JP2003063518A - Steel di can - Google Patents
Steel di canInfo
- Publication number
- JP2003063518A JP2003063518A JP2001253501A JP2001253501A JP2003063518A JP 2003063518 A JP2003063518 A JP 2003063518A JP 2001253501 A JP2001253501 A JP 2001253501A JP 2001253501 A JP2001253501 A JP 2001253501A JP 2003063518 A JP2003063518 A JP 2003063518A
- Authority
- JP
- Japan
- Prior art keywords
- amount
- chemical conversion
- steel
- coating film
- metal
- 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.)
- Granted
Links
Landscapes
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Shaping Metal By Deep-Drawing, Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はスチールを素材とし
た絞り−しごき加工して成形されるＤＩ缶に関するもの
で、塗膜密着性、耐食性に優れた缶体を提供するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a DI can formed from steel by drawing and ironing, and provides a can body having excellent coating film adhesion and corrosion resistance.
【０００２】[0002]
【従来の技術】金属缶には、筒状の缶胴を製造し、その
両端開口部に、天蓋および地蓋を巻締めたスリーピース
缶と、缶胴と地蓋が一体となった有底筒状容器に天蓋を
巻締めたツーピース缶とがある。スリーピース缶は、缶
胴を電気抵抗溶接や接着剤等で接合するため、素材とし
てはスチールの薄板が使用される。一方、ツーピース缶
の一種は、缶胴と地蓋が一体となった有底筒状容器が絞
り加工や絞り−しごき加工（Ｄｒａｗｎ ａｎｄ Ｉｒ
ｏｎｅｄ）によって得られるため一般にＤＩ缶と呼ばれ
る。このＤＩ缶は、缶胴の接合を必要とせず、素材とし
てはアルミニウム合金やスチール等の薄板が使用され
る。スチールおよびアルミニウム合金を素材としたＤＩ
缶では、缶体成形後、脱脂・化成処理工程を経て、缶の
内面側は耐食性確保の観点から塗装が、外面側は商標や
装飾のため印刷・塗装が施されて使用されている。スチ
ール素材のＤＩ缶の内面側の耐食性について言えば、化
成処理皮膜だけでは耐食性を向上させることは殆ど難し
く、結局は化成処理後に施される塗装に頼っており、し
かもその塗布量はスチールを素材としたＤＩ缶の場合は
アルミニウム合金を素材としたＤＩ缶に比べて多くして
おり、それは素材の耐食性がアルミニウム合金に比べて
スチールの方が劣ることに起因している。2. Description of the Related Art For metal cans, a tubular can body is manufactured, and a three-piece can with a canopy and a canopy wrapped around the openings at both ends, and a bottomed cylinder in which the can body and the canister are integrated. There is a two-piece can in which a canopy is wrapped around a rectangular container. In a three-piece can, since a can body is joined by electric resistance welding or an adhesive, a thin steel plate is used as a material. On the other hand, as a type of two-piece can, a bottomed cylindrical container in which a can body and a lid are integrated is drawn or drawn-ironed (Drawn and Ir).
It is generally referred to as a DI can because it is obtained by oned). This DI can does not require a can body to be joined, and a thin plate of aluminum alloy, steel or the like is used as a material. DI made from steel and aluminum alloy
In the can, after the can body is formed, a degreasing / chemical conversion treatment process is performed, and the inside surface of the can is coated from the viewpoint of ensuring corrosion resistance, and the outside surface is printed / painted for trademark or decoration. Speaking of the corrosion resistance on the inner surface side of steel DI cans, it is almost difficult to improve the corrosion resistance only with a chemical conversion coating, and in the end it depends on the coating applied after the chemical conversion treatment. In the case of the DI can, the number is higher than that of the DI can made of aluminum alloy, which is due to the fact that the corrosion resistance of the material is inferior to steel as compared to aluminum alloy.
【０００３】又、缶の外面側はスチールを素材としたＤ
Ｉ缶では印刷デザインにもよるが、印刷外観の点から多
くの場合白色塗装が施された後、印刷、クリアーが行わ
れている。しかも、スチールの場合は金属固有の分光反
射率がアルミニウム合金に比べて低いことから、黒みを
呈する色調（黒みがかった色調）となるため、白色塗料
の塗布量はアルミニウム合金を素材とした場合に比べ多
くする必要がある。このように、スチールを素材とした
ＤＩ缶の場合、内面の塗装および外面の白色塗装の塗布
量は、いずれもアルミニウム合金を素材とした場合に比
べ、多くする必要があることから、製造コストはむしろ
高くなる場合があり、金属素材の価格差はなくなってし
まうどころか、トータルコストとしても割高となる場合
もある。また、非常に希なケ−スではあるが、スチール
を素材としたＤＩ缶の場合、特に、レトルト加熱殺菌処
理を行う内容物を充填した場合に、缶外面側の塗膜が蓋
の巻締め部の中から巻締めの外まで達する局部的な浮き
が発生することがある。こうした局部浮きは商品価値を
著しく低下させることがあるので好ましくない。こうし
た缶外面塗膜が局部的に浮くと言った現象は、（１）ア
ルミニウム合金の蓋を巻しめた場合にのみ起こり、
（２）胴材がアルミニウム合金を素材としたＤＩ缶では
見られないことから、アルミニウム合金蓋とスチール缶
胴が接触して起こる「異種金属接触腐食」によるものと
考えられている。The outer surface of the can is made of steel D
Although it depends on the printing design of the I can, in many cases, printing and clearing are performed after white coating is applied from the viewpoint of printing appearance. Moreover, since steel has a lower spectral reflectance specific to metals than aluminum alloys, it gives a blackish tone (blackish tone), so the amount of white paint applied is less than that of aluminum alloys. It is necessary to make more. As described above, in the case of a DI can made of steel, it is necessary to increase the coating amount of the inner coating and the white coating of the outer surface as compared with the case where the aluminum alloy is used as the material. Rather, it may be higher, and the total cost may be higher than the price difference of metal materials. Also, although it is a very rare case, in the case of a DI can made of steel, especially, when the contents to be heat-sterilized by retort are filled, the coating film on the outer surface of the can is wrapped around the lid. Local lift may occur from the inside of the part to the outside of the winding. Such local floating is not preferable because it may significantly reduce the commercial value. The phenomenon that the coating film on the outer surface of the can floats locally occurs only when (1) the aluminum alloy lid is wound,
(2) Since the body material is not found in DI cans made of aluminum alloy, it is considered to be caused by "dissimilar metal contact corrosion" caused by contact between the aluminum alloy lid and the steel can body.
【０００４】また、近年のトータル缶コストの低減化か
ら、使用金属板の板厚の低減化（薄板化）や缶蓋である
アルミニウム合金製の開口容易缶蓋（イージーオープン
エンド、通称ＥＯＥ）の径を小さくすることが進み、例
えば、缶胴が３５０ｍｌのビール缶の場合、通称２１１
径と呼ばれ、缶胴直径は約６６ｍｍであり、当然巻締め
る缶蓋も２１１径用であったが、現在は２０６径（直径
約５８ｍｍ）化、２０４径（直径約５５ｍｍ）化、２０
２径（直径約５２ｍｍ）化となっており、更には２００
径（直径約４９ｍｍ）化が進められている。このこと
は、必然的に缶胴の開口部をネック加工又はネックイン
加工により、より小さい径に絞る、いわゆる縮径化とな
り、従って缶胴に用いられている金属は勿論、その表面
に被覆されている有機塗料にとっても厳しい加工をうけ
ることになる。ＤＩ缶成形後の化成処理はこうした耐食
性や縮径化に対応すべく改良検討がなされており、スチ
−ルを素材としたＤＩ缶の化成処理は、現在は主にリン
酸Ｓｎ系の化成処理が多く適用されている。しかし、現
在適用されているリン酸Ｓｎ系の化成処理では、スチー
ルを素材としたＤＩ缶が持つ多くの問題を解決すること
は難しい。In addition, due to the recent reduction in the total cost of cans, the thickness of metal plates used has been reduced (thinned) and the can lids made of aluminum alloy that are easy to open (easy open end, commonly known as EOE) have been used. For example, in the case of a beer can having a can body of 350 ml, the common name is 211
The diameter of the can body is about 66 mm, and naturally the can lid to be tightened was also for 211 diameter, but now it is 206 diameter (diameter about 58 mm), 204 diameter (diameter about 55 mm), 20
2 diameters (about 52 mm in diameter) and 200
The diameter (about 49 mm) is being promoted. This inevitably results in so-called diameter reduction by narrowing the opening of the can body to a smaller diameter by neck processing or neck-in processing, so that not only the metal used for the can body but also the surface thereof is coated. Even the organic paints that are used are subject to severe processing. The chemical conversion treatment after molding of DI cans has been studied for improvement in order to cope with such corrosion resistance and diameter reduction. Currently, the conversion treatment of DI cans made of steel is mainly Sn phosphate conversion treatment. Is often applied. However, it is difficult to solve many problems of DI cans made of steel by the currently applied Sn phosphate conversion treatment.
