JP3510645B2 - Adhesive sheet for solar cells - Google Patents
Adhesive sheet for solar cellsInfo
- Publication number
- JP3510645B2 JP3510645B2 JP10985393A JP10985393A JP3510645B2 JP 3510645 B2 JP3510645 B2 JP 3510645B2 JP 10985393 A JP10985393 A JP 10985393A JP 10985393 A JP10985393 A JP 10985393A JP 3510645 B2 JP3510645 B2 JP 3510645B2
- Authority
- JP
- Japan
- Prior art keywords
- solar cell
- adhesive sheet
- ethylene
- copolymer
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Photovoltaic Devices (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、太陽電池モデュールに
おいて太陽電池素子を固定するための接着シートに関す
る。さらに詳しくは、耐候性、耐吸湿性、透明性に優
れ、特別な遮水処理を省略することが可能な太陽電池用
接着シートに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive sheet for fixing a solar cell element in a solar cell module. More specifically, the present invention relates to an adhesive sheet for a solar cell which has excellent weather resistance, moisture absorption resistance, and transparency and can omit special water shielding treatment.
【０００２】[0002]
【従来の技術】シリコン半導体素子を用いた太陽電池
は、地球環境にやさしい無公害のエネルギーを収得する
手段として注目されているが、現存のものは未だ発電コ
ストが高いため、電力用としては離島における発電など
の特別な用途に限られている。このため、将来の代替エ
ネルギーとして普及させるためには、発電効率を維持し
て長期寿命を保証する必要があり、更には太陽電池モデ
ュールの構成を簡素化して発電コストを低減させる必要
がある。従来多用されている太陽電池モデュールにおい
ては、太陽電池の受光面に置かれたガラスなどの透明基
板の下に透明な接着シートを介してシリコン半導体素子
が固定されている。このような接着シートとしてエチレ
ン・酢酸ビニル共重合体の架橋物の使用が一般的である
が、該架橋物の耐吸湿性が充分高いとはいえず、そのた
め現行の太陽電池モデュールの周囲にはシリコーン処理
による遮水処理が施されている。しかし現行太陽電池の
長期寿命を損なう大きな原因の一つとして、遮水層に欠
陥があると、モデュールの隙間を通して該架橋物中に水
分が滲透し、太陽電池間を接続している配線を侵し、最
終的には発電効率が低下するという欠点がある。更には
大幅なコストダウンを図るためにモデュールの周囲に施
されているシリコーンシーラントによる遮水処理を完全
に省略する試みがある。この場合にはモデュールの隙間
を通して該架橋物に更に水分が浸透し易くなり、太陽電
池の長期寿命が更に損なわれる欠点があった。2. Description of the Related Art A solar cell using a silicon semiconductor element has been attracting attention as a means for obtaining environmentally friendly and non-polluting energy. Limited to special applications, such as power generation. For this reason, in order to disseminate as alternative energy in the future, it is necessary to maintain power generation efficiency and guarantee a long life, and furthermore, it is necessary to simplify the configuration of the solar cell module and reduce power generation costs. In a solar cell module that has been widely used, a silicon semiconductor element is fixed via a transparent adhesive sheet under a transparent substrate such as glass placed on the light receiving surface of the solar cell. As such an adhesive sheet, a cross-linked product of an ethylene / vinyl acetate copolymer is generally used, but it cannot be said that the cross-linked product has sufficiently high moisture absorption resistance. Water barrier treatment by silicone treatment is applied. However, as one of the major factors that impair the long-term life of current solar cells, if the water barrier layer is defective, moisture penetrates into the cross-linked material through the gaps between the modules, affecting the wiring connecting the solar cells. However, there is a drawback that the power generation efficiency eventually decreases. Further, there is an attempt to completely omit the water shielding treatment by a silicone sealant applied around the module in order to achieve a significant cost reduction. In this case, there is a disadvantage that moisture easily penetrates into the crosslinked product through the gaps between the modules, and the long-term life of the solar cell is further impaired.
