シクロへプチレン基、シクロオクチレン基、シクロノニレン基、シクロデシレン基、シクロドデシレン基、シクロへキサデシレン基などが挙げられる。アルカントリイル基として、シクロプロパントリイル基、シクロブタントリイル基、シクロペンタントリイル基、シクロヘキサントリイル基、シクロヘプタントリイル基、シクロオクタントリイル基、シクロノナントリイル基、シクロデカントリイル基、シクロドデカントリイル基、シクロヘキサデカントリイル基などが挙げられる。アルカンテトライル基として、シクロプロパンテトライル基、シクロブタンテトライル基、シクロペンタンテトライル基、シクロヘキサンテトライル基、シクロヘプタンテトライル基、シクロオクタンテトライル基、シクロノナンテトライル基、シクロデカンテトライル基、シクロドデカンテトライル基、シクロヘキサデカンテトライル基などが挙げられる。これらの脂環族基は置換されていても良い。置換基として、炭素数1~20のアルキル基、炭素数6~15のアリール基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。
Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
芳香族基として、それぞれへテロ原子を含んで複素環構造を持っていてもよい、炭素数5~15のアリーレン基、炭素数5~15のアレーントリイル基、炭素数5~15のアレーンテトライル基が挙げられる。アリーレン基として、フェニレン基、ナフタレンジイル基などが挙げられる。アレーントリイル基(3価)として、ベンゼントリイル基、ナフタレントリイル基などが挙げられる。アレーンテトライル基(4価)として、ベンゼンテトライル基、ナフタレンテトライル基などが挙げられる。これら芳香族基は置換されていても良い。置換基として、炭素数1~20のアルキル基、炭素数6~15のアリール基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。
As an aromatic group, each of which may contain a hetero atom and have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
上記式(1-1)、(1-2)においてX1およびX2は各々独立に、それぞれヘテロ原子ならびに置換基を含んでいてもよい、2~4価の炭素数1~20の脂肪族基、2~4価の炭素数3~20の脂環族基、2~4価の炭素数5~15の芳香族基、またはこれらの組み合わせである。
In the above formulas (1-1) and (1-2), X 1 and X 2 are each independently a divalent to tetravalent C 1-20 aliphatic optionally containing a hetero atom and a substituent. Group, a bivalent to tetravalent alicyclic group having 3 to 20 carbon atoms, a divalent to tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof.
脂肪族基として、炭素数1~20のアルキレン基、炭素数1~20のアルカントリイル基、炭素数1~20のアルカンテトライル基などが挙げられる。アルキレン基として、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、へプチレン基、オクチレン基、ノニレン基、デシレン基、ドデシレン基、へキサデシレン基などが挙げられる。アルカントリイル基として、メタントリイル基、エタントリイル基、プロパントリイル基、ブタントリイル基、ペンタントリイル基、ヘキサントリイル基、ヘプタントリイル基、オクタントリイル基、ノナントリイル基、デカントリイル基、ドデカントリイル基、ヘキサデカントリイル基などが挙げられる。アルカンテトライル基として、メタンテトライル基、エタンテトライル基、プロパンテトライル基、ブタンテトライル基、ペンタンテトライル基、ヘキサンテトライル基、ヘプタンテトライル基、オクタンテトライル基、ノナンテトライル基、デカンテトライル基、ドデカンテトライル基、ヘキサデカンテトライル基などが挙げられる。これらの脂肪族基は置換されていても良い。置換基として、炭素数1~20のアルキル基、炭素数6~15のアリール基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。
Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
脂環族基として、炭素数3~20のシクロアルキレン基、炭素数3~20のシクロアルカントリイル基、炭素数3~20のシクロアルカンテトライル基が挙げられる。シクロアルキレン基として、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、シクロへプチレン基、シクロオクチレン基、シクロノニレン基、シクロデシレン基、シクロドデシレン基、シクロへキサデシレン基などが挙げられる。アルカントリイル基として、シクロプロパントリイル基、シクロブタントリイル基、シクロペンタントリイル基、シクロヘキサントリイル基、シクロヘプタントリイル基、シクロオクタントリイル基、シクロノナントリイル基、シクロデカントリイル基、シクロドデカントリイル基、シクロヘキサデカントリイル基などが挙げられる。アルカンテトライル基として、シクロプロパンテトライル基、シクロブタンテトライル基、シクロペンタンテトライル基、シクロヘキサンテトライル基、シクロヘプタンテトライル基、シクロオクタンテトライル基、シクロノナンテトライル基、シクロデカンテトライル基、シクロドデカンテトライル基、シクロヘキサデカンテトライル基などが挙げられる。これらの脂環族基は置換されていてもよい。置換基として、炭素数1~20のアルキル基、炭素数6~15のアリール基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。
Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
芳香族基として、それぞれへテロ原子を含んで複素環構造を持っていてもよい、炭素数5~15のアリーレン基、炭素数5~15のアレーントリイル基、炭素数5~15のアレーンテトライル基が挙げられる。アリーレン基として、フェニレン基、ナフタレンジイル基などが挙げられる。アレーントリイル基(3価)として、ベンゼントリイル基、ナフタレントリイル基などが挙げられる。アレーンテトライル基(4価)として、ベンゼンテトライル基、ナフタレンテトライル基などが挙げられる。これらの芳香族基は置換されていても良い。置換基として、炭素数1~20のアルキル基、炭素数6~15のアリール基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。
As an aromatic group, each of which may contain a hetero atom and have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
上記式(1-1)、(1-2)においてs、kは0~10の整数、好ましくは0~3の整数、より好ましくは0~1の整数である。s及びkが10を超えると、環状カルボジイミド化合物は合成上困難となり、コストが大きく上昇する場合が発生するためである。かかる観点より整数は好ましくは0~3の範囲が選択される。なお、sまたはkが2以上であるとき、繰り返し単位としてのX1、あるいはX2が、他のX1、あるいはX2と異なっていてもよい。
In the above formulas (1-1) and (1-2), s and k are integers of 0 to 10, preferably integers of 0 to 3, and more preferably integers of 0 to 1. If s and k exceed 10, the cyclic carbodiimide compound is difficult to synthesize, and the cost may increase significantly. From this viewpoint, the integer is preferably in the range of 0 to 3. When s or k is 2 or more, X 1 or X 2 as a repeating unit may be different from other X 1 or X 2 .
上記式(1-3)においてX3は、それぞれヘテロ原子ならびに置換基を含んでいてもよい、2~4価の炭素数1~20の脂肪族基、2~4価の炭素数3~20の脂環族基、2~4価の炭素数5~15の芳香族基、またはこれらの組み合わせである。
In the above formula (1-3), X 3 may contain a heteroatom and a substituent, respectively, a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, and a divalent to tetravalent carbon number of 3 to 20 Or a combination thereof.
脂肪族基として、炭素数1~20のアルキレン基、炭素数1~20のアルカントリイル基、炭素数1~20のアルカンテトライル基などが挙げられる。アルキレン基として、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、へプチレン基、オクチレン基、ノニレン基、デシレン基、ドデシレン基、へキサデシレン基などが挙げられる。アルカントリイル基として、メタントリイル基、エタントリイル基、プロパントリイル基、ブタントリイル基、ペンタントリイル基、ヘキサントリイル基、ヘプタントリイル基、オクタントリイル基、ノナントリイル基、デカントリイル基、ドデカントリイル基、ヘキサデカントリイル基などが挙げられる。アルカンテトライル基として、メタンテトライル基、エタンテトライル基、プロパンテトライル基、ブタンテトライル基、ペンタンテトライル基、ヘキサンテトライル基、ヘプタンテトライル基、オクタンテトライル基、ノナンテトライル基、デカンテトライル基、ドデカンテトライル基、ヘキサデカンテトライル基などが挙げられる。これら脂肪族基は置換基を含んでいてもよく、置換基として、炭素数1~20のアルキル基、炭素数6~15のアリール基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。
Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may contain a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, and an ester group. , Ether group, aldehyde group and the like.
脂環族基として、炭素数3~20のシクロアルキレン基、炭素数3~20のシクロアルカントリイル基、炭素数3~20のシクロアルカンテトライル基が挙げられる。シクロアルキレン基として、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、シクロへプチレン基、シクロオクチレン基、シクロノニレン基、シクロデシレン基、シクロドデシレン基、シクロへキサデシレン基などが挙げられる。アルカントリイル基として、シクロプロパントリイル基、シクロブタントリイル基、シクロペンタントリイル基、シクロヘキサントリイル基、シクロヘプタントリイル基、シクロオクタントリイル基、シクロノナントリイル基、シクロデカントリイル基、シクロドデカントリイル基、シクロヘキサデカントリイル基などが挙げられる。アルカンテトライル基として、シクロプロパンテトライル基、シクロブタンテトライル基、シクロペンタンテトライル基、シクロヘキサンテトライル基、シクロヘプタンテトライル基、シクロオクタンテトライル基、シクロノナンテトライル基、シクロデカンテトライル基、シクロドデカンテトライル基、シクロヘキサデカンテトライル基などが挙げられる。これら脂環族基は置換基を含んでいてもよく、置換基として、炭素数1~20のアルキル基、炭素数6~15のアリーレン基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。
Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester. Group, ether group, aldehyde group and the like.
芳香族基として、それぞれへテロ原子を含んで複素環構造を持っていてもよい、炭素数5~15のアリーレン基、炭素数5~15のアレーントリイル基、炭素数5~15のアレーンテトライル基が挙げられる。アリーレン基として、フェニレン基、ナフタレンジイル基などが挙げられる。アレーントリイル基(3価)として、ベンゼントリイル基、ナフタレントリイル基などが挙げられる。アレーンテトライル基(4価)として、ベンゼンテトライル基、ナフタレンテトライル基などが挙げられる。これらの芳香族基は置換されていてもよい。置換基として、炭素数1~20のアルキル基、炭素数6~15のアリール基、ハロゲン原子、ニトロ基、アミド基、ヒドロキシル基、エステル基、エーテル基、アルデヒド基などが挙げられる。
As an aromatic group, each of which may contain a hetero atom and have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
また、Ar1、Ar2、R1、R2、X1、X2およびX3はヘテロ原子を含有していてもよい、また、Qが2価の結合基であるときは、Ar1、Ar2、R1、R2、X1、X2およびX3は全て2価の基である。Qが3価の結合基であるときは、Ar1、Ar2、R1、R2、X1、X2およびX3の内の一つが3価の基である。Qが4価の結合基であるときは、Ar1、Ar2、R1、R2、X1、X2およびX3の内の一つが4価の基であるか、二つが3価の基である。
Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 and X 3 may contain a hetero atom, and when Q is a divalent linking group, Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 and X 3 are all divalent groups. When Q is a trivalent linking group, one of Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 and X 3 is a trivalent group. When Q is a tetravalent linking group, one of Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 and X 3 is a tetravalent group, or two are trivalent It is a group.
本発明で用いる環状カルボジイミド化合物として、以下(a)~(c)で表される化合物が挙げられる。
Examples of the cyclic carbodiimide compound used in the present invention include compounds represented by the following (a) to (c).
--環状カルボジイミド化合物(a)--
本発明で用いる環状カルボジイミド化合物として下記式(2)で表される化合物(以下、「環状カルボジイミド化合物(a)」ということがある。)を挙げることができる。 -Cyclic carbodiimide compound (a)-
Examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (2) (hereinafter sometimes referred to as “cyclic carbodiimide compound (a)”).
本発明で用いる環状カルボジイミド化合物として下記式(2)で表される化合物(以下、「環状カルボジイミド化合物(a)」ということがある。)を挙げることができる。 -Cyclic carbodiimide compound (a)-
Examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (2) (hereinafter sometimes referred to as “cyclic carbodiimide compound (a)”).
式中、Qaは、脂肪族基、脂環族基、芳香族基またはこれらの組み合わせである2価の結合基であり、ヘテロ原子を含有していてもよい。脂肪族基、脂環族基、芳香族基は、式(1)で説明したものと同じである。但し、式(2)の化合物においては、脂肪族基、脂環族基、芳香族基は全て2価である。Qaは、下記式(2-1)、(2-2)または(2-3)で表される2価の結合基であることが好ましい。
Wherein, Q a is an aliphatic group, an alicyclic group, an aromatic group or a divalent linking group which is a combination of these, it may contain a heteroatom. The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of the formula (2), the aliphatic group, alicyclic group, and aromatic group are all divalent. Q a is preferably a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).
式中、Ara
1、Ara
2、Ra
1、Ra
2、Xa
1、Xa
2、Xa
3、sおよびkは、各々式(1-1)~(1-3)中のAr1、Ar2、R1、R2、X1、X2、X3、sおよびkと同じである。但し、これらは全て2価である。
かかる環状カルボジイミド化合物(a)としては、以下の化合物が挙げられる。 In the formula, Ar a 1 , Ar a 2 , R a 1 , R a 2 , X a 1 , X a 2 , X a 3 , s, and k are respectively in the formulas (1-1) to (1-3) Are the same as Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k. However, these are all divalent.
Examples of the cyclic carbodiimide compound (a) include the following compounds.
かかる環状カルボジイミド化合物(a)としては、以下の化合物が挙げられる。 In the formula, Ar a 1 , Ar a 2 , R a 1 , R a 2 , X a 1 , X a 2 , X a 3 , s, and k are respectively in the formulas (1-1) to (1-3) Are the same as Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k. However, these are all divalent.
Examples of the cyclic carbodiimide compound (a) include the following compounds.
--環状カルボジイミド化合物(b)--
さらに、本発明で用いる環状カルボジイミド化合物として下記式(3)で表される化合物(以下、「環状カルボジイミド化合物(b)」ということがある。)を挙げることができる。 -Cyclic carbodiimide compound (b)-
Furthermore, examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (3) (hereinafter sometimes referred to as “cyclic carbodiimide compound (b)”).
さらに、本発明で用いる環状カルボジイミド化合物として下記式(3)で表される化合物(以下、「環状カルボジイミド化合物(b)」ということがある。)を挙げることができる。 -Cyclic carbodiimide compound (b)-
Furthermore, examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (3) (hereinafter sometimes referred to as “cyclic carbodiimide compound (b)”).
式中、Qbは、脂肪族基、脂環族基、芳香族基、またはこれらの組み合わせである3価の結合基であり、ヘテロ原子を含有していてもよい。Yは、環状構造を担持する担体である。脂肪族基、脂環族基、芳香族基は、式(1)で説明したものと同じである。但し、式(3)の化合物においては、Qbを構成する基の内一つは3価である。
Qbは、下記式(3-1)、(3-2)または(3-3)で表される3価の結合基であることが好ましい。 Wherein, Q b is an aliphatic group, an alicyclic group, an aromatic group or a trivalent linking group combinations thereof, and may contain a hetero atom. Y is a carrier supporting a cyclic structure. The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (3), the inner one of the group constituting the Q b is trivalent.
Q b is preferably a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3).
Qbは、下記式(3-1)、(3-2)または(3-3)で表される3価の結合基であることが好ましい。 Wherein, Q b is an aliphatic group, an alicyclic group, an aromatic group or a trivalent linking group combinations thereof, and may contain a hetero atom. Y is a carrier supporting a cyclic structure. The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (3), the inner one of the group constituting the Q b is trivalent.
Q b is preferably a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3).
式中、Arb
1、Arb
2、Rb
1、Rb
2、Xb
1、Xb
2、Xb
3、sおよびkは、各々式(1-1)~(1-3)のAr1、Ar2、R1、R2、X1、X2、X3、sおよびkと同じである。但しこれらの内の一つは3価の基である。
Yは、単結合、二重結合、原子、原子団またはポリマーであることが好ましい。Yは結合部であり、複数の環状構造がYを介して結合し、式(3)で表される構造を形成している。
かかる環状カルボジイミド化合物(b)としては、下記化合物が挙げられる。 In the formula, Ar b 1 , Ar b 2 , R b 1 , R b 2 , X b 1 , X b 2 , X b 3 , s and k are respectively represented by the formulas (1-1) to (1-3) The same as Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k. However, one of these is a trivalent group.
Y is preferably a single bond, a double bond, an atom, an atomic group or a polymer. Y is a bonding portion, and a plurality of cyclic structures are bonded via Y to form a structure represented by the formula (3).
Examples of the cyclic carbodiimide compound (b) include the following compounds.
Yは、単結合、二重結合、原子、原子団またはポリマーであることが好ましい。Yは結合部であり、複数の環状構造がYを介して結合し、式(3)で表される構造を形成している。
かかる環状カルボジイミド化合物(b)としては、下記化合物が挙げられる。 In the formula, Ar b 1 , Ar b 2 , R b 1 , R b 2 , X b 1 , X b 2 , X b 3 , s and k are respectively represented by the formulas (1-1) to (1-3) The same as Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k. However, one of these is a trivalent group.
Y is preferably a single bond, a double bond, an atom, an atomic group or a polymer. Y is a bonding portion, and a plurality of cyclic structures are bonded via Y to form a structure represented by the formula (3).
Examples of the cyclic carbodiimide compound (b) include the following compounds.
--環状カルボジイミド化合物(c)--
本発明で用いる環状カルボジイミド化合物として下記式(4)で表される化合物(以下、「環状カルボジイミド化合物(c)」ということがある。)を挙げることができる。 -Cyclic carbodiimide compound (c)-
Examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (4) (hereinafter sometimes referred to as “cyclic carbodiimide compound (c)”).
本発明で用いる環状カルボジイミド化合物として下記式(4)で表される化合物(以下、「環状カルボジイミド化合物(c)」ということがある。)を挙げることができる。 -Cyclic carbodiimide compound (c)-
Examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (4) (hereinafter sometimes referred to as “cyclic carbodiimide compound (c)”).
式中、Qcは、脂肪族基、脂環族基、芳香族基またはこれらの組み合わせである4価の結合基であり、ヘテロ原子を保有していてもよい。Z1およびZ2は、環状構造を担持する担体である。Z1およびZ2は、互いに結合して環状構造を形成していてもよい。
脂肪族基、脂環族基、芳香族基は、式(1)で説明したものと同じである。但し、式(4)の化合物において、Qcは4価である。従って、これらの基の内の一つが4価の基であるか、二つが3価の基である。
Qcは、下記式(4-1)、(4-2)または(4-3)で表される4価の結合基であることが好ましい。 In the formula, Q c is a tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may have a hetero atom. Z 1 and Z 2 are carriers that support a cyclic structure. Z 1 and Z 2 may be bonded to each other to form a cyclic structure.
The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (4), Q c is tetravalent. Accordingly, one of these groups is a tetravalent group or two are trivalent groups.
Q c is preferably a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3).
脂肪族基、脂環族基、芳香族基は、式(1)で説明したものと同じである。但し、式(4)の化合物において、Qcは4価である。従って、これらの基の内の一つが4価の基であるか、二つが3価の基である。
Qcは、下記式(4-1)、(4-2)または(4-3)で表される4価の結合基であることが好ましい。 In the formula, Q c is a tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may have a hetero atom. Z 1 and Z 2 are carriers that support a cyclic structure. Z 1 and Z 2 may be bonded to each other to form a cyclic structure.
The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (4), Q c is tetravalent. Accordingly, one of these groups is a tetravalent group or two are trivalent groups.
Q c is preferably a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3).
Arc
1、Arc
2、Rc
1、Rc
2、Xc
1、Xc
2、Xc
3、sおよびkは、各々式(1-1)~(1-3)の、Ar1、Ar2、R1、R2、X1、X2、X3、sおよびkと同じである。但し、Arc
1、Arc
2、Rc
1、Rc
2、Xc
1、Xc
2およびXc
3は、これらの内の一つが4価の基であるか、二つが3価の基である。Z1およびZ2は各々独立に、単結合、二重結合、原子、原子団またはポリマーであることが好ましい。Z1およびZ2は結合部であり、複数の環状構造がZ1およびZ2を介して結合し、式(4)で表される構造を形成している。
かかる環状カルボジイミド化合物(c)としては、下記化合物を挙げることができる。 Ar c 1 , Ar c 2 , R c 1 , R c 2 , X c 1 , X c 2 , X c 3 , s and k are each Ar 1 in formulas (1-1) to (1-3). , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k are the same. Provided that Ar c 1 , Ar c 2 , R c 1 , R c 2 , X c 1 , X c 2 and X c 3 are one of which is a tetravalent group or two of which are trivalent It is a group. Z 1 and Z 2 are preferably each independently a single bond, a double bond, an atom, an atomic group or a polymer. Z 1 and Z 2 are bonding portions, and a plurality of cyclic structures are bonded via Z 1 and Z 2 to form a structure represented by the formula (4).
Examples of the cyclic carbodiimide compound (c) include the following compounds.
かかる環状カルボジイミド化合物(c)としては、下記化合物を挙げることができる。 Ar c 1 , Ar c 2 , R c 1 , R c 2 , X c 1 , X c 2 , X c 3 , s and k are each Ar 1 in formulas (1-1) to (1-3). , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k are the same. Provided that Ar c 1 , Ar c 2 , R c 1 , R c 2 , X c 1 , X c 2 and X c 3 are one of which is a tetravalent group or two of which are trivalent It is a group. Z 1 and Z 2 are preferably each independently a single bond, a double bond, an atom, an atomic group or a polymer. Z 1 and Z 2 are bonding portions, and a plurality of cyclic structures are bonded via Z 1 and Z 2 to form a structure represented by the formula (4).
Examples of the cyclic carbodiimide compound (c) include the following compounds.
-環状カルボジイミド化合物の製造方法-
前記環状カルボジイミド化合物は、特開2011-256337号公報に記載の方法などに基づいて合成することができる。 -Method for producing cyclic carbodiimide compound-
The cyclic carbodiimide compound can be synthesized based on the method described in JP2011-256337A.
前記環状カルボジイミド化合物は、特開2011-256337号公報に記載の方法などに基づいて合成することができる。 -Method for producing cyclic carbodiimide compound-
The cyclic carbodiimide compound can be synthesized based on the method described in JP2011-256337A.
(樹脂フィルム基材の成形)
上記の重縮合工程もしくは固相重合工程を終了した後、得られた既述の本発明のポリエステル樹脂組成物をフィルム状やシート状に成形することによって、ポリエステルフィルムを得ることができる。フィルム状やシート状に成形する場合、ポリエステル樹脂を例えばシリンダ内部にスクリュを備えた一軸混練押出機などの溶融押出機等を用いて溶融混練し、ダイから押出して成形することができる。このとき、好ましい成形温度は、250℃以上300℃以下の範囲、より好ましくは260℃以上290℃以下の範囲である。
押出し機は、一軸でも二軸でもよいが、前記カルボジイミド化合物を添加する場合は、一軸押出機で行うときは原料ポリエステル樹脂と前記カルボジイミド化合物を含有するマスターバッチをホッパー内で混合した状態で押し出すことが好ましく、二軸押出機で行うときはサイドフィーダーから前記マスターバッチを押出し、溶融状態で混合して押し出すことが好ましい。
剪断発熱による熱分解を抑制し、末端COOHの増加を抑制できるという点で二軸の方が好ましく、押出し機内を窒素置換して行なうのがより好ましい。 (Molding of resin film substrate)
After finishing the polycondensation step or the solid phase polymerization step, a polyester film can be obtained by molding the obtained polyester resin composition of the present invention into a film or sheet. When forming into a film form or a sheet form, the polyester resin can be melt-kneaded using, for example, a melt extruder such as a single-screw kneading extruder provided with a screw inside a cylinder, and extruded from a die. At this time, a preferable molding temperature is in a range of 250 ° C. or higher and 300 ° C. or lower, more preferably in a range of 260 ° C. or higher and 290 ° C. or lower.
The extruder may be uniaxial or biaxial, but when the carbodiimide compound is added, when the carbodiimide compound is added, the master batch containing the raw material polyester resin and the carbodiimide compound is extruded in a hopper. It is preferable to extrude the master batch from a side feeder when mixing with a twin screw extruder, and mix and extrude in a molten state.
Biaxial is preferable in that thermal decomposition due to shear heat generation can be suppressed and increase in terminal COOH can be suppressed, and it is more preferable to perform the nitrogen substitution inside the extruder.
上記の重縮合工程もしくは固相重合工程を終了した後、得られた既述の本発明のポリエステル樹脂組成物をフィルム状やシート状に成形することによって、ポリエステルフィルムを得ることができる。フィルム状やシート状に成形する場合、ポリエステル樹脂を例えばシリンダ内部にスクリュを備えた一軸混練押出機などの溶融押出機等を用いて溶融混練し、ダイから押出して成形することができる。このとき、好ましい成形温度は、250℃以上300℃以下の範囲、より好ましくは260℃以上290℃以下の範囲である。
押出し機は、一軸でも二軸でもよいが、前記カルボジイミド化合物を添加する場合は、一軸押出機で行うときは原料ポリエステル樹脂と前記カルボジイミド化合物を含有するマスターバッチをホッパー内で混合した状態で押し出すことが好ましく、二軸押出機で行うときはサイドフィーダーから前記マスターバッチを押出し、溶融状態で混合して押し出すことが好ましい。
剪断発熱による熱分解を抑制し、末端COOHの増加を抑制できるという点で二軸の方が好ましく、押出し機内を窒素置換して行なうのがより好ましい。 (Molding of resin film substrate)
After finishing the polycondensation step or the solid phase polymerization step, a polyester film can be obtained by molding the obtained polyester resin composition of the present invention into a film or sheet. When forming into a film form or a sheet form, the polyester resin can be melt-kneaded using, for example, a melt extruder such as a single-screw kneading extruder provided with a screw inside a cylinder, and extruded from a die. At this time, a preferable molding temperature is in a range of 250 ° C. or higher and 300 ° C. or lower, more preferably in a range of 260 ° C. or higher and 290 ° C. or lower.
The extruder may be uniaxial or biaxial, but when the carbodiimide compound is added, when the carbodiimide compound is added, the master batch containing the raw material polyester resin and the carbodiimide compound is extruded in a hopper. It is preferable to extrude the master batch from a side feeder when mixing with a twin screw extruder, and mix and extrude in a molten state.
Biaxial is preferable in that thermal decomposition due to shear heat generation can be suppressed and increase in terminal COOH can be suppressed, and it is more preferable to perform the nitrogen substitution inside the extruder.
溶融された前記ポリエステル樹脂の溶融樹脂(メルト)は、ギヤポンプ、濾過器等を通して、押出ダイから押出すことが好ましい。このとき、単層で押出してもよいし、多層で押出してもよい。
The molten resin (melt) of the polyester resin is preferably extruded from an extrusion die through a gear pump, a filter or the like. At this time, it may be extruded as a single layer or may be extruded as a multilayer.
本発明では、前記樹脂フィルム基材が、1,4-シクロヘキサンジメタノール(CHDM)由来の構造をジオール成分に含むCHDM系ポリエステルを含有する層を少なくとも1層有してもよい。なお、CHDM系ポリエステルとは、1,4-シクロヘキサンジメタノール(CHDM)由来の構造をジオール成分に含むポリエステルのことを言う。
In the present invention, the resin film substrate may have at least one layer containing a CHDM polyester containing a structure derived from 1,4-cyclohexanedimethanol (CHDM) as a diol component. The CHDM polyester refers to a polyester containing a structure derived from 1,4-cyclohexanedimethanol (CHDM) as a diol component.
-CHDM系ポリエステルを含有する層の組成-
前記CHDM系ポリエステルは、1,4-シクロヘキサンジメタノール由来の構造をジオール成分(全ジオール中)に、0.1~20モル%または80~100モル%含むことが好ましく、より好ましくは、0.5モル%以上16モル%以下あるいは83~100モル%含むことがより好ましく、1モル%以上12モル%以下あるいは86~100モル%含むことが特に好ましい。このようにCHDM由来の構造が低い領域(0.1~20モル%)、高い領域(80~100モル%)の二つの領域が存在するのは、この領域に於いてポリエステルが結晶構造を取りやすく、高い力学強度、耐熱性を発揮し易いためである。 -Composition of layer containing CHDM polyester-
The CHDM polyester preferably contains a structure derived from 1,4-cyclohexanedimethanol in a diol component (in all diols) in an amount of 0.1 to 20 mol% or 80 to 100 mol%, more preferably It is more preferably 5 mol% or more and 16 mol% or less or 83 to 100 mol%, and particularly preferably 1 mol% or more and 12 mol% or less or 86 to 100 mol%. Thus, there are two regions, a region having a low CHDM-derived structure (0.1 to 20 mol%) and a region having a high structure (80 to 100 mol%). In this region, the polyester has a crystalline structure. This is because it is easy to exhibit high mechanical strength and heat resistance.
前記CHDM系ポリエステルは、1,4-シクロヘキサンジメタノール由来の構造をジオール成分(全ジオール中)に、0.1~20モル%または80~100モル%含むことが好ましく、より好ましくは、0.5モル%以上16モル%以下あるいは83~100モル%含むことがより好ましく、1モル%以上12モル%以下あるいは86~100モル%含むことが特に好ましい。このようにCHDM由来の構造が低い領域(0.1~20モル%)、高い領域(80~100モル%)の二つの領域が存在するのは、この領域に於いてポリエステルが結晶構造を取りやすく、高い力学強度、耐熱性を発揮し易いためである。 -Composition of layer containing CHDM polyester-
The CHDM polyester preferably contains a structure derived from 1,4-cyclohexanedimethanol in a diol component (in all diols) in an amount of 0.1 to 20 mol% or 80 to 100 mol%, more preferably It is more preferably 5 mol% or more and 16 mol% or less or 83 to 100 mol%, and particularly preferably 1 mol% or more and 12 mol% or less or 86 to 100 mol%. Thus, there are two regions, a region having a low CHDM-derived structure (0.1 to 20 mol%) and a region having a high structure (80 to 100 mol%). In this region, the polyester has a crystalline structure. This is because it is easy to exhibit high mechanical strength and heat resistance.
前記CHDM系ポリエステルの1,4-シクロヘキサンジメタノール由来の構造以外のユニットを形成するための材料としては、ジオール成分として、1,2-プロパンジオール、1,3-プロパンジオール、1,4-ブタンジオール、1,2-ブタンジオール、1,3-ブタンジオール等の脂肪族ジオール類、スピログリコール、イソソルビドなどの脂環式ジオール類、ビスフェノールA、1,3―ベンゼンジメタノール,1,4-ベンセンジメタノール、9,9’-ビス(4-ヒドロキシフェニル)フルオレン、などの芳香族ジオール類等のジオールなどが代表例としてあげられるが、これらに限定されるものではない。その中でも、エチレングリコールを用いることが好ましい。
Materials for forming units other than the structure derived from 1,4-cyclohexanedimethanol of the CHDM polyester include 1,2-propanediol, 1,3-propanediol, 1,4-butane as diol components. Diols, aliphatic diols such as 1,2-butanediol and 1,3-butanediol, alicyclic diols such as spiroglycol and isosorbide, bisphenol A, 1,3-benzenedimethanol, 1,4-benzene Representative examples include diols such as aromatic diols such as dimethanol and 9,9′-bis (4-hydroxyphenyl) fluorene, but are not limited thereto. Among these, it is preferable to use ethylene glycol.
前記CHDM系ポリエステルの1,4-シクロヘキサンジメタノール由来の構造以外のユニットを形成するための材料としては、ジカルボン酸成分として、マロン酸、コハク酸、グルタル酸、アジピン酸、スベリン酸、セバシン酸、ドデカンジオン酸、ダイマー酸、エイコサンジオン酸、ピメリン酸、アゼライン酸、メチルマロン酸、エチルマロン酸等の脂肪族ジカルボン酸類、アダマンタンジカルボン酸、ノルボルネンジカルボン酸、イソソルビド、シクロヘキサンジカルボン酸、デカリンジカルボン酸、などの脂環族ジカルボン酸、イソフタル酸、フタル酸、1,4-ナフタレンジカルボン酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、1,8-ナフタレンジカルボン酸、4,4’-ジフェニルジカルボン酸、4,4’-ジフェニルエーテルジカルボン酸、5-ナトリウムスルホイソフタル酸、フェニルインダンジカルボン酸、アントラセンジカルボン酸、フェナントレンジカルボン酸、9,9’-ビス(4-カルボキシフェニル)フルオレン酸等芳香族ジカルボン酸などのジカルボン酸、もしくはそのエステル誘導体などが代表例としてあげられるが、これらに限定されるものではない。
前記CHDM系ポリエステルのジカルボン成分として、少なくともテレフタル酸由来の構造を含むことが好ましい。
本発明では前記CHDM系ポリエステルのジカルボン酸成分にテレフタル酸以外にイソフタル酸(IPA)を加えてもよい。好ましいIPA量は全ジカルボン酸中0モル%以上15モル%以下が好ましく、より好ましくは0モル%以上12モル%以下、さらに好ましくは0モル%以上9モル%以下である。 As a material for forming a unit other than the structure derived from 1,4-cyclohexanedimethanol of the CHDM-based polyester, as a dicarboxylic acid component, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, Aliphatic dicarboxylic acids such as dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, Such as alicyclic dicarboxylic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4 ′ -Diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylindane dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, aromatic dicarboxylic acid such as 9,9'-bis (4-carboxyphenyl) fluorenic acid, etc. A typical example is dicarboxylic acid or an ester derivative thereof, but it is not limited thereto.