【０００５】スチールを素材としたＤＩ缶の化成処理技
術について言えば、例えば特開平１−１７７３７９号公
報、特開平２−６０８号公報、特開平１１−２６４０７
５号公報等に開示されているが、こうした先行技術では
現在要求されている塗膜密着性や耐食性と言った性能面
で不十分であり、また前述した希に発生するレトルト加
熱殺菌処理時の缶外面側の塗膜浮きを防止できないと言
った問題を有している。スチ−ル素材のＤＩ缶は、アル
ミニウム合金素材のＤＩ缶に比べ、缶重量が重い、対内
容物耐食性が劣る、印刷外観が黒ずむ、と言った欠点が
あるが、一方缶の流がスムースである、天蓋の巻締性が
良く安定していると言った利点もあり、更には素材価格
が安価であることから、現状の缶性能が向上できればス
チール素材のＤＩ缶を使用したいと言う声は根強くあ
る。こうした状況から、スチール素材のＤＩ缶の缶体自
身の耐食性や缶内外面の塗膜の加工密着性を少しでも向
上できる新しい化成処理剤の出現の期待が強くあった。Regarding the chemical conversion treatment technology for DI cans made of steel, for example, JP-A-1-177379, JP-A-2-608, and JP-A-11-26407.
As disclosed in Japanese Patent Publication No. 5, etc., such prior art is insufficient in terms of performance such as coating film adhesion and corrosion resistance currently required, and the above-mentioned rare occurrence of retort heat sterilization treatment There is a problem that the coating film floating on the outer surface of the can cannot be prevented. DI cans made of steel materials have the disadvantages of being heavier than DI cans made of aluminum alloy materials, being inferior in corrosion resistance to contents, and having a dark printed appearance, but the can flow is smooth. There is also the advantage that the canopy is well wound and stable, and because the material price is low, there is a voice that wants to use the steel material DI can if the current can performance can be improved. It is deep-rooted. Under these circumstances, there was a strong expectation for the appearance of a new chemical conversion treatment agent that could improve the corrosion resistance of the steel body of the steel can and the processing adhesion of the coating film on the inside and outside of the can.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、スチ
ールを素材としたＤＩ缶の塗料密着性や耐食性を大幅に
改善させ、より高品質で生産歩留まりの良い缶を提供す
る点にあるDISCLOSURE OF THE INVENTION An object of the present invention is to significantly improve the paint adhesion and corrosion resistance of DI cans made of steel, and to provide cans of higher quality and good production yield.
【０００７】[0007]
【課題を解決するための手段】本発明の第１は、絞りし
ごき加工によって得られるスチール製ＤＩ缶において、
缶の内外面の鋼板表面にリン（Ｐ）−金属（Ｍ）−有機
樹脂（Ｒ）からなる化成処理皮膜が形成されており、該
化成処理皮膜がリン（Ｐ）の付着量としては、片面の付
着量として０．０５〜２．０ｍｇ／ｍ２、金属（Ｍ）が
片面の付着量として０．０５〜２．０ｍｇ／ｍ２、有機
樹脂（Ｒ）の付着量が炭素（Ｃ）量として片面の付着量
で０．５〜２０ｍｇ／ｍ２であり、かつ炭素（Ｃ）量と
金属（Ｍ）付着量の比 Ｃ／Ｍ が１〜１００であるこ
とを特徴とするスチ−ル製ＤＩ缶に関する。本発明の第
２は、請求項１記載の化成処理皮膜の金属（Ｍ）がジル
コニウム、チタニウム、スズから選ばれる１種または２
種以上であることを特徴とする請求項１記載のスチ−ル
製ＤＩ缶に関する。The first aspect of the present invention is to provide a steel DI can obtained by drawing and ironing.
A chemical conversion treatment film composed of phosphorus (P) -metal (M) -organic resin (R) is formed on the steel plate surface on the inner and outer surfaces of the can, and the chemical conversion treatment film has a phosphorus (P) adhesion amount of one side. adhesion amount of carbon (C) content of the deposited amount as 0.05 to 2.0 mg / m 2, a metal (M) is 0.05 to 2.0 mg / m 2 as an adhesion amount of the one side, an organic resin (R) of As a steel, the amount of adhesion on one side is 0.5 to 20 mg / m 2 , and the ratio C / M of the amount of carbon (C) to the amount of metal (M) is 1 to 100. Regarding DI cans. A second aspect of the present invention is one or two in which the metal (M) of the chemical conversion treatment film according to claim 1 is selected from zirconium, titanium and tin.
The steel DI can according to claim 1, wherein the DI can is at least one kind.
【０００８】本発明における缶体は、スチールを素材と
した絞り−しごき加工によって得られる、有底のツーピ
ース缶（ドロー・アイアニング缶、 ＤＩ缶）である。
スチール素材としては特に限定するものではないが、現
在ＤＩ缶として適用されている薄鋼板にＳｎめっきが施
されたブリキが使用される。好ましい具体例としては、
板厚が０．１５ｍｍ〜０．３０ｍｍの薄鋼板に片面の付
着量として１．０〜６．０ｇ／ｍ２の錫めっき鋼板があ
げられる。板厚は、主に缶強度、特に缶底の耐圧強度
（通称ボトム耐圧）によって決められ、内容物を充填し
た後の内圧によって板厚は選定され、内圧が高い例え
ば、炭酸飲料やビール等を充填・密封する内圧缶の場合
は、板厚が０．１５ｍｍ以下では、いわゆるバックリン
グと呼ばれる、缶底部が外方へ張り出した状態になる場
合があり好ましくない。一方、スチール素材の場合は、
０．３０ｍｍ以上の板厚は耐圧強度は十分に確保される
が、実質的に過剰品質であり、経済的でない。前記のバ
ックリングといった現象は、同一板厚でも金属素材の機
械的強度によって発生するか否かが分かれるため、機械
的強度が高い場合は板厚の薄手化は可能となることか
ら、板厚は、缶全体の強度バランスを考慮し、適宜選択
することが望ましい。The can body in the present invention is a bottomed two-piece can (draw / ironing can, DI can) obtained by squeezing and ironing steel.
The steel material is not particularly limited, but a tin plate obtained by Sn-plating a thin steel plate currently applied as a DI can is used. As a preferred specific example,
As a thin steel plate having a plate thickness of 0.15 mm to 0.30 mm, a tin-plated steel plate having an adhesion amount on one surface of 1.0 to 6.0 g / m 2 can be mentioned. The plate thickness is mainly determined by the strength of the can, especially the pressure resistance of the can bottom (commonly called the bottom pressure resistance), and the plate thickness is selected by the internal pressure after filling the contents. In the case of an internal pressure can to be filled and sealed, if the plate thickness is 0.15 mm or less, the bottom of the can, which is so-called buckling, may be in an outwardly protruding state, which is not preferable. On the other hand, in the case of steel material,
A plate thickness of 0.30 mm or more ensures sufficient compressive strength, but is substantially excessive quality and is not economical. The phenomenon such as the above-mentioned buckling depends on the mechanical strength of the metal material even if the plate thickness is the same.Therefore, if the mechanical strength is high, it is possible to reduce the plate thickness. It is desirable to appropriately select in consideration of the strength balance of the entire can.
