JP7023362B2 - 組成物、塗料、塗膜、太陽電池モジュールのバックシート、及び、太陽電池モジュール - Google Patents
組成物、塗料、塗膜、太陽電池モジュールのバックシート、及び、太陽電池モジュール Download PDFInfo
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- JP7023362B2 JP7023362B2 JP2020528287A JP2020528287A JP7023362B2 JP 7023362 B2 JP7023362 B2 JP 7023362B2 JP 2020528287 A JP2020528287 A JP 2020528287A JP 2020528287 A JP2020528287 A JP 2020528287A JP 7023362 B2 JP7023362 B2 JP 7023362B2
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- Prior art keywords
- coating film
- group
- acid
- vinyl
- solar cell
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- Y02E10/50—Photovoltaic [PV] energy
Description
以下に本発明を詳細に説明する。
中でも、テトラフルオロエチレン、クロロトリフルオロエチレン、及び、ビニリデンフルオライドからなる群より選択される少なくとも1種であることが好ましく、テトラフルオロエチレン及びクロロトリフルオロエチレンからなる群より選択される少なくとも1種であることがより好ましい。
水酸基含有単量体としては、例えば、2-ヒドロキシエチルビニルエーテル、3-ヒドロキシプロピルビニルエーテル、2-ヒドロキシプロピルビニルエーテル、2-ヒドロキシ-2-メチルプロピルビニルエーテル、4-ヒドロキシブチルビニルエーテル、4-ヒドロキシ-2-メチルブチルビニルエーテル、5-ヒドロキシペンチルビニルエーテル、6-ヒドロキシヘキシルビニルエーテルなどの水酸基含有ビニルエーテル類;2-ヒドロキシエチルアリルエーテル、4-ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテルなどの水酸基含有アリルエーテル類などが挙げられる。これらのなかでも、重合反応性、官能基の硬化性が優れる点で、水酸基含有ビニルエーテル類が好ましく、式(1):
CH2=CH-(CH2)l-O-(CH2)m-OH
(式中、lは0または1、mは2以上の整数)で示される水酸基含有単量体であることがより好ましく、4-ヒドロキシブチルビニルエーテル、2ーヒドロキシエチルビニルエーテル、2-ヒドロキシエチルアリルエーテル及び4-ヒドロキシブチルアリルエーテルからなる群より選択される少なくとも1種の単量体が更に好ましい。
カルボキシル基含有単量体としては、たとえば、式(2):
R1R2C=CR3-(CH2)n-COOH
(式中、R1、R2およびR3は、同じかまたは異なり、水素原子、アルキル基、カルボキシル基、アシルオキシ基、又は、アルコキシカルボニル基である。nは0以上の整数である)で示されるカルボキシル基含有単量体、それらのエステル及び酸無水物、並びに、式(3):
CH2=CH(CH2)nO(R4OCO)mR5COOH
(式中、R4およびR5は、同じかまたは異なり、いずれも飽和または不飽和の直鎖、分岐または環状のアルキレン基である。nは、0または1であり、mは、0または1である。)で表わされるカルボキシル基含有ビニルエーテル単量体からなる群より選択される少なくとも1種の単量体が好ましい。
アミノ基含有単量体としては、たとえばCH2=CH-O-(CH2)x-NH2(x=0~10)で示されるアミノビニルエーテル類;CH2=CH-O-CO(CH2)x-NH2(x=1~10)で示されるアリルアミン類;そのほかアミノメチルスチレン、ビニルアミン、アクリルアミド、ビニルアセトアミド、ビニルホルムアミドなどが挙げられる。
