JP2904339B2 - Painted metal plate for alkaline battery positive electrode can - Google Patents
Painted metal plate for alkaline battery positive electrode canInfo
- Publication number
- JP2904339B2 JP2904339B2 JP7294885A JP29488595A JP2904339B2 JP 2904339 B2 JP2904339 B2 JP 2904339B2 JP 7294885 A JP7294885 A JP 7294885A JP 29488595 A JP29488595 A JP 29488595A JP 2904339 B2 JP2904339 B2 JP 2904339B2
- Authority
- JP
- Japan
- Prior art keywords
- coating
- film
- metal plate
- positive electrode
- coating film
- 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.)
- Expired - Fee Related
Links
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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属板の表面を黒鉛粉
末、カ−ボンブラックの一方もしくは両者を含有する樹
脂塗膜で被覆したアルカリ乾電池正極缶用塗装金属板に
おいて、絞り加工で正極缶に加工しても、塗膜表層が脱
落しにくくしたものに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated metal plate for an alkaline dry battery positive electrode can having a surface coated with a resin coating containing one or both of graphite powder and carbon black. The present invention relates to a material in which the surface layer of a coating film is hardly dropped even when processed into a can.
【０００２】[0002]
【従来技術】従来、アルカリ乾電池の正極缶は、冷延鋼
板やＮｉめっき冷延鋼板を所定の形状に打ち抜いて、円
筒状などに多段絞り加工にした後、炭素系導電材を含有
させた導電性樹脂塗料を内面にスプレ−塗装やハケ塗り
塗装で塗装する方法で製造していたが、この製造方法は
塗装作業性に劣り、また、内面を均一に塗装することが
困難であった。そこで、本発明者らは先に所定の形状に
打ち抜いて、絞り加工するだけで正極缶を製造できる塗
装金属板を提案した（特開平６−３４２６５３号公
報）。2. Description of the Related Art Conventionally, a positive electrode can of an alkaline dry battery is prepared by punching a cold-rolled steel sheet or a Ni-plated cold-rolled steel sheet into a predetermined shape, performing a multi-stage drawing process into a cylindrical shape or the like, and then adding a carbon-based conductive material. However, this method is inferior in the workability of coating and it is difficult to uniformly coat the inner surface. Therefore, the present inventors have previously proposed a coated metal plate capable of manufacturing a positive electrode can simply by punching into a predetermined shape and performing drawing (Japanese Patent Laid-Open No. 6-342553).
【０００３】この塗装金属板は、導電材として、純度が
９５％以上でアスペクト比が５０以上に薄片化された平
均粒子径５０μｍ以下の黒鉛粉末および／またはＤＢＰ
を用いて測定した吸油量が２５０ｍｌ／１００ｇ以上の
カ−ボンブラックを樹脂１００重量部に対して、両者の
各配合重量部を直角座標で表示した場合の比率が黒鉛粉
末：カ−ボンブラックの比率で、（２０：０）と（１０
０：０）、（１００：０）と（５０：１５）、（５０：
１５）と（０：２０）、（０：２０）と（０：５）、お
よび（０：５）と（２０：０）の各比率を結ぶ直線（直
線も含む）で囲まれた範囲になるように含有させたエポ
キシ系樹脂、エポキシ／アクリル系樹脂、ポリエステル
系樹脂のいずれか１種を主成分とする塗膜もしくはこれ
に架橋剤を配合した塗膜で金属板の表面を被覆したもの
で、塗膜は単層にしていた。また、金属板表面には塗膜
密着性や耐食性を高めるため、クロメ−ト皮膜またはカ
−ボンブラック含有のクロメ−ト皮膜を形成することも
可能であるとしている。[0003] The coated metal plate is used as a conductive material in the form of graphite powder having a purity of 95% or more and an aspect ratio of 50 or more and exfoliated and having an average particle diameter of 50 µm or less and / or DBP.
