JPH0526802B2 - - Google Patents
Info
- Publication number
- JPH0526802B2 JPH0526802B2 JP59217784A JP21778484A JPH0526802B2 JP H0526802 B2 JPH0526802 B2 JP H0526802B2 JP 59217784 A JP59217784 A JP 59217784A JP 21778484 A JP21778484 A JP 21778484A JP H0526802 B2 JPH0526802 B2 JP H0526802B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- reaction
- film
- sheet
- carboxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 30
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- 238000002834 transmittance Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 description 40
- 238000000034 method Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 33
- 239000005340 laminated glass Substances 0.000 description 32
- 230000001681 protective effect Effects 0.000 description 31
- 239000000047 product Substances 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000007127 saponification reaction Methods 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 21
- 239000011229 interlayer Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 16
- 239000004065 semiconductor Substances 0.000 description 14
- 239000008393 encapsulating agent Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000003566 sealing material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- -1 alicyclic hydrocarbons Chemical class 0.000 description 4
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000006011 modification reaction Methods 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 229920001084 poly(chloroprene) Polymers 0.000 description 4
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- VNFXPOAMRORRJJ-UHFFFAOYSA-N (4-octylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(CCCCCCCC)=CC=C1OC(=O)C1=CC=CC=C1O VNFXPOAMRORRJJ-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- HZRGCKHLTWDLKO-UHFFFAOYSA-N OC1C(=CC=CC1(C(C)(C)C)C(C)(C)C)N1N=C2C(=N1)C=CC=C2 Chemical compound OC1C(=CC=CC1(C(C)(C)C)C(C)(C)C)N1N=C2C(=N1)C=CC=C2 HZRGCKHLTWDLKO-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- CCQVDEXHRSXSBA-UHFFFAOYSA-N diphenylmethanone (2-hydroxy-4-octoxyphenyl)-phenylmethanone Chemical class OC1=C(C(=O)C2=CC=CC=C2)C=CC(=C1)OCCCCCCCC.C1(=CC=CC=C1)C(=O)C1=CC=CC=C1 CCQVDEXHRSXSBA-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- Y02E10/549—Organic PV cells
Description
本発明は、無色でかつ透明性に富む、エチレン
−酢酸ビニル共重合体ケン化物のカルボキシル変
性樹脂の製造法に関する。
エチレン−酢酸ビニル共重合体（以下、EVA
と略称する）をケン化し、これを更に酸を用いて
変性した、いわゆるEVAケン化物のカルボキシ
ル変性樹脂は、たとえば接着剤、フイルム、粉体
塗料などとして用いられており、その製造法も広
く知られている。しかしながら従来の製造法で得
られたカルボキシル変性樹脂は、たとえばガラ
ス、アルミなどに対する接着性はすぐれてはいる
ものの着色および透明性などの点で問題が残され
ており、合せガラスおよび太陽電池モジユール分
野での工業的な利用は未だなされていない。
一般に合せガラスを接着するための中間膜とし
て、硝酸繊維素膜、酢酸繊維素膜、可塑化アクリ
ル酸エステル樹脂膜、可塑化ポリビニルブチラー
ル膜を使用することは広く知られている。就中、
可塑化ポリビニルブチラール膜はすぐれた接着力
と共に耐光安定性、低温柔軟性に関して上記の他
の中間膜に優り、自動車用、航空機用その他の安
全ガラス用として今日広く利用せられている。こ
のポリビニルブチラール膜は、ポリ酢酸ビニル樹
脂より誘導されたポリビニルアルコールの部分ア
セタール化物で、ポリビニルブチラール成分80〜
85重量％、ポリビニルアセテート成分３〜７重量
％残余がポリビニルアルコール成分から成る合成
樹脂である。該樹脂膜は、単独では剛性が大きく
合せガラス用中間膜としては柔軟性が不足し実用
に耐えない欠点がある。この点を補なう目的で蒸
気圧の小さい、高沸点可塑剤が約40重量％加えら
れている。しかしながらこの可塑化ポリビニルブ
チラール膜は、常温下で膜表面の粘着性が強く、
合せガラス接着作業前の取扱上及び輸送上多くの
困難を惹起している。従つて該樹脂膜の粘着を一
時的に除く為、膜表面に凹凸状模様を加工し、そ
の上に重炭酸ソーダ粉末を散布している。接着作
業に際してはこの粘着抑制粉末を除く為、事前に
水洗工程、乾燥工程が必要であり、更に可塑化ブ
チラール膜は吸湿性が大きく水分の含有で接着性
が低下する為、膜の含水率が0.5重量％以下にな
るまで乾燥処理しなければならない。また、可塑
化ブチラール膜は温度上昇と共に粘着性が増加し
ガラス面に対する滑性が悪く、作業性を著しく損
なう性質を有する。この性状の改善浮、並びに吸
湿抑制の為に作業場の温度を約20℃に保たなけれ
ばならない。しかも可塑化ブチラール膜を中間膜
とし、これに合せガラス板を実際に接着するにあ
たつては、通常ロール方式または減圧方式により
予備接着を行なつたあと、油圧式あるいは空気圧
式オートクレーブ内で10〜15Kg／cm2の加圧下130
〜140℃の温度で本接着を行なうという２段階の
接着方法を採ることが必須であり、製造設備も大
規模なものとならざる得ないという欠点がある。
このような欠点を解消するものとしてEVAケン
化物の酸変形体が提案されている（たとえば特公
昭47−16826号公報）。すなわち、この酸変性体
は、可塑化ブチラール膜の場合のような取扱い上
ないしは作業上の難点がなく、また接着において
も減圧方式で100℃程度に加熱するという簡単な
方法で十分接着可能であるため可塑化ブチラール
膜を中間膜とする合せガラスを製造する際に用い
られるような大規模な設備は必要としない。しか
も合せガラスの性能面においても、この酸変性体
を中間膜とする合せガラスは可塑化ブチラール膜
を中間膜とする合せガラスに匹敵する耐衝撃性、
耐熱水性を有している。しかしながら、この酸変
性体を中間膜として合せガラスを作成した場合、
この合せガラスの透明性が加熱接着後の冷却の仕
方によつて大巾に変化し、たとえば急冷するとポ
リビニルブチラールと同等の透明性が維持される
が徐冷すると透明性が著しく悪化するという欠点
を有している。しかも実際の合せガラス作成工程
で急冷法を採用することはガラスの破損に至るた
め事実上不可能である。従つて徐冷による透明性
の悪化は、該酸変性体を中間膜とする合せガラス
の至命的欠陥であつた。
更に、この酸変性体中間膜のもうひとつの欠点
は、該変性体樹脂製造工程、すなわちEVAをベ
ースポリマーとし、これをケン化、次いで酸変性
化の反応が順次断続的に行なわれる過程で、樹脂
成分が著るしく着色し、ひいては該樹脂を中間膜
とする合せガラスも又着色したものになる点であ
る。
また、近年、太陽電池を用いた太陽光発電がク
リーンでかつ永久的であることから、特に注目さ
れている。太陽電池は、光が照射されると電流を
生ずる機能のあるシリコン半導体素子やセレン半
導体素子のウエハーをインターコネクターを用い
て直列または並列に接続し、ガラス、ポリアクリ
レート、ポリカーボネートなどの上部透明保護材
とガラス、ステンレス、アルミニウム、プラスチ
ツクなどの下部基板保護材とで保護することによ
つてパツケージ化したものであり、半導体素子と
これらの各保護材との間は、普通封止材を用いて
接合されている。
封止材としては、急激な外気条件の変化による
半導体素子の損傷および充填材の亀裂や界面剥離
現象などを発生させないためにエラストマー的特
性を有することが必要であり、また太陽光を受け
る側に使用される場合には、太陽光線の透過率が
高くかつ長期間にわたる屋外放置により光線透過
率の低下などの物性面での変化の少ないものが好
ましい。従来は、こうした目的のために、過熱架
橋タイプの液状シリコンが用いられてきている
が、高価であること、塗布および接着の工程が長
く、自動化に適さないなどの欠点があつた。
このため、最近では合せガラスで実績のあるポ
リビニルブチラール樹脂のシートが利用され始め
ているが、これも太陽電池用の充填材としては必
ずしも満足できるものとはいえない。即ち、ポリ
ビニルブチラールシートは、その表面にブロツキ
ング防止のためにでん粉が付着されており、使用
に先立つて、それを水洗除去し、乾燥しなければ
ならない。また、貼り合せには、樹脂の流動性が
悪いためオートクレーブを用いる必要があり、従
つて工程時間が長く、自動化にも適さない。更
に、品質的には、対温度特性が悪く、長時間高湿
度下に放置されると失透現象を起し、光線透過率
が低下するばかりではなく、接着強度も著しく低
下し、上部透明保護材、下部基板保護材と太陽電
池素子との界面で剥離現象を起す。また、低温特
性が必ずしもよくない。
こうした問題点のあるポリビニルブチラールシ
ートに代つて、エチレン−酢酸ビニル共重合体シ
ートが太陽電池モジユールの低コスト化の視点か
ら、最近検討され始めている。しかしながら、通
常用いられるエチレン−酢酸ビニル共重合体で
は、太陽電池用の封止材として求められている特
性を満足させることができない。即ち、この共重
合体中の酢酸ビニル含量が増すと、透明性、柔軟
性などは向上するが、シートの成形性、ブロツキ
ング性などが悪化し、その両方の特性を同時に満
足させることが難かしく、また耐熱性、耐候性も
不十分である。更に、太陽電池モジユールの信頼
性を決定づける上部透明保護材および下部基板保
護材との耐久接着性も十分ではない。
更に、これらを改良したものとして、有機過酸
化物を含有したエチレン−酢酸ビニル共重合体を
封止材シートとして用い、かつ上部透明保護材お
よび下部基板保護材を接着する際、接着すべき保
護材の表面および／または封止材シートの表面を
予めプライマー処理を施し、モジユール貼り合わ
せ過程で有機過酸化物の分解温度以上に加熱する
ことによつて太陽電池を製造することが提案され
ている（たとえば特開昭58−23870号公報）。
しかしながら、予め保護材や封止材シートをプ
ライマー処理しておくことは、作業上非常に煩雑
となる。更には120〜160℃という高温で加熱処理
して過酸化物架橋を行なう工程は保護材の熱によ
る変質等の悪影響を及ぼすのみならず、封止材シ
ートの架橋収縮が起つて、ひいては太陽電池の寸
法安定性が悪くなるという欠点を有する。更に
は、加熱硬化を行つた後でも、極微量の有機過酸
化物が残存するため、耐候性が悪くなる（着色す
る）という欠点を有している。
本発明者らは、上記のごとき欠点を一挙に解決
し、合せガラス中間膜あるいは太陽電池モジユー
ルの半導体封止剤として特に有用なエチレン−酢
酸ビニル共重合体ケン化物のカルボキシル変性樹
脂の製造法について鋭意検討の結果本発明に到達
した。
すなわち本発明は、エチレン−酢酸ビニル共重
合体を50℃以上の沸点を有する有機溶媒に溶解さ
せ、この溶液中で共重合体をアルカリアルコラー
トを用いて、このアルコラート１モルに対して
0.1〜３モルの水の存在下にケン化し、次いでこ
のケン化物を含む溶液に不飽和カルボン酸または
ジカルボン酸無水物を加えて反応させ、さらにこ
の反応液を水と接触させることを特徴とする1.0
mm厚シート板の全光線透過率が90％以上、曇価が
３％以下かつ黄色度が３以下である、エチレン−
酢酸ビニル共重合体ケン化物のカルボキシル変性
樹脂の製造法である。
まず、本発明のカルボキシル変性樹脂（以下、
Ｃ−HEVAと略称することもある）の製造法に
ついて説明する。
本発明の方法において使用されるEVAとして
は、酢酸ビニル含量が約20〜50重量％のもので、
メルトインデツクス（ASTMD−1238による）
が0.5〜500を有するものが挙げられる。該EVA
は、公知のたとえば米国特許第2200429号明細書
などに記載された方法により合成する事ができ
る。
本発明の方法においては、まずこのような
