CN102448707A - 层叠膜的制造方法 - Google Patents

层叠膜的制造方法 Download PDF

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Publication number
CN102448707A
CN102448707A CN2010800238490A CN201080023849A CN102448707A CN 102448707 A CN102448707 A CN 102448707A CN 2010800238490 A CN2010800238490 A CN 2010800238490A CN 201080023849 A CN201080023849 A CN 201080023849A CN 102448707 A CN102448707 A CN 102448707A
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Prior art keywords
film
resin molding
stacked film
manufacturing approach
mentioned
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CN102448707B (zh
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桥口慎二
山口辉宪
平野一孝
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Stella Chemifa Corp
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Stella Chemifa Corp
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/026—Chemical pre-treatments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

本发明提供一种层叠膜的制造方法，该层叠膜至少层叠有2片树脂膜，该方法提高贴合面的粘接性、可靠性优异。本发明的层叠膜的制造方法是至少层叠有2片树脂膜的层叠膜的制造方法，具有以下工序：氟化处理工序，通过使含有氟原子和氧原子的处理气体与上述2片树脂膜中的至少任一方的表面的至少一部分区域进行接触而提高上述区域的粘接性；及贴合工序，将上述2片树脂膜以使上述处理气体接触的面作为贴合面的方式进行贴合。

Description

层叠膜的制造方法
技术领域
本发明涉及层叠有经氟化处理的树脂膜的层叠膜的制造方法。
背景技术
作为太阳能电池用的背板材料，为了提高耐气候性及气体阻隔性能，使用聚氟乙烯(PVF)膜等的氟树脂膜，施加有铝箔层压、铝蒸镀、Si蒸镀的聚对苯二甲酸乙二醇酯(PET)膜等。通过设置该背板而保护经不起湿度的太阳能电池免于经受水蒸气。
上述背板材料中，从长期耐久性的观点出发氟树脂膜是优异的。因此，作为背板材料的需求提高。然而，由具有C-F键的氟树脂构成的材料通常因其表面能小而显示疏水疏油性，所以存在粘接性低这样的问题。
作为提高这样的氟树脂膜的粘接性的技术，例如可举出等离子体放电处理、电晕放电处理、火焰处理、喷射处理等。这些表面改性技术是通过向树脂表面导入亲水性的官能团(例如，-COOH基、-OH基、SO3H基、SO2FX基等)而改善其粘接性。
然而，如果是上述处理方法，则需要大规模的装置，制造成本增大。此外，还存在表面改性后的经时劣化显著，无法长期维持粘接性能这样的问题。
