JP6945916B2 - 樹脂組成物 - Google Patents
樹脂組成物 Download PDFInfo
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- JP6945916B2 JP6945916B2 JP2020515118A JP2020515118A JP6945916B2 JP 6945916 B2 JP6945916 B2 JP 6945916B2 JP 2020515118 A JP2020515118 A JP 2020515118A JP 2020515118 A JP2020515118 A JP 2020515118A JP 6945916 B2 JP6945916 B2 JP 6945916B2
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- 239000011347 resin Substances 0.000 claims description 137
- 239000000203 mixture Substances 0.000 claims description 87
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- 239000000945 filler Substances 0.000 claims description 65
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000005056 polyisocyanate Substances 0.000 claims description 30
- 229920001228 polyisocyanate Polymers 0.000 claims description 30
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- 125000003118 aryl group Chemical group 0.000 claims description 10
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
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Description
本出願は、2018年3月28日に出願された大韓民国特許出願第10−2018−0035750号及び2019年3月14日に出願された大韓民国特許出願第10−2019−0029276号に基づく優先権の利益を主張し、該当大韓民国特許出願の文献に開示されたすべての内容は本明細書の一部として組み込まれる。
本出願は、樹脂組成物に関する。具体的に、本出願は、樹脂組成物と、前記樹脂組成物の硬化物と、を含むバッテリモジュール、バッテリパック及び自動車に関する。
1.Tm(溶融点)に根拠した非結晶性
10℃/分(min)の昇温速度で、25℃→50℃→−70℃―>50℃順序に温度を変化させながら、実施例及び比較例で用いられたポリオール樹脂に対するTmをQ2000(TA instruments社)を用いたDSC分析を通じて測定した。
バッテリセルの製作に用いられるアルミニウムパウチを約10mmの幅で切断した。ガラス板上に実施例及び比較例でそれぞれ用いられた樹脂組成物をローディングし、その上に前記切断したアルミニウムパウチをそのパウチのPET(poly(ethylene terephthalate))面と前記樹脂組成物が接触するようにローディングした後、25℃及び50%RHの条件で、24時間の間樹脂組成物を硬化させた。その後、前記アルミニウムパウチを引張試験器(Texture analyzer)で180゜の剥離角度と300mm/minの剥離速度で剥離しながら接着力を測定した。
前記接着力の測定と同一に樹脂組成物が硬化された試片を製作し、85℃及び85%RHの条件で10日間保管した。以後、前記2番の項目と同一の方法で接着力(S2)を測定した。
実施例及び比較例で用いられたものと同一の樹脂の混合物(フィラーを含まない)を24時間の間常温で硬化し、10℃/分の昇温速度で−75℃から50℃範囲に温度を変化しながら前記硬化物のTgをDSC分析で測定した。
<実施例1>
二液型ウレタン系組成物の製造