The dicarboxylic component of the CHDM polyester preferably includes at least a structure derived from terephthalic acid.
In the present invention, isophthalic acid (IPA) may be added to the dicarboxylic acid component of the CHDM polyester in addition to terephthalic acid. The amount of IPA is preferably 0 mol% or more and 15 mol% or less, more preferably 0 mol% or more and 12 mol% or less, and still more preferably 0 mol% or more and 9 mol% or less in the total dicarboxylic acid.
前記CHDM系ポリエステルのジカルボン成分として、少なくともテレフタル酸由来の構造を含むことが好ましい。
本発明では前記CHDM系ポリエステルのジカルボン酸成分にテレフタル酸以外にイソフタル酸(IPA)を加えてもよい。好ましいIPA量は全ジカルボン酸中0モル%以上15モル%以下が好ましく、より好ましくは0モル%以上12モル%以下、さらに好ましくは0モル%以上9モル%以下である。 As a material for forming a unit other than the structure derived from 1,4-cyclohexanedimethanol of the CHDM-based polyester, as a dicarboxylic acid component, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, Aliphatic dicarboxylic acids such as dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, Such as alicyclic dicarboxylic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4 ′ -Diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylindane dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, aromatic dicarboxylic acid such as 9,9'-bis (4-carboxyphenyl) fluorenic acid, etc. A typical example is dicarboxylic acid or an ester derivative thereof, but it is not limited thereto.
The dicarboxylic component of the CHDM polyester preferably includes at least a structure derived from terephthalic acid.
In the present invention, isophthalic acid (IPA) may be added to the dicarboxylic acid component of the CHDM polyester in addition to terephthalic acid. The amount of IPA is preferably 0 mol% or more and 15 mol% or less, more preferably 0 mol% or more and 12 mol% or less, and still more preferably 0 mol% or more and 9 mol% or less in the total dicarboxylic acid.
-積層-
本発明では前記樹脂フィルム基材が前記CHDM系ポリエステルを含有する層を有していても有していなくてもよく、有している場合も単層であっても、2以上の層を有していてもよい。すなわち、前記CHDM系ポリエステルを含有する層以外のその他の層と積層されていてもよい。特にCHDM由来の構造が80~100モル%のとき、積層構造にすることが好ましい。これは、CHDM由来の構造の比率が高くなると、ポリエチレンテレフタレート(PET)に対し、耐候性(耐加水分解性)は高くなり易いが、力学強度が弱くなり易い。
このため、他のポリエステル(例えばPET)と積層することで相補することができ、好ましい。 -Lamination-
In the present invention, the resin film substrate may or may not have a layer containing the CHDM-based polyester. You may do it. That is, you may laminate | stack with other layers other than the layer containing the said CHDM type | system | group polyester. In particular, when the structure derived from CHDM is 80 to 100 mol%, a laminated structure is preferable. When the ratio of the structure derived from CHDM is increased, the weather resistance (hydrolysis resistance) is likely to be higher than that of polyethylene terephthalate (PET), but the mechanical strength is likely to be weakened.
For this reason, it can complement by laminating with other polyester (for example, PET), and is preferred.
本発明では前記樹脂フィルム基材が前記CHDM系ポリエステルを含有する層を有していても有していなくてもよく、有している場合も単層であっても、2以上の層を有していてもよい。すなわち、前記CHDM系ポリエステルを含有する層以外のその他の層と積層されていてもよい。特にCHDM由来の構造が80~100モル%のとき、積層構造にすることが好ましい。これは、CHDM由来の構造の比率が高くなると、ポリエチレンテレフタレート(PET)に対し、耐候性(耐加水分解性)は高くなり易いが、力学強度が弱くなり易い。
このため、他のポリエステル(例えばPET)と積層することで相補することができ、好ましい。 -Lamination-
In the present invention, the resin film substrate may or may not have a layer containing the CHDM-based polyester. You may do it. That is, you may laminate | stack with other layers other than the layer containing the said CHDM type | system | group polyester. In particular, when the structure derived from CHDM is 80 to 100 mol%, a laminated structure is preferable. When the ratio of the structure derived from CHDM is increased, the weather resistance (hydrolysis resistance) is likely to be higher than that of polyethylene terephthalate (PET), but the mechanical strength is likely to be weakened.
For this reason, it can complement by laminating with other polyester (for example, PET), and is preferred.
本発明のポリエステルフィルムは、前記CHDM系ポリエステルを含有する層(P1層と称する)と、ポリエチレンテレフタレートを主成分とするポリエステルを含有する層(P2層と称する)とが積層された態様も好ましい。
The polyester film of the present invention preferably has an aspect in which a layer containing the CHDM polyester (referred to as P1 layer) and a layer containing a polyester containing polyethylene terephthalate as a main component (referred to as P2 layer) are laminated.
P2層は、ジカルボン酸ユニット中テレフタル酸ユニットを95%以上有し、かつジオールユニット中エチレングリコールユニットを95モル%以上含むものをさす。
またP2層のIVは0.7以上0.9以下が好ましく、より好ましくは0.72以上0.85以下、さらに好ましくは0.74以上0.82以下である。このようにIVを高めにすることでwet、dryサーモでの分解(分子量低下)を抑制することができる。 The P2 layer refers to a layer having 95% or more of terephthalic acid units in dicarboxylic acid units and 95 mol% or more of ethylene glycol units in diol units.
The IV of the P2 layer is preferably 0.7 or more and 0.9 or less, more preferably 0.72 or more and 0.85 or less, and still more preferably 0.74 or more and 0.82 or less. Thus, by raising IV, decomposition | disassembly (molecular weight fall) by wet and dry thermo can be suppressed.
またP2層のIVは0.7以上0.9以下が好ましく、より好ましくは0.72以上0.85以下、さらに好ましくは0.74以上0.82以下である。このようにIVを高めにすることでwet、dryサーモでの分解(分子量低下)を抑制することができる。 The P2 layer refers to a layer having 95% or more of terephthalic acid units in dicarboxylic acid units and 95 mol% or more of ethylene glycol units in diol units.
The IV of the P2 layer is preferably 0.7 or more and 0.9 or less, more preferably 0.72 or more and 0.85 or less, and still more preferably 0.74 or more and 0.82 or less. Thus, by raising IV, decomposition | disassembly (molecular weight fall) by wet and dry thermo can be suppressed.
本発明のポリエステルフィルムの製造方法に用いられる前記樹脂フィルム基材は、P1層とP2層の層数の和は、2層以上が好ましく、より好ましくは2層以上5層以下、さらに好ましくは2層以上4層以下である。中でも好ましいのが、P2層の両側をP1層で挟んだ3層構造、あるいはP1層の両側をP2層で挟んだ3層構造、P2層とP1層を積層した2層構造である。
As for the said resin film base material used for the manufacturing method of the polyester film of this invention, 2 or more layers are preferable, as for the sum of the number of layers of P1 layer and P2 layer, More preferably, they are 2 layers or more and 5 layers or less, More preferably, 2 There are 4 or more layers. Among these, a three-layer structure in which both sides of the P2 layer are sandwiched by P1 layers, a three-layer structure in which both sides of the P1 layer are sandwiched by P2 layers, or a two-layer structure in which the P2 layers and the P1 layers are stacked are preferable.
本発明のポリエステルフィルムの製造方法に用いられる前記樹脂フィルム基材が2層以上の場合、厚みはP1層の総和が全厚みの5%以上40%以上が好ましく、より好ましくは7%以上38%以上、さらに好ましくは10%以上35%以下である。この下限値以上にすることで高い耐候性を発現でき、この上限値以下にすることで高い力学強度を発現し易い。
このような積層構造は定法により調製することができ、複数の押出し機から供給されたメルト(樹脂の融体)をマルチマニフォールドダイ、フィードブロックダイを用い積層し押出すことで達成できる。
ポリエステルフィルムの各層の厚みは、フィルムの断面を、SIMSを用い測定し、P1層の特徴フラグメント、P2層の特徴フラグメントでイメージングすることで求めることができる。 When the resin film substrate used in the method for producing a polyester film of the present invention has two or more layers, the total thickness of the P1 layers is preferably 5% to 40%, more preferably 7% to 38% of the total thickness. As mentioned above, More preferably, they are 10% or more and 35% or less. High weather resistance can be expressed by setting this lower limit value or more, and high mechanical strength is easily expressed by setting this lower limit value or less.
Such a laminated structure can be prepared by an ordinary method, and can be achieved by laminating and extruding melt (resin melt) supplied from a plurality of extruders using a multi-manifold die and a feed block die.
The thickness of each layer of the polyester film can be determined by measuring the cross section of the film using SIMS and imaging with the characteristic fragment of the P1 layer and the characteristic fragment of the P2 layer.
このような積層構造は定法により調製することができ、複数の押出し機から供給されたメルト(樹脂の融体)をマルチマニフォールドダイ、フィードブロックダイを用い積層し押出すことで達成できる。
ポリエステルフィルムの各層の厚みは、フィルムの断面を、SIMSを用い測定し、P1層の特徴フラグメント、P2層の特徴フラグメントでイメージングすることで求めることができる。 When the resin film substrate used in the method for producing a polyester film of the present invention has two or more layers, the total thickness of the P1 layers is preferably 5% to 40%, more preferably 7% to 38% of the total thickness. As mentioned above, More preferably, they are 10% or more and 35% or less. High weather resistance can be expressed by setting this lower limit value or more, and high mechanical strength is easily expressed by setting this lower limit value or less.
Such a laminated structure can be prepared by an ordinary method, and can be achieved by laminating and extruding melt (resin melt) supplied from a plurality of extruders using a multi-manifold die and a feed block die.
The thickness of each layer of the polyester film can be determined by measuring the cross section of the film using SIMS and imaging with the characteristic fragment of the P1 layer and the characteristic fragment of the P2 layer.
溶融押出しされたメルトは、キャスティングドラム上で冷却され、固化されてフィルム状に成形される。また、キャスティングドラム以外の方式としては、溶融物を均一な圧力で挟圧するタッチロール方式でもよい。
The melt-extruded melt is cooled on a casting drum, solidified, and formed into a film. Further, as a system other than the casting drum, a touch roll system in which the melt is sandwiched with a uniform pressure may be used.
冷却ロール自体の温度は、10℃~80℃が好ましく、より好ましくは15℃~70℃、さらに好ましくは20℃~60℃である。
The temperature of the cooling roll itself is preferably 10 ° C. to 80 ° C., more preferably 15 ° C. to 70 ° C., and further preferably 20 ° C. to 60 ° C.
帯状に吐出された溶融樹脂(メルト)の固化後(延伸前)の厚みは、2600μm~6000μmの範囲であることで、その後の延伸を経て、所望の厚みのポリエステルフィルムを得ることができる。前記メルトの固化後の厚みは、3100μm~6000μmの範囲が好ましく、より好ましくは3300μm~5000μmであり、さらに好ましくは3500μm~4500μmの範囲である。固化後延伸前の厚みが6000μm以下であることで、メルト押出し中に皺が発生し難く、ムラの発生が抑えられる。また、固化後延伸前の厚みが2600μm以上であることが、メルトの腰が弱いために発生するチルロール(固化するための冷却ロール)への密着むらを抑制し、フィルムのむら低減の観点から好ましい。
The thickness of the molten resin (melt) discharged in a band after solidification (before stretching) is in the range of 2600 μm to 6000 μm, and a polyester film having a desired thickness can be obtained through subsequent stretching. The thickness of the melt after solidification is preferably in the range of 3100 μm to 6000 μm, more preferably in the range of 3300 μm to 5000 μm, and still more preferably in the range of 3500 μm to 4500 μm. When the thickness after solidification and before stretching is 6000 μm or less, wrinkles are unlikely to occur during melt extrusion, and unevenness is suppressed. Moreover, it is preferable that the thickness before stretching after solidification is 2600 μm or more suppresses uneven adhesion to the chill roll (cooling roll for solidification) generated due to weak melt, and is preferable from the viewpoint of reducing unevenness of the film.
本発明の製造方法では、上記製膜工程の後に、作製された押出フィルム(未延伸フィルム)を縦方向および横方向に延伸後、テンター内の熱処理ゾーンで熱固定および熱緩和を施し、冷却して巻き取る工程を含むことが好ましい。
後述するコロナ処理工程後に感光性層を作製するために感光材料用塗布液を塗布する場合は、縦方向および横方向に延伸後のフィルムの厚みは50~300μmであることが好ましく、100~250μmであることがより好ましく、150~200μmであることが特に好ましい。
また、後述するコロナ処理工程後に太陽電池用バックシートを作製するために任意の塗布液を塗布する場合は、縦方向および横方向に延伸後のフィルムの厚みは100~400μmであることが好ましく、150~350μmであることがより好ましく、200~300μmであることが特に好ましい。 In the production method of the present invention, after the film forming step, the produced extruded film (unstretched film) is stretched in the longitudinal direction and the transverse direction, and then subjected to heat setting and thermal relaxation in a heat treatment zone in the tenter and cooled. It is preferable to include a winding step.
When a photosensitive material coating solution is applied to form a photosensitive layer after the corona treatment step described later, the thickness of the film after stretching in the longitudinal and transverse directions is preferably 50 to 300 μm, and preferably 100 to 250 μm. It is more preferable that the thickness is 150 to 200 μm.
Further, in the case of applying an arbitrary coating solution for producing a solar cell backsheet after the corona treatment step described later, the thickness of the film after stretching in the longitudinal direction and the transverse direction is preferably 100 to 400 μm, More preferably, it is 150 to 350 μm, and particularly preferably 200 to 300 μm.
後述するコロナ処理工程後に感光性層を作製するために感光材料用塗布液を塗布する場合は、縦方向および横方向に延伸後のフィルムの厚みは50~300μmであることが好ましく、100~250μmであることがより好ましく、150~200μmであることが特に好ましい。
また、後述するコロナ処理工程後に太陽電池用バックシートを作製するために任意の塗布液を塗布する場合は、縦方向および横方向に延伸後のフィルムの厚みは100~400μmであることが好ましく、150~350μmであることがより好ましく、200~300μmであることが特に好ましい。 In the production method of the present invention, after the film forming step, the produced extruded film (unstretched film) is stretched in the longitudinal direction and the transverse direction, and then subjected to heat setting and thermal relaxation in a heat treatment zone in the tenter and cooled. It is preferable to include a winding step.
When a photosensitive material coating solution is applied to form a photosensitive layer after the corona treatment step described later, the thickness of the film after stretching in the longitudinal and transverse directions is preferably 50 to 300 μm, and preferably 100 to 250 μm. It is more preferable that the thickness is 150 to 200 μm.
Further, in the case of applying an arbitrary coating solution for producing a solar cell backsheet after the corona treatment step described later, the thickness of the film after stretching in the longitudinal direction and the transverse direction is preferably 100 to 400 μm, More preferably, it is 150 to 350 μm, and particularly preferably 200 to 300 μm.
<コロナ処理>
本発明の製造方法は、ポリエステルを主成分とする樹脂フィルム基材の表面をコロナ処理する工程を含む。
前記基材の一方の面のみに前記表面処理が施されていても、前記基材の両表面に前記表面処理が施されていてもよく、例えば前記樹脂フィルム基材に後述する他の機能層を塗布により両面に形成する場合は、両表面に前記表面処理が施されていることが好ましい。
前記コロナ処理の好ましい態様は、樹脂フィルム基材に対して、0.1~2.0kJ/m2であることが特に好ましく、0.15~1.0kJ/m2が更に好ましい。 <Corona treatment>
The manufacturing method of this invention includes the process of corona-treating the surface of the resin film base material which has polyester as a main component.
The surface treatment may be performed only on one surface of the base material, or the surface treatment may be performed on both surfaces of the base material. For example, other functional layers described later on the resin film base material Is preferably applied to both surfaces by applying the surface treatment.
A preferred embodiment of the corona treatment, the resin film substrate, particularly preferably from 0.1 ~ 2.0kJ / m 2, more preferably 0.15 ~ 1.0kJ / m 2.
本発明の製造方法は、ポリエステルを主成分とする樹脂フィルム基材の表面をコロナ処理する工程を含む。
前記基材の一方の面のみに前記表面処理が施されていても、前記基材の両表面に前記表面処理が施されていてもよく、例えば前記樹脂フィルム基材に後述する他の機能層を塗布により両面に形成する場合は、両表面に前記表面処理が施されていることが好ましい。
前記コロナ処理の好ましい態様は、樹脂フィルム基材に対して、0.1~2.0kJ/m2であることが特に好ましく、0.15~1.0kJ/m2が更に好ましい。 <Corona treatment>
The manufacturing method of this invention includes the process of corona-treating the surface of the resin film base material which has polyester as a main component.
The surface treatment may be performed only on one surface of the base material, or the surface treatment may be performed on both surfaces of the base material. For example, other functional layers described later on the resin film base material Is preferably applied to both surfaces by applying the surface treatment.
A preferred embodiment of the corona treatment, the resin film substrate, particularly preferably from 0.1 ~ 2.0kJ / m 2, more preferably 0.15 ~ 1.0kJ / m 2.
<コロナ処理工程後加熱>
本発明の製造方法は、前記コロナ処理後の前記樹脂フィルム基材を該樹脂フィルム基材のTgを超えて、Tmeta以下に加熱処理するコロナ処理後加熱工程を含む(ここで、Tgはガラス転移温度(単位:℃)を表す)。
前記コロナ処理工程後加熱において、樹脂フィルム基材のTgを超えて加熱処理することにより、密着性を大きく改善することができる。また、Tmeta以下で加熱処理することにより、樹脂フィルム基材が加熱ロールなどの加熱装置に粘着したり、搬送ロールに粘着したりすることがなく、製膜適性が良好となる。ここで、コロナ処理工程後に加熱するとは、コロナ処理と同時に電極対向ロールを加熱する態様を含まないことを意味する。また、コロナ処理後の加熱は、前記コロナ処理を施した側とは反対側の面にコロナ処理を施すための電極対向ロールで行わずに、コロナ処理装置とは独立した加熱装置を用いることが、製造適性の観点から好ましい。
また、このような温度範囲でコロナ処理工程後加熱を行うことで、WBL層の形成を抑制することがきる。WBL層の形成の抑制については、コロナ処理未処理のフィルム、コロナ処理だけを行ったフィルム、および、コロナ処理後に加熱処理を行ったフィルムの表面を削り取り、DSCによる結晶化温度(降温結晶化;Tc’)を測定して、コロナ処理だけを行ったフィルム表面のTc’が未処理の場合よりも高温側(結晶化が早い、すなわち低分子化)にシフトし、また、コロナ処理後に加熱処理を行ったフイルム表面のTc’では高温側へのシフトが見られないことを確認することで、抑制の有無を判断することができる。 <Heating after corona treatment process>
The manufacturing method of the present invention includes a post-corona treatment heating step in which the resin film substrate after the corona treatment is heated to Tmeta or less exceeding the Tg of the resin film substrate (where Tg is a glass transition). Temperature (unit: ° C)).
In the heating after the corona treatment step, the adhesiveness can be greatly improved by heat treatment exceeding the Tg of the resin film substrate. Moreover, by heat-processing below Tmeta, a resin film base material does not adhere to heating apparatuses, such as a heating roll, or it adheres to a conveyance roll, and film forming suitability becomes favorable. Here, heating after the corona treatment step means not including an aspect in which the electrode facing roll is heated simultaneously with the corona treatment. In addition, the heating after the corona treatment is not performed by the electrode facing roll for performing the corona treatment on the surface opposite to the side subjected to the corona treatment, and a heating device independent of the corona treatment device may be used. From the viewpoint of production suitability, it is preferable.
In addition, by performing heating after the corona treatment step in such a temperature range, formation of the WBL layer can be suppressed. Regarding the suppression of the formation of the WBL layer, the surface of the film that has not been subjected to the corona treatment, the film that has been subjected to the corona treatment alone, and the film that has been subjected to the heat treatment after the corona treatment is scraped, and the crystallization temperature by DSC (cooling crystallization; Tc ′) is measured, and the Tc ′ of the film surface that has been subjected to corona treatment alone is shifted to a higher temperature side (faster crystallization, that is, lower molecular weight) than when untreated, and heat treatment is performed after corona treatment. The presence or absence of suppression can be determined by confirming that no shift to the high temperature side is observed at Tc ′ of the film surface subjected to.
本発明の製造方法は、前記コロナ処理後の前記樹脂フィルム基材を該樹脂フィルム基材のTgを超えて、Tmeta以下に加熱処理するコロナ処理後加熱工程を含む(ここで、Tgはガラス転移温度(単位:℃)を表す)。
前記コロナ処理工程後加熱において、樹脂フィルム基材のTgを超えて加熱処理することにより、密着性を大きく改善することができる。また、Tmeta以下で加熱処理することにより、樹脂フィルム基材が加熱ロールなどの加熱装置に粘着したり、搬送ロールに粘着したりすることがなく、製膜適性が良好となる。ここで、コロナ処理工程後に加熱するとは、コロナ処理と同時に電極対向ロールを加熱する態様を含まないことを意味する。また、コロナ処理後の加熱は、前記コロナ処理を施した側とは反対側の面にコロナ処理を施すための電極対向ロールで行わずに、コロナ処理装置とは独立した加熱装置を用いることが、製造適性の観点から好ましい。
また、このような温度範囲でコロナ処理工程後加熱を行うことで、WBL層の形成を抑制することがきる。WBL層の形成の抑制については、コロナ処理未処理のフィルム、コロナ処理だけを行ったフィルム、および、コロナ処理後に加熱処理を行ったフィルムの表面を削り取り、DSCによる結晶化温度(降温結晶化;Tc’)を測定して、コロナ処理だけを行ったフィルム表面のTc’が未処理の場合よりも高温側(結晶化が早い、すなわち低分子化)にシフトし、また、コロナ処理後に加熱処理を行ったフイルム表面のTc’では高温側へのシフトが見られないことを確認することで、抑制の有無を判断することができる。 <Heating after corona treatment process>
The manufacturing method of the present invention includes a post-corona treatment heating step in which the resin film substrate after the corona treatment is heated to Tmeta or less exceeding the Tg of the resin film substrate (where Tg is a glass transition). Temperature (unit: ° C)).
In the heating after the corona treatment step, the adhesiveness can be greatly improved by heat treatment exceeding the Tg of the resin film substrate. Moreover, by heat-processing below Tmeta, a resin film base material does not adhere to heating apparatuses, such as a heating roll, or it adheres to a conveyance roll, and film forming suitability becomes favorable. Here, heating after the corona treatment step means not including an aspect in which the electrode facing roll is heated simultaneously with the corona treatment. In addition, the heating after the corona treatment is not performed by the electrode facing roll for performing the corona treatment on the surface opposite to the side subjected to the corona treatment, and a heating device independent of the corona treatment device may be used. From the viewpoint of production suitability, it is preferable.
In addition, by performing heating after the corona treatment step in such a temperature range, formation of the WBL layer can be suppressed. Regarding the suppression of the formation of the WBL layer, the surface of the film that has not been subjected to the corona treatment, the film that has been subjected to the corona treatment alone, and the film that has been subjected to the heat treatment after the corona treatment is scraped, and the crystallization temperature by DSC (cooling crystallization; Tc ′) is measured, and the Tc ′ of the film surface that has been subjected to corona treatment alone is shifted to a higher temperature side (faster crystallization, that is, lower molecular weight) than when untreated, and heat treatment is performed after corona treatment. The presence or absence of suppression can be determined by confirming that no shift to the high temperature side is observed at Tc ′ of the film surface subjected to.
本発明の製造方法では、前記コロナ処理工程後加熱の温度は、Tg~Tmetaであることが好ましく、Tg+30℃~Tg+120であることがより好ましく、Tg+60℃~Tg+90℃であることが特に好ましい。また、前記ポリエステルがPETの場合、前記コロナ処理工程後加熱の温度は、70~200℃であることが好ましく、100~180℃であることがより好ましく、130~160℃であることが特に好ましい。
前記コロナ処理をしてから好ましくは30秒以内、より好ましくは20秒以内、更に好ましくは10秒以内に前記コロナ処理工程後加熱をするのがよい。前記コロナ処理をしてから30秒以内に加熱すると、コロナ効果が減衰(ラジカルが消失)し難く、前記コロナ処理工程後加熱による密着向上効果が得られやすい。 In the production method of the present invention, the heating temperature after the corona treatment step is preferably Tg to Tmeta, more preferably Tg + 30 ° C. to Tg + 120, and particularly preferably Tg + 60 ° C. to Tg + 90 ° C. When the polyester is PET, the heating temperature after the corona treatment step is preferably 70 to 200 ° C., more preferably 100 to 180 ° C., and particularly preferably 130 to 160 ° C. .
Heating after the corona treatment step is preferably performed within 30 seconds, more preferably within 20 seconds, and even more preferably within 10 seconds after the corona treatment. When heating is performed within 30 seconds after the corona treatment, the corona effect is hardly attenuated (radical disappearance), and the adhesion improving effect by heating after the corona treatment step is easily obtained.
前記コロナ処理をしてから好ましくは30秒以内、より好ましくは20秒以内、更に好ましくは10秒以内に前記コロナ処理工程後加熱をするのがよい。前記コロナ処理をしてから30秒以内に加熱すると、コロナ効果が減衰(ラジカルが消失)し難く、前記コロナ処理工程後加熱による密着向上効果が得られやすい。 In the production method of the present invention, the heating temperature after the corona treatment step is preferably Tg to Tmeta, more preferably Tg + 30 ° C. to Tg + 120, and particularly preferably Tg + 60 ° C. to Tg + 90 ° C. When the polyester is PET, the heating temperature after the corona treatment step is preferably 70 to 200 ° C., more preferably 100 to 180 ° C., and particularly preferably 130 to 160 ° C. .
Heating after the corona treatment step is preferably performed within 30 seconds, more preferably within 20 seconds, and even more preferably within 10 seconds after the corona treatment. When heating is performed within 30 seconds after the corona treatment, the corona effect is hardly attenuated (radical disappearance), and the adhesion improving effect by heating after the corona treatment step is easily obtained.
本発明の製造方法では、前記加熱処理の方法や用いる加熱処理装置については特に制限はない。その中でも、前記加熱処理が、加熱気体(加熱エアー)の送風、赤外線の照射または加熱ロールとの接触であることが好ましいが、フィルム加熱温度の制御性や、エアーによる異物付着の問題、赤外線照射によるバルク物性変化の問題が起こりにくい観点から、加熱ロールとの接触であることがより好ましい。
In the production method of the present invention, there is no particular limitation on the heat treatment method and the heat treatment apparatus used. Among them, it is preferable that the heat treatment is air blowing of heated gas (heated air), infrared irradiation or contact with a heating roll, but controllability of film heating temperature, foreign matter adhesion due to air, infrared irradiation From the standpoint that the problem of bulk physical property change due to is less likely to occur, contact with a heating roll is more preferable.
<再度のコロナ処理>
本発明の製造方法は、前記コロナ処理後加熱工程の後に、前記樹脂フィルム基材の前記コロナ処理を施された側の表面に再度のコロナ処理を行ってもよい。また、再度のコロナ処理における出力の好ましい範囲は、いずれも同様である。
前記コロナ処理と、前記再度のコロナ処理を、異なるコロナ処理装置によって行ってもよい。
また、前記コロナ処理と前記再度のコロナ処理の間に前記樹脂フィルム基材を一度も巻き取らずに、前記再度のコロナ処理をオンラインで行うことが、巻き取りまたは送り出し時にキズ等が余計につく可能性を減らす観点から好ましい。
さらに、本発明の製造方法に含まれる全てのコロナ処理と全ての加熱処理が完了するまでの間に、前記樹脂フィルム基材を一度も巻き取らずに、オンラインで行うことがより好ましい。 <Re-corona treatment>
In the production method of the present invention, the corona treatment may be performed again on the surface of the resin film substrate on which the corona treatment has been performed after the post-corona treatment heating step. Moreover, the preferable range of the output in the second corona treatment is the same.
The corona treatment and the re-corona treatment may be performed by different corona treatment apparatuses.
Further, it is possible to carry out the re-corona treatment online without taking up the resin film base material between the corona treatment and the re-corona treatment, which may cause scratches or the like during winding or feeding. It is preferable from the viewpoint of reducing the possibility.
Furthermore, it is more preferable that the resin film base material is carried out online without taking up the resin film substrate until all the corona treatment and all the heat treatments included in the production method of the present invention are completed.
本発明の製造方法は、前記コロナ処理後加熱工程の後に、前記樹脂フィルム基材の前記コロナ処理を施された側の表面に再度のコロナ処理を行ってもよい。また、再度のコロナ処理における出力の好ましい範囲は、いずれも同様である。
前記コロナ処理と、前記再度のコロナ処理を、異なるコロナ処理装置によって行ってもよい。
また、前記コロナ処理と前記再度のコロナ処理の間に前記樹脂フィルム基材を一度も巻き取らずに、前記再度のコロナ処理をオンラインで行うことが、巻き取りまたは送り出し時にキズ等が余計につく可能性を減らす観点から好ましい。
さらに、本発明の製造方法に含まれる全てのコロナ処理と全ての加熱処理が完了するまでの間に、前記樹脂フィルム基材を一度も巻き取らずに、オンラインで行うことがより好ましい。 <Re-corona treatment>
In the production method of the present invention, the corona treatment may be performed again on the surface of the resin film substrate on which the corona treatment has been performed after the post-corona treatment heating step. Moreover, the preferable range of the output in the second corona treatment is the same.
The corona treatment and the re-corona treatment may be performed by different corona treatment apparatuses.
Further, it is possible to carry out the re-corona treatment online without taking up the resin film base material between the corona treatment and the re-corona treatment, which may cause scratches or the like during winding or feeding. It is preferable from the viewpoint of reducing the possibility.
Furthermore, it is more preferable that the resin film base material is carried out online without taking up the resin film substrate until all the corona treatment and all the heat treatments included in the production method of the present invention are completed.