另一方面，下述专利文献1中记载有如下表面改性方法：作为合成或者天然高分子材料，选择比重为1.6以下且不含醚键、碳酸酯键、酰胺键、尿烷键中的任一种的材料，使由氟气和包含氧元素的1种气体所构成的混合气体与所述合成或者天然高分子材料接触，由此赋予亲水性。
然而，上述在先技术无法适用于比重为1.6～2.2左右的树脂。这是由于比重大于1.6的合成高分子或天然高分子材料因其晶体结构增大而使氟气不易扩散，因此难以显现表面改性功能。
专利文献
专利文献1：日本特开2002-194125号
发明内容
本发明是鉴于上述问题而进行的，其目的在于提供一种层叠膜的制造方法，该层叠膜至少贴合有2片树脂膜，该方法使贴合面的粘接性提高、可靠性优异。此外，本发明的目的还在于提供具备利用上述制造方法得到的层叠膜的太阳能电池用背板。
本申请的发明人等为了解决上述以往的问题，对层叠膜的制造方法及太阳能电池用背板进行研究。其结果发现可通过采用下述构成而达成上述目的，从而完成了本发明。
即，为了解决上述课题，本发明的树脂膜的制造方法是至少层叠有2片树脂膜的层叠膜的制造方法，该方法具有：氟化处理工序，通过使含有氟原子及氧原子的处理气体与所述2片树脂膜中的至少任一方的表面的至少一部分区域进行接触，从而提高上述区域的粘接性；及贴合工序，将上述2片树脂膜以使上述处理气体接触的面作为贴合面的方式进行贴合。
根据上述方法，通过在氟化处理工序中使含有氟原子及氧原子的处理气体对树脂膜进行接触而提高其表面的粘接性。进而，在贴合工序中以上述粘接性提高的面作为贴合面，与其他树脂膜进行贴合。这样，通过对贴合面进行氟化处理而可提高贴合面的粘接性，能够制造可靠性优异的层叠膜。此外，氟化处理与以往的等离子体处理、电晕处理、火焰处理、喷射处理等相比，即使经过长期(放置)后也能维持高粘接性，可抑制经时劣化。进而，由于在短时间内容易地实现树脂膜的表面改性，所以还实现制造成本的降低。
上述构成中，优选的是上述树脂膜的任一方为乙烯乙酸乙烯共聚物膜，上述贴合工序是不使用粘接剂地与另外的树脂膜进行贴合。
上述构成中，优选的是上述贴合工序是使用粘接剂进行的。
此外，上述构成中，优选的是构成上述层叠膜的上述树脂膜为选自氟树脂膜、聚甲基丙烯酸甲酯膜、聚对苯二甲酸乙二醇酯膜、聚萘二甲酸乙二醇酯膜、聚对苯二甲酸丁二醇酯膜、聚对苯二甲酸环己烷二甲醇酯膜、聚碳酸酯膜、乙烯乙酸乙烯共聚物膜、聚烯烃系膜、聚乙烯醇缩丁醛膜及聚酰亚胺膜中的至少一种。
进而，上述构成中，优选的是在上述树脂膜中包含具备对上述处理气体显示反应性的反应性基团的其他树脂成分。由此，进一步促进氟化处理，进而实现粘接性的提高。
此外，为了解决上述课题，本发明的太阳能电池用背板的特征在于，其为具备利用上述记载的层叠膜的制造方法得到的层叠膜的结构。
由于上述记载的树脂膜经氟化处理而粘接性提高，所以能使膜相互贴合而制成层叠膜。此外，能够将该层叠体用作太阳能电池用的背板。此外，由于经处理而赋予的粘接性能长期一直维持其性能，所以在工序管理方面也优异，实现制品可靠性的提高。
本发明通过上述说明的方法，获得如下所述的效果。
即，根据本发明，由于通过使含有氟原子及氧原子的处理气体对进行贴合的至少2片树脂膜中的任一方的贴合面进行接触而提高其表面的粘接性，因此能够在与其他树脂膜贴合时使粘接性提高。此外，氟化处理与以往的等离子体处理、电晕处理、火焰处理、喷射处理等相比，能抑制粘接性的经时劣化。由此，经过长期(放置)后也能维持高粘接性。其结果能够制造可靠性优异的层叠膜。此外，由于能够在短时间内容易地进行表面改性，所以使生产效率提高，并且还实现制造成本的降低。进而，利用本发明的制造方法得到的层叠膜，可以很好地应用于例如太阳能电池用的背板中。