EVAを50℃以上の沸点をする有機溶媒に溶解さ
せる。かかる有機溶媒として、たとえばベンゼ
ン、トルエン、Ｏ−キシレン、ｍ−キシレン、エ
チルベンゼン、プロピルベンゼンなどの芳香族炭
化水素類、あるいはたとえばｎ−ヘキサン、シク
ロヘキサンなどの脂肪族、脂環族炭化水素類を挙
げることが出来る。これら有機溶媒のうち、好ま
しいものとして水を共沸するキシレン、トルエン
などの芳香族炭化水素類および100〜200℃の沸を
有する溶媒を挙げることができる。これら溶媒は
EVAを溶解させるに必要な量を用いれば充分で
あるが、次の反応を円滑に進行させるためには通
常EVA100重量部に対して150〜500重量部の溶媒
を用いるのが好ましい。
次いで、このようにして調整されたEVA溶液
は、これに低級アルコールが加えられたのち、特
定量の水の存在下にアルカリアルコラート触媒を
用いてケン化反応に付される。
低級アルコールとしては、たとえばメチルアル
コール、エチルアルコール、プロピルアルコー
ル、イソプロピルアルコール、ブチルアルコー
ル、イソブチルアルコール、sec−ブチルアルコ
ール、tert−ブチルアルコールなどを挙げること
ができ、通常メタノールが用いられる。これら低
級アルコールは、意図するケン化度によつても異
なるが、通常原料EVA中の酢酸ビニルのモル数
に対し、ほぼ0.1〜10倍モル、好ましくは１〜８
倍モルが用いられる。触媒としてのアルカリアル
コラートとしては、たとえばナトリウムメトキサ
イド、ナトリウムエトキサイド、カリウムメトキ
サイド、カリウムエトキサイド、リチウムメノキ
サイド、カリウム−ｔ−ブトキサイドなどアルカ
リ金属のアルコラートが用いられる。これらアル
カリアルコラート触媒の使用量は意図するケン化
度によつて変わるが通常原料EVA中に存在する
酢酸ビニルのモル数のほぼ0.01〜１倍モル、好ま
しくは0.01〜0.2倍モルである。
本発明の方法では、このようなケン化反応の工
程においてアルカリアルコラート１モルに対して
0.1〜３モルの水を存在させることを特徴とする
ものであり、0.1モルより少ない場合には、ケン
化物の着色防止効果はほとんど認められず、また
３モルを越えた場合には意図するケン化度を有す
るケン化物を導びくために過剰のアルカリ触媒お
よびアルコールを必要とし、このことは経済的に
不利なばかりでなく、このような条件下に製造さ
れたケン化物から得られるカルボキシル変性体
は、合せガラス中間膜などの製品とした場合不透
明さが増すなど品質面においても問題が生じる。
本発明のケン化反応は、従来から行なわれてい
る条件、たとえば40〜60℃で行なわれ、一体の時
間、たとえば0.5〜３時間経過した時点で、反応
系に水を加えて反応を完全に停止させる。意図す
るケン化度のものを得るためには、低級アルコー
ル、水および触媒の量を調節すればよい。水の存
在下でのケン化反応は、水が存在しない条件下で
のケン化反応と比べ一般に過剰量のアルコールを
必要とする。本発明のこの工程におけるケン化度
については、特に制限はないが通常ほぼ10〜80
％、好ましくは30〜70％のケン化度を有するケン
化物を生成させる。
上記ケン化反応での反応液は、引き続いて不飽
和カルボン酸あるいは酸無水物による酸変性反応
に付されるが、この反応に先だつてケン化反応液
を加熱して、反応の停止に用いた水および反応に
よつて副生した低沸点物を留去させ取り除いてお
く処理をしておくことが好ましい。特に酸無水物
を用いる場合には、水が反応系に存在すると変性
反応に支障を来たすため、実質的に水を取り除い
ておくことが必要である。
不飽和カルボン酸を反応させるには、ラジカル
形成物質の存在下に加熱することによつて行なわ
れる。ここで、不飽和カルボン酸とは一般式
CHR′＝CRCOOHにおいてＲおよびR′が水素、
アルキル基、カルボキシル基またはカルボン酸エ
ステルで示されるものであり、具体的にはたとえ
ばアクリル酸、メタクリル酸、クロトン酸、イタ
コン酸などのモノカルボン酸、ジカルボン酸があ
げられる。不飽和カルボン酸の使用量は、該ケン
化物に対して多くとも約５重量％、好ましくは約
0.2〜３重量％程度である。ラジカル形成物質と
はグラフト重合の実施温度で容易に分解してラジ
カルを形成することのできる物質であり、たとえ
ば過酸化ベンゾイル、過酸化ラウロイル、過酸化
ジクミルなどの有機過酸化物やα，α′−アゾビス
イソブチロニトリルなどの含窒素化合物などがあ
げられる。これらのラジカル形成物質は、該ケン
化物に対して約0.05〜３重量％、好ましくは約
0.1〜１重量％の量で用いられる。加熱温度は用
いられる不飽和カルボン酸あるいは溶剤の種類な
どによつて一概にはいえないが、およそ50〜150
℃であり、加熱時間は約0.1〜５時間である。ま
た酸無水物を反応させるには、熱処理した反応液
に酸無水物を加え、約50〜150℃で約0.1〜５時間
加熱することによつておこなわれる。ここで用い
られる酸無水物とは、一般式
The present invention relates to a method for producing a carboxyl-modified resin of a saponified ethylene-vinyl acetate copolymer, which is colorless and highly transparent. Ethylene-vinyl acetate copolymer (hereinafter referred to as EVA)
EVA saponified carboxyl-modified resin, which is obtained by saponifying EVA (hereinafter referred to as EVA) and modifying it with acid, is used in adhesives, films, powder coatings, etc., and its production method is also widely known. It is being However, although carboxyl-modified resins obtained by conventional manufacturing methods have excellent adhesion to glass, aluminum, etc., problems remain in terms of coloration and transparency, and they are used in the fields of laminated glass and solar cell modules. It has not yet been used industrially. It is generally known that a cellulose nitrate film, a cellulose acetate film, a plasticized acrylic acid ester resin film, and a plasticized polyvinyl butyral film are used as interlayer films for bonding laminated glass. In particular,
Plasticized polyvinyl butyral films are superior to other interlayer films mentioned above in terms of excellent adhesion, light stability, and low-temperature flexibility, and are now widely used in safety glass for automobiles, aircraft, and other applications. This polyvinyl butyral film is a partially acetalized product of polyvinyl alcohol derived from polyvinyl acetate resin, and has a polyvinyl butyral component of 80 to 80%.
It is a synthetic resin consisting of 85% by weight of polyvinyl acetate component and 3-7% by weight of polyvinyl alcohol component. When used alone, the resin film has the disadvantage of being too rigid and lacking in flexibility as an interlayer film for laminated glass, making it unsuitable for practical use. To compensate for this point, approximately 40% by weight of a high boiling point plasticizer with low vapor pressure is added. However, this plasticized polyvinyl butyral film has a strong adhesive surface at room temperature.
This causes many difficulties in handling and transporting the laminated glass before bonding. Therefore, in order to temporarily remove the adhesion of the resin film, an uneven pattern is formed on the surface of the film, and soda bicarbonate powder is sprinkled on the pattern. In order to remove this adhesion suppressing powder during adhesion work, a washing process and a drying process are required in advance.Furthermore, the plasticized butyral film has high hygroscopicity and adhesion decreases when it contains water, so the water content of the film is low. It must be dried until it becomes less than 0.5% by weight. Furthermore, the plasticized butyral film increases in stickiness as the temperature rises and has poor lubricity on glass surfaces, which significantly impairs workability. In order to improve this property and suppress moisture absorption, the temperature of the workplace must be maintained at approximately 20°C. In addition, the plasticized butyral film is used as an interlayer film, and when the glass plate is actually bonded to this film, preliminary bonding is usually performed using a roll method or vacuum method, and then the process is carried out in a hydraulic or pneumatic autoclave for 10 minutes. ~130 under pressure of 15Kg/ cm2
It is essential to adopt a two-step adhesion method in which main adhesion is performed at a temperature of ~140°C, and there is a drawback that the manufacturing equipment must be large-scale.
To overcome these drawbacks, acid modified forms of saponified EVA have been proposed (for example, Japanese Patent Publication No. 16826/1982). In other words, this acid-modified material does not have the handling or work difficulties that plasticized butyral films do, and can be bonded by a simple method of heating to about 100°C under reduced pressure. Therefore, large-scale equipment such as that used when manufacturing laminated glass using a plasticized butyral film as an interlayer film is not required. Moreover, in terms of the performance of laminated glass, laminated glass with this acid-modified material as an interlayer film has impact resistance comparable to laminated glass with a plasticized butyral film as an interlayer film.
