JP5754205B2 - Lead acid battery - Google Patents
Lead acid battery Download PDFInfo
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- JP5754205B2 JP5754205B2 JP2011072554A JP2011072554A JP5754205B2 JP 5754205 B2 JP5754205 B2 JP 5754205B2 JP 2011072554 A JP2011072554 A JP 2011072554A JP 2011072554 A JP2011072554 A JP 2011072554A JP 5754205 B2 JP5754205 B2 JP 5754205B2
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- JP
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- Prior art keywords
- battery case
- film
- battery
- resin
- lead
- 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.)
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- 239000002253 acid Substances 0.000 title claims description 12
- -1 polyethylene Polymers 0.000 claims description 17
- 230000002093 peripheral effect Effects 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- 238000003860 storage Methods 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 7
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229920001230 polyarylate Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- LTFHFBUUWUDKLP-UHFFFAOYSA-N 2-[(2-hydroxyphenyl)methyl]-4,5,6,7-tetrahydroisoindole-1,3-dione Chemical compound C1(C2=C(C(N1CC1=CC=CC=C1O)=O)CCCC2)=O LTFHFBUUWUDKLP-UHFFFAOYSA-N 0.000 description 1
- QYBWIXBVMQYFIL-UHFFFAOYSA-N 2-chlorobenzotriazole Chemical compound C1=CC=CC2=NN(Cl)N=C21 QYBWIXBVMQYFIL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920000314 poly p-methyl styrene Polymers 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000003466 welding Methods 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)
Description
本発明は鉛蓄電池に関し、特に電槽の外周部にフィルムを配置したものに関する。 The present invention relates to a lead-acid battery, and more particularly to a battery having a film disposed on the outer periphery of a battery case.
鉛蓄電池は、電槽内に配置された電極群と電解液（希硫酸）との化学反応により充放電を行う。従って、鉛蓄電池の化学反応には電解液が必須であるが、希硫酸は危険物であり電解液の漏洩には危険が伴うため、電槽の破損、ひび割れ、劣化に対して十分注意する必要がある。 The lead acid battery is charged and discharged by a chemical reaction between an electrode group disposed in the battery case and an electrolytic solution (dilute sulfuric acid). Therefore, electrolytes are indispensable for chemical reactions of lead-acid batteries, but dilute sulfuric acid is a dangerous substance and there is a danger of leakage of electrolytes, so it is necessary to pay sufficient attention to damage, cracks, and deterioration of the battery case. There is.
鉛蓄電池に使用される電槽は、主にポリプロピレン（以下ＰＰと言う）、ＡＢＳ樹脂、変性ＰＰＥ等を成型して使用される。これらの合成樹脂製電槽は、電解液（希硫酸）に対して十分な耐性を有し、水分透過率が少なく耐衝撃性も高いことから長らく使用されており、他の材質のものはあまり見受けられない。 The battery case used for the lead storage battery is mainly used by molding polypropylene (hereinafter referred to as PP), ABS resin, modified PPE, or the like. These battery containers made of synthetic resin have been used for a long time because they have sufficient resistance to electrolyte (dilute sulfuric acid), low moisture permeability, and high impact resistance. I can't see it.
特許文献１に記載されているように、鉛蓄電池電槽材料としてＰＰは一般的に使用されている。
しかしながら、ＰＰ及びＡＢＳは電槽材料として優れた特性を有する反面、紫外線に曝されると樹脂の劣化が進行し、脆化、強度低下等が起こる。その結果、電槽に破損、ひび、割れ等が発生しやすくなり、電解液が漏洩する可能性が高くなる。
鉛蓄電池は製造工場出荷時から設置される迄の間に、太陽光、蛍光灯等に含まれる紫外線に曝されることが多い。設置工事等の都合により、屋外へ長期間放置される場合もある。
As described in Patent Document 1, PP is generally used as a lead-acid battery case material.