附图说明
图1是表示在本发明实施方式的层叠膜制造方法中使用的反应装置的一例的模式图。
图2是示意地表示具备上述层叠膜的太阳能电池用背板的截面模式图。
具体实施方式
本发明实施方式的层叠膜的制造方法至少包括：氟化处理工序，对至少2片的树脂膜的至少任一方进行氟化处理；及贴合工序，将上述2片树脂膜以使上述处理气体接触的面作为贴合面的方式进行贴合。
上述氟化处理工序的目的在于，通过对树脂膜的表面进行氟化处理而实现粘接性的提高。虽然因进行氟化处理而粘接性提高的原因尚未明确，但推测因树脂膜表面被变粗糙而可增大所谓的投锚效果，此外还导入了有助于粘接的取代基(具体而言，-COOH基、-COF基等)，所以粘接性提高。氟化处理工序可以是对进行层叠的树脂膜的全部进行氟化处理，也可以是仅对任一方进行氟化处理。此时，使处理气体接触的区域优选为树脂膜贴合面的整个面。但是本发明并不受此限定，可以是仅使树脂膜表面的至少一部分区域进行表面改性的方式。这种情况下，树脂膜的部分表面改性可以通过对树脂膜表面的规定区域进行遮蔽而进行。作为用于遮蔽的遮蔽材料，除了需具有进行处理的温度以上的耐热性之外没有特别限定，例如可举出由聚四氟乙烯、聚四氟氯乙烯、聚氟乙烯、聚偏氟乙烯、聚二氯二氟乙烯、聚三氟氯乙烯等氟树脂，陶瓷、聚酰亚胺、聚醚醚酮(PEEK)等构成的遮蔽材料。
上述处理气体只要是含有氟原子及氧原子的混合气体，就没有特别限定。作为包含氟原子的气体没有受到特别限定，例如，可举出氟化氢(HF)、氟(F2)、三氟化氯(ClF3)、四氟化硫(SF4)、三氟化硼(BF3)、三氟化氮(NF3)等。这些气体可以单独使用，或者可以将两种以上并用。
上述氟化处理工序中，上述包含氟原子的气体的浓度例如为0.001～99vol％的范围。但是，包含氟原子的气体即使少量也能充分发挥其效果。因此从制造成本及安全性的观点出发，例如可设定为0.001～50vol％，更优选设定为0.001～10vol％。
另外，作为包含氧原子的气体没有受到特别限定，例如可举出氧气(O2)、二氧化硫气体(SO2)、碳酰氟(COF2)等。这些气体可以单独使用，或者可以将两种以上并用。
上述氟化处理工序中，上述包含氧原子的气体的浓度例如为0.001～99vol％的范围。但是，包含氧原子的气体即使少量也能充分发挥其效果。因此也从制造成本的观点出发，该气体也优选为低浓度，具体而言，例如为0.01～50vol％，更优选为0.1～20vol％。
此外，上述混合气体在低浓度能充分发挥其效果。因此从制造成本、安全性的观点出发，优选使干燥空气、氮、氩、氦、氖、氪、氙等非活性气体作为第3成分混合用于稀释。
氟化处理的处理时间没有受到特别限定，但树脂膜与处理气体的反应在反应初期爆发性地发生。因此，以比较短时间的处理就得到粘接性提高的效果。具体而言，例如为1秒～600分钟的范围内，优选为1秒～100分钟，更优选为1秒～30分钟。如果处理时间超过100分钟，则存在氟化过度进行而粘接性下降的情形。
氟化处理的处理温度没有受到特别限定，但是若考虑到树脂膜的耐热温度(添加有添加剂时为其耐热温度)，则优选为-50℃～150℃的范围内，更优选为0℃～100℃。
上述树脂膜可以是单层，也可以是层叠有至少2个膜的层叠结构。此外，树脂膜的厚度(层叠结构时为总厚度)没有受到特别限定，例如，优选为1～1000μm的范围内，更优选为5～750μm的范围内。此时，贴合的树脂膜的厚度可以相互不同。进而，树脂膜的平面形状没有受到特别限定，可根据需要适当设定。