Has hot water resistance. However, when laminated glass is created using this acid-modified product as an interlayer film,
The transparency of this laminated glass varies greatly depending on how it is cooled after heat bonding.For example, when it is cooled rapidly, it maintains the same transparency as polyvinyl butyral, but when it is slowly cooled, the transparency deteriorates significantly. have. Moreover, it is virtually impossible to employ the rapid cooling method in the actual laminated glass production process because it would lead to glass breakage. Therefore, deterioration in transparency due to slow cooling was a fatal defect in laminated glass using the acid-modified product as an interlayer film. Furthermore, another drawback of this acid-modified interlayer film is that during the process of manufacturing the modified resin, in which EVA is used as a base polymer, the reactions of saponification and then acid modification are performed intermittently in sequence. The resin component is significantly colored, and as a result, the laminated glass using the resin as an interlayer film is also colored. Furthermore, in recent years, solar power generation using solar cells has attracted particular attention because it is clean and permanent. Solar cells are made by connecting wafers of silicon semiconductor elements or selenium semiconductor elements, which have the function of generating current when irradiated with light, in series or parallel using interconnectors, and then using an upper transparent protective material such as glass, polyacrylate, or polycarbonate. It is packaged by protecting the semiconductor element with a lower substrate protective material such as glass, stainless steel, aluminum, or plastic, and the semiconductor element and each of these protective materials are usually bonded using a sealing material. has been done. The encapsulant must have elastomeric properties to prevent damage to the semiconductor element due to sudden changes in outside air conditions, cracks in the filler, and interfacial peeling phenomena. When used, it is preferable to use a material that has a high transmittance to sunlight and that does not change in physical properties such as a decrease in light transmittance when left outdoors for a long period of time. Conventionally, superheated crosslinking type liquid silicone has been used for this purpose, but it has drawbacks such as being expensive, requiring long coating and adhesion processes, and being unsuitable for automation. For this reason, sheets of polyvinyl butyral resin, which has a proven track record in laminated glass, have recently begun to be used, but this is not necessarily satisfactory as a filler for solar cells. That is, a polyvinyl butyral sheet has starch attached to its surface to prevent blocking, and must be washed with water and dried before use. Furthermore, since the fluidity of the resin is poor, it is necessary to use an autoclave for bonding, which requires a long process time and is not suitable for automation. Furthermore, in terms of quality, it has poor temperature characteristics, and if left in high humidity for a long time, devitrification occurs, which not only reduces light transmittance, but also significantly reduces adhesive strength, making it difficult to protect the upper transparent layer. A peeling phenomenon occurs at the interface between the lower substrate protective material and the solar cell element. In addition, low-temperature characteristics are not necessarily good. In place of polyvinyl butyral sheets, which have these problems, ethylene-vinyl acetate copolymer sheets have recently begun to be considered from the perspective of reducing the cost of solar cell modules. However, the commonly used ethylene-vinyl acetate copolymer cannot satisfy the characteristics required as a sealing material for solar cells. That is, as the vinyl acetate content increases in this copolymer, transparency and flexibility improve, but sheet formability and blocking properties deteriorate, making it difficult to satisfy both properties at the same time. , heat resistance and weather resistance are also insufficient. Furthermore, the durable adhesiveness with the upper transparent protective material and the lower substrate protective material, which determines the reliability of the solar cell module, is also insufficient. Furthermore, as an improvement on these, an ethylene-vinyl acetate copolymer containing an organic peroxide is used as a sealing material sheet, and when the upper transparent protective material and the lower substrate protective material are bonded, the protective material to be bonded is It has been proposed to manufacture solar cells by subjecting the surface of the material and/or the surface of the encapsulant sheet to a primer treatment in advance and heating the material to a temperature higher than the decomposition temperature of the organic peroxide during the module bonding process. (For example, Japanese Patent Application Laid-Open No. 58-23870). However, it is very complicated to perform primer treatment on the protective material or the sealing material sheet in advance. Furthermore, the process of performing peroxide crosslinking by heat treatment at a high temperature of 120 to 160°C not only has an adverse effect such as heat-induced deterioration of the protective material, but also causes crosslinking shrinkage of the encapsulant sheet, which can lead to damage to the solar cell. It has the disadvantage of poor dimensional stability. Furthermore, even after heat curing, a very small amount of organic peroxide remains, resulting in poor weather resistance (coloring). The present inventors have developed a method for producing a carboxyl-modified resin of a saponified ethylene-vinyl acetate copolymer that solves the above-mentioned drawbacks at once and is particularly useful as a semiconductor encapsulant for laminated glass interlayer films or solar cell modules. As a result of intensive studies, we have arrived at the present invention. That is, in the present invention, an ethylene-vinyl acetate copolymer is dissolved in an organic solvent having a boiling point of 50°C or higher, and the copolymer is dissolved in this solution using an alkali alcoholate, and the amount is
It is characterized by saponifying in the presence of 0.1 to 3 moles of water, then adding an unsaturated carboxylic acid or dicarboxylic anhydride to a solution containing this saponified product to cause a reaction, and further contacting this reaction solution with water. 1.0
The total light transmittance of the mm thick sheet plate is 90% or more, the haze value is 3% or less, and the yellowness is 3 or less.
This is a method for producing a carboxyl-modified resin of a saponified vinyl acetate copolymer. First, the carboxyl-modified resin of the present invention (hereinafter referred to as
The manufacturing method of C-HEVA (sometimes abbreviated as C-HEVA) will be explained. The EVA used in the method of the present invention has a vinyl acetate content of about 20 to 50% by weight,
Melt index (according to ASTMD-1238)
is 0.5 to 500. The EVA
can be synthesized by a known method such as that described in US Pat. No. 2,200,429. In the method of the present invention, first, such
Dissolve EVA in an organic solvent with a boiling point of 50°C or higher. Examples of such organic solvents include aromatic hydrocarbons such as benzene, toluene, O-xylene, m-xylene, ethylbenzene, and propylbenzene, and aliphatic and alicyclic hydrocarbons such as n-hexane and cyclohexane. I can do it. Among these organic solvents, aromatic hydrocarbons such as xylene and toluene, which azeotrope water, and solvents having a boiling temperature of 100 to 200°C are preferred. These solvents
It is sufficient to use the amount necessary to dissolve EVA, but in order to make the next reaction proceed smoothly, it is usually preferable to use 150 to 500 parts by weight of the solvent per 100 parts by weight of EVA. Next, a lower alcohol is added to the EVA solution prepared in this way, and then subjected to a saponification reaction using an alkali alcoholate catalyst in the presence of a specific amount of water. Examples of the lower alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and tert-butyl alcohol, and methanol is usually used. These lower alcohols vary depending on the intended degree of saponification, but are usually approximately 0.1 to 10 times the mole of vinyl acetate in the raw material EVA, preferably 1 to 8 times the mole of vinyl acetate in the raw material EVA.
Double molar ratio is used. As the alkali alcoholate as a catalyst, an alkali metal alcoholate such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium amenoxide, potassium t-butoxide, etc. is used. The amount of the alkali alcoholate catalyst to be used varies depending on the intended degree of saponification, but is usually about 0.01 to 1 times the mole of vinyl acetate present in the raw material EVA, preferably 0.01 to 0.2 times the mole. In the method of the present invention, in the saponification reaction step, per mole of alkali alcoholate,
It is characterized by the presence of 0.1 to 3 moles of water; if it is less than 0.1 mole, the coloring prevention effect of the saponified product is hardly observed, and if it exceeds 3 moles, the intended saponification Excess alkali catalyst and alcohol are required to produce a saponified product with a high degree of hydrogenation, which is not only economically disadvantageous, but also reduces the carboxyl-modified product obtained from the saponified product produced under such conditions. However, when used as products such as laminated glass interlayer films, problems arise in terms of quality, such as increased opacity. The saponification reaction of the present invention is carried out under conventional conditions, for example at 40 to 60°C, and after a certain period of time, for example 0.5 to 3 hours, water is added to the reaction system to complete the reaction. make it stop. In order to obtain the intended degree of saponification, the amounts of lower alcohol, water and catalyst may be adjusted. Saponification reactions in the presence of water generally require an excess amount of alcohol compared to saponification reactions in the absence of water. The degree of saponification in this step of the present invention is not particularly limited, but is usually approximately 10 to 80.
%, preferably 30 to 70%. The reaction solution in the above saponification reaction is subsequently subjected to an acid modification reaction using an unsaturated carboxylic acid or an acid anhydride, but prior to this reaction, the saponification reaction solution is heated and used to stop the reaction. It is preferable to carry out a treatment in which water and low-boiling substances produced as by-products in the reaction are distilled off and removed. Particularly when an acid anhydride is used, the presence of water in the reaction system will impede the modification reaction, so it is necessary to substantially remove water. The unsaturated carboxylic acid is reacted by heating in the presence of a radical-forming substance. Here, unsaturated carboxylic acid has the general formula
In CHR′=CRCOOH, R and R′ are hydrogen,
It is represented by an alkyl group, a carboxyl group, or a carboxylic acid ester, and specific examples include monocarboxylic acids and dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid. The amount of unsaturated carboxylic acid used is at most about 5% by weight, preferably about 5% by weight, based on the saponified product.
It is about 0.2 to 3% by weight. Radical-forming substances are substances that can easily decompose to form radicals at the graft polymerization temperature, such as organic peroxides such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, α, α' Examples include nitrogen-containing compounds such as -azobisisobutyronitrile. These radical-forming substances are present in an amount of about 0.05 to 3% by weight, preferably about
It is used in an amount of 0.1-1% by weight. The heating temperature cannot be determined unconditionally depending on the type of unsaturated carboxylic acid or solvent used, but it is approximately 50 to 150℃.
