JP2006036876A - Sealing material for solar battery and solar battery module using the same - Google Patents
Sealing material for solar battery and solar battery module using the same Download PDFInfo
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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
- B32B17/10788—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
Abstract
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用エチレン共重合体組成物及び該エチレン共重合体組成物からなる封止材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、柔軟性、加工性、接着性、架橋性、絶縁性に優れ、太陽電池素子の下部側に好適に使用される封止材用エチレン共重合体組成物及び該エチレン共重合体組成物からなる封止材を使用した太陽電池モジュールに関する。 The present invention relates to an ethylene copolymer composition for sealing a solar cell for fixing a solar cell element in a solar cell module, and a solar cell in which the solar cell element is sealed with a sealing material comprising the ethylene copolymer composition. Regarding modules. More specifically, it is excellent in flexibility, workability, adhesiveness, crosslinkability, insulation, and is preferably used for the lower side of the solar cell element, and an ethylene copolymer composition for a sealing material and the ethylene copolymer composition. The present invention relates to a solar cell module using a sealing material made of a material.
無尽蔵な自然エネルギーを利用し、二酸化炭素の削減やその他の環境問題の改善が図れる水力発電、風力発電並びに太陽光発電など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、近年その普及が著しく進んでいる。 Hydroelectric power generation, wind power generation, and solar power generation, which use inexhaustible natural energy to reduce carbon dioxide and improve other environmental problems, are in the spotlight. Among these, solar power generation has seen remarkable improvements in performance, such as power generation efficiency of solar cell modules, but the price has declined and the national and local governments have promoted the introduction of residential solar power generation systems. Its spread is remarkably advanced.
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。この封止材は、透明で光による発電を阻害しないこと、熱によって溶け出し、崩れるようなことはしないこと（耐熱性）、保護材であるガラスやバックシートとの接着が良好であること、太陽光によって著しい劣化や黄変を起こさないことなど、様々な性能が求められ、これを満たすために種々の配合処方が検討されている。例えば、透明性、耐熱性、接着性、柔軟性、成形性、耐久性などを勘案した代表的な処方として、エチレン・酢酸ビニル共重合体に有機過酸化物及びシランカップリング剤の配合物を太陽電池封止材として使用することが知られている（例えば特許文献１参照）。この提案における具体的な配合例においては、耐熱性や接着性を重視するところから、有機過酸化物やシランカップリング剤はかなり多量に配合されている。 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 sealing materials to prevent foreign substances from entering and moisture from entering together with buffering. This sealing material is transparent and does not impede power generation by light, does not melt or break down by heat (heat resistance), has good adhesion to the protective material glass or backsheet, Various performances, such as not causing remarkable deterioration and yellowing by sunlight, are required, and various compounding formulas are being studied to satisfy this. For example, as a typical formulation considering transparency, heat resistance, adhesiveness, flexibility, moldability, durability, etc., a blend of an organic peroxide and a silane coupling agent is added to an ethylene / vinyl acetate copolymer. It is known to use as a solar cell sealing material (see, for example, Patent Document 1). In a specific blending example in this proposal, the organic peroxide and the silane coupling agent are blended in a considerably large amount because importance is placed on heat resistance and adhesiveness.
その一方で太陽電池では、発電した電気を確実に配線を経由して取り出せることが必要であり、そのため封止材には、電気がリークしない電気絶縁性が求められている。例えば、ＪＩＳ Ｃ８９１７においては、モジュールの耐久試験において、高温試験（８５℃×１０００時間）、耐湿試験（８５℃×９０±５％ＲＨ）で絶縁特性が１００ＭΩ以上あることが規定されている。しかるに上記提案において具体例で示された封止材では、絶縁抵抗率が低下する場合があり、配合処方によっては問題になることがあった。とくに近年、下部保護材側の封止材には、酸化チタンを配合することによって発電効率を高めることが行なわれているが、酸化チタンを配合したエチレン・極性モノマー共重合体封止材、例えば０．５重量％以上の酸化チタンを配合したエチレン・極性モノマー共重合体封止材においては、とくに絶縁抵抗率の低下が大きくなることを見出した。 On the other hand, in the solar cell, it is necessary to reliably take out the generated electricity via the wiring. Therefore, the sealing material is required to have an electrical insulation property that does not leak electricity. For example, JIS C8917 stipulates that the insulation characteristics of a module endurance test are 100 MΩ or more in a high temperature test (85 ° C. × 1000 hours) and a moisture resistance test (85 ° C. × 90 ± 5% RH). However, in the sealing materials shown in the specific examples in the above proposal, the insulation resistivity may be lowered, which may cause a problem depending on the formulation. In particular, in recent years, the sealing material on the lower protective material side has been improved to improve power generation efficiency by blending titanium oxide, but an ethylene / polar monomer copolymer sealing material blended with titanium oxide, for example, In the ethylene / polar monomer copolymer encapsulant containing 0.5% by weight or more of titanium oxide, the inventors have found that the decrease in insulation resistivity is particularly large.
