JPH03283354A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPH03283354A JPH03283354A JP2083612A JP8361290A JPH03283354A JP H03283354 A JPH03283354 A JP H03283354A JP 2083612 A JP2083612 A JP 2083612A JP 8361290 A JP8361290 A JP 8361290A JP H03283354 A JPH03283354 A JP H03283354A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- aromatic isocyanate
- polyurethane resin
- sealed lead
- layers
- 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.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 14
- -1 aromatic isocyanate Chemical class 0.000 claims abstract description 12
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims abstract 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005001 laminate film Substances 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 229920003054 adipate polyester Polymers 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 235000011037 adipic acid Nutrition 0.000 abstract 1
- 239000001361 adipic acid Substances 0.000 abstract 1
- 238000003475 lamination Methods 0.000 abstract 1
- 239000007767 bonding agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
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
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は密閉形鉛電池の電槽材料に関するものである。[Detailed description of the invention] Industrial applications The present invention relates to a battery case material for a sealed lead-acid battery.
従来の技術
ポータプル機器等の薄形化に伴い、これらの電源として
用いられる密閉形鉛電池も薄形化されつつある。特に薄
形化に対して効果があるのは電槽の薄形化であり、従来
のＡＢＳ樹脂等の射出成形電槽に代わって、特開昭６１
−２０６１５８号公報に提案されているように、シート
状もしくはフィルム状のラミネート構造合成樹脂電槽が
用いられている。これは、従来からの食品包装等に用い
られてきた技術であり、合成樹脂電槽の中間層にポリ塩
化ビニリデン等のガスバリア性フィルムを配することに
より、従来のＡＢＳ樹脂製電槽に比べて、耐水蒸気透過
性、耐酸素透過性の面で、約１７２０程度の厚みにする
ことができ、非常に効果があった。BACKGROUND ART As portable devices and the like become thinner, sealed lead batteries used as power sources for these devices are also becoming thinner. Particularly effective in reducing the thickness of the battery case is the reduction in the thickness of the battery case.
As proposed in Japanese Patent No. 206158, a sheet-like or film-like laminated synthetic resin container is used. This is a technology that has traditionally been used in food packaging, etc., and by placing a gas barrier film such as polyvinylidene chloride in the middle layer of a synthetic resin container, it is more effective than conventional ABS resin containers. In terms of water vapor permeability and oxygen permeability, it was possible to achieve a thickness of approximately 1720 mm, which was very effective.
また、このラミネート構造合成樹脂電槽の各材料は、ポ
リエチレングリコールやポリプロピレングリコール等の
ポリエーテル型ポリオールと、ヘキサメヂレンジイソシ
アホートやキシリレンジイソシアネート等の脂肪族イソ
シアネートとの反応によるポリウレタン系樹脂により接
合されており、これは従来の食品包装を主とずる包装資
材として用いられ、実績のあるものであった。In addition, each material of this laminated synthetic resin battery case is made of polyurethane resin produced by the reaction of polyether type polyols such as polyethylene glycol and polypropylene glycol with aliphatic isocyanates such as hexamethylene diisocyanate and xylylene diisocyanate. This has been used as a packaging material, mainly for conventional food packaging, and has a proven track record.
発明が解決しようとする課題
前述の従来技術では、種々のシート状もしくはフィルム
状樹脂を積層したラミネート構造電槽とすることにより
、薄くて且つ耐水蒸気透過性、耐酸素透過性にすぐれた
電槽を得ることができたが、この各種異種材料を接合す
る接合剤に問題があり、高温多湿雰囲気中等で電池が長
期使用された場合、この接合剤と被接合剤との界面が剥
離してしまうことがあった。以下、この現象をｒ層間剥
離」と称する。Problems to be Solved by the Invention In the above-mentioned prior art, a battery case that is thin and has excellent water vapor permeability and oxygen permeability is created by laminating various sheet-like or film-like resins. However, there is a problem with the bonding agent that joins these various dissimilar materials, and if the battery is used for a long time in a high temperature and humid atmosphere, the interface between the bonding agent and the material to be bonded will peel off. Something happened. Hereinafter, this phenomenon will be referred to as "r-layer delamination."