℃, and the heating time is about 0.1 to 5 hours. The acid anhydride is reacted by adding the acid anhydride to the heat-treated reaction solution and heating the mixture at about 50 to 150°C for about 0.1 to 5 hours. The acid anhydride used here has the general formula
【式】で表わ
されるもので、Ｒはたとえば二価の芳香族あるい
は脂肪族残基を示し、具体的には、たとえば無水
マレイン酸、無水コハク酸、無水グルタル酸、無
水フタル酸、無水イタコン酸、無水トリメリツト
酸、無水ハイミツク酸などがあげられる。上記の
反応で酸無水物はケン化物中に含有されるOH基
により開環して[Formula], R represents, for example, a divalent aromatic or aliphatic residue, specifically, for example, maleic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, itaconic anhydride. , trimellitic anhydride, heimic anhydride, etc. In the above reaction, the acid anhydride is ring-opened by the OH group contained in the saponified product.
【式】となつているも
のと推定される。酸無水物の量は該ケン化物中に
含有されるビニルアルコール単位のうち、少なく
とも約２モル％以上、好ましくは約５〜50モル％
を反応させる（エステル化する）に必要な量であ
る。
このような酸変性反応によつて得られた反応液
は、次いで水と接触させる。水と接触させる方法
としては、たとえば反応液中に水を注入する方法
あるいは水中に反応液を注入する方法などを挙げ
ることができる。これらいずれの方法においても
激しく撹拌下に注入混合して反応液と水とを充分
に接触せしめるのがよい。またカラムを用いてこ
の中で向流接触せしめる方法を採つてもよい。水
の量は特に制限があるものではないが、通常反応
液中の固型分100重量部に対して、水をほぼ200〜
1000（好ましくは300〜600）重量部が用いられる。
接触温度は室温でも充分であるが、通常加温
（80°〜120℃）された状態の中で接触させる。
このように水と充分接触させた反応液は、たと
えばこれらを加熱して反応液中に存在する溶媒を
撹拌下にある程度まで留去（水と共沸する溶媒を
用いた場合には、水と一緒に留去）して、反応液
を乳化させる。反応液中の固形分100重量部に対
して、溶媒の量を10〜100（好ましくは20〜80）重
量部と調節することにより最も良好な乳化状態を
保つことができる。なお、反応液から溶媒を留去
したのち、水と接触させ、次いで乳化させる方法
を採つてもよい。乳化した系を激しく撹拌しなが
ら冷却（酸変性反応によつて生成したカルボキシ
ル変性樹脂の融点50〜100℃よりも低い温度まで）
することにより、EVAケン化物のカルボキシル
変性樹脂が顆粒状で析出する。このようにして顆
粒状で析出したカルボキシル変性樹脂は、たとえ
ば過や遠心分離などの公知の分離手段を用いて
分離したあと、たとえば真空乾燥や流動乾燥など
の公知の乾燥手段を用いて乾燥することにより採
取することができる。
上記方法によつて1.0mm厚シート板の全光線透
過率が90％以上、曇価が３％以下かつ黄色度が３
以下である、エチレン−酢酸ビニル共重合体ケン
化物のカルボキシル変性樹脂を得ることができ
る。
ここで全光線透過率および曇価はASTM
D1003−61（Standard Method of Test for
Haze and Luminous Transmittance of
Transparent Plastics）に準拠して測定した値、
黄色度はASTM D1925−70（Standard Method
of Test for Yellowness Index of Plastics）に
準拠して算出した値を表わす。なお、1.0mm厚の
シート板は、１mm厚のスペーサーと加熱プレス成
形機を用いてカルボキシル変性体を130℃×100
Kg／cm2×５分間の条件下でプレスして作成したも
のを用いた。
本発明の方法によつて得られるカルボキシル変
性体は、無色で、かつ透明性に優れているため、
合せガラスの中間膜、太陽電池の封止剤として特
に有用であり、その他たとえばポリカーボネート
樹脂、ポリメチルメタクリレート樹脂あるいはガ
ラス板など透明な基材の接着剤として利用でき
る。
本発明の方法によつて得られるＣ−HEVAを
合せガラス用中間膜として用いるには、慣用の加
工法、たとえばカレンダーロール法、押出シート
キヤステイング法、インフレーシヨンチヨープ法
などにより製膜する。膜の厚さは特定されないが
通常100〜800μである。この際、膜の片面あるい
は両面に公知の方法、たとえばエンボスロール法
などによつて凹凸模様をつけることもできる。ま
た、Ｃ−HEVAを、たとえば冷凍粉砕するなど
の公知の手段によつて一旦粉末とした後、加熱焼
結せしめて製膜し中間膜として用いることもでき
る。なお、製膜工程において耐光性改善の目的で
紫外線吸収剤、更に選択的光線透過性を得る目的
で特定の着色材料を合せガラスとしての性能を損
なわない範囲で添加することも可能である。
本発明の方法によつて得られるＣ−HEVAか
ら中間膜を製造し、この中間膜を用いる減圧方式
での合せガラスの製造は次のようにして行なうこ
とができる。
まず、複数枚のガラス板の間に１枚ないし複数
枚の中間膜をはさみ、組立体を形成する。この
際、装飾用などの目的で、たとえば印刷されたプ
ラスチツクフイルム、紙あるいは木皮など、また
機能性を付与する目的で、たとえば偏光などの機
能をもつたフイルムを２枚の中間膜ではさむこと
もできる。中間膜上に適当なインキを用いて任意
の膜様を形成してもよい。次に組立体を排気減圧
した雰囲気中で大気圧により押圧しながら加熱す
る。排気減圧にした状態で大気圧により押圧する
ためには組立体を排気口を設けたゴムあるいはプ
ラスチツク製の袋の中に入れ真空ポンプで排気
し、真空バツグを形成する方法、および木製ある
いは金属製などの真空枠中に組立体を置き、たと
えばテトロン、ポリビニールアルコールなどのプ
ラスチツクフイルム、あるいはシリコンゴム、ネ
オプレーンゴムなどのゴムシートでカバーし、そ
の内容を減圧状態にして大気圧による押圧を行な
う方法などがある。この際、組立体と真空枠との
間にたとえばシリコンゴム、ネオプレンゴムなど
でつくられた凹凸面のあるシート（凹面は連続し
ている）を置くことは中間膜の脱泡性の点から好
ましい。また組立体周辺に組立体厚みより数mm以
上厚い金属性または木性の枠を置き、組立体周辺
部に大気圧による押圧が掛らないようにすること
は組立体周辺部からの中間膜樹脂の流失および製
品合せガラスに生ずる歪みを軽減する上で好まし
い。
なお、プラスチツク製袋の材質としては、たと
えばネオプレンゴム、ブチルゴム等の合成ゴム、
Al／ナイロン、Al／PET、ポリプロピレン／６
−ナイロン、PP／ポリエステル等のプラスチツ
ク積層体フイルムを挙げることができる。
次に、上述のようにして得られた真空バツグあ
るいは真空状態に保たれた真空枠は所定時間所定
温度で加熱炉中に入れられ加熱される。加熱源と
しては、たとえば熱水、熱風、赤外線、超遠赤外
線、高周波など通常考えられる加熱方式から自由
に選ぶことができる。加熱温度は通常80〜130℃
である。また減圧度は通常100Torr以下、好まし
くは30Torr以下とする。
所定時間経過後、真空ポンプの運転を止め真空
バツグあるいは真空枠中の圧力を大気圧に戻す
が、すぐに加熱炉からとり出さないで５分程度加
熱炉中に保持することが好ましい。これは、合せ
ガラス接着中にガラス周辺部に生ずる歪みをとり
のぞくための、いわゆるアニール操作である。
以上のようにして、合せガラスを製造すること
ができる。中間膜の厚さは、用途によつても異な
るが通常100〜800μである。
次に、Ｃ−HEVAを封止材として用いる場合、
通常シートの形で用いられるが、そのシート成形
は、Ｔダイ押出機などを用いる常用の方法によつ
て行うことができる。すなわち、実質的に分解し
ない成形温度でシート状に押出し、好ましくはエ
ンボス模様入り取引ロールを通すことによつて成
形が行われる。任意のエンボス模様の形成は、シ
ートブロツキング防止および太陽電池のモジユル
化過程での脱気に際して有効である。
シートの厚みは特に規定されないが、一般には
約0.1〜１mm程度である。
また、より厳しい耐光性が要求される場合に
は、Ｃ−HEVAに耐光安定剤を添加しておくこ
とが好ましく、たとえば、封止材としての透明性
をそこなわない範囲において、２−ヒドロキシ−
４−メトキシベンゾフエノン、２，2′−ジヒドロ
キシ−４−メトキシベンゾフエノン、２−ヒドロ
キシ−４−メトキシ−2′−カルボキシベンゾフエ
ノン、２−ヒドロキシ−４−ｎ−オクトキシベン
ゾフエノンなどのベンゾフエノン系、２−（2′−
ヒドロキシ−３，３−ジ第３ブチルフエニル）ベ
ンゾトリアゾール、２−（2′−ヒドロキシ−５−
メチルフエニル）ベンゾトリアゾール、２−
（2′−ヒドロキシ−５−第３オクチルフエニル）
ベンゾトリアゾールなどのベンゾトリアゾール
系、フエニルサリチレート、ｐ−オクチルフエニ
ルサリチレートなどのサリチル酸エステル系、ニ
ツケル錯塩系、ヒンダードアミン系などが耐光安
定剤として用いられる。これらの耐光安定剤はま
た、ヒンダードフエノール系、ホスフアイト系な
どの酸化防止剤と併用することによつて、そこに
相乗効果が期待できる場合もある。
更に、太陽電池モジユールとしての性能を損な
わない範囲においてＣ−HEVAに他の樹脂や無
機充填材を添加してもよい。
太陽電池モジユールは、次のようにして製造す
ることができる。太陽電池用半導体素子がシリコ
ンやセレンの半導体ウエハーからなる場合には、
これらの素子を少くとも２枚の封止材シートで挾
み、更にその両側に保護材、即ち上部透明保護材
と下部基板保護材とを重ね合せ、真空下で加熱接
着させて貼り合せることにより行われる。この
際、太陽電池素子をＣ−HEVAからなる少くと
も２枚の封止材シートで予めラミネート化し、上
部透明保護材および下部基板保護材と貼り合せて
もよい。加熱は、90〜110℃間で行うことが望し
い。この加熱処理によつて、封止材と各保護材と
は強固に接着され、太陽電池素子が２枚の封止材
シートでラミネート化され、かつそれがその上部
透明保護材と下部基板保護材とに強固に貼り合さ
れた太陽電池モジユールがそこに形成される。
また、太陽電池用半導体素子がガラス、プラス
チツク、セラミツク、ステンレスなどの保護材上