本発明の製造方法では、コロナ処理工程を複数回行う場合、コロナ処理工程を連続して行わず、複数回のコロナ処理の間に加熱工程を行うことが、WBL層の形成を抑制する観点から好ましい。さらに、コロナ処理と熱処理をともに複数回行なう場合、コロナ処理と加熱処理を交互に行うことが好ましい。すなわち、コロナ処理とその後の加熱処理を1組の複合処理として行うことが好ましい。
なお、コロナ処理と熱処理をともに複数回行なう場合もコロナ処理の回数と加熱工程の回数は同じでなくてもよく、2回目以降のコロナ処理の後に加熱工程を行わずに、後述する塗布工程を行なってもよい。また、本発明の製造方法において、加熱ロールが2個以上連続して配置されている態様や、複数個の加熱ヒーターを用いる態様を否定するものではない。
コロナ処理とその後の加熱処理を1組の複合処理を考えた場合、この複合処理は複数回行ってもよい。本発明者らにて、コロナ処理および加熱処理を交互に繰り返し行い、各過程での接触角および結晶化温度(Tc’)がどのように変化するかを調べた結果、コロナ処理によって接触角は低下するが、加熱することで増加し、例えば、コロナ→加熱→コロナ→加熱の複数回処理を行った後の接触角は、未処理の場合よりも増加した。また、Tc’については、同じ処理を行った結果では、未処理の場合よりも低温側にシフトした。
このことから、コロナ処理とその後の加熱処理の複合処理を繰り返すことで、官能基をより増やすことができ、更にWBL層の生成を抑制するだけでなく、ラジカルの架橋が進行し、表面が強化(分子量が増大)する効果があると考えられる。また、表面が強化された状態であれば、加熱後にコロナ処理を行ってもWBL層の生成が少なく、著しい密着低下を引き起こさない。
コロナ処理とその後の熱処理の複合処理は、複合処理として1~3回であることが好ましく、1~2回であることがより好ましい。なお、2回目以降の加熱処理の好ましい態様についても、前記コロナ処理後加熱工程と同様である。
具体的に図面を参照して、本発明の製造方法におけるコロナ処理と加熱処理の好ましい態様について説明する。図1~図4に記載の本発明の製造方法に用いられる製造装置では、巻き出しロール10から樹脂フィルム基材が巻き出され、コロナ処理用電極1と電極対向ロール12などから構成されるコロナ処理装置によって樹脂フィルム基材の少なくとも一方の表面に、好ましくは搬送されながらコロナ処理を施される。コロナ処理後、樹脂フィルム基材に対し、図1および図4に記載の加熱ロール2に接触させたり、図2に記載の加熱気体送風ゾーン3中で加熱気体を送風したり、図3に記載の赤外ヒーター4(カーボンヒータなど)から赤外線を照射したりすることで、本発明で規定する温度範囲となるように樹脂フィルム基材表面が加熱される。加熱ロール2の加熱方法や配置方法については特に制限はなく、公知の方法を用いることができる。加熱気体送風ゾーン3における送風の方法や送風口の配置、送風の向き、フィルムのいずれの面に対して送風するかなどについても特に制限はなく、公知の方法を用いることができる。赤外ヒーター4における赤外線の照射量、配置などについても特に制限はなく、公知の方法を用いることができる。
前記コロナ処理後加熱工程の後、図1に記載のようにそのまま巻き取りロール11に巻き取られてもよい。また、図4に記載のように、再度のコロナ処理や、再度の加熱処理を行ってもよく、その場合はオンラインでフィルムを一度も巻き取らずにすべてのコロナ処理および加熱処理を行ってもよい。 In the manufacturing method of the present invention, when the corona treatment step is performed a plurality of times, the corona treatment step is not performed continuously, and the heating step is performed between the plurality of corona treatments from the viewpoint of suppressing the formation of the WBL layer. preferable. Furthermore, when both the corona treatment and the heat treatment are performed a plurality of times, it is preferable to perform the corona treatment and the heat treatment alternately. That is, it is preferable to perform the corona treatment and the subsequent heat treatment as a set of combined treatments.
In addition, when performing both a corona treatment and heat processing several times, the frequency | count of a corona treatment and the frequency | count of a heating process may not be the same, and the application process mentioned later is not performed after the corona treatment of the 2nd time or later. You may do it. Moreover, in the manufacturing method of this invention, the aspect by which two or more heating rolls are arrange | positioned continuously, and the aspect using a some heater are not denied.
When the corona treatment and the subsequent heat treatment are considered as one set of composite treatment, this composite treatment may be performed a plurality of times. As a result of investigating how the contact angle and the crystallization temperature (Tc ′) change in each process by alternately repeating the corona treatment and the heat treatment by the present inventors, the contact angle is reduced by the corona treatment. Although it decreases, it increases by heating. For example, the contact angle after performing a plurality of treatments of corona → heating → corona → heating is increased as compared with the case of no treatment. As for Tc ′, the result of the same treatment shifted to a lower temperature side than the case of no treatment.
From this, it is possible to increase the functional groups by repeating the combined treatment of corona treatment and subsequent heat treatment, and not only suppress the formation of the WBL layer, but also promote radical crosslinking and strengthen the surface. It is considered that there is an effect of increasing the molecular weight. In addition, if the surface is strengthened, even if corona treatment is performed after heating, the generation of the WBL layer is small, and a significant decrease in adhesion is not caused.
The combined treatment of the corona treatment and the subsequent heat treatment is preferably 1 to 3 times as the combined treatment, and more preferably 1 to 2 times. In addition, about the preferable aspect of the heat processing after the 2nd time, it is the same as that of the said post-corona-processing heating process.
With reference to drawings specifically, the preferable aspect of the corona treatment and heat processing in the manufacturing method of this invention is demonstrated. In the manufacturing apparatus used for the manufacturing method of the present invention described in FIGS. 1 to 4, a resin film base material is unwound from an unwindingroll 10, and is composed of a corona treatment electrode 1, an electrode facing roll 12, and the like. A corona treatment is preferably applied to at least one surface of the resin film substrate by a treatment device while being conveyed. After the corona treatment, the resin film substrate is brought into contact with the heating roll 2 shown in FIG. 1 and FIG. 4, or the heated gas is blown in the heated gas blowing zone 3 shown in FIG. By irradiating infrared rays from the infrared heater 4 (carbon heater or the like), the surface of the resin film substrate is heated so as to be within the temperature range defined in the present invention. There is no restriction | limiting in particular about the heating method and arrangement | positioning method of the heating roll 2, A well-known method can be used. There are no particular restrictions on the method of blowing air in the heated gas blowing zone 3, the arrangement of the blowing ports, the direction of blowing, and on which side of the film the air is blown, and known methods can be used. There is no restriction | limiting in particular also about the irradiation amount of infrared rays, arrangement | positioning, etc. in the infrared heater 4, A well-known method can be used.
After the heating process after the corona treatment, the film may be wound around the windingroll 11 as shown in FIG. In addition, as shown in FIG. 4, the corona treatment may be performed again or the heat treatment may be performed again. In that case, all the corona treatment and the heat treatment may be performed without winding the film online. Good.
なお、コロナ処理と熱処理をともに複数回行なう場合もコロナ処理の回数と加熱工程の回数は同じでなくてもよく、2回目以降のコロナ処理の後に加熱工程を行わずに、後述する塗布工程を行なってもよい。また、本発明の製造方法において、加熱ロールが2個以上連続して配置されている態様や、複数個の加熱ヒーターを用いる態様を否定するものではない。
コロナ処理とその後の加熱処理を1組の複合処理を考えた場合、この複合処理は複数回行ってもよい。本発明者らにて、コロナ処理および加熱処理を交互に繰り返し行い、各過程での接触角および結晶化温度(Tc’)がどのように変化するかを調べた結果、コロナ処理によって接触角は低下するが、加熱することで増加し、例えば、コロナ→加熱→コロナ→加熱の複数回処理を行った後の接触角は、未処理の場合よりも増加した。また、Tc’については、同じ処理を行った結果では、未処理の場合よりも低温側にシフトした。
このことから、コロナ処理とその後の加熱処理の複合処理を繰り返すことで、官能基をより増やすことができ、更にWBL層の生成を抑制するだけでなく、ラジカルの架橋が進行し、表面が強化(分子量が増大)する効果があると考えられる。また、表面が強化された状態であれば、加熱後にコロナ処理を行ってもWBL層の生成が少なく、著しい密着低下を引き起こさない。
コロナ処理とその後の熱処理の複合処理は、複合処理として1~3回であることが好ましく、1~2回であることがより好ましい。なお、2回目以降の加熱処理の好ましい態様についても、前記コロナ処理後加熱工程と同様である。
具体的に図面を参照して、本発明の製造方法におけるコロナ処理と加熱処理の好ましい態様について説明する。図1~図4に記載の本発明の製造方法に用いられる製造装置では、巻き出しロール10から樹脂フィルム基材が巻き出され、コロナ処理用電極1と電極対向ロール12などから構成されるコロナ処理装置によって樹脂フィルム基材の少なくとも一方の表面に、好ましくは搬送されながらコロナ処理を施される。コロナ処理後、樹脂フィルム基材に対し、図1および図4に記載の加熱ロール2に接触させたり、図2に記載の加熱気体送風ゾーン3中で加熱気体を送風したり、図3に記載の赤外ヒーター4(カーボンヒータなど)から赤外線を照射したりすることで、本発明で規定する温度範囲となるように樹脂フィルム基材表面が加熱される。加熱ロール2の加熱方法や配置方法については特に制限はなく、公知の方法を用いることができる。加熱気体送風ゾーン3における送風の方法や送風口の配置、送風の向き、フィルムのいずれの面に対して送風するかなどについても特に制限はなく、公知の方法を用いることができる。赤外ヒーター4における赤外線の照射量、配置などについても特に制限はなく、公知の方法を用いることができる。
前記コロナ処理後加熱工程の後、図1に記載のようにそのまま巻き取りロール11に巻き取られてもよい。また、図4に記載のように、再度のコロナ処理や、再度の加熱処理を行ってもよく、その場合はオンラインでフィルムを一度も巻き取らずにすべてのコロナ処理および加熱処理を行ってもよい。 In the manufacturing method of the present invention, when the corona treatment step is performed a plurality of times, the corona treatment step is not performed continuously, and the heating step is performed between the plurality of corona treatments from the viewpoint of suppressing the formation of the WBL layer. preferable. Furthermore, when both the corona treatment and the heat treatment are performed a plurality of times, it is preferable to perform the corona treatment and the heat treatment alternately. That is, it is preferable to perform the corona treatment and the subsequent heat treatment as a set of combined treatments.
In addition, when performing both a corona treatment and heat processing several times, the frequency | count of a corona treatment and the frequency | count of a heating process may not be the same, and the application process mentioned later is not performed after the corona treatment of the 2nd time or later. You may do it. Moreover, in the manufacturing method of this invention, the aspect by which two or more heating rolls are arrange | positioned continuously, and the aspect using a some heater are not denied.
When the corona treatment and the subsequent heat treatment are considered as one set of composite treatment, this composite treatment may be performed a plurality of times. As a result of investigating how the contact angle and the crystallization temperature (Tc ′) change in each process by alternately repeating the corona treatment and the heat treatment by the present inventors, the contact angle is reduced by the corona treatment. Although it decreases, it increases by heating. For example, the contact angle after performing a plurality of treatments of corona → heating → corona → heating is increased as compared with the case of no treatment. As for Tc ′, the result of the same treatment shifted to a lower temperature side than the case of no treatment.
From this, it is possible to increase the functional groups by repeating the combined treatment of corona treatment and subsequent heat treatment, and not only suppress the formation of the WBL layer, but also promote radical crosslinking and strengthen the surface. It is considered that there is an effect of increasing the molecular weight. In addition, if the surface is strengthened, even if corona treatment is performed after heating, the generation of the WBL layer is small, and a significant decrease in adhesion is not caused.
The combined treatment of the corona treatment and the subsequent heat treatment is preferably 1 to 3 times as the combined treatment, and more preferably 1 to 2 times. In addition, about the preferable aspect of the heat processing after the 2nd time, it is the same as that of the said post-corona-processing heating process.
With reference to drawings specifically, the preferable aspect of the corona treatment and heat processing in the manufacturing method of this invention is demonstrated. In the manufacturing apparatus used for the manufacturing method of the present invention described in FIGS. 1 to 4, a resin film base material is unwound from an unwinding
After the heating process after the corona treatment, the film may be wound around the winding
<塗布工程>
本発明の製造方法は、前記コロナ処理後加熱工程の後に前記樹脂フィルム基材の前記コロナ処理を施された側の表面上にポリマー溶液を塗布する工程を含む。
本発明の製造方法は、前記コロナ処理後加熱工程の後に塗布工程を行う場合、前記コロナ処理後加熱工程と塗布工程の間にその他の工程を含んでいても、含まなくてもよい。
すなわち、前記コロナ処理後加熱工程の直後に塗布工程を行ってもよく、前記コロナ処理後加熱工程の後に再度のコロナ処理を行った後に塗布工程を行ってもよい。さらに前記再度のコロナ処理後の後に加熱処理を行った後に、塗布工程を行ってもよい。 <Application process>
The manufacturing method of this invention includes the process of apply | coating a polymer solution on the surface by the side of the said corona treatment of the said resin film base material after the said post-corona treatment heating process.
The manufacturing method of the present invention may or may not include other steps between the post-corona treatment heating step and the coating step when the coating step is performed after the post-corona treatment heating step.
That is, the coating process may be performed immediately after the heating process after the corona treatment, or the coating process may be performed after performing the corona treatment again after the heating process after the corona treatment. Furthermore, the coating process may be performed after the heat treatment after the re-corona treatment.
本発明の製造方法は、前記コロナ処理後加熱工程の後に前記樹脂フィルム基材の前記コロナ処理を施された側の表面上にポリマー溶液を塗布する工程を含む。
本発明の製造方法は、前記コロナ処理後加熱工程の後に塗布工程を行う場合、前記コロナ処理後加熱工程と塗布工程の間にその他の工程を含んでいても、含まなくてもよい。
すなわち、前記コロナ処理後加熱工程の直後に塗布工程を行ってもよく、前記コロナ処理後加熱工程の後に再度のコロナ処理を行った後に塗布工程を行ってもよい。さらに前記再度のコロナ処理後の後に加熱処理を行った後に、塗布工程を行ってもよい。 <Application process>
The manufacturing method of this invention includes the process of apply | coating a polymer solution on the surface by the side of the said corona treatment of the said resin film base material after the said post-corona treatment heating process.
The manufacturing method of the present invention may or may not include other steps between the post-corona treatment heating step and the coating step when the coating step is performed after the post-corona treatment heating step.
That is, the coating process may be performed immediately after the heating process after the corona treatment, or the coating process may be performed after performing the corona treatment again after the heating process after the corona treatment. Furthermore, the coating process may be performed after the heat treatment after the re-corona treatment.
本発明のポリエステルフィルムの製造方法では、前記塗布工程においてポリマー溶液により形成される塗布層は、特に機能に制限はなく、任意の機能層として用いることができる。
また、前記塗布層は、前記樹脂フィルム基材の表面に接触させて配置される層である。前記塗布層は、表面処理された樹脂フィルム基材との密着が改善される。 In the method for producing a polyester film of the present invention, the coating layer formed from the polymer solution in the coating step is not particularly limited in function, and can be used as an arbitrary functional layer.
Moreover, the said application layer is a layer arrange | positioned in contact with the surface of the said resin film base material. The coating layer has improved adhesion to the surface-treated resin film substrate.
また、前記塗布層は、前記樹脂フィルム基材の表面に接触させて配置される層である。前記塗布層は、表面処理された樹脂フィルム基材との密着が改善される。 In the method for producing a polyester film of the present invention, the coating layer formed from the polymer solution in the coating step is not particularly limited in function, and can be used as an arbitrary functional layer.
Moreover, the said application layer is a layer arrange | positioned in contact with the surface of the said resin film base material. The coating layer has improved adhesion to the surface-treated resin film substrate.
前記塗布工程によって前記樹脂フィルム基材の前記コロナ処理を施された側の表面に形成された塗布層は、ポリエステルフィルムを構成する任意の層に適用することができる。ポリマー層は、例えば、後述する下塗り層やその他の機能層として適用することができる。その中でも下塗り層として用いることが特に好ましい。
The coating layer formed on the surface of the resin film substrate on the side subjected to the corona treatment by the coating step can be applied to any layer constituting the polyester film. The polymer layer can be applied as, for example, an undercoat layer described later or other functional layers. Among them, it is particularly preferable to use it as an undercoat layer.
(1)下塗層の形成
本発明の製造方法では、前記塗布工程として、下塗層用塗布液を前記樹脂フィルム基材に塗布する工程を含むことが好ましい。 (1) Formation of undercoat layer In the manufacturing method of this invention, it is preferable that the said application | coating process includes the process of apply | coating the coating liquid for undercoat layers to the said resin film base material.
本発明の製造方法では、前記塗布工程として、下塗層用塗布液を前記樹脂フィルム基材に塗布する工程を含むことが好ましい。 (1) Formation of undercoat layer In the manufacturing method of this invention, it is preferable that the said application | coating process includes the process of apply | coating the coating liquid for undercoat layers to the said resin film base material.
(2)その他の塗布層の形成
本発明の製造方法では、前記下塗り層としての塗布層の上に、さらにその他の層を積層する工程を含んでいてもよい。
本発明の製造方法では、その他の機能層を塗布により設けてもよい。 (2) Formation of other coating layers The production method of the present invention may further include a step of laminating other layers on the coating layer as the undercoat layer.
In the production method of the present invention, other functional layers may be provided by coating.
本発明の製造方法では、前記下塗り層としての塗布層の上に、さらにその他の層を積層する工程を含んでいてもよい。
本発明の製造方法では、その他の機能層を塗布により設けてもよい。 (2) Formation of other coating layers The production method of the present invention may further include a step of laminating other layers on the coating layer as the undercoat layer.
In the production method of the present invention, other functional layers may be provided by coating.
(1-1)感光材料の製造方法への適用時の下塗層の形成
本発明の製造方法を感光材料の製造方法に適用する場合の塗布液については、例えば特開2007-270066号公報に記載の構成の材料を用いることができる。 (1-1) Formation of an undercoat layer when applied to a method for producing a photosensitive material A coating solution for applying the production method of the present invention to a method for producing a photosensitive material is disclosed in, for example, JP-A-2007-270066. Materials having the structure described can be used.
本発明の製造方法を感光材料の製造方法に適用する場合の塗布液については、例えば特開2007-270066号公報に記載の構成の材料を用いることができる。 (1-1) Formation of an undercoat layer when applied to a method for producing a photosensitive material A coating solution for applying the production method of the present invention to a method for producing a photosensitive material is disclosed in, for example, JP-A-2007-270066. Materials having the structure described can be used.
具体的に図面を用いて、本発明の感光材料の製造方法について説明する。本発明の感光材料の製造方法は、以下の工程により、図5に記載の感光材料が形成されることが好ましい。ハロゲン化銀感光材料の製造工程では、まず、支持体24(ポリエステルフィルムなどの樹脂フィルム基材)の表面側にラテックス系下塗液を塗布し(ステップS1)、これを乾燥させることにより(ステップS2)、ラテックス系下塗層23を形成することが好ましい。次に、ラテックス系塗布層の表面にゼラチン系下塗液を塗布した後(ステップS3)、ゼラチン系下塗層の表面側に感材塗布液を塗布し(ステップS4)、乾燥させることによって(ステップS5)、感材塗布層21を形成する。
The method for producing the photosensitive material of the present invention will be described specifically with reference to the drawings. In the method for producing a photosensitive material of the present invention, the photosensitive material shown in FIG. 5 is preferably formed by the following steps. In the production process of the silver halide light-sensitive material, first, a latex base coating solution is applied to the surface side of the support 24 (resin film substrate such as polyester film) (step S1) and dried (step S2). ), And the latex base coat layer 23 is preferably formed. Next, after applying the gelatin-based undercoat liquid to the surface of the latex-based coating layer (step S3), the photosensitive material coating liquid is applied to the surface side of the gelatin-based undercoat layer (step S4) and dried (step). S5), the photosensitive material coating layer 21 is formed.
本発明の製造方法における前記コロナ処理工程および前記コロナ処理後加熱工程方法は、たとえば上記のステップS1、S2で下塗層を形成する際に適用することができる。本発明の製造方法を適用することによって、ラテックス系下塗層と樹脂フィルム基材との密着性を向上させることができる。
The corona treatment step and the post-corona treatment heating step method in the production method of the present invention can be applied, for example, when the undercoat layer is formed in the above steps S1 and S2. By applying the production method of the present invention, the adhesion between the latex undercoat layer and the resin film substrate can be improved.
前記下塗層用塗布液は、親水性コロイドを含むが、親水性コロイドとしては、ゼラチン、フタル化ゼラチン、マレイン化ゼラチンなどのアシル化ゼラチン:カルボキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体:アクリル酸、メタクリル酸もしくはアミド(アクリルアミド等)などをゼラチンにグラフトさせたグラフト化ゼラチン:ポリビニルアルコール:ポリヒドロキシアルキルアクリレート:ポリビニルピロリドン:ビニルピロリドン・酢酸ビニル共重合体:ガゼイン:アガロース:アルブミン:アルギン酸ソーダ:ポリサッカライド:寒天:でんぷん:グラフトでんぷん:ポリアクリルアミド:ポリエチレンイミンアシル化物:これらの部分加水分解物などの合成もしくは天然の親水性高分子化合物:等が挙げられる。これらの材料は、単独もしくは混合して使用できる。これらの中でもゼラチンが好ましい。また、親水性コロイドの他に、バインダーとして、アクリル樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリスチレン樹脂、SBR、PVDC樹脂等も併用することができる。
The coating solution for the undercoat layer contains a hydrophilic colloid. Examples of the hydrophilic colloid include acylated gelatin such as gelatin, phthalated gelatin, and maleated gelatin: cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose: acrylic acid, Grafted gelatin obtained by grafting methacrylic acid or amide (such as acrylamide) onto gelatin: polyvinyl alcohol: polyhydroxyalkyl acrylate: polyvinyl pyrrolidone: vinyl pyrrolidone / vinyl acetate copolymer: gazein: agarose: albumin: sodium alginate: polysaccharide : Agar: Starch: Grafted starch: Polyacrylamide: Polyethyleneimine acylated product: Synthetic or natural hydrophilic polymer such as partial hydrolyzate: etc. And the like. These materials can be used alone or in combination. Among these, gelatin is preferable. In addition to the hydrophilic colloid, an acrylic resin, polyester resin, polyurethane resin, polystyrene resin, SBR, PVDC resin, or the like can be used in combination as a binder.
前記下塗層用塗布液は、下塗層形成前に、温度50~80℃で10分~5時間保持することが好ましいが、より好ましくは、温度60~70℃で30分~3時間、さらに好ましくは温度60~70℃で1~2時間である。
The undercoat layer coating solution is preferably maintained at a temperature of 50 to 80 ° C. for 10 minutes to 5 hours, more preferably at a temperature of 60 to 70 ° C. for 30 minutes to 3 hours, before forming the undercoat layer. More preferably, the temperature is 60 to 70 ° C. for 1 to 2 hours.
前記下塗層用塗布液は、そのpHが4~8であることが塗布液の安定性の観点から好ましく、より好ましくはpHが5~8であり、さらに好ましくはpHが6~7である。
The pH of the coating solution for the undercoat layer is preferably 4 to 8 from the viewpoint of the stability of the coating solution, more preferably 5 to 8, and still more preferably 6 to 7. .
前記下塗層用塗布液は、炭素数3以下の一価の飽和アルコールを含むことが、塗布時のハジキ故障を抑制する観点から好ましい。この一価の飽和アルコールとしては、メタノール、エタノール、プロパノール、イソプロパノール等が好適に挙げられる。これら一価の飽和アルコールは一種単独で用いてもよく、2種以上併用してもよい。また、これら一価の飽和アルコールは、上記目的のために意図的に添加されるが、例えば、後述するような溶媒を兼ねて添加される場合もあり、また、塗布液中に含まれる素材の溶媒、素材の合成、精製過程等で使用する溶媒等として、あるいは薬品貯蔵タンク・配管等の洗浄溶剤として使用される場合に、塗布液に混ざってしまうことがある。ただし、塗布液中のアルコール含有量は、20重量%以下であることが好ましく、より好ましくは1~10重量%である。
The undercoat layer coating solution preferably contains a monovalent saturated alcohol having 3 or less carbon atoms from the viewpoint of suppressing repelling failure during coating. Preferable examples of the monovalent saturated alcohol include methanol, ethanol, propanol, and isopropanol. These monovalent saturated alcohols may be used alone or in combination of two or more. In addition, these monovalent saturated alcohols are intentionally added for the above-mentioned purpose. For example, they may be added also as a solvent as described later. When used as a solvent, a solvent used in the synthesis of a material, a purification process, or the like, or as a cleaning solvent for a chemical storage tank, piping, etc., it may be mixed with the coating solution. However, the alcohol content in the coating solution is preferably 20% by weight or less, more preferably 1 to 10% by weight.
前記下塗層塗布液には、架橋剤、マット剤、染料、フィラー、界面活性剤などを含んでもよい。架橋剤としては、エポキシ、イソシアネート、メラミンなどの公知の化合物が用いられる。また、特開昭51-114120号公報などに記載されている活性ハロゲン架橋剤も好ましい。マット剤は、製造における高速搬送性を良くする目的で好適に用いられる。マット剤としては、平均粒径が0.1~8μm、好ましくは0.2~5μm程度のスチレン、ポリメチルメタクリレート、シリカなどの微粒子が用いられている。マット剤の使用量は、熱現像感光材料1m2当たり1~200mgが好ましく、2~100mgがより好ましい。フィラーとしては、コロイダルシリカ等を用いることができる。界面活性剤としては、アニオン、ノニオン、カチオン界面活性剤を用いることができる。染料としては、アンチハレーション、色調調整用染料などを用いることができる。
The undercoat layer coating solution may contain a crosslinking agent, a matting agent, a dye, a filler, a surfactant, and the like. As the crosslinking agent, known compounds such as epoxy, isocyanate, and melamine are used. Further, active halogen crosslinking agents described in JP-A No. 51-114120 are also preferred. The matting agent is preferably used for the purpose of improving high-speed transportability in production. As the matting agent, fine particles such as styrene, polymethyl methacrylate and silica having an average particle diameter of 0.1 to 8 μm, preferably about 0.2 to 5 μm are used. The amount of the matting agent used is preferably 1 to 200 mg, more preferably 2 to 100 mg, per 1 m 2 of the photothermographic material. As the filler, colloidal silica or the like can be used. As the surfactant, an anionic, nonionic or cationic surfactant can be used. As the dye, antihalation, a color tone adjusting dye, and the like can be used.
前記下塗層塗布液は、水系、有機溶媒系いずれでもよいが、コストや環境の点からは水系分散液であることが好ましい。ここで「水系分散液」とは、塗布液の溶媒(分散媒)の30質量%以上、より好ましくは50質量%以上が水である塗布液をいう。具体的な溶媒組成としては、例えば、水以外に以下の混合溶液が挙げられる。水/メタノール=85/15、水/メタノール=70/30、水/メタノール/ジメチルホルムアミド(DMF)=80/15/5、水/イソプロピルアルコール=60/40等(ただしここで数字は質量比を表す)。
The undercoat layer coating solution may be either aqueous or organic solvent, but is preferably an aqueous dispersion from the viewpoint of cost and environment. Here, the “aqueous dispersion” refers to a coating liquid in which 30% by mass or more, more preferably 50% by mass or more, of the solvent (dispersion medium) of the coating liquid is water. Specific examples of the solvent composition include the following mixed solutions in addition to water. Water / methanol = 85/15, water / methanol = 70/30, water / methanol / dimethylformamide (DMF) = 80/15/5, water / isopropyl alcohol = 60/40, etc. To express).
前記下塗層は、上記の下塗層用塗布液を用いて、塗布・乾燥し、形成されたものである。本発明では、塗布方法としてバーコーターが用いられる。その際の条件として、Wet塗布量が7.0ml/m2以上30ml/m2以下、好ましくは8.0ml/m2以上10ml/m2以下に設定される。Wet塗布量を7.0ml/m2未満だと、塗布液に凝集が発生した際にすぐに面状故障が発生するが、7.0ml/m2以上とすることによって、凝集が発生しても面状故障の発生を防止できる。また、Wet塗布量が30ml/m2を超えると、塗布ムラ等の面状故障が発生するが、Wet塗布量を30ml/m2以下とすることによってこれを防止できる。
The undercoat layer is formed by applying and drying the above undercoat layer coating solution. In the present invention, a bar coater is used as a coating method. As conditions for the, Wet coating amount of 7.0 ml / m 2 or more 30 ml / m 2 or less, is preferably set to less than 8.0 ml / m 2 or more 10 ml / m 2. That's Wet coating weight less than 7.0 ml / m 2, but soon planar failure occurs when the aggregate in the coating solution is generated by a 7.0 ml / m 2 or more, aggregation occurs Can also prevent the occurrence of surface failure. Further, when the wet coating amount exceeds 30 ml / m 2 , a surface failure such as coating unevenness occurs, but this can be prevented by setting the wet coating amount to 30 ml / m 2 or less.
前記下塗層は1層のみ設けても、2層以上設けてもよい。ただし、複数の下塗層を設ける場合には、各下塗層をバーコーターによって逐次塗布するとともに、その各塗布時においてWet塗布量を7.0ml/m2以上30ml/m2以下、好ましくは8.0ml/m2以上10ml/m2以下に設定する。これにより、各下塗層において面状故障の発生を防止できる。なお、各下塗層の厚さは、1層あたり0.05~5μm、より好ましくは0.1~3μm程度が好ましい。
The undercoat layer may be provided alone or in two or more layers. However, in the case of providing a plurality of subbing layers, each subbing layer together sequentially applied by a bar coater, its Wet coating amount at the time of each coating 7.0 ml / m 2 or more 30 ml / m 2 or less, preferably 8.0 ml / m 2 or more 10 ml / m 2 set below. Thereby, the occurrence of planar failure can be prevented in each undercoat layer. The thickness of each undercoat layer is preferably about 0.05 to 5 μm, more preferably about 0.1 to 3 μm per layer.
前記下塗層の塗布後の乾燥方法は特に限定されるものではないが、例えば25~200℃程度の温度で0.5~20分間程度とすればよく、この条件で乾燥させることができる。
The drying method after application of the undercoat layer is not particularly limited. For example, the drying method may be performed at a temperature of about 25 to 200 ° C. for about 0.5 to 20 minutes, and can be dried under these conditions.
以上はハロゲン化銀感光材料の下塗りに適用した例であるが、その他の感光材料、光学フィルム材料の下塗りに対しても好適に用いることができる。また、下塗り素材としても、水分散系ラテックス、ゼラチン、PVA等、ポリエステル樹脂バインダー、ポリウレタン樹脂バインダー、UV効果樹脂、グラフト重合用素材等を用いた場合においても同様の効果が得られる。
The above is an example applied to the undercoating of the silver halide photosensitive material, but it can also be suitably used for the undercoating of other photosensitive materials and optical film materials. The same effect can be obtained when an undercoat material such as water-dispersed latex, gelatin, PVA, or the like, a polyester resin binder, a polyurethane resin binder, a UV effect resin, a graft polymerization material, or the like is used.
(2-1)感光材料の製造方法への適用時のその他の塗布層の形成
本発明の製造方法で得られた本発明のポリエステルフィルムを感光材料に用いる場合、前記その他の機能層としては、感光性層(感材塗布層)や画像形成層を挙げることができる。 (2-1) Formation of other coating layers when applied to a method for producing a photosensitive material When the polyester film of the present invention obtained by the production method of the present invention is used for a photosensitive material, the other functional layers are: Examples thereof include a photosensitive layer (photosensitive material coating layer) and an image forming layer.
本発明の製造方法で得られた本発明のポリエステルフィルムを感光材料に用いる場合、前記その他の機能層としては、感光性層(感材塗布層)や画像形成層を挙げることができる。 (2-1) Formation of other coating layers when applied to a method for producing a photosensitive material When the polyester film of the present invention obtained by the production method of the present invention is used for a photosensitive material, the other functional layers are: Examples thereof include a photosensitive layer (photosensitive material coating layer) and an image forming layer.
前記感光性層や有機銀塩含有層について説明する。感光性層は、感光性ハロゲン化銀を含有することが好ましい。画像形成層は有機銀塩を含有する有機銀塩含有層である。通常、画像形成層は感光性銀塩である感光性ハロゲン化銀が含有された感光性層(乳剤層)でもあり、このような場合、以下、感光性層と画像形成層とを区別無く用いる場合がある。
The photosensitive layer and the organic silver salt-containing layer will be described. The photosensitive layer preferably contains a photosensitive silver halide. The image forming layer is an organic silver salt-containing layer containing an organic silver salt. Usually, the image forming layer is also a photosensitive layer (emulsion layer) containing a photosensitive silver halide which is a photosensitive silver salt. In such a case, hereinafter, the photosensitive layer and the image forming layer are used without distinction. There is a case.
