CN102137894A - 乙烯醋酸乙烯酯共聚物组合物、乙烯醋酸乙烯酯共聚物膜及其制造方法 - Google Patents
乙烯醋酸乙烯酯共聚物组合物、乙烯醋酸乙烯酯共聚物膜及其制造方法 Download PDFInfo
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- CN102137894A CN102137894A CN2009801339246A CN200980133924A CN102137894A CN 102137894 A CN102137894 A CN 102137894A CN 2009801339246 A CN2009801339246 A CN 2009801339246A CN 200980133924 A CN200980133924 A CN 200980133924A CN 102137894 A CN102137894 A CN 102137894A
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- Prior art keywords
- vinyl acetate
- acetate copolymer
- ethylene vinyl
- film
- eva
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- 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.)
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims abstract description 132
- 239000005038 ethylene vinyl acetate Substances 0.000 title claims abstract description 126
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 29
- 238000007789 sealing Methods 0.000 claims description 20
- 239000005340 laminated glass Substances 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 125000005591 trimellitate group Chemical group 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000003490 calendering Methods 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 3
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- -1 trimellitic acid ester Chemical class 0.000 abstract description 37
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract 1
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- 239000000758 substrate Substances 0.000 description 11
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- 150000002148 esters Chemical class 0.000 description 6
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- 238000010792 warming Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 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
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-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