ポリオール:主剤組成物には、前記化学式2で表示されるカプロラクトン系ポリオールとして、繰り返し単位の数(化学式2のm)が約1〜3程度のレベルであり、ポリオール由来の単位(化学式2のY)としては、1,4−ブタンジオールを含むポリオールを含む樹脂(Brookfield LV type粘度計で測定するとき、約280cPの粘度を有する)を所定量用いた。
前記製造された組成物に対して、上述した方式で測定したガラス転移温度(Tg)は、0℃未満であった。そして、上述した方式で測定された溶融点(Tm)は、11℃であった。また、接着力(S1)は、449gf/10mmであり、接着力間の割合(S2/S1)は、70%以上であった。これから、実施例1の組成物は、過量のフィラーを含む場合にもバッテリモジュールに対する注入時に適切な工程性を提供することができ、硬化後には優れた接着性及び接着信頼性を有することが分かる。
二液型ウレタン系組成物の製造
ポリオール化学式2のY単位の形成時にネオペンチルグリコール(neopentyl glycol)を変更して用いたこと以外は(製造されたポリオールの粘度はBrookfield LV type粘度計で測定するとき、約300cPの粘度を有する)、実施例1と同一に組成物を製造した。
前記製造された組成物に対して、上述した方式で測定したガラス転移温度(Tg)は、0℃未満であった。上記用いられたポリオールは、結晶性が弱くて(非結晶性)DSC上で結晶化温度(Tc)及び溶融温度(Tm)が測定されなかった。また、接着力(S1)は、467gf/10mmであり、接着力間の割合(S2/S1)は、70%以上であった。これから、実施例2の組成物は、過量のフィラーを含む場合にもバッテリモジュールに対する注入時に適切な工程性を提供することができ、硬化後には優れた接着性及び接着信頼性を有することが分かる。
二液型ウレタン系組成物の製造
主剤成分に用いられる樹脂として、エーテル系ポリオールであるPPG(水酸基が360mgKOH/g)を用いたこと以外は、実施例1と同一に組成物を製造した。
前記製造された組成物に対して、上述した方式で測定したガラス転移温度は、0℃未満であり、溶融点は、15℃未満で観察された。また、接着力(S1)は、116gf/10mmであり、接着力間の割合(S2/S1)は、70%以上であった。これから、本願の構成のうちエステル系ポリオールを有しない比較例1の組成物は、バッテリモジュールにおいてバッテリセルをケースに接着させるために必要な十分な接着力を提供できない点が分かる。
二液型ウレタン系組成物の製造
硬化剤成分に芳香族ジイソシアネートであるメチレンジフェニルジイソシアネート(MDI、Methylene Diphenyl Diisocyanate)を用いたこと以外は、実施例1と同一に組成物を製造した。
前記製造された組成物に対して、上述した方式で測定したガラス転移温度(Tg)は、0℃超過であり、溶融点(Tm)は、15℃以下であった。また、接着力(S1)は、666gf/10mmであり、接着力間の割合(S2/S1)は、70%以上であった。これから、芳香族イソシアネートを硬化成分で用いる比較例2の組成物は、硬化速度が速くて注入工程性と保存安定性が良くなく、その硬化物が高いガラス転移温度を有するので、低温での耐衝撃特性や耐振動特性などが要求されるバッテリモジュール用素材として不適合であることが分かる。
二液型ウレタン系組成物の製造
主剤成分で化学式2の繰り返し単位mが11であること以外は、実施例1と同一に組成物を製造した。
前記製造された組成物に対して、上述した方式で測定したガラス転移温度(Tg)は、0℃以下であり、溶融点(Tm)は、20℃を超過した。また、接着力(S1)は、467gf/10mmであり、接着力間の割合(S2/S1)は、70%以上であった。これから、本願で要求される十分に低い結晶性を有しないポリオールを用いた比較例3の組成物は、常温での結晶性によりバッテリモジュール内で接着剤で用いられる組成物に対する注入工程性が良くないことが分かる。
10a:下部板
10b:側壁
10c:上部板
10d:ガイド部
20:バッテリセル
30:樹脂層
50a:注入ホール
50b:観察ホール
40:絶縁層
100:パウチ型バッテリセル
110:電極組立体
120:外装材
121:上部パウチ
122:下部パウチ
S:シーリング部
Claims (16)
- エステル系ポリオール樹脂含有主剤成分;ポリイソシアネート含有硬化剤成分;及びフィラーを含む二液型ウレタン系組成物であって、
前記エステル系ポリオール樹脂は、DSC(Differential Scanning calorimetry)分析で結晶化温度(Tc)と溶融温度(Tm)が観察されない非結晶性ポリオールであるか溶融温度(Tm)が15℃未満であり、
