JP2013159777A - Resin for use in sealing material of solar cell - Google Patents
Resin for use in sealing material of solar cell Download PDFInfo
- Publication number
- JP2013159777A JP2013159777A JP2012025839A JP2012025839A JP2013159777A JP 2013159777 A JP2013159777 A JP 2013159777A JP 2012025839 A JP2012025839 A JP 2012025839A JP 2012025839 A JP2012025839 A JP 2012025839A JP 2013159777 A JP2013159777 A JP 2013159777A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- vinyl acetate
- ethylene
- acetate copolymer
- mfr
- 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.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 52
- 239000011347 resin Substances 0.000 title claims abstract description 52
- 239000003566 sealing material Substances 0.000 title abstract description 13
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 41
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 41
- 239000000155 melt Substances 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 15
- 239000008393 encapsulating agent Substances 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 description 23
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- -1 (t-butyl) Peroxy Chemical group 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical compound CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- BOCBOJPUWMTAJB-UHFFFAOYSA-N (2-butylphenyl) 2-hydroxybenzoate Chemical compound CCCCC1=CC=CC=C1OC(=O)C1=CC=CC=C1O BOCBOJPUWMTAJB-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- ZNCDSAZBKYUMAB-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)octane Chemical compound CCCCCCCC(OOC(C)(C)C)OOC(C)(C)C ZNCDSAZBKYUMAB-UHFFFAOYSA-N 0.000 description 1
- MPJPKEMZYOAIRN-UHFFFAOYSA-N 1,3,5-tris(2-methylprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CC(=C)CN1C(=O)N(CC(C)=C)C(=O)N(CC(C)=C)C1=O MPJPKEMZYOAIRN-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-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
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000011074 autoclave method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000004956 cell adhesive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 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
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- QRMPKOFEUHIBNM-UHFFFAOYSA-N p-dimethylcyclohexane Natural products CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 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
Abstract
Description
本発明は、太陽電池封止材に用いる太陽電池封止材用樹脂に関する。 The present invention relates to a resin for a solar cell sealing material used for a solar cell sealing material.
近年、世界的な温暖化現象により環境に対する意識が高まり、炭酸ガス等の温暖化ガスを発生しないエネルギーシステムとして太陽電池が急速に普及し始めている。太陽電池は、単結晶、多結晶のシリコン、アモルファスシリコン、化合物半導体等の太陽電池セルを表面保護材、封止材及び、裏側表面保護材等で積層し、真空ラミネ−ション法等を利用して製造されている。 In recent years, the global warming phenomenon has heightened awareness of the environment, and solar cells are rapidly spreading as energy systems that do not generate carbon dioxide and other warming gases. Solar cells are made by stacking solar cells such as single crystal, polycrystalline silicon, amorphous silicon, and compound semiconductors with surface protection materials, sealing materials, and backside surface protection materials, etc., and using a vacuum lamination method or the like. Manufactured.
太陽電池に用いられる封止材としては、透明性、柔軟性、電気絶縁性、耐久性等の性能が求められ、エチレン−酢酸ビニル共重合体を主体とするシートが多く使用されている（特許文献１〜３など）。 As sealing materials used for solar cells, performance such as transparency, flexibility, electrical insulation and durability is required, and a sheet mainly composed of ethylene-vinyl acetate copolymer is used (patents). Literature 1-3 etc.).
太陽電池は、太陽電池セル、表面保護材、封止材及び裏側表面保護材等を積層し、真空ラミネ−ション法等を利用して製造されている。この際の加熱において、封止材が収縮してしまうことにより、太陽電池セルの破損、ずれが発生することがある。このため、上記した発明では、太陽電池を製造する際、エチレン−酢酸ビニル共重合体を主体とするシートからなる封止材を加熱架橋させながら表面保護材等と接着させている。しかしながら、この加熱架橋においても封止材の収縮が発生することがあり、これにより太陽電池セルの破損、ずれが発生することがあった。 A solar cell is manufactured by stacking solar cells, a surface protective material, a sealing material, a back side surface protective material, and the like and using a vacuum lamination method or the like. In the heating at this time, the sealing material contracts, so that the solar cell may be damaged or displaced. For this reason, in the above-described invention, when a solar cell is manufactured, a sealing material made of a sheet mainly composed of an ethylene-vinyl acetate copolymer is bonded to a surface protective material or the like while being heat-crosslinked. However, shrinkage of the sealing material may occur even in this thermal crosslinking, which may cause damage or shift of the solar battery cell.
一般に、太陽電池封止材は、樹脂を主成分とする原料をＴダイフラットフィルム製膜法等でシート成形される。太陽電池封止材は架橋剤を含有するため、架橋反応や架橋剤の分解を抑制する必要から、成形温度を十分上げることができず、シートの加熱架橋時の収縮が大きくなってしまっていた。 In general, a solar cell encapsulant is formed from a raw material mainly composed of a resin by a T-die flat film forming method or the like. Since the solar cell encapsulant contains a cross-linking agent, it is necessary to suppress the cross-linking reaction and the decomposition of the cross-linking agent, so the molding temperature cannot be raised sufficiently, and the shrinkage at the time of heat cross-linking of the sheet has increased. .
太陽電池用封止材の加熱架橋時の収縮を小さくするためには、太陽電池用接着シートの生産速度を低下させることも考えられるが、生産性が低下するといった問題点が発生する。 In order to reduce the shrinkage at the time of heat crosslinking of the solar cell encapsulant, it is conceivable to reduce the production rate of the solar cell adhesive sheet, but this causes a problem that the productivity is lowered.