【０００９】次に、本発明で適用される化成処理皮膜に
ついて述べる。本発明に適用されるスチール素材のＤＩ
缶の化成処理皮膜は、リン（Ｐ）−金属（Ｍ）−有機樹
脂（Ｒ）から成る有機無機複合型化成処理皮膜である。
リン（Ｐ）の付着量としては、片面の付着量として０．
０５〜２．０ｍｇ／ｍ２、金属（Ｍ）の付着量は片面の
付着量として０．０５〜２．０ｍｇ／ｍ２、有機樹脂
（Ｒ）の付着量は炭素（Ｃ）量として０．５〜２０ｍｇ
／ｍ２であり、かつ炭素（Ｃ）量と金属（Ｍ）付着量の
比 Ｃ／Ｍ が１〜１００である。こうした化成処理に
よって析出する皮膜は、通常交換皮膜と呼ばれ、鋼板や
アルミニウムの局部溶解によって起こる水素イオンの還
元によりその部位では局部的にｐＨが上昇し、有機樹脂
や金属イオンが溶解出来なくなり、析出するもので、析
出箇所は鉄の露出部と考えられている。リン（Ｐ）−金
属（Ｍ）−有機樹脂（Ｒ）からなる化成処理皮膜は、対
内容物耐食性の向上や缶内外面の塗膜密着性の向上だけ
でなく、前述したレトルト加熱殺菌処理を行う内容物を
充填した場合に発生する、缶外面側の局部的塗膜浮き防
止に特に効果がある。Next, the chemical conversion coating applied in the present invention will be described. DI of steel material applied to the present invention
The chemical conversion treatment film of the can is an organic-inorganic composite type chemical conversion treatment film composed of phosphorus (P) -metal (M) -organic resin (R).
The amount of phosphorus (P) attached was 0.
05-2.0 mg / m < 2 >, the amount of metal (M) deposited is 0.05-2.0 mg / m < 2 > as the amount deposited on one surface, and the amount of organic resin (R) is deposited as the amount of carbon (C) of 0. 5-20 mg
/ M 2 , and the ratio C / M of the amount of carbon (C) and the amount of metal (M) attached is 1 to 100. The film deposited by such a chemical conversion treatment is usually called an exchange film, the pH locally increases at the site due to the reduction of hydrogen ions caused by the local dissolution of the steel sheet or aluminum, and the organic resin and metal ions cannot be dissolved, It precipitates, and the place of precipitation is considered to be an exposed part of iron. The chemical conversion treatment film consisting of phosphorus (P) -metal (M) -organic resin (R) not only improves the corrosion resistance of the contents and the adhesion of the coating film on the inner and outer surfaces of the can, but also uses the retort heat sterilization treatment described above. It is particularly effective in preventing localized coating film floating on the outer surface of the can, which occurs when the contents are filled.
【００１０】リン（Ｐ）は鋼板やアルミニウムの局部溶
解を促すための物質ではあるが、有機樹脂や金属イオン
と同時に析出される。従って、リン（Ｐ）の付着量が直
接缶体の耐食性や塗膜密着性に関与するものではない
が、皮膜の品質管理面からはリン（Ｐ）の付着量は重要
である。リン（Ｐ）の付着量の下限値である０．０５ｍ
ｇ／ｍ２未満では有機樹脂（Ｒ）や金属（Ｍ）の析出が
不十分で、対内容物耐食性や缶内外面の塗膜密着性が共
に劣り好ましくない。一方、リン（Ｐ）の付着量の上限
値である２．０ｍｇ／ｍ２を超えても、有機樹脂（Ｒ）
や金属（Ｍ）の析出による対内容物耐食性や缶内外面の
塗膜密着性の向上効果は飽和し経済的でない。化成処理
後に施される缶の内外面塗膜との密着性や、缶内面の耐
食性向上からは、基本的には有機樹脂（Ｒ）の付着量が
重要である。有機樹脂（Ｒ）は直接測定ができないた
め、付着炭素（Ｃ）量として測定され、片面の付着炭素
（Ｃ）として０．５〜２０ｍｇ／ｍ２である。炭素
（Ｃ）量の下限値である０．５ｍｇ／ｍ２未満では有機
樹脂（Ｒ）の析出が不十分で、鉄露出部を十分に覆うこ
とができず、対内容物耐食性や缶内外面の塗膜密着性が
共に劣り好ましくない。特に、密着性については、前述
したネック加工の高縮径化に対し、特にレトルト殺菌処
理を行う場合に塗膜剥離を起こすことがあるので重要な
要件となる。また、缶内面の耐食性についても、実用上
問題ない量とは言え、鉄溶出量が多めになることがあ
り、好ましくない。一方、炭素（Ｃ）量の上限値である
２０ｍｇ／ｍ２を超えても、有機樹脂（Ｒ）の析出によ
る対内容物耐食性や缶内外面の塗膜密着性の向上効果は
飽和し経済的でない。Phosphorus (P) is a substance for promoting local dissolution of steel plate and aluminum, but it is deposited at the same time as the organic resin and metal ions. Therefore, the adhered amount of phosphorus (P) does not directly relate to the corrosion resistance and coating film adhesion of the can body, but the adhered amount of phosphorus (P) is important from the viewpoint of quality control of the film. The lower limit of the amount of phosphorus (P) deposited is 0.05 m
When it is less than g / m 2 , the organic resin (R) and the metal (M) are not sufficiently deposited, and the corrosion resistance against the contents and the coating film adhesion on the inner and outer surfaces of the can are both poor, which is not preferable. On the other hand, even if the upper limit of the amount of phosphorus (P) attached is 2.0 mg / m 2 , the organic resin (R)
The effect of improving the corrosion resistance against the contents and the adhesion of the coating film on the inner and outer surfaces of the can due to the precipitation of metal or metal (M) is saturated and not economical. The adhesion amount of the organic resin (R) is basically important in terms of the adhesion to the coating film on the inner and outer surfaces of the can that is applied after the chemical conversion treatment and the improvement of the corrosion resistance of the inner surface of the can. Since the organic resin (R) cannot be directly measured, it is measured as the amount of attached carbon (C) and is 0.5 to 20 mg / m 2 as the amount of attached carbon (C) on one surface. If the lower limit of the amount of carbon (C) is less than 0.5 mg / m 2 , the precipitation of the organic resin (R) is insufficient and the exposed iron part cannot be sufficiently covered, and the corrosion resistance against contents and the inside and outside surfaces of the can The coating film adhesion is poor, which is not preferable. In particular, the adhesiveness is an important requirement for the above-described higher diameter reduction of the necking, because peeling of the coating film may occur particularly when the retort sterilization treatment is performed. Also, regarding the corrosion resistance of the inner surface of the can, although it is a practically acceptable amount, the iron elution amount may be large, which is not preferable. On the other hand, even if the upper limit of the amount of carbon (C) exceeds 20 mg / m2, the effect of improving the corrosion resistance against the contents and the adhesion of the coating film on the inner and outer surfaces of the can is saturated due to the precipitation of the organic resin (R), which is not economical. .
【００１１】前述したように、レトルト加熱殺菌処理で
発生する外面塗膜の局部浮きは、蓋であるアルミニウム
と胴であるスチールとの接触によって起こる「異種金属
接触腐食」によるもので、蓋であるアルミニウムが陽極
反応として溶解し、胴であるスチール面で陰極反応であ
る酸素の還元反応が起こっている。従って、局部浮きは
陰極アルカリピールと判断される。従って、外面塗膜の
局部浮きを防止するには、（１）陰極反応である酸素の
還元反応を抑制する表面にすること、（２）もし腐食が
起こってもアルカリピールが起こり難い密着力を有する
表面にすることが考えられる。本発明のリン（Ｐ）−金
属（Ｍ）−有機樹脂（Ｒ）からなる化成処理皮膜の金属
（Ｍ）は、前述した陰極反応である酸素の還元反応を抑
制しており、更に有機樹脂（Ｒ）と共存させることで、
化成処理皮膜の上層に存在する塗膜がアルカリピールが
起こり難い密着力を有する化成処理皮膜となっているも
のと推定される。従って、本発明のように有機樹脂
（Ｒ）と金属（Ｍ）を共析させることで、前述した缶外
面側の塗膜浮き防止に効果が顕著にみられる。As described above, the local floating of the outer coating film caused by the retort heat sterilization treatment is caused by the "corrosion of dissimilar metal contact" caused by the contact between the aluminum cover and the steel cover. Aluminum is dissolved as an anodic reaction, and a reduction reaction of oxygen, which is a cathodic reaction, occurs on the steel surface of the body. Therefore, the local floating is judged to be the cathode alkaline peel. Therefore, in order to prevent the local floating of the outer coating film, (1) the surface that suppresses the reduction reaction of oxygen, which is a cathodic reaction, should be used. (2) If the corrosion force occurs, the alkaline peeling is unlikely to occur. It is conceivable that the surface has. The metal (M) of the chemical conversion coating of phosphorus (P) -metal (M) -organic resin (R) of the present invention suppresses the above-mentioned cathode reduction reaction of oxygen, and further the organic resin ( By coexisting with R),
It is presumed that the coating film existing on the upper layer of the chemical conversion treatment film is a chemical conversion treatment film having an adhesive force that hardly causes alkali peel. Therefore, by co-depositing the organic resin (R) and the metal (M) as in the present invention, the effect of preventing the coating film floating on the outer surface side of the can is remarkably observed.