そこで本発明の目的は、酸化チタンのような白色系無機顔料を配合した太陽電池封止材においても、耐熱性、接着性、柔軟性、成形性、耐久性などが優れると共に、絶縁抵抗の低下を防ぎ、絶縁特性に優れた封止材となり得るエチレン共重合体組成物及び該エチレン共重合体組成物からなる封止材により太陽電池素子を封止してなる太陽電池モジュールを提供することにある。 Therefore, the object of the present invention is to provide a solar cell encapsulating material containing a white inorganic pigment such as titanium oxide, which has excellent heat resistance, adhesiveness, flexibility, moldability, durability, etc., and a decrease in insulation resistance. To provide a solar cell module in which a solar cell element is sealed with an ethylene copolymer composition that can serve as a sealing material that is excellent in insulating properties and a sealing material that comprises the ethylene copolymer composition is there.
すなわち本発明によれば、エチレン・極性モノマー共重合体に白色系無機顔料、架橋剤及びアリル基及び／又は（メタ）アクリロキシ基を含有する架橋助剤を配合してなる太陽電池封止用エチレン共重合体組成物が提供される。このようなエチレン共重合体組成物には、好ましくはさらにシランカップリング剤が配合される。 That is, according to the present invention, an ethylene / polar monomer copolymer is blended with a white inorganic pigment, a crosslinking agent and a crosslinking aid containing an allyl group and / or a (meth) acryloxy group. A copolymer composition is provided. In such an ethylene copolymer composition, a silane coupling agent is preferably further blended.
本発明によればまた、上記エチレン共重合体組成物からなる封止材及び該封止材で太陽電池素子が封止されてなる太陽電池モジュールが提供される。とりわけ太陽電池素子が、無機顔料不含の架橋された透明な太陽電池封止材と白色系無機顔料を含有する上記架橋されたエチレン共重合体組成物からなる封止材とにより封止されてなる太陽電池モジュールが提供される。 According to this invention, the solar cell module by which a solar cell element is sealed with the sealing material which consists of the said ethylene copolymer composition, and this sealing material is provided. In particular, the solar cell element is encapsulated with a crosslinked transparent solar cell encapsulant containing no inorganic pigment and an encapsulant made of the above crosslinked ethylene copolymer composition containing a white inorganic pigment. A solar cell module is provided.
本発明によれば、耐熱性、接着性、柔軟性、成形性、耐久性などが優れると共に、絶縁特性の優れた白色系太陽電池封止材及び該封止材により太陽電池素子を封止してなる太陽電池モジュールを提供することができる。 According to the present invention, heat resistance, adhesiveness, flexibility, moldability, durability, etc. are excellent, and a white solar cell encapsulant with excellent insulating properties and a solar cell element are encapsulated with the encapsulant. A solar cell module can be provided.
本発明における太陽電池封止用エチレン共重合体組成物は、エチレン・極性モノマー共重合体に必須成分として白色系無機顔料、架橋剤及びアリル基及び／又は（メタ）アクリロキシ基を有する架橋助剤を必須成分として含有するものである。上記エチレン・極性モノマー共重合体の極性モノマーとしては、酢酸ビニル、プロピオン酸ビニルのようなビニルエステル、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸イソブチル、アクリル酸ｎ−ブチル、アクリル酸イソオクチル、メタクリル酸メチル、メタクリル酸イソブチル、マレイン酸ジメチル等の不飽和カルボン酸エステル、アクリル酸、メタクリル酸、フマル酸、イタコン酸、マレイン酸モノメチル、マレイン酸モノエチル、無水マレイン酸、無水イタコン酸等の不飽和カルボン酸、これら不飽和カルボン酸の塩、一酸化炭素、二酸化硫黄などの一種又は二種以上などを例示することができる。不飽和カルボン酸の塩としては、リチウム、ナトリウム、カリウムなどの１価金属、マグネシウム、カルシウム、亜鉛などの多価金属の塩などを挙げることができる。 The ethylene copolymer composition for encapsulating solar cells in the present invention is a crosslinking aid having a white inorganic pigment, a crosslinking agent and an allyl group and / or a (meth) acryloxy group as essential components in the ethylene / polar monomer copolymer. Is contained as an essential component. Examples of polar monomers of the ethylene / polar monomer copolymer include vinyl acetate, vinyl esters such as vinyl propionate, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, and acrylic acid. Unsaturated carboxylic acid esters such as isooctyl, methyl methacrylate, isobutyl methacrylate, dimethyl maleate, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride, etc. Examples thereof include one or more of unsaturated carboxylic acids, salts of these unsaturated carboxylic acids, carbon monoxide, sulfur dioxide, and the like. Examples of the salt of the unsaturated carboxylic acid include salts of monovalent metals such as lithium, sodium and potassium, and salts of polyvalent metals such as magnesium, calcium and zinc.