【０００３】[0003]
【発明が解決しようとする課題】そこで、接着シートと
してエチレン・酢酸ビニル共重合体の架橋物等の材料に
代る耐吸湿性の優れた材料が求められていた。このよう
な材料は単に吸湿性が小さいのみでなく、太陽電池用接
着シートとして望まれる性能、即ち、透明性、加工性、
耐候性、耐熱性等が優れ、またシリコン素子の保護のた
め柔軟性に富むものでなければならなかった。Therefore, there has been a demand for a material having excellent moisture absorption resistance in place of a material such as a crosslinked product of ethylene / vinyl acetate copolymer as an adhesive sheet. Such a material is not only low in hygroscopicity, but also the performance desired as an adhesive sheet for a solar cell, ie, transparency, workability,
It must be excellent in weather resistance, heat resistance, and the like, and must be highly flexible to protect the silicon element.
【０００４】本発明者らは鋭意検討の結果、特定のエチ
レン・（メタ）アクリル酸エステル共重合体を使用する
ことにより、上記問題が解決できることを見出した。
尚、従来、一般的にエチレン・（メタ）アクリル酸エス
テル共重合体を太陽電池用の接着シートとして使用でき
ることは知られているが、本発明で特定した組成の共重
合体を前述した目的で使用することについては全く知ら
れていない。例えば、特公平２−４０７０９号公報によ
れば、接着シートとしてエチレン・不飽和脂肪酸エステ
ル共重合体が使用できること、より具体的にはアクリル
酸エチル含量が３５重量％のエチレン・アクリル酸エチ
ル共重合体を使用した例があることが認められる。しか
しこの提案では湿度サイクル試験における剥離強度につ
いては検討されているが、吸湿による前記した性能低下
については何ら留意されておらず、また上記の如き組成
のエチレン・アクリル酸エチル共重合体を接着シートと
して使用したのでは耐吸湿性に優れた製品を得ることは
できない。As a result of intensive studies, the present inventors have found that the above problem can be solved by using a specific ethylene / (meth) acrylate copolymer.
In the past, it is generally known that an ethylene / (meth) acrylate copolymer can be used as an adhesive sheet for a solar cell. However, a copolymer having the composition specified in the present invention is used for the above-mentioned purpose. Nothing is known about its use. For example, according to Japanese Patent Publication No. 2-40709, an ethylene / unsaturated fatty acid ester copolymer can be used as an adhesive sheet, more specifically, an ethylene / ethyl acrylate copolymer having an ethyl acrylate content of 35% by weight. It is recognized that there are examples using coalescence. However, in this proposal, the peel strength in the humidity cycle test is examined, but no consideration is given to the above-mentioned performance degradation due to moisture absorption, and the ethylene / ethyl acrylate copolymer having the above composition is bonded to an adhesive sheet. A product excellent in moisture absorption resistance cannot be obtained.
【０００５】[0005]
【課題を解決するための手段】本発明は、太陽電池モデ
ュールにおける太陽電池素子を固定する接着シートとし
て、（メタ）アクリル酸エステル含有量が１５〜３２重
量％のエチレン・（メタ）アクリル酸エステル共重合体
（但しエチレン ・ (メタ)アクリル酸エステル・エチレン
性不飽和シラン化合物共重合体を除く）の架橋性組成物
を使用したことを特徴とする太陽電池用接着シート、及
びこのような組成物を架橋して得られたゲル分率７０〜
９８％の架橋物接着シート層を有する太陽電池モデュー
ルに関する。SUMMARY OF THE INVENTION The present invention provides an adhesive sheet for fixing a solar cell element in a solar cell module, comprising an ethylene / (meth) acrylate having a (meth) acrylate content of 15 to 32% by weight. Copolymer
(However, ethylene / (meth) acrylate / ethylene
Adhesive sheet for a solar cell, characterized by using a crosslinkable composition ( excluding the unsaturated unsaturated silane compound copolymer) , and a gel fraction of 70 to 50 obtained by crosslinking such a composition.