The ratio of the carbon black having an oil absorption of 250 ml / 100 g or more measured by using the above formula is 100 parts by weight of the resin and the blending parts of the two are indicated by rectangular coordinates. (20: 0) and (10
0: 0), (100: 0) and (50:15), (50:
15) and (0:20), (0:20) and (0: 5), and (0: 5) and (20: 0) in the range surrounded by straight lines (including straight lines) connecting the respective ratios. A metal plate whose surface is coated with a coating mainly composed of any one of an epoxy resin, an epoxy / acrylic resin, and a polyester resin or a coating containing a crosslinking agent. The coating was a single layer. It is also stated that a chromate film or a chromate film containing carbon black can be formed on the surface of the metal plate in order to enhance the adhesion of the coating film and the corrosion resistance.
【０００４】しかしながら、この塗装金属板は、絞り加
工で正極缶に加工する際、しごきにより塗膜表層が脱落
して、ポンチやダイスに付着し、次第に蓄積されて、形
状不良や打痕が発生するという問題があった。However, when this coated metal plate is processed into a positive electrode can by drawing, the surface layer of the coating film falls off due to ironing, adheres to punches and dies, gradually accumulates, and a defective shape or dent occurs. There was a problem of doing.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、絞り加工時
のこの塗膜表層脱落が発生しないアルカリ乾電池正極缶
用塗装金属板を提供するものである。SUMMARY OF THE INVENTION The present invention is to provide a coated metal plate for a positive electrode can of an alkaline dry battery in which the surface layer of the coating film does not drop off during drawing.
【０００６】[0006]
【課題を解決するための手段】本発明は、導電材とし
て、純度が９５％以上でアスペクト比が５０以上に薄片
化された平均粒子径５０μｍ以下の黒鉛粉末および／ま
たはＤＢＰを用いて測定した吸油量が２５０ｍｌ／１０
０ｇ以上のカ−ボンブラックを含有させた樹脂塗膜で金
属板の表面を被覆した塗装金属板において、樹脂塗膜を
２層構造にして、上塗り塗膜の導電材含有量を下塗り塗
膜より少なくし、上塗り塗膜の体積抵抗率を１×１０6
Ω・ｃｍ以上、１×１０7Ω・ｃｍ未満にするととも
に、下塗り塗膜のそれを１×１０4Ω・ｃｍ未満にし
た。According to the present invention, the conductive material is measured using graphite powder and / or DBP having an average particle diameter of 50 μm or less and exfoliated to a purity of 95% or more and an aspect ratio of 50 or more. Oil absorption 250ml / 10
In a coated metal plate in which the surface of a metal plate is coated with a resin coating film containing 0 g or more of carbon black, the resin coating film has a two-layer structure, and the conductive material content of the top coating film is lower than that of the undercoat coating film. Reduce the volume resistivity of the top coat to 1 × 10 6
Ω · cm or more and less than 1 × 10 7 Ω · cm, and that of the undercoat film was less than 1 × 10 4 Ω · cm.
【０００７】[0007]
【作用】本発明者らは、塗膜が単層である従来の塗装金
属板の絞り加工時の塗膜表層脱落を防止すべく、種々検
討した結果、塗膜を２層構造にして、上塗り塗膜の導電
材含有量を下塗り塗膜より少なくすることにより上塗り
塗膜の加工性を高めたところ、塗膜表層が脱落しにくく
なることを見いだしたのである。しかし、上塗り塗膜の
導電材含有量をあまり少なくすると、導電性が損なわ
れ、電池性能が低下するので、体積抵抗率で１×１０6
Ω・ｃｍ以上、１×１０7Ω・ｃｍ未満にすることが必
要であった。一方、下塗り塗膜は導電材含有量を多くす
るのであるが、その含有量を体積抵抗率で１×１０4Ω
・ｃｍ未満にすると、加工性を良好にすることができる
ことを見いだした。The present inventors have conducted various studies to prevent the coating film surface layer from falling off during drawing of a conventional painted metal plate having a single coating film. When the workability of the overcoating film was enhanced by making the conductive material content of the coating film smaller than that of the undercoating film, it was found that the surface layer of the coating film became difficult to fall off. However, if the content of the conductive material in the overcoat is too small, the conductivity is impaired and the battery performance is reduced, so that the volume resistivity is 1 × 10 6.