好適なエチレン・極性モノマー共重合体としてより具体的には、エチレン・酢酸ビニル共重合体のようなエチレン・ビニルエステル共重合体、エチレン・アクリル酸メチル共重合体、エチレン・アクリル酸エチル共重合体、エチレン・メタクリル酸メチル共重合体、エチレン・アクリル酸イソブチル共重合体、エチレン・アクリル酸ｎ−ブチル共重合体のようなエチレン・不飽和カルボン酸エステル共重合体、エチレン・アクリル酸共重合体、エチレン・メタクリル酸共重合体、エチレン・アクリル酸イソブチル・メタクリル酸共重合体のようなエチレン・不飽和カルボン酸共重合体及びそのアイオノマーなどを代表例として例示することができる。これらの中では、エチレン・酢酸ビニル共重合体又はエチレン・（メタ）アクリル酸エステル共重合体が特に好ましい。 More specifically, preferred ethylene / polar monomer copolymers include ethylene / vinyl ester copolymers such as ethylene / vinyl acetate copolymers, ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers. Ethylene / methyl methacrylate copolymer, ethylene / isobutyl acrylate copolymer, ethylene / unsaturated carboxylic acid ester copolymer such as ethylene / n-butyl acrylate copolymer, ethylene / acrylic acid copolymer Typical examples include a polymer, an ethylene / methacrylic acid copolymer, an ethylene / unsaturated carboxylic acid copolymer such as an ethylene / isobutyl acrylate / methacrylic acid copolymer, and an ionomer thereof. Among these, an ethylene / vinyl acetate copolymer or an ethylene / (meth) acrylic ester copolymer is particularly preferable.
本発明において使用されるエチレン・極性モノマー共重合体における好適な極性モノマー含量は、その種類によっても若干異なる。例えばエチレン・酢酸ビニル共重合体やエチレン・不飽和カルボン酸エステル共重合体の場合には、耐熱性、接着性、柔軟性、成形性、耐久性、絶縁性などを考慮すると、極性モノマー含有量が１０〜４０重量％、好ましくは１５〜３０重量％のものが好ましく、またエチレン・不飽和カルボン酸共重合体又はそのアイオノマーにおいては、エチレン含量が６５〜９５重量％、好ましくは７０〜９０重量％、不飽和カルボン酸含量が２〜２０重量％、好ましくは５〜２０重量％、中和度が９０％以下、好ましくは８０％以下のものが好ましい。 The suitable polar monomer content in the ethylene / polar monomer copolymer used in the present invention is slightly different depending on the kind. For example, in the case of ethylene / vinyl acetate copolymer or ethylene / unsaturated carboxylic acid ester copolymer, polar monomer content considering heat resistance, adhesiveness, flexibility, moldability, durability, insulation, etc. Is 10 to 40% by weight, preferably 15 to 30% by weight. In the ethylene / unsaturated carboxylic acid copolymer or its ionomer, the ethylene content is 65 to 95% by weight, preferably 70 to 90% by weight. %, Unsaturated carboxylic acid content is 2 to 20% by weight, preferably 5 to 20% by weight, and neutralization degree is 90% or less, preferably 80% or less.
このようなエチレン・極性モノマー共重合体としては、成形加工性、機械的強度などを考慮すると、ＪＩＳ Ｋ７２１０−１９９９、１９０℃、２１６０ｇ荷重におけるメルトフローレート（ＭＦＲ、以下同じ）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。これらエチレン・酢酸ビニル共重合体、エチレン・不飽和カルボン酸エステル共重合体及びエチレン・不飽和カルボン酸共重合体は、高温、高圧下のラジカル共重合により得ることができる。またエチレン・不飽和カルボン酸共重合体のアイオノマーは、エチレン・不飽和カルボン酸共重合体と金属化合物を反応させることによって得ることができる。 As such an ethylene / polar monomer copolymer, in consideration of molding processability, mechanical strength, and the like, the melt flow rate (MFR, the same applies hereinafter) at JIS K7210-1999, 190 ° C. and 2160 g load is 1 to 100 g / It is preferred to use 10 minutes, in particular 5 to 50 g / 10 minutes. These ethylene / vinyl acetate copolymers, ethylene / unsaturated carboxylic acid ester copolymers and ethylene / unsaturated carboxylic acid copolymers can be obtained by radical copolymerization under high temperature and high pressure. An ionomer of an ethylene / unsaturated carboxylic acid copolymer can be obtained by reacting an ethylene / unsaturated carboxylic acid copolymer with a metal compound.