また、樹脂シートの温度が該樹脂の軟化点以下に低下する前にアニール処理する製造方法、架橋剤を含有する樹脂層と、架橋剤を含有しない樹脂層とを積層する多層の太陽電池封止材シート、樹脂シートを樹脂の融点よりも高い温度の冷却ロールの表面に載せ、搬送する製造方法等が開示されている。しかしながら、これらはアニール処理等に時間をかける必要があり、生産性が低下する恐れがあった。 Also, a manufacturing method in which an annealing treatment is performed before the temperature of the resin sheet falls below the softening point of the resin, a multilayer solar cell sealing in which a resin layer containing a crosslinking agent and a resin layer not containing the crosslinking agent are laminated The manufacturing method etc. which mount and convey a material sheet and a resin sheet on the surface of the cooling roll of temperature higher than melting | fusing point of resin are disclosed. However, these require time for annealing and the like, and there is a risk that productivity may be reduced.
本発明は、上記のような状況を鑑みてなされたものであって、加熱時の収縮が小さい太陽電池封止材用の樹脂を提供することを目的とする。 This invention is made | formed in view of the above situations, Comprising: It aims at providing the resin for solar cell sealing materials with the small shrinkage | contraction at the time of a heating.
本発明は、上記のような問題点を解決することができる太陽電池封止材用の樹脂を開発するために鋭意研究を重ねた結果、特定のエチレン−酢酸ビニル共重合体を用いることで、上記の問題点を解決することを見出し、この知見に基づいて本発明を完成するに至った。 As a result of intensive research to develop a resin for solar cell encapsulant that can solve the above problems, the present invention uses a specific ethylene-vinyl acetate copolymer, The present inventors have found that the above problems can be solved, and have completed the present invention based on this finding.
すなわち、本発明は、以下の通りのものである。
［１］ ＪＩＳ Ｋ７２１０：１９９９（コードＤ、温度：１９０℃、荷重：２．１６ｋｇ）にしたがって測定したメルトフローレイト（ＭＦＲ）が１５ｇ／１０分以上、５０ｇ／１０分以下であり、数平均分子量に対する重量平均分子量の比で表される分子量分布が２．０以上、３．０以下であり、分子量１０５以上の分子の占有率が全体の３．０重量％以下であり、かつ該メルトフローレイト（ＭＦＲ）と１００℃での溶融張力（ＭＴ）との関係が下記式（１）を満たす、太陽電池封止材用エチレン−酢酸ビニル共重合体樹脂。
８．５≧ ４×ｌｏｇ（ＭＦＲ）＋ＭＴ 式（１）
［２］ ［１］に記載の太陽電池封止材用エチレン−酢酸ビニル共重合体樹脂からなることを特徴とする太陽電池封止材。
That is, the present invention is as follows.
[1] The melt flow rate (MFR) measured in accordance with JIS K7210: 1999 (code D, temperature: 190 ° C., load: 2.16 kg) is 15 g / 10 min or more and 50 g / 10 min or less, and the number average molecular weight the weight average molecular weight of the molecular weight distribution represented by the ratio of 2.0 or more with respect to, and 3.0 or less, the occupancy of molecular weight 105 or more molecules is at total 3.0 wt% or less, and the melt flow An ethylene-vinyl acetate copolymer resin for encapsulating solar cells, wherein the relationship between the rate (MFR) and the melt tension (MT) at 100 ° C. satisfies the following formula (1).
8.5 ≧ 4 × log (MFR) + MT Formula (1)
[2] A solar cell encapsulant comprising the ethylene-vinyl acetate copolymer resin for a solar cell encapsulant according to [1].
本発明は、真空ラミネーション時における加熱時収縮が少ない、太陽電池封止材用のエチレン−酢酸ビニル共重合体樹脂を提供することができる。 INDUSTRIAL APPLICABILITY The present invention can provide an ethylene-vinyl acetate copolymer resin for a solar cell encapsulant that has little shrinkage during heating during vacuum lamination.
以下、本発明を詳細に説明する。
本発明の太陽電池封止材用エチレン−酢酸ビニル共重合体樹脂は、メルトフローレイト（ＪＩＳ Ｋ７２１０：１９９９ コードＤ、温度１９０℃、荷重２．１６ｋｇ；以下、ＭＦＲと略す）が１５ｇ／１０分以上、５０ｇ／１０分以下であり、好ましくは２０ｇ／１０分以上、４０ｇ／１０分以下である。ＭＦＲが１５ｇ／分より小さいと成形加工時に異方性が大きくなり、加熱収縮が大きくなり好ましくない。一方、ＭＦＲが５０ｇ／１０分を超えると、真空ラミネート時に樹脂のはみ出しが大きくなり好ましくない。
Hereinafter, the present invention will be described in detail.
The ethylene-vinyl acetate copolymer resin for solar cell encapsulant of the present invention has a melt flow rate (JIS K7210: 1999 code D, temperature 190 ° C., load 2.16 kg; hereinafter abbreviated as MFR) of 15 g / 10 min. As described above, it is 50 g / 10 min or less, preferably 20 g / 10 min or more and 40 g / 10 min or less. An MFR of less than 15 g / min is not preferable because anisotropy increases during molding and heat shrinkage increases. On the other hand, if the MFR exceeds 50 g / 10 minutes, the protrusion of the resin becomes large during vacuum lamination, which is not preferable.
また、ＧＰＣから求められる数平均分子量に対する重量平均分子量の比で表される分子量分布が２．０以上、３．０以下であることが必要である。分子量分布が２未満になると、成形加工時にメルトフラクチャーの発生や押出性の低下が発生しやすく好ましくない。一方、３を超えると高分子量成分が増え、成形加工時の異方性が大きくなり、加熱収縮が大きくなり好ましくない。 Further, it is necessary that the molecular weight distribution represented by the ratio of the weight average molecular weight to the number average molecular weight obtained from GPC is 2.0 or more and 3.0 or less. When the molecular weight distribution is less than 2, it is not preferable because melt fracture and extrusion deterioration are likely to occur during molding. On the other hand, if it exceeds 3, the high molecular weight component increases, the anisotropy during molding increases, and heat shrinkage increases, which is not preferable.