It was necessary to be not less than Ω · cm and less than 1 × 10 7 Ω · cm. On the other hand, the undercoating film increases the conductive material content, but the content is determined to be 1 × 10 4 Ω in volume resistivity.
・ It was found that when the diameter is less than cm, workability can be improved.
【０００８】上塗り塗膜は、膜厚を１〜３μｍにするの
が好ましい。１μｍ未満では絞り加工時のかじりに対し
て充分な膜厚がないため、塗膜脱落を起こし易く、３μ
ｍを超えると、導電性不足を生じる。下塗り塗膜の膜厚
は上塗り塗膜の２〜５倍程度にするのが望ましい。２倍
未満では絞り加工後の塗膜が薄くなるため、耐食性が不
充分となり、５倍を超えると、塗膜密着性が低下して、
塗膜脱落が起こり易くなる。[0008] It is preferable that the thickness of the overcoat film is 1 to 3 µm. When the thickness is less than 1 μm, there is not a sufficient film thickness against galling during drawing, and the coating film is liable to fall off.
If it exceeds m, conductivity will be insufficient. The thickness of the undercoat film is desirably about 2 to 5 times the thickness of the overcoat film. If it is less than 2 times, the paint film after drawing becomes thin, so the corrosion resistance is insufficient. If it exceeds 5 times, the adhesion of the paint film decreases,
The coating film easily falls off.
【０００９】塗膜樹脂は、上塗り塗膜、下塗り塗膜を同
種、異種でもよい。樹脂としては従来使用していたエポ
キシ系、エポキシ−アクリル系、ポリエステル系等のほ
かにシリコ−ン系、フッ素系、オレフィン系などを使用
してもよい。これらの樹脂は架橋剤を含有していてもよ
い。The coating resin may be the same type or different types of the top coat and the undercoat. As the resin, a silicone-based, fluorine-based, olefin-based resin or the like may be used in addition to the conventionally used epoxy-based, epoxy-acrylic-based, polyester-based resin and the like. These resins may contain a crosslinking agent.
【００１０】[0010]
【実施例】板厚０.２５ｍｍのＮｉめっき鋼板をアルカ
リ脱脂して、リン酸塩処理、湯洗を施した後、ＣｒＯ3
７０ｇ/ｌ、全クロムの４０％の３価クロム、シリカ２.
５％、アクリル系エマルジョン樹脂４％を含有する塗布
型クロメ−ト処理液を塗布して、クロム付着量１０ｍｇ
／ｍ2のクロメ−ト皮膜を形成し、乾燥した。その後引
き続いてクロメ−ト皮膜の上に下記要領でフッ素系樹脂
塗料（フッ化ビニリデン樹脂７０重量部とアクリル樹脂
３０重量部の混合物）の下塗り塗膜と上塗り塗膜とを形
成した。EXAMPLES Ni plating steel sheet having a thickness of 0.25mm by alkaline degreasing, phosphating, after performing hot water, CrO 3
70 g / l, 40% of total chromium, trivalent chromium, silica 2.
A coating type chromate treatment solution containing 5% and 4% of an acrylic emulsion resin is applied, and a chromium adhesion amount of 10 mg is applied.
/ M 2 of chromate film was formed and dried. Thereafter, an undercoat film and an overcoat film of a fluororesin paint (a mixture of 70 parts by weight of vinylidene fluoride resin and 30 parts by weight of an acrylic resin) were formed on the chromate film in the following manner.
【００１１】（１）下塗り塗膜 （Ａ）塗料 樹脂１００重量部に対して純度９９.５％、アスペクト
比１００、ＤＢＰ吸油量１６７ｍｌ／１００ｇ、平均粒
子径１０μｍの黒鉛粉末およびＤＢＰ吸油量５００ｍｌ
／１００ｇのカ−ボンブラックを配合したもの。 （Ｂ）塗装条件 乾燥塗膜厚で６μｍになるようにバ−コ−タ−で塗装し
て、最高到達板温２５０℃、乾燥時間６０秒で焼付硬化
させた。(1) Undercoating film (A) Paint 99.5% purity, 100 parts by weight of resin, aspect ratio 100, DBP oil absorption 167 ml / 100 g, average particle diameter 10 μm Graphite powder and DBP oil absorption 500 ml
/ 100g of carbon black blended. (B) Coating conditions Coating was performed with a bar coater so that the thickness of the dried coating film became 6 μm, and the coating film was baked and cured at a maximum temperature of 250 ° C. and a drying time of 60 seconds.