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- PMAAOHONJPSASX-UHFFFAOYSA-N 2-butylperoxypropan-2-ylbenzene Chemical group CCCCOOC(C)(C)C1=CC=CC=C1 PMAAOHONJPSASX-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/24—Calendering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
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Abstract
本发明的目的在于提供粘合性和制膜性二者均优异的乙烯醋酸乙烯酯共聚物膜。一种乙烯醋酸乙烯酯共聚物组合物,其特征在于,其含有乙烯醋酸乙烯酯共聚物、交联剂和偏苯三酸酯,且相对于100质量份前述乙烯醋酸乙烯酯共聚物,含有0.01~3.0质量份前述偏苯三酸酯。
Description
技术领域
本发明涉及乙烯醋酸乙烯酯共聚物膜,尤其涉及适合于太阳能电池用密封膜以及夹层玻璃(laminated glass)用中间膜的乙烯醋酸乙烯酯共聚物膜。
背景技术
乙烯醋酸乙烯酯共聚物(EVA)膜由于具有优异的透明性、粘合性,因此,除了夹层玻璃用中间膜和太阳能电池用密封膜以外,还广泛用作用于将光学滤波器设置在等离子体显示器(PDP)的前面滤波器上的粘合膜等。
例如,如图2所示,太阳能电池具有下述构成:通过表面侧密封膜23A和背面侧密封膜23B,将多个硅发电元件等发电元件24密封在由玻璃基板等构成的表面侧透明保护部件21与背面侧保护部件(背板)22之间。在该太阳能电池中,EVA膜用作表面侧密封膜23A和背面侧密封膜23B。
EVA膜可通过对含有乙烯醋酸乙烯酯共聚物和交联剂等的组合物进行成膜来制作。这样,通过使用交联剂使EVA交联,可以提高EVA膜的粘合性、耐久性。作为交联剂,优选使用在100℃以上产生自由基的有机过氧化物(专利文献1)。
通过将这种EVA组合物投入到混合辊(Mixing Roll)等中,进行熔融混炼,然后制膜为膜状,由此来获得EVA膜。作为制膜方法,具体而言,可以使用挤出成形法、压延成形法、注射成形法或加热压制法等。其中,由于压延成形法能够高速生产具有均一厚度的EVA膜,因此是特别有用的。压延成形法是将熔融混炼的EVA组合物投入到加热辊中进行压延而成形为膜状的方法。
然而,EVA组合物在制膜用装置上的贴附性高,例如贴附到加热辊等上,难以成形为膜状。另外,即使能够将EVA组合物成形为膜状,也存在所得EVA膜表面平滑性低的问题。
因此,使用将增塑剂、润滑剂添加到EVA组合物中来提高制膜性的方法。例如,专利文献1中公开了将邻苯二甲酸二辛酯等增塑剂添加到EVA组合物中的方法。
现有技术文献
专利文献
专利文献1:日本特开2005-29588号公报
发明内容
发明要解决的问题
EVA膜必需具有优异的粘合性。然而,在添加有增塑剂、润滑剂的EVA膜中,虽然制膜性提高,但有时粘合性降低,期望有进一步的改善。
因此,本发明的目的在于提供粘合性和制膜性二者均优异的乙烯醋酸乙烯酯共聚物膜。
用于解决问题的方案
本发明通过提供一种乙烯醋酸乙烯酯共聚物组合物来解决上述问题,该组合物的特征在于,含有乙烯醋酸乙烯酯共聚物、交联剂和偏苯三酸酯,且相对于100质量份前述乙烯醋酸乙烯酯共聚物,含有0.01~3.0质量份前述偏苯三酸酯。
发明的效果
本发明的乙烯醋酸乙烯酯共聚物组合物由于含有偏苯三酸酯,在制膜工序中,可以高度防止该组合物在加热辊等制膜用装置上的贴附,从而具有优异的制膜性。此外,即使为了使制膜工序中的贴附性降低而添加偏苯三酸酯,通过将偏苯三酸酯的含量控制在特定范围内,也可以提高使用该组合物形成的EVA膜对透明基材等被粘物的粘合性。因此,根据本发明,可以提供制膜性和粘合性二者均优异的乙烯醋酸乙烯酯共聚物膜。
附图说明
图1表示本发明的EVA膜的利用压延成形法的制造方法的一个例子。
图2为使用本发明的EVA膜的太阳能电池的说明图。
图3为使用本发明的EVA膜的夹层玻璃的剖面图。
图4为用于说明180°剥离试验法的示意图。
附图标记说明
11 混炼机
12 输送带
13 混炼辊
14 输送带
15 压延辊
15A、15B、15C、15D 压延辊
16 输出辊(take-off roll)
17 冷却辊
18 卷取机
19 EVA薄片
21 表面侧透明保护部件
22 背面侧保护部件
23A、23B EVA薄膜
24 发电元件
31A、31B 透明基板
32 夹层玻璃用中间膜
41 玻璃基板
42 PET薄膜
43 EVA膜
具体实施方式
本发明的乙烯醋酸乙烯酯共聚物组合物(以下也简称为“EVA组合物”)至少含有乙烯醋酸乙烯酯共聚物、交联剂和偏苯三酸酯作为基本成分。