本発明の太陽電池封止材用エチレン−酢酸ビニル共重合体樹脂は、分子量１０５以上の分子の占有率が樹脂全体の３．０重量％以下である。３．０重量％を超えると、樹脂の長鎖分岐が多くなり、成形加工時の異方性が大きくなり、加熱時の収縮が大きくなり好ましくない。 Solar cell encapsulant for ethylene of the present invention - vinyl acetate copolymer resin, occupancy of molecular weight 105 or more molecules is less than 3.0% by weight of the total resin. If it exceeds 3.0% by weight, the long chain branching of the resin increases, the anisotropy during molding increases, and the shrinkage during heating increases, which is not preferable.
本発明の太陽電池封止材用エチレン−酢酸ビニル共重合体樹脂は、上記のメルトフローレイト（ＭＦＲ）と溶融張力（ＭＴ）の関係が下記式（１）を満足するものである。
８．５≧ ４×ｌｏｇ（ＭＦＲ）＋ＭＴ 式（１）
The relationship between the melt flow rate (MFR) and the melt tension (MT) of the ethylene-vinyl acetate copolymer resin for solar cell encapsulant of the present invention satisfies the following formula (1).
8.5 ≧ 4 × log (MFR) + MT Formula (1)
一般に、ＭＴは、ＭＦＲが高くなると低くなる傾向にあるが、ＭＦＲとＭＴが式（１）の関係を満足することにより、成形加工時における樹脂の異方性が小さくなり、加熱収縮を小さくすることが出来る。樹脂が式（１）を満足しない場合、即ち右辺の値が８．５を超えると加熱収縮が大きくなり好ましくない。また、式（１）の右辺の値は６．０以上であることが好ましい。 In general, MT tends to decrease as MFR increases, but when MFR and MT satisfy the relationship of formula (1), anisotropy of the resin during molding processing decreases and heat shrinkage decreases. I can do it. When the resin does not satisfy the formula (1), that is, when the value on the right side exceeds 8.5, the heat shrinkage becomes unfavorable. Moreover, it is preferable that the value of the right side of Formula (1) is 6.0 or more.
ここで、溶融張力（ＭＴ）は、例えばノズル径２．０９５ｍｍ、長さ８．０ｍｍのキャピラリーを備えた、東洋精機（株）製のキャピログラフ１Ｄを用いて測定することができる。この装置を用いて、６０ｍｍ／分でエチレン−酢酸ビニル共重合体樹脂を１００℃で押し出し、２ｍ／分で引き取る時の張力を測定して得ることができる。 Here, the melt tension (MT) can be measured using a Capillograph 1D manufactured by Toyo Seiki Co., Ltd. having a capillary with a nozzle diameter of 2.095 mm and a length of 8.0 mm, for example. Using this apparatus, the ethylene-vinyl acetate copolymer resin is extruded at 100 ° C. at 60 mm / min, and the tension at the time of taking out at 2 m / min can be measured.
本発明に用いられるエチレン−酢酸ビニル共重合体樹脂は、１００〜３５０ＭＰａの高圧下で、重合開始剤として空気及び、パーオキサイドなどの遊離基発生剤の存在下で重合して得られるエチレンと酢酸ビニルの共重合ポリマーである。エチレン−酢酸ビニル共重合体樹脂の分子構造及び、基本物性は、主に重合圧力、重合温度で調整することができる。例えば、メルトフローレイト（ＭＦＲ）は、重合圧力が低く重合温度が高い程大きくなる。また、溶融張力（ＭＴ）は、メルトフローレイト（ＭＦＲ）、樹脂の長鎖分岐成分量で調整することができるが、重合圧力を高くし、重合温度を低くすることで長鎖分岐成分は減少し、溶融張力を下げることができる。
本発明のエチレン−酢酸ビニル共重合体樹脂の製造方式はオートクレーブ方式、チューブラー方式が挙げられるが、チューブラー方式で製造されることが好ましく、チューブラー方式で製造する場合、平均重合反応温度を２４０℃以下、重合圧力を２５０ＭＰａ以上で製造することが好ましい。より好ましくは、平均重合反応温度が２３０℃以下、１８０℃以上、重合圧力が２６０ＭＰａ以上である。また、分子量分布を狭くするために、重合容器中の重合温度分布を均一に近づけることが好ましい。なお、チューブラー方式では、リアクターにエチレン、酢酸ビニル及び、重合開始剤をフィードする箇所が通常複数箇所あり、各フィード部分近傍では原料等投入により一旦温度が下がるが、その後反応熱により温度が上昇する。次のフィード部分では、また原料等投入により温度が下がるが、また反応熱が発生し温度が上昇する。リアクター内ではこのように場所によって温度が不均一になりうるが、本発明ではフィード後の各高温ピークの差を１５℃以下、またピーク温度とボトム温度の差を６０℃以下にすることが好ましい。さらに分子量分布を狭くするためには、重合開始剤として空気を用いないことが好ましい。また、酢酸ビニル含有量は特に２５〜４０重量％であることが好ましい。この重合反応条件で製造することにより、本発明の範囲を満たすエチレン−酢酸共重合体を得ることができる。本発明を満たす範囲であれば２種類以上のエチレン−酢酸ビニル共重合体樹脂を任意の比率でドライブレンド、又はメルトブレンドしたものを使用することができる。
The ethylene-vinyl acetate copolymer resin used in the present invention is obtained by polymerizing ethylene and acetic acid under a high pressure of 100 to 350 MPa in the presence of air and a free radical generator such as peroxide as a polymerization initiator. It is a copolymer of vinyl. The molecular structure and basic physical properties of the ethylene-vinyl acetate copolymer resin can be adjusted mainly by the polymerization pressure and the polymerization temperature. For example, the melt flow rate (MFR) becomes larger as the polymerization pressure is lower and the polymerization temperature is higher. The melt tension (MT) can be adjusted by the melt flow rate (MFR) and the amount of long-chain branching component of the resin, but the long-chain branching component decreases by increasing the polymerization pressure and lowering the polymerization temperature. Thus, the melt tension can be lowered.