前記感光性層における、ハロゲン化銀の粒子サイズ、形状、ハロゲン化銀粒子最表面に存在させる金属錯体の種類、ハロゲン化銀粒子に含有させることのできる金属原子、ハロゲン化銀乳剤の脱塩法や化学増感法、感光性層中に含まれる感光性ハロゲン化銀の種類と添加量、感光性ハロゲン化銀の形成方法、感光性ハロゲン化銀と併用される有機銀塩、感光性ハロゲン化銀と有機銀塩との混合方法や比率、ハロゲン化銀を感光性層中に添加するタイミング、還元剤、現像促進剤、カブリ防止剤、安定剤、安定剤前駆体、色調剤、可塑剤、潤滑剤、かぶらせ物質、超硬調化剤、各種染料や顔料、酸化防止剤、紫外線吸収剤、被覆助剤については特開2007-270066号公報に記載の態様を好ましく用いることができる。
In the photosensitive layer, silver halide grain size, shape, type of metal complex present on the outermost surface of the silver halide grain, metal atom that can be contained in the silver halide grain, desalting method of silver halide emulsion And chemical sensitization method, type and amount of photosensitive silver halide contained in photosensitive layer, formation method of photosensitive silver halide, organic silver salt used in combination with photosensitive silver halide, photosensitive halogenation Mixing method and ratio of silver and organic silver salt, timing of adding silver halide to the photosensitive layer, reducing agent, development accelerator, antifoggant, stabilizer, stabilizer precursor, colorant, plasticizer, For lubricants, fogging substances, ultra-high contrast agents, various dyes and pigments, antioxidants, UV absorbers, and coating aids, the embodiments described in JP-A-2007-270066 can be preferably used.
前記感光性層に用いる感光性ハロゲン化銀乳剤に含有されるゼラチンとしては、種々のゼラチンを使用することができる。感光性ハロゲン化銀乳剤の有機銀塩含有塗布液中での分散状態を良好に維持するために、分子量は、500~60,000の低分子量ゼラチンを使用することが好ましい。これらの低分子量ゼラチンは粒子形成時あるいは脱塩処理後の分散時に使用してもよいが、脱塩処理後の分散時に使用することが好ましい。
As the gelatin contained in the photosensitive silver halide emulsion used for the photosensitive layer, various gelatins can be used. In order to maintain a good dispersion state of the photosensitive silver halide emulsion in the organic silver salt-containing coating solution, it is preferable to use low molecular weight gelatin having a molecular weight of 500 to 60,000. These low molecular weight gelatins may be used at the time of particle formation or dispersion after desalting, but are preferably used at the time of dispersion after desalting.
前記画像形成層である有機銀塩含有層のバインダーは、いかなるポリマーであってもよく、好適なバインダーは透明又は半透明で、一般に無色であり、天然樹脂やポリマー及びコポリマー、合成樹脂やポリマー及びコポリマー、その他フィルムを形成する媒体、例えば、ゼラチン類、ゴム類、ポリ(ビニルアルコール)類、ヒドロキシエチルセルロース類、セルロースアセテート類、セルロースアセテートブチレート類、ポリ(ビニルピロリドン)類、カゼイン、デンプン、ポリ(アクリル酸)類、ポリ(メチルメタクリル酸)類、ポリ(塩化ビニル)類、ポリ(メタクリル酸)類、スチレン-無水マレイン酸共重合体類、スチレン-アクリロニトリル共重合体類、スチレン-ブタジエン共重合体類、ポリ(ビニルアセタール)類(例えば、ポリ(ビニルホルマール)及びポリ(ビニルブチラール))、ポリ(エステル)類、ポリ(ウレタン)類、フェノキシ樹脂、ポリ(塩化ビニリデン)類、ポリ(エポキシド)類、ポリ(カーボネート)類、ポリ(酢酸ビニル)類、ポリ(オレフィン)類、セルロースエステル類、ポリ(アミド)類がある。バインダーは、水もしくは有機溶媒又はエマルションから被覆形成してもよい。
バインダーとなるポリマーは単独種で用いてもよいし、必要に応じて2種以上を併用してもよい。また、ガラス転移温度が20℃以上のものとガラス転移温度が20℃未満のものを組み合わせて用いてもよい。Tgの異なるポリマーを2種以上ブレンドして使用する場合には、その重量平均Tgが上記の範囲に入ることが好ましい。 The binder of the organic silver salt-containing layer as the image forming layer may be any polymer. Suitable binders are transparent or translucent and generally colorless. Natural resins and polymers and copolymers, synthetic resins and polymers and Copolymers and other film-forming media such as gelatins, rubbers, poly (vinyl alcohol) s, hydroxyethylcelluloses, cellulose acetates, cellulose acetate butyrates, poly (vinylpyrrolidone) s, casein, starch, poly (Acrylic acid) s, poly (methyl methacrylic acid) s, poly (vinyl chloride) s, poly (methacrylic acid) s, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymer Polymers, poly (vinyl acetal) s (eg, (Vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride) s, poly (epoxides), poly (carbonates), poly (acetic acid) Vinyl), poly (olefin) s, cellulose esters, and poly (amides). The binder may be formed from water or an organic solvent or an emulsion.
The polymer used as a binder may be used alone or in combination of two or more as required. Further, a glass transition temperature of 20 ° C. or higher and a glass transition temperature of less than 20 ° C. may be used in combination. When two or more kinds of polymers having different Tg are blended and used, the weight average Tg is preferably within the above range.
バインダーとなるポリマーは単独種で用いてもよいし、必要に応じて2種以上を併用してもよい。また、ガラス転移温度が20℃以上のものとガラス転移温度が20℃未満のものを組み合わせて用いてもよい。Tgの異なるポリマーを2種以上ブレンドして使用する場合には、その重量平均Tgが上記の範囲に入ることが好ましい。 The binder of the organic silver salt-containing layer as the image forming layer may be any polymer. Suitable binders are transparent or translucent and generally colorless. Natural resins and polymers and copolymers, synthetic resins and polymers and Copolymers and other film-forming media such as gelatins, rubbers, poly (vinyl alcohol) s, hydroxyethylcelluloses, cellulose acetates, cellulose acetate butyrates, poly (vinylpyrrolidone) s, casein, starch, poly (Acrylic acid) s, poly (methyl methacrylic acid) s, poly (vinyl chloride) s, poly (methacrylic acid) s, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymer Polymers, poly (vinyl acetal) s (eg, (Vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride) s, poly (epoxides), poly (carbonates), poly (acetic acid) Vinyl), poly (olefin) s, cellulose esters, and poly (amides). The binder may be formed from water or an organic solvent or an emulsion.
The polymer used as a binder may be used alone or in combination of two or more as required. Further, a glass transition temperature of 20 ° C. or higher and a glass transition temperature of less than 20 ° C. may be used in combination. When two or more kinds of polymers having different Tg are blended and used, the weight average Tg is preferably within the above range.
前記有機銀塩含有層塗布液のバインダーは水系溶媒に分散可能なポリマーが特に好ましい。
前記水系溶媒に分散可能なポリマーの好ましい態様としては、アクリル系ポリマー、ポリ(エステル)類、ゴム類(例えばSBR樹脂)、ポリ(ウレタン)類、ポリ(塩化ビニル)類、ポリ(酢酸ビニル)類、ポリ(塩化ビニリデン)類、ポリ(オレフィン)類等の疎水性ポリマーを好ましく用いることができる。これらポリマーとしては直鎖のポリマーでも枝分かれしたポリマーでもまた架橋されたポリマーでもよいし、単一のモノマーが重合したいわゆるホモポリマーでもよいし、2種類以上のモノマーが重合したコポリマーでもよい。コポリマーの場合はランダムコポリマーでも、ブロックコポリマーでもよい。
前記ポリマーラテックスとしては、特に、スチレン-ブタジエン共重合体のラテックスが好ましい。 The binder of the organic silver salt-containing layer coating solution is particularly preferably a polymer that can be dispersed in an aqueous solvent.
Preferred embodiments of the polymer dispersible in the aqueous solvent include acrylic polymers, poly (esters), rubbers (eg, SBR resin), poly (urethanes), poly (vinyl chloride) s, poly (vinyl acetate) , Hydrophobic polymers such as poly (vinylidene chloride) s and poly (olefins) can be preferably used. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more types of monomers. In the case of a copolymer, it may be a random copolymer or a block copolymer.
The polymer latex is particularly preferably a styrene-butadiene copolymer latex.
前記水系溶媒に分散可能なポリマーの好ましい態様としては、アクリル系ポリマー、ポリ(エステル)類、ゴム類(例えばSBR樹脂)、ポリ(ウレタン)類、ポリ(塩化ビニル)類、ポリ(酢酸ビニル)類、ポリ(塩化ビニリデン)類、ポリ(オレフィン)類等の疎水性ポリマーを好ましく用いることができる。これらポリマーとしては直鎖のポリマーでも枝分かれしたポリマーでもまた架橋されたポリマーでもよいし、単一のモノマーが重合したいわゆるホモポリマーでもよいし、2種類以上のモノマーが重合したコポリマーでもよい。コポリマーの場合はランダムコポリマーでも、ブロックコポリマーでもよい。
前記ポリマーラテックスとしては、特に、スチレン-ブタジエン共重合体のラテックスが好ましい。 The binder of the organic silver salt-containing layer coating solution is particularly preferably a polymer that can be dispersed in an aqueous solvent.
Preferred embodiments of the polymer dispersible in the aqueous solvent include acrylic polymers, poly (esters), rubbers (eg, SBR resin), poly (urethanes), poly (vinyl chloride) s, poly (vinyl acetate) , Hydrophobic polymers such as poly (vinylidene chloride) s and poly (olefins) can be preferably used. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more types of monomers. In the case of a copolymer, it may be a random copolymer or a block copolymer.
The polymer latex is particularly preferably a styrene-butadiene copolymer latex.
前記有機銀塩含有層塗布液には必要に応じてゼラチン、ポリビニルアルコール、メチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロースなどの親水性ポリマーを添加してもよい。
前記有機銀塩含有層塗布液は、いわゆるチキソトロピー流体であることが好ましい。 If necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose may be added to the organic silver salt-containing layer coating solution.
The organic silver salt-containing layer coating solution is preferably a so-called thixotropic fluid.
前記有機銀塩含有層塗布液は、いわゆるチキソトロピー流体であることが好ましい。 If necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose may be added to the organic silver salt-containing layer coating solution.
The organic silver salt-containing layer coating solution is preferably a so-called thixotropic fluid.
前記画像形成層には架橋のための架橋剤、塗布性改良のための界面活性剤などを添加してもよい。
In the image forming layer, a crosslinking agent for crosslinking, a surfactant for improving coating properties, and the like may be added.
本発明の適用例においては、上記各層は、いかなる方法で塗布されてもよい。具体的には、エクストルージョンコーティング、スライドコーティング、カーテンコーティング、浸漬コーティング、ナイフコーティング、フローコーティング、又は米国特許第2,681,294号に記載の種類のホッパーを用いる押出コーティングを含む種々のコーティング操作が用いられ、Stephen F. Kistler、Petert M. Schweizer著“LIQUID FILM COATING”(CHAPMAN & HALL社刊、1997年)399頁から536頁記載のエクストルージョンコーティング、又はスライドコーティングが好ましく用いられ、特に好ましくはスライドコーティングが用いられる。スライドコーティングに使用されるスライドコーターの形状の例は同書427頁のFigure 11b.1にある。また、所望により同書399頁から536頁記載の方法、米国特許第2,761,791号明細書及び英国特許第837,095号明細書に記載の方法により2層又はそれ以上の層を同時に被覆することができる。
In the application example of the present invention, the respective layers may be applied by any method. Specifically, various coating operations including extrusion coating, slide coating, curtain coating, dip coating, knife coating, flow coating, or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294. Is used, and Stephen F. Kistler, Peter M. Extrusion coating or slide coating described in pages 399 to 536 of “LIQUID FILM COATING” (CHAPMAN & HALL, 1997) by Schweizer is preferably used, and slide coating is particularly preferably used. An example of the shape of the slide coater used for the slide coating is shown in FIG. 11b. 1 If desired, two or more layers may be simultaneously coated by the method described on pages 399 to 536 of the same document, the method described in US Pat. No. 2,761,791 and British Patent No. 837,095. can do.
その他の各層の好ましい態様については特開2007-270066号公報に記載の態様を挙げることができる。
Other preferred embodiments of each layer include the embodiments described in JP-A-2007-270066.
前記感光性層以外のその他の層については特開2007-270066号公報に記載の非感光性層を用いることでき、例えば表面保護層、バック層、アンチハレーション層を挙げることができ、同文献に記載の態様を好ましく用いることができる。
As other layers other than the photosensitive layer, a non-photosensitive layer described in JP-A-2007-270066 can be used, and examples thereof include a surface protective layer, a back layer, and an antihalation layer. The described embodiment can be preferably used.
(1-2)太陽電池保護シートの製造方法への適用時の下塗層の形成
本発明の製造方法を太陽電池保護シートの製造方法に適用する場合、前記下塗層を塗布するための方法や用いる塗布液の溶媒には、特に制限はなく、例えば、特開2011-29397に記載の構成の材料等も用いることができるが、本発明はそれに拘るものではない。
前記塗布方法としては、例えば、グラビアコーター、バーコーターなどの公知の塗布方法を利用することができる。
前記下塗層用塗布液に用いる溶媒は、水でもよいし、トルエンやメチルエチルケトン等の有機溶媒でもよい。溶媒は1種類を単独で用いてもよいし、2種類以上を混合して用いてもよい。
また、塗布は、2軸延伸した後の樹脂フィルム基材に塗布してもよいし、1軸延伸後の樹脂フィルム基材に塗布した後に初めの延伸と異なる方向に延伸する方法でもよい。さらに、延伸前の基材に塗布した後に2方向に延伸してもよい。
前記下塗層用塗布液の塗布量は、求める下塗層の厚みに応じて変えることが好ましく、2g/m2以下であることが好ましく、より好ましくは0.05g/m2~2g/m2であり、更に好ましくは0.1g/m2~1.5g/m2である。
前記下塗層用塗布液が前記無機酸化物フィラーを含む場合、その塗布量は0.005~0.05g/m2であることが好ましく、0.005~0.03g/m2であることがより好ましく、0.005~0.02g/m2であることが特に好ましい。 (1-2) Formation of undercoat layer when applied to solar cell protective sheet manufacturing method When the manufacturing method of the present invention is applied to a solar cell protective sheet manufacturing method, a method for applying the undercoat layer There is no particular limitation on the solvent of the coating solution to be used, and for example, materials having a structure described in JP2011-29397A can be used, but the present invention is not limited thereto.
As the coating method, for example, a known coating method such as a gravure coater or a bar coater can be used.
The solvent used for the coating solution for the undercoat layer may be water or an organic solvent such as toluene or methyl ethyl ketone. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
The coating may be applied to the resin film substrate after biaxial stretching, or may be a method of stretching in a direction different from the initial stretching after coating to the resin film substrate after uniaxial stretching. Furthermore, you may extend | stretch in 2 directions, after apply | coating to the base material before extending | stretching.
The coating amount of the coating solution for the undercoat layer is preferably changed according to the desired thickness of the undercoat layer, preferably 2 g / m 2 or less, more preferably 0.05 g / m 2 to 2 g / m. 2 , more preferably 0.1 g / m 2 to 1.5 g / m 2 .
Said case of undercoat layer coating liquid containing the inorganic oxide filler, the coating amount is preferably from 0.005 ~ 0.05g / m 2, is 0.005 ~ 0.03g / m 2 Is more preferable, and 0.005 to 0.02 g / m 2 is particularly preferable.
本発明の製造方法を太陽電池保護シートの製造方法に適用する場合、前記下塗層を塗布するための方法や用いる塗布液の溶媒には、特に制限はなく、例えば、特開2011-29397に記載の構成の材料等も用いることができるが、本発明はそれに拘るものではない。
前記塗布方法としては、例えば、グラビアコーター、バーコーターなどの公知の塗布方法を利用することができる。
前記下塗層用塗布液に用いる溶媒は、水でもよいし、トルエンやメチルエチルケトン等の有機溶媒でもよい。溶媒は1種類を単独で用いてもよいし、2種類以上を混合して用いてもよい。
また、塗布は、2軸延伸した後の樹脂フィルム基材に塗布してもよいし、1軸延伸後の樹脂フィルム基材に塗布した後に初めの延伸と異なる方向に延伸する方法でもよい。さらに、延伸前の基材に塗布した後に2方向に延伸してもよい。
前記下塗層用塗布液の塗布量は、求める下塗層の厚みに応じて変えることが好ましく、2g/m2以下であることが好ましく、より好ましくは0.05g/m2~2g/m2であり、更に好ましくは0.1g/m2~1.5g/m2である。
前記下塗層用塗布液が前記無機酸化物フィラーを含む場合、その塗布量は0.005~0.05g/m2であることが好ましく、0.005~0.03g/m2であることがより好ましく、0.005~0.02g/m2であることが特に好ましい。 (1-2) Formation of undercoat layer when applied to solar cell protective sheet manufacturing method When the manufacturing method of the present invention is applied to a solar cell protective sheet manufacturing method, a method for applying the undercoat layer There is no particular limitation on the solvent of the coating solution to be used, and for example, materials having a structure described in JP2011-29397A can be used, but the present invention is not limited thereto.
As the coating method, for example, a known coating method such as a gravure coater or a bar coater can be used.
The solvent used for the coating solution for the undercoat layer may be water or an organic solvent such as toluene or methyl ethyl ketone. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
The coating may be applied to the resin film substrate after biaxial stretching, or may be a method of stretching in a direction different from the initial stretching after coating to the resin film substrate after uniaxial stretching. Furthermore, you may extend | stretch in 2 directions, after apply | coating to the base material before extending | stretching.
The coating amount of the coating solution for the undercoat layer is preferably changed according to the desired thickness of the undercoat layer, preferably 2 g / m 2 or less, more preferably 0.05 g / m 2 to 2 g / m. 2 , more preferably 0.1 g / m 2 to 1.5 g / m 2 .
Said case of undercoat layer coating liquid containing the inorganic oxide filler, the coating amount is preferably from 0.005 ~ 0.05g / m 2, is 0.005 ~ 0.03g / m 2 Is more preferable, and 0.005 to 0.02 g / m 2 is particularly preferable.
前記下塗層用塗布液の厚みは、好ましくは0.05μm~2μmであり、更に好ましくは0.1μm~1.5μmである。厚みが0.05μm以上であることにより、必要な接着性を確保しやすい。
The thickness of the undercoat layer coating solution is preferably 0.05 μm to 2 μm, more preferably 0.1 μm to 1.5 μm. When the thickness is 0.05 μm or more, it is easy to ensure necessary adhesiveness.
前記下塗層用塗布液(好ましくは、後述する複合ポリマーを含むポリマー層用塗布液)は、塗布溶媒として水を用いた水系でもよいし、トルエンやメチルエチルケトン等の有機溶媒を用いた溶剤系でもよい。中でも、環境負荷の観点から、水を溶媒とすることが好ましい。塗布溶媒は、1種類を単独で用いてもよいし、2種類以上を混合して用いてもよい。
The undercoat layer coating solution (preferably, a polymer layer coating solution containing a composite polymer described later) may be an aqueous system using water as a coating solvent, or a solvent system using an organic solvent such as toluene or methyl ethyl ketone. Good. Among these, from the viewpoint of environmental burden, it is preferable to use water as a solvent. A coating solvent may be used individually by 1 type, and may mix and use 2 or more types.
前記下塗層用塗布液としては、これに含まれる溶媒中の50質量%以上、好ましくは80質量%以上、より好ましくは90質量%以上が水である水系分散液であることが好ましい。水系分散液は、環境負荷の点で好ましく、また水の割合が50質量%以上であることにより、環境負荷が特に小さくなる点で有利である。
The undercoat layer coating liquid is preferably an aqueous dispersion in which 50% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more of the solvent contained therein is water. The aqueous dispersion is preferable in terms of environmental load, and is advantageous in that the environmental load is particularly reduced when the ratio of water is 50% by mass or more.
前記下塗層用塗布液には、必要に応じて、架橋剤、界面活性剤、フィラー、複合ポリマーなどのバインダー等を添加してもよい。
In the coating solution for the undercoat layer, a binder such as a crosslinking agent, a surfactant, a filler, and a composite polymer may be added as necessary.
前記下塗層用塗布液が、架橋剤を含むことが、得られるポリエステルフィルムの塗布層を架橋構造にして、より湿熱耐久性を改善する観点から好ましい。
本発明では、前記下塗層用塗布液に架橋剤を添加して、後述する得られるポリマー層が架橋構造を有するようにすることが好ましい。
前記架橋剤としては、エポキシ系、イソシアネート系、メラミン系、カルボジイミド系、オキサゾリン系等の架橋剤を挙げることができる。その中でも、湿熱経時後の密着性を確保する観点から、本発明ではオキサゾリン系の架橋剤を用いることが好ましい。 It is preferable that the undercoat layer coating solution contains a crosslinking agent from the viewpoint of improving the wet heat durability by making the resulting polyester film coating layer into a crosslinked structure.
In the present invention, it is preferable to add a crosslinking agent to the undercoat layer coating solution so that the polymer layer to be described later has a crosslinked structure.
Examples of the crosslinking agent include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Among these, from the viewpoint of securing adhesion after wet heat aging, it is preferable to use an oxazoline-based crosslinking agent in the present invention.
本発明では、前記下塗層用塗布液に架橋剤を添加して、後述する得られるポリマー層が架橋構造を有するようにすることが好ましい。
前記架橋剤としては、エポキシ系、イソシアネート系、メラミン系、カルボジイミド系、オキサゾリン系等の架橋剤を挙げることができる。その中でも、湿熱経時後の密着性を確保する観点から、本発明ではオキサゾリン系の架橋剤を用いることが好ましい。 It is preferable that the undercoat layer coating solution contains a crosslinking agent from the viewpoint of improving the wet heat durability by making the resulting polyester film coating layer into a crosslinked structure.
In the present invention, it is preferable to add a crosslinking agent to the undercoat layer coating solution so that the polymer layer to be described later has a crosslinked structure.
Examples of the crosslinking agent include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Among these, from the viewpoint of securing adhesion after wet heat aging, it is preferable to use an oxazoline-based crosslinking agent in the present invention.
前記オキサゾリン系架橋剤の具体例としては、2-ビニル-2-オキサゾリン、2-ビニル-4-メチル-2-オキサゾリン、2-ビニル-5-メチル-2-オキサゾリン、2-イソプロペニル-2-オキサゾリン、2-イソプロペニル-4-メチル-2-オキサゾリン、2-イソプロペニル-5-エチル-2-オキサゾリン、2,2’-ビス-(2-オキサゾリン)、2,2’-メチレン-ビス-(2-オキサゾリン)、2,2’-エチレン-ビス-(2-オキサゾリン)、2,2’-トリメチレン-ビス-(2-オキサゾリン)、2,2’-テトラメチレン-ビス-(2-オキサゾリン)、2、2’-ヘキサメチレン-ビス-(2-オキサゾリン)、2,2’-オクタメチレン-ビス-(2-オキサゾリン)、2,2’-エチレン-ビス-(4,4’-ジメチル-2-オキサゾリン)、2,2’-p-フェニレン-ビス-(2-オキサゾリン)、2,2’-m-フェニレン-ビス-(2-オキサゾリン)、2,2’-m-フェニレン-ビス-(4,4’-ジメチル-2-オキサゾリン)、ビス-(2-オキサゾリニルシクロヘキサン)スルフィド、ビス-(2-オキサゾリニルノルボルナン)スルフィド等が挙げられる。さらに、これらの化合物の(共)重合体も好ましく用いられる。
また、オキサゾリン基を有する化合物として、エポクロスK2010E、同K2020E、同K2030E、同WS-500、同WS-700(いずれも日本触媒化学工業(株)製)等も利用できる。 Specific examples of the oxazoline-based crosslinking agent include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2,2'-bis- (2-oxazoline), 2,2'-methylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline), 2,2′-trimethylene-bis- (2-oxazoline), 2,2′-tetramethylene-bis- (2-oxazoline) ), 2,2′-hexamethylene-bis- (2-oxazoline), 2,2′-octamethylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4 ′) Dimethyl-2-oxazoline), 2,2'-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene- Examples thereof include bis- (4,4′-dimethyl-2-oxazoline), bis- (2-oxazolinylcyclohexane) sulfide, and bis- (2-oxazolinyl norbornane) sulfide. Furthermore, (co) polymers of these compounds are also preferably used.
Further, as a compound having an oxazoline group, Epocros K2010E, K2020E, K2030E, WS-500, WS-700 (all manufactured by Nippon Shokubai Chemical Co., Ltd.) and the like can be used.
また、オキサゾリン基を有する化合物として、エポクロスK2010E、同K2020E、同K2030E、同WS-500、同WS-700(いずれも日本触媒化学工業(株)製)等も利用できる。 Specific examples of the oxazoline-based crosslinking agent include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2,2'-bis- (2-oxazoline), 2,2'-methylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline), 2,2′-trimethylene-bis- (2-oxazoline), 2,2′-tetramethylene-bis- (2-oxazoline) ), 2,2′-hexamethylene-bis- (2-oxazoline), 2,2′-octamethylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4 ′) Dimethyl-2-oxazoline), 2,2'-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene- Examples thereof include bis- (4,4′-dimethyl-2-oxazoline), bis- (2-oxazolinylcyclohexane) sulfide, and bis- (2-oxazolinyl norbornane) sulfide. Furthermore, (co) polymers of these compounds are also preferably used.
Further, as a compound having an oxazoline group, Epocros K2010E, K2020E, K2030E, WS-500, WS-700 (all manufactured by Nippon Shokubai Chemical Co., Ltd.) and the like can be used.
前記カルボジイミド系架橋剤の具体例として、カルボジライトV-02-L2(日清紡ケミカル(株)製)の他、以下の化合物などを挙げることができる。カルボジライトSV-02(日清紡ケミカル(株)製)、カルボジライトE-01(日清紡ケミカル(株)製)。
Specific examples of the carbodiimide-based crosslinking agent include carbodilite V-02-L2 (manufactured by Nisshinbo Chemical Co., Ltd.) and the following compounds. Carbodilite SV-02 (Nisshinbo Chemical Co., Ltd.), Carbodilite E-01 (Nisshinbo Chemical Co., Ltd.).
本発明の製造方法では、前記下塗層用塗布液が、バインダーに対して5~50質量%の架橋剤を含有することが、好ましく、10~40質量%の架橋剤を含有することがより好ましく、20~40質量%の架橋剤を含有することが特に好ましい。架橋剤の添加量が5質量%以上であると、塗布層の強度及び密着性を保持しながら充分な架橋効果が得られ、50質量%以下であると、塗布液のポットライフを長く保つことができる。
In the production method of the present invention, the coating solution for the undercoat layer preferably contains 5 to 50% by mass of a crosslinking agent, and more preferably contains 10 to 40% by mass of the crosslinking agent with respect to the binder. Preferably, it contains 20 to 40% by mass of a crosslinking agent. When the addition amount of the crosslinking agent is 5% by mass or more, a sufficient crosslinking effect is obtained while maintaining the strength and adhesion of the coating layer, and when it is 50% by mass or less, the pot life of the coating solution is kept long. Can do.
前記界面活性剤としては、アニオン系やノニオン系等の公知の界面活性剤を用いることができる。界面活性剤を添加する場合、その添加量は0.1~15mg/m2が好ましく、より好ましくは0.5~5mg/m2である。界面活性剤の添加量は、0.1mg/m2以上であると、ハジキの発生を抑えて良好な層形成が得られ、15mg/m2以下であると、接着を良好に行うことができる。
As the surfactant, a known surfactant such as an anionic or nonionic surfactant can be used. When a surfactant is added, the addition amount is preferably 0.1 to 15 mg / m 2 , more preferably 0.5 to 5 mg / m 2 . When the addition amount of the surfactant is 0.1 mg / m 2 or more, generation of a repellency is suppressed and a favorable layer formation is obtained, and when it is 15 mg / m 2 or less, adhesion can be performed satisfactorily. .
前記下塗層用塗布液には、更に、フィラーを添加してもよい。
前記無機酸化物フィラーとしては、例えば、シリカ、炭酸カルシウム、酸化マグネシウム、炭酸マグネシウム、酸化錫等が挙げられる。中でも、湿熱雰囲気に曝されたときの接着性の低下が小さい点で、酸化錫、シリカの微粒子が好ましく、シリカがより好ましい。 A filler may be further added to the undercoat layer coating solution.
Examples of the inorganic oxide filler include silica, calcium carbonate, magnesium oxide, magnesium carbonate, and tin oxide. Among these, tin oxide and silica fine particles are preferable, and silica is more preferable in that the decrease in adhesiveness when exposed to a humid heat atmosphere is small.
前記無機酸化物フィラーとしては、例えば、シリカ、炭酸カルシウム、酸化マグネシウム、炭酸マグネシウム、酸化錫等が挙げられる。中でも、湿熱雰囲気に曝されたときの接着性の低下が小さい点で、酸化錫、シリカの微粒子が好ましく、シリカがより好ましい。 A filler may be further added to the undercoat layer coating solution.
Examples of the inorganic oxide filler include silica, calcium carbonate, magnesium oxide, magnesium carbonate, and tin oxide. Among these, tin oxide and silica fine particles are preferable, and silica is more preferable in that the decrease in adhesiveness when exposed to a humid heat atmosphere is small.
前記無機酸化物フィラーの粒径は、体積平均粒径で10~700nm程度が好ましく、より好ましくは20~300nm程度である。粒径がこの範囲内であると、より良好な易接着性を得ることができる。粒径は、レーザー解析/散乱式粒子径分布測定装置LA950〔(株)堀場製作所製〕により測定される値である。
The particle size of the inorganic oxide filler is preferably about 10 to 700 nm, more preferably about 20 to 300 nm in terms of volume average particle size. When the particle size is within this range, better easy adhesion can be obtained. The particle size is a value measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 (manufactured by Horiba, Ltd.).
前記無機酸化物フィラーの形状には、特に制限はなく、球形、不定形、針状形等のいずれのものを用いることができる。
The shape of the inorganic oxide filler is not particularly limited, and any shape such as a spherical shape, an irregular shape, or a needle shape can be used.
前記無機酸化物フィラーの含有量は、前記下塗層用塗布液中のバインダーに対して、5~400質量%の範囲とすることが好ましい。無機微粒子の含有量は、5質量%以上であれば湿熱雰囲気に曝されたときに良好な接着性が保持でき、400質量%以下であれば下塗層の上に積層する白色含有層の面状が悪化しにくくなる。
中でも、前記無機酸化物フィラーの含有量は、50~300質量%の範囲がより好ましい。 The content of the inorganic oxide filler is preferably in the range of 5 to 400% by mass with respect to the binder in the undercoat layer coating solution. If the content of the inorganic fine particles is 5% by mass or more, good adhesiveness can be maintained when exposed to a humid heat atmosphere, and if it is 400% by mass or less, the surface of the white content layer laminated on the undercoat layer. The condition becomes difficult to deteriorate.
In particular, the content of the inorganic oxide filler is more preferably in the range of 50 to 300% by mass.
中でも、前記無機酸化物フィラーの含有量は、50~300質量%の範囲がより好ましい。 The content of the inorganic oxide filler is preferably in the range of 5 to 400% by mass with respect to the binder in the undercoat layer coating solution. If the content of the inorganic fine particles is 5% by mass or more, good adhesiveness can be maintained when exposed to a humid heat atmosphere, and if it is 400% by mass or less, the surface of the white content layer laminated on the undercoat layer. The condition becomes difficult to deteriorate.
In particular, the content of the inorganic oxide filler is more preferably in the range of 50 to 300% by mass.
前記前記下塗層用塗布液は、バインダーを含有することができる。本発明の製造方法では、バインダーとして、下塗層が後述の複合ポリマー、ポリオレフィン樹脂、ポリウレタン樹脂、ポリビニルアルコール樹脂、ポリアクリル樹脂およびポリエステル樹脂からなる群より選択される少なくとも1種の樹脂を含むことが好ましく、後述の複合ポリマー、ポリエステル、ポリウレタン、アクリル樹脂、ポリオレフィン等を用いることがより好ましい。また、これらのバインダーは単独で用いても、2種以上用いてもよい。
The undercoat layer coating solution may contain a binder. In the production method of the present invention, the undercoat layer contains at least one resin selected from the group consisting of a composite polymer, a polyolefin resin, a polyurethane resin, a polyvinyl alcohol resin, a polyacrylic resin, and a polyester resin, which will be described later, as a binder. It is more preferable to use a composite polymer, polyester, polyurethane, acrylic resin, polyolefin or the like described later. These binders may be used alone or in combination of two or more.