上述树脂膜没有受到特别限定，可以举出氟树脂膜、聚甲基丙烯酸甲酯(PMMA)膜、聚对苯二甲酸乙二醇酯(PET)膜、聚萘二甲酸乙二醇酯(PEN)膜、聚对苯二甲酸丁二醇酯(PBT)膜、聚对苯二甲酸环己烷二甲醇酯(PCT)膜、聚碳酸酯(PC)膜、乙烯乙酸乙烯共聚物(EVA)膜、聚烯烃系膜、聚乙烯醇缩丁醛(PVB)膜、聚酰亚胺(PI)膜等。
具体而言，上述氟树脂膜例如可举出由聚偏氟乙烯(PVDF)、聚氟乙烯(PVF)、聚氯三氟乙烯(PCTFE)、乙烯-氯三氟乙烯共聚物(ETCFE)、乙烯-四氟乙烯共聚物(ETFE)等的一种或二种以上形成的膜。
使用乙烯乙酸乙烯共聚物膜作为树脂膜时，在该膜中通常添加有有机过氧化物。如果将该有机过氧化物进行热分解，则在乙烯乙酸乙烯共聚物膜的表面产生粘接性的功能。因此，在使用乙烯乙酸乙烯共聚物膜时，能在上述贴合工序中省略粘接剂的使用。所添加的有机过氧化物没有受到特别限定，例如可举出叔丁基过氧化碳酸2-乙基己酯、2，5-二甲基己烷-2，5-二氢过氧化物、2，5-二甲基-2，5-二(叔丁基过氧化)己烷-3、二叔丁基过氧化物、过氧化二异丙苯、2，5-二甲基-2，5-二(叔丁基过氧化)己烷、α，α’-双(叔丁基过氧化异丙基)苯、正丁基-4，4-双(叔丁基过氧化)丁烷、2，2-双(叔丁基过氧化)丁烷、1，1-双(叔丁基过氧化)环己烷、1，1-双(叔丁基过氧化)3，3，5-三甲基环己烷、叔丁基过氧化苯甲酸酯、过氧化苯甲酰等。
上述有机过氧化物的含有量没有受到特别限定，优选相对于乙烯乙酸乙烯共聚物膜的总重量为0.1～10重量％的范围内，更优选为0.1～5重量％的范围内。如果含有量小于0.1重量％，则存在即使进行氟化处理也不能得到充分的粘接性的情形。另一方面，如果含有量超过10重量％，则存在无法维持乙烯乙酸乙烯共聚物的特性的情形。
使用氟树脂膜作为树脂膜时，存在无法通过氟化处理而赋予充分的粘接性的情形。在该情形下，也可以使用经复合化的2层结构膜。例如，使表面侧的膜为PVDF∶PMMA＝70∶30、使背面侧的膜为PVDF∶PMMA＝30∶70。与氟树脂PVDF相比，PMMA的因氟化处理产生的效果大，在若是PVDF单质膜则粘接力不足的情形下，也可通过含有PMMA而制成具有充分粘接力的膜。
优选上述氟树脂膜中含有其他树脂成分。作为上述其他树脂成分，只要在其分子结构内具备对上述处理气体显示反应性的官能基团就没有受到特别限定。如果包含该其他树脂成分，则通过包含氟原子的气体与上述显示反应性的官能基团进行反应，从而实现氟化处理的促进。由此，进一步实现粘接性的提高。
作为对上述处理气体显示反应性的官能基团，例如可举出含氮基团、含硅基团、含氧基团、含磷基团、含硫基团、烃基、含卤素基团等。作为上述含氮基团，例如可举出酰胺基、氨基等。作为含硅基团，例如可以举出三烷基甲硅烷基、硅醚基、-Si(CH3)2O-基等。作为含氧基团，例如可举出酯基、碳酸酯基、醚基等。作为含磷基团，例如可举出磷酰胆碱基等。作为含硫基团，例如可举出磺基、磺酰基等。作为烃基，例如可举出甲基、亚甲基、苯基等。作为含卤素基团，例如可举出-CHX-基、-CHX2基、-CX3基、-CX2-基(X是选自F原子、Cl原子、Br原子及I原子中的至少任一种)等。
更详细而言，上述其他树脂成分例如为聚甲基丙烯酸甲酯(PMMA)、聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸环己烷二甲醇酯(PCT)、聚碳酸酯(PC)、聚烯烃等。这些树脂成分可以单独使用，或者可以将两种以上并用。此外，其他树脂成分优选为除作为氟树脂膜的构成材料而例示的高分子化合物以外的物质。
上述可添加的树脂的添加量没有受到特别限定，相对于氟树脂膜的总重量优选为0.1～90重量％的范围内，更优选为0.1～80重量％的范围内。如果添加量超过90重量％，则存在不能维持氟树脂自身的性能的情形。