The production method of the ethylene-vinyl acetate copolymer resin of the present invention includes an autoclave method and a tubular method, but it is preferably produced by a tubular method, and when produced by a tubular method, the average polymerization reaction temperature is set. It is preferable to produce at 240 ° C. or lower and a polymerization pressure of 250 MPa or higher. More preferably, the average polymerization reaction temperature is 230 ° C. or lower, 180 ° C. or higher, and the polymerization pressure is 260 MPa or higher. Further, in order to narrow the molecular weight distribution, it is preferable to make the polymerization temperature distribution in the polymerization vessel close to uniform. In the tubular system, there are usually multiple locations where ethylene, vinyl acetate, and a polymerization initiator are fed into the reactor, and the temperature once decreases due to charging of raw materials in the vicinity of each feed portion, but then the temperature increases due to reaction heat. To do. In the next feed portion, the temperature is lowered by the addition of raw materials and the like, but reaction heat is generated and the temperature rises. In the reactor, the temperature may be uneven depending on the location as described above, but in the present invention, the difference between the high temperature peaks after feeding is preferably 15 ° C. or less, and the difference between the peak temperature and the bottom temperature is preferably 60 ° C. or less. . In order to further narrow the molecular weight distribution, it is preferable not to use air as a polymerization initiator. The vinyl acetate content is particularly preferably 25 to 40% by weight. By producing under the polymerization reaction conditions, an ethylene-acetic acid copolymer that satisfies the scope of the present invention can be obtained. Within the range satisfying the present invention, two or more kinds of ethylene-vinyl acetate copolymer resins which are dry blended or melt blended at an arbitrary ratio can be used.
本発明の太陽電池封止材用エチレン−酢酸ビニル共重合体樹脂は、架橋剤による架橋速度、架橋度も高くすることができ、良好である。 The ethylene-vinyl acetate copolymer resin for solar cell encapsulant of the present invention is good because the crosslinking rate and the degree of crosslinking by the crosslinking agent can be increased.
太陽電池封止材としての成形加工法は、インフレーション成形法、Ｔダイフラット成形法、カレンダー成型法等で成形することができるが、熱収縮を抑える観点からＴダイフラット成形法が好ましい。また、太陽電池封止材としてブロッキング防止のためエンボス加工を施すことが好ましい。 The molding method as the solar cell encapsulant can be molded by an inflation molding method, a T-die flat molding method, a calendar molding method, or the like, but a T-die flat molding method is preferable from the viewpoint of suppressing thermal shrinkage. Moreover, it is preferable to emboss as a solar cell sealing material in order to prevent blocking.
本発明で用いるエチレン−酢酸ビニル共重合体樹脂を用いた太陽電池封止材には、架橋剤として有機過酸化物のほか、架橋助剤、接着促進剤、酸化防止剤、耐候安定剤、紫外線吸収剤等が添加される。これらの添加剤として特に限定はないが、上記有機過酸化物としては、２，５−ジメチルヘキサン；２，５−ジハイドロパーオキサイド；２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン；３−ジ−ｔ−ブチルパーオキサイド；ｔ−ジクミルパーオキサイド；２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン；ジクミルパーオキサイド；α，α’−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン；ｎ−ブチル−４，４−ビス（ｔ−ブチルパーオキシ）ブタン；２，２−ビス（ｔ−ブチルパーオキシ）ブタン；１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン；１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサン；ｔ−ブチルパーオキシベンゾエート；ベンゾイルパーオキサイド等が挙げられる。上記架橋助剤としては、トリアリルイソシアヌレート、トリメタリルイソシアヌレート等が挙げられる。上記接着促進剤としては、ビニルトリエトキシシラン、ビニルトリクロロシラン、ビニルトリス（β−メトキシ−エトキシ）シラン、γ−グリシドキシプロピル−トリピルトリ−メトキシシラン、β−（３，４エポキシシクロヘキシル）−エチルトリメトキシシラン、γ−グリシドキシプロピル−トリメトキシシラン、γ−アミノプロピルトリエトキシシラン等が挙げられる。酸化防止剤としては、２，６−ジ−ｔ−ブチル−４−メチルフェノール（ジブチルヒドロキシトルエン）、ｎ−オクタデシル−３−（４−ヒドロキ−３，５−ジ−ｔ−ブチルフェニル）プロピオネート、テトラキス（メチレン（３，５−ジ−ｔ−ブチル−４−ヒドロキシハイドロシンナメート））メタン、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレン−ジ−ホスフォナイト、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト、サイクリックネオペンタンテトライルビス（２，４−ｔ−ブチルフェニルフォスファイト）等が挙げられる。紫外線吸収剤としては、２−ヒドロキシ−４−オクトキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−５−スルフォベンゾフェノン、２−（２’−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾール、ｐ−ｔ−ブチルフェニルサリシレート等が挙げられる。それぞれ単独で使用しても良いし、２種類以上を併用しても構わない。
本発明のエチレン−酢酸ビニル共重合体樹脂は、太陽電池封止材用途に好適に用いられる。
The solar cell encapsulant using the ethylene-vinyl acetate copolymer resin used in the present invention includes an organic peroxide as a crosslinking agent, a crosslinking aid, an adhesion promoter, an antioxidant, a weathering stabilizer, an ultraviolet ray. An absorbent or the like is added. Although there is no limitation in particular as these additives, As said organic peroxide, 2,5-dimethylhexane; 2,5-dihydroperoxide; 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexane; 3-di-t-butyl peroxide; t-dicumyl peroxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne; dicumyl peroxide; α, α '-Bis (t-butylperoxyisopropyl) benzene; n-butyl-4,4-bis (t-butylperoxy) butane; 2,2-bis (t-butylperoxy) butane; 1,1-bis (T-butylperoxy) cyclohexane; 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane; t-butylperoxybenzoate; benzoylper Kisaido, and the like. Examples of the crosslinking aid include triallyl isocyanurate and trimethallyl isocyanurate. Examples of the adhesion promoter include vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxy-ethoxy) silane, γ-glycidoxypropyl-tripyltri-methoxysilane, β- (3,4 epoxy cyclohexyl) -ethyltri Examples include methoxysilane, γ-glycidoxypropyl-trimethoxysilane, and γ-aminopropyltriethoxysilane. Antioxidants include 2,6-di-t-butyl-4-methylphenol (dibutylhydroxytoluene), n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, Tetrakis (methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)) methane, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-di-phosphonite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2,4-t-butylphenyl phosphite) and the like. Examples of the ultraviolet absorber include 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2- (2′-hydroxy-5-methylphenyl) benzotriazole, pt- And butylphenyl salicylate. Each may be used alone or in combination of two or more.