藺
シアネートの反応によるポリウレタン系樹脂であり、食
品包装用途で広く使用されているものの、鉛電池電層用
途では、食品包装用途に比べて長寿命が必要であること
、耐水性および耐硫酸性が必要なこと、有機酸等が排出
しないこと、といった条件が必要であり、従来技術では
問題があった。It is a polyurethane resin produced by the reaction of cyanate, and is widely used in food packaging applications.However, in lead-acid battery conductor applications, it requires a longer life than food packaging applications, and has poor water resistance and sulfuric acid resistance. The conventional technology had problems because it requires certain conditions such as the following conditions and the fact that organic acids and the like are not discharged.
本発明は、これらの課題を解決するものである。The present invention solves these problems.
課題を解決するための手段
接合剤について鋭意検討した結果、接合剤組成としてポ
リエステル型ポリオールと芳香族イソシアネートの反応
により得られるボリウレタルを用い、芳香族イソシアネ
−１・とじて、芳香族多イソシアネートを用いたポリウ
レタン系樹脂が、高温多湿放置等における層間剥離発生
時間等の性能が最良の接合剤であることを見い出した。Means to Solve the Problem As a result of intensive studies on bonding agents, we decided to use polyurethane, which is obtained by the reaction of polyester-type polyol and aromatic isocyanate, as the bonding agent composition, and to use aromatic isocyanate-1 and aromatic polyisocyanate. It has been found that the polyurethane resin used in this study is the best bonding agent in terms of performance such as time required for delamination to occur when left in high temperature and humidity.
作用
従来のポリエチレングリコールやポリプロピレングリコ
ールに代表されるポリエーテル型ポリオールの分子凝集
力を工とした場合、本発明な
に使用するヘリエステル型ポリオールの分子凝集力は約
２．９となり、水蒸気や硫酸に対する耐性が向上するば
かりか、遊離有機酸の発生が大幅に低減する。Effect When considering the molecular cohesive force of conventional polyether type polyols such as polyethylene glycol and polypropylene glycol, the molecular cohesive force of the heliester type polyol used in the present invention is approximately 2.9, which means that water vapor and sulfuric acid Not only is the resistance improved, but the generation of free organic acids is significantly reduced.
また、ヘキサメチレンジイネシアネート、キシリレンジ
イソシアネートに代表される脂肪族イソシアネートに比
べて、芳香族イソシアネートは耐酸性、耐水性の面で良
好であり、特にその骨格構造により、耐熱性が大きい。Furthermore, compared to aliphatic isocyanates such as hexamethylene diinecyanate and xylylene diisocyanate, aromatic isocyanates have better acid resistance and water resistance, and in particular, have greater heat resistance due to their skeletal structure.
更に、この芳香族イソシアネートとして、ヂ。Furthermore, as this aromatic isocyanate, di.
４′
≠−ジフェニルメタンジイソシアネート等の芳香族多イ
ソシアネートを用いることにより更に上述の効果が向上
する。The above-mentioned effects are further improved by using an aromatic polyisocyanate such as 4'≠-diphenylmethane diisocyanate.
よって、これらの組み合わせに基くポリウレタン系樹脂
は、前述の耐酸性、耐酸性−耐水性等の面で優れると共
に層間剥離耐久性が大幅に向上することがわかった。Therefore, it has been found that polyurethane resins based on these combinations are excellent in the above-mentioned acid resistance, acid resistance-water resistance, etc., and have significantly improved interlayer peeling durability.
実施例
外表面よりポリエチレンテレフタレート（ＰＵＴ）層２
５μｍ、ポリ塩化ビニリデン（１’ＶＤＣ）層１５μｍ
、無延伸ポリプロピレン（ＣＰＰ）層６０μｍを積層し
た電槽材料を用いて、２Ｖ−２Ａｈの鉛蓄電池を作成し
た。作成仕様は、従来品、比較品１、比較晶２、本発明
晶１、本発明晶２の計５種類であり、接合剤組成をそれ
ぞれ第１表に示した。Exception: Polyethylene terephthalate (PUT) layer 2 from the surface
5μm, polyvinylidene chloride (1'VDC) layer 15μm
A 2V-2Ah lead-acid battery was created using a battery case material in which a 60 μm thick unstretched polypropylene (CPP) layer was laminated. There were a total of five types of production specifications: conventional product, comparative product 1, comparative product 2, invention crystal 1, and invention crystal 2, and the bonding agent compositions are shown in Table 1.