シリル基含有単量体としては、例えば、シリコーン系ビニル単量体が挙げられる。シリコーン系ビニル単量体としては、たとえばCH2=CHCO2(CH2)3Si(OCH3)3、CH2=CHCO2(CH2)3Si(OC2H5)3、CH2=C(CH3)CO2(CH2)3Si(OCH3)3、CH2=C(CH3)CO2(CH2)3Si(OC2H5)3、CH2=CHCO2(CH2)3SiCH3(OC2H5)2、CH2=C(CH3)CO2(CH2)3SiC2H5(OCH3)2、CH2=C(CH3)CO2(CH2)3Si(CH3)2(OC2H5)、CH2=C(CH3)CO2(CH2)3Si(CH3)2OH、CH2=CH(CH2)3Si(OCOCH3)3、CH2=C(CH3)CO2(CH2)3SiC2H5(OCOCH3)2、CH2=C(CH3)CO2(CH2)3SiCH3(N(CH3)COCH3)2、CH2=CHCO2(CH2)3SiCH3〔ON(CH3)C2H5〕2、CH2=C(CH3)CO2(CH2)3SiC6H5〔ON(CH3)C2H5〕2などの(メタ)アクリル酸エステル類;CH2=CHSi[ON=C(CH3)(C2H5)]3、CH2=CHSi(OCH3)3、CH2=CHSi(OC2H5)3、CH2=CHSiCH3(OCH3)2、CH2=CHSi(OCOCH3)3、CH2=CHSi(CH3)2(OC2H5)、CH2=CHSi(CH3)2SiCH3(OCH3)2、CH2=CHSiC2H5(OCOCH3)2、CH2=CHSiCH3〔ON(CH3)C2H5〕2、ビニルトリクロロシランまたはこれらの部分加水分解物などのビニルシラン類;トリメトキシシリルエチルビニルエーテル、トリエトキシシリルエチルビニルエーテル、トリメトキシシリルブチルビニルエーテル、メチルジメトキシシリルエチルビニルエーテル、トリメトキシシリルプロピルビニルエーテル、トリエトキシシリルプロピルビニルエーテルなどのビニルエーテル類などが例示される。
上記硬化性官能基含有含フッ素ポリマーとしては、上記(1)~(5)の中でも、耐候性及び防湿性の観点から、(1)、(2)及び(5)のポリマーが好ましい。
パーフルオロオレフィン単位を主体とするパーフルオロオレフィン系ポリマーは、パーフルオロオレフィン単位を含むことが好ましい。上記パーフルオロオレフィン単位は、パーフルオロオレフィン系ポリマーの全重合単位に対して、20~49モル%であることが好ましい。より好ましい下限は30モル%であり、更に好ましい下限は40モル%である。より好ましい上限は47モル%である。
CTFE単位を主体とするCTFE系ポリマーとしては、たとえばCTFE/ヒドロキシブチルビニルエーテル/他の単量体の共重合体などが挙げられる。CTFE系ポリマーの硬化性ポリマー塗料としては、たとえば旭硝子(株)製のルミフロン(登録商標)、大日本インキ製造(株)製のフルオネート(登録商標)、セントラル硝子(株)製のセフラルコート(登録商標)、東亜合成(株)製のザフロン(登録商標)などが例示できる。
VdF単位を主体とするVdF系ポリマーとしては、たとえばVdF/TFE/ヒドロキシブチルビニルエーテル/他の単量体の共重合体などが挙げられる。
フルオロアルキル単位を主体とするフルオロアルキル基含有ポリマーとしては、たとえばCF3CF2(CF2CF2)nCH2CH2OCOCH=CH2(n=3と4の混合物)/2-ヒドロキシエチルメタクリレート/ステアリルアクリレート共重合体などが挙げられる。フルオロアルキル基含有ポリマーとしては、たとえばダイキン工業(株)製のユニダイン(登録商標)やエフトーン(登録商標)、デュポン社製のゾニール(登録商標)などが例示できる。
上記酢酸ビニル単位を主体とする酢酸ビニル系ポリマーとしては、含フッ素単量体/酢酸ビニル/式(1)で示される水酸基含有単量体/式(2)で示されるカルボキシル基含有単量体の共重合体が挙げられる。上記共重合体は、含フッ素単量体/酢酸ビニル/式(1)で示される水酸基含有単量体/式(2)で示されるカルボキシル基含有単量体のモル比が15~50/20~75/5~22/0.1~5であることが好ましく、15~50/23~75/5~22/0.1~5であることがより好ましい。
上記ペンタメチレンジイソシアネート系硬化剤としては、ペンタメチレンジイソシアネート(PDI)に基づくブロックイソシアネート化合物、及び、ペンタメチレンジイソシアネート(PDI)から誘導されるポリイソシアネート化合物からなる群より選択される少なくとも1種が好ましい。
上記ブロックイソシアネートとしては、ペンタメチレンジイソシアネートから誘導されるポリイソシアネート化合物(以下、ポリイソシアネート化合物(II)ともいう。)をブロック化剤で反応させて得られるものが好ましい。