相对于100质量份乙烯醋酸乙烯酯共聚物,EVA组合物中的偏苯三酸酯的含量为0.01~3.0质量份,优选为0.1~1.0质量份。偏苯三酸酯的含量低于0.01质量份时,组合物有可能贴附到加热辊等制膜装置上而无法获得充分的制膜性,而超过3.0质量份时,有可能不能充分提高所得EVA膜的粘合性。
作为偏苯三酸酯,优选使用偏苯三酸三烷基酯。偏苯三酸三烷基酯的各烷基的碳原子数优选为1~12,特别优选为3~10。
作为偏苯三酸三烷基酯,具体而言,可列举出偏苯三酸三甲酯、偏苯三酸三乙酯、偏苯三酸三正丙酯、偏苯三酸三异丙酯、偏苯三酸三正丁酯、偏苯三酸三正戊酯、偏苯三酸三正己酯、偏苯三酸三正庚酯、偏苯三酸三正辛酯、偏苯三酸三(2-乙基己基)酯等偏苯三酸酯类等。
其中,作为偏苯三酸酯,优选列举出偏苯三酸三正辛酯。
相对于100质量份前述乙烯醋酸乙烯酯共聚物,本发明的EVA组合物中使用的乙烯醋酸乙烯酯共聚物的醋酸乙烯酯含量优选为20~35质量份,更优选为20~30质量份,特别优选为24~28质量份。由此,可以提高EVA组合物的制膜性。
本发明的EVA组合物通过使EVA交联能够提高所得EVA膜的粘合性和耐久性,因此含有交联剂。
作为交联剂,优选使用有机过氧化物。前述有机过氧化物只要在100℃以上的温度下分解而产生自由基,则可以使用任何有机过氧化物。有机过氧化物一般考虑成膜温度、组合物的制备条件、固化温度、被粘物的耐热性、贮藏稳定性来选择。尤其,半衰期10小时的分解温度优选为70℃以上,特别优选为80~120℃。
作为前述有机过氧化物,从与乙烯醋酸乙烯酯共聚物的相容性的观点来看,例如可优选列举出叔丁基过氧基-2-乙基己基碳酸酯、2,5-二甲基正己烷-2,5-二氢过氧化物、2,5-二甲基-2,5-二(叔丁基过氧基)己烷-3-二叔丁基过氧化物、叔丁基枯基过氧化物、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、二枯基过氧化物、α,α’-双(叔丁基过氧基异丙基)苯、正丁基-4,4-双(叔丁基过氧基)戊酸酯、1,1-双(叔丁基过氧基)环己烷、1,1-双(叔丁基过氧基)-3,3,5-三甲基环己烷、过氧化苯甲酸叔丁酯、过氧化苯甲酰、过氧化乙酸叔丁酯、过氧化甲乙酮、2,5-二甲基己基-2,5-双过氧化苯甲酸酯、丁基氢过氧化物、对薄荷烷氢过氧化物、过氧化对-氯苯甲酰、羟基庚基过氧化物、过氧化氯己酮、过氧化辛酰、过氧化癸酰、过氧化月桂酰、过氧化辛酸枯基酯、过氧化琥珀酸、过氧化乙酰、过氧化间苯甲酰、过氧化异丁酸叔丁酯和过氧化2,4-二氯苯甲酰。它们可以单独使用一种,也可以将两种以上混合使用。
在前述有机过氧化物当中,从可以使EVA高度交联,提高EVA膜的粘合性的观点出发,特别优选使用叔丁基过氧基-2-乙基己基碳酸酯、2,5-二甲基-2,5-二(叔丁基过氧基)己烷。
相对于100质量份乙烯醋酸乙烯酯共聚物,EVA组合物中的交联剂的含量优选为1.0~5.0质量份,更优选为2.0~4.0质量份。由此,能够将EVA高度交联,可以获得粘合性优异的EVA膜。
为了改良或调整所得EVA膜的各种物性(机械强度、粘合性、透明性等光学特性、耐热性、耐光性、交联速度等),尤其为了改良机械强度,根据需要,本发明的EVA组合物可以进一步含有粘合促进剂、含丙烯酰氧基的化合物、含甲基丙烯酰氧基的化合物和/或含环氧基的化合物等各种添加剂。
作为前述粘合促进剂,特别优选使用硅烷偶联剂。由此,可以形成具有优异粘合力的EVA膜。作为前述硅烷偶联剂,可列举出γ-氯丙基甲氧基硅烷、乙烯基乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三乙酰氧基硅烷、γ-环氧丙氧基丙基三甲氧基硅烷、γ-环氧丙氧基丙基三乙氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷、乙烯基三氯硅烷、γ-巯基丙基三甲氧基硅烷、γ-氨基丙基三乙氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷。这些硅烷偶联剂可以单独使用,或者可以将两种以上组合使用。
相对于100质量份乙烯醋酸乙烯酯共聚物,前述硅烷偶联剂的含量优选为5质量份以下,特别优选为0.1~2.0质量份。
作为前述含丙烯酰氧基的化合物和前述含甲基丙烯酰氧基的化合物,通常有丙烯酸或甲基丙烯酸衍生物,例如可列举出丙烯酸或甲基丙烯酸的酯、酰胺。作为酯残基的例子,可列举出甲基、乙基、十二烷基、硬脂基(stearyl)、月桂基等直链状烷基,环己基、四氢糠基、氨基乙基、2-羟乙基、3-羟丙基、3-氯-2-羟丙基。作为酰胺的例子,可列举出双丙酮丙烯酰胺。另外,还可列举出乙二醇、三乙二醇、聚丙二醇、聚乙二醇、三羟甲基丙烷、季戊四醇等多元醇与丙烯酸或甲基丙烯酸的酯。