【００１２】金属（Ｍ）の付着量は片面の付着量として
０．０５〜２．０ｍｇ／ｍ２である。金属（Ｍ）の付着
量の下限値を下回る値である０．０５ｍｇ／ｍ２未満で
も、リン（Ｐ）付着量や有機樹脂（Ｒ）の付着量が本発
明の範囲内であれば対内容物耐食性や缶内外面の塗膜密
着性は確保されるが、金属（Ｍ）の付着量の下限値を下
回る値である０．０５ｍｇ／ｍ２未満では前述した酸素
の還元反応を抑制する効果は劣り、レトルト加熱殺菌処
理で発生する外面塗膜の局部浮きを防止することができ
ず好ましくない。一方、金属（Ｍ）の付着量の上限値で
ある２．０ｍｇ／ｍ２を超えても、レトルト加熱殺菌処
理で発生する外面塗膜の局部浮きの防止効果は飽和し経
済的でない。リン（Ｐ）−金属（Ｍ）−有機樹脂（Ｒ）
からなる化成処理皮膜の場合、缶性能や化成処理の安定
性からリン（Ｐ）の付着量としては、片面の付着量とし
て０．１〜１．５ｍｇ／ｍ２、金属（Ｍ）の付着量は片
面の付着量として０．１〜１．８ｍｇ／ｍ２、有機樹脂
（Ｒ）の付着量は炭素（Ｃ）量として１．０〜１５ｍｇ
／ｍ２が、特に好ましい範囲である。更に、リン（Ｐ）
−金属（Ｍ）−有機樹脂（Ｒ）からなる化成処理皮膜の
場合、特にレトルト加熱殺菌処理で発生する缶外面塗膜
の局部浮きの防止の点からは、炭素（Ｃ）量と金属
（Ｍ）付着量の比である Ｃ／Ｍ 比が重要で、本発明
では１〜１００である。The amount of metal (M) deposited is 0.05 to 2.0 mg / m 2 as the amount deposited on one surface. Even if it is less than 0.05 mg / m 2, which is a value below the lower limit of the amount of metal (M) deposited, if the amount of phosphorus (P) deposited and the amount of organic resin (R) deposited are within the range of the present invention, Corrosion resistance and coating film adhesion on the inner and outer surfaces of the can are secured, but if it is less than 0.05 mg / m 2, which is less than the lower limit of the amount of metal (M) deposited, the above-described oxygen reduction reaction is suppressed. Is inferior, and it is not preferable because local floating of the outer coating film generated by the retort heat sterilization treatment cannot be prevented. On the other hand, even when the upper limit of the amount of the metal (M) deposited is 2.0 mg / m 2 , the effect of preventing the local floating of the outer coating film generated by the retort heat sterilization treatment is saturated, which is not economical. Phosphorus (P) -metal (M) -organic resin (R)
In the case of a chemical conversion treatment film consisting of, the amount of phosphorus (P) deposited is 0.1 to 1.5 mg / m 2 on one side, and the amount of metal (M) deposited from the can performance and the stability of the chemical conversion treatment. Is 0.1 to 1.8 mg / m 2 on one side, and the amount of organic resin (R) is 1.0 to 15 mg on carbon (C).
/ M 2 is a particularly preferred range. Furthermore, phosphorus (P)
In the case of a chemical conversion coating consisting of metal (M) -organic resin (R), especially from the viewpoint of preventing local floating of the coating film on the outer surface of the can, which occurs during retort heat sterilization treatment, the amount of carbon (C) and metal (M). ) The C / M ratio, which is the ratio of the adhered amount, is important and is 1 to 100 in the present invention.
【００１３】炭素（Ｃ）量と金属（Ｍ）付着量の比であ
る Ｃ／Ｍ 比は内外面に施される塗膜の密着性とレト
ルト加熱殺菌処理で発生する缶外面塗膜の局部浮きの防
止との兼備と言った観点から重要で、Ｃ／Ｍ 比が下限
値である１未満では、塗膜との密着性が不十分で、缶外
面塗膜の局部浮きが起こる危険性があり好ましくはな
い。一方、上限値である１００を超えても、缶外面塗膜
の局部浮き防止効果は飽和する。炭素（Ｃ）量と金属
（Ｍ）付着量の比である Ｃ／Ｍ 比は、５〜５０の範
囲が、缶外面塗膜の局部浮き防止効果と化成処理の安定
性を考慮すると最適である。また、リン（Ｐ）−金属
（Ｍ）−有機樹脂（Ｒ）からなる化成処理皮膜の金属
（Ｍ）としては、ジルコニウム、チタニウム、スズから
選ばれる１種または２種以上であるが、特にジルコニウ
ムが缶特性の安定性や化成処理の安定性等から最適であ
る。本発明を実施する方法は特別なものでなく、現在ア
ルミニウム合金やスチールを素材として製造されている
ＤＩ缶の脱脂・化成処理方法が適用できる。具体的に
は、ＤＩ加工後の缶体をアルカリ脱脂した後、例えばリ
ン酸または縮合リン酸とフルオロジルコニウム酸のよう
なフッ化ジルコニウムやフルオロチタン酸のようなフッ
化チタニウム、リン酸スズの一種と水溶性有機樹脂、例
えば水溶性フェノール樹脂、水溶性アクリル樹脂等を含
む水溶液に必要に応じて、反応性を促進させるためにフ
ッ化水素酸またはフッ化化合物を添加した処理液を、缶
体にスプレー塗布した後、水洗、乾燥し硬化させる方法
や缶体を処理液に浸漬した後、水洗、乾燥し硬化させる
方法等が適宜適用できる。乾燥硬化方法としては熱風で
の乾燥、電気炉での乾燥等の方法が適用でき、温度は１
５０℃〜２５０℃で乾燥時間は１０秒〜２分程度であ
る。The C / M ratio, which is the ratio of the amount of carbon (C) and the amount of metal (M) deposited, is the adhesion of the coating film applied to the inner and outer surfaces and the local floating of the coating film on the outer surface of the can generated by the retort heat sterilization treatment. It is important from the viewpoint of prevention of the above, and if the C / M ratio is less than the lower limit value of 1, the adhesion to the coating film is insufficient, and there is a risk of local floating of the coating film on the outer surface of the can. Not preferred. On the other hand, even if the upper limit of 100 is exceeded, the effect of preventing local floating of the coating film on the outer surface of the can is saturated. The C / M ratio, which is the ratio of the amount of carbon (C) and the amount of metal (M) deposited, is in the range of 5 to 50, which is optimal in view of the effect of preventing local floating of the coating film on the outer surface of the can and the stability of chemical conversion treatment. . Further, the metal (M) of the chemical conversion treatment film composed of phosphorus (P) -metal (M) -organic resin (R) is one or more selected from zirconium, titanium and tin, and particularly zirconium. Is optimal from the viewpoint of stability of can characteristics and stability of chemical conversion treatment. The method for carrying out the present invention is not special, and a degreasing / chemical conversion treatment method for DI cans currently manufactured using aluminum alloy or steel as a raw material can be applied. Specifically, after degreasing the can body after DI processing with alkali, for example, phosphoric acid or condensed phosphoric acid and zirconium fluoride such as fluorozirconic acid, titanium fluoride such as fluorotitanic acid, and a kind of tin phosphate. And a water-soluble organic resin, for example, a water-soluble phenolic resin, a water-soluble acrylic resin, etc., in an aqueous solution containing hydrofluoric acid or a fluorinated compound to promote reactivity, if necessary, A method of spray-coating on, followed by washing with water, drying and curing, a method of immersing the can body in a treatment liquid, followed by washing with water, drying and curing can be appropriately applied. As the drying and curing method, methods such as drying with hot air and drying with an electric furnace can be applied, and the temperature is 1
The drying time is about 10 seconds to 2 minutes at 50 ° C to 250 ° C.
