JP4779074B2 - Sheet for solar cell encapsulant - Google Patents

Sheet for solar cell encapsulant Download PDF

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JP4779074B2
JP4779074B2 JP2004291666A JP2004291666A JP4779074B2 JP 4779074 B2 JP4779074 B2 JP 4779074B2 JP 2004291666 A JP2004291666 A JP 2004291666A JP 2004291666 A JP2004291666 A JP 2004291666A JP 4779074 B2 JP4779074 B2 JP 4779074B2
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solar cell
ethylene
parts
sheet
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JP2005126708A (en
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孝一 西嶋
康久 細合
理絵 佐藤
哲也 中村
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Mitsui Chemicals Tohcello Inc
Dow Mitsui Polychemicals Co Ltd
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Du Pont Mitsui Polychemicals Co Ltd
Mitsui Chemicals Tohcello Inc
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    • 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
    • B32B17/1055—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 resin layer, i.e. interlayer
    • B32B17/10743—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 resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • 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
    • B32B17/1055—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 resin layer, i.e. interlayer
    • B32B17/10697—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 resin layer, i.e. interlayer being cross-linked
    • 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
    • B32B17/1055—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 resin layer, i.e. interlayer
    • B32B17/10788—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 resin layer, i.e. interlayer containing ethylene vinylacetate

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  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Photovoltaic Devices (AREA)

Description

本発明は、太陽電池モジュールにおける太陽電池素子を固定するための太陽電池封止材用シート及び該太陽電池封止材用シートにより太陽電池素子を封止した太陽電池モジュールに関する。さらに詳しくは、透明性、柔軟性、加工性、耐候性、架橋性に優れ、しかも絶縁性に優れた太陽電池封止材用シート及び該シートを使用した太陽電池モジュールに関する。   The present invention relates to a solar cell encapsulant sheet for fixing a solar cell element in a solar cell module and a solar cell module in which the solar cell element is sealed with the solar cell encapsulant sheet. More specifically, the present invention relates to a sheet for a solar cell encapsulant that is excellent in transparency, flexibility, workability, weather resistance, crosslinkability, and excellent in insulation, and a solar cell module using the sheet.

近年の環境問題の高まりを背景に、クリーンなエネルギーとして水力発電、風力発電並びに太陽光発電が脚光を浴びている。このうち太陽光発電は、太陽電池モジュールの発電効率等の性能向上が著しい一方、価格の低下が進んだこと、国や自治体が住宅用太陽光発電システム導入促進事業を進めてきたことから、ここ数年その普及が著しく進んでいる。   Against the background of increasing environmental problems in recent years, hydroelectric power generation, wind power generation and solar power generation are attracting attention as clean energy. Among these, solar power generation is here because the power generation efficiency of solar cell modules has been significantly improved, but the price has declined, and the national and local governments have promoted the introduction of residential solar power generation systems. The spread has been remarkable for several years.

太陽光発電は、シリコンセル半導体（太陽電池素子）を用いて太陽光エネルギーを直接電気エネルギーに変換するが、ここで用いられている太陽電池素子は直接外気と接触するとその機能が低下するため、太陽電池素子を封止材ないし保護膜で挟み、緩衝とともに、異物の混入や水分等の侵入を防いでいる。この封止材には太陽電池の機能安定化を図るため、封止材の耐電圧性能に加え、絶縁性能を向上させ、半導体中の電流リークをできる限り防ぐ必要がある。すなわち封止材の体積抵抗率の増大が、太陽光発電システムの性能向上に重要である。   Photovoltaic power generation converts solar energy directly into electrical energy using a silicon cell semiconductor (solar cell element), but the solar cell element used here has a reduced function when in direct contact with the outside air, The solar cell element is sandwiched between a sealing material or a protective film to prevent foreign substances from entering or moisture from entering together with buffering. In order to stabilize the function of the solar cell, it is necessary for this encapsulant to improve the insulation performance in addition to the withstand voltage performance of the encapsulant and prevent current leakage in the semiconductor as much as possible. That is, an increase in the volume resistivity of the sealing material is important for improving the performance of the photovoltaic power generation system.

この太陽電池封止材用シートとしては、透明性、柔軟性、易成形性、耐久性の面から酢酸ビニル含有量が２５〜３３重量％のエチレン・酢酸ビニル共重合体の架橋物の使用が一般的である（例えば特許文献１参照）。ところがエチレン・酢酸ビニル共重合体は酢酸ビニル含有量が高いほど体積抵抗率が低く、また吸湿すると体積抵抗率がさらに低下するという問題がある。   As this solar cell encapsulant sheet, use of a cross-linked product of an ethylene / vinyl acetate copolymer having a vinyl acetate content of 25 to 33% by weight in terms of transparency, flexibility, easy moldability and durability. It is general (see, for example, Patent Document 1). However, the ethylene / vinyl acetate copolymer has a problem that the volume resistivity is lower as the vinyl acetate content is higher, and the volume resistivity is further reduced when moisture is absorbed.

これらの対策として、エチレン・酢酸ビニル共重合体の酢酸ビニル含有量を下げることが考えられるが、この場合透明性が低下し、太陽光受光量が減少し、太陽電池としての出力が低下すると共にシートの柔軟性が低下し、太陽電池素子を破損させる虞があった。   As measures against these, it is conceivable to reduce the vinyl acetate content of the ethylene-vinyl acetate copolymer. In this case, however, the transparency decreases, the amount of received sunlight decreases, and the output as a solar cell decreases. There was a possibility that the flexibility of the sheet was lowered and the solar cell element was damaged.