【００１２】（２）上塗り塗膜 （Ａ）塗料 樹脂１００重量部に対して純度９９.５％、アスペクト
比１５０、ＤＢＰ吸油量２３６ｍｌ／１００ｇ、平均粒
子径５μｍの黒鉛粉末および／またはＤＢＰ吸油量５５
９ｍｌ／１００ｇのカ−ボンブラックを配合したもの。 （Ｂ）塗装条件 乾燥塗膜厚で２μｍになるようにバ−コ−タ−で塗装し
て、最高到達板温２５０℃、乾燥時間６０秒で焼付硬化
させた。(2) Overcoating film (A) Paint 100% by weight of resin 99.5% purity, aspect ratio 150, DBP oil absorption 236ml / 100g, average particle diameter 5μm Graphite powder and / or DBP oil absorption 55
A blend of 9 ml / 100 g of carbon black. (B) Coating conditions Coating was performed with a bar coater so that the thickness of the dried coating film was 2 μm, and the coating was baked and cured at a maximum temperature of 250 ° C. and a drying time of 60 seconds.
【００１３】以上のようにして製造した塗装鋼板の塗膜
密着性、絞り加工性、短絡電流を下記要領で評価した。
表１に塗膜構造を、表２に塗膜性能を示す。 （１）塗膜密着性試験 ＪＩＳ Ｋ ５４００に準拠してゴバン目、ゴバン目エリ
クセン、デュポン衝撃の各試験を実施し、これらの試験
での塗膜剥離状態を総合し、◎（良好）、○、△、×
（不良）で評価した。The coating film adhesion, drawability, and short-circuit current of the coated steel sheet manufactured as described above were evaluated in the following manner.
Table 1 shows the coating film structure, and Table 2 shows the coating film performance. (1) Coating film adhesion test The following tests were conducted for Goban eyes, Goban eyes Eriksen, and Dupont impact in accordance with JIS K 5400, and the peeling state of the coating films in these tests was comprehensively evaluated. , △, ×
(Poor) was evaluated.
【００１４】（２）絞り加工性試験 単３型のアルカリ乾電池の正極缶に絞り加工（ブランキ
ング径５５ｍｍ、最終直径１３.８５ｍｍ）で連続加工
して、１０万個加工後の塗膜剥離状態を◎（良好）、
○、△、×（不良）で評価した。 （３）短絡電流試験 前記絞り加工性試験で製造した正極缶を温度６０℃、相
対湿度９０％の雰囲気に２０日間放置し、短絡電流残存
率を９５％以上◎、９０％以上９５％未満○、９０％未
満×で評価した。(2) Drawability Test A continuous process is performed by drawing (blanking diameter 55 mm, final diameter 13.85 mm) on the positive electrode can of AA alkaline batteries, and the peeling state of the coating film after processing 100,000 pieces ◎ (good),
△, Δ, × (poor) were evaluated. (3) Short-circuit current test The positive electrode can produced in the drawability test was left in an atmosphere at a temperature of 60 ° C and a relative humidity of 90% for 20 days, and the short-circuit current residual ratio was 95% or more ◎, 90% or more and less than 95%. , Less than 90%.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【表２】 [Table 2]
【００１７】[0017]
【発明の効果】以上のように、本発明の導電性塗装金属
板は、絞り加工でアルカリ乾電池正極缶に連続加工して
も、塗膜表層が脱落しない。As described above, the conductive coated metal sheet of the present invention does not lose its surface layer even when it is continuously processed into a positive electrode can of an alkaline dry battery by drawing.