本発明において、上記エチレン・極性モノマー共重合体に配合される白色系無機顔料は、着色あるいは発電効率向上のために配合するものであって、例えば酸化チタン、炭酸カルシウム、亜鉛華、鉛白、リトポン、バライト、沈降性硫酸バリウム、石膏などを例示することができる。とくに太陽電池素子の受光側と反対面の封止材に使用するときに、発電効率の向上に効果的であるところから、酸化チタンを使用するのが好ましい。無機顔料の好適な配合量は、発電効率、絶縁抵抗などを考慮すると、エチレン・極性モノマー共重合体１００重量部当たり、０．５〜１００重量部、好ましくは０．５〜５０重量部、特に好ましくは４〜５０重量部の範囲である。 In the present invention, the white inorganic pigment blended in the ethylene / polar monomer copolymer is blended for coloring or improving power generation efficiency, and includes, for example, titanium oxide, calcium carbonate, zinc white, lead white, Examples include lithopone, barite, precipitated barium sulfate, and gypsum. In particular, when used as a sealing material on the surface opposite to the light receiving side of the solar cell element, it is preferable to use titanium oxide because it is effective in improving the power generation efficiency. A suitable blending amount of the inorganic pigment is 0.5 to 100 parts by weight, preferably 0.5 to 50 parts by weight, particularly 100 parts by weight of the ethylene / polar monomer copolymer, in consideration of power generation efficiency, insulation resistance and the like. Preferably it is the range of 4-50 weight part.
本発明の太陽電池封止用エチレン共重合体組成物には、太陽電池モジュールに組み込まれた状態における高温使用時の溶融流れ防止等の耐熱性を付与するために、架橋剤が配合される。架橋剤としては、太陽電池モジュールの生産性を考慮すると、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（１１９℃）、第３ブチルパーオキシ−２−エチルヘキシルイソプロピルカーボネート（１２１℃）、第３ブチルパーオキシアセテート（１２３℃）、第３ブチルパーオキシベンゾエート（１２５℃）、第３ブチルクミルパーオキサイド（１４２℃）、ジクミルパーオキサイド（１３５℃）、２，５−ジメチル−２，５−ビス（第３ブチルパーオキシ）ヘキサン（１４０℃）、ジ第３ブチルパーオキサイド（１４９℃）、１，３−ビス（２−第３ブチルパーオキシイソプロピル）ベンゼン（１３７℃）、２，５−ジメチル−２，５−ビス（ベンゾイルパーオキシ）ヘキサン（１１８℃）、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（１１２℃）、１，１−ビス（第３ブチルパーオキシ）シクロヘキサン（１１２℃）、１，１−ビス（第３アミルパーオキシ）シクロヘキサン（１１２℃）、２，２−ビス（第３ブチルパーオキシ）ブタン（１１２℃）、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（１０２℃）、ｎ−ブチル−４，４−ビス（第３ブチルパーオキシ）バレレート（１２９℃）、エチル−３，３−ビス（第３ブチルパーオキシ）ブチレート（１３５℃）、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（括弧内の温度は１時間半減期温度）。架橋剤はエチレン・極性モノマー共重合体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 ethylene copolymer composition for sealing a solar cell of the present invention is blended with a crosslinking agent in order to impart heat resistance such as prevention of melt flow during use at a high temperature in a state of being incorporated in a solar cell module. In consideration of the productivity of the solar cell module, it is preferable to use an organic peroxide having a decomposition temperature (a half-life of 1 hour) of 90 to 180 ° C., particularly 100 to 150 ° C., as the crosslinking agent. Examples of such organic peroxides include tertiary butyl peroxyisopropyl carbonate (119 ° C.), tertiary butyl peroxy-2-ethylhexyl isopropyl carbonate (121 ° C.), tertiary butyl peroxyacetate (123 ° C.), third Butyl peroxybenzoate (125 ° C.), tertiary butyl cumyl peroxide (142 ° C.), dicumyl peroxide (135 ° C.), 2,5-dimethyl-2,5-bis (tertiary butyl peroxy) hexane (140 ° C), di-tert-butyl peroxide (149 ° C), 1,3-bis (2-tert-butylperoxyisopropyl) benzene (137 ° C), 2,5-dimethyl-2,5-bis (benzoylperoxy) ) Hexane (118 ° C.), 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyl -3,1,1-bis (tertiary butyl peroxy) -3,3,5-trimethylcyclohexane (112 ° C.), 1,1-bis (tertiary butyl peroxy) cyclohexane (112 ° C.), 1,1 -Bis (tertiary amylperoxy) cyclohexane (112 ° C), 2,2-bis (tertiarybutylperoxy) butane (112 ° C), methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-bisper Oxybenzoate, tertiary butyl hydroperoxide, p-menthane hydroperoxide, benzoyl peroxide, p-chlorobenzoyl peroxide, tertiary butyl peroxyisobutyrate (102 ° C.), n-butyl-4,4-bis (Tertiary butyl peroxy) valerate (129 ° C.), ethyl-3,3-bis (tertiary butyl pero Shi) butyrate (135 ° C.), hydroxyheptyl peroxide, the temperature of the di-cyclohexanone etc. peroxide (the parenthesized data are 1 hour half-life temperature). It is effective to add the crosslinking agent in an amount of 0.1 to 5 parts by weight, particularly 0.5 to 3 parts by weight, based on 100 parts by weight of the ethylene / polar monomer copolymer.