上述のように太陽光発電においては、各部分からのコストダウンと性能向上のための研究開発が繰り広げられているが、より一層の普及のためにはさらなるエネルギー変換効率の向上、材料費の削減及び薄膜化が図られている。その中で、エチレン・酢酸ビニル共重合体の体積抵抗率の低さが問題になりつつある。   As described above, in photovoltaic power generation, research and development for cost reduction and performance improvement from each part is being carried out, but for further diffusion, further improvement of energy conversion efficiency and reduction of material costs In addition, the film thickness is reduced. Among them, the low volume resistivity of the ethylene / vinyl acetate copolymer is becoming a problem.

特公昭６２−１４１１１号公報Japanese Examined Patent Publication No. 62-14111

そこで本発明の目的は、透明性、柔軟性、加工性、耐候性、架橋性に優れ、しかも絶縁性が大幅に改善された太陽電池封止材用シート及び該封止材用シートを用いた太陽電池モジュールを提供することにある。   Accordingly, an object of the present invention is to use a sheet for a solar cell encapsulant that is excellent in transparency, flexibility, workability, weather resistance, crosslinkability, and greatly improved in insulation, and the sheet for encapsulant. The object is to provide a solar cell module.

すなわち本発明は、酢酸ビニル含有量が１５〜４７重量％のエチレン・酢酸ビニル共重合体（Ａ）１０〜９０重量％と（メタ）アクリル酸エステル含有量が１０〜４０重量％のエチレン・（メタ）アクリル酸エステル共重合体（Ｂ）９０〜１０重量％（上記（Ａ）と（Ｂ）の合計を１００重量％とする）からなり、エチレン含有量が６０〜８５重量％である組成物に、（Ａ）と（Ｂ）の合計１００重量部に対し、架橋剤として分解温度（半減期が１時間である温度）が９０〜１８０℃の有機過酸化物を０．１〜５重量部あるいは該架橋剤０．１〜５重量部と架橋助剤５重量部以下を配合した架橋性エチレン共重合体組成物を用いることを特徴とする太陽電池封止材用シートに関する。 That is, the present invention relates to an ethylene / vinyl acetate copolymer (A) having a vinyl acetate content of 15 to 47% by weight and an ethylene / (meth) acrylate content of 10 to 40% by weight. A composition comprising 90 to 10% by weight of a (meth) acrylic acid ester copolymer (B) (the total of (A) and (B) is 100% by weight), and having an ethylene content of 60 to 85% by weight . In addition, 0.1 to 5 parts by weight of an organic peroxide having a decomposition temperature (temperature at which the half-life is 1 hour) as a crosslinking agent is 100 to 5 parts by weight based on a total of 100 parts by weight of (A) and (B). Or it is related with the sheet | seat for solar cell sealing materials characterized by using the crosslinkable ethylene copolymer composition which mix | blended 0.1-5 weight part of this crosslinking agent and 5 weight part or less of crosslinking adjuvant .

本発明はまた、酢酸ビニル含有量が１５〜４７重量％のエチレン・酢酸ビニル共重合体（Ａ）１０〜９０重量％と（メタ）アクリル酸エステル含有量が１０〜４０重量％のエチレン・（メタ）アクリル酸エステル共重合体（Ｂ）９０〜１０重量％（上記（Ａ）と（Ｂ）の合計を１００重量％とする）からなり、エチレン含有量が６０〜８５重量％である組成物に、（Ａ）と（Ｂ）の合計１００重量部に対し、架橋剤として分解温度（半減期が１時間である温度）が９０〜１８０℃の有機過酸化物を０．１〜５重量部あるいは該架橋剤０．１〜５重量部と架橋助剤５重量部以下を配合した架橋性エチレン共重合体組成物を架橋してなるゲル分率が７０％以上の架橋物からなる封止材層で太陽電池素子が封止されてなる太陽電池モジュールに関する。 The present invention also provides an ethylene / vinyl acetate copolymer (A) having a vinyl acetate content of 15 to 47% by weight and an ethylene / (ethylene) copolymer having a (meth) acrylate content of 10 to 40% by weight. A composition comprising 90 to 10% by weight of a (meth) acrylic acid ester copolymer (B) (the total of (A) and (B) is 100% by weight) and having an ethylene content of 60 to 85% by weight . In addition, 0.1 to 5 parts by weight of an organic peroxide having a decomposition temperature (temperature at which the half-life is 1 hour) as a crosslinking agent is 100 to 5 parts by weight based on a total of 100 parts by weight of (A) and (B). Alternatively, a sealing material comprising a crosslinked product having a gel fraction of 70% or more obtained by crosslinking a crosslinkable ethylene copolymer composition containing 0.1 to 5 parts by weight of the crosslinking agent and 5 parts by weight or less of a crosslinking aid. Solar cell module in which solar cell elements are sealed with layers .

本発明によれば、従来使用されていたエチレン・酢酸ビニル共重合体からなる太陽電池封止材用シートに比較して、透明性、加工性、柔軟性、耐候性、架橋特性などは実質的に変わるところがなく、絶縁性が改良された封止材用シートを提供することができ、これを用いた太陽電池モジュールにおいては性能が安定化される。   According to the present invention, transparency, workability, flexibility, weather resistance, cross-linking characteristics, etc. are substantially higher than those of a conventionally used sheet for encapsulating solar cells made of an ethylene / vinyl acetate copolymer. Thus, a sheet for a sealing material with improved insulation can be provided, and the performance of a solar cell module using this sheet is stabilized.