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 前田 靖治 千葉県市川市高谷新町７番地の１ 日新 製鋼株式会社 技術研究所 塗覆装研究 部内 (72)発明者 村上 雅洋 千葉県市川市高谷新町７番地の１ 日新 製鋼株式会社 技術研究所 塗覆装研究 部内 (72)発明者 牧野 智訓 千葉県市川市高谷新町７番地の１ 日新 製鋼株式会社 技術研究所 塗覆装研究 部内 (72)発明者 上杉 武人 大阪府守口市京阪本通２丁目５番５号 三洋エクセル株式会社内 (72)発明者 栗村 正明 大阪府守口市京阪本通２丁目５番５号 三洋エクセル株式会社内 (72)発明者 鹿田 和裕 大阪府守口市京阪本通２丁目５番５号 三洋エクセル株式会社内 (56)参考文献 特開 平６−342653（ＪＰ，Ａ) 特開 昭61−115972（ＪＰ，Ａ) 実開 平３−112997（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 2/02 H01M 2/22 - 2/26 H01M 6/04 - 6/12 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuji Maeda 1-7-1 Nishinmachi, Takayashinmachi, Ichikawa-shi, Chiba Co., Ltd. Nishishin Steel Engineering Co., Ltd. Technical Research Laboratory Paint-coating Research Department (72) Inventor Masahiro Murakami Takamachi-Shinmachi, Ichikawa-shi, Chiba 7-in-1 Nisshin Steel Co., Ltd.Technical Research Laboratory, Paint Coating Research Department (72) Inventor Tomonori Makino 7-in-1 Nisshin Steel Co., Ltd.Technical Research Laboratory Coating Coating Research Department, 72 Inventor Taketo Uesugi 2-5-5-Keihanhondori, Moriguchi-shi, Osaka Sanyo Excel Co., Ltd. (72) Inventor Masaaki Kurimura 2-5-5-Keihanhondori, Moriguchi-shi, Osaka Sanyo Excel Co., Ltd. (72 ) Inventor Kazuhiro Shikata 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Excel Co., Ltd. (56) References JP-A-6-342653 (JP A) Patent Akira 61-115972 (JP, A) JitsuHiraku flat 3-112997 (JP, U) (58 ) investigated the field (Int.Cl. 6, DB name) H01M 2/02 H01M 2/22 - 2 / 26 H01M 6/04-6/12
Claims (1)
スペクト比が５０以上に薄片化された平均粒子径５０μ
ｍ以下の黒鉛粉末および／またはＤＢＰを用いて測定し
た吸油量が２５０ｍｌ／１００ｇ以上のカ−ボンブラッ
クを含有させた樹脂塗膜で金属板の表面を被覆した塗装
金属板において、樹脂塗膜を２層構造にして、上塗り塗
膜の導電材含有量を下塗り塗膜より少なくし、上塗り塗
膜の体積抵抗率を１×１０6Ω・ｃｍ以上、１×１０7Ω
・ｃｍ未満にするとともに、下塗り塗膜のそれを１×１
０4Ω・ｃｍ未満にしたことを特徴とするアルカリ乾電
池正極缶用塗装金属板。1. A conductive material having an average particle diameter of 50 μm, which is sliced to a purity of 95% or more and an aspect ratio of 50 or more.
m of graphite powder and / or DBP, the oil absorption of which is 250 ml / 100 g or more. With a two-layer structure, the conductive material content of the overcoat is lower than that of the undercoat, and the volume resistivity of the overcoat is 1 × 10 6 Ω · cm or more and 1 × 10 7 Ω.
・ Less than 1 cm
0 4 Omega · alkaline batteries cathode can for coated metal sheets, characterized in that it has less than cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7294885A JP2904339B2 (en) | 1995-10-18 | 1995-10-18 | Painted metal plate for alkaline battery positive electrode can |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7294885A JP2904339B2 (en) | 1995-10-18 | 1995-10-18 | Painted metal plate for alkaline battery positive electrode can |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09115493A JPH09115493A (en) | 1997-05-02 |
| JP2904339B2 true JP2904339B2 (en) | 1999-06-14 |
Family
ID=17813514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7294885A Expired - Fee Related JP2904339B2 (en) | 1995-10-18 | 1995-10-18 | Painted metal plate for alkaline battery positive electrode can |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2904339B2 (en) |
-
1995
- 1995-10-18 JP JP7294885A patent/JP2904339B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09115493A (en) | 1997-05-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19990302 |
|
| LAPS | Cancellation because of no payment of annual fees |