前記下塗層用塗布液は、分子中に下記一般式(I)で表されるポリシロキサン構造単位と非ポリシロキサン系構造単位とを含む前記複合ポリマーを少なくとも一種を含有することが好ましい。
一般式(I)
一般式(I)中、R1およびR2はそれぞれ独立に、水素原子、ハロゲン原子または1価の有機基を表し、nは1以上の整数を表す。R1およびR2は互いに同一であっても異なっていてもよい。複数のR1は互いに同一であっても異なっていてもよく、複数のR2は互いに同一であっても異なっていてもよい。
The undercoat layer coating solution preferably contains at least one of the composite polymers including a polysiloxane structural unit represented by the following general formula (I) and a non-polysiloxane structural unit in the molecule.
Formula (I)
In general formula (I), R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and n represents an integer of 1 or more. R 1 and R 2 may be the same or different from each other. A plurality of R 1 may be the same or different from each other, and a plurality of R 2 may be the same or different from each other.
一般式(I)
Formula (I)
この複合ポリマーを含有することにより、支持体である表面処理された樹脂フィルム基材との間の湿熱環境下における長期の密着耐久性、すなわち熱や水分が与えられて劣化しやすい剥離耐性、形状安定性を従来に比べて飛躍的に向上させることができる。
By containing this composite polymer, long-term adhesion durability in a moist heat environment with the surface-treated resin film substrate that is the support, that is, peeling resistance, shape that easily deteriorates when given heat or moisture Stability can be dramatically improved compared to the conventional case.
前記複合ポリマーは、下記一般式(I)で表されるポリシロキサン構造単位と非ポリシロキサン系構造単位とが共重合した共重合体であり、ブロック共重合体であっても、ランダム共重合体であってもよい。前記複合ポリマーはブロック共重合体であることが好ましい。前記一般式(I)で表されるポリシロキサン構造単位、及び共重合される非ポリシロキサン系構造単位は、それぞれ一種単独でもよく、二種以上であってもよい。
The composite polymer is a copolymer in which a polysiloxane structural unit represented by the following general formula (I) and a non-polysiloxane structural unit are copolymerized, and even if it is a block copolymer, a random copolymer It may be. The composite polymer is preferably a block copolymer. Each of the polysiloxane structural unit represented by the general formula (I) and the non-polysiloxane structural unit to be copolymerized may be one kind or two or more kinds.
前記一般式(I)で表されるポリシロキサン構造単位は、線状、分岐状あるいは環状の構造を有する、各種のポリシロキサンに由来するポリシロキサンセグメントである好ましい。
The polysiloxane structural unit represented by the general formula (I) is preferably a polysiloxane segment derived from various polysiloxanes having a linear, branched or cyclic structure.
前記複合ポリマー中の前記一般式(I)で表されるポリシロキサンセグメント構造単位について、好ましい態様を説明する。
前記R1およびR2はそれぞれ独立に、水素原子、ハロゲン原子または1価の有機基を表す。 A preferable aspect is demonstrated about the polysiloxane segment structural unit represented by the said general formula (I) in the said composite polymer.
R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group.
前記R1およびR2はそれぞれ独立に、水素原子、ハロゲン原子または1価の有機基を表す。 A preferable aspect is demonstrated about the polysiloxane segment structural unit represented by the said general formula (I) in the said composite polymer.
R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group.
前記R1及びR2で表されるハロゲン原子としては、フッ素原子、塩素原子、ヨウ素原子等を挙げることができる。
Examples of the halogen atom represented by R 1 and R 2 include a fluorine atom, a chlorine atom, and an iodine atom.
前記1価の有機基は、Si原子と共有結合可能な1価の有機基を表すことが好ましい。
R1およびR2で表される前記「Si原子と共有結合可能な1価の有機基」は、無置換でも置換基を有してもよく、例えば、アルキル基(例:メチル基、エチル基など)、アリール基(例:フェニル基など)、アラルキル基(例:ベンジル基、フェニルエチルなど)、アルコキシ基(例:メトキシ基、エトキシ基、プロポキシ基など)、アリールオキシ基(例;フェノキシ基など)、メルカプト基、アミノ基(例:アミノ基、ジエチルアミノ基など)、アミド基等が挙げられる。
その中でも、樹脂フィルム基材との密着性及び湿熱環境下での耐久性の点で、前記R1およびR2はそれぞれ独立に、水素原子、塩素原子、臭素原子、無置換の又は置換された炭素数1~4のアルキル基(特にメチル基、エチル基)、無置換の又は置換されたフェニル基、メルカプト基、無置換のアミノ基およびアミド基が好ましい。前記R1およびR2はそれぞれ独立により好ましくは、湿熱環境下での耐久性の点で、無置換の又は置換されたアルコキシ基であり、さらに好ましくは炭素数1~4の無置換アルコキシ基である。 The monovalent organic group preferably represents a monovalent organic group that can be covalently bonded to a Si atom.
The above-mentioned “monovalent organic group capable of covalent bonding with Si atom” represented by R 1 and R 2 may be unsubstituted or substituted, for example, an alkyl group (eg, methyl group, ethyl group) Etc.), aryl groups (eg: phenyl groups, etc.), aralkyl groups (eg: benzyl groups, phenylethyl etc.), alkoxy groups (eg: methoxy groups, ethoxy groups, propoxy groups etc.), aryloxy groups (eg: phenoxy groups) Etc.), mercapto group, amino group (eg, amino group, diethylamino group, etc.), amide group and the like.
Among them, the R 1 and R 2 are each independently a hydrogen atom, a chlorine atom, a bromine atom, an unsubstituted or substituted, in terms of adhesion to a resin film substrate and durability in a wet heat environment. Alkyl groups having 1 to 4 carbon atoms (particularly methyl and ethyl groups), unsubstituted or substituted phenyl groups, mercapto groups, unsubstituted amino groups and amide groups are preferred. R 1 and R 2 are each independently more preferably an unsubstituted or substituted alkoxy group, and more preferably an unsubstituted alkoxy group having 1 to 4 carbon atoms, from the viewpoint of durability in a moist heat environment. is there.
R1およびR2で表される前記「Si原子と共有結合可能な1価の有機基」は、無置換でも置換基を有してもよく、例えば、アルキル基(例:メチル基、エチル基など)、アリール基(例:フェニル基など)、アラルキル基(例:ベンジル基、フェニルエチルなど)、アルコキシ基(例:メトキシ基、エトキシ基、プロポキシ基など)、アリールオキシ基(例;フェノキシ基など)、メルカプト基、アミノ基(例:アミノ基、ジエチルアミノ基など)、アミド基等が挙げられる。
その中でも、樹脂フィルム基材との密着性及び湿熱環境下での耐久性の点で、前記R1およびR2はそれぞれ独立に、水素原子、塩素原子、臭素原子、無置換の又は置換された炭素数1~4のアルキル基(特にメチル基、エチル基)、無置換の又は置換されたフェニル基、メルカプト基、無置換のアミノ基およびアミド基が好ましい。前記R1およびR2はそれぞれ独立により好ましくは、湿熱環境下での耐久性の点で、無置換の又は置換されたアルコキシ基であり、さらに好ましくは炭素数1~4の無置換アルコキシ基である。 The monovalent organic group preferably represents a monovalent organic group that can be covalently bonded to a Si atom.
The above-mentioned “monovalent organic group capable of covalent bonding with Si atom” represented by R 1 and R 2 may be unsubstituted or substituted, for example, an alkyl group (eg, methyl group, ethyl group) Etc.), aryl groups (eg: phenyl groups, etc.), aralkyl groups (eg: benzyl groups, phenylethyl etc.), alkoxy groups (eg: methoxy groups, ethoxy groups, propoxy groups etc.), aryloxy groups (eg: phenoxy groups) Etc.), mercapto group, amino group (eg, amino group, diethylamino group, etc.), amide group and the like.
Among them, the R 1 and R 2 are each independently a hydrogen atom, a chlorine atom, a bromine atom, an unsubstituted or substituted, in terms of adhesion to a resin film substrate and durability in a wet heat environment. Alkyl groups having 1 to 4 carbon atoms (particularly methyl and ethyl groups), unsubstituted or substituted phenyl groups, mercapto groups, unsubstituted amino groups and amide groups are preferred. R 1 and R 2 are each independently more preferably an unsubstituted or substituted alkoxy group, and more preferably an unsubstituted alkoxy group having 1 to 4 carbon atoms, from the viewpoint of durability in a moist heat environment. is there.
前記nは1~5000であることが好ましく、1~1000であることが特に好ましい。
The n is preferably 1 to 5000, particularly preferably 1 to 1000.
前記複合ポリマー分子全体に対して、前記一般式(I)で表されるポリシロキサン構造単位は15~85質量%であることが好ましく、その中でも樹脂フィルム基材との密着性及び湿熱環境下での耐久性の点で、20~80質量%の範囲がより好ましい。
ポリシロキサン構造単位の比率は、15質量%以上であれば樹脂フィルム基材との密着性及び湿熱環境下に曝された際の密着耐久性が改善し、85質量%以下であれば塗布液が安定になる。 The polysiloxane structural unit represented by the general formula (I) is preferably 15 to 85% by mass with respect to the entire composite polymer molecule. Among them, the adhesiveness with the resin film substrate and the wet heat environment are preferable. From the viewpoint of durability, the range of 20 to 80% by mass is more preferable.
If the ratio of the polysiloxane structural unit is 15% by mass or more, the adhesion with the resin film substrate and the adhesion durability when exposed to a moist heat environment are improved. Become stable.
ポリシロキサン構造単位の比率は、15質量%以上であれば樹脂フィルム基材との密着性及び湿熱環境下に曝された際の密着耐久性が改善し、85質量%以下であれば塗布液が安定になる。 The polysiloxane structural unit represented by the general formula (I) is preferably 15 to 85% by mass with respect to the entire composite polymer molecule. Among them, the adhesiveness with the resin film substrate and the wet heat environment are preferable. From the viewpoint of durability, the range of 20 to 80% by mass is more preferable.
If the ratio of the polysiloxane structural unit is 15% by mass or more, the adhesion with the resin film substrate and the adhesion durability when exposed to a moist heat environment are improved. Become stable.
また、前記複合ポリマー中、前記一般式(I)で表されるポリシロキサン構造単位部分と共重合する、非ポリシロキサン系構造単位部分としては、非ポリシロキサン系構造単位が繰り返し単位として共重合している以外は特に制限されるものではなく、任意のポリマーに由来のポリマーセグメントのいずれであってもよい。ポリマーセグメントの前駆体である重合体(前駆ポリマー)としては、例えば、ビニル系重合体、ポリエステル系重合体、ポリウレタン系重合体等の各種の重合体等が好ましく挙げられ、すなわち、本発明では前記非ポリシロキサン系構造単位が、ビニル系構造単位、ポリエステル系構造単位およびポリウレタン系構造単位の少なくとも一種であることが好ましい。すなわち、本発明では複合ポリマーの非ポリシロキサン系構造単位が、ビニル系構造単位、ポリエステル系構造単位およびポリウレタン系構造単位の少なくとも一種であることが好ましい。調製が容易なこと及び耐加水分解性に優れる点から、ビニル系重合体及びポリウレタン系重合体がより好ましい。
Further, in the composite polymer, the non-polysiloxane structural unit portion copolymerized with the polysiloxane structural unit portion represented by the general formula (I) is a non-polysiloxane structural unit copolymerized as a repeating unit. The polymer segment is not particularly limited except that it may be any polymer segment derived from any polymer. As the polymer (precursor polymer) that is a precursor of the polymer segment, for example, various polymers such as a vinyl polymer, a polyester polymer, and a polyurethane polymer are preferably exemplified. The non-polysiloxane structural unit is preferably at least one of a vinyl structural unit, a polyester structural unit, and a polyurethane structural unit. That is, in the present invention, the non-polysiloxane structural unit of the composite polymer is preferably at least one of a vinyl structural unit, a polyester structural unit, and a polyurethane structural unit. From the viewpoint of easy preparation and excellent hydrolysis resistance, a vinyl polymer and a polyurethane polymer are more preferable.
前記ビニル系重合体の代表的な例としては、アクリル系重合体、カルボン酸ビニルエステル系重合体、芳香族ビニル系重合体、フルオロオレフィン系重合体等の各種の重合体が挙げられる。中でも、設計の自由度の観点から、アクリル系重合体が特に好ましい。
なお、非ポリシロキサン系構造単位を構成する重合体は、1種単独でもよいし、2種以上の併用であってもよい。 Typical examples of the vinyl polymer include various polymers such as an acrylic polymer, a carboxylic acid vinyl ester polymer, an aromatic vinyl polymer, and a fluoroolefin polymer. Among these, acrylic polymers are particularly preferable from the viewpoint of design freedom.
In addition, the polymer which comprises a nonpolysiloxane type structural unit may be single 1 type, and 2 or more types of combined use may be sufficient as it.
なお、非ポリシロキサン系構造単位を構成する重合体は、1種単独でもよいし、2種以上の併用であってもよい。 Typical examples of the vinyl polymer include various polymers such as an acrylic polymer, a carboxylic acid vinyl ester polymer, an aromatic vinyl polymer, and a fluoroolefin polymer. Among these, acrylic polymers are particularly preferable from the viewpoint of design freedom.
In addition, the polymer which comprises a nonpolysiloxane type structural unit may be single 1 type, and 2 or more types of combined use may be sufficient as it.
また、非ポリシロキサン系構造単位をなす前駆ポリマーは、酸基及び中和された酸基の少なくとも1つ並びに/又は加水分解性シリル基を含有するものが好ましい。このような前駆ポリマーのうち、ビニル系重合体は、例えば、(a)酸基を含むビニル系単量体と加水分解性シリル基及び/又はシラノール基を含むビニル系単量体とを、これらと共重合可能な単量体と共重合させる方法、(2)予め調製した水酸基並びに加水分解性シリル基及び/又はシラノール基を含むビニル系重合体にポリカルボン酸無水物を反応させる方法、(3)予め調製した酸無水基並びに加水分解性シリル基及び/又はシラノール基を含むビニル系重合体を、活性水素を有する化合物(水、アルコール、アミン等)と反応させる方法などの各種方法を利用して調製することができる。
このような前駆ポリマーは、例えば、特開2009-52011号公報の段落番号0021~0078に記載の方法を利用して製造、入手することができる。 The precursor polymer constituting the non-polysiloxane structural unit preferably contains at least one of an acid group and a neutralized acid group and / or a hydrolyzable silyl group. Among such precursor polymers, the vinyl polymer includes, for example, (a) a vinyl monomer containing an acid group and a vinyl monomer containing a hydrolyzable silyl group and / or a silanol group. (2) a method of reacting a polycarboxylic acid anhydride with a vinyl polymer containing a previously prepared hydroxyl group and hydrolyzable silyl group and / or silanol group, 3) Utilizing various methods such as a method in which a vinyl polymer containing an acid anhydride group and a hydrolyzable silyl group and / or silanol group prepared in advance is reacted with a compound having active hydrogen (water, alcohol, amine, etc.). Can be prepared.
Such a precursor polymer can be produced and obtained by using, for example, the method described in paragraph Nos. 0021 to 0078 of JP-A-2009-52011.
このような前駆ポリマーは、例えば、特開2009-52011号公報の段落番号0021~0078に記載の方法を利用して製造、入手することができる。 The precursor polymer constituting the non-polysiloxane structural unit preferably contains at least one of an acid group and a neutralized acid group and / or a hydrolyzable silyl group. Among such precursor polymers, the vinyl polymer includes, for example, (a) a vinyl monomer containing an acid group and a vinyl monomer containing a hydrolyzable silyl group and / or a silanol group. (2) a method of reacting a polycarboxylic acid anhydride with a vinyl polymer containing a previously prepared hydroxyl group and hydrolyzable silyl group and / or silanol group, 3) Utilizing various methods such as a method in which a vinyl polymer containing an acid anhydride group and a hydrolyzable silyl group and / or silanol group prepared in advance is reacted with a compound having active hydrogen (water, alcohol, amine, etc.). Can be prepared.
Such a precursor polymer can be produced and obtained by using, for example, the method described in paragraph Nos. 0021 to 0078 of JP-A-2009-52011.
前記下塗層用塗布液は、バインダーとして、前記複合ポリマーを単独で用いてもよいし、他のポリマーと併用してもよい。他のポリマーを併用する場合、前記複合ポリマーの比率は、全バインダーの30質量%以上が好ましく、より好ましくは60質量%以上である。複合ポリマーの比率が30質量%以上であることにより、樹脂フィルム基材との密着性及び湿熱環境下での耐久性により優れる。
The undercoat layer coating solution may be used alone or in combination with another polymer as a binder. When another polymer is used in combination, the ratio of the composite polymer is preferably 30% by mass or more, more preferably 60% by mass or more of the total binder. When the ratio of the composite polymer is 30% by mass or more, the adhesiveness with the resin film substrate and the durability under a wet heat environment are more excellent.
前記複合ポリマーの分子量は5000~100,000であることが好ましく、10000~50,000であることがより好ましい。
The molecular weight of the composite polymer is preferably 5000 to 100,000, more preferably 10,000 to 50,000.
前記複合ポリマーの調製には、(i)前記非ポリシロキサン系構造単位の前駆ポリマーと、前記一般式(I)で表されるポリシロキサン構造単位を有する特定のポリシロキサンとを反応させる方法、(ii)前記非ポリシロキサン系構造単位の前駆ポリマーの存在下に、R1及び/又はR2が加水分解性基である前記一般式(I)で表されるポリシロキサン構造単位の構造を有するシラン化合物を加水分解縮合させる方法、等の方法を利用することができる。
前記(ii)の方法で用いられるシラン化合物としては、各種シラン化合物が挙げられるが、アルコキシシラン化合物が特に好ましい。 For the preparation of the composite polymer, (i) a method of reacting a precursor polymer of the non-polysiloxane structural unit with a specific polysiloxane having a polysiloxane structural unit represented by the general formula (I), ii) Silane having the structure of the polysiloxane structural unit represented by the general formula (I) in which R 1 and / or R 2 is a hydrolyzable group in the presence of the precursor polymer of the non-polysiloxane structural unit. A method of hydrolyzing and condensing a compound can be used.
Examples of the silane compound used in the method (ii) include various silane compounds, and alkoxysilane compounds are particularly preferable.
前記(ii)の方法で用いられるシラン化合物としては、各種シラン化合物が挙げられるが、アルコキシシラン化合物が特に好ましい。 For the preparation of the composite polymer, (i) a method of reacting a precursor polymer of the non-polysiloxane structural unit with a specific polysiloxane having a polysiloxane structural unit represented by the general formula (I), ii) Silane having the structure of the polysiloxane structural unit represented by the general formula (I) in which R 1 and / or R 2 is a hydrolyzable group in the presence of the precursor polymer of the non-polysiloxane structural unit. A method of hydrolyzing and condensing a compound can be used.
Examples of the silane compound used in the method (ii) include various silane compounds, and alkoxysilane compounds are particularly preferable.
前記(i)の方法により複合ポリマーを調製する場合、例えば、前駆ポリマーとポリシロキサンの混合物に、必要に応じて水と触媒を加え、20~150℃程度の温度で30分~30時間程度(好ましくは50~130℃で1~20時間)反応させることにより調製することができる。触媒としては、酸性化合物、塩基性化合物、金属含有化合物等の各種のシラノール縮合触媒を添加することができる。
また、前記(ii)の方法により複合ポリマーを調製する場合、例えば、前駆ポリマーとアルコキシシラン化合物の混合物に、水とシラノール縮合触媒を添加して、20~150℃程度の温度で30分~30時間程度(好ましくは50~130℃で1~20時間)加水分解縮合を行うことにより調製することができる。 When preparing the composite polymer by the method (i), for example, water and a catalyst are added to the mixture of the precursor polymer and polysiloxane as necessary, and the temperature is about 20 to 150 ° C. for about 30 minutes to 30 hours ( (Preferably, the reaction can be performed at 50 to 130 ° C. for 1 to 20 hours). As a catalyst, various silanol condensation catalysts, such as an acidic compound, a basic compound, and a metal containing compound, can be added.
When preparing the composite polymer by the method (ii), for example, water and a silanol condensation catalyst are added to the mixture of the precursor polymer and the alkoxysilane compound, and the temperature is about 20 to 150 ° C. for 30 minutes to 30 minutes. It can be prepared by performing hydrolysis condensation for about an hour (preferably at 50 to 130 ° C. for 1 to 20 hours).
また、前記(ii)の方法により複合ポリマーを調製する場合、例えば、前駆ポリマーとアルコキシシラン化合物の混合物に、水とシラノール縮合触媒を添加して、20~150℃程度の温度で30分~30時間程度(好ましくは50~130℃で1~20時間)加水分解縮合を行うことにより調製することができる。 When preparing the composite polymer by the method (i), for example, water and a catalyst are added to the mixture of the precursor polymer and polysiloxane as necessary, and the temperature is about 20 to 150 ° C. for about 30 minutes to 30 hours ( (Preferably, the reaction can be performed at 50 to 130 ° C. for 1 to 20 hours). As a catalyst, various silanol condensation catalysts, such as an acidic compound, a basic compound, and a metal containing compound, can be added.
When preparing the composite polymer by the method (ii), for example, water and a silanol condensation catalyst are added to the mixture of the precursor polymer and the alkoxysilane compound, and the temperature is about 20 to 150 ° C. for 30 minutes to 30 minutes. It can be prepared by performing hydrolysis condensation for about an hour (preferably at 50 to 130 ° C. for 1 to 20 hours).
(2-2)太陽電池保護シートの製造方法への適用時のその他の塗布層の形成
本発明の製造方法を太陽電池保護シートの製造方法に適用する場合、前記その他の機能層としては、白色顔料層、易接着性層、バック層などを挙げることができる。 (2-2) Formation of other coating layers when applied to a method for producing a solar cell protective sheet When the production method of the present invention is applied to a method for producing a solar cell protective sheet, the other functional layer may be white. A pigment layer, an easily adhesive layer, a back layer and the like can be mentioned.
本発明の製造方法を太陽電池保護シートの製造方法に適用する場合、前記その他の機能層としては、白色顔料層、易接着性層、バック層などを挙げることができる。 (2-2) Formation of other coating layers when applied to a method for producing a solar cell protective sheet When the production method of the present invention is applied to a method for producing a solar cell protective sheet, the other functional layer may be white. A pigment layer, an easily adhesive layer, a back layer and the like can be mentioned.
白色顔料層の形成は、顔料を含有するポリマーシートを基材に貼合する方法、基材形成時に白色顔料層を共押出しする方法、塗布による方法等により行なえる。具体的には、樹脂フィルム基材の表面に直にあるいは厚み2μm以下の下塗層を介して、貼合、共押出し、塗布等することにより白色顔料層を形成することができる。形成された白色顔料層は、樹脂フィルム基材の表面に直に接した状態であっても、あるいは下塗層を介して積層した状態であってもよい。
上記のうち、塗布による方法は、簡便であると共に、均一性で薄膜での形成が可能である点で好ましい。 The white pigment layer can be formed by a method in which a polymer sheet containing a pigment is bonded to a substrate, a method in which the white pigment layer is coextruded when forming the substrate, a method by coating, or the like. Specifically, the white pigment layer can be formed by bonding, co-extrusion, coating, or the like directly on the surface of the resin film substrate or through an undercoat layer having a thickness of 2 μm or less. The formed white pigment layer may be in a state of being in direct contact with the surface of the resin film substrate or may be in a state of being laminated via an undercoat layer.
Among the methods described above, the method by coating is preferable because it is simple and can be formed in a thin film with uniformity.
上記のうち、塗布による方法は、簡便であると共に、均一性で薄膜での形成が可能である点で好ましい。 The white pigment layer can be formed by a method in which a polymer sheet containing a pigment is bonded to a substrate, a method in which the white pigment layer is coextruded when forming the substrate, a method by coating, or the like. Specifically, the white pigment layer can be formed by bonding, co-extrusion, coating, or the like directly on the surface of the resin film substrate or through an undercoat layer having a thickness of 2 μm or less. The formed white pigment layer may be in a state of being in direct contact with the surface of the resin film substrate or may be in a state of being laminated via an undercoat layer.
Among the methods described above, the method by coating is preferable because it is simple and can be formed in a thin film with uniformity.
塗布による場合、塗布方法としては、例えば、グラビアコーター、バーコーターなどの公知の塗布方法を利用することができる。
塗布液は、塗布溶媒として水を用いた水系でもよいし、トルエンやメチルエチルケトン等の有機溶媒を用いた溶剤系でもよい。中でも、環境負荷の観点から、水を溶媒とすることが好ましい。塗布溶媒は、1種類を単独で用いてもよいし、2種類以上を混合して用いてもよい。
白色顔料層用塗布液を前記下塗層上に塗布することが好ましい。 In the case of coating, as a coating method, for example, a known coating method such as a gravure coater or a bar coater can be used.
The coating solution may be an aqueous system using water as an application solvent, or a solvent system using an organic solvent such as toluene or methyl ethyl ketone. Especially, it is preferable to use water as a solvent from a viewpoint of environmental impact. A coating solvent may be used individually by 1 type, and may mix anduse 2 or more types.
It is preferable to apply the white pigment layer coating solution onto the undercoat layer.
塗布液は、塗布溶媒として水を用いた水系でもよいし、トルエンやメチルエチルケトン等の有機溶媒を用いた溶剤系でもよい。中でも、環境負荷の観点から、水を溶媒とすることが好ましい。塗布溶媒は、1種類を単独で用いてもよいし、2種類以上を混合して用いてもよい。
白色顔料層用塗布液を前記下塗層上に塗布することが好ましい。 In the case of coating, as a coating method, for example, a known coating method such as a gravure coater or a bar coater can be used.
The coating solution may be an aqueous system using water as an application solvent, or a solvent system using an organic solvent such as toluene or methyl ethyl ketone. Especially, it is preferable to use water as a solvent from a viewpoint of environmental impact. A coating solvent may be used individually by 1 type, and may mix and
It is preferable to apply the white pigment layer coating solution onto the undercoat layer.
本発明における白色顔料層の機能は、入射光のうち太陽電池セルを通過して発電に使用されずにバックシートに到達した光を反射させて太陽電池セルに戻すことにより、太陽電池モジュールの発電効率を上げることにある。
The function of the white pigment layer in the present invention is to generate power of the solar cell module by reflecting the light that has passed through the solar cell and has reached the back sheet without being used for power generation, and returns it to the solar cell. It is to increase efficiency.
前記白色顔料層は、白色顔料の少なくとも一種を含有する。
前記白色顔料としては、例えば、酸化チタン、硫酸バリウム、酸化珪素、酸化アルミニウム、酸化マグネシウム、炭酸カルシウム、カオリン、タルク、群青、紺青、カーボンブラック等の無機顔料、フタロシアニンブルー、フタロシアニングリーン等の有機顔料を、適宜選択して含有することができる。 The white pigment layer contains at least one kind of white pigment.
Examples of the white pigment include inorganic pigments such as titanium oxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc, ultramarine blue, bitumen, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green. Can be appropriately selected and contained.
前記白色顔料としては、例えば、酸化チタン、硫酸バリウム、酸化珪素、酸化アルミニウム、酸化マグネシウム、炭酸カルシウム、カオリン、タルク、群青、紺青、カーボンブラック等の無機顔料、フタロシアニンブルー、フタロシアニングリーン等の有機顔料を、適宜選択して含有することができる。 The white pigment layer contains at least one kind of white pigment.
Examples of the white pigment include inorganic pigments such as titanium oxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc, ultramarine blue, bitumen, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green. Can be appropriately selected and contained.
前記白色顔料層に好適なバインダーは、ポリエステル、ポリウレタン、アクリル樹脂、ポリオレフィン等であり、耐久性の観点からは、アクリル樹脂、ポリオレフィンが好ましい。また、アクリル樹脂としては、アクリルとシリコーンとの複合樹脂も好ましい。好ましいバインダーの例としては、ポリオレフィンの例としてケミパールS-120、S-75N(ともに三井化学(株)製)、アクリル樹脂の例としてジュリマーET-410、SEK-301(ともに日本純薬(株)製)、アクリルとシリコーンとの複合樹脂の例としてセラネートWSA1060、WSA1070(ともにDIC(株)製)、H7620、H7630、H7650(ともに旭化成ケミカルズ(株)製)などを挙げることができる。
The binder suitable for the white pigment layer is polyester, polyurethane, acrylic resin, polyolefin or the like, and acrylic resin or polyolefin is preferable from the viewpoint of durability. As the acrylic resin, a composite resin of acrylic and silicone is also preferable. Examples of preferred binders include Chemipearl S-120 and S-75N (both manufactured by Mitsui Chemicals, Inc.) as polyolefins, and Julimer ET-410 and SEK-301 (both Nippon Pure Chemical Industries, Ltd.) as examples of acrylic resins. Examples of the composite resin of acrylic and silicone include Ceranate WSA1060, WSA1070 (both manufactured by DIC Corporation), H7620, H7630, H7650 (both manufactured by Asahi Kasei Chemicals Corporation), and the like.
本発明における白色顔料層には、バインダーおよび顔料以外に、必要に応じて、更に架橋剤、界面活性剤、フィラー等の添加剤を添加してもよい。
In addition to the binder and the pigment, additives such as a crosslinking agent, a surfactant, and a filler may be further added to the white pigment layer in the present invention as necessary.
前記架橋剤としては、エポキシ系、イソシアネート系、メラミン系、カルボジイミド系、オキサゾリン系等の架橋剤を挙げることができる。中でも、オキサゾリン系の架橋剤が好ましく、具体的には後述の易接着性層に使用可能なものを好適に用いることができる。
架橋剤を添加する場合、その添加量としては、白色顔料層中のバインダーに対して、5~50質量%が好ましく、より好ましくは10~40質量%である。架橋剤の添加量は、5質量%以上であると、白色顔料層の強度及び接着性を保持しながら充分な架橋効果が得られ、50質量%以下であると、塗布液のポットライフを長く保てる。 Examples of the crosslinking agent include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Among these, an oxazoline-based crosslinking agent is preferable, and specifically, an oxazoline-based crosslinking agent that can be used for an easily-adhesive layer described later can be suitably used.
When the cross-linking agent is added, the addition amount is preferably 5 to 50% by mass, more preferably 10 to 40% by mass with respect to the binder in the white pigment layer. When the addition amount of the crosslinking agent is 5% by mass or more, a sufficient crosslinking effect is obtained while maintaining the strength and adhesiveness of the white pigment layer, and when it is 50% by mass or less, the pot life of the coating liquid is prolonged. I can keep it.
架橋剤を添加する場合、その添加量としては、白色顔料層中のバインダーに対して、5~50質量%が好ましく、より好ましくは10~40質量%である。架橋剤の添加量は、5質量%以上であると、白色顔料層の強度及び接着性を保持しながら充分な架橋効果が得られ、50質量%以下であると、塗布液のポットライフを長く保てる。 Examples of the crosslinking agent include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Among these, an oxazoline-based crosslinking agent is preferable, and specifically, an oxazoline-based crosslinking agent that can be used for an easily-adhesive layer described later can be suitably used.
When the cross-linking agent is added, the addition amount is preferably 5 to 50% by mass, more preferably 10 to 40% by mass with respect to the binder in the white pigment layer. When the addition amount of the crosslinking agent is 5% by mass or more, a sufficient crosslinking effect is obtained while maintaining the strength and adhesiveness of the white pigment layer, and when it is 50% by mass or less, the pot life of the coating liquid is prolonged. I can keep it.
前記界面活性剤としては、アニオン系やノニオン系等の公知の界面活性剤が挙げられる。界面活性剤を添加する場合、その添加量は0.1~15mg/m2が好ましく、より好ましくは0.5~5mg/m2である。界面活性剤の添加量は、0.1mg/m2以上であると、ハジキの発生を抑えて良好な層形成が得られ、15mg/m2以下であると、接着を良好に行なうことができる。
Examples of the surfactant include known surfactants such as anionic and nonionic surfactants. When a surfactant is added, the addition amount is preferably 0.1 to 15 mg / m 2 , more preferably 0.5 to 5 mg / m 2 . When the addition amount of the surfactant is 0.1 mg / m 2 or more, generation of repellency can be suppressed and good layer formation can be obtained, and when it is 15 mg / m 2 or less, adhesion can be performed satisfactorily. .