作为前述含环氧基的化合物,可列举出三缩水甘油基三(2-羟乙基)异氰脲酸酯、新戊二醇二缩水甘油醚、1,6-己二醇二缩水甘油醚、烯丙基缩水甘油醚、2-乙基己基缩水甘油醚、苯基缩水甘油醚、苯酚(亚乙基氧基)5缩水甘油醚、对-叔丁基苯基缩水甘油醚、己二酸二缩水甘油酯、邻苯二甲酸二缩水甘油酯、甲基丙烯酸缩水甘油酯、丁基缩水甘油醚。
相对于100质量份乙烯醋酸乙烯酯共聚物,前述含丙烯酰氧基的化合物、前述含甲基丙烯酰氧基的化合物或前述含环氧基的化合物通常分别含有0.5~5.0质量份,特别优选含有1.0~4.0质量份。
此外,本发明的EVA组合物可以含有紫外线吸收剂、光稳定剂和/或防老剂。
对前述紫外线吸收剂没有特别限制,可优选列举出2-羟基-4-甲氧基二苯甲酮、2-羟基-4-正十二烷氧基二苯甲酮、2,4-二羟基二苯甲酮、2,2’-二羟基-4-甲氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮等二苯甲酮系紫外线吸收剂。另外,相对于100质量份乙烯醋酸乙烯酯共聚物,上述二苯甲酮系紫外线吸收剂的配合量优选为0.01~5质量份。
作为前述光稳定剂,优选使用称为受阻胺系的光稳定剂,例如可列举出LA-52、LA-57、LA-62、LA-63、LA-63p、LA-67、LA-68(均为(株)ADEKA制造)、Tinuvin744、Tinuvin 770、Tinuvin765、Tinuvin144、Tinuvin 622LD、CHIMASSORB 944LD(均为Ciba Specialty Chemicals制造)、UV-3034(BF Goodrich公司制造)等。另外,上述光稳定剂可以单独使用,也可以将两种以上组合使用。其配合量相对于100质量份乙烯醋酸乙烯酯共聚物优选为0.01~5质量份。
作为前述防老剂,例如可列举出N,N’-己烷-1,6-二基双[3-(3,5-二叔丁基-4-羟苯基)丙酰胺]等受阻酚系抗氧化剂、磷系热稳定剂、内酯系热稳定剂、维生素E系热稳定剂、硫系热稳定剂等。
为了将上述EVA组合物制膜来获得EVA膜,使用在将EVA组合物熔融混炼之后成形为膜状的方法。
例如,可以使用以下方法:从料斗等原料供给部将EVA组合物投入到混合辊中,进行熔融混炼,接着,通过由挤出机挤出为膜状、或者通过压制加工,从而成形为膜状的方法。或者,还可使用将EVA组合物投入到具有多个辊的压延辊中,连续进行熔融混炼与薄片化,从而成形为膜状的方法。作为其它方法,从料斗等原料供给部将树脂组合物投入到混炼挤出机(例如双螺杆挤出机)中,进行熔融混炼,此后挤出为膜状,由此来获得。
其中,优选使用将EVA组合物熔融混炼之后通过压延成形法成形为膜状的方法。目前的EVA组合物特别容易贴附在加热的压延辊上,因此,通过在压延成形法中使用上述EVA组合物,尤其可以发挥本申请发明的效果。
图1中示出了通过压延成形法对本发明的EVA组合物进行制膜的方法的一个例子。将EVA组合物(原料)投入到混炼机11中,熔融混炼后,用输送带12运送混炼物10,供给混炼辊13。用混炼辊13形成膜状的混炼物通过输送带14运送,用压延辊15(第一辊15A、第二辊15B、第三辊15C、第四辊15D)压延,压延过的薄片用输出辊16输出。此后,用5个冷却辊17冷却,所得EVA薄片19用卷取机18卷取。此后,根据需要,可以将EVA薄片裁断为规定的大小。
EVA组合物熔融混炼时的温度优选为50~90℃,尤其优选为55~70℃。熔融混炼优选进行1分钟~30分钟,特别优选进行5分钟~15分钟。由此,能够以不在压延辊等制膜装置上粘附的程度使EVA组合物适度熔融。
使用压延成形法将EVA组合物的熔融混炼物成形为膜状时,压延辊的温度优选为50~90℃,特别优选为55~80℃。由此,可以显著防止EVA组合物的熔融混炼物在压延辊上的贴附。
压延辊的旋转速度优选为1~30m/分钟,特别优选为1~20m/分钟。
EVA膜的厚度可以根据用途来决定,可以在50μm~2mm的范围内。
通过对本发明的EVA组合物进行制膜所获得的EVA膜由于具有优异的制膜性,因此表面平滑性优异,且具有均一的厚度。此外,前述EVA膜对塑料基材、玻璃基材等透明基材显示了优异的粘合性。因此,前述EVA膜优选作为粘合膜使用。
作为EVA膜的用途,可列举出太阳能电池用密封膜、夹层玻璃用中间膜、光学滤波器用粘合膜等。目前的EVA膜对透明基材中的塑料薄膜的粘合性低,因此,通过将本发明的EVA膜作为塑料薄膜用粘合膜使用,尤其可以发挥其效果。因此,本发明的EVA膜特别优选用作大多使用塑料薄膜作为保护部件的太阳能电池用密封膜。
对使用本发明的EVA膜的太阳能电池的结构没有特别限制,可列举出如下结构等:在通过使太阳能电池用密封膜介于表面侧透明保护部件与背面侧保护部件之间并使之交联一体化来密封发电元件的太阳能电池中,使用EVA膜作为前述太阳能电池用密封膜。
在太阳能电池中,为了密封电池而使密封膜交联固化,本发明的EVA膜在交联固化之后显示了优异的粘合性。