に形成されている場合には、封止材シートを中間
層とし、いずれか一方の保護材の内向面（封止材
シート接触面）上に半導体素子を形成させた上部
透明保護材および下部基板保護材を前記中間層封
止材シートの上下に重ね、具体的には下部基板保
護材上面に形成させた半導体素子の上に封止材シ
ートおよび上部透明保護材を、または上部透明保
護材下面に形成させた半導体素子の下に封止材シ
ートおよび下部基板保護材をそれぞれ順次重ね、
これを前記の場合と同様に真空下で加熱接着させ
ると、半導体素子を形成させた一方の保護材、封
止材シートおよび他方の保護材が強固に貼り合さ
れる太陽電池モジユールが形成される。
このようにして、接着、形成された太陽電池モ
ジユールは、保護材と封止材との剥離強度が大き
く、湿度条件下における耐剥離性にすぐれている
などの良好な初期接着性および耐久接着性を示
し、また紫外線照射に対する変化が少なく、光線
透過率も良好であるなど、太陽電池モジユールに
求められる諸物性をいずれも十分に満足させてい
るということができる。
次に、実施例を挙げて本発明を更に具体的に説
明する。
実施例 １
撹拌機、コンデンサー、温度計ならびに窒素ガ
ス導入管を装備した20ステンレス製反応器に工
業用キシレン５および高圧重合法で合成された
メルトインデツクス（ｇ／10min.；ASTM1238
−65Tによる。以下同じ。）30、酢酸ビニル含量
33重量％のEVA2Kgを入れ、内温が40〜50℃にな
るまで加温して均一の溶液とした。この溶液に予
め調整したメタノール194ｇ、24％のナトリウム
メトキサイド−メタノール溶液69ｇおよび水7.2
ｇを添加し、撹拌下45〜55℃で60分間反応させた
後、水27ｇを加えてケン化反応を完全に停止させ
た。得られたケン化物のケン化度は、ほぼ50％で
あつた。次いで窒素ガス気流下、内温をあげて低
沸点物を留去させながら120℃まで上昇させた。
アクリル酸20ｇと過酸化ベンゾイル２ｇを加え
120℃で30分間撹拌下にグラフト反応を行ないケ
ン化物を酸で変性させた。引き続いてこの粘調反
応溶液を窒素ガスの加圧下にコンデンサー、窒素
ガス導入管、温度計を装備した20ヘンシエルミ
キサーに移し、内温を100℃まで下げた後、80℃
に加温した温水12を加えた。この場合物を回転
数510rpmの撹拌下に加熱して系内に残存するキ
シレンの量が固形分100重量部に対し、60重量部
になるまでキシレンを水との共沸により留去し
た。キシレンの留去を終えた時点で、系は乳化し
た。
この乳化物をヘンシエルミキサーのジヤケツト
に冷水を入れながら、510rpmの撹拌下に冷却を
行なうと、平均流径２mmの顆粒状物が得られた。
これを遠心分離し、さらに真空下50℃で４時間乾
燥し、表−に示す物性を有するカルボンキシル
変性樹脂1385ｇを得た。
比較例
実施例で用いた20ステンレス製反応器に工
業用キシレン７と高圧重合法で合成されたメル
トインデツクス30、酢酸ビニル含量33重量％の
EVA2Kgを入れ、内温が40〜45℃になるまで加温
して均一の溶液とした。この溶液に予め調整した
メタノール85ｇおよび24％のナトリウムメトキサ
イド−メタノール溶液69ｇを添加し、撹拌下43〜
48℃で60分間反応させた後、水35ｇを加えてケン
加反応を完全に停止させた。このケン化物のケン
化度は約50％であつた。この溶液を実施例と同
様にグラフト反応を行なつてケン化物を酸で変性
した後、20ヘンシエルミキサーに移し、実施例
と同様に処理して表−に示す性質を有するカ
ルボキシル変性樹脂1830ｇを得た。
比較例
実施例と同様にケン化反応およびグラフト反
応を行なつた後、反応溶液を20ヘンシエルミキ
サーに移し、510rpmの撹拌下工業用メタノール
６をゆつくり添加し、平均粒径300μの粉末状
物を得た。これを遠心分離した後、もう一度20
ヘンシエルミキサーに移し、メタノール６を加
えて30分間撹拌下洗浄した。沈澱物を遠心分離
し、さらに真空乾燥したのち表−に示す物性を
有するカルボキシル変性樹脂1750ｇを得た。
比較例
比較例と同様にケン化反応およびグラフト反
応を行なつた後、反応溶液を20ヘンシエルミキ
サーに移し、以後比較例と同様に処理したとこ
ろ、表−に示す物性を有するカルボキシル変性
樹脂1730ｇが得られた。It is estimated that [Formula]. The amount of acid anhydride is at least about 2 mol% or more, preferably about 5 to 50 mol% of the vinyl alcohol units contained in the saponified product.
This is the amount required to react (esterify). The reaction solution obtained by such acid modification reaction is then brought into contact with water. Examples of the method of contacting with water include a method of injecting water into the reaction solution or a method of injecting the reaction solution into water. In any of these methods, it is preferable that the reaction solution and water be brought into sufficient contact with each other by injection and mixing under vigorous stirring. Alternatively, a method may be adopted in which a column is used to bring about countercurrent contact. There is no particular limit to the amount of water, but usually approximately 200 to 200 parts of water is added to 100 parts by weight of solids in the reaction solution.
1000 (preferably 300-600) parts by weight are used.
Although room temperature is sufficient for the contact temperature, contact is usually made in a heated state (80° to 120° C.). The reaction solution that has been brought into sufficient contact with water can be heated, for example, to distill off the solvent present in the reaction solution to a certain extent while stirring (if a solvent that is azeotropic with water is used, to emulsify the reaction solution. The best emulsified state can be maintained by adjusting the amount of solvent to 10 to 100 (preferably 20 to 80) parts by weight based on 100 parts by weight of solids in the reaction solution. Alternatively, a method may be adopted in which the solvent is distilled off from the reaction solution, the solution is brought into contact with water, and then emulsified. Cool the emulsified system while stirring vigorously (to a temperature lower than the melting point of 50-100℃ of carboxyl-modified resin produced by acid modification reaction)
By doing so, the carboxyl-modified resin of saponified EVA is precipitated in the form of granules. The carboxyl-modified resin precipitated in the form of granules is separated using a known separation method such as filtration or centrifugation, and then dried using a known drying method such as vacuum drying or fluidized drying. It can be collected by By the above method, the total light transmittance of the 1.0 mm thick sheet plate is 90% or more, the haze value is 3% or less, and the yellowness is 3.
The following carboxyl-modified resin of saponified ethylene-vinyl acetate copolymer can be obtained. Here, the total light transmittance and haze value are ASTM
D1003−61 (Standard Method of Test for
Haze and Luminous Transmittance of
Transparent Plastics),
Yellowness is determined by ASTM D1925−70 (Standard Method
of Test for Yellowness Index of Plastics). Note that 1.0 mm thick sheet plates are made by molding the carboxyl modified product at 130℃ x 100 using a 1 mm thick spacer and a hot press molding machine.