氟化处理后的树脂膜可以用水、醇等清洗液进行清洗。由此，可去除吸附于树脂膜表面的未反应F2、因反应生成的HF，能够形成稳定性优异的粘接性表面。
上述贴合工序是将至少2片树脂膜以使氟化处理面作为贴合面的方式使两者贴合而制作层叠膜的工序。贴合可以使用粘接剂。但是，贴合的树脂膜的任一方为乙烯乙酸乙烯共聚物膜时，能够不用粘接剂地将两者进行贴合。
作为上述粘接剂，没有受到特别限定，例如可以使用聚氨酯系粘接剂、环氧系粘接剂、合成橡胶系粘接剂等。此外，也可以使用压敏性粘接剂(粘合剂)。作为上述压敏性粘接剂，没有受到特别限定，例如可以使用丙烯酸系粘合剂、橡胶系粘合剂、聚氨酯系粘合剂等。
使用聚氨酯系粘接剂、环氧系粘接剂、合成橡胶系粘接剂等作为粘接剂时，可以对贴合后的层叠体进行加热压接。这种情况下，作为加热温度，优选为20～200℃的范围内，更优选为25～150℃的范围内。此外，压力优选为0.1～500kPa的范围内，更优选为0.1～200kPa的范围内。进而，压接时间虽然因粘接剂的种类不同而异，但优选为1分钟～24小时的范围内。另外，可边利用压接辊等挤压方法挤压边进行压接。
贴合方法可以根据所用粘接剂的种类而适当变更。例如，在液态粘接剂的情况下，可举出在树脂膜的至少任一方涂布粘接剂后将两者进行贴合而使上述粘接剂干燥的方法。这种情况下，涂布量可根据干燥后的粘接剂层的厚度而适宜设定。另外，在膜状粘接剂的情况下，可举出使粘接剂贴合在层叠的树脂膜的至少任一方后使两者贴合的方法。
此外，在使用粘接剂的情形下，优选对贴合的树脂膜的全部贴合面实施氟化处理。由此，与将实施有氟化处理的树脂膜与未实施有氟化处理的树脂膜进行贴合而得的层叠膜相比，能够进一步提高两者的粘接性。
在贴合的树脂膜中的一方为乙烯乙酸乙烯共聚物膜而不使用粘接剂地进行贴合时，优选进行加热压接。这种情况下，作为加热温度，优选为50～200℃的范围内，更优选为100～150℃的范围内。此外，压力优选为0.1～500kPa的范围内，更优选为0.1～101.3kPa的范围内。进而，压接时间优选为10秒～24小时的范围内，更优选为10秒～60分钟的范围内。此外，可边利用压接辊等挤压手段挤压边进行压接。另外也可以使用真空层压装置进行。
本实施方式中，上述氟化处理工序例如可以使用图1所示的反应装置进行。即，准备进行树脂膜氟化处理的反应容器4，在该反应容器4内载置树脂膜5。作为反应容器4没有受到特别限定，例如可以使用不锈钢制、铝制或镍制等的反应容器。
接着，在对反应容器4内进行减压时，将真空管线7的阀门打开进行真空排气，达到规定的压力下(例如，10Pa)后，将真空管线7的阀门关闭。
接着，根据需要，将供给包含氟原子的气体的第1供给管线1、供给包含氧原子的气体的第2供给管线2、供给非活性气体的第3供给管线3的阀门适宜地根据需要打开，将被调整成规定浓度的处理气体导入反应容器4。
由此，使处理气体与树脂膜5接触，进行该膜5的氟化处理。对氟化处理后的树脂膜5的粘接性可通过适宜地根据需要设定处理气体的浓度、处理时间、处理温度、气体流量而进行控制。但是，在树脂膜5的表面面积大时，需要使用与该尺寸对应的处理条件及反应容器。反应可以边在常压下、加压下、减压下连续地供给处理气体边进行，或者也可以在大气压封入下、加压封入下、减压封入下进行。
对处理气体中的包含氟原子的气体的浓度可利用从上述第1供给管线1～第3供给管线3分别供给的气体量而进行调整。
流通于反应容器4内部的处理气体的气体流量没有受到特别限定，但气体流量快时存在反应爆发性地发生的情形。因此，在反应初期适当地设定包含氟原子的气体的浓度及流量是重要的。即，可根据反应的进行状况而使浓度、流量适宜地增大或减小。另外，气体流量也可以根据反应容器4的大小及树脂膜5的形状而适宜设定。