在前述太阳能电池中,为了充分密封发电元件,如图2所示,将表面侧透明保护部件21、表面侧密封膜23A、硅发电元件等发电元件24、背面侧密封膜23B和背面侧保护部件22层叠,按照加热加压等常规方法,使密封膜交联固化即可。
为了获得高密封性,前述交联固化优选进行至密封膜的凝胶率为80质量%以上。为了使密封膜以这种凝胶率交联固化,例如,可以用真空层压机,在温度135~180℃,进一步140~180℃,尤其155~180℃、脱气时间0.1~5分钟、压制压力0.1~1.5kg/cm2、压制时间5~15分钟的条件下将前述层叠体加热压接。
在这种太阳能电池中,本发明的EVA膜可以在表面侧密封膜和背面侧密封膜的至少一方中使用。
另外,在本发明中,对于发电元件来说,受光面侧称为“表面侧”,发电元件的与受光面相反面侧称为“背面侧”。
本发明的太阳能电池中使用的表面侧透明保护部件通常可以是硅酸盐玻璃等玻璃基板。玻璃基板的厚度一般为0.1~10mm,优选为0.3~5mm。玻璃基板一般可以是化学或热强化的玻璃基板。
本发明中使用的背面侧保护部件是PET等塑料薄膜,考虑到耐热性、耐湿热性,可以是氟化聚乙烯薄膜,尤其是将氟化聚乙烯薄膜/Al/氟化聚乙烯薄膜依次层叠而成的薄膜。
接着,作为使用本发明的EVA膜的夹层玻璃的结构,如图3所示,可列举出如下结构等:在将中间膜32夹持在两片透明基板31A、31B之间,使之交联一体化而形成的夹层玻璃中,使用本发明的EVA膜作为前述中间膜32。
为了制作这种夹层玻璃,可以使用将本发明的EVA膜夹持在2片透明基板之间,获得未压接层叠体,然后,将该未压接层叠体脱气,进行加热压接的手段等。通过加热压接,将EVA膜交联固化,可以与透明基板粘合一体化。
加热压接例如通过在80~120℃的温度下预备压接,在100~150℃(尤其130℃附近)加热处理10分钟~1小时来进行。交联后的冷却一般在室温下进行,尤其冷却越快越优选。
另外,在本发明中,夹层玻璃中的“玻璃”是指透明基板总体,因此,“夹层玻璃”是指在透明基板中夹持中间膜而形成的材料。
对夹层玻璃中使用的透明基板没有特别限制,例如可以使用硅酸盐玻璃、无机玻璃板、无着色透明玻璃板等玻璃板,此外可以使用塑料薄膜。作为前述塑料薄膜,可列举出聚对苯二甲酸乙二醇酯(PET)薄膜、聚萘二甲酸乙二醇酯(PEN)薄膜、聚丁酸乙二醇酯(polyethylene butyrate)薄膜,PET薄膜是优选的。透明基板的厚度一般为0.05~20mm左右。
在夹层玻璃中,配置在中间膜的两侧的各个透明基板可以使用同一透明基板,也可以组合使用不同的透明基板。优选考虑透明基板的强度与夹层玻璃的用途来决定透明基板的组合。
本发明的夹层玻璃中的透明基板的一方为玻璃板,另一方为塑料薄膜时,还可以设计成在耐冲击性、耐贯通性、透明性等上具有适度性能。因此,可以用于例如各种车身、建筑物等装备的窗户玻璃等的玻璃,或陈列柜(showcase)、橱窗(show window)等的玻璃。
另外,在透明基板均为玻璃板的情况下,可以设计成显示特别优异的耐冲击性、提高的耐贯通性,可以在包括夹层玻璃在内的各种用途中使用。
在一方为塑料薄膜的夹层玻璃例如汽车的侧窗玻璃(sideglass)和嵌入玻璃的情况下,由于不需要挡风玻璃那样的厚度,因此塑料薄膜3的厚度一般是在0.02~2mm的范围内,优选为0.02~1.2mm的范围。中间膜和塑料薄膜的厚度可以根据使用该玻璃的场所等而变化。
本发明中使用的玻璃板通常是硅酸盐玻璃。玻璃板厚在薄膜强化玻璃的情况下根据其设置场所等而不同。例如,在用于汽车的侧窗玻璃和嵌入玻璃时,不需要象挡风玻璃那样厚,一般为0.1~10mm,优选为0.3~5mm。前述1片玻璃板1可以是化学或热强化的玻璃板。
在适合于汽车挡风玻璃等的双方均为玻璃板的夹层玻璃的情况下,玻璃板的厚度一般为0.5~10mm,优选为1~8mm。
本发明的夹层玻璃具有塑料薄膜作为透明基板时,塑料薄膜表面上优选进一步具有硬涂层。由此,可以赋予夹层玻璃以抗划伤性。
实施例
以下通过实施例来说明本发明。另外,本发明不受以下实施例限制。
(实施例1)
将按下述配方含有各材料的EVA组合物供给辊磨机,在60℃下熔融混炼10分钟,然后进行压延成形,制作EVA膜(厚度0.4mm)。在压延成形时,压延辊的温度设定为64℃,旋转速度设定为10m/分钟。
EVA组合物的配方:
乙烯-醋酸乙烯酯共聚物(相对于100质量份EVA的醋酸乙烯酯的含量28质量份)100质量份
交联剂(叔丁基过氧化基-2-乙基己基碳酸酯)3质量份
交联助剂(异氰脲酸三烯丙酯)2质量份,以及
硅烷偶联剂(γ-甲基丙烯酰氧基丙基三甲氧基硅烷)0.5质量份
润滑剂(偏苯三酸三正辛酯)0.01质量份。
(实施例2~5、比较例1和2)
除了按表1所示的含量使用润滑剂以外,与实施例1同样地制作EVA膜。