A material prepared by pressing under conditions of Kg/cm 2 ×5 minutes was used. The carboxyl modified product obtained by the method of the present invention is colorless and has excellent transparency;
It is particularly useful as an interlayer film for laminated glass and as a sealant for solar cells, and can also be used as an adhesive for transparent substrates such as polycarbonate resins, polymethyl methacrylate resins, and glass plates. In order to use C-HEVA obtained by the method of the present invention as an interlayer film for laminated glass, it is formed into a film by a conventional processing method, such as a calender roll method, an extrusion sheet casting method, or an inflation coating method. . The thickness of the membrane is not specified, but is usually 100-800μ. At this time, an uneven pattern can be formed on one or both sides of the film by a known method such as an embossing roll method. Alternatively, C-HEVA can be once made into powder by a known method such as freezing and pulverization, and then heated and sintered to form a film and used as an intermediate film. In addition, in the film forming process, it is also possible to add an ultraviolet absorber for the purpose of improving light resistance, and furthermore, a specific coloring material for the purpose of obtaining selective light transmittance, within a range that does not impair the performance as a laminated glass. An interlayer film is produced from C-HEVA obtained by the method of the present invention, and laminated glass can be produced by a reduced pressure method using this interlayer film as follows. First, one or more interlayer films are sandwiched between a plurality of glass plates to form an assembly. At this time, for decorative purposes, such as printed plastic film, paper, or tree bark, or for the purpose of adding functionality, for example, a film with functions such as polarization may be sandwiched between two interlayer films. can. Any desired film shape may be formed on the intermediate film using a suitable ink. Next, the assembly is heated while being pressed by atmospheric pressure in an evacuated and depressurized atmosphere. In order to press the bag with atmospheric pressure under reduced pressure, the assembly is placed in a rubber or plastic bag with an exhaust port and evacuated with a vacuum pump to form a vacuum bag, and a wooden or metal bag is used. A method in which the assembly is placed in a vacuum frame, covered with a plastic film made of Tetoron, polyvinyl alcohol, etc., or a rubber sheet made of silicone rubber, neoprene rubber, etc., and the contents are reduced in pressure and pressed by atmospheric pressure. and so on. At this time, it is preferable to place a sheet with a concave and convex surface (concave surface is continuous) made of silicone rubber, neoprene rubber, etc. between the assembly and the vacuum frame from the viewpoint of degassing the intermediate film. . In addition, placing a metal or wooden frame several mm thicker than the assembly thickness around the assembly to prevent pressure from atmospheric pressure from being applied to the periphery of the assembly is recommended. This is preferable in terms of reducing the loss of water and the distortion that occurs in the product laminated glass. In addition, examples of materials for plastic bags include synthetic rubber such as neoprene rubber and butyl rubber,
Al/nylon, Al/PET, polypropylene/6
- Plastic laminate films such as nylon, PP/polyester etc. may be mentioned. Next, the vacuum bag obtained as described above or the vacuum frame maintained in a vacuum state is placed in a heating furnace and heated at a predetermined temperature for a predetermined period of time. The heating source can be freely selected from conventional heating methods such as hot water, hot air, infrared rays, ultra-far infrared rays, and high frequency. Heating temperature is usually 80-130℃
It is. Further, the degree of pressure reduction is usually 100 Torr or less, preferably 30 Torr or less. After a predetermined period of time has elapsed, the operation of the vacuum pump is stopped and the pressure in the vacuum bag or vacuum frame is returned to atmospheric pressure, but it is preferable not to take it out of the heating furnace immediately but to hold it in the heating furnace for about 5 minutes. This is a so-called annealing operation to eliminate distortions that occur around the glass during bonding of the laminated glass. In the manner described above, laminated glass can be manufactured. The thickness of the interlayer film varies depending on the application, but is usually 100 to 800 μm. Next, when using C-HEVA as a sealing material,
It is usually used in the form of a sheet, and the sheet can be formed by a conventional method using a T-die extruder or the like. That is, forming is carried out by extrusion into sheets, preferably through embossed trading rolls, at forming temperatures that do not substantially decompose. Formation of an arbitrary embossed pattern is effective in preventing sheet blocking and degassing during the process of modularizing solar cells. Although the thickness of the sheet is not particularly limited, it is generally about 0.1 to 1 mm. In addition, when stricter light resistance is required, it is preferable to add a light resistance stabilizer to C-HEVA. For example, 2-hydroxy-
4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone benzophenones such as 2-(2′-
Hydroxy-3,3-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5-
methylphenyl)benzotriazole, 2-
(2'-hydroxy-5-tertiary octylphenyl)
Benzotriazole-based stabilizers such as benzotriazole, salicylic acid ester-based stabilizers such as phenyl salicylate and p-octylphenyl salicylate, nickel complex salt-based stabilizers, hindered amine-based stabilizers, and the like are used as light stabilizers. When these light stabilizers are used in combination with antioxidants such as hindered phenols and phosphites, a synergistic effect may be expected. Furthermore, other resins and inorganic fillers may be added to C-HEVA within a range that does not impair the performance as a solar cell module. The solar cell module can be manufactured as follows. When semiconductor elements for solar cells are made of silicon or selenium semiconductor wafers,
These elements are sandwiched between at least two encapsulant sheets, and protective materials, that is, an upper transparent protective material and a lower substrate protective material, are layered on both sides of the sheets and bonded together by heating under vacuum. It will be done. At this time, the solar cell element may be laminated in advance with at least two encapsulant sheets made of C-HEVA and bonded to the upper transparent protective material and the lower substrate protective material. Heating is preferably performed at a temperature of 90 to 110°C. Through this heat treatment, the encapsulant and each protective material are firmly bonded, the solar cell element is laminated with two encapsulant sheets, and the upper transparent protective material and the lower substrate protective material are laminated together. A solar cell module is formed therein which is firmly bonded to the solar cell module. In addition, when a semiconductor element for a solar cell is formed on a protective material such as glass, plastic, ceramic, or stainless steel, an encapsulant sheet is used as an intermediate layer, and the inner surface of one of the protective materials (sealing material) is used as an intermediate layer. An upper transparent protective material and a lower substrate protective material on which a semiconductor element is formed (contact surface of the material sheet) are stacked on top and bottom of the intermediate layer encapsulant sheet, specifically, a semiconductor element formed on the upper surface of the lower substrate protective material. An encapsulant sheet and an upper transparent protective material are sequentially stacked on top, or an encapsulant sheet and a lower substrate protector are stacked under the semiconductor element formed on the lower surface of the upper transparent protective material, respectively,
When this is heated and bonded under vacuum in the same way as in the above case, a solar cell module is formed in which one protective material on which the semiconductor element is formed, the sealing material sheet, and the other protective material are firmly bonded. . The solar cell module bonded and formed in this way has good initial adhesion and durable adhesion, such as high peel strength between the protective material and the encapsulant, and excellent peel resistance under humid conditions. In addition, it can be said that it fully satisfies all the physical properties required for a solar cell module, such as little change in response to ultraviolet irradiation and good light transmittance. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Melt index (g/10 min.; ASTM1238
-according to 65T. same as below. ) 30, vinyl acetate content
2 kg of 33% by weight EVA was added and heated until the internal temperature reached 40 to 50°C to form a uniform solution. To this solution, 194 g of pre-prepared methanol, 69 g of 24% sodium methoxide-methanol solution and 7.2 g of water.
After adding 27 g of water and reacting at 45 to 55° C. for 60 minutes with stirring, 27 g of water was added to completely stop the saponification reaction. The degree of saponification of the saponified product obtained was approximately 50%. Next, under a nitrogen gas stream, the internal temperature was raised to 120°C while distilling off low-boiling substances.
Add 20g of acrylic acid and 2g of benzoyl peroxide.
A graft reaction was carried out at 120°C for 30 minutes with stirring to denature the saponified product with acid. Subsequently, this viscous reaction solution was transferred under nitrogen gas pressure to a 20 Henschel mixer equipped with a condenser, nitrogen gas inlet tube, and thermometer, and the internal temperature was lowered to 100°C, and then heated to 80°C.
12 liters of warm water was added to the mixture. In this case, the product was heated under stirring at a rotational speed of 510 rpm, and the xylene remaining in the system was distilled off by azeotropic distillation with water until the amount of xylene remaining in the system became 60 parts by weight based on 100 parts by weight of solid content. At the end of xylene distillation, the system became emulsified. When this emulsion was cooled while stirring at 510 rpm while pouring cold water into the jacket of a Henschel mixer, granules with an average flow diameter of 2 mm were obtained.
This was centrifuged and further dried under vacuum at 50° C. for 4 hours to obtain 1385 g of a carboxyl-modified resin having the physical properties shown in the table. Comparative Example Into the 20 stainless steel reactor used in the example, industrial xylene 7, melt index 30 synthesized by high-pressure polymerization method, and vinyl acetate content of 33% by weight were added.
2 kg of EVA was added and heated until the internal temperature reached 40 to 45°C to form a uniform solution. 85 g of methanol prepared in advance and 69 g of 24% sodium methoxide-methanol solution were added to this solution, and while stirring,
After reacting at 48° C. for 60 minutes, 35 g of water was added to completely stop the saponification reaction. The degree of saponification of this saponified product was approximately 50%. This solution was subjected to a graft reaction in the same manner as in the example to modify the saponified product with an acid, and then transferred to a 20 Henschel mixer and treated in the same manner as in the example to obtain 1830 g of a carboxyl-modified resin having the properties shown in the table. Obtained. Comparative Example After carrying out the saponification reaction and grafting reaction in the same manner as in the example, the reaction solution was transferred to a 20 Henschel mixer, and while stirring at 510 rpm, industrial methanol 6 was slowly added to form a powder with an average particle size of 300μ. I got something. After centrifuging this, once again 20
The mixture was transferred to a Henschel mixer, and washed with 6 methanol and stirred for 30 minutes. After centrifuging the precipitate and vacuum drying, 1750 g of a carboxyl-modified resin having the physical properties shown in the table was obtained. Comparative Example After carrying out the saponification reaction and grafting reaction in the same manner as in the comparative example, the reaction solution was transferred to a 20 Henschel mixer and treated in the same manner as in the comparative example. As a result, 1730 g of carboxyl-modified resin having the physical properties shown in the table was obtained. was gotten.
【表】
実施例
撹拌後、コンデンサー、温度計ならびに窒素ガ
ス導入管を装備した20ステンレス製反応器に工
業用キシレン５ｇと高圧重合法で合成されたメル
トインデツクス30、酢酸ビニル含量33重量％の
EVA2Kgを入れ、内温が40〜50℃になるまで加温
して均一の溶液とした。この溶液に予め調整した
メタノール904ｇ、24％のナトリウムメトキシサ
イド−メタノール溶液103ｇおよび水6.6ｇを添加
し、撹拌下45〜55℃で60分間反応させた後、水40
ｇを加えてケン化反応を完全に停止させた。この
ようにして得られたケン化物のケン化度は約70％
であつた。次いで窒素ガス気流下で内温を上げて
低沸点物及び水を留去させながら125℃まで上昇
させた。この温度で工業用キシレン１Kgを留出さ
せた後、窒素ガスの供給を止め、内温が100℃に
なるまで冷却した。ヘキサヒドロ無水フタル酸
106ｇを反応器に添加し、撹拌下100〜105℃で60
分間反応を行なつた。この反応溶液で窒素ガスの
加圧下にコンデンサー、窒素ガス導入管、温度計
を装備した20ヘンシエルミキサーに移し、80℃
に加温した温水12を加えた。この混合物を回転
数510rpmの撹拌下に加熱を行ない系内に残存す
るキシレンの量が固形分100重量部に対し、70重
量部になるまで、キシレンを水との共沸により留
去した。キシレンの留去を終えた時点で系は乳化
していた。この乳化物をヘンシエルミキサーのジ
ヤケツトに水を入れながら510rpmの撹拌下に冷
却を行なうと平均粒径２mmの顆粒状物が得られ
た。これを遠心分離し、さらに真空下50℃で４時
間乾燥し、下記の物性を有するカルボキシル変性
樹脂1920ｇを得た。
ビニルアルコール含量 7.0モル％
酸含量 1.9モル％
酢酸ソーダ含量 0.1wt％
メルトインデツクス（ｇ／10min） 15
着色度 全く着色せず
実施例
撹拌機、コンデンサー、温度計ならびに窒素ガ
ス導入管を装備した20ステンレス製反応器に工
業用キシレン６ｇおよび高圧重合法で合成された
メルトインデツクス（ｇ／10min.；ASTM1238
−65Tによる。以下同じ）30、酢酸ビニル含量33
重量％のEVA2Kgを入れ、内温が40〜50℃になる
まで加温して均一の溶液とした。この溶液に予め
調整したメタノール905ｇ、24％のナトリウムメ
トキサイド−メタノール溶液102および水6.6ｇ
を添加し、撹拌下45〜55℃で60分間反応させた
後、水31ｇを加えてケン化反応を完全に停止させ
た。得られたケン化物のケン化度は、ほぼ70％で
あつた。次いで窒素ガス気流下、内温をあげて低
沸点物を留去させながら120℃まで上昇させた。
アクリル酸26ｇと過酸化ベンゾイル２ｇを加え、
120℃で30分間撹拌下にグラフト反応を行ないケ
ン化物を酸で変性させた。
以下実施例と同様に処理して次に示す物性を
有するカルボキシル変性樹脂1770ｇを得た。
このもののビニルアルコール含量は9.6モル％、
アクリル酸含量は0.5wt％、酢酸ソーダ含量は
0.1wt％、メルトインデツクスは18ｇ／10min.で
あり、着色は全く認められなかつた。
実験例
実施例、、および比較例１−で得た６
種類のカルボキシル変性樹脂を用いて加熱ブレス
成形機によつて130℃×100Kg／cm2×５分間の条件
下で１mm厚のシート板を作成した。この１mm厚シ
ート板の全光線透過率、曇価及び黄色度の測定値
を表−に示す。[Table] Example After stirring, 5 g of industrial xylene and melt index 30 synthesized by high-pressure polymerization method, with a vinyl acetate content of 33% by weight, were placed in a 20 stainless steel reactor equipped with a condenser, a thermometer, and a nitrogen gas inlet tube.