However, PP and ABS have excellent characteristics as battery case materials, but when exposed to ultraviolet rays, deterioration of the resin proceeds, resulting in embrittlement, strength reduction, and the like. As a result, the battery case is likely to be damaged, cracked, cracked, etc., and the possibility that the electrolyte will leak increases.
Lead storage batteries are often exposed to ultraviolet rays contained in sunlight, fluorescent lamps, etc. between the time of shipment from the manufacturing factory and the time of installation. Depending on the installation work, etc., it may be left outdoors for a long time.
本発明は、ＰＰ、ＡＢＳ等の鉛蓄電池電槽用材料としての優れた特性を維持しつつ、太陽光や蛍光灯などに含まれる紫外線に曝されても、電槽樹脂の劣化を抑制する機能を有する鉛蓄電池を提供することを目的とする。 The present invention maintains the excellent characteristics as a lead-acid battery battery case such as PP and ABS, and suppresses deterioration of the battery case resin even when exposed to ultraviolet rays contained in sunlight or fluorescent lamps. It aims at providing lead acid battery which has.
（１）電槽と、この電槽の外周面に密着して配置されるフィルムとを備え、前記フィルムはポリエチレンに２−（３−ｔｅｒｔ−ブチル−２−ヒドロキシ−５−メチルフェニル）−５−クロロ−２Ｈ−ベンゾトリアゾールを添加したものであることを特徴とする鉛蓄電池。
（２）項（１）において、フィルムの厚みを、５０〜１００μｍとする鉛蓄電池。
(1) A battery case and a film disposed in close contact with the outer peripheral surface of the battery case are provided, and the film is made of 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5 on polyethylene. -Lead acid battery characterized by adding chloro-2H-benzotriazole .
(2) The lead acid battery according to item (1), wherein the thickness of the film is 50 to 100 μm.
本発明によれば、２−（３−ｔｅｒｔ−ブチル−２−ヒドロキシ−５−メチルフェニル）−５−クロロ−２Ｈ−ベンゾトリアゾールを添加することにより紫外線吸収機能を有するポリエチレンフィルムを電槽の外周面に密着して配置することにより、電槽が直接紫外線に曝されることがなくなる。その結果、紫外線による電槽樹脂の劣化が抑制され、脆化、強度低下等を抑えることができる。また、電解液を充填している電槽には、従来通りＰＰ、ＡＢＳ等を使用することができるので、鉛蓄電池の電槽用材料としての優れた特性を低下させることがない。
フィルム厚さを５０〜１００μｍとした場合、照射される紫外線をほぼ全て吸収することができるため、電槽樹脂の劣化が進行し難い。また、電槽外周面に密着させて配置することが容易で、コストも抑えることができる。
According to the present invention, a polyethylene film having an ultraviolet absorption function can be obtained by adding 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole. The battery case is not directly exposed to ultraviolet rays by being placed in close contact with the surface. As a result, deterioration of the battery case resin due to ultraviolet rays is suppressed, and embrittlement, strength reduction, and the like can be suppressed. Moreover, since PP, ABS, etc. can be used for the battery case filled with electrolyte solution as usual, the outstanding characteristic as a battery material of a lead storage battery is not deteriorated.
When the film thickness is 50 to 100 μm, almost all of the irradiated ultraviolet rays can be absorbed, so that the battery case resin hardly deteriorates. Moreover, it is easy to arrange | position closely to a battery case outer peripheral surface, and can also suppress cost.