【００１４】本発明の有機無機複合化成処理皮膜は、化
成処理後の加熱乾燥により有機樹脂の重合反応が起こ
り、高分子的な皮膜を形成する性質を有している。しか
も、有機樹脂が処理皮膜の表層に富化して存在するた
め、塗料との密着力が強固なものとなり、前述した、胴
部径２１１径の缶体開口部の２０４径（直径約５４ｍ
ｍ）化や２０２径（直径約５２ｍｍ）化、更には２００
径（直径約４９ｍｍ）化へのネック加工にも耐えるだけ
でなく高腐食性の内容物に対しても高耐食性を有する優
れた缶体が得られる。従って、高縮径となるネック加工
ほど有機無機複合化成処理皮膜は有利である。本発明の
スチ−ルを素材としたＤＩ缶は、従来のリン酸スズ系化
成処理に比べ、缶体の品質特性は著しく向上し、対内容
物耐食性、缶内外面の塗膜密着性が大幅に改善されるだ
けでなく、希に発生するレトルト加熱殺菌処理での缶外
面塗膜の局部浮きも抑えることができる。また、塗膜密
着性が大幅に改善されるので、缶外面に直接装飾印刷を
施す代わりに、接着剤層を備えた印刷フィルムを貼着す
る方法も採用することができる。The organic-inorganic composite chemical conversion treatment film of the present invention has the property of forming a polymer film by the polymerization reaction of the organic resin caused by heating and drying after the chemical conversion treatment. Moreover, since the organic resin is enriched and present in the surface layer of the treated film, the adhesive force with the paint becomes strong, and the 204-dia.
m), 202 diameter (diameter about 52 mm), and 200
It is possible to obtain an excellent can body that not only withstands necking to a diameter (diameter of about 49 mm) but also has high corrosion resistance against highly corrosive contents. Therefore, the organic-inorganic composite chemical conversion treatment film is more advantageous as the necking becomes higher in diameter. The DI can made of the steel of the present invention has significantly improved quality characteristics of the can body as compared with the conventional tin phosphate chemical conversion treatment, has a high corrosion resistance against contents, and has a large coating adhesion on the inner and outer surfaces of the can. In addition to being improved, it is possible to suppress the local floating of the coating film on the outer surface of the can, which occurs rarely during the retort heat sterilization treatment. Further, since the coating film adhesion is greatly improved, a method of attaching a printing film having an adhesive layer instead of directly performing decorative printing on the outer surface of the can can be adopted.
【００１５】[0015]
【実施例】以下、実施例にて、本発明の方法の効果を具
体的に説明するが、本発明はこれにより何ら限定される
ものではない。尚、本実施例で行った評価方法は以下の
通りである。
（１）化成処理皮膜の有機樹脂付着量を示す炭素（Ｃ）
量は、島津製作所（株）製の全有機体炭素計（ＴＯＣ−
５０００／ＳＳＭ−５０００Ａ固体試料ＴＯＣ測定シス
テム）にて測定した。
（２）化成処理皮膜のリン（Ｐ）および金属（Ｍ）付着
量は、理学電機工業株式会社製の蛍光Ｘ線（Ｘ−ＲＡＹ
ＳＰＥＣＴＲＯ−ＭＥＴＥＲ）にて測定した。
（３）塗膜のデュポン衝撃密着性評価は、内外面塗装缶
のネック加工部を切り出し、３００ｇ−３０ｃｍの条件
でデュポン衝撃試験をおこない、セロファンテープ剥離
試験で塗膜の剥離状態を観察した。
◎：塗膜剥離なし ○：微小塗膜剥離僅かに発生
△：塗膜剥離中程度に発生 ×：塗膜剥離大きく発生
（４）塗膜の碁盤目密着性評価は、内外面塗装缶の缶胴
部を切り出し、１ｍｍ間隔にＮＴカッター（商品名；折
り取りタイプのカッター）で塗膜面に下地金属に達する
傷を碁盤目状に１００の升目を入れ、１２５℃で３０分
間のレトルト加熱処理を行った後セロファンテ−プ剥離
試験を行い塗膜の剥離状態を観察した。
◎：塗膜剥離なし ○：塗膜剥離１〜５％発生
△：塗膜剥離６〜１５％発生 ×：塗膜剥離１６％以上発生
（５）外面塗膜浮き評価は、缶体に水を満注状態で充填
し、アルミニウム合金製のＥＯＥ缶蓋で巻締めた後、１
３０℃で３０分間のレトルト加熱処理を行い、外面塗膜
の浮きの発生状況を評価した。
◎：塗膜浮きなし ○：塗膜浮き０．０１〜０．１％発生
△：塗膜浮き０．２〜２％発生 ×：塗膜剥離２％以上発生
（６）耐食性評価は、市販のペットボトルに充填されて
いたお茶またはコ−ラを缶体内に所定量充填し、アルミ
ニウム合金製のＥＯＥ缶蓋で巻締めた後、３８℃で６ヶ
月貯蔵し腐食状況を観察した。
◎：腐食なし ○：僅かに変色程度の表面腐食発生
△：表面腐食発生 ×：塗膜浮き、または鋼板の孔食を
伴う腐食発生EXAMPLES The effects of the method of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. The evaluation method used in this example is as follows. (1) Carbon (C) indicating the amount of organic resin adhered to the chemical conversion coating
The amount is the total organic carbon meter (TOC- manufactured by Shimadzu Corporation).
5000 / SSM-5000A solid sample TOC measurement system). (2) Phosphorus (P) and metal (M) adhesion amounts of the chemical conversion coating are fluorescent X-ray (X-RAY manufactured by Rigaku Denki Kogyo Co., Ltd.).