2 kg of EVA was added and heated until the internal temperature reached 40 to 50°C to form a homogeneous solution. To this solution, 904 g of methanol prepared in advance, 103 g of 24% sodium methoxide-methanol solution and 6.6 g of water were added, and after reacting for 60 minutes at 45-55°C with stirring, 40 g of methanol was added.
g was added to completely stop the saponification reaction. The degree of saponification of the saponified product obtained in this way is approximately 70%.
It was hot. Next, the internal temperature was raised to 125° C. under a nitrogen gas stream while distilling off low-boiling substances and water. After distilling 1 kg of industrial xylene at this temperature, the supply of nitrogen gas was stopped and the reactor was cooled until the internal temperature reached 100°C. Hexahydrophthalic anhydride
Add 106g to the reactor and heat at 100-105℃ for 60 minutes under stirring.
The reaction was carried out for minutes. This reaction solution was transferred to a 20° Henschel mixer equipped with a condenser, nitrogen gas inlet tube, and thermometer under nitrogen gas pressure, and heated to 80°C.
12 liters of warm water was added to the mixture. This mixture was heated with stirring at a rotational speed of 510 rpm, and xylene was distilled off by azeotropic distillation with water until the amount of xylene remaining in the system became 70 parts by weight based on 100 parts by weight of solid content. The system was emulsified by the time the xylene had finished distilling off. This emulsion was cooled while stirring at 510 rpm while adding water to the jacket of a Henschel mixer to obtain granules with an average particle size of 2 mm. This was centrifuged and further dried under vacuum at 50° C. for 4 hours to obtain 1920 g of a carboxyl-modified resin having the following physical properties. Vinyl alcohol content 7.0 mol% Acid content 1.9 mol% Sodium acetate content 0.1 wt% Melt index (g/10min) 15 Degree of coloration No coloring Example 20 Equipped with a stirrer, condenser, thermometer and nitrogen gas inlet tube Melt index (g/10 min.; ASTM1238
-according to 65T. (same below) 30, vinyl acetate content 33
2 kg of EVA (wt%) was added and heated until the internal temperature reached 40 to 50°C to form a homogeneous solution. To this solution, 905 g of pre-prepared methanol, 102 g of 24% sodium methoxide-methanol solution and 6.6 g of water
was added and reacted for 60 minutes at 45 to 55°C with stirring, and then 31 g of water was added to completely stop the saponification reaction. The degree of saponification of the saponified product obtained was approximately 70%. Next, under a nitrogen gas stream, the internal temperature was raised to 120°C while distilling off low-boiling substances.
Add 26g of acrylic acid and 2g of benzoyl peroxide,
A graft reaction was carried out at 120°C for 30 minutes with stirring to denature the saponified product with acid. Thereafter, 1770 g of a carboxyl-modified resin having the following physical properties was obtained by processing in the same manner as in the examples. The vinyl alcohol content of this product is 9.6 mol%.
Acrylic acid content is 0.5wt%, sodium acetate content is
The content was 0.1 wt%, the melt index was 18 g/10 min., and no coloration was observed. Experimental Example 6 obtained in Example and Comparative Example 1-
A sheet plate with a thickness of 1 mm was prepared using various carboxyl-modified resins using a heating press molding machine under conditions of 130° C. x 100 kg/cm 2 x 5 minutes. Table 1 shows the measured values of total light transmittance, haze value, and yellowness of this 1 mm thick sheet plate.
【表】
参考例
実施例、、および比較例〜で得た６
種類のカルボキシル変性樹脂を用いてＴ−ダイ押
出し法によつて380μ厚のフイルムとなし、これ
をエンボスロールの間を通過させて、見掛け厚
440μの、片面に連続した凹凸模様のあるフイル
ムを作成した。このフイルムを62cm角に切断した
ものを厚さ３mmで２尺角のフロートガラスの間に
挾み組立体を調製した。ステンレス製真空枠架台
上に厚さ３mmのエンボス仕様を施こしたネオプレ
ンゴムをひき、その上に該組立体を載置した。該
組立体の各周辺から10mmはなした位置に高さ10
mm、幅10mmの木製の棒４本で囲み、上部より50μ
厚のポリエチレンテレフタレートフイルムで覆い
真空枠を作成した。
真空ポンプを運転しながら真空枠内部の圧力が
10mmHg以下となるように脱気した状態で100℃に
設定した超遠赤外線加熱炉に挿入した。20分経過
後、真空ポンプの運転をとめ、真空枠中の圧力を
大気圧に戻し、さらに５分間加熱を続け、その後
取り出し、室温でゆつくりと冷却した。該組立体
はいずれも気泡は残留しておらず、接着層厚みは
約0.38mmであつた。このようにして製作した合せ
ガラスの外観評価の結果を表−に示す。[Table] Reference Example 6 obtained in Examples and Comparative Examples~
A film with a thickness of 380 μm was made by T-die extrusion using various carboxyl-modified resins, and the film was passed between embossing rolls to give an apparent thickness of
A 440μ film with a continuous uneven pattern on one side was created. This film was cut into 62 cm square pieces and sandwiched between 2 square pieces of float glass with a thickness of 3 mm to prepare an assembly. A 3 mm thick embossed neoprene rubber was placed on a stainless steel vacuum frame stand, and the assembly was placed on top of it. 10mm in height from each periphery of the assembly.
mm, surrounded by 4 wooden sticks with a width of 10 mm, 50 μ from the top
A vacuum frame was created by covering it with a thick polyethylene terephthalate film. While operating the vacuum pump, the pressure inside the vacuum frame increases.
It was degassed to 10 mmHg or less and inserted into an ultra-far infrared heating furnace set at 100°C. After 20 minutes, the vacuum pump was stopped, the pressure in the vacuum frame was returned to atmospheric pressure, and heating was continued for an additional 5 minutes, after which it was taken out and slowly cooled at room temperature. There were no remaining air bubbles in any of the assemblies, and the adhesive layer thickness was about 0.38 mm. Table 1 shows the results of the appearance evaluation of the laminated glass produced in this way.
【表】
参考例
実施例によつて製造したカルボキシル変性樹
脂100部に0.5部のチヌビン326（チバ・ガイギー社
製品）をメルトブレンドしてペレツトを作成し、
このペレツトとＴ−ダイ押出成形機を用いて樹脂
温度100℃でシール状に押出し、エンボス模様入
り引取ロールでシール両面にエンボス模様を付し
ながら厚さ0.4mmのＣ−HEVAの膜（シール）を
調製した。
このようにして得られたシートを厚さ３mm、直
径30cmのフロートガラスでつくられた円型の一組
の曲面ガラスの間に挾持させ、これをCPP／６
−ナイロン積層体から作成した袋の中に入れ、袋
の開口部をヒートシールした後、室温下で脱気口
より島津製KD−300型真空ポンプで排気した。
真空をひいたままの状態でこの真空袋を60℃の温
水に３分間浸漬し、次いで煮沸水に15分間浸漬し
て加熱した。袋を煮沸水から取り出し、これを50
℃の温水に３分間浸漬し冷却した後、真空ポンプ
の運転をとめ、真空袋を開いて曲面ガラスをとり
出した。このようにして無色、透明で、かつ気泡
の残留していない装着層厚み約0.4mmの曲面合わ
せガラスが得られた。
なお、真空袋として透明のものを用いたため合
わせガラス製造中内部の状態が十分に観察出来
た。
この曲面合わせガラスを、まず65℃の温水に３
浸漬し、引続いて沸騰水中にほぼ鉛直の状態で２
時間保持する耐熱性試験を行なつたが、合わせガ
ラスの白濁あるいは剥離などの損傷は全く生じな
かつた。
参考例
実施例によつて製造したカルボキシル変性樹
脂100部に0.5重量部のチヌビン326（チバ・ガイギ
ー社製品）をメルトブレンドしてペレツトを作成
し、押出機を用いて参考例と同様に厚さ0.4mm
の両面をエンボスシート作成した。
このエンボスシートを用いて参考例と同様の
方法で曲面合わせガラスを製造したところ無色・
透明でかつ残留気泡のない合わせガラスを得た。
参考例と同様に耐熱性試験を行なつたとこ
ろ、合わせガラスには全く損傷は生じなかつた。
参考例
実施例によつて製造したカルボキシル変性樹
脂100部に0.5部のチヌビン326（チバ・ガイギー社
製品）をメルトブレンドしてペレツトを作成し、
このペレツトをＴ−ダイ押出成形機を用いて、樹
脂温度95℃でシート状に押出し、エンボス模様入
り引取ロールでシート両面にエンボス模様を付け
ることによつて、厚さ0.5mmのエンボスシートに
成形した。
このようにして得られた２枚のエンボスシート
の間に、複数個の太陽電池用シリコン半導体ウエ
ハーをインターコネクターを用いて直列に配列
し、この上面に透明平板ガラスを、また下面にポ
リフツ素ビニルシートをそれぞれ重ね合せ、真空
ラミネーターを用いて、加熱温度100℃で５〜10
分間加熱して溶融貼り合わせを行ない、両保護材
とも強固に接着させて、モジユールを作成した。
得られたモジユールについて、温湿度サイクル
試験を行なつた。試験は、楠本化成温湿度サイク
ル試験機を用いて23℃、相対湿度50％で４時間お
よび40℃、相対温度90％で10時間を１サイクルと
して40サイクル実施し、その外観変化を剥離性に
ついて観察した。
また、前記エンボスシートを、透明板ガラスま
たはポリフツ化ビニルシートにそれぞれ重ね合
せ、前記貼り合せ条件下で平板ガラス−エンボス
シート積層物およびポリフツ化ビニルシート−エ
ンボスシート積層物を作成し、これらの積層物の
剥離強度を、引張試験機を用いて、引張速度200
mm／分、温度23℃のＴ−型剥離で５試料片につい
て測定し、その平均値をとつて接着性の評価とし
た。
更に、前記作成した太陽電池モジユールを東洋
理化工業製サンシヤインウエザオメーターを用い
て、ブラツクパネル温度62℃、２時間サイクルの
条件で促進耐候試験を行ない、500時間、1000時
間及び2000時間での外観を観察した。
参考例
実施例によつて製造したカルボキシル変性樹
脂100部に0.5重量部のチヌビン326（チバ・ガイギ
ー社製品）をメルトブレンドとしてペレツトを作
成し、押出機を用いて参考例と同様な厚さ
800μの両面エンボスシートを作成した。
このエンボスシートを用い、参考例と同様な
方法で太陽電池モジユール及び各種積層物を作成
し、参考例と同様な性能試験を行つた。
以上の各実施例で行つた性能試験の結果を表−
にまとめた。[Table] Reference Example Pellets were prepared by melt-blending 0.5 parts of Tinuvin 326 (product of Ciba-Geigy) with 100 parts of the carboxyl-modified resin produced in the example.