架橋剤として有機過酸化物を使用する代わりに、光によりエチレン共重合体組成物の架橋が可能となるように光増感剤を使用することもできる。光増感剤としては、例えば、ベンゾイン、ベンゾフェノン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ジベンジル、５−ニトロアセナフテン、ヘキサクロロシクロペンタジエン、パラニトロジフェニル、パラニトロアニリン、２，４，６−トリニトロアニリン、１，２−ベンズアントラキノン、３−メチル−１，３−ジアザー１，９−ベンザンスロンなどを上げることができる。これら光増感剤は、エチレン・極性モノマー共重合体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。 Instead of using an organic peroxide as a crosslinking agent, a photosensitizer can also be used so that the ethylene copolymer composition can be crosslinked by light. Examples of the photosensitizer include benzoin, benzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 5-nitroacenaphthene, hexachlorocyclopentadiene, paranitrodiphenyl, paranitroaniline, 2 , 4,6-trinitroaniline, 1,2-benzanthraquinone, 3-methyl-1,3-diazer 1,9-benzanthrone and the like. These photosensitizers are effectively blended in an amount of 0.1 to 5 parts by weight, particularly 0.5 to 3 parts by weight, based on 100 parts by weight of the ethylene / polar monomer copolymer.
本発明において、上記エチレン・極性モノマー共重合体に配合される架橋助剤は、アリル基や（メタ）アクリロキシ基などの不飽和基を１個以上、好ましくは２個以上有する化合物であり、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などを挙げることができる。これらの中では、とくにトリアリルイソシアヌレートやジアリルフタレートが架橋特性、耐久性の点から好適である。このような架橋助剤の配合は、ゲル分率の向上及び絶縁抵抗の低下防止に効果的である。架橋助剤はエチレン・極性モノマー共重合体１００重量部に対し、０．１〜５重量部、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。 In the present invention, the crosslinking auxiliary compounded in the ethylene / polar monomer copolymer is a compound having one or more, preferably two or more unsaturated groups such as an allyl group or a (meth) acryloxy group. Specifically, polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, poly ( And a (meth) acryloxy compound. Of these, triallyl isocyanurate and diallyl phthalate are particularly preferred from the viewpoint of crosslinking characteristics and durability. The blending of such a crosslinking aid is effective for improving the gel fraction and preventing the insulation resistance from decreasing. It is effective to add the crosslinking aid in an amount of 0.1 to 5 parts by weight, particularly 0.1 to 3 parts by weight, based on 100 parts by weight of the ethylene / polar monomer copolymer.
本発明の太陽電池封止材においては、太陽電池素子や保護材との接着性改良のために上記エチレン・極性モノマー共重合体にシランカップリング剤を適量配合することが好ましい。このようなシランカップリング剤としては、ビニル基や（メタ）アクリロキシ基のような不飽和基、ハロアルキル基、アミノ基、メルカプト基及びエポキシ基から選ばれる基とともに、アルコキシ基、アシル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を挙げることができる。これらの具体例としては、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、ビニルトリアセトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、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−メルカプトプロピルトリエトキシシランなどを例示することができる。これらの中では、少量の使用で接着性改良効果の大きいことから、γ−メタクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシランなどを使用することが好ましい。これらシランカップリング剤は、接着性改良効果及び絶縁抵抗を考慮すると、エチレン・極性モノマー共重合体１００重量部に対し、０．０００１〜１．０重量部、とくに０．０１〜１．０重量部の割合で配合するのが効果的である。 In the solar cell encapsulating material of the present invention, it is preferable to add an appropriate amount of a silane coupling agent to the ethylene / polar monomer copolymer in order to improve adhesion to the solar cell element and the protective material. Such silane coupling agents include groups selected from unsaturated groups such as vinyl groups and (meth) acryloxy groups, haloalkyl groups, amino groups, mercapto groups and epoxy groups, as well as alkoxy groups and acyl groups. A silane coupling agent having a hydrolyzable group can be mentioned. Specific examples thereof include vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxy. Examples include silane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. it can. Among these, it is preferable to use γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and the like because a small amount of use has a large effect of improving adhesiveness. These silane coupling agents are in the range of 0.0001 to 1.0 parts by weight, particularly 0.01 to 1.0 parts by weight, based on 100 parts by weight of the ethylene / polar monomer copolymer, in view of the adhesive improvement effect and the insulation resistance. It is effective to mix in proportions of parts.