(比较例3和4)
除了按表1所示的配方使用聚氧亚乙基烷基醚磷酸酯作为润滑剂以外,与实施例1同样地制作EVA膜。
(评价)
按照下述步骤评价上述制作的各EVA膜。结果汇总在表1中。
1.辊贴附性
在EVA膜的制造工序中,通过压延辊将EVA组合物的熔融混炼物压延加工时,在压延辊上的EVA组合物的熔融混炼物上刻上10cm宽的刻痕,用推拉力计(Push-Pull Gauge,DIGITALFORCE GAUGE ZP-500N,IMADA Co.,Ltd.制造)测定从压延辊上剥落时的力。由此获得的值作为辊贴附性(N/10cm)评价。辊贴附性越小,制膜性越好。
2.粘合性的评价
根据180°剥离试验(JIS K6584,1994年)评价EVA膜与PET薄膜的粘合性。180°剥离试验具体而言根据下述步骤如图4所示那样进行。
在玻璃基板(厚度2.5mm)41上,依次将EVA膜43和PET薄膜(厚度0.05mm)42层叠,用真空层压机将所得层叠体真空脱气,在90℃的温度下预备压接之后,进一步放入烘箱内,在温度110℃的条件下加热处理30分钟。接着,在23℃、50%RH气氛下,将层叠体放置24小时之后,剥离EVA膜43与PET薄膜42之间的一部分,将PET薄膜42进行180°折叠,使用拉伸试验机(株式会社岛津制作所制造,Autograph)测定拉伸速度100mm/分钟时的剥离力作为PET粘合力(N/cm)。
表1
如表1所示,可以看出,实施例1~5的EVA膜具有低的辊贴附性,制膜性优异。此外可以看出,实施例1~5的EVA膜还具有优异的PET粘合性,适合作为透明基材等的粘合膜。
Claims (11)
1.一种乙烯醋酸乙烯酯共聚物组合物,其特征在于,其含有乙烯醋酸乙烯酯共聚物、交联剂和偏苯三酸酯,
且相对于100质量份所述乙烯醋酸乙烯酯共聚物,含有0.01~3.0质量份所述偏苯三酸酯。
2.根据权利要求1所述的乙烯醋酸乙烯酯共聚物组合物,其中,所述偏苯三酸酯是偏苯三酸三烷基酯。
3.根据权利要求2所述的乙烯醋酸乙烯酯共聚物组合物,其特征在于,所述偏苯三酸三烷基酯的烷基的碳原子数为1~12。
4.根据权利要求1~3的任一项所述的乙烯醋酸乙烯酯共聚物组合物,其特征在于,相对于100质量份所述乙烯醋酸乙烯酯共聚物,含有1.0~5.0质量份所述交联剂。
5.一种乙烯醋酸乙烯酯共聚物膜,其是对权利要求1~4的任一项所述的组合物进行制膜而成的。
6.一种乙烯醋酸乙烯酯共聚物膜的制造方法,其特征在于,对权利要求1~4的任一项所述的组合物进行熔融混炼,然后成形为膜状。
7.根据权利要求6所述的乙烯醋酸乙烯酯共聚物膜的制造方法,其特征在于,对权利要求1~4的任一项所述的组合物进行熔融混炼,然后通过压延成形法成形为膜状。
8.根据权利要求7所述的乙烯醋酸乙烯酯共聚物膜的制造方法,其特征在于,压延辊的温度为55~90℃。
9.一种乙烯醋酸乙烯酯共聚物膜,其是通过权利要求6~8的任一项所述的方法而获得的。
10.一种太阳能电池,该太阳能电池是使密封膜介于表面侧透明保护部件与背面侧保护部件之间,使之交联一体化而将发电元件密封来形成的,其特征在于,
所述密封膜是权利要求5或9所述的乙烯醋酸乙烯酯共聚物膜。
11.一种夹层玻璃,其是将中间膜夹持在两片透明基板之间,使之交联一体化而形成的,其特征在于,
所述中间膜是权利要求5或9所述的乙烯醋酸乙烯酯共聚物膜。
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EP (1) | EP2319884A4 (zh) |
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CN (1) | CN102137894A (zh) |
WO (1) | WO2010024176A1 (zh) |
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CN103087643A (zh) * | 2011-11-03 | 2013-05-08 | 天津彩达新材料科技有限公司 | 一种太阳能光伏组件封装用eva胶膜及其制备方法 |
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DE102009026021A1 (de) * | 2009-06-24 | 2010-12-30 | Saint-Gobain Sekurit Deutschland Gmbh & Co. Kg | Scheibe mit beheizbaren, optisch transparenten Sensorfeld |