前記白色顔料層には、上記の顔料とは別に、さらに、シリカ等の無機酸化物フィラーを添加してもよい。無機酸化物フィラーを添加する場合、その添加量は、白色顔料層中のバインダーに対して、20質量%以下が好ましく、より好ましくは15質量%以下である。無機酸化物フィラーの添加量が20質量%以下であると、顔料の比率低下を抑えつつ必要な反射率を得ることができる。
In addition to the above pigment, an inorganic oxide filler such as silica may be added to the white pigment layer. When adding an inorganic oxide filler, the addition amount is preferably 20% by mass or less, more preferably 15% by mass or less, with respect to the binder in the white pigment layer. When the added amount of the inorganic oxide filler is 20% by mass or less, a necessary reflectance can be obtained while suppressing a decrease in the ratio of the pigment.
本発明の太陽電池保護シートには、特に太陽電池用のバックシートとして用いる場合、前記複合ポリマーを含有するポリマー層(特に白色顔料層)の上に、さらに易接着性層が設けられていてもよい。易接着性層は、バックシートを電池側基板(電池本体)の太陽電池素子(以下、発電素子ともいう)を封止する封止材と強固に接着するための層である。
When the solar cell protective sheet of the present invention is used as a back sheet for a solar cell, even if an easy-adhesive layer is further provided on the polymer layer (particularly a white pigment layer) containing the composite polymer. Good. The easy-adhesion layer is a layer for firmly bonding the back sheet to a sealing material that seals a solar cell element (hereinafter also referred to as a power generation element) of the battery side substrate (battery body).
易接着性層は、バインダー、無機微粒子を用いて構成することができ、必要に応じて、さらに添加剤などの他の成分を含んで構成されてもよい。易接着性層は、電池側基板の発電素子を封止するエチレン-ビニルアセテート(EVA;エチレン-酢酸ビニル共重合体)系封止材に対して、10N/cm以上(好ましくは20N/cm以上)の接着力を有するように構成されていることが好ましい。接着力が10N/cm以上であると、密着性を維持し得る湿熱耐性が得られやすい。
The easy-adhesion layer can be formed using a binder and inorganic fine particles, and may further include other components such as additives as necessary. The easy-adhesion layer is 10 N / cm or more (preferably 20 N / cm or more) with respect to an ethylene-vinyl acetate (EVA: ethylene-vinyl acetate copolymer) -based sealing material that seals the power generation element of the battery side substrate. It is preferable that it is comprised so that it may have the adhesive force of (). When the adhesive force is 10 N / cm or more, it is easy to obtain wet heat resistance capable of maintaining adhesion.
なお、接着力は、易接着性層中のバインダー及び無機微粒子の量を調節する方法、バックシートの封止材と接着する面にコロナ処理を施す方法などにより調整が可能である。
The adhesive strength can be adjusted by adjusting the amount of the binder and inorganic fine particles in the easy-adhesive layer, or applying a corona treatment to the surface of the back sheet that is bonded to the sealing material.
易接着性層は、バインダーの少なくとも一種を含有することができる。
易接着性層に好適なバインダーとしては、例えば、ポリエステル、ポリウレタン、アクリル樹脂、ポリオレフィン等が挙げられ、中でも耐久性の観点から、アクリル樹脂、ポリオレフィンが好ましい。また、アクリル樹脂として、アクリルとシリコーンとの複合樹脂も好ましい。 The easy-adhesion layer can contain at least one binder.
Examples of the binder suitable for the easy-adhesive layer include polyester, polyurethane, acrylic resin, polyolefin, and the like. Among these, acrylic resin and polyolefin are preferable from the viewpoint of durability. As the acrylic resin, a composite resin of acrylic and silicone is also preferable.
易接着性層に好適なバインダーとしては、例えば、ポリエステル、ポリウレタン、アクリル樹脂、ポリオレフィン等が挙げられ、中でも耐久性の観点から、アクリル樹脂、ポリオレフィンが好ましい。また、アクリル樹脂として、アクリルとシリコーンとの複合樹脂も好ましい。 The easy-adhesion layer can contain at least one binder.
Examples of the binder suitable for the easy-adhesive layer include polyester, polyurethane, acrylic resin, polyolefin, and the like. Among these, acrylic resin and polyolefin are preferable from the viewpoint of durability. As the acrylic resin, a composite resin of acrylic and silicone is also preferable.
好ましいバインダーの例としては、ポリオレフィンの具体例としてケミパールS-120、S-75N(ともに三井化学(株)製)、アクリル樹脂の具体例としてジュリマーET-410、SEK-301(ともに日本純薬(株)製)、アクリルとシリコーンとの複合樹脂の具体例としてセラネートWSA1060、WSA1070(ともにDIC(株)製)とH7620、H7630、H7650(ともに旭化成ケミカルズ(株)製)などを挙げることができる。
Examples of preferred binders include Chemipearl S-120 and S-75N (both manufactured by Mitsui Chemicals) as specific examples of polyolefins, and Jurimer ET-410 and SEK-301 (both Nippon Pure Chemical (both manufactured by Mitsui Chemicals, Inc.)). As a specific example of the composite resin of acrylic and silicone, Ceranate WSA1060, WSA1070 (both manufactured by DIC Corporation) and H7620, H7630, H7650 (both manufactured by Asahi Kasei Chemicals Corporation) and the like can be given.
バインダーの易接着性層中における含有量は、0.05~5g/m2の範囲とする。中でも、0.08~3g/m2の範囲が好ましい。バインダーの含有量は、0.05g/m2未満であると所望とする接着力が得られず、5g/m2を超えると良好な面状が得られない。
The content of the binder in the easy-adhesive layer is in the range of 0.05 to 5 g / m 2 . Of these, the range of 0.08 to 3 g / m 2 is preferable. The content of the binder is not adhesive strength is obtained and desired to be less than 0.05 g / m 2, not exceeding 5 g / m 2 good surface state is obtained.
易接着性層は、無機微粒子の少なくとも一種を含有することができる。
無機微粒子としては、例えば、シリカ、炭酸カルシウム、酸化マグネシウム、炭酸マグネシウム、酸化錫等が挙げられる。中でも、湿熱雰囲気に曝されたときの密着性の低下が小さい点で、酸化錫、シリカの微粒子が好ましい。 The easily adhesive layer can contain at least one kind of inorganic fine particles.
Examples of the inorganic fine particles include silica, calcium carbonate, magnesium oxide, magnesium carbonate, and tin oxide. Among these, fine particles of tin oxide and silica are preferable in that the decrease in adhesion when exposed to a humid heat atmosphere is small.
無機微粒子としては、例えば、シリカ、炭酸カルシウム、酸化マグネシウム、炭酸マグネシウム、酸化錫等が挙げられる。中でも、湿熱雰囲気に曝されたときの密着性の低下が小さい点で、酸化錫、シリカの微粒子が好ましい。 The easily adhesive layer can contain at least one kind of inorganic fine particles.
Examples of the inorganic fine particles include silica, calcium carbonate, magnesium oxide, magnesium carbonate, and tin oxide. Among these, fine particles of tin oxide and silica are preferable in that the decrease in adhesion when exposed to a humid heat atmosphere is small.
無機微粒子の粒径は、体積平均粒径で10~700nm程度が好ましく、より好ましくは20~300nm程度である。粒径がこの範囲内であると、より良好な易接着性を得ることができる。粒径は、レーザー解析/散乱式粒子径分布測定装置LA950〔(株)堀場製作所製〕により測定される値である。
The particle size of the inorganic fine particles is preferably about 10 to 700 nm, more preferably about 20 to 300 nm in terms of volume average particle size. When the particle size is within this range, better easy adhesion can be obtained. The particle size is a value measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 (manufactured by Horiba, Ltd.).
無機微粒子の形状には、特に制限はなく、球形、不定形、針状形等のいずれのものを用いることができる。
The shape of the inorganic fine particles is not particularly limited, and any shape such as a spherical shape, an irregular shape, or a needle shape can be used.
無機微粒子の含有量は、易接着性層中のバインダーに対して、5~400質量%の範囲とする。無機微粒子の含有量は、5質量%未満であると、湿熱雰囲気に曝されたときに良好な接着性が保持できず、400質量%を超えると、易接着性層の面状が悪化する。
中でも、無機微粒子の含有量は、50~300質量%の範囲が好ましい。 The content of the inorganic fine particles is in the range of 5 to 400% by mass with respect to the binder in the easy-adhesive layer. When the content of the inorganic fine particles is less than 5% by mass, good adhesiveness cannot be maintained when exposed to a moist heat atmosphere, and when it exceeds 400% by mass, the surface state of the easily adhesive layer is deteriorated.
In particular, the content of inorganic fine particles is preferably in the range of 50 to 300% by mass.
中でも、無機微粒子の含有量は、50~300質量%の範囲が好ましい。 The content of the inorganic fine particles is in the range of 5 to 400% by mass with respect to the binder in the easy-adhesive layer. When the content of the inorganic fine particles is less than 5% by mass, good adhesiveness cannot be maintained when exposed to a moist heat atmosphere, and when it exceeds 400% by mass, the surface state of the easily adhesive layer is deteriorated.
In particular, the content of inorganic fine particles is preferably in the range of 50 to 300% by mass.
易接着性層には、架橋剤の少なくとも一種を含有することができる。
易接着性層に好適な架橋剤としては、エポキシ系、イソシアネート系、メラミン系、カルボジイミド系、オキサゾリン系等の架橋剤を挙げることができる。中でも、湿熱経時後の密着性を確保する観点から、オキサゾリン系架橋剤が特に好ましい。 The easily adhesive layer can contain at least one crosslinking agent.
Examples of the crosslinking agent suitable for the easily adhesive layer include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Among these, an oxazoline-based cross-linking agent is particularly preferable from the viewpoint of ensuring adhesion after wet heat aging.
易接着性層に好適な架橋剤としては、エポキシ系、イソシアネート系、メラミン系、カルボジイミド系、オキサゾリン系等の架橋剤を挙げることができる。中でも、湿熱経時後の密着性を確保する観点から、オキサゾリン系架橋剤が特に好ましい。 The easily adhesive layer can contain at least one crosslinking agent.
Examples of the crosslinking agent suitable for the easily adhesive layer include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Among these, an oxazoline-based cross-linking agent is particularly preferable from the viewpoint of ensuring adhesion after wet heat aging.
架橋剤の易接着性層中における含有量としては、易接着性層中のバインダーに対して、5~50質量%が好ましく、中でもより好ましくは20~40質量%である。架橋剤の含有量は、5質量%以上であると、良好な架橋効果が得られ、着色層の強度や密着性を保持することができ、50質量%以下であると、塗布液のポットライフを長く保つことができる。
The content of the crosslinking agent in the easy-adhesive layer is preferably 5 to 50% by mass, more preferably 20 to 40% by mass, based on the binder in the easy-adhesive layer. When the content of the crosslinking agent is 5% by mass or more, a good crosslinking effect can be obtained, and the strength and adhesion of the colored layer can be maintained. When the content is 50% by mass or less, the pot life of the coating liquid Can be kept long.
本発明における易接着性層には、必要に応じて、更に、ポリスチレン、ポリメチルメタクリレート、シリカ等の公知のマット剤、アニオン系やノニオン系などの公知の界面活性剤などを添加してもよい。
If necessary, the easily adhesive layer in the present invention may further contain a known matting agent such as polystyrene, polymethylmethacrylate, or silica, or a known surfactant such as anionic or nonionic. .
易接着性層の形成は、易接着性を有するポリマーシートを基材に貼合する方法や、塗布による方法が挙げられる。中でも、塗布による方法は、簡便であると共に、均一性で薄膜での形成が可能である点で好ましい。塗布方法としては、例えば、グラビアコーターやバーコーターなどの公知の塗布法を利用することができる。塗布液の調製に用いる塗布溶媒は、水でもよいし、トルエンやメチルエチルケトン等の有機溶媒でもよい。塗布溶媒は、1種類を単独で用いてもよいし、2種類以上を混合して用いてもよい。
The formation of the easy-adhesion layer includes a method of bonding a polymer sheet having easy adhesion to a substrate and a method by coating. Especially, the method by application | coating is preferable at the point which is easy and can form in a thin film with uniformity. As a coating method, for example, a known coating method such as a gravure coater or a bar coater can be used. The coating solvent used for preparing the coating solution may be water or an organic solvent such as toluene or methyl ethyl ketone. A coating solvent may be used individually by 1 type, and may mix and use 2 or more types.
易接着性層の厚みには、特に制限はないが、通常は0.05~8μmが好ましく、より好ましくは0.1~5μmの範囲である。易接着性層の厚みは、0.05μm以上であると必要な易接着性を好適に得ることができ、8μm以下であると面状がより良好になる。
また、易接着性層は、着色層の効果を低減させないために、透明であることが好ましい。 The thickness of the easy-adhesion layer is not particularly limited, but is usually preferably 0.05 to 8 μm, more preferably 0.1 to 5 μm. When the thickness of the easy-adhesion layer is 0.05 μm or more, necessary easy adhesion can be suitably obtained, and when it is 8 μm or less, the surface shape becomes better.
The easy-adhesion layer is preferably transparent so as not to reduce the effect of the colored layer.
また、易接着性層は、着色層の効果を低減させないために、透明であることが好ましい。 The thickness of the easy-adhesion layer is not particularly limited, but is usually preferably 0.05 to 8 μm, more preferably 0.1 to 5 μm. When the thickness of the easy-adhesion layer is 0.05 μm or more, necessary easy adhesion can be suitably obtained, and when it is 8 μm or less, the surface shape becomes better.
The easy-adhesion layer is preferably transparent so as not to reduce the effect of the colored layer.
<太陽電池モジュール>
太陽電池モジュールは、太陽光が入射する透明性の基板と、太陽電池素子と、太陽電池裏面保護シートとを含む。前記太陽電池モジュールは、太陽光の光エネルギーを電気エネルギーに変換する太陽電池素子を、太陽光が入射する透明性の基板と本発明のポリエステルフィルムを含む太陽電池裏面保護シートとの間に配置し、該基板とバックシートとの間をエチレン-ビニルアセテート系封止材で封止して構成されていることが好ましい。 <Solar cell module>
The solar cell module includes a transparent substrate on which sunlight is incident, a solar cell element, and a solar cell back surface protection sheet. In the solar cell module, a solar cell element for converting light energy of sunlight into electric energy is disposed between a transparent substrate on which sunlight is incident and a solar cell back surface protective sheet including the polyester film of the present invention. The substrate and the back sheet are preferably sealed with an ethylene-vinyl acetate sealing material.
太陽電池モジュールは、太陽光が入射する透明性の基板と、太陽電池素子と、太陽電池裏面保護シートとを含む。前記太陽電池モジュールは、太陽光の光エネルギーを電気エネルギーに変換する太陽電池素子を、太陽光が入射する透明性の基板と本発明のポリエステルフィルムを含む太陽電池裏面保護シートとの間に配置し、該基板とバックシートとの間をエチレン-ビニルアセテート系封止材で封止して構成されていることが好ましい。 <Solar cell module>
The solar cell module includes a transparent substrate on which sunlight is incident, a solar cell element, and a solar cell back surface protection sheet. In the solar cell module, a solar cell element for converting light energy of sunlight into electric energy is disposed between a transparent substrate on which sunlight is incident and a solar cell back surface protective sheet including the polyester film of the present invention. The substrate and the back sheet are preferably sealed with an ethylene-vinyl acetate sealing material.
太陽電池モジュール、太陽電池セル、バックシート以外の部材については、例えば、「太陽光発電システム構成材料」(杉本栄一監修、(株)工業調査会、2008年発行)に詳細に記載されている。
Components other than solar cell modules, solar cells, and backsheets are described in detail in, for example, “Solar Power Generation System Constituent Materials” (supervised by Eiichi Sugimoto, Industrial Research Committee, Inc., issued in 2008).
透明性の基板は、太陽光が透過し得る光透過性を有していればよく、光を透過する基材から適宜選択することができる。発電効率の観点からは、光の透過率が高いものほど好ましく、このような基板として、例えば、ガラス基板、アクリル樹脂などの透明樹脂などを好適に用いることができる。
The transparent substrate only needs to have a light-transmitting property through which sunlight can be transmitted, and can be appropriately selected from base materials that transmit light. From the viewpoint of power generation efficiency, the higher the light transmittance, the better. For such a substrate, for example, a glass substrate, a transparent resin such as an acrylic resin, or the like can be suitably used.
太陽電池素子としては、単結晶シリコン、多結晶シリコン、アモルファスシリコンなどのシリコン系、銅-インジウム-ガリウム-セレン、銅-インジウム-セレン、カドミウム-テルル、ガリウム-砒素などのIII-V族やII-VI族化合物半導体系など、各種公知の太陽電池素子を適用することができる。
Examples of solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenide, and II. Various known solar cell elements such as -VI group compound semiconductor systems can be applied.
以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す実施例に限定されるものではない。なお、特に断りのない限り、「部」は質量基準である。
The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the examples shown below. Unless otherwise specified, “part” is based on mass.
[実施例1]:感光材料用の塗布液との密着性の検討
下記にて作製する樹脂フィルム基材に対して、後述の感光材料用の塗布層塗布液との密着性の検討を行った。 [Example 1]: Examination of adhesiveness with coating solution for photosensitive material The adhesiveness with coating layer coating solution for photosensitive material described below was examined for the resin film substrate prepared below. .
下記にて作製する樹脂フィルム基材に対して、後述の感光材料用の塗布層塗布液との密着性の検討を行った。 [Example 1]: Examination of adhesiveness with coating solution for photosensitive material The adhesiveness with coating layer coating solution for photosensitive material described below was examined for the resin film substrate prepared below. .
<樹脂フィルム基材の作製>
-PETの作製-
以下に示すように、テレフタル酸及びエチレングリコールを直接反応させて水を留去し、エステル化した後、減圧下で重縮合を行なう直接エステル化法を用いて、ポリエステル樹脂を得た。
(1)エステル化反応
第一エステル化反応槽に、高純度テレフタル酸4.7トンとエチレングリコール1.8トンを90分かけて混合してスラリー形成させ、3800kg/hの流量で連続的に第一エステル化反応槽に供給した。更にクエン酸がTi金属に配位したクエン酸キレートチタン錯体(VERTEC AC-420、ジョンソン・マッセイ社製)のエチレングリコール溶液を連続的に供給し、反応槽内温度251℃、攪拌下で、平均滞留時間約4.3時間で反応を行なった。このとき、クエン酸キレートチタン錯体は、Ti添加量が元素換算値で9ppmとなるように連続的に添加した。このとき、得られたオリゴマーの酸価は500eq/トンであった。
この反応物を第二エステル化反応槽に移送し、攪拌下、反応槽内温度250℃で、平均滞留時間で1.2時間反応させ、酸価が190eq/トンのオリゴマーを得た。第二エステル化反応槽は内部が3ゾーンに仕切られており、第2ゾーンから酢酸マグネシウムのエチレングリコール溶液を、Mg添加量が元素換算値で75ppmになるように連続的に供給し、続いて第3ゾーンから、リン酸トリメチルのエチレングリコール溶液を、P添加量が元素換算値で65ppmになるように連続的に供給した。
(2)重縮合反応
上記で得られたエステル化反応生成物を連続的に第一重縮合反応槽に供給し、攪拌下、反応温度270℃、反応槽内圧力20torr(2.67×10-3MPa)で、平均滞留時間約1.8時間で重縮合させた。
更に、第二重縮合反応槽に移送し、この反応槽において攪拌下、反応槽内温度276℃、反応槽内圧力3.0torr(3.99×10-4MPa)で滞留時間約1.2時間の条件で反応(重縮合)させた。
次いで、更に第三重縮合反応槽に移送し、この反応槽では、反応槽内温度278℃、反応槽内圧力1.0torr(1.33×10-4MPa)で、滞留時間1.5時間の条件で反応(重縮合)させ、ポリエチレンテレフタレート(PET)を得た。
次に、得られた反応物を、冷水にストランド状に吐出し、直ちにカッティングしてポリエステル樹脂のペレット<断面:長径約4mm、短径約2mm、長さ:約3mm>を作製した。
このペレットの固有粘度を測定した結果、IV=0.65であった。 <Preparation of resin film substrate>
-Production of PET-
As shown below, a polyester resin was obtained using a direct esterification method in which terephthalic acid and ethylene glycol were directly reacted to distill off water and esterify, followed by polycondensation under reduced pressure.
(1) Esterification reaction In a first esterification reactor, 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol are mixed over 90 minutes to form a slurry, and continuously at a flow rate of 3800 kg / h. It supplied to the 1st esterification reaction tank. Further, an ethylene glycol solution of a citrate chelate titanium complex (VERTEC AC-420, manufactured by Johnson Matthey) in which citric acid is coordinated to Ti metal was continuously supplied, and the average temperature was 251 ° C. with stirring in the reaction vessel. The reaction was carried out with a residence time of about 4.3 hours. At this time, the citric acid chelate titanium complex was continuously added so that the amount of Ti added was 9 ppm in terms of element. At this time, the acid value of the obtained oligomer was 500 eq / ton.
This reaction product was transferred to a second esterification reaction vessel and reacted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of 1.2 hours to obtain an oligomer having an acid value of 190 eq / ton. The inside of the second esterification reaction tank is partitioned into three zones, and an ethylene glycol solution of magnesium acetate is continuously supplied from the second zone so that the amount of Mg added is 75 ppm in terms of element, From the third zone, an ethylene glycol solution of trimethyl phosphate was continuously supplied so that the added amount of P was 65 ppm in terms of element.
(2) the polycondensation reaction above-obtained esterification reaction product supplied to the first polycondensation reaction vessel continuously stirring, the reaction temperature 270 ° C., the reaction vessel pressure 20 torr (2.67 × 10 - 3 MPa) and polycondensation with an average residence time of about 1.8 hours.
Further, it was transferred to the second double condensation reaction tank, and in this reaction tank, with stirring, the reaction tank temperature was 276 ° C., the reaction tank pressure was 3.0 torr (3.99 × 10 −4 MPa), and the residence time was about 1.2. The reaction (polycondensation) was performed under the conditions of time.
Subsequently, it was further transferred to the third triple condensation reaction tank, in which the temperature in the reaction tank was 278 ° C., the pressure in the reaction tank was 1.0 torr (1.33 × 10 −4 MPa), and the residence time was 1.5 hours. The reaction (polycondensation) was carried out under the following conditions to obtain polyethylene terephthalate (PET).
Next, the obtained reaction product was discharged into cold water in a strand shape and immediately cut to prepare polyester resin pellets (cross section: major axis: about 4 mm, minor axis: about 2 mm, length: about 3 mm).
As a result of measuring the intrinsic viscosity of this pellet, it was IV = 0.65.
-PETの作製-
以下に示すように、テレフタル酸及びエチレングリコールを直接反応させて水を留去し、エステル化した後、減圧下で重縮合を行なう直接エステル化法を用いて、ポリエステル樹脂を得た。
(1)エステル化反応
第一エステル化反応槽に、高純度テレフタル酸4.7トンとエチレングリコール1.8トンを90分かけて混合してスラリー形成させ、3800kg/hの流量で連続的に第一エステル化反応槽に供給した。更にクエン酸がTi金属に配位したクエン酸キレートチタン錯体(VERTEC AC-420、ジョンソン・マッセイ社製)のエチレングリコール溶液を連続的に供給し、反応槽内温度251℃、攪拌下で、平均滞留時間約4.3時間で反応を行なった。このとき、クエン酸キレートチタン錯体は、Ti添加量が元素換算値で9ppmとなるように連続的に添加した。このとき、得られたオリゴマーの酸価は500eq/トンであった。
この反応物を第二エステル化反応槽に移送し、攪拌下、反応槽内温度250℃で、平均滞留時間で1.2時間反応させ、酸価が190eq/トンのオリゴマーを得た。第二エステル化反応槽は内部が3ゾーンに仕切られており、第2ゾーンから酢酸マグネシウムのエチレングリコール溶液を、Mg添加量が元素換算値で75ppmになるように連続的に供給し、続いて第3ゾーンから、リン酸トリメチルのエチレングリコール溶液を、P添加量が元素換算値で65ppmになるように連続的に供給した。
(2)重縮合反応
上記で得られたエステル化反応生成物を連続的に第一重縮合反応槽に供給し、攪拌下、反応温度270℃、反応槽内圧力20torr(2.67×10-3MPa)で、平均滞留時間約1.8時間で重縮合させた。
更に、第二重縮合反応槽に移送し、この反応槽において攪拌下、反応槽内温度276℃、反応槽内圧力3.0torr(3.99×10-4MPa)で滞留時間約1.2時間の条件で反応(重縮合)させた。
次いで、更に第三重縮合反応槽に移送し、この反応槽では、反応槽内温度278℃、反応槽内圧力1.0torr(1.33×10-4MPa)で、滞留時間1.5時間の条件で反応(重縮合)させ、ポリエチレンテレフタレート(PET)を得た。
次に、得られた反応物を、冷水にストランド状に吐出し、直ちにカッティングしてポリエステル樹脂のペレット<断面:長径約4mm、短径約2mm、長さ:約3mm>を作製した。
このペレットの固有粘度を測定した結果、IV=0.65であった。 <Preparation of resin film substrate>
-Production of PET-
As shown below, a polyester resin was obtained using a direct esterification method in which terephthalic acid and ethylene glycol were directly reacted to distill off water and esterify, followed by polycondensation under reduced pressure.
(1) Esterification reaction In a first esterification reactor, 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol are mixed over 90 minutes to form a slurry, and continuously at a flow rate of 3800 kg / h. It supplied to the 1st esterification reaction tank. Further, an ethylene glycol solution of a citrate chelate titanium complex (VERTEC AC-420, manufactured by Johnson Matthey) in which citric acid is coordinated to Ti metal was continuously supplied, and the average temperature was 251 ° C. with stirring in the reaction vessel. The reaction was carried out with a residence time of about 4.3 hours. At this time, the citric acid chelate titanium complex was continuously added so that the amount of Ti added was 9 ppm in terms of element. At this time, the acid value of the obtained oligomer was 500 eq / ton.
This reaction product was transferred to a second esterification reaction vessel and reacted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of 1.2 hours to obtain an oligomer having an acid value of 190 eq / ton. The inside of the second esterification reaction tank is partitioned into three zones, and an ethylene glycol solution of magnesium acetate is continuously supplied from the second zone so that the amount of Mg added is 75 ppm in terms of element, From the third zone, an ethylene glycol solution of trimethyl phosphate was continuously supplied so that the added amount of P was 65 ppm in terms of element.
(2) the polycondensation reaction above-obtained esterification reaction product supplied to the first polycondensation reaction vessel continuously stirring, the reaction temperature 270 ° C., the reaction vessel pressure 20 torr (2.67 × 10 - 3 MPa) and polycondensation with an average residence time of about 1.8 hours.
Further, it was transferred to the second double condensation reaction tank, and in this reaction tank, with stirring, the reaction tank temperature was 276 ° C., the reaction tank pressure was 3.0 torr (3.99 × 10 −4 MPa), and the residence time was about 1.2. The reaction (polycondensation) was performed under the conditions of time.
Subsequently, it was further transferred to the third triple condensation reaction tank, in which the temperature in the reaction tank was 278 ° C., the pressure in the reaction tank was 1.0 torr (1.33 × 10 −4 MPa), and the residence time was 1.5 hours. The reaction (polycondensation) was carried out under the following conditions to obtain polyethylene terephthalate (PET).
Next, the obtained reaction product was discharged into cold water in a strand shape and immediately cut to prepare polyester resin pellets (cross section: major axis: about 4 mm, minor axis: about 2 mm, length: about 3 mm).
As a result of measuring the intrinsic viscosity of this pellet, it was IV = 0.65.
-固相重合-
上記で得られたペレットを、40Paに保たれた真空容器中、220℃の温度で30時間保持して、固相重合を行なった。 -Solid state polymerization-
The pellets obtained above were held in a vacuum vessel maintained at 40 Pa at a temperature of 220 ° C. for 30 hours for solid phase polymerization.
上記で得られたペレットを、40Paに保たれた真空容器中、220℃の温度で30時間保持して、固相重合を行なった。 -Solid state polymerization-
The pellets obtained above were held in a vacuum vessel maintained at 40 Pa at a temperature of 220 ° C. for 30 hours for solid phase polymerization.
-樹脂フィルム基材の成形-
以上のように固相重合を経た後のペレットを、280℃で溶融して金属ドラムの上にキャストし、厚さ約3mmの樹脂フィルム基材を作成した。上記製膜工程の後に、作製された押出フィルム(未延伸フィルム)を縦方向および横方向に延伸後、テンター内の熱処理ゾーンで225℃で熱固定を行った後、熱緩和を施し、冷却して巻き取る工程を行った。こうして、厚み175μmの樹脂フィルム基材(以下、「PET基材」と称する。)を得た。このフィルムについて、DSCによりTmetaを求めたところ、215℃であった。 -Molding of resin film substrate-
The pellets after undergoing solid phase polymerization as described above were melted at 280 ° C. and cast on a metal drum to prepare a resin film substrate having a thickness of about 3 mm. After the film forming step, the produced extruded film (unstretched film) is stretched in the longitudinal direction and the transverse direction, heat-set at 225 ° C. in a heat treatment zone in the tenter, then subjected to heat relaxation and cooled. The winding process was performed. In this way, a resin film substrate (hereinafter referred to as “PET substrate”) having a thickness of 175 μm was obtained. With respect to this film, Tmeta was determined to be 215 ° C. by DSC.
以上のように固相重合を経た後のペレットを、280℃で溶融して金属ドラムの上にキャストし、厚さ約3mmの樹脂フィルム基材を作成した。上記製膜工程の後に、作製された押出フィルム(未延伸フィルム)を縦方向および横方向に延伸後、テンター内の熱処理ゾーンで225℃で熱固定を行った後、熱緩和を施し、冷却して巻き取る工程を行った。こうして、厚み175μmの樹脂フィルム基材(以下、「PET基材」と称する。)を得た。このフィルムについて、DSCによりTmetaを求めたところ、215℃であった。 -Molding of resin film substrate-
The pellets after undergoing solid phase polymerization as described above were melted at 280 ° C. and cast on a metal drum to prepare a resin film substrate having a thickness of about 3 mm. After the film forming step, the produced extruded film (unstretched film) is stretched in the longitudinal direction and the transverse direction, heat-set at 225 ° C. in a heat treatment zone in the tenter, then subjected to heat relaxation and cooled. The winding process was performed. In this way, a resin film substrate (hereinafter referred to as “PET substrate”) having a thickness of 175 μm was obtained. With respect to this film, Tmeta was determined to be 215 ° C. by DSC.
<感光材料用の樹脂フィルム基材の塗布前処理>
(コロナ処理条件)
得られたPET基材に対して、コロナ処理および加熱処理工程をこの順序で行った。用いた装置の概略図を図1~図4に示す。
実施例1では、得られたPET基材を、巻き出しロール10から巻き出し、電極対向ロール12によって搬送しながら、コロナ処理用電極1によってコロナ処理を以下の条件で行った。すなわち、後述の塗布液を塗布する前のPET基材の一方の表面に対して、20W・min/m2の出力でコロナ処理を施した。
製造順序、並びに、コロナ処理の回数および出力を下記表1に記載した。
<コロナ処理設備>
高周波電源AGI-023(春日電機製)およびSUS5型4山300mm電極(春日電機製)を使用した。
<放電量(出力)(単位:kJ/m2)>
コロナ処理時に印加した電力量(kJ/s)と、コロナ処理幅(電極幅:m)およびフィルムの引取り速度(m/min)を用いて、放電量(kJ/m2)を算出した。 <Pretreatment for application of resin film substrate for photosensitive material>
(Corona treatment conditions)
The corona treatment and the heat treatment process were performed in this order on the obtained PET substrate. A schematic diagram of the apparatus used is shown in FIGS.
In Example 1, the obtained PET base material was unwound from the unwindingroll 10 and conveyed by the electrode facing roll 12, and the corona treatment was performed by the corona treatment electrode 1 under the following conditions. That is, a corona treatment was performed at an output of 20 W · min / m 2 on one surface of the PET base material before applying a coating liquid described later.
The production order, the number of corona treatments and the output are shown in Table 1 below.