It measured by SPECTRO-METER). (3) For the evaluation of the DuPont impact adhesion of the coating film, the necked portion of the inner and outer surface coating can was cut out, the DuPont impact test was performed under the condition of 300 g-30 cm, and the peeled state of the coating film was observed by the cellophane tape peeling test. ◎: No peeling of coating film ○: Small peeling of coating film occurs slightly △: Medium peeling of coating film occurs ×: Large peeling of coating film occurs (4) The cross-cut adhesion of the coating film can be evaluated for inner and outer coating cans. Cut out the body part and put 100 squares in a grid pattern on the coating surface with an NT cutter (trade name; breaking type cutter) at 1 mm intervals, and heat the retort at 125 ° C for 30 minutes. After that, a cellophane tape peeling test was performed to observe the peeled state of the coating film. ⊚: No peeling of coating film ◯: 1 to 5% of peeling coating film occurred: 6 to 15% of peeling coating film occurred: 16% or more of peeling of coating film (5) External surface coating floating: Fill it in a fully-filled state, wrap it with an EOE can lid made of aluminum alloy, and then
The retort heat treatment was performed at 30 ° C. for 30 minutes, and the occurrence of floating of the outer coating film was evaluated. ◎: No coating film floating ○: Coating film floating 0.01 to 0.1% occurred Δ: Coating film floating 0.2 to 2% occurred ×: Coating film peeling occurred 2% or more (6) Corrosion resistance evaluation A predetermined amount of tea or coffee that had been filled in a PET bottle was filled in a can, and after being tightly wound with an EOE can lid made of an aluminum alloy, it was stored at 38 ° C. for 6 months and the corrosion state was observed. ◎: No corrosion ○: Slightly discolored surface corrosion occurred △: Surface corrosion occurred ×: Corrosion accompanied by floating coating film or pitting corrosion of steel sheet
【００１６】実験例１
板厚０．２２ｍｍの薄鋼板にＳｎめっきを片面付着量と
して２．８ｇ／ｍ２を両面に施したブリキを用いてＤＩ
成形を行い、缶胴外径２１１径（約６６ｍｍ）で内容物
充填量が３５０ｍｌの缶になるように開口端面側をトリ
ミングしてスチール製ＤＩ缶を作成し、直ちに現行のス
チ−ルＤＩ缶用のアルカリ脱脂剤でスプレー脱脂・水洗
処理した後、リン酸−フッ化ジルコニウム−水溶性フェ
ノール樹脂−フッ化水素酸からなるリン（Ｐ）−金属
（Ｍ）−有機樹脂（Ｒ）系で濃度、処理時間等の処理条
件を変化させ、スプレーで化成処理を行ったのち水洗、
純水水洗処理を行い、２１０℃で４０秒間乾燥した。得
られた缶の化成処理皮膜量は、それぞれ次の通りであ
る。リン付着量０．０３ｍｇ／ｍ２、Ｚｒ付着量０．０
２ｍｇ／ｍ２、Ｃ付着量０．３１ｍｇ／ｍ２、Ｃ／Ｍが
１５．５０の化成処理（テスト１）、リン付着量０．０
７ｍｇ／ｍ２、Ｚｒ付着量０．０７ｍｇ／ｍ２、Ｃ付着
量０．８５ｍｇ／ｍ ２、Ｃ／Ｍが１２．１４の化成処理
（テスト２）、リン付着量０．１１ｍｇ／ｍ ２、Ｚｒ付
着量０．１８ｍｇ／ｍ２、Ｃ付着量２．３２ｍｇ／
ｍ２、Ｃ／Ｍが１２．８９の化成処理（テスト３）、リ
ン付着量０．３２ｍｇ／ｍ２、Ｚｒ付着量０．３１ｍｇ
／ｍ２、Ｃ付着量３．５４ｍｇ／ｍ２、Ｃ／Ｍが１１．
４２の化成処理（テスト４）、リン付着量０．５６ｍｇ
／ｍ２、Ｚｒ付着量０．４５ｍｇ／ｍ２、Ｃ付着量７．
０６ｍｇ／ｍ２、Ｃ／Ｍが１５．６９の化成処理（テス
ト５）、リン付着量１．０７ｍｇ／ｍ２、Ｚｒ付着量
０．８６ｍｇ／ｍ２、Ｃ付着量１３．１２ｍｇ／ｍ２、
Ｃ／Ｍが１５．２６の化成処理（テスト６）、リン付着
量１．７０ｍｇ／ｍ２、Ｚｒ付着量１．７８ｍｇ／
ｍ２、Ｃ付着量１９．７５ｍｇ／ｍ２、Ｃ／Ｍが１１．
１０の化成処理（テスト７）、リン付着量０．９５ｍｇ
／ｍ２、Ｚｒ付着量０．６５ｍｇ／ｍ２、Ｃ付着量０．
５８ｍｇ／ｍ２、Ｃ／Ｍが０．８９の化成処理（テスト
８）。また、比較のため、前記の缶高さと同一の高さに
なるようにトリミングしたスチ−ル製ＤＩ缶を、脱脂処
理は本発明例と同様に行い、化成処理を現行のリン酸Ｓ
ｎ系の処理（テスト９）を行ったリン付着量が１．０３
ｍｇ／ｍ２の缶も併せて作成した。次いで、缶の外面に
は酸化チタンを含有する市販のアクリル・アミノ系白色
塗料をロール塗装で１５０〜１６０ｍｇ／ｄｍ２塗装
し、乾燥・焼き付けを行い、更に印刷を施し、その上に
市販のポリエステル・エポキシ・アミノ系クリヤー塗料
をロール塗装で６０ｍｇ／ｄｍ２塗装してから乾燥・焼
き付けを行った後、缶の内面には市販のエポキシ・フェ
ノール系内面用塗料をスプレー塗装で７０〜８０ｍｇ／
ｄｍ２塗装し、乾燥・焼き付けを行った後、内外面塗装
缶の開口部に、ネック加工とフランジ加工とを行い、開
口部径が２０２径の缶を作成した。こうして得た、内外
面塗装缶の塗膜密着性を調べるため、デュポン衝撃密着
性評価および碁盤目密着性評価を行った。また、外面の
レトルト加熱殺菌処理での塗膜浮きを調べるため、缶体
に水を満注状態で充填し、開口部にアルミニウム合金製
のＥＯＥ缶蓋を巻締めた後、１３０℃で３０分間レトル
ト加熱殺菌処理を行い、外面塗膜の浮き発生率を評価し
た。耐食性を調べるため、市販のペットボトルに充填さ
れていたお茶またはコーラを、缶体内に所定量充填し、
開口部にアルミニウム合金製のＥＯＥ缶蓋を巻締めた
後、３８℃で６ヶ月間貯蔵し腐食状況を観察した。実験
例１で行った、本発明のスチール製ＤＩ缶の化成処理皮
膜および比較例の化成処理皮膜の明細、そして各種の評
価結果を表１に示した。Experimental Example 1
Sn plating on a thin steel plate with a plate thickness of 0.22mm
Then 2.8 g / mTwoDI using a tin plate on both sides
After molding, the contents of the can body outer diameter 211 diameter (about 66 mm)
Trim the open end so that the filling amount is 350 ml.
To make a steel DI can and immediately
Spray degreasing / washing with alkaline degreaser for CHeel DI can
After treatment, phosphoric acid-zirconium fluoride-water soluble
Nole resin-phosphorus (P) -metal consisting of hydrofluoric acid
(M) -Organic resin (R) -based treatment conditions such as concentration and treatment time
After changing the conditions and performing chemical conversion treatment by spraying, washing with water,
It was washed with pure water and dried at 210 ° C. for 40 seconds. Profit
The amount of chemical conversion coating on each of the cans is as follows.
It Phosphorus deposition amount 0.03mg / mTwo, Zr adhesion amount 0.0
2 mg / mTwo, C adhesion amount 0.31 mg / mTwo, C / M
Chemical conversion treatment of 15.50 (test 1), phosphorus deposition amount 0.0
7 mg / mTwo, Zr adhesion amount 0.07mg / mTwo, C adhesion
Amount 0.85mg / m Two, C / M 12.14 chemical conversion treatment
(Test 2), Phosphorus deposition amount 0.11 mg / m Two, With Zr
Wearing amount 0.18 mg / mTwo, C deposit 2.32 mg /
mTwo, C / M 12.89 chemical conversion treatment (test 3),
Deposition amount 0.32 mg / mTwo, Zr adhesion amount 0.31mg
/ MTwo, C adhesion amount 3.54mg / mTwo, C / M is 11.
42 chemical conversion treatment (test 4), phosphorus deposition amount 0.56mg
/ MTwo, Zr adhesion amount 0.45mg / mTwo, C deposition amount 7.
06 mg / mTwo, C / M 15.69 chemical conversion treatment (test
5), phosphorus adhesion amount 1.07 mg / mTwo, Zr adhesion amount
0.86 mg / mTwo, C adhesion amount 13.12 mg / mTwo,
Chemical conversion treatment with C / M of 15.26 (Test 6), phosphorus adhesion
Amount 1.70 mg / mTwo, Zr adhesion amount 1.78 mg /
mTwo, C adhesion amount 19.75 mg / mTwo, C / M is 11.
Chemical conversion treatment of 10 (test 7), phosphorus adhesion amount 0.95mg
/ MTwo, Zr adhesion amount 0.65mg / mTwo, C adhesion amount 0.
58 mg / mTwo, C / M 0.89 chemical conversion treatment (test
8). For comparison, the height is the same as the can height above.
Remove the steel DI can that has been trimmed to
The procedure is the same as in the present invention, and the chemical conversion treatment is performed using the current phosphoric acid S.
The amount of phosphorus deposited after the n-type treatment (test 9) is 1.03
mg / mTwoI also made a can. Then on the outside of the can
Is a commercially available acrylic / amino white containing titanium oxide
Roll coating of paint 150-160mg / dmTwoPainting
Then, dry and bake it, and then print it on top of it.