上記ポリイソシアネート化合物(II)としては、例えば、ペンタメチレンジイソシアネートと3価以上の脂肪族多価アルコールとを付加重合して得られるアダクト、ペンタメチレンジイソシアネートからなるイソシアヌレート構造体(ヌレート構造体)、及び、ペンタメチレンジイソシアネートからなるビウレットを挙げることができる。
上記一般式(6)中のR4は、上記3価以上の脂肪族多価アルコールに基づく炭化水素基であり、炭素数3~10の脂肪族炭化水素基がより好ましく、炭素数3~6の脂肪族炭化水素基が更に好ましい。
上記kは、3価以上の脂肪族多価アルコールの価数に対応する数である。上記kとして、より好ましくは3~10の整数であり、更に好ましくは3~6の整数である。
上記イソシアヌレート構造体としては、上記イソシアネートの三量化反応により得られる三量体、五量化反応により得られる五量体、七量化反応により得られる七量体等を挙げることができる。
中でも、下記一般式(7):
ペンタメチレンジイソシアネートと、上記のような3価以上の脂肪族多価アルコールとを付加重合することにより、上記アダクトが得られる。
中でも、活性メチレン化合物、オキシム類が好ましく、活性メチレン化合物がより好ましい。
上記ペンタメチレンジイソシアネート系硬化剤中の官能基数が0.1~5当量、好ましくは0.5~1.5当量、更に好ましくは0.7~1.2当量となる割合である。
酸触媒としては、ドデシルベンゼンスルホン酸、アミンでブロックされたドデシルベンゼンスルホン酸、パラトルエンスルホン酸、酸性リン酸フェニル、アミンでブロックしたジノニルナフタレンスルホン酸、および、酸性リン酸フェニルからなる群より選択される少なくとも1種であることが好ましい。
硬化促進剤は1種を用いてもよく、2種以上を併用してもよい。
顔料として具体的には、白色顔料である酸化チタン、炭酸カルシウムや、黒色顔料であるカーボンブラック、Cu-Cr-Mn合金等の複合金属類等の無機顔料;フタロシアニン系、キナクリドン系又はアゾ系等の有機顔料等が挙げられるが、これらのみに限定されるものではない。
紫外線吸収剤としては、有機系、無機系のいずれの紫外線吸収剤も用いることができる。有機化合物系では、例えばサリチル酸エステル系、ベンゾトリアゾール系、ベンゾフェノン系、シアノアクリレート系等の紫外線吸収剤等があげられ、無機系では酸化亜鉛、酸化セリウム等のフィラー型無機系紫外線吸収剤等が好ましい。
中でも、エステル類がより好ましく、酢酸ブチルが更に好ましい。
太陽電池モジュールのバックシートのコーティングに用いる場合、上記塗膜は水不透過性シート等の基材の片面又は両面に形成される。
本発明の組成物から得られる塗膜が基材の片面に形成され、かつ該基材の他方の面が非塗装面である場合には、該塗膜は、巻き取り工程において、基材の非塗装面と接触することになる。一方、上記塗膜が基材の片面に形成され、かつ該基材の他方の面に他の塗料から得られる塗膜(後述する硬化性官能基を有しない含フッ素ポリマー塗料の硬化塗膜、ポリエステル塗料の塗膜、プライマー層等)や他のシートが設けられている場合には、本発明の組成物から得られる塗膜は、巻き取り工程において、基材上の他の塗料から得られる塗膜や他のシートと接触することになる。また、本発明の組成物から得られる塗膜が基材の両面に形成されている場合には、該塗膜は、巻き取り工程において、基材の他方の面に形成された同じ種類の塗膜と接触することになる。
本発明の組成物から得られる塗膜は、これらのいずれの場合にも、接触する面に対して優れた耐ブロッキング性を発揮することができる。
上記塗膜は、上記水不透過性シートの片面にのみ形成されてもよいし、両面に形成されてもよい。
図1に示される第1の構造において、太陽電池セル1は、封止剤層2に封止されており、該封止材層2は、表面層3とバックシート4とで挟まれている。バックシート4は更に水不透過性シート5と本発明の組成物から得られる硬化塗膜6とから構成されている。この第1の構造では、硬化塗膜6は封止材層2側にのみ設けられている。
上記表面層3には、通常ガラス板が用いられるが、樹脂シート等のフレキシブルな材料を用いてもよい。
塗膜7を構成する材料は、硬化性官能基を有しない含フッ素ポリマー塗料の硬化塗膜でも、含フッ素ポリマーシートでも、ポリエステルシートでも、ポリエステル塗料の塗膜でもよい。
また、上記塗膜と封止材層との接着性をさらに向上させるために、上記塗膜に従来公知の表面処理を行ってもよい。表面処理としては、例えばコロナ放電処理、プラズマ放電処理、化成処理、ブラスト処理等が例示できる。
なお、プライマー層の形成は、従来公知のプライマー用塗料を用いて、常法により行う。プライマー用の塗料としては、例えばエポキシ樹脂、ウレタン樹脂、アクリル樹脂、シリコーン樹脂、ポリエステル樹脂等が代表例として挙げられる。