<Corona treatment equipment>
A high frequency power supply AGI-023 (manufactured by Kasuga Denki) and a SUS5 type four-crest 300 mm electrode (manufactured by Kasuga Denki) were used.
<Discharge amount (output) (unit: kJ / m 2 )>
The discharge amount (kJ / m 2 ) was calculated using the amount of electric power (kJ / s) applied during the corona treatment, the corona treatment width (electrode width: m), and the film take-up speed (m / min).
(コロナ処理条件)
得られたPET基材に対して、コロナ処理および加熱処理工程をこの順序で行った。用いた装置の概略図を図1~図4に示す。
実施例1では、得られたPET基材を、巻き出しロール10から巻き出し、電極対向ロール12によって搬送しながら、コロナ処理用電極1によってコロナ処理を以下の条件で行った。すなわち、後述の塗布液を塗布する前のPET基材の一方の表面に対して、20W・min/m2の出力でコロナ処理を施した。
製造順序、並びに、コロナ処理の回数および出力を下記表1に記載した。
<コロナ処理設備>
高周波電源AGI-023(春日電機製)およびSUS5型4山300mm電極(春日電機製)を使用した。
<放電量(出力)(単位:kJ/m2)>
コロナ処理時に印加した電力量(kJ/s)と、コロナ処理幅(電極幅:m)およびフィルムの引取り速度(m/min)を用いて、放電量(kJ/m2)を算出した。 <Pretreatment for application of resin film substrate for photosensitive material>
(Corona treatment conditions)
The corona treatment and the heat treatment process were performed in this order on the obtained PET substrate. A schematic diagram of the apparatus used is shown in FIGS.
In Example 1, the obtained PET base material was unwound from the unwinding
The production order, the number of corona treatments and the output are shown in Table 1 below.
<Corona treatment equipment>
A high frequency power supply AGI-023 (manufactured by Kasuga Denki) and a SUS5 type four-crest 300 mm electrode (manufactured by Kasuga Denki) were used.
<Discharge amount (output) (unit: kJ / m 2 )>
The discharge amount (kJ / m 2 ) was calculated using the amount of electric power (kJ / s) applied during the corona treatment, the corona treatment width (electrode width: m), and the film take-up speed (m / min).
(加熱処理工程条件)
上記にて一方の表面に対してコロナ処理を施したPET基材について、加熱ロール2を用いて搬送しながら、以下の条件で加熱した。すなわち、加熱ロールに接しているフィルム表面温度が130℃(上記PET基材のガラス転移温度Tgに対して、Tg+60℃となるよう加熱ロールの温度を制御した。また、加熱処理工程後のPET基材は巻き取りロール11に巻き取った。
加熱処理工程の有無、方法、温度について、下記表1に記載した。
コロナ処理後から、コロナ処理工程後加熱を始めるまでの時間は3秒とした。なお、他の実施例でもこの時間は同様とした。 (Heat treatment process conditions)
About the PET base material which performed the corona treatment with respect to one surface above, it heated on the following conditions, conveying using theheating roll 2. FIG. That is, the film surface temperature in contact with the heating roll was 130 ° C. (the temperature of the heating roll was controlled to be Tg + 60 ° C. with respect to the glass transition temperature Tg of the PET substrate. Also, the PET base after the heat treatment step) The material was taken up on a take-up roll 11.
The presence / absence, method, and temperature of the heat treatment step are shown in Table 1 below.
The time from the corona treatment to the start of heating after the corona treatment step was 3 seconds. This time is the same in other examples.
上記にて一方の表面に対してコロナ処理を施したPET基材について、加熱ロール2を用いて搬送しながら、以下の条件で加熱した。すなわち、加熱ロールに接しているフィルム表面温度が130℃(上記PET基材のガラス転移温度Tgに対して、Tg+60℃となるよう加熱ロールの温度を制御した。また、加熱処理工程後のPET基材は巻き取りロール11に巻き取った。
加熱処理工程の有無、方法、温度について、下記表1に記載した。
コロナ処理後から、コロナ処理工程後加熱を始めるまでの時間は3秒とした。なお、他の実施例でもこの時間は同様とした。 (Heat treatment process conditions)
About the PET base material which performed the corona treatment with respect to one surface above, it heated on the following conditions, conveying using the
The presence / absence, method, and temperature of the heat treatment step are shown in Table 1 below.
The time from the corona treatment to the start of heating after the corona treatment step was 3 seconds. This time is the same in other examples.
<塗布工程>
(感光材料用の塗布液の調製、樹脂フィルム基材の塗布前処理面への塗布)
前記コロナ処理後加熱工程の後の、前記コロナ処理を施した側のPET基材の表面に、下記組成のラテックス系下塗層用とゼラチンの下塗層を手塗り塗布(バーコーター)でこの順に形成し、恒温槽で乾燥した。
下塗層の塗布では、ラテックス系下塗層用の塗布液として、トリアジン系硬膜剤を含有したスチレンブタジエンゴム(SBR)液を、乾燥後厚み0.3μmとなるように行った。
その後、ゼラチン系液を、乾燥後厚み0.1μmとなるように行った。
その後、更にその上に、ハロゲン化銀塩を含有したゼラチン分散液(エマルジョン層)(乾燥後厚み:2μm)を塗布した。
得られたフィルムを実施例1のポリエステルフィルムとした。 <Application process>
(Preparation of coating solution for photosensitive material, application to pre-coated surface of resin film substrate)
After the corona treatment heating step, on the surface of the PET substrate on the corona treatment side, a latex undercoat layer and a gelatin undercoat layer having the following composition are coated by hand (bar coater). It formed in order and dried with the thermostat.
In the application of the undercoat layer, a styrene butadiene rubber (SBR) solution containing a triazine-based hardener was applied as a coating solution for the latex undercoat layer so as to have a thickness of 0.3 μm after drying.
Thereafter, the gelatin solution was dried to a thickness of 0.1 μm.
Thereafter, a gelatin dispersion (emulsion layer) containing a silver halide salt (thickness after drying: 2 μm) was further applied thereon.
The obtained film was used as the polyester film of Example 1.
(感光材料用の塗布液の調製、樹脂フィルム基材の塗布前処理面への塗布)
前記コロナ処理後加熱工程の後の、前記コロナ処理を施した側のPET基材の表面に、下記組成のラテックス系下塗層用とゼラチンの下塗層を手塗り塗布(バーコーター)でこの順に形成し、恒温槽で乾燥した。
下塗層の塗布では、ラテックス系下塗層用の塗布液として、トリアジン系硬膜剤を含有したスチレンブタジエンゴム(SBR)液を、乾燥後厚み0.3μmとなるように行った。
その後、ゼラチン系液を、乾燥後厚み0.1μmとなるように行った。
その後、更にその上に、ハロゲン化銀塩を含有したゼラチン分散液(エマルジョン層)(乾燥後厚み:2μm)を塗布した。
得られたフィルムを実施例1のポリエステルフィルムとした。 <Application process>
(Preparation of coating solution for photosensitive material, application to pre-coated surface of resin film substrate)
After the corona treatment heating step, on the surface of the PET substrate on the corona treatment side, a latex undercoat layer and a gelatin undercoat layer having the following composition are coated by hand (bar coater). It formed in order and dried with the thermostat.
In the application of the undercoat layer, a styrene butadiene rubber (SBR) solution containing a triazine-based hardener was applied as a coating solution for the latex undercoat layer so as to have a thickness of 0.3 μm after drying.
Thereafter, the gelatin solution was dried to a thickness of 0.1 μm.
Thereafter, a gelatin dispersion (emulsion layer) containing a silver halide salt (thickness after drying: 2 μm) was further applied thereon.
The obtained film was used as the polyester film of Example 1.
<感光材料用のポリエステルフィルムの評価>
-1.密着性-
上記のようにして作製した実施例1のポリエステルフィルムのサンプルシートを特開2007-270066号公報の[0046]に記載の方法で密着性試験を行った。すなわち、実施例1のポリエステルフィルムのサンプルを水に浸し、密着試験機(ふちこすり機)でこすり、乾燥後に5段階で下記の基準にしたがって評価を行った。
1:1.5mmを超えて剥離
2:1.0mmを超えて、1.5mm以下で剥離
3:0.5mmを超えて、1.0mm以下で剥離
4:0.3mmを超えて、0.5mm以下で剥離
5:0.3mm以下で剥離
密着性の評価は、数字が大きいほど下塗層との密着性が大きく、3以上が実用上許容可能な範囲である。
得られた結果を下記表1に記載した。 <Evaluation of polyester film for photosensitive material>
-1. Adhesiveness
A sample sheet of the polyester film of Example 1 produced as described above was subjected to an adhesion test by the method described in JP-A-2007-270066, [0046]. That is, the polyester film sample of Example 1 was immersed in water, rubbed with an adhesion tester (edge cutting machine), and evaluated according to the following criteria in five stages after drying.
1: More than 1.5 mm, peeling 2: more than 1.0 mm, 1.5 mm or less, peeling 3: more than 0.5 mm, 1.0 mm or less, peeling 4: more than 0.3 mm; Peeling at 5 mm or less 5: Peeling at 0.3 mm or less In the evaluation of adhesion, the larger the number, the greater the adhesion with the undercoat layer, and 3 or more is a practically acceptable range.
The obtained results are shown in Table 1 below.
-1.密着性-
上記のようにして作製した実施例1のポリエステルフィルムのサンプルシートを特開2007-270066号公報の[0046]に記載の方法で密着性試験を行った。すなわち、実施例1のポリエステルフィルムのサンプルを水に浸し、密着試験機(ふちこすり機)でこすり、乾燥後に5段階で下記の基準にしたがって評価を行った。
1:1.5mmを超えて剥離
2:1.0mmを超えて、1.5mm以下で剥離
3:0.5mmを超えて、1.0mm以下で剥離
4:0.3mmを超えて、0.5mm以下で剥離
5:0.3mm以下で剥離
密着性の評価は、数字が大きいほど下塗層との密着性が大きく、3以上が実用上許容可能な範囲である。
得られた結果を下記表1に記載した。 <Evaluation of polyester film for photosensitive material>
-1. Adhesiveness
A sample sheet of the polyester film of Example 1 produced as described above was subjected to an adhesion test by the method described in JP-A-2007-270066, [0046]. That is, the polyester film sample of Example 1 was immersed in water, rubbed with an adhesion tester (edge cutting machine), and evaluated according to the following criteria in five stages after drying.
1: More than 1.5 mm, peeling 2: more than 1.0 mm, 1.5 mm or less, peeling 3: more than 0.5 mm, 1.0 mm or less, peeling 4: more than 0.3 mm; Peeling at 5 mm or less 5: Peeling at 0.3 mm or less In the evaluation of adhesion, the larger the number, the greater the adhesion with the undercoat layer, and 3 or more is a practically acceptable range.
The obtained results are shown in Table 1 below.
-2.工程適性-
上記の方法に従ってポリエステルフィルムに下塗液を塗布した。その際のハンドリング性を検討したとき、特に問題がない場合に○評価とし、問題がある場合を×評価とした。
得られた結果を下記表1に記載した。 -2. Process suitability
The primer solution was applied to the polyester film according to the method described above. When the handling property at that time was examined, it was evaluated as ○ when there was no problem, and × when there was a problem.
The obtained results are shown in Table 1 below.
上記の方法に従ってポリエステルフィルムに下塗液を塗布した。その際のハンドリング性を検討したとき、特に問題がない場合に○評価とし、問題がある場合を×評価とした。
得られた結果を下記表1に記載した。 -2. Process suitability
The primer solution was applied to the polyester film according to the method described above. When the handling property at that time was examined, it was evaluated as ○ when there was no problem, and × when there was a problem.
The obtained results are shown in Table 1 below.
-3.塗布工程前のフィルム表面近傍における樹脂フィルム基材の結晶化温度-
塗布工程前のフィルム表面近傍における樹脂フィルム基材の結晶化温度について、表面を切削し、GPCによって熱分析で結晶化温度を測定した。
得られた結果を下記表1に記載した。 -3. The crystallization temperature of the resin film substrate near the film surface before the coating process
About the crystallization temperature of the resin film base material in the film surface vicinity before an application | coating process, the surface was cut and the crystallization temperature was measured by thermal analysis by GPC.
The obtained results are shown in Table 1 below.
塗布工程前のフィルム表面近傍における樹脂フィルム基材の結晶化温度について、表面を切削し、GPCによって熱分析で結晶化温度を測定した。
得られた結果を下記表1に記載した。 -3. The crystallization temperature of the resin film substrate near the film surface before the coating process
About the crystallization temperature of the resin film base material in the film surface vicinity before an application | coating process, the surface was cut and the crystallization temperature was measured by thermal analysis by GPC.
The obtained results are shown in Table 1 below.
[実施例2~11、比較例1~6]
実施例1において、フィルム製造方法を下記表1に示すように変更したこと以外は、実施例1と同様にして、各実施例および比較例のポリエステルフィルムフィルムを作製した。
比較例1および2では、加熱ロールを除去した設備を用いて、コロナ処理を1回または2回行った樹脂フィルム基材に対して、塗布工程を行った。比較例3では、加熱ロールを用いて加熱処理を行った後にコロナ処理を行い、コロナ処理後に加熱をしなかった。比較例4では、コロナ処理と加熱処理を同時に行った。比較例5では、樹脂フィルム基材のTg未満の温度で、コロナ処理後の加熱処理を行った。実施例4および6では、加熱処理後に樹脂フィルム基材をそのまま図4のように搬送し、オンラインで2回目以降のコロナ処理や2回目以降の加熱処理を行った。 [Examples 2 to 11, Comparative Examples 1 to 6]
In Example 1, polyester film films of Examples and Comparative Examples were produced in the same manner as Example 1 except that the film production method was changed as shown in Table 1 below.
In Comparative Examples 1 and 2, the coating process was performed on the resin film substrate that had been subjected to corona treatment once or twice using the equipment from which the heating roll was removed. In Comparative Example 3, the corona treatment was performed after the heat treatment using the heating roll, and no heating was performed after the corona treatment. In Comparative Example 4, the corona treatment and the heat treatment were performed simultaneously. In Comparative Example 5, the heat treatment after the corona treatment was performed at a temperature lower than Tg of the resin film substrate. In Examples 4 and 6, the resin film base material was directly conveyed as shown in FIG. 4 after the heat treatment, and the second and subsequent corona treatments and the second and subsequent heat treatments were performed online.
実施例1において、フィルム製造方法を下記表1に示すように変更したこと以外は、実施例1と同様にして、各実施例および比較例のポリエステルフィルムフィルムを作製した。
比較例1および2では、加熱ロールを除去した設備を用いて、コロナ処理を1回または2回行った樹脂フィルム基材に対して、塗布工程を行った。比較例3では、加熱ロールを用いて加熱処理を行った後にコロナ処理を行い、コロナ処理後に加熱をしなかった。比較例4では、コロナ処理と加熱処理を同時に行った。比較例5では、樹脂フィルム基材のTg未満の温度で、コロナ処理後の加熱処理を行った。実施例4および6では、加熱処理後に樹脂フィルム基材をそのまま図4のように搬送し、オンラインで2回目以降のコロナ処理や2回目以降の加熱処理を行った。 [Examples 2 to 11, Comparative Examples 1 to 6]
In Example 1, polyester film films of Examples and Comparative Examples were produced in the same manner as Example 1 except that the film production method was changed as shown in Table 1 below.
In Comparative Examples 1 and 2, the coating process was performed on the resin film substrate that had been subjected to corona treatment once or twice using the equipment from which the heating roll was removed. In Comparative Example 3, the corona treatment was performed after the heat treatment using the heating roll, and no heating was performed after the corona treatment. In Comparative Example 4, the corona treatment and the heat treatment were performed simultaneously. In Comparative Example 5, the heat treatment after the corona treatment was performed at a temperature lower than Tg of the resin film substrate. In Examples 4 and 6, the resin film base material was directly conveyed as shown in FIG. 4 after the heat treatment, and the second and subsequent corona treatments and the second and subsequent heat treatments were performed online.
実施例7では、樹脂フィルム基材を以下の方法で製造したPENに変更した。
(PENの製造方法)
2,6ーナフタレンジカルボン酸ジメチルエステル100部とエチレングリコール(EGと略記する)51部とを酢酸コバルト四水塩0.005部(0.2モル)、酢酸カルシウム一水塩0.014部(0.02モル)および酢酸マグネシウム四水塩0.036部(1.7モル)をエステル交換触媒として用い、常法に従ってエステル交換反応させ、三酸化アンチモンのEG1%溶液0.98部(1.0モル)を添加したのち、トリメチルフォスフェート0.045部(3.2モル)を添加し、エステル交換反応を終了せしめた。次に引き続き常法通り高温高真空下で重縮合反応を行い、その後ストランド型のチップとした。上記にて得られたPEN基材のガラス転移温度Tgは約120℃であった。また、このポリエチレンナフタレートを押出機に投入して溶融押出後、縦方向次いで横方向に延伸して175μm厚みのフィルムを作成した。これについて示差走査熱量測定を行い、微小吸熱ピークTmetaを測定した結果、約230℃であった。 In Example 7, the resin film substrate was changed to PEN produced by the following method.
(Manufacturing method of PEN)
0.005 part (0.2 mol) of cobalt acetate tetrahydrate and 0.014 part of calcium acetate monohydrate (100 parts of 2,6-naphthalenedicarboxylic acid dimethyl ester and 51 parts of ethylene glycol (abbreviated as EG)) 0.02 mol) and 0.036 parts (1.7 mol) of magnesium acetate tetrahydrate as a transesterification catalyst were subjected to a transesterification according to a conventional method to obtain 0.98 parts of anEG 1% solution of antimony trioxide (1. 0 mol) was added, and 0.045 part (3.2 mol) of trimethyl phosphate was added to complete the transesterification reaction. Subsequently, a polycondensation reaction was performed under high temperature and high vacuum as usual, and then a strand type chip was obtained. The glass transition temperature Tg of the PEN substrate obtained above was about 120 ° C. Further, this polyethylene naphthalate was charged into an extruder and melt-extruded, and then stretched in the machine direction and then in the transverse direction to form a film having a thickness of 175 μm. This was subjected to differential scanning calorimetry, and a minute endothermic peak Tmeta was measured and found to be about 230 ° C.
(PENの製造方法)
2,6ーナフタレンジカルボン酸ジメチルエステル100部とエチレングリコール(EGと略記する)51部とを酢酸コバルト四水塩0.005部(0.2モル)、酢酸カルシウム一水塩0.014部(0.02モル)および酢酸マグネシウム四水塩0.036部(1.7モル)をエステル交換触媒として用い、常法に従ってエステル交換反応させ、三酸化アンチモンのEG1%溶液0.98部(1.0モル)を添加したのち、トリメチルフォスフェート0.045部(3.2モル)を添加し、エステル交換反応を終了せしめた。次に引き続き常法通り高温高真空下で重縮合反応を行い、その後ストランド型のチップとした。上記にて得られたPEN基材のガラス転移温度Tgは約120℃であった。また、このポリエチレンナフタレートを押出機に投入して溶融押出後、縦方向次いで横方向に延伸して175μm厚みのフィルムを作成した。これについて示差走査熱量測定を行い、微小吸熱ピークTmetaを測定した結果、約230℃であった。 In Example 7, the resin film substrate was changed to PEN produced by the following method.
(Manufacturing method of PEN)
0.005 part (0.2 mol) of cobalt acetate tetrahydrate and 0.014 part of calcium acetate monohydrate (100 parts of 2,6-naphthalenedicarboxylic acid dimethyl ester and 51 parts of ethylene glycol (abbreviated as EG)) 0.02 mol) and 0.036 parts (1.7 mol) of magnesium acetate tetrahydrate as a transesterification catalyst were subjected to a transesterification according to a conventional method to obtain 0.98 parts of an
実施例8では、樹脂フィルム基材を以下の方法で製造したポリ(1,4-シクロヘキシレンジメチレンテレフタレート)(以下、PCDMTとも言う)に変更した。
(1)CHDM系ポリエステルの調製
第1工程:ジカルボン酸成分としてテレフタル酸(TPA)、ジオール成分として1,4-シクロヘキサンジメタノール(CHDM)を用い、触媒として酢酸マグネシウム、三酸化アンチモンを150℃、窒素雰囲気下で溶融後、攪拌しながら230℃まで3時間かけて昇温し、メタノールを留出させ、エステル交換反応を終了した。
第2工程:エステル交換反応終了後、リン酸をエチレングリコールに溶解したエチレングリコール溶液を添加した。
第3工程:重合反応を最終到達温度285℃、真空度0.1Torrで行い、ポリエステルを得、これをペレット化した。
第4工程:上記で得られたポリエステルペレットを、窒素気流中210℃で24時間、固相重合した。
上記樹脂を乾燥した後、2軸押出し機で真空下、285℃で溶融、キャストドラム上に押出し、剥離ロールにて剥離後、縦方向に3.5倍、横方向に4倍延伸した。なお、延伸時の温度は、縦延伸が90℃、横延伸が120℃である。
このあと210℃で熱固定したあと、205℃で縦、横方向にそれぞれ5%ずつ緩和させて250μm厚みの二軸延伸ポリエステルフィルムを得た。これについて示差走査熱量測定を行い、微小吸熱ピークTmetaを測定した結果、195℃であった。 In Example 8, the resin film substrate was changed to poly (1,4-cyclohexylenedimethylene terephthalate) (hereinafter also referred to as PCDMT) produced by the following method.
(1) Preparation of CHDM polyester First step: Using terephthalic acid (TPA) as a dicarboxylic acid component, 1,4-cyclohexanedimethanol (CHDM) as a diol component, magnesium acetate and antimony trioxide as a catalyst at 150 ° C. After melting in a nitrogen atmosphere, the temperature was raised to 230 ° C. over 3 hours with stirring, methanol was distilled off, and the transesterification reaction was completed.
Second step: After completion of the transesterification reaction, an ethylene glycol solution in which phosphoric acid was dissolved in ethylene glycol was added.
Third step: The polymerization reaction was performed at a final temperature of 285 ° C. and a vacuum of 0.1 Torr to obtain a polyester, which was pelletized.
Fourth step: The polyester pellets obtained above were subjected to solid phase polymerization in a nitrogen stream at 210 ° C. for 24 hours.
After drying the resin, it was melted at 285 ° C. under vacuum with a twin screw extruder, extruded onto a cast drum, peeled off with a peeling roll, and then stretched 3.5 times in the longitudinal direction and 4 times in the transverse direction. The temperature during stretching is 90 ° C. for longitudinal stretching and 120 ° C. for lateral stretching.
Then, after heat setting at 210 ° C., it was relaxed by 5% in each of the longitudinal and lateral directions at 205 ° C. to obtain a biaxially stretched polyester film having a thickness of 250 μm. It was 195 degreeC as a result of performing differential scanning calorimetry about this and measuring the micro endothermic peak Tmeta.
(1)CHDM系ポリエステルの調製
第1工程:ジカルボン酸成分としてテレフタル酸(TPA)、ジオール成分として1,4-シクロヘキサンジメタノール(CHDM)を用い、触媒として酢酸マグネシウム、三酸化アンチモンを150℃、窒素雰囲気下で溶融後、攪拌しながら230℃まで3時間かけて昇温し、メタノールを留出させ、エステル交換反応を終了した。
第2工程:エステル交換反応終了後、リン酸をエチレングリコールに溶解したエチレングリコール溶液を添加した。
第3工程:重合反応を最終到達温度285℃、真空度0.1Torrで行い、ポリエステルを得、これをペレット化した。
第4工程:上記で得られたポリエステルペレットを、窒素気流中210℃で24時間、固相重合した。
上記樹脂を乾燥した後、2軸押出し機で真空下、285℃で溶融、キャストドラム上に押出し、剥離ロールにて剥離後、縦方向に3.5倍、横方向に4倍延伸した。なお、延伸時の温度は、縦延伸が90℃、横延伸が120℃である。
このあと210℃で熱固定したあと、205℃で縦、横方向にそれぞれ5%ずつ緩和させて250μm厚みの二軸延伸ポリエステルフィルムを得た。これについて示差走査熱量測定を行い、微小吸熱ピークTmetaを測定した結果、195℃であった。 In Example 8, the resin film substrate was changed to poly (1,4-cyclohexylenedimethylene terephthalate) (hereinafter also referred to as PCDMT) produced by the following method.
(1) Preparation of CHDM polyester First step: Using terephthalic acid (TPA) as a dicarboxylic acid component, 1,4-cyclohexanedimethanol (CHDM) as a diol component, magnesium acetate and antimony trioxide as a catalyst at 150 ° C. After melting in a nitrogen atmosphere, the temperature was raised to 230 ° C. over 3 hours with stirring, methanol was distilled off, and the transesterification reaction was completed.
Second step: After completion of the transesterification reaction, an ethylene glycol solution in which phosphoric acid was dissolved in ethylene glycol was added.
Third step: The polymerization reaction was performed at a final temperature of 285 ° C. and a vacuum of 0.1 Torr to obtain a polyester, which was pelletized.
Fourth step: The polyester pellets obtained above were subjected to solid phase polymerization in a nitrogen stream at 210 ° C. for 24 hours.
After drying the resin, it was melted at 285 ° C. under vacuum with a twin screw extruder, extruded onto a cast drum, peeled off with a peeling roll, and then stretched 3.5 times in the longitudinal direction and 4 times in the transverse direction. The temperature during stretching is 90 ° C. for longitudinal stretching and 120 ° C. for lateral stretching.
Then, after heat setting at 210 ° C., it was relaxed by 5% in each of the longitudinal and lateral directions at 205 ° C. to obtain a biaxially stretched polyester film having a thickness of 250 μm. It was 195 degreeC as a result of performing differential scanning calorimetry about this and measuring the micro endothermic peak Tmeta.
実施例9では、樹脂フィルム基材を以下の方法で製造したPCDMTとPETの積層体に変更した。
実施例1にて得られたPET樹脂と、実施例8にて得られたPCDMT樹脂を2軸押出し機で真空下、285℃で溶融押出し、フィードブロックダイを用いてキャストドラム上に押出し、下記構成の積層フィルムを作成した。
PCDMT/PET/PCDMT、3層、厚み比率1.5/7/1.5
これを縦方向に3.5倍、横方向に4倍延伸した。なお、延伸時の温度は、縦延伸が100℃、横延伸が130℃である。
このあと210℃で熱固定したあと、205℃で縦、横方向にそれぞれ5%ずつ緩和させて250μm厚みの二軸延伸ポリエステルフィルムを得た。 In Example 9, the resin film substrate was changed to a laminate of PCDMT and PET produced by the following method.
The PET resin obtained in Example 1 and the PCDMT resin obtained in Example 8 were melt-extruded at 285 ° C. under vacuum with a twin-screw extruder, and extruded onto a cast drum using a feed block die. A laminated film having a structure was prepared.
PCDMT / PET / PCDMT, 3 layers, thickness ratio 1.5 / 7 / 1.5
This was stretched 3.5 times in the longitudinal direction and 4 times in the transverse direction. The stretching temperature is 100 ° C. for longitudinal stretching and 130 ° C. for lateral stretching.
Then, after heat setting at 210 ° C., it was relaxed by 5% in each of the longitudinal and lateral directions at 205 ° C. to obtain a biaxially stretched polyester film having a thickness of 250 μm.
実施例1にて得られたPET樹脂と、実施例8にて得られたPCDMT樹脂を2軸押出し機で真空下、285℃で溶融押出し、フィードブロックダイを用いてキャストドラム上に押出し、下記構成の積層フィルムを作成した。
PCDMT/PET/PCDMT、3層、厚み比率1.5/7/1.5
これを縦方向に3.5倍、横方向に4倍延伸した。なお、延伸時の温度は、縦延伸が100℃、横延伸が130℃である。
このあと210℃で熱固定したあと、205℃で縦、横方向にそれぞれ5%ずつ緩和させて250μm厚みの二軸延伸ポリエステルフィルムを得た。 In Example 9, the resin film substrate was changed to a laminate of PCDMT and PET produced by the following method.
The PET resin obtained in Example 1 and the PCDMT resin obtained in Example 8 were melt-extruded at 285 ° C. under vacuum with a twin-screw extruder, and extruded onto a cast drum using a feed block die. A laminated film having a structure was prepared.
PCDMT / PET / PCDMT, 3 layers, thickness ratio 1.5 / 7 / 1.5
This was stretched 3.5 times in the longitudinal direction and 4 times in the transverse direction. The stretching temperature is 100 ° C. for longitudinal stretching and 130 ° C. for lateral stretching.
Then, after heat setting at 210 ° C., it was relaxed by 5% in each of the longitudinal and lateral directions at 205 ° C. to obtain a biaxially stretched polyester film having a thickness of 250 μm.
実施例10では図3に記載の製造装置を用いてコロナ処理を行った後、赤外ヒーターを用いてコロナ処理後加熱処理を行った。実施例11では図2に記載の製造装置を用いてコロナ処理を行った後、加熱気体送風ゾーンにおける加熱気体の送風によってコロナ処理後加熱処理を行った。
In Example 10, the corona treatment was performed using the manufacturing apparatus shown in FIG. 3, and then the heat treatment was performed after the corona treatment using an infrared heater. In Example 11, after the corona treatment was performed using the manufacturing apparatus illustrated in FIG. 2, the heat treatment after the corona treatment was performed by blowing the heated gas in the heated gas blowing zone.
各実施例および比較例の樹脂フィルムについて、実施例1のポリエステルフィルムと同様に評価を行った。その結果を下記表1に記載した。
The resin films of each Example and Comparative Example were evaluated in the same manner as the polyester film of Example 1. The results are shown in Table 1 below.
上記表1より、実施例のポリエステルフィルムの製造方法で得られたポリエステルフィルムは、いずれも樹脂フィルム基材と塗布層との密着性が良好であり、製膜適性にも優れることがわかった。なお、得られたポリエステルフィルムの表面にキズなども生じていなかった。
一方、比較例1~3および5のポリエステルフィルムは樹脂フィルム基材と塗布層との密着性が悪かった。比較例4のポリエステルフィルムは、連続製膜を行った時に電極対向ロールの寿命が短くなったため長期に亘って製膜できず、製膜適性の観点から問題があることがわかった。比較例6のポリエステルフィルムは、樹脂フィルム基材が加熱ロールに粘着してしまい、製膜適性に問題があることがわかった。 From the said Table 1, it turned out that all the polyester films obtained with the manufacturing method of the polyester film of an Example have favorable adhesiveness of a resin film base material and an application layer, and are excellent also in film forming ability. In addition, there were no scratches on the surface of the obtained polyester film.
On the other hand, the polyester films of Comparative Examples 1 to 3 and 5 had poor adhesion between the resin film substrate and the coating layer. The polyester film of Comparative Example 4 was found to have a problem from the viewpoint of film formation suitability because it could not be formed over a long period of time because the life of the electrode facing roll was shortened when continuous film formation was performed. As for the polyester film of the comparative example 6, it turned out that a resin film base material adheres to a heating roll, and there exists a problem in film forming suitability.
一方、比較例1~3および5のポリエステルフィルムは樹脂フィルム基材と塗布層との密着性が悪かった。比較例4のポリエステルフィルムは、連続製膜を行った時に電極対向ロールの寿命が短くなったため長期に亘って製膜できず、製膜適性の観点から問題があることがわかった。比較例6のポリエステルフィルムは、樹脂フィルム基材が加熱ロールに粘着してしまい、製膜適性に問題があることがわかった。 From the said Table 1, it turned out that all the polyester films obtained with the manufacturing method of the polyester film of an Example have favorable adhesiveness of a resin film base material and an application layer, and are excellent also in film forming ability. In addition, there were no scratches on the surface of the obtained polyester film.
On the other hand, the polyester films of Comparative Examples 1 to 3 and 5 had poor adhesion between the resin film substrate and the coating layer. The polyester film of Comparative Example 4 was found to have a problem from the viewpoint of film formation suitability because it could not be formed over a long period of time because the life of the electrode facing roll was shortened when continuous film formation was performed. As for the polyester film of the comparative example 6, it turned out that a resin film base material adheres to a heating roll, and there exists a problem in film forming suitability.