本発明の太陽電池封止材用シートは、酢酸ビニル含有量が１５〜４７重量％、好ましくは２０〜３５重量％のエチレン・酢酸ビニル共重合体（Ａ）が１０〜９０重量％、好ましくは２５〜８０重量％、さらに好ましくは３０〜７０重量％と、（メタ）アクリル酸エステル含有量が１０〜４０重量％、好ましくは１５〜３５重量％のエチレン・（メタ）アクリル酸エステル共重合体（Ｂ）が９０〜１０重量％、好ましくは７５〜２０重量％、さらに好ましくは７０〜３０重量％（エチレン・酢酸ビニル共重合体（Ａ）とエチレン・（メタ）アクリル酸エステル共重合体（Ｂ）の合計が１００重量％）とからなる組成物であって、該組成物中のエチレン含有量が６０〜８５重量％である架橋性エチレン共重合体組成物が使用される。ここで（メタ）アクリル酸エステルとは、アクリル酸エステル又はメタクリル酸エステルを意味し、通常はアクリル酸又はメタクリル酸の炭素数１〜１０のアルキルエステル、とくに炭素数２〜８のアルキルエステルが好ましい。具体的には、アクリル酸メチル、アクリル酸エチル、アクリル酸イソブチル、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、メタクリル酸メチル、メタクリル酸ｎ−ブチルなどを例示することができる。   The sheet for solar cell encapsulant of the present invention has a vinyl acetate content of 15 to 47% by weight, preferably 20 to 35% by weight of ethylene / vinyl acetate copolymer (A), preferably 10 to 90% by weight, preferably An ethylene / (meth) acrylate copolymer having a content of 25 to 80 wt%, more preferably 30 to 70 wt%, and a (meth) acrylate content of 10 to 40 wt%, preferably 15 to 35 wt% (B) is 90 to 10% by weight, preferably 75 to 20% by weight, more preferably 70 to 30% by weight (ethylene / vinyl acetate copolymer (A) and ethylene / (meth) acrylic acid ester copolymer ( A crosslinkable ethylene copolymer composition in which the total content of B) is 100% by weight) and the ethylene content in the composition is 60 to 85% by weight is used. Here, the (meth) acrylic acid ester means an acrylic acid ester or a methacrylic acid ester, and usually an alkyl ester having 1 to 10 carbon atoms, particularly an alkyl ester having 2 to 8 carbon atoms, is preferred. . Specific examples include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and n-butyl methacrylate.

上記エチレン・酢酸ビニル共重合体（Ａ）において、酢酸ビニル含有量が前記範囲を下回るものを使用すると、太陽電池封止材用シートの透明性、柔軟性が低下するので好ましくない。また酢酸ビニル含有量が前記範囲を上回るものを使用すると、太陽電池封止材用シートのべた付きが顕著となり、著しく加工性を損なうので好ましくない。また上記エチレン・（メタ）アクリル酸エステル共重合体（Ｂ）において、（メタ）アクリル酸エステルの含有量が前記範囲を下回るものを使用すると、太陽電池封止材用シートの透明性、架橋特性が低下するので好ましくない。また（メタ）アクリル酸エステルの含有量が前記範囲を上回るものを使用すると、太陽電池封止材用シートのべた付きが顕著となるので好ましくない。   In the said ethylene-vinyl acetate copolymer (A), when the vinyl acetate content is less than the above range, the transparency and flexibility of the solar cell encapsulant sheet are lowered, which is not preferable. Moreover, when a vinyl acetate content exceeding the said range is used, since the stickiness of the sheet | seat for solar cell sealing materials will become remarkable and workability will be impaired remarkably, it is unpreferable. In the ethylene / (meth) acrylic acid ester copolymer (B), if the content of the (meth) acrylic acid ester is lower than the above range, the transparency and cross-linking characteristics of the solar cell encapsulant sheet Is unfavorable because it decreases. Moreover, when the (meth) acrylic acid ester content exceeds the above range, the stickiness of the solar cell encapsulant sheet becomes remarkable, such being undesirable.

またエチレン・酢酸ビニル共重合体（Ａ）とエチレン・（メタ）アクリル酸エステル共重合体（Ｂ）の配合比率において、エチレン・酢酸ビニル共重合体（Ａ）の配合比率が前記範囲を下回ると架橋特性が低下し、好ましくない。またその配合比率が前記範囲を上回ると、絶縁性が低下するので好ましくない。   Moreover, in the blending ratio of the ethylene / vinyl acetate copolymer (A) and the ethylene / (meth) acrylic acid ester copolymer (B), the blending ratio of the ethylene / vinyl acetate copolymer (A) is below the above range. This is not preferable because the cross-linking properties are lowered. Moreover, since the insulation will fall when the mixture ratio exceeds the said range, it is unpreferable.