氟化处理结束后，只打开气体供给管线中第3供给管线3的阀门而导入非活性气体，以规定的流量将反应容器4内的处理气体置换为非活性气体。此时也预先打开排气管线6的阀门。其后，在关闭第3供给管线3及排气管线6的阀门的同时打开真空管线7的阀门，进行真空排气至反应容器4内成为规定压力(例如，10Pa)以下。
接着，关闭真空管线7的阀门，打开第3供给管线3的阀门，导入非活性气体至成为大气压。一旦反应容器4内显示大气压就打开排气管线6的阀门，取出经氟化处理的树脂膜5。
通过以上方法得到的树脂膜5具有高粘接性，可很好地应用于例如太阳能电池用背板等。用于太阳能电池用背板时，例如可以是如图2所示的方式。即，使上述树脂膜5介由粘接剂贴合在树脂膜8的两面。上述树脂膜5具备针对水蒸气、氧气等的气体阻隔性。此时，如上所述，树脂膜5因实施有氟化处理而具有优异的粘接性。其结果，能够制作出可靠性优异的太阳能电池用背板。
实施例
下面，对本发明的优选的实施例例示性地进行详细说明。但是只要对该实施例所记载的材料、配合量等没有特别限定性的记载，就不将本发明的范围仅限定于此。
(实施例1)
本实施例中，使用多层膜作为树脂膜5。上述多层膜是经复合化的2层结构膜，将表面侧的膜调整为PVDF∶PMMA＝70∶30，将背面侧的膜调整为PVDF∶PMMA＝30∶70。将该多层膜导入反应容器4，打开真空管线7的阀门，减压至反应容器4内成为10Pa以下。
接着，关闭真空管线7的阀门，同时打开供给氟气的第1供给管线1、供给氧气的第2供给管线2及供给氮气(非活性气体)的第3供给管线3的阀门，将调整成氟气/氮气/氧气＝0.5∶4.5∶95(体积比)、总流量为1.0L/min的处理气体(混合气体)导入反应容器4内至成为大气压。进而，同时关闭第1供给管线1、第2供给管线2及第3供给管线3的阀门，使反应容器内成为密闭状态，原样保持300秒。此外，将反应容器4内的温度保持在30℃。经过规定时间后，打开供给氮气的第3供给管线3及排气管线6的阀门，以20L/min的流量将反应容器4内的氟气/氮气/氧气的混合气体置换成氮气。其后，关闭第3供给管线3及排气管线6的阀门，打开真空管线7的阀门，减压至反应容器内成为10Pa以下。
接着，关闭真空管线7的阀门后打开第3供给管线3的阀门，将氮气以1.0L/min的流量导入反应容器4内至成为大气压。反应容器4内显示大气压后，打开排气管线6的阀门，取出处理后的多层膜。
将取出的多层膜用室温的UPW(超纯水)搅拌清洗1小时。清洗后，用氮气吹扫表面的UPW，其后在室温下减压干燥至成为10Pa以下。使干燥后的多层片材以使表面侧的膜(PVDF∶PMMA＝70∶30)作为贴合面的方式与未处理的乙烯乙酸乙烯共聚物膜(协荣化工公司制)进行加热压接而贴合。贴合是通过在温度为135℃、压力为2.5kPa的条件下压接30分钟而进行的。其后，从装置取出自然冷却。由此，制作了本实施例的层叠膜。
(实施例2～7)
在实施例2～7中，进行氟化处理时的条件如下表1所示进行，除此以外，与上述实施例1同样地制作实施例2～7的层叠膜。其中，在实施例6中由于处理气体使用仅由氟气和氧气形成的气体，所以在向反应容器4内导入处理气体时使第3供给管线3成为关闭的状态。
(比较例1)
在本比较例中，对在实施例1中使用的多层膜未进行氟化处理，除此以外，与上述实施例1同样地使多层膜和乙烯乙酸乙烯共聚物膜进行贴合，制作了本比较例的层叠膜。
[表1]
Figure BPA00001476500900111
(实施例8、9)
在实施例8和9中，使用PVDF膜作为树脂膜，进而进行氟化处理时的条件如下表2所示地进行，除此以外，与上述实施例1同样地制作了实施例8和9的层叠膜。