[実施例12~22、比較例7~12]:太陽電池バックシート用の塗布層塗布液との密着性の検討
各実施例で形成した樹脂フィルム基材に対して、実施例1~11および比較例1~6と同様の態様でコロナ処理および加熱処理を行った。 [Examples 12 to 22, Comparative Examples 7 to 12]: Examination of Adhesion with Coating Layer Coating Solution for Solar Battery Back Sheet Examples 1 to 11 and Corona treatment and heat treatment were performed in the same manner as in Comparative Examples 1-6.
各実施例で形成した樹脂フィルム基材に対して、実施例1~11および比較例1~6と同様の態様でコロナ処理および加熱処理を行った。 [Examples 12 to 22, Comparative Examples 7 to 12]: Examination of Adhesion with Coating Layer Coating Solution for Solar Battery Back Sheet Examples 1 to 11 and Corona treatment and heat treatment were performed in the same manner as in Comparative Examples 1-6.
その後、前記コロナ処理後加熱工程の後の、前記コロナ処理を施した側のPET基材の表面に、下記の組成の太陽電池バックシート用の塗布層塗布液を塗布し、密着性の検討を行った。
Thereafter, a coating layer coating solution for a solar battery backsheet having the following composition is applied to the surface of the PET substrate on the side subjected to the corona treatment after the heating step after the corona treatment, and the adhesion is examined. went.
<複合ポリマー水分散物P-1の合成>
(工程1)
撹拌装置、滴下ロートを備え、窒素ガス置換した反応容器に、プロピレングリコールモノ-n-プロピルエーテル(PNP)81部、イソプロピルアルコール(IPA)360部、フェニルトリメトキシシラン(PTMS)110部、及びジメチルジメトキシシラン(DMDMS)71部を仕込み、窒素ガス雰囲気下に撹拌しながら80℃に昇温した。
(工程2)
次いで、この反応容器内に同温度で、メチルメタクリレート(MMA)260部、n-ブチルメタクリレート(BMA)200部、n-ブチルアクリレート(BA)110部、アクリル酸(AA)30部、3-メタクリロイルオキシプロピルトリメトキシシラン(MPTMS)19部、tert-ブチルパーオキシ-2-エチルヘキサノエート31.5部(TBPO)、及びPNP31.5部からなる混合物を4時間かけて滴下した。その後、同温度で2.5時間加熱撹拌を行い、重量平均分子量が29,300の、カルボキシル基と加水分解性シリル基を含むアクリル系ポリマーの溶液を得た。
(工程3)
次いで、これに脱イオン水54.8部を加え、16時間加熱撹拌を継続してアルコキシシランを加水分解し、さらにアクリル系ポリマーと縮合させることにより、不揮発分(NV)=56.3質量%、溶液酸価=22.3mgKOH/gの、カルボキシル基含有アクリル系ポリマーに由来する構造単位とポリシロキサン構造単位とを有する複合ポリマーの溶液を得た。
(工程4)
次に、この溶液に同温度で、撹拌しながらトリエチルアミン42部を添加して10分間撹拌を行った。これにより、含有されるカルボキシル基の100%が中和された。
(工程5)
その後、同温度で脱イオン水1250部を1.5時間かけて滴下して転相乳化させた後、50℃に昇温して30分間撹拌を行った。次いで、内温40℃で3.5時間をかけて、有機溶剤とともに水の一部分を減圧下除去した。 <Synthesis of Composite Polymer Water Dispersion P-1>
(Process 1)
In a reaction vessel equipped with a stirrer and a dropping funnel and purged with nitrogen gas, 81 parts of propylene glycol mono-n-propyl ether (PNP), 360 parts of isopropyl alcohol (IPA), 110 parts of phenyltrimethoxysilane (PTMS), and dimethyl 71 parts of dimethoxysilane (DMDMS) was charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen gas atmosphere.
(Process 2)
Next, at the same temperature in this reaction vessel, 260 parts of methyl methacrylate (MMA), 200 parts of n-butyl methacrylate (BMA), 110 parts of n-butyl acrylate (BA), 30 parts of acrylic acid (AA), 3-methacryloyl A mixture of 19 parts of oxypropyltrimethoxysilane (MPTMS), 31.5 parts of tert-butylperoxy-2-ethylhexanoate (TBPO), and 31.5 parts of PNP was added dropwise over 4 hours. Thereafter, the mixture was heated and stirred at the same temperature for 2.5 hours to obtain an acrylic polymer solution having a weight average molecular weight of 29,300 and containing a carboxyl group and a hydrolyzable silyl group.
(Process 3)
Next, 54.8 parts of deionized water was added thereto, and heating and stirring were continued for 16 hours to hydrolyze the alkoxysilane and further condense with an acrylic polymer, so that the non-volatile content (NV) = 56.3 mass%. A solution of a composite polymer having a structural unit derived from a carboxyl group-containing acrylic polymer and a polysiloxane structural unit having a solution acid value = 22.3 mgKOH / g was obtained.
(Process 4)
Next, 42 parts of triethylamine was added to this solution while stirring at the same temperature, and stirring was performed for 10 minutes. Thereby, 100% of the contained carboxyl groups were neutralized.
(Process 5)
Thereafter, 1250 parts of deionized water was added dropwise at the same temperature over 1.5 hours for phase inversion emulsification, and then the mixture was heated to 50 ° C. and stirred for 30 minutes. Next, a part of water was removed under reduced pressure together with the organic solvent over 3.5 hours at an internal temperature of 40 ° C.
(工程1)
撹拌装置、滴下ロートを備え、窒素ガス置換した反応容器に、プロピレングリコールモノ-n-プロピルエーテル(PNP)81部、イソプロピルアルコール(IPA)360部、フェニルトリメトキシシラン(PTMS)110部、及びジメチルジメトキシシラン(DMDMS)71部を仕込み、窒素ガス雰囲気下に撹拌しながら80℃に昇温した。
(工程2)
次いで、この反応容器内に同温度で、メチルメタクリレート(MMA)260部、n-ブチルメタクリレート(BMA)200部、n-ブチルアクリレート(BA)110部、アクリル酸(AA)30部、3-メタクリロイルオキシプロピルトリメトキシシラン(MPTMS)19部、tert-ブチルパーオキシ-2-エチルヘキサノエート31.5部(TBPO)、及びPNP31.5部からなる混合物を4時間かけて滴下した。その後、同温度で2.5時間加熱撹拌を行い、重量平均分子量が29,300の、カルボキシル基と加水分解性シリル基を含むアクリル系ポリマーの溶液を得た。
(工程3)
次いで、これに脱イオン水54.8部を加え、16時間加熱撹拌を継続してアルコキシシランを加水分解し、さらにアクリル系ポリマーと縮合させることにより、不揮発分(NV)=56.3質量%、溶液酸価=22.3mgKOH/gの、カルボキシル基含有アクリル系ポリマーに由来する構造単位とポリシロキサン構造単位とを有する複合ポリマーの溶液を得た。
(工程4)
次に、この溶液に同温度で、撹拌しながらトリエチルアミン42部を添加して10分間撹拌を行った。これにより、含有されるカルボキシル基の100%が中和された。
(工程5)
その後、同温度で脱イオン水1250部を1.5時間かけて滴下して転相乳化させた後、50℃に昇温して30分間撹拌を行った。次いで、内温40℃で3.5時間をかけて、有機溶剤とともに水の一部分を減圧下除去した。 <Synthesis of Composite Polymer Water Dispersion P-1>
(Process 1)
In a reaction vessel equipped with a stirrer and a dropping funnel and purged with nitrogen gas, 81 parts of propylene glycol mono-n-propyl ether (PNP), 360 parts of isopropyl alcohol (IPA), 110 parts of phenyltrimethoxysilane (PTMS), and dimethyl 71 parts of dimethoxysilane (DMDMS) was charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen gas atmosphere.
(Process 2)
Next, at the same temperature in this reaction vessel, 260 parts of methyl methacrylate (MMA), 200 parts of n-butyl methacrylate (BMA), 110 parts of n-butyl acrylate (BA), 30 parts of acrylic acid (AA), 3-methacryloyl A mixture of 19 parts of oxypropyltrimethoxysilane (MPTMS), 31.5 parts of tert-butylperoxy-2-ethylhexanoate (TBPO), and 31.5 parts of PNP was added dropwise over 4 hours. Thereafter, the mixture was heated and stirred at the same temperature for 2.5 hours to obtain an acrylic polymer solution having a weight average molecular weight of 29,300 and containing a carboxyl group and a hydrolyzable silyl group.
(Process 3)
Next, 54.8 parts of deionized water was added thereto, and heating and stirring were continued for 16 hours to hydrolyze the alkoxysilane and further condense with an acrylic polymer, so that the non-volatile content (NV) = 56.3 mass%. A solution of a composite polymer having a structural unit derived from a carboxyl group-containing acrylic polymer and a polysiloxane structural unit having a solution acid value = 22.3 mgKOH / g was obtained.
(Process 4)
Next, 42 parts of triethylamine was added to this solution while stirring at the same temperature, and stirring was performed for 10 minutes. Thereby, 100% of the contained carboxyl groups were neutralized.
(Process 5)
Thereafter, 1250 parts of deionized water was added dropwise at the same temperature over 1.5 hours for phase inversion emulsification, and then the mixture was heated to 50 ° C. and stirred for 30 minutes. Next, a part of water was removed under reduced pressure together with the organic solvent over 3.5 hours at an internal temperature of 40 ° C.
こうして固形分濃度が42質量%、平均粒子径が110nmの、ポリシロキサン構造単位とカルボキシル基含有アクリル系ポリマーに由来する構造単位とを含む複合ポリマーの水分散物P-1を得た。水分散物P-1は、ポリシロキサン構造単位が約25%であり、アクリル系ポリマー構造単位が約75%である。
Thus, an aqueous dispersion P-1 of a composite polymer containing a polysiloxane structural unit having a solid content concentration of 42% by mass and an average particle diameter of 110 nm and a structural unit derived from a carboxyl group-containing acrylic polymer was obtained. The aqueous dispersion P-1 has a polysiloxane structural unit of about 25% and an acrylic polymer structural unit of about 75%.
<太陽電池バックシート用の塗布層塗布液の調製>
下記の(i)~(iv)の成分を混合し、ポリシロキサン構造単位を含む複合ポリマーを含有する太陽電池バックシート用の塗布層塗布液を調製した。
(塗布層用塗布液1の組成)
(i)複合ポリマー水分散物P-1 ・・・45.9部
(バインダー、固形分濃度42質量%)
(ii)オキサゾリン化合物(架橋剤) ・・・7.7部
(エポクロスWS-700、日本触媒化学工業(株)製、固形分:25質量%)
(iii)ポリオキシアルキレンアルキルエーテル ・・・2.0部
(ナ口アクティーCL95、三洋化成工業(株)製、固形分:1質量%)
(iv)蒸留水 ・・・44.4部 <Preparation of coating solution for solar cell backsheet>
The following components (i) to (iv) were mixed to prepare a coating solution for a solar cell backsheet containing a composite polymer containing a polysiloxane structural unit.
(Composition ofcoating solution 1 for coating layer)
(I) Composite polymer aqueous dispersion P-1 45.9 parts (binder, solid concentration 42 mass%)
(Ii) Oxazoline compound (crosslinking agent) 7.7 parts (Epocross WS-700, manufactured by Nippon Shokubai Chemical Industry Co., Ltd., solid content: 25% by mass)
(Iii) Polyoxyalkylene alkyl ether: 2.0 parts (Naguchi Acty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
(Iv) Distilled water ... 44.4 parts
下記の(i)~(iv)の成分を混合し、ポリシロキサン構造単位を含む複合ポリマーを含有する太陽電池バックシート用の塗布層塗布液を調製した。
(塗布層用塗布液1の組成)
(i)複合ポリマー水分散物P-1 ・・・45.9部
(バインダー、固形分濃度42質量%)
(ii)オキサゾリン化合物(架橋剤) ・・・7.7部
(エポクロスWS-700、日本触媒化学工業(株)製、固形分:25質量%)
(iii)ポリオキシアルキレンアルキルエーテル ・・・2.0部
(ナ口アクティーCL95、三洋化成工業(株)製、固形分:1質量%)
(iv)蒸留水 ・・・44.4部 <Preparation of coating solution for solar cell backsheet>
The following components (i) to (iv) were mixed to prepare a coating solution for a solar cell backsheet containing a composite polymer containing a polysiloxane structural unit.
(Composition of
(I) Composite polymer aqueous dispersion P-1 45.9 parts (binder, solid concentration 42 mass%)
(Ii) Oxazoline compound (crosslinking agent) 7.7 parts (Epocross WS-700, manufactured by Nippon Shokubai Chemical Industry Co., Ltd., solid content: 25% by mass)
(Iii) Polyoxyalkylene alkyl ether: 2.0 parts (Naguchi Acty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
(Iv) Distilled water ... 44.4 parts
<塗布層の形成>
得られた太陽電池バックシート用の塗布層塗布液を、前記PETの前記コロナ処理後加熱工程の後の、前記コロナ処理を施した側のPET基材の表面に、バインダー量が3.0g/m2になるように塗布し、180℃で1分間乾燥させて、乾燥厚み3μmの、ポリシロキサン構造単位を含む複合ポリマーを含有する塗布層を形成した。
得られたポリエステルフィルムを、実施例12~22および比較例7~12のポリエステルフィルムとした。 <Formation of coating layer>
The obtained coating solution for a solar battery backsheet was applied to the surface of the PET substrate on the side subjected to the corona treatment after the post-corona treatment heating step of the PET, with a binder amount of 3.0 g / The coating layer was applied to m 2 and dried at 180 ° C. for 1 minute to form a coating layer containing a composite polymer containing a polysiloxane structural unit having a dry thickness of 3 μm.
The obtained polyester films were used as polyester films of Examples 12 to 22 and Comparative Examples 7 to 12.
得られた太陽電池バックシート用の塗布層塗布液を、前記PETの前記コロナ処理後加熱工程の後の、前記コロナ処理を施した側のPET基材の表面に、バインダー量が3.0g/m2になるように塗布し、180℃で1分間乾燥させて、乾燥厚み3μmの、ポリシロキサン構造単位を含む複合ポリマーを含有する塗布層を形成した。
得られたポリエステルフィルムを、実施例12~22および比較例7~12のポリエステルフィルムとした。 <Formation of coating layer>
The obtained coating solution for a solar battery backsheet was applied to the surface of the PET substrate on the side subjected to the corona treatment after the post-corona treatment heating step of the PET, with a binder amount of 3.0 g / The coating layer was applied to m 2 and dried at 180 ° C. for 1 minute to form a coating layer containing a composite polymer containing a polysiloxane structural unit having a dry thickness of 3 μm.
The obtained polyester films were used as polyester films of Examples 12 to 22 and Comparative Examples 7 to 12.
(太陽電池バックシート用のポリエステルフィルム評価)
-1.密着性-
得られた実施例12~22および比較例7~12のポリエステルフィルムについて、100℃/15分の熱水処理を行った。
その後、実施例1と同様に密着評価試験機(ふちこすり機)を使用して剥離量を測定し、実施例1と同様に5段階で評価した。 (Evaluation of polyester film for solar battery back sheet)
-1. Adhesiveness
The obtained polyester films of Examples 12 to 22 and Comparative Examples 7 to 12 were subjected to hot water treatment at 100 ° C./15 minutes.
After that, the peel amount was measured using an adhesion evaluation tester (a fluffing machine) in the same manner as in Example 1, and evaluated in five steps as in Example 1.
-1.密着性-
得られた実施例12~22および比較例7~12のポリエステルフィルムについて、100℃/15分の熱水処理を行った。
その後、実施例1と同様に密着評価試験機(ふちこすり機)を使用して剥離量を測定し、実施例1と同様に5段階で評価した。 (Evaluation of polyester film for solar battery back sheet)
-1. Adhesiveness
The obtained polyester films of Examples 12 to 22 and Comparative Examples 7 to 12 were subjected to hot water treatment at 100 ° C./15 minutes.
After that, the peel amount was measured using an adhesion evaluation tester (a fluffing machine) in the same manner as in Example 1, and evaluated in five steps as in Example 1.
-2.連続製膜適性-
得られた実施例12~22および比較例7~12のポリエステルフィルムについて、実施例1と同様に連続製膜時の安定性を検討したとき、特に問題がない場合に○評価とし、問題がある場合を×評価とした。 -2. Suitability for continuous film formation
Regarding the obtained polyester films of Examples 12 to 22 and Comparative Examples 7 to 12, when the stability at the time of continuous film formation was examined in the same manner as in Example 1, there was a problem when there was no particular problem and it was evaluated as ○. Case was evaluated as x evaluation.
得られた実施例12~22および比較例7~12のポリエステルフィルムについて、実施例1と同様に連続製膜時の安定性を検討したとき、特に問題がない場合に○評価とし、問題がある場合を×評価とした。 -2. Suitability for continuous film formation
Regarding the obtained polyester films of Examples 12 to 22 and Comparative Examples 7 to 12, when the stability at the time of continuous film formation was examined in the same manner as in Example 1, there was a problem when there was no particular problem and it was evaluated as ○. Case was evaluated as x evaluation.
実施例12~22および比較例7~12のポリエステルフィルムの評価は、それぞれ実施例1~11および比較例1~6と同様の傾向であった。
The evaluation of the polyester films of Examples 12 to 22 and Comparative Examples 7 to 12 had the same tendency as Examples 1 to 11 and Comparative Examples 1 to 6, respectively.
1 コロナ処理用電極
2 加熱ロール
3 加熱気体送風ゾーン
4 赤外ヒーター
10 巻き出しロール
11 巻き取りロール
12 電極対向ロール
21 感光性層(感光剤層)
22 ゼラチン系下塗り層
23 ラテックス系下塗り層
24 支持体
25 帯電防止剤層(バック層)
26 プロテクト層(バック層)
31 バックシート(太陽電池保護シート)
32 支持体
33 塗布層(複合ポリマー層)
34 バック層
35 封止材
36 太陽電池素子
37 透明性のフロント基板
38 太陽電池モジュール DESCRIPTION OFSYMBOLS 1 Electrode for corona treatment 2 Heating roll 3 Heated gas ventilation zone 4 Infrared heater 10 Unwinding roll 11 Winding roll 12 Electrode facing roll 21 Photosensitive layer (photosensitive agent layer)
22 Gelatin-basedundercoat layer 23 Latex-based undercoat layer 24 Support 25 Antistatic agent layer (back layer)
26 Protective layer (back layer)
31 Back sheet (solar cell protection sheet)
32Support 33 Application Layer (Composite Polymer Layer)
34Back layer 35 Sealing material 36 Solar cell element 37 Transparent front substrate 38 Solar cell module
2 加熱ロール
3 加熱気体送風ゾーン
4 赤外ヒーター
10 巻き出しロール
11 巻き取りロール
12 電極対向ロール
21 感光性層(感光剤層)
22 ゼラチン系下塗り層
23 ラテックス系下塗り層
24 支持体
25 帯電防止剤層(バック層)
26 プロテクト層(バック層)
31 バックシート(太陽電池保護シート)
32 支持体
33 塗布層(複合ポリマー層)
34 バック層
35 封止材
36 太陽電池素子
37 透明性のフロント基板
38 太陽電池モジュール DESCRIPTION OF
22 Gelatin-based
26 Protective layer (back layer)
31 Back sheet (solar cell protection sheet)
32
34
Claims (14)
- ポリエステルを主成分とする樹脂フィルム基材の表面をコロナ処理する工程と、
前記コロナ処理後の前記樹脂フィルム基材を該樹脂フィルム基材のTgを超えて、Tmeta以下に加熱処理するコロナ処理後加熱工程と、
前記コロナ処理後加熱工程の後に前記樹脂フィルム基材の前記コロナ処理を施された側の表面上にポリマー溶液を塗布する工程と
を含むことを特徴とするポリエステルフィルムの製造方法(ここで、Tgはガラス転移温度、Tmetaは示差走査熱量測定にて求められる微小吸熱ピーク(単位:℃)を表す)。 A step of corona-treating the surface of the resin film base material containing polyester as a main component;
A post-corona treatment heating step of heat-treating the resin film substrate after the corona treatment to Tmeta or less exceeding the Tg of the resin film substrate;
And a step of applying a polymer solution on the surface of the resin film substrate on the side subjected to the corona treatment after the heating step after the corona treatment, wherein a method for producing a polyester film (here, Tg Is a glass transition temperature, and Tmeta is a minute endothermic peak (unit: ° C.) obtained by differential scanning calorimetry). - 前記樹脂フィルム基材がポリエチレンテレフタレートまたはポリ(1,4-シクロヘキシレンジメチレンテレフタレート)の単層フィルム、あるいは、それらのうち1種または2種を含む積層体であることを特徴とする請求項1に記載のポリエステルフィルムの製造方法。 2. The resin film substrate is a monolayer film of polyethylene terephthalate or poly (1,4-cyclohexylenedimethylene terephthalate), or a laminate including one or two of them. The manufacturing method of the polyester film of description.
- 前記コロナ処理後加熱工程における前記樹脂フィルム基材の表面温度が70~220℃であることを特徴とする請求項1または2に記載のポリエステルフィルムの製造方法。 The method for producing a polyester film according to claim 1 or 2, wherein the surface temperature of the resin film substrate in the heating step after the corona treatment is 70 to 220 ° C.
- 前記コロナ処理工程の前に前記樹脂フィルム基材を加熱するコロナ処理前加熱工程を含み、
前記コロナ処理前加熱工程と、前記コロナ処理後加熱工程を、異なる加熱処理装置によって行うことを特徴とする請求項1~3のいずれか一項に記載のポリエステルフィルムの製造方法。 Including a heating step before corona treatment for heating the resin film substrate before the corona treatment step,
The method for producing a polyester film according to any one of claims 1 to 3, wherein the heating step before the corona treatment and the heating step after the corona treatment are performed by different heat treatment apparatuses. - 前記コロナ処理後加熱工程の後に、前記樹脂フィルム基材の前記コロナ処理を施された側の表面に再度のコロナ処理を行うことを特徴とする請求項1~4のいずれか一項に記載のポリエステルフィルムの製造方法。 The corona treatment is performed again on the surface of the resin film base on which the corona treatment has been performed after the post-corona treatment heating step. A method for producing a polyester film.
- 前記コロナ処理と、前記再度のコロナ処理を、異なるコロナ処理装置によって行うことを特徴とする請求項5に記載のポリエステルフィルムの製造方法。 The method for producing a polyester film according to claim 5, wherein the corona treatment and the re-corona treatment are performed by different corona treatment apparatuses.
- 前記加熱処理が、加熱気体の送風、赤外線の照射または加熱ロールとの接触であることを特徴とする請求項1~6のいずれか一項に記載のポリエステルフィルムの製造方法。 The method for producing a polyester film according to any one of claims 1 to 6, wherein the heat treatment is heating gas blowing, infrared irradiation, or contact with a heating roll.
- 前記加熱ロールが、前記コロナ処理における電極対向ロールとは異なるロールであることを特徴とする請求項7に記載のポリエステルフィルムの製造方法。 The method for producing a polyester film according to claim 7, wherein the heating roll is a roll different from the electrode facing roll in the corona treatment.
- 前記コロナ処理工程および前記加熱処理を、いずれも前記樹脂フィルム基材を搬送しながら行うことを特徴とする請求項1~8のいずれか一項に記載のポリエステルフィルムの製造方法。 The method for producing a polyester film according to any one of claims 1 to 8, wherein both the corona treatment step and the heat treatment are carried out while the resin film substrate is conveyed.
- 前記コロナ処理工程の前に、前記樹脂フィルム基材を二軸延伸する工程を含むことを特徴とする請求項1~9のいずれか一項に記載のポリエステルフィルムの製造方法。 The method for producing a polyester film according to any one of claims 1 to 9, further comprising a step of biaxially stretching the resin film substrate before the corona treatment step.
- 請求項1~10のいずれか一項に記載のポリエステルフィルムの製造方法を含むことを特徴とする太陽電池保護シートの製造方法。 A method for producing a solar cell protective sheet comprising the method for producing a polyester film according to any one of claims 1 to 10.
- 請求項1~10のいずれか一項に記載のポリエステルフィルムの製造方法を含むことを特徴とする感光材料の製造方法。 A method for producing a photosensitive material, comprising the method for producing a polyester film according to any one of claims 1 to 10.
- 請求項1~10のいずれか一項に記載のポリエステルフィルムの製造方法によって製造されたことを特徴とするポリエステルフィルム。 A polyester film produced by the method for producing a polyester film according to any one of claims 1 to 10.
- ポリエステルを主成分とする樹脂フィルム基材の表面をコロナ処理する工程と、
前記コロナ処理後の前記樹脂フィルム基材を該樹脂フィルム基材のTgを超えて、Tmeta以下に加熱処理するコロナ処理後加熱工程と、
前記コロナ処理後加熱工程の後に前記樹脂フィルム基材の前記コロナ処理を施された側の表面上にポリマー溶液を塗布する工程を含み、
前記ポリマー溶液が水系分散液であることを特徴とするポリエステルフィルムと水系分散液との密着性向上方法(ここで、Tgはガラス転移温度、Tmetaは示差走査熱量測定にて求められる微小吸熱ピーク(単位:℃)を表す)。 A step of corona-treating the surface of the resin film base material containing polyester as a main component;
A post-corona treatment heating step of heat-treating the resin film substrate after the corona treatment to Tmeta or less exceeding the Tg of the resin film substrate;
Including a step of applying a polymer solution on the surface of the resin film substrate on which the corona treatment has been performed after the heating step after the corona treatment,
Method for improving adhesion between polyester film and aqueous dispersion, wherein the polymer solution is an aqueous dispersion (where Tg is a glass transition temperature, Tmeta is a minute endothermic peak determined by differential scanning calorimetry ( Unit: ° C)).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-137306 | 2011-06-21 | ||
JP2011137306 | 2011-06-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012176829A1 true WO2012176829A1 (en) | 2012-12-27 |
Family
ID=47422660
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/065823 WO2012176829A1 (en) | 2011-06-21 | 2012-06-21 | Method for improving adhesion between polyester film and aqueous dispersion and process for manufacturing polyester film |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP5715093B2 (en) |
WO (1) | WO2012176829A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016216668A (en) * | 2015-05-25 | 2016-12-22 | 国立大学法人東京工業大学 | Method and apparatus for controlling resin surface using plasma |
JP2019089933A (en) * | 2017-11-14 | 2019-06-13 | フタムラ化学株式会社 | Hydrophilization treatment method of thermoplastic sheet-like material |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4829316B1 (en) * | 1969-05-24 | 1973-09-08 | ||
JPS4885658A (en) * | 1972-01-08 | 1973-11-13 | ||
JPH01202750A (en) * | 1988-02-09 | 1989-08-15 | Fuji Photo Film Co Ltd | Production of photographic base |
JP2001122996A (en) * | 1999-10-28 | 2001-05-08 | Bridgestone Corp | Surface treatment of fluorine resin and production of laminated body |
JP2003230862A (en) * | 2002-02-07 | 2003-08-19 | Fuji Photo Film Co Ltd | Coating method |
JP2007184402A (en) * | 2006-01-06 | 2007-07-19 | Teijin Dupont Films Japan Ltd | Polyester film for protecting rear surface of solar cell |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4983767A (en) * | 1972-12-15 | 1974-08-12 | ||
JPS5946786B2 (en) * | 1975-03-26 | 1984-11-14 | 帝人株式会社 | Adhesion method between metal and polyester sheet |
JPS5935920A (en) * | 1982-08-23 | 1984-02-27 | Diafoil Co Ltd | Biaxially oriented polyester film and preparation thereof |
JP2570304B2 (en) * | 1987-07-13 | 1997-01-08 | 東レ株式会社 | Method for producing polyester film |
US5096784A (en) * | 1989-12-20 | 1992-03-17 | Hoechst Celanese Corporation | Polyester film with nodule surface |
JPH06317876A (en) * | 1993-03-11 | 1994-11-15 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
KR19990077681A (en) * | 1998-03-10 | 1999-10-25 | 스티븐 피이 유리치 | Process for producing oriented polymeric film with improved surface quality |
-
2012
- 2012-06-21 JP JP2012139374A patent/JP5715093B2/en active Active
- 2012-06-21 WO PCT/JP2012/065823 patent/WO2012176829A1/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4829316B1 (en) * | 1969-05-24 | 1973-09-08 | ||
JPS4885658A (en) * | 1972-01-08 | 1973-11-13 | ||
JPH01202750A (en) * | 1988-02-09 | 1989-08-15 | Fuji Photo Film Co Ltd | Production of photographic base |
JP2001122996A (en) * | 1999-10-28 | 2001-05-08 | Bridgestone Corp | Surface treatment of fluorine resin and production of laminated body |
JP2003230862A (en) * | 2002-02-07 | 2003-08-19 | Fuji Photo Film Co Ltd | Coating method |
JP2007184402A (en) * | 2006-01-06 | 2007-07-19 | Teijin Dupont Films Japan Ltd | Polyester film for protecting rear surface of solar cell |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016216668A (en) * | 2015-05-25 | 2016-12-22 | 国立大学法人東京工業大学 | Method and apparatus for controlling resin surface using plasma |
JP2019089933A (en) * | 2017-11-14 | 2019-06-13 | フタムラ化学株式会社 | Hydrophilization treatment method of thermoplastic sheet-like material |
JP7067902B2 (en) | 2017-11-14 | 2022-05-16 | フタムラ化学株式会社 | Hydrophilization treatment method for thermoplastic sheet containing carbon material |
Also Published As
Publication number | Publication date |
---|---|
JP2013028799A (en) | 2013-02-07 |
JP5715093B2 (en) | 2015-05-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5661386B2 (en) | Polyester film and method for producing the same, solar cell backsheet, and solar cell module | |
KR20120030309A (en) | Polyester film, method for producing the same, back sheet for solar cells, and solar cell module | |
WO2013027543A1 (en) | Polyester film and method for manufacturing same, solar battery back sheet, and solar battery module | |
CN103443933A (en) | Solar cell backsheet, method of manufacturing same, and solar cell module | |
JP5722287B2 (en) | SOLAR CELL BACK SHEET, ITS MANUFACTURING METHOD, AND SOLAR CELL MODULE | |
JP5752733B2 (en) | Polyester film, solar cell backsheet, and solar cell module | |
TW201317317A (en) | Back sheet for solar cell and solar cell module | |
US20140190562A1 (en) | Solar cell backsheet and solar cell module | |
WO2013024892A1 (en) | Solar cell back sheet, method for manufacturing same, and solar cell module | |
JP5623952B2 (en) | SOLAR CELL POLYMER SHEET AND METHOD FOR PRODUCING THE SAME, SOLAR CELL BACK SHEET, AND SOLAR CELL MODULE | |
JP5715093B2 (en) | Method for improving adhesion between polyester film and aqueous dispersion, and method for producing polyester film | |
JP5763021B2 (en) | SOLAR CELL POLYMER SHEET, PROCESS FOR PRODUCING THE SAME, AND SOLAR CELL MODULE | |
TWI499064B (en) | White polyester film for solar cell, solar cell back encapsulant and solar cell module using same | |
JP5295161B2 (en) | Method for producing thermoplastic resin film | |
KR20140059185A (en) | Polymer sheet for solar cells and solar cell module | |
KR101711065B1 (en) | Resin composition, production method therefor, polyethylene terephthalate film, and back sheet for solar cell module | |
JP5562889B2 (en) | LAMINATED FILM, SOLAR CELL BACK SHEET, AND METHOD FOR PRODUCING LAMINATED FILM | |
WO2014098222A1 (en) | Laminated film, solar-cell-module back sheet, and solar cell module | |
JP6032981B2 (en) | SOLAR CELL BACK SHEET, MANUFACTURING METHOD THEREOF, AND SOLAR CELL MODULE | |
JP6096135B2 (en) | White polyester film and method for producing the same, solar cell module and method for producing the same | |
JP2010280189A (en) | Laminated polyester film for solar cell reverse seal material | |
JPWO2016031340A1 (en) | Solar cell back surface protection sheet and solar cell module | |
JP2016036026A (en) | Protective sheet for solar batteries, manufacturing method thereof, and solar battery module | |
WO2013161787A1 (en) | Polyester film, back sheet for solar cell module, and solar cell module | |
JP5694092B2 (en) | Polyester film and method for producing the same, solar cell backsheet and solar cell module |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12802152 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12802152 Country of ref document: EP Kind code of ref document: A1 |