US20120024376A1 (en) * | 2009-08-07 | 2012-02-02 | Toyochem Co., Ltd. | Method for producing resin composition for solar cell sealing material, resin composition for solar cell sealing material, solar cell sealing material, and solar cell module |
JP5606772B2 (ja) * | 2010-04-13 | 2014-10-15 | 株式会社Ihi | カレンダ装置 |
KR101213389B1 (ko) * | 2010-08-12 | 2012-12-18 | 삼성토탈 주식회사 | 태양전지 봉지재용 에틸렌비닐아세테이트 공중합체 시트의 제조방법 |
MY161007A (en) | 2010-10-08 | 2017-03-31 | Mitsui Chemicals Inc | Solar cell sealing material, and solar cell module |
CN103189996B (zh) | 2010-11-02 | 2016-04-13 | 三井化学株式会社 | 太阳能电池密封材料及太阳能电池模块 |
JP5871812B2 (ja) | 2010-11-17 | 2016-03-01 | 三井化学東セロ株式会社 | 太陽電池封止材およびそれを用いた太陽電池モジュール |
JP2014207251A (ja) * | 2011-08-12 | 2014-10-30 | フジプレアム株式会社 | 太陽電池モジュール |
US9595630B2 (en) | 2011-08-18 | 2017-03-14 | Mitsui Chemicals Tohcello, Inc. | Solar cell sealing material, method for manufacturing solar cell sealing material, and solar cell module |
DE102011113160A1 (de) * | 2011-09-14 | 2013-03-14 | Evonik Röhm Gmbh | Polymere Materialien für Außenanwendungen mit selbstheilenden Oberflächeneigenschaften nach Verkratzen oder Abrasionsbeschädigung |
CN102676068B (zh) * | 2011-10-24 | 2013-12-25 | 浙江大东南包装股份有限公司 | 一种基于在线交联的eva胶膜的生产工艺 |
JP5852234B2 (ja) | 2012-04-27 | 2016-02-03 | 三井化学東セロ株式会社 | 太陽電池封止材シートの製造方法 |
JP6001087B2 (ja) | 2012-11-21 | 2016-10-05 | 三井化学東セロ株式会社 | 太陽電池封止材および太陽電池モジュール |
JP6166377B2 (ja) | 2013-10-10 | 2017-07-19 | 三井化学東セロ株式会社 | 太陽電池封止用シートセットおよび太陽電池モジュール |
KR20170008811A (ko) | 2014-06-27 | 2017-01-24 | 미쓰이 가가쿠 토세로 가부시키가이샤 | 태양 전지 밀봉재용 수지 조성물, 태양 전지 밀봉재 및 태양 전지 모듈 |
EP3358629B1 (en) | 2015-09-29 | 2020-08-26 | Dow-Mitsui Polychemicals Co., Ltd. | Multilayer sheet for solar cell sealing material, method for manufacturing multilayer sheet for solar cell sealing material, and solar cell module |
TWI614222B (zh) * | 2015-11-12 | 2018-02-11 | Chen tai wei | 膠合玻璃中間膜之製法與膠合玻璃及其製法 |
US20190221692A1 (en) * | 2018-01-12 | 2019-07-18 | Jiaxiong Wang | Flexible Transparent-Semitransparent Hybrid Solar Window Membrane Module |
CN113249058A (zh) * | 2021-04-07 | 2021-08-13 | 深圳市高仁电子新材料有限公司 | 一种eva光学胶及其制备方法 |