また太陽光線中の紫外線に基づく封止材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、例えば各種ヒンダードフェノール系やホスファイト系のものが好適に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などが使用できる。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・極性モノマー共重合体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 sealing material based on ultraviolet rays in sunlight, it is effective to blend at least one of an antioxidant, a light stabilizer, and an ultraviolet absorber. As the antioxidant, for example, various hindered phenols and phosphites can be preferably used. 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, and 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, 2- (2′-hydroxy-5-third octylphenyl) benzotriazole, salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate are used. it can. These antioxidants, light stabilizers, and ultraviolet absorbers are each effective 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 ethylene / polar monomer copolymer. Is.
本発明の太陽電池封止用エチレン共重合体組成物にはまた、任意にその他添加剤を配合することができる。例えば変色防止剤として、カドミウム、バリウム等の金属の脂肪酸塩を配合することができる。また下部保護材側の封止材においては、透明性は要求されないので、着色、発電効率向上などの目的で、有機顔料、染料、無機充填剤などを配合することができる。例えばガラスビーズや光拡散剤などを例示することができる。 The ethylene copolymer composition for sealing a solar cell of the present invention can also optionally contain other additives. For example, a fatty acid salt of a metal such as cadmium or barium can be blended as a discoloration preventing agent. Also, since the sealing material on the lower protective material side does not require transparency, organic pigments, dyes, inorganic fillers, and the like can be blended for the purpose of coloring and improving power generation efficiency. For example, glass beads and light diffusing agents can be exemplified.
上記本発明のエチレン共重合体組成物は、一般にはシート状に成形して太陽電池封止材として使用される。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・極性モノマー共重合体、白色系無機顔料、有機過酸化物及び架橋助剤、必要に応じて添加されるシランカップリング剤、その他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、有機過酸化物を配合する場合にはそれ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。勿論、上記各種添加剤は、マスターバッチにより添加することができる。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。太陽電池素子の封止状態においては、上記本発明のエチレン共重合体組成物は、耐熱性の面から、エチレン共重合体が架橋されていることが好ましい。この場合、エチレン共重合体組成物の架橋度（後述するゲル分率）は、絶縁特性を考慮すると、７０〜９８％の範囲にあることが好ましく、特に８０〜９８％の範囲にあることが好ましい。架橋は、本発明のエチレン共重合体組成物を１００〜２００℃程度に加熱することによって行なうことができる。 The ethylene copolymer composition of the present invention is generally shaped into a sheet and used as a solar cell encapsulant. The sealing material sheet can be molded by a known method using a T-die extruder, a calendar molding machine, an inflation molding machine, or the like. For example, an extruder hopper is prepared by dry blending an ethylene / polar monomer copolymer, a white inorganic pigment, an organic peroxide and a crosslinking aid, a silane coupling agent added if necessary, and other additives in advance. When an organic peroxide is blended, it can be obtained by extrusion molding into a sheet at a molding temperature at which it does not substantially decompose. Of course, the above-mentioned various additives can be added by a master batch. The sheet thickness is not particularly defined, but is usually about 0.2 to 1.2 mm. In the sealed state of the solar cell element, it is preferable that the ethylene copolymer composition of the present invention is crosslinked from the viewpoint of heat resistance. In this case, the degree of crosslinking (gel fraction described later) of the ethylene copolymer composition is preferably in the range of 70 to 98%, particularly in the range of 80 to 98% in consideration of the insulating properties. preferable. Crosslinking can be performed by heating the ethylene copolymer composition of the present invention to about 100 to 200 ° C.
このような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を挙げることができる。このような構成の太陽電池モジュールにおいては、下部保護材側の封止材として本発明のものを使用し、上部透明保護材の封止材としては透明性良好なものを使用する必要性があるところから、本発明の封止剤から無機顔料を除いた架橋性エチレン共重合体組成物を用いるのが好ましい。また他のタイプの太陽電池モジュールとして、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を例示することができ、この封止材用シートとして本発明のエチレン共重合体組成物を使用することができる。 A solar cell module can be manufactured by fixing a solar cell element with an upper and lower protective material using such a sheet | seat for sealing materials. Examples of such solar cell modules include various types. For example, the thing of the structure pinched | interposed by the sealing material from the both sides of a solar cell element like upper transparent protective material / sheet for sealing material / solar cell element / sheet for sealing material / lower protective material can be mentioned. In the solar cell module having such a configuration, it is necessary to use the material of the present invention as the sealing material on the lower protective material side and to use a material with good transparency as the sealing material of the upper transparent protective material. Therefore, it is preferable to use a crosslinkable ethylene copolymer composition obtained by removing the inorganic pigment from the sealing agent of the present invention. In addition, as another type of solar cell module, a solar cell element formed on the inner peripheral surface of the upper transparent protective material, for example, an amorphous solar cell element formed on a fluororesin-based sheet by sputtering or the like, and a sealing material The structure of forming the sheet | seat for a sheet | seat and a lower protective material can be illustrated, and the ethylene copolymer composition of this invention can be used as this sheet | seat for sealing materials.