It relates to a solar cell module having a 98% crosslinked product adhesive sheet layer.
【０００６】太陽電池モデュールの典型的な構成は、太
陽電池素子が２枚の接着シートの間に挟まれ、接着シー
トの上、下部に、上部透明保護材及び下部保護材が設け
られたものである。本発明においては、このようなモデ
ュールを製造する際の接着シートとして上記共重合体の
架橋性組成物を用い、その成形時に溶融接着と架橋が行
われるものである。[0006] A typical configuration of a solar cell module is such that a solar cell element is sandwiched between two adhesive sheets, and an upper transparent protective material and a lower protective material are provided above and below the adhesive sheet. is there. In the present invention, a crosslinkable composition of the above copolymer is used as an adhesive sheet for producing such a module, and fusion bonding and crosslinking are performed at the time of molding.
【０００７】太陽電池素子としては、アモルファスシリ
コン、結晶シリコン、多結晶シリコンなどが代表的なも
のであるが、セレン、ガリウム、ヒ素、その他種々のも
のが知られており、いずれも本発明において用いること
ができる。As typical solar cell elements, amorphous silicon, crystalline silicon, polycrystalline silicon and the like are typical. Selenium, gallium, arsenic and other various elements are known, and all of them are used in the present invention. be able to.
【０００８】本発明において用いられる接着シート材料
は、（メタ）アクリル酸エステル含有量が１５〜３２重
量％、好ましくは２０〜３０重量％のエチレン・（メ
タ）アクリル酸エステル共重合体の架橋性組成物であ
る。ここに（メタ）アクリル酸エステルはアクリル酸エ
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
ましく、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−ブチルなどを例示できる。The adhesive sheet material used in the present invention has a crosslinkability of an ethylene / (meth) acrylate copolymer having a (meth) acrylate content of 15 to 32% by weight, preferably 20 to 30% by weight. A composition. Here, (meth) acrylic acid ester means acrylic acid ester or methacrylic acid ester, usually, an alkyl ester of acrylic acid or methacrylic acid having 1 to 10 carbon atoms, particularly preferably an alkyl ester having 2 to 8 carbon atoms, Specific examples include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and n-butyl methacrylate.
【０００９】（メタ）アクリル酸エステル含有量が前記
範囲より少ない共重合体を用いると、透明性、柔軟性が
劣るため好ましくなく、またその含有量が前記範囲より
多くなると吸湿し易くなるため好ましくない。前記共重
合体としてはまた１９０℃、２１６０ｇ荷重におけるメ
ルトフローレートが１〜１００ｇ／１０分、とくに５〜
５０ｇ／１０分のものを使用するのが好ましい。Use of a copolymer having a (meth) acrylate content less than the above range is not preferred because of poor transparency and flexibility, and a content higher than the above range is preferred because the composition tends to absorb moisture. Absent. The copolymer also has a melt flow rate at 190 ° C. and a load of 2160 g of 1 to 100 g / 10 min, particularly 5 to 5 g.
It is preferable to use one with 50 g / 10 minutes.