(比较例2)
在本比较例中，对实施例8中使用的PVDF膜未进行氟化处理，除此以外，与上述实施例1同样地使PVDF膜和乙烯乙酸乙烯共聚物膜进行贴合，制作了本比较例的层叠膜。
[表2]
Figure BPA00001476500900121
(实施例10、11)
在实施例10和11中，使用PVF膜(DuPont公司制，商品名：Tedlar，厚度：50μm)作为树脂膜，进而进行氟化处理时的条件如下表3所示地进行，除此以外，与上述实施例1同样地制作了实施例10和11的层叠膜。
(比较例3)
在本比较例中，对实施例10中使用的PVF膜未进行氟化处理，除此以外，与上述实施例1同样地使PVF膜和乙烯乙酸乙烯共聚物膜进行贴合，制作了本比较例的层叠膜。
[表3]
Figure BPA00001476500900122
(实施例12、13)
在实施例12和13中，使用PET膜(Toray公司制，商品名：LumirrorS-10、厚度：50μm)作为树脂膜，进而进行氟化处理时的条件如下表4所示地进行，除此以外，与上述实施例1同样地制作了实施例12和13的层叠膜。
(比较例4)
在本比较例中，对实施例12中使用的PET膜未进行氟化处理，除此以外，与上述实施例1同样地使PET膜和乙烯乙酸乙烯共聚物膜进行贴合，制作了本比较例的层叠膜。
[表4]
Figure BPA00001476500900131
(实施例14、15)
在实施例14和15中，使用ETFE膜(Daikin工业公司制，商品名：Neoflon，厚度：50μm)作为树脂膜，进而进行氟化处理时的条件如下表5所示地进行，除此以外，与上述实施例1同样地制作了实施例14和15的层叠膜。
(比较例5)
在本比较例中，对实施例14中使用的ETFE膜未进行氟化处理，除此以外，与上述实施例1同样地使ETFE膜和乙烯乙酸乙烯共聚物膜进行贴合，制作了本比较例的层叠膜。
[表5]
Figure BPA00001476500900132
(实施例16)
在实施例16中，作为树脂膜使用了PI膜(DuPont公司制，商品名：Kapton、厚度：45μm制)，进而进行氟化处理时的条件如下表6所示地进行，除此以外，与上述实施例1同样地制作了实施例16的层叠膜。
(比较例6)
在本比较例中，对实施例16中使用的PI膜未进行氟化处理，除此以外，与上述实施例1同样地使PI膜和乙烯乙酸乙烯共聚物膜进行贴合，制作了本比较例的层叠膜。
[表6]
Figure BPA00001476500900141
(实施例17)
在实施例17中，使用ETFE膜(Daikin工业公司制，商品名：Neoflon，厚度：50μm)作为树脂膜，进而在下表7所示的条件下进行氟化处理。
氟化处理后，将取出的ETFE膜用室温的UPW(超纯水)搅拌清洗1小时。清洗后，用氮气吹扫表面的UPW，其后在室温下减压干燥至成为10Pa以下。使用聚酯系粘接剂(ThreeBond公司制，商品名：Pando 156A)使经干燥的ETFE膜与PET膜(Toray公司制，商品名：Lumirror S-10、厚度：50μm)进行贴合。贴合是在温度25℃、大气压下的条件下放置24小时而进行的。由此，制作了本实施例的层叠膜。
(比较例7)
在本比较例中，对实施例17中使用的ETFE膜未进行氟化处理，除此以外，与上述实施例17同样地使ETFE膜和PET膜介由聚酯系粘接剂进行贴合，制作了本比较例的层叠膜。
[表7]
Figure BPA00001476500900151
(实施例18)
在实施例18中，使用PVF膜(DuPont公司制，商品名：Tedlar，厚度：50μm)作为树脂膜，进而进行氟化处理时的条件如下表8所示地进行，除此以外，与上述实施例17同样地制作了实施例18的层叠膜。