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JPS508847A (zh) * | 1973-05-26 | 1975-01-29 | ||
EP0488886A1 (en) * | 1990-11-30 | 1992-06-03 | Taoka Chemical Co., Ltd | Composition of ethylene-vinyl acetate copolymers |
JP4768217B2 (ja) | 2003-07-07 | 2011-09-07 | 株式会社ブリヂストン | 透明フィルム |
US20050058795A1 (en) * | 2003-09-15 | 2005-03-17 | Beck Harold D. | Vinyl ester hose and method for manufacture of such hose |
US20050059763A1 (en) * | 2003-09-15 | 2005-03-17 | Beck Harold D. | Elastomer compositions for use in a hydrocarbon resistant hose |
US7169842B2 (en) * | 2003-09-15 | 2007-01-30 | Dayco Products, Llc | Elastomer compositions for use in a hydrocarbon resistant hose |
US20060270783A1 (en) * | 2003-09-15 | 2006-11-30 | Dayco Products, Llc | Elastomer compositions for use in a hydrocarbon resistant hose |
JP4912122B2 (ja) * | 2006-11-14 | 2012-04-11 | 三井・デュポンポリケミカル株式会社 | 架橋性エチレン共重合体組成物、該共重合体組成物からなる太陽電池素子封止用シートおよびこれを用いた太陽電池モジュール |
US7691225B2 (en) * | 2007-01-15 | 2010-04-06 | Nitto Denko Corporation | Thermal-release double-coated pressure-sensitive adhesive tape or sheet and method of processing adherend |
-
2008
- 2008-08-29 JP JP2008222082A patent/JP2010053298A/ja active Pending
-
2009
- 2009-08-20 CN CN2009801339246A patent/CN102137894A/zh active Pending
- 2009-08-20 US US13/060,499 patent/US20110168262A1/en not_active Abandoned
- 2009-08-20 EP EP09809828A patent/EP2319884A4/en not_active Withdrawn
- 2009-08-20 WO PCT/JP2009/064566 patent/WO2010024176A1/ja active Application Filing
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103087643A (zh) * | 2011-11-03 | 2013-05-08 | 天津彩达新材料科技有限公司 | 一种太阳能光伏组件封装用eva胶膜及其制备方法 |
CN103087643B (zh) * | 2011-11-03 | 2015-10-14 | 天津彩达新材料科技有限公司 | 一种太阳能光伏组件封装用eva胶膜及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2010053298A (ja) | 2010-03-11 |
US20110168262A1 (en) | 2011-07-14 |
EP2319884A1 (en) | 2011-05-11 |
WO2010024176A1 (ja) | 2010-03-04 |
EP2319884A4 (en) | 2012-05-30 |
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