【００１０】上記共重合体の架橋性組成物は、該共重合
体を高温で架橋することができる架橋剤を含んでおり、
場合によりさらに架橋助剤を含んでいてもよい。接着シ
ートは融着によって太陽電池素子を固定するものである
から、接着シートそれ自体の製造時には、上記架橋剤等
は上記共重合体を実質的に架橋させるものであってはな
らない。また太陽電池モデュール製造時における接着シ
ートによる融着と架橋は通常多段階で行うのが好まし
く、融着可能な温度条件下ではあるが実質的に架橋を起
こさない温度での仮接着段階と、完全な接着と架橋を行
うより高温度の操作段階をとるのがよい。また最終的に
は耐熱性良好な太陽電池モデュールを得るために、共重
合体のゲル分率（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が行われ
る。したがってこれら諸条件を満足できるような架橋剤
等の種類及び配合量を選択する必要がある。The crosslinkable composition of the copolymer contains a crosslinking agent capable of crosslinking the copolymer at a high temperature,
In some cases, a crosslinking aid may be further contained. Since the adhesive sheet fixes the solar cell element by fusion, the cross-linking agent or the like must not substantially cross-link the copolymer during the production of the adhesive sheet itself. In addition, fusion and cross-linking with the adhesive sheet at the time of manufacturing the solar cell module are generally preferably performed in multiple steps, and a temporary bonding step at a temperature under which fusing is possible but substantially not causing cross-linking, It is better to take a higher temperature operation stage than to perform a good adhesion and crosslinking. Finally, in order to obtain a solar cell module having good heat resistance, the gel fraction of the copolymer (1 g of a sample was immersed in 100 ml of xylene, heated at 110 ° C. for 24 hours, filtered through a 20-mesh wire gauze and unfiltered. (Measured mass fraction of melt) 70-98%,
Crosslinking is preferably performed so as to be about 80 to 95%. Therefore, it is necessary to select the type and the amount of the crosslinking agent or the like that can satisfy these conditions.
【００１１】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１２０〜１６
０℃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。The crosslinking agent has a decomposition temperature (a temperature at which the half-life is 1 hour) of 90 to 180 ° C., particularly 120 to 16 ° C.
It is preferred to use an organic peroxide at 0 ° C. Such organic peroxides include, for example, tertiary butyl peroxyisopropyl carbonate, tertiary butyl peroxy acetate, tertiary butyl peroxy benzoate, 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,
Tertiary butyl hydroperoxide, p-menthane hydroperoxide, benzoyl peroxide, p-
Chlorobenzoyl peroxide, tertiary butyl peroxyisobutyrate, hydroxyheptyl peroxide, dichlorohexanone peroxide and the like can be mentioned.
【００１２】有機過酸化物は、その種類によっても異な
るが、エチレン共重合体１００重量部に対し、０．１〜
５重量部、好ましくは０．５〜３重量部程度配合するの
がよい。The organic peroxide varies depending on the type thereof, but is preferably 0.1 to 100 parts by weight based on 100 parts by weight of the ethylene copolymer.
5 parts by weight, preferably about 0.5 to 3 parts by weight is blended.
【００１３】接着シートの架橋を容易に行わせるため
に、架橋助剤を用いることができる。かかる架橋助剤と
して例えばトリアリルシアヌレート、トリアリルイソシ
アヌレート、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、ジヒニルベ
ンゼン、ジアリルフタレートなどを例示することができ
る。架橋助剤は、エチレン共重合体１００重量部に対
し、０．５〜５重量部程度配合すると効果的である。[0013] A crosslinking aid may be used to facilitate crosslinking of the adhesive sheet. Examples of such a crosslinking assistant include triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, dihinylbenzene, and diallyl phthalate. It is effective to mix the crosslinking aid with about 0.5 to 5 parts by weight based on 100 parts by weight of the ethylene copolymer.
【００１４】本発明の太陽電池用接着シートに用いる架
橋性組成物にはまた、その他の各種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は、例えば、上部
保護材や下部保護材に対する接着性を向上させるための
接着付与剤、紫外線吸収剤、耐光安定剤、酸化防止剤な
どを例示することができる。The crosslinkable composition used in the adhesive sheet for a solar cell of the present invention can also contain other various additives. Examples of such additives include an adhesion imparting agent for improving the adhesion to the upper protective material and the lower protective material, an ultraviolet absorber, a light stabilizer, an antioxidant, and the like.