＜電槽＞
本発明で述べる電槽は、その内部にセパレータを介して積層される正極板と負極板を有する電極群と、この電極群を浸漬させる電解液とを収容し易くするように、上面が開放された電槽本体と、この開放された上面を覆う蓋体とを備えたものが好ましい。
（電槽本体）
電槽本体は、上面が開放されていれば、特にその形状を限定されるものではなく、立方体、直方体、多角柱等とすることができるが、成形性及び搬送時の無効空間を減らせることから、立方体又は直方体形状とすることが好ましい。
電槽本体の材質は、鉛蓄電池の特性を低下させない限り特に制限されるものではない。具体的には、ＰＰ、ＡＢＳ、変性ＰＰＥ等を用いることができ、中でも、ＰＰを用いることが電解液に対する耐性、水分透過率の低さ、耐衝撃性の高さ、更には後述する蓋体との熱溶着の容易性から好ましい。
（蓋体）
蓋体は、先に述べた電槽本体の開放された上面を覆うものであれば、特に制限されるものではなく、材質についても電槽本体と同じでも、異なるものでも使用できる。但し、熱膨張による変形で蓋体の脱落が発生しないように、熱膨張係数が同程度の材質を用いることが好ましく、熱溶着性の面からも電槽本体と同じ材質を用いることが好ましい。
<Battery>
The battery case described in the present invention has an open upper surface so that it can easily accommodate an electrode group having a positive electrode plate and a negative electrode plate laminated through a separator therein and an electrolyte solution in which the electrode group is immersed. It is preferable that the battery case has a main body and a lid that covers the opened upper surface.
(Battery body)
The shape of the battery case body is not particularly limited as long as the upper surface is open, and can be a cube, a rectangular parallelepiped, a polygonal column, etc., but can reduce the formability and the invalid space during transportation. From this, it is preferable to form a cube or a rectangular parallelepiped.
The material of the battery case body is not particularly limited as long as the characteristics of the lead storage battery are not deteriorated. Specifically, PP, ABS, modified PPE, etc. can be used. Among them, the use of PP is resistant to electrolyte solution, low moisture permeability, high impact resistance, and a lid which will be described later. From the viewpoint of ease of thermal welding with.
(Lid)
The lid is not particularly limited as long as it covers the open upper surface of the battery case main body described above, and the same material as the battery case main body or a different one can be used. However, it is preferable to use a material having the same thermal expansion coefficient so that the lid body does not fall off due to deformation due to thermal expansion, and it is preferable to use the same material as that of the battery case main body from the viewpoint of thermal weldability.
＜正極板・負極板＞
正極板及び負極板は、格子基板に活物質を保持させたものであり、鋳造格子基板又はエキスパンド格子基板にペースト状活物質を保持させたペースト式極板を用いることができる。また、クラッドチューブに鉛粉を充填して製造するクラッド式極板を用いても良い。
格子基板の材質は、主原料を鉛とするもので、これにスズ、カルシウム、アンチモン等を添加することができ、特に、カルシウム及びスズを用いることが好ましい。カルシウムを添加することにより、自己放電の割合を減少させることができるが、その際の課題である集電体の腐食の起こり易さをスズの添加により抑制することができる。
ペースト式極板は、クラッド式極板より製造が容易である。ペースト状活物質の調製は、特に限定されるものではないが、一酸化鉛を含んだ鉛粉、水、硫酸等（正極、負極の特性に合わせてカットファイバ−、炭素粉末、リグニン、硫酸バリウム、鉛丹等の添加物を加える場合もある）を混練して作製するのが好ましい。
<Positive electrode plate / Negative electrode plate>
The positive electrode plate and the negative electrode plate are obtained by holding an active material on a lattice substrate, and a paste-type electrode plate in which a pasty active material is held on a cast lattice substrate or an expanded lattice substrate can be used. Further, a clad electrode plate manufactured by filling a clad tube with lead powder may be used.
The lattice substrate is made of lead as a main raw material, and tin, calcium, antimony, and the like can be added thereto. In particular, calcium and tin are preferably used. Although the proportion of self-discharge can be reduced by adding calcium, the ease of corrosion of the current collector, which is a problem at that time, can be suppressed by adding tin.
Paste electrode plates are easier to manufacture than clad electrode plates. The preparation of the paste active material is not particularly limited, but lead powder containing lead monoxide, water, sulfuric acid, etc. (cut fiber, carbon powder, lignin, barium sulfate according to the characteristics of the positive electrode and the negative electrode) In some cases, additives such as red lead may be added).