フッ素樹脂:硬化性TFE系共重合体溶液、商品名 ゼッフルGK570、ダイキン工業(株)製
ジオール:シクロヘキサン含有ジオール、商品名 Sovermol908(下記構造を有する化合物)、BASF社製
消光剤:CP4-8991、グレースコーポレーション社製
ベンゼン環含有メラミン樹脂:M-85、美螺絲社製
硬化促進剤(酸触媒):CYCAT600、Cytec,Inc.より市販のドデシルベンゼンスルホン酸の70質量%イソプロパノール溶液)
PDI系硬化剤:D3725N、三井化学(株)社製
XDI系硬化剤:タケネートD120N、三井化学(株)社製
HDI系硬化剤:スミジュールN3300、住化バイエルウレタン社製
硬化性TFE系共重合体溶液(ダイキン工業(株)製のゼッフルGK570、固形分65質量%、水酸基価60mgKOH/g、溶剤:酢酸ブチル)202質量部、白色顔料として酸化チタン(デュポン(株)製のR960)263.0質量部、酢酸ブチル167.0質量部を攪拌下に予備混合した後、直径1.2mmのガラスビーズを632質量部入れ、顔料分散機にて1500rpmで1時間分散させた。その後、#80メッシュのフルイでガラスビーズをろ過し、その溶液に硬化性TFE系共重合体溶液(ゼッフルGK570)を283.0質量部、酢酸ブチル85.0質量部加えて白色塗料を調製した。
水不透過性シートとして、PETフィルム(東材製のDS10、厚さ250μm。シートA)を使用し、このシートAの片面に2000Wでコロナ処理を行い、調製例1で調製した塗料1を乾燥膜厚が10μmとなるようにコーターにて塗装し、150℃で2分間乾燥して2層構造のバックシートA1を作製した。
実施例1で得られたガラス/EVA/バックシート接着サンプルA1を、初期状態とPCT(プレッシャークッカーテスト、121℃、湿度100%RH、2気圧)48時間後において、EVA/バックシート層間の密着性をピール試験にて測定した。測定サンプルのEVA/バックシート部分を幅1cm×15cmに切り込みを入れ、テンシロン(オリエンテック製)を用いて180度剥離試験を行い、EVA/バックシート間の接着強度を、N/cmを単位として測定した。
剥離強度と同様に、初期状態とPCT48時間後の塗膜に対して、目視で評価した。
剥離強度と同様に、初期状態とPCT48時間後の塗膜に対して、目視で評価した。
JIS C-2151に準じて、マイクロメーター(ミツトヨ社製)で測定した。
塗料の成分を表1又は2に記載されたように変更したこと以外は調製例1と同様にして塗料を調製し、実施例1と同様にして2層構造のバックシート、ガラス/EVA/バックシートの接着サンプルを作製した。
結果を表1又は2に示す。
2:封止材層
3:表面層
4:バックシート
5:水不透過性シート
6:硬化塗膜
7:他の塗膜
Claims (10)
- 含フッ素単量体に基づく重合単位と、水酸基含有単量体及びカルボキシル基含有単量体からなる群より選択される少なくとも1種の硬化性官能基含有単量体に基づく重合単位とを含む硬化性官能基含有含フッ素ポリマー、ペンタメチレンジイソシアネート系硬化剤、ポリオール化合物、及び、メラミン樹脂を含み、
塗料であり、
EVA層と密着する塗膜層に用いられることを特徴とする組成物。 - 含フッ素単量体は、テトラフルオロエチレン、クロロトリフルオロエチレン、及び、ビニリデンフルオライドからなる群より選択される少なくとも1種である請求項1記載の組成物。
- 更に、酸触媒を含む請求項1又は2記載の組成物。
- 更に顔料を含む請求項1、2又は3記載の組成物。
- 更に紫外線吸収剤を含む請求項1、2、3又は4記載の組成物。
- 請求項1、2、3、4又は5記載の組成物から得られることを特徴とする塗膜。
- 基材、及び、
請求項1、2、3、4又は5記載の組成物から得られる層を含むことを特徴とする積層体。 - 基材は、金属、コンクリート、又は、プラスチックからなる請求項7記載の積層体。
- 水不透過性シート、及び、
前記水不透過性シートの少なくとも一方の面に形成された請求項1、2、3、4又は5記載の組成物から得られる塗膜
を有することを特徴とする太陽電池モジュールのバックシート。 - 水不透過性シート、
前記水不透過性シートの少なくとも一方の面に形成された請求項1、2、3、4又は5記載の組成物から得られる塗膜、及び、
前記塗膜の上に形成された封止材層
を有することを特徴とする太陽電池モジュール。