【００１５】接着付与剤としては例えばシランカップリ
ング剤、チタンカップリング剤などであり、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、また耐光安定剤と
してはヒンダードアミン系のものが使用できる。また酸
化防止剤としては、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。Examples of the adhesion-imparting agent include a silane coupling agent and a titanium coupling agent. Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone and 2,2'-dihydroxy-4-methoxy. Benzophenone, 2-hydroxy-4-methoxy-2-
Carboxybenzophenone, 2-hydroxy-4-n-
Benzophenones such as octoxybenzophenone, 2
-(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5-methylphenyl) benzotriazole, 2- (2 '
Benzotriazoles such as -hydroxy-5-tert-octylphenyl) benzotriazole, and salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate can be used. Hindered amines can be used. As the antioxidant, hindered phenol-based or phosphite-based antioxidants can be used.
【００１６】接着シートの成形は、Ｔ−ダイ押出機など
を用いる公知の方法によって行なうことができる。即
ち、エチレン共重合体、有機過酸化物および必要に応じ
て添加される耐光安定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。
押し出しの際、エンボス模様入り引取ロールを通して成
形すれば、任意のエンボス模様のシートが得られ、この
ようなエンボスシートはブロッキング防止および太陽電
池のモデュール化過程での脱気に対して有効であるので
好ましい。The formation of the adhesive sheet can be performed by a known method using a T-die extruder or the like. That is, an ethylene copolymer, an organic peroxide and an additive such as a light stabilizer which is added as required are dry-blended in advance and supplied from a hopper of an extruder, and the organic peroxide does not substantially decompose. Extrusion into a sheet at the molding temperature.
During extrusion, if formed through an embossed-patterned take-up roll, a sheet with an arbitrary embossed pattern can be obtained.Since such an embossed sheet is effective for blocking prevention and degassing in the process of modularizing a solar cell, preferable.
【００１７】シートの厚みは特に規定されないが、一般
には約０．１〜１ｍｍ程度である。保護材との接着性を
向上させるためにこのシート表面にプライマー処理を行
なう場合には、引取ロールの後に設けられた有機シラン
化合物または有機チタネート化合物の溶液槽にシートを
通し、シート表面に有機シラン化合物または有機チタネ
ート化合物の層を形成させることにより、一般に行われ
る。Although the thickness of the sheet is not particularly limited, it is generally about 0.1 to 1 mm. When a primer treatment is performed on the sheet surface to improve the adhesiveness with the protective material, the sheet is passed through a solution tank of an organic silane compound or an organic titanate compound provided after a take-off roll, and the organic silane is applied to the sheet surface. This is generally done by forming a layer of a compound or an organic titanate compound.
【００１８】太陽電池モデュールにおける上部保護材と
しては、ガラス、プラスチックス等、下部保護材として
は、プラスチックス、セラミック、ステンレス、アルミ
ニウムなど種々のものから選ぶことができる。In the solar cell module, the upper protective material can be selected from glass, plastics and the like, and the lower protective material can be selected from various materials such as plastics, ceramics, stainless steel and aluminum.
【００１９】太陽電池素子、本発明の接着シート、上部
保護材及び下部保護材から太陽電池モデュールを製造す
るには、前述の特公平２−４０７０９号公報に開示され
たような公知の方法に準じて行うことができる。In order to produce a solar cell module from the solar cell element, the adhesive sheet of the present invention, the upper protective material and the lower protective material, a known method as disclosed in the aforementioned Japanese Patent Publication No. 2-40709 is used. Can be done.
【００２０】[0020]
【実施例】［実施例１］
各種添加剤を表１に示す割合で配合したエチレン・アク
リル酸エチル共重合体組成物をＴダイ押出成形機を用い
て樹脂温度１００℃にて０．５ｍｍ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、吸湿性及び透明性を評価した。結果
を表２に示す。EXAMPLES Example 1 An ethylene / ethyl acrylate copolymer composition containing various additives in the proportions shown in Table 1 was applied to a T-die extruder at a resin temperature of 100 ° C. and a thickness of 0.5 mm. Extruded into sheets. Using this extruded sheet, crosslinking properties, hygroscopicity and transparency were evaluated by the following methods (1) to (3). Table 2 shows the results.