さらにエチレン・酢酸ビニル共重合体（Ａ）とエチレン・（メタ）アクリル酸エステル共重合体（Ｂ）からなる架橋性エチレン共重合体組成物において、組成物中におけるエチレン含有量は６０〜８５重量％の範囲にある。すなわちエチレン含有量が前記範囲を下回ると太陽電池封止材用シートのべた付きが顕著となるので好ましくなく、一方エチレン含有量が前記範囲を上回ると封止材用シートの透明性が低下するので好ましくない。上記架橋性エチレン共重合体組成物中の樹脂成分（（Ａ）及び（Ｂ）からなるエチレン共重合体成分）として、１９０℃、２１６０ｇ荷重（ＪＩＳ Ｋ７２１０−１９９９）におけるメルトフローレートは、加工性の点から０．５〜１５０ｇ／１０分の範囲にあることが好ましく、またその構成成分であるエチレン・酢酸ビニル共重合体及びエチレン・（メタ）アクリル酸エステル共重合体のメルトフローレート（ＪＩＳ Ｋ７２１０−１９９９、１９０℃、２１６０ｇ荷重）もそれぞれ０．５〜１５０ｇ／１０分の範囲にあることが好ましい。   Furthermore, in the crosslinkable ethylene copolymer composition comprising the ethylene / vinyl acetate copolymer (A) and the ethylene / (meth) acrylic acid ester copolymer (B), the ethylene content in the composition is 60 to 85% by weight. % Range. That is, when the ethylene content is less than the above range, the stickiness of the solar cell encapsulant sheet becomes remarkable, which is not preferable. On the other hand, when the ethylene content exceeds the above range, the transparency of the encapsulant sheet decreases. It is not preferable. As the resin component (the ethylene copolymer component comprising (A) and (B)) in the crosslinkable ethylene copolymer composition, the melt flow rate at 190 ° C. and 2160 g load (JIS K7210-1999) is a workability. From the point of view, it is preferably in the range of 0.5 to 150 g / 10 minutes, and the melt flow rate (JIS) of ethylene / vinyl acetate copolymer and ethylene / (meth) acrylic acid ester copolymer, which are its constituent components (K7210-1999, 190 ° C., 2160 g load) is also preferably in the range of 0.5 to 150 g / 10 min.

本発明の上記架橋性エチレン共重合体組成物からなる太陽電池封止材用シートは、太陽電池モジュールに組み込まれた状態においては、該架橋性エチレン共重合体組成物が架橋されていることが好ましい。これにより透明性を維持しつつ、高温での使用時における溶融流れ防止等の耐熱性を付与することができる。そのためには太陽電池封止材用シートとして、上記架橋性エチレン共重合体組成物に架橋剤あるいは架橋剤と架橋助剤が配合されていることが好ましい。   When the sheet for solar cell encapsulant comprising the above crosslinkable ethylene copolymer composition of the present invention is incorporated in a solar cell module, the crosslinkable ethylene copolymer composition may be crosslinked. preferable. Thereby, heat resistance, such as prevention of a melt flow at the time of use at high temperature, can be provided, maintaining transparency. For that purpose, it is preferable that a crosslinking agent or a crosslinking agent and a crosslinking assistant are blended in the crosslinkable ethylene copolymer composition as a sheet for a solar cell encapsulant.

架橋剤としては、分解温度（半減期が１時間である温度）が９０〜１８０℃、とくに１００〜１５０℃の有機過酸化物を用いるのが好ましい。このような有機過酸化物として例えば第３ブチルパーオキシイソプロピルカーボネート、第３ブチルパーオキシアセテート、第３ブチルパーオキシベンゾエート、ジクミルパーオキサイド、２，５−ジメチル−２，５−ビス（第３ブチルパーオキシ）ヘキサン、ジ第３ブチルパーオキサイド、２，５−ジメチル−２，５−ビス（第３ブチルパーオキシ）ヘキシン−３、１，１−ビス（第３ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（第３ブチルパーオキシ）シクロヘキサン、メチルエチルケトンパーオキサイド、２，５−ジメチルヘキシル−２，５−ビスパーオキシベンゾエート、第３ブチルハイドロパーオキサイド、ｐ−メンタンハイドロパーオキサイド、ベンゾイルパーオキサイド、ｐ−クロルベンゾイルパーオキサイド、第３ブチルパーオキシイソブチレート、ヒドロキシヘプチルパーオキサイド、ジクロヘキサノンパーオキサイドなどが挙げられる。   As the crosslinking agent, it is preferable to use an organic peroxide having a decomposition temperature (temperature at which the half-life is 1 hour) of 90 to 180 ° C., particularly 100 to 150 ° C. Examples of such organic peroxides include tertiary butyl peroxyisopropyl carbonate, tertiary butyl peroxyacetate, tertiary butyl peroxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-bis (third Butylperoxy) hexane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, tert-butyl hydroperoxide, p- Menthane hydroperoxide, benzoyl peroxide, p-chlorobenzo Peroxide, tert-butylperoxy isobutyrate, hydroxyheptyl peroxide, and di cyclohexanone peroxide.

架橋剤はエチレン・酢酸ビニル共重合体及びエチレン・（メタ）アクリル酸エステル共重合体の合計１００重量部に対し、０．１〜５重量部、とくに０．５〜３重量部の割合で配合するのが効果的である。   The crosslinking agent is blended in an amount of 0.1 to 5 parts by weight, particularly 0.5 to 3 parts by weight, based on a total of 100 parts by weight of the ethylene / vinyl acetate copolymer and the ethylene / (meth) acrylic acid ester copolymer. It is effective to do.