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TWI264441B (en) * | 2003-12-05 | 2006-10-21 | Daikin Ind Ltd | Cold curing aqueous composition |
JP5127123B2 (ja) | 2005-07-22 | 2013-01-23 | ダイキン工業株式会社 | 太陽電池のバックシート |
CN102754219A (zh) * | 2010-02-05 | 2012-10-24 | 东丽株式会社 | 太阳能电池背面密封片材用膜 |
EP2540785B1 (en) * | 2010-02-26 | 2016-02-10 | Asahi Glass Company, Limited | Use of a coating composition for preparing a solar heat-collecting reflector, solar heat-collecting reflector and method for producing same |
KR101732391B1 (ko) * | 2010-03-31 | 2017-05-04 | 디아이씨 가부시끼가이샤 | 함불소 경화성 수지 및 그것을 사용한 활성 에너지선 경화성 조성물 |
WO2015111709A1 (ja) * | 2014-01-24 | 2015-07-30 | 関西ペイント株式会社 | 耐衝撃性を有する塗膜を形成するための塗料組成物 |
WO2016152631A1 (ja) * | 2015-03-26 | 2016-09-29 | リンテック株式会社 | 塗膜保護フィルム |
EP3273489B1 (en) | 2015-03-31 | 2021-02-24 | Daikin Industries, Ltd. | Back sheet of solar cell module, and solar cell module |
US20170166772A1 (en) * | 2015-12-09 | 2017-06-15 | Honeywell International Inc. | Processes for coating substrates with polymers formed from trans-1,3,3,3-tetrafluoropropene and vinylidene difluoride |
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JP2007526366A (ja) | 2004-02-23 | 2007-09-13 | ライプニッツ−インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク | 低エネルギー表面を有する耐磨耗性及び耐アルカリ性コーティング又は成形体 |
JP2011162598A (ja) | 2010-02-05 | 2011-08-25 | Dic Corp | コーティング剤組成物 |
WO2012121291A1 (ja) | 2011-03-09 | 2012-09-13 | 三井化学株式会社 | ペンタメチレンジイソシアネート、ペンタメチレンジイソシアネートの製造方法、ポリイソシアネート組成物、ポリウレタン樹脂およびポリウレア樹脂 |
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KR20200090225A (ko) | 2020-07-28 |
US20200392363A1 (en) | 2020-12-17 |
TWI744568B (zh) | 2021-11-01 |
US11746252B2 (en) | 2023-09-05 |
CN109988466A (zh) | 2019-07-09 |
WO2019101065A1 (zh) | 2019-05-31 |
JP2021504518A (ja) | 2021-02-15 |
CN111511852A (zh) | 2020-08-07 |
KR102449432B1 (ko) | 2022-09-30 |
CA3083003A1 (en) | 2020-05-19 |
TW201930493A (zh) | 2019-08-01 |
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