＜セパレータ＞
セパレータは、正極板と負極板との間に介在し、正極と負極との短絡を阻止できるものであれば、特に限定されるものではない。
より具体的には、ポリエチレン、ガラス不織布、ポリプロピレン等の材料からなる多孔質シート、およびこれらの材料からなる繊維の混織物等を、セパレータとして用いることができる。
<Separator>
The separator is not particularly limited as long as it is interposed between the positive electrode plate and the negative electrode plate and can prevent a short circuit between the positive electrode and the negative electrode.
More specifically, a porous sheet made of a material such as polyethylene, glass nonwoven fabric, or polypropylene, and a mixed fabric of fibers made of these materials can be used as the separator.
＜電解液＞
電解液は、特に限定されるものでないが、希硫酸を精製水で希釈し、質量パーセント濃度で約３０質量％前後に調合したものを、電池容量・寿命等を考慮した適正な濃度に調整して注液するのが好ましい。要求特性に合わせて硫酸マグネシウム、シリカゲル等の添加剤を加える場合もある。
<Electrolyte>
The electrolytic solution is not particularly limited, but diluted sulfuric acid with purified water and adjusted to a concentration of about 30% by mass concentration is adjusted to an appropriate concentration considering battery capacity and life. It is preferable to inject the liquid. Additives such as magnesium sulfate and silica gel may be added according to the required characteristics.
＜紫外線吸収機能を有するフィルム＞
紫外線吸収機能を有するフィルムは、紫外線吸収剤を含有する熱可塑性樹脂、又はベンゾフェノン骨格を有する熱可塑性樹脂を用い作製する。
（紫外線吸収剤）
紫外線吸収剤は、公知の紫外線吸収剤の中から適宜選択して使用することができる。具体的に述べると、ベンゾトリアゾール系の紫外線吸収剤としては、２−（３−ｔｅｒｔ−ブチル−２−ヒドロキシ−５−メチルフェニル）−５−クロロ−２Ｈ−ベンゾトリアゾール、２−（３，５−ジ−ｔｅｒｔ−ペンチル−２−ヒドキシフェニル）−２Ｈ−ベンゾトリアゾール、２−（２−ヒドロキシ−５−メチルフェニル）−２Ｈ−ベンゾトリアゾール、２−（２−ヒドロキシ−４−オクチルオキシフェニル）−２−ベンゾトリアゾール、２−（２−ヒドロキシ−５−ｔｅｒｔ−オクチルフェニル）−２Ｈ−ベンゾトリアゾール、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４−メチル−６−（３，４，５，６−テトラヒドロフタルイミドメチルフェノール等を用いることができる。
また、ベンゾフェノン系の紫外線吸収剤として、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン−５−スルホン酸（３水塩）、２−ヒドロキシ−４−オクチルオキシベンゾフェノン、４−ドデシルオキシ−２−ヒドロキシベンゾフェノン、２，２’４，４’−テトラヒドロキシベンゾフェノン等を用いることもできる。
（熱可塑性樹脂）
先に述べた紫外線吸収剤を含有させる熱可塑性樹脂は、特に制限されるものではなく、具体的には、ＡＢＳ、ＡＣＳ、ＡＥＳ、ＡＳ、ＡＳＡ、非晶性コポリエステル樹脂、フッ化エチレンポリプロピレンコポリマー樹脂、ポリアリレート樹脂、ポリエチレン樹脂、ポリエチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリサルホン樹脂、ポリパラビニルフェノール樹脂、ポリパラメチルスチレン樹脂、ポリアリルアミン樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンサルファイド樹脂、ポリプロピレン樹脂、等を用いることができる。特にポリプロピレン樹脂、ポリエチレン樹脂、ポリエチレンテレフタレート樹脂を用いることが、先に述べた紫外線吸収剤の添加や、フィルムの作製を容易に行うことが出来て好ましい。
（ベンゾフェノン骨格を有する熱可塑性樹脂）
ポリアリレート樹脂はベンゾフェノン骨格を有し、ベンゾフェノン骨格は紫外線を吸収する特性がある。フィルムをポリアリレート樹脂で作製すると、紫外線吸収効果を有するフィルムを得ることができる。
（フィルムの厚み）
フィルムの厚みは、特に制限されるものではないが、５０〜１００μｍであることが好ましい。５０μｍ未満であると、紫外線を吸収しきれずに徐々に紫外線の透過量が増加し電槽樹脂の劣化が起こる。１００μｍを超えると徐々にフィルムの剛性が上がり、電槽外周面への張り付けが困難となる上コストアップとなる。
<Film with ultraviolet absorbing function>
The film having an ultraviolet absorbing function is manufactured using a thermoplastic resin containing an ultraviolet absorber or a thermoplastic resin having a benzophenone skeleton.