前記ポリイソシアネートは、非芳香族ポリイソシアネートであることを特徴とする、二液型ウレタン系組成物。 - 前記エステル系ポリオール樹脂と非芳香族ポリイソシアネートの混合物は、硬化後0℃未満のガラス転移温度(Tg)を有することを特徴とする、請求項1に記載の二液型ウレタン系組成物。
- 前記エステル系ポリオール樹脂及び非芳香族ポリイソシアネートは、それぞれ10,000cP未満の粘度を有することを特徴とする、請求項1または2に記載の二液型ウレタン系組成物。
- 前記エステル系ポリオール樹脂及び非芳香族ポリイソシアネートは、それぞれ2,000cP以下の粘度を有することを特徴とする、請求項3に記載の二液型ウレタン系組成物。
- 化学式1において、カルボン酸由来の単位Xは、フタル酸単位、イソフタル酸単位、テレフタル酸単位、トリメリット酸単位、テトラヒドロフタル酸単位、ヘキサヒドロフタル酸単位、テトラクロロフタル酸単位、シュウ酸単位、アジピン酸単位、アゼライン酸単位、セバシン酸単位、コハク酸単位、リンゴ酸単位、グルタル酸単位、マロン酸単位、ピメリン酸単位、スベリン酸単位、2,2−ジメチルコハク酸単位、3,3−ジメチルグルタル酸単位、2,2−ジメチルグルタル酸単位、マレイン酸単位、フマル酸単位、イタコン酸単位及び脂肪酸単位からなる群より選択された一つ以上の単位であることを特徴とする、請求項5に記載の二液型ウレタン系組成物。
- 化学式1及び2において、前記ポリオール由来の単位Yは、エチレングリコール単位、プロピレングリコール単位、1,2−ブチレングリコール単位、2,3−ブチレングリコール単位、1,3−プロパンジオール単位、1,3−ブタンジオール単位、1,4−ブタンジオール単位、1,6−ヘキサンジオール単位、ネオペンチルグリコール単位、1,2−エチルへキシルジオール単位、1,5−ペンタンジオール単位、1,9−ノナンジオール単位、1,10−デカンジオール単位、1,3−シクロヘキサンジメタノール単位、1,4−シクロヘキサンジメタノール単位、グリセリン単位及びトリメチロールプロパン単位からなる群より選択されるいずれか一つ又は2個以上の単位であることを特徴とする、請求項5に記載の二液型ウレタン系組成物。
- 非芳香族ポリイソシアネートは、脂環族ポリイソシアネート、脂環族ポリイソシアネートのカルボジイミド変性ポリイソシアネート又は脂環族ポリイソシアネートのイソシアヌレート変性ポリイソシアネートであることを特徴とする、請求項1に記載の二液型ウレタン系組成物。
- 前記フィラーは、アルミナ、AlN(aluminum nitride)、BN(boron nitride)、窒化ケイ素(silicon nitride)、SiC又はBeOを含むことを特徴とする、請求項1から8のいずれか一項に記載の二液型ウレタン系組成物。
- 前記エステル系ポリオール樹脂及び非芳香族ポリイソシアネートの含量を合わせた100重量部に対して、50〜2,000重量部のフィラーを含むことを特徴とする、請求項1から9のいずれか一項に記載の二液型ウレタン系組成物。
- 前記エステル系ポリオール樹脂及び非芳香族ポリイソシアネートの含量を合わせた100重量部に対して、100〜2,000重量部のフィラーを含むことを特徴とする、請求項9に記載の二液型ウレタン系組成物。
- 硬化後に常温で測定された接着力(S1)が150gf/10mm以上であることを特徴とする、請求項1から11のいずれか一項に記載の二液型ウレタン系組成物。
- 硬化後に40〜100℃及び75%の相対湿度条件で10日間保管された後に測定された接着力(S2)の前記接着力(S1)に対する割合が70%以上であることを特徴とする、請求項12に記載の二液型ウレタン系組成物。
- 上部板、下部板及び側壁を有し、前記上部板、下部板及び側壁により内部空間が形成されているモジュールケース;
前記モジュールケースの内部空間に存在する複数のバッテリセル;及び
請求項1から13のいずれか一項に規定の二液型ウレタン系組成物が硬化されて形成され、前記複数のバッテリセルと接触する樹脂層を含むことを特徴とする、バッテリモジュール。 - 請求項14に規定のバッテリモジュールを一つ以上含むことを特徴とする、バッテリパック。
- 請求項14に規定のバッテリモジュール又は請求項15に規定のバッテリパックを含むことを特徴とする、自動車。
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