Commercially available polyester / epoxy / amino clear paint
Roll coated with 60mg / dmTwoAfter painting, dry and bake
After staking, the inner surface of the can is covered with a commercially available epoxy
70 ~ 80mg / of spray paint
dmTwoAfter painting, drying and baking, paint inside and outside
Perform neck processing and flange processing on the opening of the can and open it.
A can having a diameter of 202 was prepared. Thus obtained inside and outside
DuPont impact adhesion to check the adhesion of the coating on the surface coating can
The property evaluation and the cross-cut adhesion evaluation were performed. Also on the outside
In order to check the coating film floating during retort heat sterilization treatment, can body
Filled with water in a full state, and the opening is made of aluminum alloy
After tightening the EOE can lid, retort at 130 ° C for 30 minutes.
Heat sterilization treatment is performed to evaluate the occurrence rate of floating on the outer coating.
It was To check the corrosion resistance, it was filled in a commercial PET bottle.
Fill the can with a predetermined amount of tea or cola,
An EOE can lid made of aluminum alloy was wound around the opening.
Then, it was stored at 38 ° C. for 6 months and the corrosion state was observed. Experiment
Example 1 steel DI cans of the present invention treated by chemical conversion treatment
Details of the film and the chemical conversion coating of the comparative example, and various evaluations
The valency results are shown in Table 1.
【００１７】[0017]
【表１】 [Table 1]
【００１８】表１から判るように、本発明の化成処理を
施したテスト２〜テスト７（本発明例１〜６）のスチー
ル製ＤＩ缶は、内外面の塗膜密着性に優れ、また、外面
塗膜の浮き発生率に対しても良好な性能を示し、内容物
耐食性にも優れていることが判る。それに反し、テスト
１（比較例１）のＺｒ付着量およびＣ付着量が共に本発
明の下限値未満の場合は、内外面の塗膜密着性は劣り、
外面塗膜の浮き発生率も高く、内容物耐食性も劣る。ま
た、テスト８（比較例２）のＣ／Ｍが１以下の場合も、
やはり内外面の塗膜密着性は劣り、外面塗膜の浮き発生
率も高い。また、現行のリン酸Ｓｎ系化成処理を施した
テスト９（比較例３）の場合、内外面の塗膜密着性は本
発明の化成処理皮膜を有する缶と遜色ないが、外面塗膜
の浮き発生率は高いことがわかる。As can be seen from Table 1, the steel DI cans of Test 2 to Test 7 (Invention Examples 1 to 6) subjected to the chemical conversion treatment of the present invention are excellent in the adhesion of the coating film on the inner and outer surfaces, and It can be seen that the performance of the outer coating film is good even with respect to the floating rate, and the corrosion resistance of the content is also excellent. On the contrary, when both the Zr adhesion amount and the C adhesion amount of Test 1 (Comparative Example 1) are less than the lower limit value of the present invention, the adhesion of the coating film on the inner and outer surfaces is poor,
The floating rate of the outer coating is high and the corrosion resistance of the contents is poor. Also, when the C / M of the test 8 (Comparative example 2) is 1 or less,
After all, the adhesion of the coating film on the inner and outer surfaces is inferior, and the floating rate of the outer coating film is high. In addition, in the case of the test 9 (Comparative Example 3) in which the current Sn-based phosphoric acid conversion treatment is applied, the coating adhesion on the inner and outer surfaces is comparable to that of the can having the chemical conversion treatment film of the present invention, but the outer coating film floats. It can be seen that the incidence is high.
【００１９】実験例２
板厚０．２２ｍｍの薄鋼板に、缶の内面に当たる面には
Ｓｎめっきを片面付着量として２．８ｇ／ｍ２、缶の外
面に当たる面にはＳｎめっきを片面付着量として５．６
ｇ／ｍ２のブリキを用いて実験例１と同一径のＤＩ成形
を行い、実験例１の手順に従いトリミングした後、直ち
に現行のスチール製ＤＩ缶用のアルカリ脱脂剤でスプレ
ー脱脂・水洗処理した後、リン酸−フッ化チタニウム−
水溶性フェノール樹脂−フッ化水素酸からなるリン
（Ｐ）−金属（Ｍ）−有機樹脂（Ｒ）系で濃度、処理時
間等の処理条件を変化させ、スプレーで化成処理を行っ
たのち水洗、純水水洗処理を行い、２１０℃で４０秒間
乾燥した。得られた缶の化成処理皮膜量は、それぞれ次
の通りである。リン付着量０．１２ｍｇ／ｍ２、Ｔｉ付
着量０．０７ｍｇ／ｍ２、Ｃ付着量１．５１ｍｇ／
ｍ２、Ｃ／Ｍが２１．５７の化成処理（テスト１０）、
リン付着量０．３５ｍｇ／ｍ２、Ｔｉ付着量０．２３ｍ
ｇ／ｍ２、Ｃ付着量３．２４ｍｇ／ｍ２、Ｃ／Ｍが１
４．０９の化成処理（テスト１１）、リン付着量０．８
３ｍｇ／ｍ２、Ｔｉ付着量０．７４ｍｇ／ｍ２、Ｃ付着
量１０．３５ｍｇ／ｍ２、Ｃ／Ｍが１３．９９の化成処
理（テスト１２）、リン付着量１．２６ｍｇ／ｍ２、Ｔ
ｉ付着量１．３６ｍｇ／ｍ２、Ｃ付着量１４．７２ｍｇ
／ｍ２、Ｃ／Ｍが１０．８２の化成処理（テスト１
３）。また、比較のため、前記の缶高さにトリミングし
たスチール製ＤＩ缶に脱脂処理は本発明例と同様に行
い、化成処理を現行のリン酸Ｓｎ系の処理（テスト１
４）を行ったリン付着量が０．８７ｍｇ／ｍ２の缶も併
せて作成した。その後、缶の外面及び内面に、実験例１
と同一の塗装及び印刷を施し、更に、内外面塗装缶の開
口部に、ネックイン加工とフランジ加工とを行って、開
口部径が２０２径の缶を作成した。こうして得た、内外
面塗装缶を、実験例１の手順に従って、缶の内外面の塗
膜密着性、外面塗膜の塗膜浮き発生率および缶内面の耐
食性を調べた。実験２で行った、本発明のスチール製Ｄ
Ｉ缶の化成処理皮膜および比較例の化成処理皮膜の明
細、そして各種の評価結果を表２に示した。Experimental Example 2 A thin steel plate having a plate thickness of 0.22 mm was coated with Sn plating on the inner surface of the can in an amount of 2.8 g / m 2 on one side and Sn plating on the surface of the outer surface of the can. As 5.6
DI molding having the same diameter as in Experimental Example 1 was performed using a tin plate of g / m 2 , trimmed according to the procedure of Experimental Example 1, and immediately spray-degreased / washed with an existing alkaline degreasing agent for steel DI cans. After that, phosphoric acid-titanium fluoride-
Water-soluble phenolic resin-phosphorus (P) -metal (M) -organic resin (R) system consisting of hydrofluoric acid, the treatment conditions such as concentration and treatment time are changed, chemical conversion treatment is performed by spraying, and then washing with water, It was washed with pure water and dried at 210 ° C. for 40 seconds. The amount of chemical conversion coating of the obtained cans is as follows. Phosphorus deposition amount 0.12 mg / m 2 , Ti deposition amount 0.07 mg / m 2 , C deposition amount 1.51 mg /
m 2 , C / M 21.57 chemical conversion treatment (test 10),
Phosphorus deposition amount 0.35 mg / m 2 , Ti deposition amount 0.23 m
g / m 2 , C adhesion amount 3.24 mg / m 2 , C / M is 1
Chemical conversion treatment of 4.09 (test 11), phosphorus deposition amount 0.8
3 mg / m 2 , Ti adhesion amount 0.74 mg / m 2 , C adhesion amount 10.35 mg / m 2 , C / M 13.99 chemical conversion treatment (test 12), phosphorus adhesion amount 1.26 mg / m 2 , T
i adhesion amount 1.36 mg / m 2 , C adhesion amount 14.72 mg
/ M 2 , C / M 10.82 chemical conversion treatment (Test 1
3). For comparison, degreasing treatment was performed on the steel DI can trimmed to the above can height in the same manner as in the example of the present invention, and the chemical conversion treatment was performed using the existing phosphoric acid Sn-based treatment (Test 1).