(UV absorber)
The ultraviolet absorber can be used by appropriately selecting from known ultraviolet absorbers. Specifically, as the benzotriazole-based ultraviolet absorber, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5 -Di-tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) 2-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4, 5,6-tetrahydrophthalimidomethylphenol or the like can be used.
Further, as a benzophenone-based ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (trihydrate), 2-hydroxy-4 -Octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, etc. can also be used.
(Thermoplastic resin)
The thermoplastic resin containing the ultraviolet absorber described above is not particularly limited, and specifically, ABS, ACS, AES, AS, ASA, amorphous copolyester resin, fluorinated ethylene polypropylene copolymer Resin, polyarylate resin, polyethylene resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polysulfone resin, polyparavinylphenol resin, polyparamethylstyrene resin, polyallylamine resin, polyphenylene ether resin, polyphenylene sulfide resin, polypropylene resin, etc. Can be used. In particular, it is preferable to use a polypropylene resin, a polyethylene resin, or a polyethylene terephthalate resin because the addition of the ultraviolet absorber described above and the production of a film can be easily performed.
(Thermoplastic resin with benzophenone skeleton)
The polyarylate resin has a benzophenone skeleton, and the benzophenone skeleton absorbs ultraviolet rays. When the film is made of polyarylate resin, a film having an ultraviolet absorption effect can be obtained.
(Film thickness)
The thickness of the film is not particularly limited, but is preferably 50 to 100 μm. If it is less than 50 μm, ultraviolet rays cannot be absorbed and the amount of transmitted ultraviolet rays gradually increases, causing deterioration of the battery case resin. If it exceeds 100 μm, the rigidity of the film gradually increases, and it becomes difficult to attach the outer peripheral surface of the battery case, and the cost increases.
＜フィルムの配置位置＞
先に述べたフィルムは、電槽の外周面に密着される。尚、本明細書にて述べる外周面は、電槽の上面、側面及び底面を意味するが、必ずしもその全てに対して配置される必要はなく、外周面の一部のみに配置することもできる。例えば、電槽の底面は、紫外線の影響を受けにくいことから、この底面を除いた部分にフィルムを配置することができる。
（フィルムの密着方法）
フィルムを電槽に密着する方法は、特に制限されるものではないが、例えば接着剤により電槽本体とフィルムを接着すること、鉛蓄電池に対してフィルムを巻きつけること、筒状又は袋状のフィルムを、電池に被せた後に加温によりフィルムを収縮させて密着させる等の手法を用いることができる。
<Position of film>
The film described above is closely attached to the outer peripheral surface of the battery case. In addition, although the outer peripheral surface described in this specification means the upper surface, side surface, and bottom surface of a battery case, it does not necessarily need to be arrange | positioned with respect to all, and can also arrange | position only to a part of outer peripheral surface. . For example, since the bottom surface of the battery case is not easily affected by ultraviolet rays, a film can be disposed on a portion other than the bottom surface.