【００２１】[0021]
【表１】 [Table 1]
【００２２】（１）架橋特性（ゲル分率）
Ｔダイ押出成形機を用いて押出したシートを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
って架橋シートを作成する。この架橋シート１ｇを１０
０ｍｌ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。(1) Crosslinking Characteristics (Gel Fraction) A sheet extruded using a T-die extruder is heated under pressure using a compression molding machine at 150 ° C. for 20 minutes to prepare a crosslinked sheet. 1 g of this crosslinked sheet is 10
It was immersed in 0 ml of xylene, heated at 110 ° C. for 24 hours, filtered through a wire mesh to collect insoluble matter, dried, and weighed to obtain a gel fraction to evaluate the crosslinking property.
【００２３】（２）吸湿性
上記の架橋シートを５０℃、９０％ＲＨの雰囲気下に２
４時間静置した後直ちに秤量し、更に室温で２４時間減
圧乾燥して減圧乾燥後の減量を求めて吸湿性を評価し
た。(2) Hygroscopicity The above cross-linked sheet is subjected to an atmosphere at 50 ° C. and 90% RH.
Immediately after standing for 4 hours, it was weighed immediately, further dried under reduced pressure at room temperature for 24 hours, and the weight loss after drying under reduced pressure was determined to evaluate the hygroscopicity.
【００２４】（３）透明性
厚さ３ｍｍのガラス板の間に押出シートをはさんで、真
空ラミネーターを用いて加熱温度１１０℃で溶融貼り合
わせを行った（仮接着）。この仮接着積層物を更に常圧
下で１５０℃で３０分間、ホットプレート上で加熱する
ことによって有機過酸化物を分解させ上記Ｔダイシート
を架橋させると共にガラス板に強固に接着させてガラス
積層板を作成し、５００ｎｍの光線透過率を測定して透
明性を評価した。(3) Transparency The extruded sheet was sandwiched between glass plates having a thickness of 3 mm, and melt-bonded at a heating temperature of 110 ° C. using a vacuum laminator (temporary bonding). The temporary adhesive laminate is further heated at 150 ° C. for 30 minutes under normal pressure on a hot plate to decompose the organic peroxide, crosslink the T-die sheet, and firmly adhere to the glass plate to form a glass laminate. It was prepared and the light transmittance at 500 nm was measured to evaluate the transparency.
【００２５】［実施例２］
実施例１のエチレン・アクリル酸エチル共重合体に代え
てエチレン・アクリル酸ｎ−ブチル共重合体（ｎ−ブチ
ルアクリル酸含量２５重量％、ＭＦＲ５ｄｇ／分）を用
いた以外は実施例１と同様にして押出シートを作成し、
その押出シートの品質を評価した。結果を表２に示す。Example 2 An ethylene / ethyl acrylate copolymer (n-butyl acrylic acid content 25% by weight, MFR 5 dg / min) was used in place of the ethylene / ethyl acrylate copolymer of Example 1. Extruded sheet was prepared in the same manner as in Example 1 except for
The quality of the extruded sheet was evaluated. Table 2 shows the results.
【００２６】［実施例３］ 実施例１の表１の重合体及び添加剤に更にトリアリルイ
ソシアヌレートを２．０重量部、オクタデシル−３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）
プロピオネートを０．１重量部添加した以外は実施例１
と同様にして押出シートを作成し、その押出シートの品
質を評価した。評価結果を表２に示す。 Example 3 The polymers and additives shown in Table 1 of Example 1
2.0 parts by weight of soocyanurate, octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Example 1 except that 0.1 part by weight of propionate was added.
Create an extruded sheet in the same manner as
Quality was assessed. Table 2 shows the evaluation results.