また架橋助剤の具体例としては、ポリアリル化合物やポリ（メタ）アクリロキシ化合物のような多不飽和化合物を例示することができる。より具体的には、トリアリルイソシアヌレート、トリアリルシアヌレート、ジアリルフタレート、ジアリルフマレート、ジアリルマレエートのようなポリアリル化合物、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレートのようなポリ（メタ）アクリロキシ化合物、ジビニルベンゼンなどを挙げることができる。架橋助剤はエチレン・酢酸ビニル共重合体及びエチレン・（メタ）アクリル酸エステル共重合体の合計１００重量部に対し、５重量部以下、とくに０．１〜３重量部の割合で配合するのが効果的である。   Specific examples of the crosslinking aid include polyunsaturated compounds such as polyallyl compounds and poly (meth) acryloxy compounds. More specifically, polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, etc. Examples include poly (meth) acryloxy compounds and divinylbenzene. The crosslinking aid is blended in an amount of 5 parts by weight or less, particularly 0.1 to 3 parts by weight, based on 100 parts by weight of the total of ethylene / vinyl acetate copolymer and ethylene / (meth) acrylate copolymer. Is effective.

本発明の封止材用シートには、必要に応じ、本発明の目的を損なわない範囲で、（Ａ）、（Ｂ）以外の樹脂あるいはその他種々の添加剤を配合することができる。このような添加剤として具体的には、シランカップリング剤、チタンカップリング剤のような接着付与剤、酸化防止剤、光安定剤、紫外線吸収剤、着色剤、光拡散剤、難燃剤、変色防止剤などを例示することができる。着色剤としては、顔料、無機化合物や染料等が挙げられる。とくに白色の着色剤としては、酸化チタンや酸化亜鉛が挙げられる。太陽電池素子の受光側の封止材に配合する場合は、その透明性を損なうものは好ましくないが、太陽電池素子の受光側と反対面の封止材に配合する場合にはそのような制約を受けない。   The sealing material sheet of the present invention can be blended with resins other than (A) and (B) or various other additives as long as the purpose of the present invention is not impaired. Specific examples of such additives include adhesion imparting agents such as silane coupling agents and titanium coupling agents, antioxidants, light stabilizers, ultraviolet absorbers, colorants, light diffusing agents, flame retardants, and discoloration. An inhibitor etc. can be illustrated. Examples of the colorant include pigments, inorganic compounds and dyes. In particular, examples of white colorants include titanium oxide and zinc oxide. When blended with the sealing material on the light-receiving side of the solar cell element, it is not preferable to impair the transparency, but when blended with the sealing material on the surface opposite to the light-receiving side of the solar cell element, such restrictions Not receive.

接着付与剤は、保護材や太陽電池素子等に対する接着性を向上させるのに有用であり、その例としては、アミノ基又はエポキシ基とともに、アルコキシ基のような加水分解可能な基を有するシランカップリング剤やチタンカップリング剤などを挙げることができる。シランカップリング剤として具体的には、Ｎ−（β−アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシランなどを例示することができる。これら接着付与剤は、エチレン・酢酸ビニル共重合体及びエチレン・（メタ）アクリル酸エステル共重合体の合計１００重量部に対し、５重量部以下、とくに０．０２〜３重量部の割合で配合するのが効果的である。   The adhesion-imparting agent is useful for improving adhesion to a protective material, a solar cell element, and the like. Examples thereof include a silane cup having an amino group or an epoxy group and a hydrolyzable group such as an alkoxy group. Examples thereof include a ring agent and a titanium coupling agent. Specific examples of the silane coupling agent include N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ-aminopropyltriethoxy. Examples include silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. These adhesion-imparting agents are blended at a ratio of 5 parts by weight or less, particularly 0.02 to 3 parts by weight, based on a total of 100 parts by weight of the ethylene / vinyl acetate copolymer and the ethylene / (meth) acrylic acid ester copolymer. It is effective to do.

また太陽光線中の紫外線に基づく封止材用シートの劣化を防ぐために、酸化防止剤、光安定剤、紫外線吸収剤の少なくとも一種を配合するのが効果的である。酸化防止剤として各種ヒンダードフェノール系やホスファイト系のものを使用することができる。また光安定剤としては、ヒンダードアミン系のものが好適に使用することができる。また紫外線吸収剤としては例えば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′，５′−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のものが使用できる。これら、酸化防止剤、光安定剤及び紫外線吸収剤は、エチレン・酢酸ビニル共重合体及びエチレン・（メタ）アクリル酸エステル共重合体の合計１００重量部に対し、それぞれ５重量部以下、とくに０．１〜３重量部の割合で配合するのが効果的である。   Moreover, in order to prevent deterioration of the sheet | seat for sealing materials based on the ultraviolet-ray in sunlight, it is effective to mix | blend at least 1 type of antioxidant, a light stabilizer, and an ultraviolet absorber. Various hindered phenols and phosphites can be used as the antioxidant. Moreover, as a light stabilizer, a hindered amine type thing can be used conveniently. Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone, 2-hydroxy. Benzophenones such as -4-n-octoxybenzophenone, 2- (2'-hydroxy-3 ', 5'-ditert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5-methylphenyl) benzo Benzotriazoles such as triazole and 2- (2'-hydroxy-5-third octylphenyl) benzotriazole, salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate can be used. . These antioxidants, light stabilizers and ultraviolet absorbers are each 5 parts by weight or less, particularly 0 parts per 100 parts by weight in total of the ethylene / vinyl acetate copolymer and the ethylene / (meth) acrylate copolymer. It is effective to mix in the proportion of 1-3 parts by weight.