The ethylene-vinyl acetate copolymer resin of the present invention is suitably used for solar cell encapsulant applications.
本発明について、以下実施例を用いて具体的に説明する。尚、本発明はこれら実施例に限定されるものではない。実施例および比較例における物性測定方法、評価方法は以下の通りである。
（１）メルトフローレイト（ＭＦＲ）測定
ＪＩＳ Ｋ７２１０：１９９９ コードＤ（温度＝１９０℃、荷重＝２．１６ｋｇ）に準拠し、測定した。
The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. The physical property measurement methods and evaluation methods in Examples and Comparative Examples are as follows.
(1) Melt flow rate (MFR) measurement It measured based on JISK7210: 1999 code | cord | chord (temperature = 190 degreeC, load = 2.16kg).
（２）酢酸ビニル含有量
ＪＩＳ Ｋ７１９２：１９９９に準拠し測定した。
（３）分子量及び、分子量分布測定
ＧＰＣから求められる重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）を分子量分布とした。ＧＰＣ測定は、ウォーターズ社製ＧＰＣＶ２０００を用い、カラムは昭和電工（株）製ＵＴ−８０７（１本）と東ソー（株）製ＧＭＨＨＲ−Ｈ（Ｓ）ＨＴ（２本）を直列に接続して使用し、移動相オルト−ジクロロベンゼン（ＯＤＣＢ）、カラム温度１４０℃、流量１．０ｍｌ／分、試料濃度２０ｍｇ／１５ｍｌ（ＯＤＣＢ）、試料溶解温度１４０℃、試料溶解時間２時間の条件で行った。分子量の校正は、Ｍｗが１０５０〜２０６万の範囲の東ソー（株）製標準ポリスチレンの１２点で行い、それぞれの標準ポリスチレンのＭｗに係数０．４３を乗じてポリエチレン換算分子量とし、溶出時間とポリエチレン換算分子量のプロットから一次校正直線を作成し、分子量を決定した。
(2) Vinyl acetate content Measured according to JIS K7192: 1999.
(3) Measurement of molecular weight and molecular weight distribution The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined from GPC was defined as the molecular weight distribution. For GPC measurement, GPCV2000 manufactured by Waters Co., Ltd. was used, and the column was used by connecting UT-807 (1) manufactured by Showa Denko KK and GMHHR-H (S) HT (2) manufactured by Tosoh Corporation in series. Then, mobile phase ortho-dichlorobenzene (ODCB), column temperature 140 ° C., flow rate 1.0 ml / min, sample concentration 20 mg / 15 ml (ODCB), sample dissolution temperature 140 ° C., sample dissolution time 2 hours were performed. Calibration of molecular weight is performed at 12 points of standard polystyrene manufactured by Tosoh Corp. with Mw in the range of 1,050 to 2,060,000, and Mw of each standard polystyrene is multiplied by a coefficient of 0.43 to obtain polyethylene equivalent molecular weight. Elution time and polyethylene A primary calibration line was created from the converted molecular weight plot, and the molecular weight was determined.
（４）溶融張力（ＭＴ）測定
２．０９５ｍｍ径、長さ８．０ｍｍのキャピラリーを備えた東洋精機（株）製；キャピログラフ１Ｄを用い、６０ｍｍ／分でエチレン−酢酸ビニル共重合体樹脂を１００℃で押し出し、２ｍ／分で引き取る時の張力を測定して得た。
（５）フィルムの作製
北進産業製ダイフラットフィルム製膜機（スクリュー径４０ｍｍ、ダイス３００ｍｍ幅）を用い、シリンダー温度１００℃、ダイス温度１００℃、引き取り速度８ｍ／分で、厚さ１５０ミクロンメートルのエチレン−酢酸ビニル共重合体フィルムを得た。
(4) Melt tension (MT) measurement Toyo Seiki Co., Ltd. equipped with a capillary having a diameter of 2.095 mm and a length of 8.0 mm; Capillograph 1D was used and 100 ethylene / vinyl acetate copolymer resin was used at 60 mm / min. It was obtained by measuring the tension at the time of extrusion at 2 ° C. and extruding at 2 m / min.
(5) Production of film Using a die flat film film forming machine (screw diameter 40 mm, die 300 mm width) manufactured by Hokushin Sangyo, with a cylinder temperature of 100 ° C., a die temperature of 100 ° C., a take-up speed of 8 m / min, and a thickness of 150 μm An ethylene-vinyl acetate copolymer film was obtained.