【００２７】［比較例１］
実施例１のエチレン・アクリル酸エチル共重合体に代え
てエチレン・アクリル酸エチル共重合体（アクリル酸エ
チル含量３５重量％、ＭＦＲ２５ｄｇ／分）を用いた以
外は実施例１と同様にして押出シートを作成し、その押
出シートの品質を評価した。結果を表２に示す。Comparative Example 1 The procedure of Example 1 was repeated except that the ethylene / ethyl acrylate copolymer was replaced with an ethylene / ethyl acrylate copolymer (ethyl acrylate content: 35% by weight, MFR: 25 dg / min). Extruded sheets were prepared in the same manner as in Example 1, and the quality of the extruded sheets was evaluated. Table 2 shows the results.
【００２８】［比較例２］
実施例１のエチレン・アクリル酸エチル共重合体に代え
てエチレン・酢酸ビニル共重合体（酢酸ビニル含量３３
重量％、ＭＦＲ３０ｄｇ／分）を用いまた２，５−ジメ
チル−２，５−ビス（ｔ−ブチルパーオキシ）ヘキサン
の配合量を１．５重量部にした以外は実施例１と同様に
して押出シートを作成し、その押出シートの品質を評価
した。結果を表２に示す。Comparative Example 2 An ethylene / vinyl acetate copolymer (vinyl acetate content: 33) was used in place of the ethylene / ethyl acrylate copolymer of Example 1.
Extruded in the same manner as in Example 1 except that the amount of 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane was changed to 1.5 parts by weight. Sheets were made and the quality of the extruded sheets was evaluated. Table 2 shows the results.
【００２９】［比較例３］
比較例２のエチレン・酢酸ビニル共重合体に代えてエチ
レン・酢酸ビニル共重合体（酢酸ビニル含量２５重量
％、ＭＦＲ２０ｄｇ／分）を用いた以外は比較例３と同
様にして押出シートを作成し、その押出シートの品質を
評価した。結果を表２に示す。Comparative Example 3 Comparative Example 3 was repeated except that an ethylene / vinyl acetate copolymer (vinyl acetate content: 25% by weight, MFR: 20 dg / min) was used instead of the ethylene / vinyl acetate copolymer of Comparative Example 2. Similarly, an extruded sheet was prepared, and the quality of the extruded sheet was evaluated. Table 2 shows the results.
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【発明の効果】本発明の接着シートは、柔軟性、透明
性、耐候性、耐熱性、耐吸湿性等に優れているため、シ
リコンシーラントを使用しない太陽電池モデュールに用
いても、吸湿による品質低下がなく、耐久性の優れた製
品を得ることができる。The adhesive sheet of the present invention is excellent in flexibility, transparency, weather resistance, heat resistance, moisture absorption resistance and the like. It is possible to obtain a product with no deterioration and excellent durability.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−186610（ＪＰ，Ａ) 特開 昭59−22978（ＪＰ，Ａ) 特開 昭61−148251（ＪＰ，Ａ) 特開 昭58−38771（ＪＰ，Ａ) 特公 平２−40709（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) C09J 4/00 - 201/10 H01L 31/04 - 31/058 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-186610 (JP, A) JP-A-59-22978 (JP, A) JP-A-61-148251 (JP, A) JP-A-58-1983 38771 (JP, A) JP 2-40709 (JP, B2) (58) Field surveyed (Int. Cl. 7 , DB name) C09J 4/00-201/10 H01L 31/04-31/058
Claims (2)
子を固定する接着シートとして（メタ）アクリル酸エス
テル含有量が１５〜３２重量％のエチレン・（メタ）ア
クリル酸エステル共重合体（但しエチレン ・ (メタ)アク
リル酸エステル・エチレン性不飽和シラン化合物共重合
体を除く）の架橋性組成物を使用したことを特徴とする
太陽電池用接着シート。1. A as an adhesive sheet for fixing a solar cell element in a solar cell module (meth) acrylic ester content of 15 to 32% by weight of ethylene (meth) acrylic acid ester copolymer (provided that ethylene (meth )
Copolymerization of acrylate and ethylenically unsaturated silane compound
An adhesive sheet for a solar cell, comprising using the crosslinkable composition ( excluding the body) .