(Film adhesion method)
The method for adhering the film to the battery case is not particularly limited. For example, the battery case body and the film are bonded with an adhesive, the film is wound around a lead storage battery, a cylindrical shape or a bag shape. For example, a technique of shrinking the film by heating and causing the film to adhere after the film is placed on the battery can be used.
＜鉛蓄電池＞
本発明にて述べる鉛蓄電池は、先に述べたフィルムを電槽の外周面に密着させたものであれば他に限定されるものではない。鉛又は鉛合金製の格子基板にペースト状活物質を保持させたペースト式正負極板を、セパレータを介して組み立て極板群とし、この極板群を電槽内に配置し、電槽内に電解液を注入したものを用いることができる。また、クラッドチューブに鉛粉を充填して製造するクラッド式極板を用いた鉛蓄電池にも適用できる。
<Lead battery>
The lead storage battery described in the present invention is not limited to any other type as long as the above-described film is adhered to the outer peripheral surface of the battery case. A paste-type positive and negative electrode plate in which a paste-like active material is held on a lattice substrate made of lead or a lead alloy is assembled into an electrode plate group through a separator, and this electrode plate group is arranged in the battery case. What injected the electrolyte solution can be used. Further, the present invention can also be applied to a lead storage battery using a clad electrode plate manufactured by filling a clad tube with lead powder.
以下、本発明の実施例を、詳細に説明する。 Examples of the present invention will be described in detail below.
＜参考例１＞
縦：１６０mm × 横：５００mm × 高さ：２３０mmの電槽本体及び蓋体が、共にＰＰである鉛蓄電池と、ポリアリレート製で厚みが１００μｍのフィルム（オージーフィルム株式会社製、ＡＲＢフィルム）を準備し、蓄電池の上下面を除く電槽本体周囲面に、前記ポリアリレートフィルムを引っ張りながら１重に巻き付けて密着させ、紫外線吸収フィルム付き鉛蓄電池Ａを作製した。
ここで電槽は、蓋体には黒に着色した樹脂材料を用い、電槽本体には未着色（乳白色）の樹脂材料を用いたので、特に、紫外線により劣化が進みやすい電槽本体の周囲面に紫外線吸収フィルムを適用した。
< Reference Example 1>
Prepared: lead acid battery with length: 160 mm x width: 500 mm x height: 230 mm, both PP battery and polyarylate, 100 μm thick (ARB Film, ARB film) Then, the polyarylate film was stretched in close contact with the peripheral surface of the battery case main body except for the upper and lower surfaces of the storage battery, and the lead storage battery A with an ultraviolet absorbing film was produced.
Here, the battery case uses a resin material colored black for the lid, and an uncolored (milky white) resin material for the battery case body. An ultraviolet absorbing film was applied to the surface.
＜実施例１＞
参考例１にて用いた電槽本体及び蓋体と同仕様の鉛蓄電池を準備し、フィルム材質をポリエチレンにその質量に対し、紫外線吸収剤として２−（３−ｔｅｒｔ−ブチル−２−ヒドロキシ−５−メチルフェニル）−５−クロロ−２Ｈ−ベンゾトリアゾールを２質量％添加し、厚みを１００μｍとしたものへ変更した以外は参考例１と同様にして紫外線吸収フィルム付き鉛蓄電池Ｂを作製した。
＜比較例１＞
参考例１及び実施例１にて用いた電槽本体及び蓋体と同仕様の鉛蓄電池を準備し、紫外線吸収フィルムを配置しない鉛蓄電池Ｃを作製した。
<Example 1 >
A lead storage battery having the same specifications as the battery case and lid used in Reference Example 1 is prepared, and the film material is polyethylene and its mass is 2- (3-tert-butyl-2-hydroxy-) as an ultraviolet absorber. A lead storage battery B with an ultraviolet absorbing film was prepared in the same manner as in Reference Example 1 except that 2% by mass of 5-methylphenyl) -5-chloro-2H-benzotriazole was added and the thickness was changed to 100 μm.