（６）加熱収縮率測定
上記Ｔダイ成形加工により得られたエチレン−酢酸ビニル共重合体フィルムから、幅１３ｍｍ、長さ１５０ｍｍの試験片を、フィルムの縦方向から５枚採り、それぞれの中央部に１００ｍｍの距離をおいて標点をつける。縦方向はフィルムの引取り方向に対して平行方向とした。このサンプルを１００℃に保持された熱風循環式恒温槽に垂直につるし、１分間加熱した後取り出し、室温に３０分間放置してから標点間距離を測定して、次の式によって算出し、その平均を求めた。
Ｓ（％）＝〔（Ｌ０−Ｌ）／Ｌ０〕×１００
Ｓ ：加熱収縮率（％）
Ｌ０：加熱前の標点間距離（ｍｍ）
Ｌ ：加熱後の標点間距離（ｍｍ）
熱収縮率を以下の基準によって評価した。
◎（優）：熱収縮率 ６０％未満
○（良）：熱収縮率 ６０％以上７０％未満
×（不可）：熱収縮率 ７０％以上
(6) Measurement of heat shrinkage rate From the ethylene-vinyl acetate copolymer film obtained by the T-die molding process, five test pieces having a width of 13 mm and a length of 150 mm were taken from the longitudinal direction of the film, and the respective central portions were taken. Place a mark at a distance of 100 mm. The longitudinal direction was parallel to the film take-up direction. This sample was suspended vertically in a hot air circulation thermostat kept at 100 ° C., heated for 1 minute, taken out, allowed to stand at room temperature for 30 minutes, then measured the distance between the gauge points, calculated by the following formula: The average was obtained.
S (%) = [(L0−L) / L0] × 100
S: Heat shrinkage rate (%)
L0: Distance between gauge points before heating (mm)
L: Distance between gauge points after heating (mm)
The thermal shrinkage rate was evaluated according to the following criteria.
◎ (excellent): heat shrinkage rate of less than 60% ○ (good): heat shrinkage rate of 60% or more and less than 70% × (impossible): heat shrinkage rate of 70% or more
［エチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−１）の調製］
チューブラーリアクターにて、エチレン中に酢酸ビニルを１４ｍｏｌ％、平均重合反応温度は２１０℃、重合圧力２６５ＭＰａ、重合開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエートを用いエチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−１）を重合した。得られたエチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−１）はＭＦＲが２０ｇ／分、酢酸ビニル含有量が２８重量％、数平均分子量に対する重量平均分子量の比で表される分子量分布が２．６、分子量１０５以上の占有率が全体の２．６％重量、溶融張力が２．４ｇ、４×ｌｏｇ（ＭＦＲ）＋ＭＴの値が７．８であった。
[Preparation of ethylene-vinyl acetate copolymer resin (EVA-1)]
In a tubular reactor, 14 mol% of vinyl acetate in ethylene, an average polymerization reaction temperature of 210 ° C., a polymerization pressure of 265 MPa, t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and ethylene-vinyl acetate Polymer resin (EVA-1) was polymerized. The obtained ethylene-vinyl acetate copolymer resin (EVA-1) has an MFR of 20 g / min, a vinyl acetate content of 28% by weight, and a molecular weight distribution represented by a ratio of the weight average molecular weight to the number average molecular weight. 6, 2.6% by weight of molecular weight 105 or more occupancy whole, melt tension 2.4 g, it was a value of 4 × log (MFR) + MT is 7.8.
［エチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−２）の調製］
チューブラーリアクターにて、エチレン中に酢酸ビニルを１４ｍｏｌ％、平均重合反応温度２００℃、重合圧力２６５ＭＰａ、重合開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエートを用いエチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−１）を重合した。得られたエチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−２）はＭＦＲが３０ｇ／分、酢酸ビニル含有量が２８重量％、数平均分子量に対する重量平均分子量の比で表される分子量分布が２．６、分子量１０５以上の占有率が全体の２．３％重量、溶融張力が１．８ｇ、４×ｌｏｇ（ＭＦＲ）＋ＭＴの値が７．７であった。
[Preparation of ethylene-vinyl acetate copolymer resin (EVA-2)]
In a tubular reactor, 14 mol% of vinyl acetate in ethylene, an average polymerization reaction temperature of 200 ° C., a polymerization pressure of 265 MPa, t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and ethylene-vinyl acetate copolymer The combined resin (EVA-1) was polymerized. The obtained ethylene-vinyl acetate copolymer resin (EVA-2) has an MFR of 30 g / min, a vinyl acetate content of 28% by weight, and a molecular weight distribution represented by a ratio of the weight average molecular weight to the number average molecular weight. 6, 2.3% by weight of molecular weight 105 or more occupancy whole, melt tension 1.8g, a value of 4 × log (MFR) + MT was 7.7.
［エチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−３）の調製］
チューブラーリアクターにて、エチレン中に酢酸ビニルを１４ｍｏｌ％、平均重合反応温度２１５℃、重合圧力２６５ＭＰａ、重合開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエートを用いエチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−１）を重合した。得られたエチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−３）はＭＦＲが４０ｇ／分、酢酸ビニル含有量が２８重量％、数平均分子量に対する重量平均分子量の比で表される分子量分布が２．５、分子量１０５以上の占有率が全体の１．９％重量、溶融張力が１．３ｇ、４×ｌｏｇ（ＭＦＲ）＋ＭＴの値が７．７であった。
[Preparation of ethylene-vinyl acetate copolymer resin (EVA-3)]
In a tubular reactor, 14 mol% of vinyl acetate in ethylene, average polymerization reaction temperature of 215 ° C., polymerization pressure of 265 MPa, ethylene-vinyl acetate copolymer using t-butylperoxy-2-ethylhexanoate as a polymerization initiator The combined resin (EVA-1) was polymerized. The obtained ethylene-vinyl acetate copolymer resin (EVA-3) has an MFR of 40 g / min, a vinyl acetate content of 28% by weight, and a molecular weight distribution represented by the ratio of the weight average molecular weight to the number average molecular weight is 2. The occupation ratio of molecular weight 10 5 or more was 1.9% by weight of the whole, the melt tension was 1.3 g, and the value of 4 × log (MFR) + MT was 7.7.
［エチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−４）の調製］
オートクレーブリアクターにて、エチレン中に酢酸ビニルを１４ｍｏｌ％、平均重合反応温度１９５℃、重合圧力２１０ＭＰａ、重合開始剤としてｔ−ブチルパーオキシピバレートを用いエチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−４）を重合した。得られたエチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−１）はＭＦＲが３０ｇ／分、酢酸ビニル含有量が２８重量％、数平均分子量に対する重量平均分子量の比で表される分子量分布が３．４、分子量１０５以上の占有率が全体の５．６％重量、溶融張力が３．４ｇ、４×ｌｏｇ（ＭＦＲ）＋ＭＴの値が９．３であった。
[Preparation of ethylene-vinyl acetate copolymer resin (EVA-4)]
In an autoclave reactor, 14 mol% of vinyl acetate in ethylene, an average polymerization reaction temperature of 195 ° C., a polymerization pressure of 210 MPa, t-butyl peroxypivalate as a polymerization initiator, ethylene-vinyl acetate copolymer resin (EVA-4 ) Was polymerized. The obtained ethylene-vinyl acetate copolymer resin (EVA-1) has an MFR of 30 g / min, a vinyl acetate content of 28% by weight, and a molecular weight distribution represented by the ratio of the weight average molecular weight to the number average molecular weight is 3. 4, 5.6% by weight of molecular weight 105 or more occupancy whole, melt tension 3.4 g, a value of 4 × log (MFR) + MT was 9.3.
［エチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−５）の調製］
オートクレーブリアクターにて、エチレン中に酢酸ビニルを１３ｍｏｌ％、平均重合反応温度１８０℃、重合圧力２１０ＭＰａ、重合開始剤としてｔ−ブチルパーオキシピバレートを用いエチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−５）を重合した。得られたエチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−１）はＭＦＲが１０ｇ／分、酢酸ビニル含有量が２６重量％、数平均分子量に対する重量平均分子量の比で表される分子量分布が３．１、分子量１０５以上の占有率が全体の７．４％重量、溶融張力が９．０ｇ、４×ｌｏｇ（ＭＦＲ）＋ＭＴの値が１２．８であった。
[Preparation of ethylene-vinyl acetate copolymer resin (EVA-5)]
In an autoclave reactor, 13 mol% of vinyl acetate in ethylene, an average polymerization reaction temperature of 180 ° C., a polymerization pressure of 210 MPa, t-butyl peroxypivalate as a polymerization initiator, ethylene-vinyl acetate copolymer resin (EVA-5) ) Was polymerized. The obtained ethylene-vinyl acetate copolymer resin (EVA-1) has an MFR of 10 g / min, a vinyl acetate content of 26% by weight, and a molecular weight distribution represented by the ratio of the weight average molecular weight to the number average molecular weight is 3. 1, 7.4% by weight of molecular weight 105 or more occupancy whole, melt tension 9.0 g, a value of 4 × log (MFR) + MT was 12.8.
［実施例１〜３］
エチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−１）、（ＥＶＡ−２）、（ＥＶＡ−３）を１００℃の樹脂温度でＴ−ダイキャスト成形し、物性評価をおこなった。なお式１が８．５以下のものは成立、８．５を超えるものは不成立として表示する。
得られたフィルムを用いた加熱収縮率の評価を表１に示す。加熱収縮率が少なく、優れていることがわかる。
[Examples 1 to 3]
Ethylene-vinyl acetate copolymer resins (EVA-1), (EVA-2), and (EVA-3) were T-die cast molded at a resin temperature of 100 ° C., and physical properties were evaluated. In addition, the thing of Formula 1 below 8.5 is displayed, and the thing exceeding 8.5 is displayed as unsatisfied.
Table 1 shows the evaluation of the heat shrinkage using the obtained film. It can be seen that the heat shrinkage rate is small and excellent.
［比較例１〜２］
エチレン−酢酸ビニル共重合体樹脂（ＥＶＡ−４）、（ＥＶＡ−５）を１００℃の樹脂温度でＴ−ダイキャスト成形し、物性評価をおこなった。なお式１が８．５以下のものは成立、８．５を超えるものは不成立として表示する。
得られたフィルムを用いた加熱収縮率の評価を表１に示す。加熱収縮率が大きくなっていることがわかる。
[Comparative Examples 1-2]
Ethylene-vinyl acetate copolymer resins (EVA-4) and (EVA-5) were T-die cast molded at a resin temperature of 100 ° C., and physical properties were evaluated. In addition, the thing of Formula 1 below 8.5 is displayed, and the thing exceeding 8.5 is displayed as unsatisfied.
Table 1 shows the evaluation of the heat shrinkage using the obtained film. It can be seen that the heat shrinkage rate is increased.
本発明のエチレン−酢酸ビニル共重合体樹脂は、加熱時の収縮が小さく太陽電池封止材用途に好適に用いられる。 The ethylene-vinyl acetate copolymer resin of the present invention has a small shrinkage during heating and is suitably used for solar cell encapsulating materials.