(比较例8)
在本比较例中，对实施例18中使用的PVF膜未进行氟化处理，除此以外，与上述实施例17同样地使PVF膜和PET膜介由聚酯系粘接剂进行贴合，制作了本比较例的层叠膜。
[表8]
Figure BPA00001476500900152
(实施例19)
在实施例19中，使用PI膜(DuPont公司制，商品名：Kapton，厚度：45μm)作为树脂膜，进而进行氟化处理时的条件如下表9所示地进行。进而，使用合成橡胶系粘接剂(ThreeBond公司制，商品名：ThreeBond 1521)作为粘接剂，除此以外，与上述实施例17同样地制作了实施例19的层叠膜。
(比较例9)
在本比较例中，对实施例19中使用的PI膜未进行氟化处理，除此以外，与上述实施例17同样地使PI膜和PET膜介由合成橡胶系粘接剂进行贴合，制作了本比较例的层叠膜。
[表9]
Figure BPA00001476500900161
(实施例20)
利用实施例11中经氟化处理的一对PVF膜，夹入实施例12中经氟化处理的PET膜，在各层间配置未处理的乙烯乙酸乙烯共聚物膜，利用加热压接而贴合。贴合是在温度为135℃、压力为2.5kPa的条件下压接30分钟而进行的。其后，从装置取出，自然冷却至室温。由此，制作了本实施例的PVF-EVA间剥离强度为20N/cm以上、PET-EVA间剥离强度为25N/cm以上的由5层形成的太阳能电池用背板。应予说明，上述剥离强度是以与如下所示的剥离试验相同的方法进行测定的。
(剥离试验)
剥离试验是通过对实施例1～16及比较例1～6的层叠膜测定从乙烯乙酸乙烯共聚物膜剥离树脂膜时的剥离粘合力(剥离强度)而进行的。另外，对实施例17～19及比较例7～9的层叠膜，是通过测定从PET膜剥离树脂膜时的剥离粘着力(剥离强度)而进行的。该剥离试验是按照JIS  K6854-1(90度剥离)进行的。条件设为：温度为25℃，相对湿度为20～50％Rh，夹持移动速度为50mm/分钟，试样(层叠膜)的宽为1cm。结果示于上述表1～9。
符号的说明
1    第1供给管线
2    第2供给管线
3    第3供给管线
4    反应容器
5    树脂膜
6    排气管线
7    真空管线
8    树脂膜

Claims (6)

1.一种层叠膜的制造方法，该层叠膜至少层叠有2片树脂膜，该制造方法具有以下工序：
氟化处理工序，通过使含有氟原子及氧原子的处理气体与所述2片树脂膜中的至少任一方的表面的至少一部分区域进行接触，从而使所述区域的粘接性提高；及
贴合工序，将所述2片树脂膜以使所述处理气体接触的面作为贴合面的方式进行贴合。
2.如权利要求1所述的层叠膜的制造方法，其中，所述树脂膜的任一方为乙烯乙酸乙烯共聚物膜，所述贴合工序是不使用粘接剂地与另外的树脂膜进行贴合。
3.如权利要求1所述的层叠膜的制造方法，其中，所述贴合工序是使用粘结剂进行的。
4.如权利要求1所述的层叠膜的制造方法，其中，构成所述层叠膜的所述树脂膜为选自氟树脂膜、聚甲基丙烯酸甲酯膜、聚对苯二甲酸乙二醇酯膜、聚萘二甲酸乙二醇酯膜、聚对苯二甲酸丁二醇酯膜、聚对苯二甲酸环己烷二甲醇酯膜、聚碳酸酯膜、乙烯乙酸乙烯共聚物膜、聚烯烃系膜、聚乙烯醇缩丁醛膜、及聚酰亚胺膜中的至少任1种。
5.如权利要求1～4中任一项所述的层叠膜的制造方法，其中，所述树脂膜中包含其他树脂成分，所述其他树脂成分具备对所述处理气体显示反应性的反应性基团。
6.一种太阳能电池用背板，具备利用权利要求1～5中任一项所述的层叠膜的制造方法而得的层叠膜。
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