<Comparative Example 1>
A lead storage battery having the same specifications as the battery case main body and the lid used in Reference Example 1 and Example 1 was prepared, and a lead storage battery C without an ultraviolet absorbing film was prepared.
＜評価＞
参考例１、実施例１及び比較例１にて作製した鉛蓄電池Ａ〜Ｃを、屋外に６ヶ月放置後、電槽側面の強度を比較した。強度は電槽側面から試験片を切り出し「ＪＩＳ−Ｋ−７１１０」に基づきアイゾット衝撃値を測定し、初期値に対する保持率で比較した。
評価結果を、下記表１に記載する。
<Evaluation>
The lead storage batteries A to C produced in Reference Example 1, Example 1 and Comparative Example 1 were left outdoors for 6 months, and then the strength of the battery case was compared. For the strength, a test piece was cut out from the side surface of the battery case, the Izod impact value was measured based on “JIS-K-7110”, and the retention was compared with the initial value.
The evaluation results are shown in Table 1 below.
強度保持率 ◎：保持率90%以上、○：保持率60〜90%未満、△：保持率60%未満
初期のアイゾット衝撃値を100としたときの保持率
上記表１より明らかなように、比較例1では屋外放置で紫外線による電槽樹脂の強度低下があったのに対して、参考例1では強度低下はほとんど無く、実施例１ではわずかな強度低下がみられた。
Strength retention ratio ◎: Retention ratio 90% or more, ○: Retention ratio 60 to less than 90%, △: Retention ratio less than 60% Retention ratio when initial Izod impact value is 100 As shown in Table 1 above, In Comparative Example 1, there was a decrease in strength of the battery case resin due to ultraviolet rays when left outdoors, whereas in Reference Example 1, there was almost no decrease in strength, and in Example 1 , a slight decrease in strength was observed.
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| KR102178899B1 (en) * | 2016-12-26 | 2020-11-13 | 주식회사 엘지화학 | Cylindrical Battery Cell Comprising Heat Shrinkage Tube Including UV Stabilizer |
| JP6791372B2 (en) * | 2016-12-26 | 2020-11-25 | エルジー・ケム・リミテッド | Cylindrical battery cell with heat shrinkable tube containing UV absorber |
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| JPS5072144A (en) * | 1973-10-30 | 1975-06-14 | ||
| JPS6132951A (en) * | 1984-07-25 | 1986-02-15 | Shin Kobe Electric Mach Co Ltd | Sealed lead storage battery |
| JPH042038A (en) * | 1990-04-18 | 1992-01-07 | Matsushita Electric Ind Co Ltd | Lead acid battery |
| JPH04155746A (en) * | 1990-10-18 | 1992-05-28 | Matsushita Electric Ind Co Ltd | Thermal insulation device for lead-acid battery |
| JPH11198330A (en) * | 1998-01-12 | 1999-07-27 | Unitika Ltd | Weather resistant polycarbonate resin plate |
| ATE239052T1 (en) * | 1998-11-10 | 2003-05-15 | Procter & Gamble | FILM WITH UV BARRIER PROPERTIES |
| JP2001357821A (en) * | 2000-06-16 | 2001-12-26 | Yuasa Corp | Battery container for control valve type lead-acid battery and its manufacturing method |
| JP2006269087A (en) * | 2005-03-22 | 2006-10-05 | Matsushita Electric Ind Co Ltd | Lead storage battery package |
| JP2006348098A (en) * | 2005-06-14 | 2006-12-28 | Daicel Polymer Ltd | Resin composition for casing of lead storage battery |
| JP5481773B2 (en) * | 2007-08-08 | 2014-04-23 | 三菱エンジニアリングプラスチックス株式会社 | Aromatic polycarbonate resin composition and molded article thereof |
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| CN108886112B (en) * | 2016-11-28 | 2019-10-11 | 大日本印刷株式会社 | Battery use packing material, the manufacturing method of battery use packing material and battery |
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