これらの鉛蓄電池を各２０個ずつ作成し、６０°Ｃ２本
発明品は共に従来品に比較して約２倍以上の眉間剥離耐
久性があり、特に酸価が１以下のグリコールアジピン酸
ポリエステルを用いた零発明晶２が最も良好な接合剤を
含むごとを確認した。20 of each of these lead-acid batteries were made at 60°C.2 Both of the products of the present invention have about twice the glabella peeling durability compared to conventional products, and in particular, glycol adipate polyester with an acid value of 1 or less was used. It was confirmed that the used Zero Invention Crystal 2 contained the best bonding agent.
発明の効果
本発明による密閉形鉛電池は、従来品に比べて高温多湿
等の苛酷な状態下でもラミネートフィルムの層間剥離の
発生が大幅に遅延されるたる
め、層間剥離によ導；酸素の内部への侵入によ第
１
表
り発生ずる容量低下を防止することができ、長期信転性
を有する点において、工業上非常に有用なものである。Effects of the Invention In the sealed lead-acid battery according to the present invention, the occurrence of interlayer delamination of the laminate film is significantly delayed compared to conventional products even under harsh conditions such as high temperature and humidity. It is industrially very useful in that it can prevent a decrease in capacity that would occur due to intrusion into the interior and has long-term reliability.
第１図は従来品、比較品、本発明品のラミネートフィル
ム層間剥離加速試験結果を示す比較図である。FIG. 1 is a comparative diagram showing the results of an accelerated laminate film delamination test of a conventional product, a comparative product, and a product of the present invention.
Claims (1)
リエステル型ポリオールと芳香族イソシアネートとの反
応により得られたポリウレタン系樹脂により接合されて
いることを特徴とする密閉形鉛電池。 ２）ポリエステル型ポリオールが酸価が１以下のグリコ
ールアジピン酸ポリエステルであることを特徴とする請
求項１記載の密閉形鉛電池。 ３）芳香族イソシアネートが、多イソシアネート類であ
ることを特徴とする請求項１記載の密閉形鉛電池。[Claims] 1) A sealed lead-acid battery characterized in that the layers of a laminate film covering a power generating element are joined by a polyurethane resin obtained by a reaction between a polyester polyol and an aromatic isocyanate. . 2) The sealed lead battery according to claim 1, wherein the polyester type polyol is a glycol adipate polyester having an acid value of 1 or less. 3) The sealed lead-acid battery according to claim 1, wherein the aromatic isocyanate is a polyisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2083612A JPH03283354A (en) | 1990-03-30 | 1990-03-30 | Sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2083612A JPH03283354A (en) | 1990-03-30 | 1990-03-30 | Sealed lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03283354A true JPH03283354A (en) | 1991-12-13 |
Family
ID=13807314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2083612A Pending JPH03283354A (en) | 1990-03-30 | 1990-03-30 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03283354A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5267718B1 (en) * | 2012-11-01 | 2013-08-21 | 東洋インキＳｃホールディングス株式会社 | Polyurethane adhesive for battery packaging material, battery packaging material, battery container and battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57207667A (en) * | 1981-06-12 | 1982-12-20 | Goodrich Co B F | Adhesive composition and composite material therefrom |
| JPS61206158A (en) * | 1985-03-08 | 1986-09-12 | Matsushita Electric Ind Co Ltd | Sealed lead-acid battery |
-
1990
- 1990-03-30 JP JP2083612A patent/JPH03283354A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57207667A (en) * | 1981-06-12 | 1982-12-20 | Goodrich Co B F | Adhesive composition and composite material therefrom |
| JPS61206158A (en) * | 1985-03-08 | 1986-09-12 | Matsushita Electric Ind Co Ltd | Sealed lead-acid battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5267718B1 (en) * | 2012-11-01 | 2013-08-21 | 東洋インキＳｃホールディングス株式会社 | Polyurethane adhesive for battery packaging material, battery packaging material, battery container and battery |
| WO2014068986A1 (en) * | 2012-11-01 | 2014-05-08 | 東洋インキＳｃホールディングス株式会社 | Polyurethane adhesive for packaging materials for batteries, packaging material for batteries, battery container, and battery |
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