This pellet is extruded into a seal using a T-die extrusion molding machine at a resin temperature of 100°C, and an embossed pattern is applied to both sides of the seal using a take-up roll with an embossed pattern, forming a 0.4 mm thick C-HEVA film (seal). was prepared. The sheet thus obtained was sandwiched between a pair of circular curved glasses made of float glass with a thickness of 3 mm and a diameter of 30 cm.
- The bag was placed in a bag made from a nylon laminate, the opening of the bag was heat-sealed, and the bag was evacuated at room temperature using a Shimadzu model KD-300 vacuum pump through the degassing port.
The vacuum bag was immersed in warm water at 60° C. for 3 minutes while the vacuum was still applied, and then immersed in boiling water for 15 minutes to heat it. Remove the bag from the boiling water and add 50
After cooling by immersing in hot water at ℃ for 3 minutes, the operation of the vacuum pump was stopped, the vacuum bag was opened, and the curved glass was taken out. In this way, a curved laminated glass that was colorless, transparent, and had a mounting layer thickness of about 0.4 mm without any remaining air bubbles was obtained. In addition, since a transparent vacuum bag was used, the internal state of the laminated glass could be sufficiently observed during manufacture. First, soak this curved laminated glass in warm water at 65°C for 30 minutes.
immersion and then submerged in boiling water in an almost vertical position for 2 hours.
A heat resistance test was conducted in which the laminated glass was kept for a long time, but no damage such as clouding or peeling of the laminated glass occurred. Reference Example Pellets were prepared by melt-blending 0.5 parts by weight of Tinuvin 326 (product of Ciba Geigy) with 100 parts of the carboxyl-modified resin produced in the example, and the pellets were made into pellets using an extruder to the same thickness as in the reference example. 0.4mm
An embossed sheet was created on both sides. When curved laminated glass was manufactured using this embossed sheet in the same manner as the reference example, it was colorless.
A transparent laminated glass without residual bubbles was obtained. When a heat resistance test was conducted in the same manner as in the reference example, no damage occurred to the laminated glass. Reference Example Pellets were prepared by melt-blending 0.5 parts of Tinuvin 326 (product of Ciba Geigy) with 100 parts of the carboxyl-modified resin produced in the example.
This pellet is extruded into a sheet using a T-die extrusion molding machine at a resin temperature of 95°C, and an embossed pattern is applied to both sides of the sheet using a take-up roll with an embossed pattern, thereby forming an embossed sheet with a thickness of 0.5 mm. did. A plurality of silicon semiconductor wafers for solar cells are arranged in series between the two embossed sheets obtained in this way using interconnectors, and transparent flat glass is placed on the top surface and polyfluorinated vinyl is placed on the bottom surface. Stack the sheets on top of each other and use a vacuum laminator to heat them for 5 to 10 minutes at a heating temperature of 100℃.
The two protective materials were melted and bonded together by heating for a minute, and both protective materials were firmly adhered to form a module. The obtained module was subjected to a temperature and humidity cycle test. The test was conducted using a Kusumoto Kasei temperature/humidity cycle tester for 40 cycles, one cycle being 4 hours at 23℃ and 50% relative humidity and 10 hours at 40℃ and 90% relative temperature, and the change in appearance was evaluated for peelability. Observed. Further, the embossed sheet is laminated on a transparent plate glass or a polyfluorinated vinyl sheet, respectively, to create a flat glass-embossed sheet laminate and a polyfluorinated vinyl sheet-embossed sheet laminate under the laminating conditions, and these laminates are produced. The peel strength was measured using a tensile tester at a tensile speed of 200
Five sample pieces were measured by T-peel at a temperature of 23° C. at a temperature of 23° C., and the average value was taken to evaluate the adhesion. Furthermore, the solar cell module prepared above was subjected to an accelerated weathering test using a Sunshine Weatherometer manufactured by Toyo Rika Kogyo under the conditions of a black panel temperature of 62°C and a 2-hour cycle. The appearance was observed. Reference Example Pellets were prepared by melt blending 100 parts of the carboxyl-modified resin produced according to the example and 0.5 parts by weight of Tinuvin 326 (product of Ciba Geigy), and the pellets were made into pellets using an extruder to the same thickness as the reference example.
An 800μ double-sided embossed sheet was created. Using this embossed sheet, solar cell modules and various laminates were created in the same manner as in the reference example, and the same performance tests as in the reference example were conducted. The results of the performance tests conducted in each of the above examples are shown below.
summarized in.
Claims (1)
沸点を有する有機溶媒に溶解させ、この溶液中で
共重合体をアルカリアルコラートを用いて、この
アルカリアルコラート１モルに対して0.1〜３モ
ルの水の存在下にケン化し、次いでこのケン化物
を含む溶液に不飽和カルボン酸またはジカルボン
酸無水物を加えて反応させ、さらにこの反応液を
水と接触させることを特徴とする1.0mm厚シート
板の全光線透過率が90％以上、曇価が３％以下か
つ黄色度が３以下である、エチレン−酢酸ビニル
共重合体ケン化物のカルボキシル変性樹脂の製造
法。1 Dissolve the ethylene-vinyl acetate copolymer in an organic solvent with a boiling point of 50°C or higher, and dissolve the copolymer in this solution using an alkali alcoholate, and add 0.1 to 3 moles of water per mole of the alkali alcoholate. A 1.0 mm thick sheet plate characterized by saponifying the saponified product in the presence of the saponified product, then adding an unsaturated carboxylic acid or dicarboxylic acid anhydride to the solution containing the saponified product to cause a reaction, and further contacting the reaction solution with water. A method for producing a carboxyl-modified resin of a saponified ethylene-vinyl acetate copolymer, which has a total light transmittance of 90% or more, a haze value of 3% or less, and a yellowness value of 3 or less.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21778484A JPS6195007A (en) | 1984-10-16 | 1984-10-16 | Colorless and transparent carboxyl modified resin of saponified ethylene-vinyl acetate copolymer, its production and use |
| DE8484113355T DE3480341D1 (en) | 1983-11-07 | 1984-11-06 | Resin from saponified ethylene-vinyl acetate copolymers, production and use thereof |
| EP84113355A EP0145928B1 (en) | 1983-11-07 | 1984-11-06 | Resin from saponified ethylene-vinyl acetate copolymers, production and use thereof |
| US06/668,822 US4614781A (en) | 1983-11-07 | 1984-11-06 | Resin from saponified ethylene-vinyl acetate copolymers, production and use thereof |
| CA000467116A CA1226097A (en) | 1983-11-07 | 1984-11-06 | Resin from saponified ethylene vinyl-acetate copolymers, production and use thereof |
| KR1019840006959A KR920004617B1 (en) | 1983-11-07 | 1984-11-07 | Coloress and transparent carboxyl modified resin of saponified ethylen-vinyl acetate copolymer, its production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21778484A JPS6195007A (en) | 1984-10-16 | 1984-10-16 | Colorless and transparent carboxyl modified resin of saponified ethylene-vinyl acetate copolymer, its production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6195007A JPS6195007A (en) | 1986-05-13 |
| JPH0526802B2 true JPH0526802B2 (en) | 1993-04-19 |
Family
ID=16709673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21778484A Granted JPS6195007A (en) | 1983-11-07 | 1984-10-16 | Colorless and transparent carboxyl modified resin of saponified ethylene-vinyl acetate copolymer, its production and use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6195007A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001220474A (en) * | 1999-11-30 | 2001-08-14 | Takeda Chem Ind Ltd | Water-based emulsion composition and adhesive composition |
| JP5128730B2 (en) * | 2000-08-31 | 2013-01-23 | 株式会社クラレ | Process for producing saponified ethylene-vinyl acetate copolymer |
| JP5281071B2 (en) * | 2010-12-15 | 2013-09-04 | 株式会社クラレ | Method for producing ethylene-vinyl acetate copolymer partially saponified pellets |
| JP6186675B2 (en) * | 2012-07-05 | 2017-08-30 | 日本電気硝子株式会社 | Glass resin laminate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5521447A (en) * | 1978-08-01 | 1980-02-15 | Takeda Chem Ind Ltd | Separation and purification of saponified product from ethylene-vinyl acetate copolymer |
| JPS5589304A (en) * | 1978-12-27 | 1980-07-05 | Du Pont Mitsui Polychem Co Ltd | Preparation of saponified olefin vinyl ester copolymer or its grafted product |
-
1984
- 1984-10-16 JP JP21778484A patent/JPS6195007A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5521447A (en) * | 1978-08-01 | 1980-02-15 | Takeda Chem Ind Ltd | Separation and purification of saponified product from ethylene-vinyl acetate copolymer |
| JPS5589304A (en) * | 1978-12-27 | 1980-07-05 | Du Pont Mitsui Polychem Co Ltd | Preparation of saponified olefin vinyl ester copolymer or its grafted product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6195007A (en) | 1986-05-13 |
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