本発明の太陽電池封止材用シートの成形は、Ｔ−ダイ押出機、カレンダー成形機、インフレーション成形機などを使用する公知の方法によって行なうことができる。例えばエチレン・酢酸ビニル共重合体、エチレン・（メタ）アクリル酸エステル共重合体、有機過酸化物および必要に応じて添加される架橋助剤、接着付与剤、酸化防止剤、光安定剤、紫外線吸収剤等の添加剤を予めドライブレンドして押出機のホッパーから供給し、有機過酸化物が実質的に分解しない成形温度でシート状に押出成形することによって得ることができる。シート厚みは特に規定されないが、通常０．２〜１．２ｍｍ程度である。   The sheet | seat for solar cell sealing materials of this invention can be shape | molded by the well-known method using a T-die extruder, a calendar molding machine, an inflation molding machine, etc. For example, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer, organic peroxide and cross-linking aid added as needed, adhesion promoter, antioxidant, light stabilizer, ultraviolet light Additives such as an absorbent can be dry blended in advance and supplied from a hopper of an extruder and extruded into a sheet at a molding temperature at which the organic peroxide does not substantially decompose. The sheet thickness is not particularly defined, but is usually about 0.2 to 1.2 mm.

本発明の封止材用シートを用い、太陽電池素子を上下の保護材で固定することにより太陽電池モジュールを製作することができる。このような太陽電池モジュールとしては、種々のタイプのものを例示することができる。例えば上部透明保護材／封止材用シート／太陽電池素子／封止材用シート／下部保護材のように太陽電池素子の両側から封止材で挟む構成のもの、下部基板保護材の内周面上に形成させた太陽電池素子上に封止材用シートと上部透明保護材を形成させるような構成のもの、上部透明保護材の内周面上に形成させた太陽電池素子、例えばフッ素樹脂系シート上にアモルファス太陽電池素子をスパッタリング等で作成したものの上に封止材用シートと下部保護材を形成させるような構成のものなどを挙げることができる。   A solar cell module can be produced by fixing the solar cell element with upper and lower protective materials using the sheet for sealing material of the present invention. Examples of such solar cell modules include various types. For example, an upper transparent protective material / encapsulant sheet / solar cell element / encapsulant sheet / lower protective material sandwiched between both sides of the solar cell element, the inner circumference of the lower substrate protective material Solar cell element formed on the inner peripheral surface of the upper transparent protective material, such as one having a structure for forming the sealing material sheet and the upper transparent protective material on the solar cell element formed on the surface The thing of the structure which forms the sheet | seat for sealing materials and the lower protective material on what produced the amorphous solar cell element on the system sheet | seat by sputtering etc. can be mentioned.

太陽電池素子としては、単結晶シリコン、多結晶シリコン、アモルファスシリコンなどのシリコン系、ガリウムー砒素、銅ーインジウムーセレン、カドミウムーテルルなどのIIIーＶ族やIIーVI族化合物半導体系等の各種太陽電池素子を用いることができる。本発明の封止材用シートはとくにアモルファス太陽電池素子、例えばアモルファスシリコンの封止に有用である。   Solar cell elements include single-crystal silicon, polycrystalline silicon, amorphous silicon, and other silicon systems, and gallium-arsenic, copper-indium-selenium, cadmium-tellurium, and other III-V group and II-VI group compound semiconductor systems. Various solar cell elements can be used. The sheet for sealing material of the present invention is particularly useful for sealing an amorphous solar cell element, for example, amorphous silicon.

太陽電池モジュールを構成する上部保護材としては、ガラス、アクリル樹脂、ポリカーボネート、ポリエステル、フッ素含有樹脂などを例示することができる。また下部保護材としては、金属や各種熱可塑性樹脂フイルムなどの単体もしくは多層のシートであり、例えば、錫、アルミ、ステンレススチールなどの金属、ガラス等の無機材料、ポリエステル、無機物蒸着ポリエステル、フッ素含有樹脂、ポリオレフィンなどの１層もしくは多層のシートを例示することができる。本発明の封止材用シートは、これらの上部又は下部保護材に対して良好な接着性を示す。   Examples of the upper protective material constituting the solar cell module include glass, acrylic resin, polycarbonate, polyester, and fluorine-containing resin. The lower protective material is a single or multi-layer sheet of metal or various thermoplastic resin films, for example, metals such as tin, aluminum, stainless steel, inorganic materials such as glass, polyester, inorganic vapor-deposited polyester, fluorine-containing A single layer or multilayer sheet of resin, polyolefin, etc. can be exemplified. The sheet | seat for sealing materials of this invention shows favorable adhesiveness with respect to these upper or lower protective materials.

太陽電池モジュールの製造は、架橋剤が実質的に分解せず、かつ本発明の封止材用シートが溶融するような温度で、太陽電池素子や保護材に該封止材用シートを仮接着し、次いで昇温して充分な接着と架橋を行なえばよい。最終的には耐熱性良好な太陽電池モジュールを得るために、封止材用シート層のゲル分率（試料１ｇをキシレン１００ｍｌに浸漬し、１１０℃、２４時間加熱した後、２０メッシュ金網で濾過し未溶融分の質量分率を測定）が７０〜９８％、好ましくは８０〜９５％程度になるように架橋するのがよい。したがってこれら諸条件を満足できるように添加剤処方を選べばよく、例えば架橋剤等の種類及び配合量を適宜選択すればよい。   The solar cell module is manufactured by temporarily adhering the sealing material sheet to the solar cell element or the protective material at a temperature at which the crosslinking agent does not substantially decompose and the sealing material sheet of the present invention melts. Then, the temperature may be raised and sufficient adhesion and crosslinking may be performed. Finally, in order to obtain a solar cell module with good heat resistance, the gel fraction of the sealing material sheet layer (1 g of sample was immersed in 100 ml of xylene, heated at 110 ° C. for 24 hours, and then filtered through a 20 mesh wire mesh. It is preferable to crosslink so that the mass fraction of unmelted portion is 70 to 98%, preferably about 80 to 95%. Therefore, an additive formulation may be selected so that these various conditions can be satisfied. For example, the type and blending amount of a crosslinking agent and the like may be appropriately selected.