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 sealing material of the present invention is particularly useful for sealing an amorphous solar cell element such as 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 sealing material 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重量分率を測定）が、好ましくは７０〜９８％、特に好ましくは８０〜９８％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. The weight fraction of the unmelted portion is preferably 70 to 98%, particularly preferably about 80 to 98%. 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及び物性評価方法を以下に示す。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the raw material and physical-property evaluation method which were used by the Example and the comparative example are shown below.
１．原料
（１）ＥＶＡ樹脂Ａ：エチレン・酢酸ビニル共重合体（酢酸ビニル含量：２８重量％、ＭＦＲ：１５ｇ／１０分）
（２）ＥＶＡ樹脂Ｂ：エチレン・酢酸ビニル共重合体（酢酸ビニル含量：１９重量％、ＭＦＲ：１５ｇ／１０分）
（３）白色ＭＢ：ＴｉＯ２６０重量％配合マスターバッチ、ベースポリマーは上記ＥＶＡ樹脂Ａ
（４）架橋剤Ａ：２，５−ジメチル−２，５−ビス（第３ブチルパーオキシ）ヘキサン、商品名：ルパゾール１０１、アトフィナ吉富（株）製、１時間半減期温度：１４０℃
（５）架橋剤Ｂ：第３ブチルパーオキシ−２−エチルヘキシルカーボネート、商品名：ルパゾールＴＢＥＣ、アトフィナ吉富（株）製、１時間半減期温度：１２１℃
（６）架橋助剤：トリアリルイソシアヌレート（ＴＡＩＣ）、関東化学（株）製
（７）シランカップリング剤：γ−メタクリロキシプロピルトリメトキシシラン、商品名：ＫＢＭ５０３、信越化学（株）製
1. Raw material (1) EVA resin A: ethylene / vinyl acetate copolymer (vinyl acetate content: 28 wt%, MFR: 15 g / 10 min)
(2) EVA resin B: ethylene / vinyl acetate copolymer (vinyl acetate content: 19% by weight, MFR: 15 g / 10 min)
(3) White MB: TiO 2 60 wt% blended masterbatch, base polymer is the above EVA resin A
(4) Crosslinking agent A: 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, trade name: Lupazole 101, manufactured by Atofina Yoshitomi Co., Ltd., 1 hour half-life temperature: 140 ° C.
(5) Crosslinking agent B: tertiary butyl peroxy-2-ethylhexyl carbonate, trade name: Lupazole TBEC, manufactured by Atofina Yoshitomi, 1 hour half-life temperature: 121 ° C.
(6) Crosslinking assistant: triallyl isocyanurate (TAIC), manufactured by Kanto Chemical Co., Ltd. (7) Silane coupling agent: γ-methacryloxypropyltrimethoxysilane, trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.
２．物性測定方法
（１）ゲル分率の測定
下記例におけるコンパウンドを、１５０℃の圧縮成形機を用いて１５分間加圧下で加熱することにより、厚み１ｍｍの架橋シートを作成した。この架橋シートから約１ｇを精秤して（Ｗ１）、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て１１０℃で真空乾燥し、その重量を求めた（Ｗ２）。ゲル分率は、以下の式により求めた。
ゲル分率（％）＝Ｗ２／Ｗ１×１００
2. Physical property measurement method (1) Measurement of gel fraction The compound in the following example was heated under pressure for 15 minutes using a compression molding machine at 150 ° C. to prepare a 1 mm thick crosslinked sheet. About 1 g of this cross-linked sheet is precisely weighed (W1), immersed in 100 ml of xylene, heated at 110 ° C. for 24 hours, filtered through a wire mesh to collect the insoluble matter and vacuum dried at 110 ° C. The weight was determined (W2). The gel fraction was determined by the following formula.
Gel fraction (%) = W2 / W1 × 100
（２）絶縁抵抗値
前記（１）の手段により作成した架橋シートを、ＪＩＳ Ｋ−６９１１に従い、所定のダンベルに打ち抜き、８５℃、８５％ＲＨの条件に放置し、初期値、１週間後及び３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。
(2) Insulation resistance value The cross-linked sheet prepared by the means of (1) above is punched into a predetermined dumbbell according to JIS K-6911 and left under conditions of 85 ° C. and 85% RH. The insulation resistance after 3 weeks was measured using a volume resistivity meter (manufactured by Aligent Technologies) under the conditions of 1000 V and a heating time of 60 seconds.