５〜３２重量％、ゲル分率７０〜９８％のエチレン・
（メタ）アクリル酸エステル共重合体（但しエチレン ・
(メタ)アクリル酸エステル・エチレン性不飽和シラン化
合物共重合体を除く）架橋物からなる太陽電池用接着シ
ート層を有する太陽電池モデュール。2. A (meth) acrylate ester content of 1
5 to 32% by weight of ethylene.
(Meth) acrylate copolymer(However, ethylene ・
(Meth) acrylate / ethylenically unsaturated silanization
Excluding compound copolymer)Adhesive sheet for solar cell made of cross-linked material
A solar cell module having a heating layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10985393A JP3510645B2 (en) | 1993-04-14 | 1993-04-14 | Adhesive sheet for solar cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10985393A JP3510645B2 (en) | 1993-04-14 | 1993-04-14 | Adhesive sheet for solar cells |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06299125A JPH06299125A (en) | 1994-10-25 |
| JP3510645B2 true JP3510645B2 (en) | 2004-03-29 |
Family
ID=14520853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10985393A Expired - Lifetime JP3510645B2 (en) | 1993-04-14 | 1993-04-14 | Adhesive sheet for solar cells |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3510645B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8168885B2 (en) | 2007-02-12 | 2012-05-01 | E.I. Du Pont De Nemours And Company | Low modulus solar cell encapsulant sheets with enhanced stability and adhesion |
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|---|---|---|---|---|
| JP4779074B2 (en) * | 2003-10-03 | 2011-09-21 | 三井・デュポンポリケミカル株式会社 | Sheet for solar cell encapsulant |
| WO2006085603A1 (en) * | 2005-02-10 | 2006-08-17 | Du Pont-Mitsui Polychemicals Co., Ltd. | Process for producing solar cell sealing material |
| US20070012352A1 (en) * | 2005-07-18 | 2007-01-18 | Bp Corporation North America Inc. | Photovoltaic Modules Having Improved Back Sheet |
| JPWO2007094445A1 (en) * | 2006-02-17 | 2009-07-09 | 三井・デュポンポリケミカル株式会社 | Solar cell encapsulant |
| US8581094B2 (en) | 2006-09-20 | 2013-11-12 | Dow Global Technologies, Llc | Electronic device module comprising polyolefin copolymer |
| US20080115825A1 (en) | 2006-09-20 | 2008-05-22 | Patel Rajen M | Electronic Device Module Comprising an Ethylene Multi-Block Copolymer |
| JP5394840B2 (en) * | 2009-07-15 | 2014-01-22 | ユニチカ株式会社 | Etching protection material |
| US20130008506A1 (en) | 2010-02-02 | 2013-01-10 | Zeon Corporation | Resin composition for encapsulating solar cell and solar module |
| EP2623526B1 (en) | 2010-09-29 | 2017-07-26 | Zeon Corporation | Hydrogenated block copolymer having alkoxysilyl group, and use therefor |
| JP5820132B2 (en) * | 2011-03-09 | 2015-11-24 | 株式会社ブリヂストン | Solar cell sealing film and solar cell using the same |
| US9493688B2 (en) | 2012-11-15 | 2016-11-15 | Zeon Corporation | Resin composition and molded article comprising same |
| JP2015151540A (en) * | 2014-02-19 | 2015-08-24 | シーアイ化成株式会社 | resin film |
| CN104356982A (en) * | 2014-11-13 | 2015-02-18 | 无锡中洁能源技术有限公司 | Solar cell back panel insulating rubber and preparation method thereof |
-
1993
- 1993-04-14 JP JP10985393A patent/JP3510645B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8168885B2 (en) | 2007-02-12 | 2012-05-01 | E.I. Du Pont De Nemours And Company | Low modulus solar cell encapsulant sheets with enhanced stability and adhesion |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06299125A (en) | 1994-10-25 |
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