以下、実施例により本発明をさらに詳細に説明する。尚、実施例及び比較例で用いた原料を表１に示す。   Hereinafter, the present invention will be described in more detail with reference to examples. The raw materials used in the examples and comparative examples are shown in Table 1.

Figure 0004779074
Figure 0004779074

［実施例１］
表１に示すＥＶＡ−１を５０重量部、ＥＥＡ−１を５０重量部、合計１００重量部に対し、架橋剤（商品名：ルパゾール１０１、アトフィナ吉富（株）製）１．５重量部及びトリアリルイソシアヌレート（ＴＡＩＣ）２重量部、シランカップリング剤（商品名：ＫＢＭ５０３、信越化学（株）製）０．５重量部を配合した共重合体組成物を、Ｔ−ダイ成形機を用いて、樹脂温度１２０℃にて０．６ｍｍ厚のシートに押出した。この押出シートを用いて、下記（１）〜（３）の方法により、架橋特性、吸湿量、絶縁抵抗を評価した。 [Example 1]
50 parts by weight of EVA-1 and 50 parts by weight of EEA-1 shown in Table 1 are combined with 100 parts by weight in total, 1.5 parts by weight of a crosslinking agent (trade name: Lupasol 101, manufactured by Atofina Yoshitomi Co., Ltd.) Using a T-die molding machine, a copolymer composition containing 2 parts by weight of allyl isocyanurate (TAIC) and 0.5 parts by weight of a silane coupling agent (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used. And extruded at a resin temperature of 120 ° C. to a 0.6 mm thick sheet. Using this extruded sheet, the crosslinking properties, moisture absorption, and insulation resistance were evaluated by the following methods (1) to (3).

（１）架橋特性（ゲル分率）
Ｔ−ダイ成形機を用いて作成したシートを、１５０℃の圧縮成形機を用いて２０分間加圧下で加熱することにより架橋シートを作成した。この架橋シート１ｇを１００ｍｌのキシレンに浸漬し、１１０℃、２４時間加熱した後、金網で濾過して不溶解分を捕集し、乾燥後秤量することによってゲル分率を求めて架橋特性を評価した。その結果を表２に示す。 (1) Cross-linking properties (gel fraction)
A cross-linked sheet was prepared by heating a sheet prepared using a T-die molding machine under pressure using a compression molding machine at 150 ° C. for 20 minutes. 1 g of this cross-linked sheet is immersed in 100 ml of xylene, heated at 110 ° C. for 24 hours, filtered through a wire mesh to collect the insoluble matter, and dried and weighed to determine the gel fraction and evaluate the cross-linking properties. did. The results are shown in Table 2.

（２）吸湿量
前記手段により作成した架橋シートを、８５℃、８５％ＲＨの条件に放置し、１週間後の吸湿量を、水分計（カールフィッシャー法：KYOTO ELECTRONIC（株）製）で測定した。
評価結果を、表２に示す。 (2) Moisture absorption The cross-linked sheet prepared by the above means is left under conditions of 85 ° C. and 85% RH, and the moisture absorption after one week is measured with a moisture meter (Karl Fischer method: manufactured by KYOTO ELECTRONIC Co., Ltd.). did.
The evaluation results are shown in Table 2.

（３）絶縁抵抗値
前記（１）の手段により作成した架橋シートを、８５℃、８５％ＲＨの条件に放置し、初期値及び１週間後の絶縁抵抗を、体積抵抗率測定機（Aligent Technologies社製）を用いて、１０００Ｖ、加電時間６０秒の条件で測定した。この結果を表２に示す。 (3) Insulation resistance value The cross-linked sheet prepared by means of (1) above is left under the conditions of 85 ° C. and 85% RH, and the initial value and the insulation resistance after one week are determined by a volume resistivity measuring machine (Aligent Technologies The measurement was performed under the conditions of 1000 V and a charging time of 60 seconds. The results are shown in Table 2.

［実施例２］
実施例１において、ＥＥＡ−１の代わりにＥＥＡ−２を用いた以外は実施例１と全く同様にしてゲル分率、吸湿量及び絶縁抵抗値の評価を行なった。これらの結果を表２に示す。 [Example 2]
In Example 1, the gel fraction, moisture absorption, and insulation resistance value were evaluated in exactly the same manner as in Example 1 except that EEA-2 was used instead of EEA-1. These results are shown in Table 2.

［実施例３］
実施例１の共重合体組成物を、ＥＶＡ−１を６０重量部、ＥＥＡ−１を４０重量部、架橋剤（商品名：ルパゾール１０１、アトフィナ吉富（株）製）を２．５重量部及びシランカップリング剤（商品名：ＫＢＭ５０３、信越化学（株）製）０．５重量部からなる共重合体組成物に変更した以外は実施例１と全く同様にしてゲル分率、吸湿量および絶縁抵抗値の評価を行なった。これらの結果を表２に示す。 [Example 3]
60 parts by weight of EVA-1, 40 parts by weight of EEA-1, 2.5 parts by weight of a crosslinking agent (trade name: Lupasol 101, manufactured by Atofina Yoshitomi Corp.) and the copolymer composition of Example 1 The gel fraction, moisture absorption and insulation were exactly the same as in Example 1 except that the silane coupling agent (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to a copolymer composition consisting of 0.5 parts by weight. The resistance value was evaluated. These results are shown in Table 2.