［実施例１］
上記ＥＶＡ樹脂Ａペレットを４５８５ｇ、白色ＭＢを４１５ｇ、架橋剤Ａ（商品名：ルパゾール１０１）を６０ｇ、架橋助剤（ＴＡＩＣ）を１００ｇ及びシランカップリング剤（商品名：ＫＢＭ５０３）を２５ｇ混合し、含浸のため一昼夜放置した。得られた含浸ペレットを、押出機（Ｌ／Ｄ＝２６、フルフライトスクリュー、圧縮比２．６）を用いて加工温度１００℃にて混練し、均一なコンパウンドとした。得られたコンパウンドを用いて、上記（１）〜（２）の方法により、ゲル分率及び絶縁抵抗を評価した。結果を表１に示す。
[Example 1]
4585 g of the above EVA resin A pellet, 415 g of white MB, 60 g of crosslinking agent A (trade name: Lupazole 101), 100 g of crosslinking aid (TAIC) and 25 g of silane coupling agent (trade name: KBM503) are mixed. It was left overnight for impregnation. The obtained impregnated pellets were kneaded using an extruder (L / D = 26, full flight screw, compression ratio 2.6) at a processing temperature of 100 ° C. to obtain a uniform compound. Using the obtained compound, the gel fraction and the insulation resistance were evaluated by the methods (1) to (2) above. The results are shown in Table 1.
［実施例２］
実施例１において、シランカップリング剤（商品名：ＫＢＭ５０３）の使用量を５ｇに変更した以外は、実施例１と同様に行なった。得られたコンパウンドを用いて、上記（１）〜（２）の方法により、ゲル分率及び絶縁抵抗を評価した。結果を表１に示す。
[Example 2]
In Example 1, it carried out like Example 1 except having changed the usage-amount of the silane coupling agent (brand name: KBM503) into 5 g. Using the obtained compound, the gel fraction and the insulation resistance were evaluated by the methods (1) to (2) above. The results are shown in Table 1.
［実施例３］
実施例１において、ＥＶＡ樹脂Ａ４５８５ｇの代わりにＥＶＡ樹脂Ａ２２９２．５ｇ、ＥＶＡ樹脂Ｂを２２９２．５ｇとし、シランカップリング剤（商品名：ＫＢＭ５０３）の使用量を５ｇに変更した以外は、実施例１と同様に行なった。得られたコンパウンドを用いて、上記（１）〜（２）の方法により、ゲル分率及び絶縁抵抗を評価した。結果を表１に示す。
[Example 3]
Example 1 except that EVA resin A 2292.5 g and EVA resin B were changed to 2292.5 g instead of EVA resin A 4585 g, and the amount of the silane coupling agent (trade name: KBM503) was changed to 5 g in Example 1. It carried out like. Using the obtained compound, the gel fraction and the insulation resistance were evaluated by the methods (1) to (2) above. The results are shown in Table 1.
［比較例１］
架橋助剤を配合しなかった以外は、実施例１と同様に行なった。得られたコンパウンドを用いて、上記（１）〜（２）の方法により、ゲル分率及び絶縁抵抗を評価した。結果を表１に示す。
[Comparative Example 1]
The same procedure as in Example 1 was carried out except that no crosslinking aid was added. Using the obtained compound, the gel fraction and the insulation resistance were evaluated by the methods (1) to (2) above. The results are shown in Table 1.
［比較例２］
架橋助剤を配合しなかった以外は、実施例２と同様に行なった。得られたコンパウンドを用いて、上記（１）〜（２）の方法により、ゲル分率及び絶縁抵抗を評価した。結果を表１に示す
[Comparative Example 2]
The same procedure as in Example 2 was performed except that the crosslinking aid was not blended. Using the obtained compound, the gel fraction and the insulation resistance were evaluated by the methods (1) to (2) above. The results are shown in Table 1.
［比較例３］
架橋助剤を配合しなかった以外は、実施例３と同様に行なった。得られたコンパウンドを用いて、上記（１）〜（２）の方法により、ゲル分率及び絶縁抵抗を評価した。結果を表１に示す。
[Comparative Example 3]
The same procedure as in Example 3 was performed except that no crosslinking aid was added. Using the obtained compound, the gel fraction and the insulation resistance were evaluated by the methods (1) to (2) above. The results are shown in Table 1.
［比較例４］
架橋剤Ａの代わりに架橋剤Ｂ（ルパゾールＴＢＥＣ）を用い、架橋助剤を配合しなかった以外は、実施例１と同様に行なった。得られたコンパウンドを用いて、上記（１）〜（２）の方法により、ゲル分率及び絶縁抵抗を評価した。結果を表１に示す。
[Comparative Example 4]
The same procedure as in Example 1 was performed except that the crosslinking agent B (Lupazole TBEC) was used in place of the crosslinking agent A and no crosslinking assistant was added. Using the obtained compound, the gel fraction and the insulation resistance were evaluated by the methods (1) to (2) above. The results are shown in Table 1.
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