JP6040901B2 - ラミネート積層体用接着剤組成物、これを使用した積層体、および二次電池 - Google Patents
ラミネート積層体用接着剤組成物、これを使用した積層体、および二次電池 Download PDFInfo
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- JP6040901B2 JP6040901B2 JP2013195475A JP2013195475A JP6040901B2 JP 6040901 B2 JP6040901 B2 JP 6040901B2 JP 2013195475 A JP2013195475 A JP 2013195475A JP 2013195475 A JP2013195475 A JP 2013195475A JP 6040901 B2 JP6040901 B2 JP 6040901B2
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- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
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- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OKQVTLCUHATGDD-UHFFFAOYSA-N n-(benzotriazol-1-ylmethyl)-2-ethyl-n-(2-ethylhexyl)hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1 OKQVTLCUHATGDD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
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- 229920003251 poly(α-methylstyrene) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Description
この積層体には、二次電池として求められる防湿性、密封性、耐突き刺し性、絶縁性、耐熱・耐寒性、耐腐食性等が求められるが、特に、電解質に溶解しない耐電解質性が必須である。
特開平9−283101号においては、積層体の最内層にマレイン酸変性ポリオレフィン樹脂を使用し、ヒートシール部を同様のマレイン酸変性ポリオレフィン樹脂で構成することにより、密封信頼性を向上させた封入袋が提案されている(例えば、特許文献1参照。)。該技術はマレイン酸変性ポリオレフィン樹脂は金属との接着性およびヒートシール性に優れるため、一般的には接着性樹脂として使用されている。しかし上記のような電池の封止フィルムとして使用すると、積層直後には優れた接着力を示すが、耐電解質性が低く、経時で層間剥離を生じ、封止フィルムとして使用することができない
また、その積層体を二次電池用積層体として用いた場合、プロピレンカーボネートやエチレンカーボネートといった電解質に対して、優れた耐性を有する為、経時での層間剥離を生じることがない。
、酸基含有ポリオレフィン樹脂が挙げられる。
2−アミノ−1,3,4−チアジアゾール、2−アミノチアゾール、2−アミノベンゾチアゾール等のチアゾール類;
また、本発明の積層体は、作成後エージングを行うことが好ましい。エージング条件は、室温〜100℃で、12〜240時間の間であり、この間に接着強度が生じる。
測定装置;東ソー株式会社製 HLC−8220
検出器;RI(示差屈折計)
測定条件;カラム温度 40℃ 溶媒 テトラヒドロフラン
また、本発明に用いる水酸基を含有する樹脂(A)のガラス転移温度は、下記の条件により求めた。
測定方法;DSC(示差走査熱量分析)法
およびアルミニウム箔
塗布:バーコーター
乾燥条件:80℃、60秒 エージング条件:40℃、3日
塗布量:5g/m2(ドライ)
接着強度:株式会社エー・アンド・ディー製テンシロン試験 15mm幅 180°剥離強度
耐電解質性:エチレンカーボネート/ジメチルカーボネート/エチルメチルカーボネート=1/1/1
25℃−14日間浸漬後の接着強度保持率
○:90%以上、△:90〜70%、×:70%以下
ユニストール P−401(三井化学株式会社製)酸基含有ポリオレフィン樹脂、固形分酸価55mgKOH/g 加熱残分8%
ユニストール P−902(三井化学株式会社製)酸基含有ポリオレフィン樹脂、
固形分酸価55mgKOH/g 加熱残分22%
ユニストール P−801(三井化学株式会社製)水酸基含有ポリオレフィン樹脂、固形分水酸基価40mgKOH/g 加熱残分16%
キュアゾール 2E4MZ(四国化成工業株式会社製)イミダゾール 不揮発分100%
BT120(城北化学工業株式会社製)ベンゾトリアゾール 不揮発分100%
デナコール EX−321(ナガセケムテックス株式会社製)エポキシ樹脂、エポキシ当量140 不揮発分100%
エピクロン 860(DIC株式会社製)ビスフェノールA型エポキシ樹脂、エポキシ当量240 不揮発分100%
バーノック D−750(DIC株式会社製)ポリイソシアネート化合物、NCO%13.0 不揮発分75%
Claims (5)
- 酸基又は水酸基含有ポリオレフィン樹脂(A)、トリアゾール環、ピロール環、ピラゾール環、チアゾール環及びイミダゾール環からなる群から選択される構造を有する化合物である、窒素原子を環構造中に有する五員環構造の複素環状化合物(B)、及び前記酸基又は水酸基含有ポリオレフィン樹脂(A)と反応性を有する硬化剤(C)を、前記ポリオレフィン樹脂(A)100重量部に対して、前記複素環状化合物(B)を0.01〜10重量部となる割合、かつ、前記硬化剤(C)を0.1〜30重量部となる割合で含有することを特徴とするラミネート用接着剤組成物。
- 酸基又は水酸基含有ポリオレフィン樹脂(A)が、酸価が1〜200mgKOH/gの酸基を含有する変性ポリオレフィン樹脂および/または水酸基価が1〜200mgKOH/gの水酸基を含有する変性ポリオレフィン樹脂である請求項1記載のラミネート用接着剤組成物。
- 前記硬化剤(C)がエポキシ化合物、ポリイソシアネート化合物、及び、メラミン樹脂からなる群の少なくとも1つの化合物である請求項1、2又は3記載のラミネート用接着剤組成物。
- 請求項1〜3の何れか1つに記載のラミネート用接着剤を金属層とポリオレフィン樹脂層との間に使用した積層体。
- 請求項4記載の積層体を含む二次電池。
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