Claims (2)
８．５≧ ４×ｌｏｇ（ＭＦＲ）＋ＭＴ 式（１） Melt flow rate (MFR) measured according to JIS K7210: 1999 (code D, temperature: 190 ° C., load: 2.16 kg) is 15 g / 10 min or more and 50 g / 10 min or less, and the weight average with respect to the number average molecular weight the molecular weight distribution represented by the ratio of molecular weight of 2.0 or more and 3.0 or less, the molecular weight 10 5 or more molecules occupancy of not more than 3.0 wt% of the total, and the melt flow rate (MFR ) And a melt tension (MT) at 100 ° C. satisfying the following formula (1), an ethylene-vinyl acetate copolymer resin for a solar cell encapsulant.
8.5 ≧ 4 × log (MFR) + MT Formula (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012025839A JP2013159777A (en) | 2012-02-09 | 2012-02-09 | Resin for use in sealing material of solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012025839A JP2013159777A (en) | 2012-02-09 | 2012-02-09 | Resin for use in sealing material of solar cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2013159777A true JP2013159777A (en) | 2013-08-19 |
Family
ID=49172302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012025839A Pending JP2013159777A (en) | 2012-02-09 | 2012-02-09 | Resin for use in sealing material of solar cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2013159777A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016108537A (en) * | 2014-12-03 | 2016-06-20 | ハンファ トータル ペトロケミカル カンパニー リミテッド | Ethylene vinyl acetate copolymer resin for solar cell encapsulation sheet and manufacturing method therefor |
| JP2016125053A (en) * | 2014-12-29 | 2016-07-11 | ハンファ トータル ペトロケミカル カンパニー リミテッド | Ethylene vinyl acetate copolymer resin for solar cell encapsulant sheet, and production process therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009004437A (en) * | 2007-06-19 | 2009-01-08 | Mitsui Chemical Fabro Inc | Solar cell sealing sheet and method of manufacturing the same |
| JP2010100032A (en) * | 2008-09-25 | 2010-05-06 | Sekisui Chem Co Ltd | Method for manufacturing adhesive sheet for solar cell |
| WO2012140897A1 (en) * | 2011-04-14 | 2012-10-18 | 三井化学東セロ株式会社 | Resin sheet for sealing solar cell, solar cell module using same, and method for manufacturing solar cell module |
-
2012
- 2012-02-09 JP JP2012025839A patent/JP2013159777A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009004437A (en) * | 2007-06-19 | 2009-01-08 | Mitsui Chemical Fabro Inc | Solar cell sealing sheet and method of manufacturing the same |
| JP2010100032A (en) * | 2008-09-25 | 2010-05-06 | Sekisui Chem Co Ltd | Method for manufacturing adhesive sheet for solar cell |
| WO2012140897A1 (en) * | 2011-04-14 | 2012-10-18 | 三井化学東セロ株式会社 | Resin sheet for sealing solar cell, solar cell module using same, and method for manufacturing solar cell module |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016108537A (en) * | 2014-12-03 | 2016-06-20 | ハンファ トータル ペトロケミカル カンパニー リミテッド | Ethylene vinyl acetate copolymer resin for solar cell encapsulation sheet and manufacturing method therefor |
| JP2016125053A (en) * | 2014-12-29 | 2016-07-11 | ハンファ トータル ペトロケミカル カンパニー リミテッド | Ethylene vinyl acetate copolymer resin for solar cell encapsulant sheet, and production process therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPWO2011152314A1 (en) | Sealing material for solar cell module and manufacturing method thereof | |
| TWI534194B (en) | Sealing resin sheet of solar cell and solar cell modules using the same and manufacturing method thereof | |
| KR101187466B1 (en) | Method for manufacturing ethylene vinyl acetate copolymer for solar cell encapsulant and the resin obtained by the same | |
| US20180337297A1 (en) | Solar cell module | |
| JP2006303233A (en) | Adhesive sheet for solar cell | |
| JP2012214050A (en) | Method for producing solar cell sealing sheet, and solar cell module | |
| JP6011050B2 (en) | Solar cell encapsulant | |
| JP5655671B2 (en) | Manufacturing method of sealing material sheet | |
| KR101127671B1 (en) | Resin compositions for sealing material of solar cell | |
| JP2013159777A (en) | Resin for use in sealing material of solar cell | |
| JP2014240473A (en) | Resin sealing sheet and method of producing the same, and solar cell module | |
| JP2007299917A (en) | Adhesive sheet for solar cell | |
| JP6155680B2 (en) | Manufacturing method of solar cell module and solar cell module manufactured by the manufacturing method | |
| JP6173400B2 (en) | Ethylene vinyl acetate copolymer resin for solar cell encapsulant sheet and method for producing the same | |
| JP2010100032A (en) | Method for manufacturing adhesive sheet for solar cell | |
| JP6542782B2 (en) | Sealing material for solar cell and solar cell module | |
| KR101645100B1 (en) | Ethylene vinyl acetate copolymer for solar cell encapsulant and the method of manufacturing the copolymer | |
| JP6586175B2 (en) | Resin sheet, laminated glass and solar cell module | |
| WO2017038374A1 (en) | Electron beam-crosslinkable ethylene-based resin composition, electron beam cross-linked body, electron beam cross-linked body producing method, and laminated body | |
| JP2017078136A (en) | Ethylene-vinyl acetate copolymer resin, sheet molding prepared therewith, solar cell sealing material, solar cell module, and method for producing ethylene-vinyl acetate copolymer resin | |
| JP6794750B2 (en) | Encapsulant sheet for solar cell module, solar cell module using it, and manufacturing method of solar cell module | |
| JP2006303234A (en) | Adhesive sheet for solar cell | |
| JP6205783B2 (en) | Manufacturing method of solar cell module | |
| JP5762484B2 (en) | Resin sheet for sealing and solar cell using the same | |
| JP2013176899A (en) | Resin sealing sheet, and solar cell module |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150119 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150514 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150604 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20150826 |