［比較例１］
実施例１において、ＥＶＡ−１を用いずＥＥＡ−１を１００重量部用いた以外は実施例１と全く同様にしてゲル分率、吸湿量および絶縁抵抗値の評価を行なった。これらの結果を表２に示す。 [Comparative Example 1]
In Example 1, gel fraction, moisture absorption, and insulation resistance were evaluated in exactly the same manner as in Example 1 except that 100 parts by weight of EEA-1 was used without using EVA-1. These results are shown in Table 2.

Figure 0004779074
Figure 0004779074

Claims (5)

酢酸ビニル含有量が１５〜４７重量％のエチレン・酢酸ビニル共重合体（Ａ）１０〜９０重量％と（メタ）アクリル酸エステル含有量が１０〜４０重量％のエチレン・（メタ）アクリル酸エステル共重合体（Ｂ）９０〜１０重量％（上記（Ａ）と（Ｂ）の合計を１００重量％とする）からなり、エチレン含有量が６０〜８５重量％である組成物に、（Ａ）と（Ｂ）の合計１００重量部に対し、架橋剤として分解温度（半減期が１時間である温度）が９０〜１８０℃の有機過酸化物を０．１〜５重量部あるいは該架橋剤０．１〜５重量部と架橋助剤５重量部以下を配合した架橋性エチレン共重合体組成物を用いることを特徴とする太陽電池封止材用シート。 Ethylene / vinyl acetate copolymer (A) having a vinyl acetate content of 15 to 47% by weight (A) and ethylene / (meth) acrylate ester having a (meth) acrylate content of 10 to 40% by weight Copolymer (B) comprising 90 to 10% by weight (the total of (A) and (B) is 100% by weight), and having an ethylene content of 60 to 85% by weight , (A) And (B) in a total of 100 parts by weight, 0.1 to 5 parts by weight of an organic peroxide having a decomposition temperature (temperature at which the half-life is 1 hour) as a crosslinking agent is 90 to 180 ° C. A sheet for a solar cell encapsulating material, wherein a crosslinkable ethylene copolymer composition containing 1 to 5 parts by weight and 5 parts by weight or less of a crosslinking aid is used. 架橋性エチレン共重合体組成物中の樹脂成分のメルトフローレート（ＪＩＳ Ｋ７２１０−１９９９、１９０℃、２１６０ｇ荷重）が０．５〜１５０ｇ／１０分の範囲にあることを特徴とする請求項１記載の太陽電池封止材用シート。   The melt flow rate (JIS K7210-1999, 190 ° C., 2160 g load) of the resin component in the crosslinkable ethylene copolymer composition is in the range of 0.5 to 150 g / 10 minutes. Sheet for solar cell encapsulant. さらにシランカップリング剤、紫外線吸収剤、光安定剤及び酸化防止剤から選ばれる添加剤が配合されてなる請求項１又は２記載の太陽電池封止材用シート。 Furthermore , the sheet | seat for solar cell sealing materials of the Claim 1 or 2 formed by mix | blending the additive chosen from a silane coupling agent, a ultraviolet absorber, a light stabilizer, and antioxidant. 酢酸ビニル含有量が１５〜４７重量％のエチレン・酢酸ビニル共重合体（Ａ）１０〜９０重量％と（メタ）アクリル酸エステル含有量が１０〜４０重量％のエチレン・（メタ）アクリル酸エステル共重合体（Ｂ）９０〜１０重量％（上記（Ａ）と（Ｂ）の合計を１００重量％とする）からなり、エチレン含有量が６０〜８５重量％である組成物に、（Ａ）と（Ｂ）の合計１００重量部に対し、架橋剤として分解温度（半減期が１時間である温度）が９０〜１８０℃の有機過酸化物を０．１〜５重量部あるいは該架橋剤０．１〜５重量部と架橋助剤５重量部以下を配合した架橋性エチレン共重合体組成物を架橋してなるゲル分率が７０％以上の架橋物からなる封止材層で太陽電池素子が封止されてなる太陽電池モジュール。 Ethylene / vinyl acetate copolymer (A) having a vinyl acetate content of 15 to 47% by weight (A) and ethylene / (meth) acrylate ester having a (meth) acrylate content of 10 to 40% by weight Copolymer (B) comprising 90 to 10% by weight ( the total of (A) and (B) is 100% by weight), and having an ethylene content of 60 to 85% by weight , (A) And (B) in a total of 100 parts by weight, 0.1 to 5 parts by weight of an organic peroxide having a decomposition temperature (temperature at which the half-life is 1 hour) as a crosslinking agent is 90 to 180 ° C. A solar cell element with a sealing material layer comprising a crosslinked product having a gel fraction of 70% or more obtained by crosslinking a crosslinkable ethylene copolymer composition containing 1 to 5 parts by weight and 5 parts by weight or less of a crosslinking aid A solar cell module in which is sealed. 太陽電池素子がアモルファス太陽電池素子である請求項４記載の太陽電池モジュール。   The solar cell module according to claim 4, wherein the solar cell element is an amorphous solar cell element.
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