A can having the amount of adhered phosphorus of 0.87 mg / m 2 which was subjected to 4) was also prepared. Then, Experimental Example 1 was applied to the outer surface and the inner surface of the can.
The same coating and printing as the above was applied, and the neck-in processing and the flange processing were performed on the opening of the inner and outer surface coated cans to prepare a can having an opening diameter of 202 diameters. The thus-obtained inner and outer surface coated cans were examined for coating film adhesion on the inner and outer surfaces of the cans, coating film floating occurrence rate of the outer surface coating films, and corrosion resistance on the inner surface of the cans according to the procedure of Experimental Example 1. Steel D of the present invention, which was conducted in Experiment 2
Table 2 shows the details of the chemical conversion coating of the I can and the chemical conversion coating of the comparative example, and various evaluation results.
【００２０】[0020]
【表２】 [Table 2]
【００２１】表２から判るように、本発明の化成処理を
施したテスト１０〜テスト１３（本発明例７〜１０）の
スチール製ＤＩ缶は、内外面の塗膜密着性に優れ、ま
た、外面塗膜の浮き発生率に対しても良好な性能を示
し、内容物耐食性にも優れていることが判る。一方、比
較例である現行のリン酸Ｓｎ系化成処理を施したテスト
１４（比較例４）は、内外面の塗膜密着性は本発明の化
成処理皮膜を有する缶と遜色ないが、外面塗膜の浮き発
生率は高いことがわかる。As can be seen from Table 2, the steel DI cans of Test 10 to Test 13 (Examples 7 to 10 of the present invention) subjected to the chemical conversion treatment of the present invention have excellent coating film adhesion on the inner and outer surfaces, and It can be seen that the performance of the outer coating film is good even with respect to the floating rate, and the corrosion resistance of the content is also excellent. On the other hand, in the test 14 (Comparative Example 4) in which the current phosphoric acid Sn-based chemical conversion treatment is performed as a comparative example, the coating adhesion on the inner and outer surfaces is comparable to the can having the chemical conversion coating of the present invention, but the outer surface coating It can be seen that the floating rate of the film is high.
【００２２】[0022]
【発明の効果】以上説明したように、本発明の化成処理
を施したスチール製ＤＩ缶は、缶の内外面に塗装される
塗膜の密着性に優れ、また内面の対内容物耐食性にも優
れていることから、品質の安定性が向上できる。更に、
特に、内容物を充填後にレトルト加熱殺菌処理を行う用
途に対しても、希に外面の塗膜浮きが発生することがあ
るトラブルがほぼ完全に解消できる。こうした優れた特
性を有していることから、単に品質が向上できるだけで
はなく、製造面でも安心して生産できるため、生産性が
大幅に向上でき、経済的効果も大きいものがある。As described above, the steel DI can which has been subjected to the chemical conversion treatment of the present invention is excellent in the adhesion of the coating film applied to the inner and outer surfaces of the can and is also resistant to corrosion of the inner surface against the contents. Since it is excellent, the stability of quality can be improved. Furthermore,
In particular, even for applications in which the retort heat sterilization treatment is performed after filling the contents, the trouble that the coating film on the outer surface rarely occurs can be almost completely eliminated. Due to these excellent characteristics, not only the quality can be improved but also the manufacturing can be carried out with peace of mind, so that the productivity can be greatly improved and the economic effect is large.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２３Ｃ 22/07 Ｃ２３Ｃ 22/36 22/36 Ｂ６５Ｄ 1/00 Ｂ (72)発明者 太田原 幸子 神奈川県相模原市西橋本５丁目５番１号 大和製罐株式会社総合研究所内 (72)発明者 沖山 賢一 神奈川県相模原市西橋本５丁目５番１号 大和製罐株式会社東京工場内 Ｆターム(参考） 3E033 AA06 BA08 BB08 CA14 CA20 DA08 FA01 GA02 3E062 AA04 AC03 JA01 JB23 JC06 4F100 AA04B AA04C AA17B AA17C AA21B AA21C AA27B AA27C AA28B AA28C AB03A AB21 AK01B AK01C AK25G AK33 AK35G AK41G AK53G BA03 BA06 BA10B BA10C GB16 YY00B YY00C 4K026 AA02 AA10 AA12 AA25 BA03 BB06 BB08 CA16 CA23 CA26 CA28 CA39 DA15 DA16 EA08─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C23C 22/07 C23C 22/36 22/36 B65D 1/00 B (72) Inventor Sachiko Otawara Sagamihara City, Kanagawa Prefecture Nishihashimoto 5-5-1 Yamato Seikan Co., Ltd. Research Institute (72) Inventor Kenichi Okiyama 5-5-1 Nishibashimoto, Sagamihara-shi, Kanagawa Yamato Seikan Co., Ltd. F-term (Reference) 3E033 AA06 BA08 BB08 CA14 CA20 DA08 FA01 GA02 3E062 AA04 AC03 JA01 JB23 JC06 4F100 AA04B AA04C AA17B AA17C AA21B AA21C AA27B AA27C AA28B AA28C AB03A AB21 AK01B AK01C AK25G AK33 AK35G AK41G AK53G BA03 BA06 BA10B BA10C GB16 YY00B YY00C 4K026 AA02 AA10 AA12 AA25 BA03 BB06 BB08 CA16 CA23 CA26 CA28 CA39 DA15 DA16 EA08
Claims (2)
ル製ＤＩ缶において、缶の内外面の鋼板表面にリン
（Ｐ）−金属（Ｍ）−有機樹脂（Ｒ）からなる化成処理
皮膜が形成されており、該化成処理皮膜がリン（Ｐ）の
付着量としては、片面の付着量として０．０５〜２．０
ｍｇ／ｍ２、金属（Ｍ）が片面の付着量として０．０５
〜２．０ｍｇ／ｍ２、有機樹脂（Ｒ）の付着量が炭素
（Ｃ）量として片面の付着量で０．５〜２０ｍｇ／ｍ２
であり、かつ炭素（Ｃ）量と金属（Ｍ）付着量の比 Ｃ
／Ｍ が１〜１００であることを特徴とするスチール製
ＤＩ缶。1. A steel DI can obtained by drawing and ironing, wherein a chemical conversion coating film of phosphorus (P) -metal (M) -organic resin (R) is formed on the steel plate surface of the inner and outer surfaces of the can. The amount of phosphorus (P) deposited on the chemical conversion coating is 0.05 to 2.0 as the amount deposited on one surface.
mg / m 2 , metal (M) is 0.05 on one side
~2.0mg / m 2, 0.5~20mg / m 2 at a coverage of one side as adhesion amount of carbon (C) content of the organic resin (R)
And the ratio C of the amount of carbon (C) and the amount of metal (M) attached
/ M is 1 to 100, a steel DI can.
（Ｍ）がジルコニウム、チタニウム、スズから選ばれる
１種または２種以上であることを特徴とする請求項１記
載のスチール製ＤＩ缶。2. The steel DI can according to claim 1, wherein the metal (M) of the chemical conversion treatment film according to claim 1 is one or more selected from zirconium, titanium and tin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001253501A JP4865163B2 (en) | 2001-08-23 | 2001-08-23 | Steel DI can |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001253501A JP4865163B2 (en) | 2001-08-23 | 2001-08-23 | Steel DI can |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003063518A true JP2003063518A (en) | 2003-03-05 |
| JP4865163B2 JP4865163B2 (en) | 2012-02-01 |
Family
ID=19081815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001253501A Expired - Lifetime JP4865163B2 (en) | 2001-08-23 | 2001-08-23 | Steel DI can |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4865163B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119866A (en) * | 2005-10-28 | 2007-05-17 | Jfe Steel Kk | Surface-treated metal plate, its production method, resin-coated metal plate, metal can and can cover |
| JP2012082515A (en) * | 2010-09-15 | 2012-04-26 | Jfe Steel Corp | Steel sheet for container and its manufacturing method |
| EP2071055A4 (en) * | 2006-09-08 | 2016-03-16 | Nippon Steel & Sumitomo Metal Corp | Steel plate for container, and method for production thereof |
| WO2016056627A1 (en) * | 2014-10-09 | 2016-04-14 | 新日鐵住金株式会社 | Chemical conversion treated steel sheet, and method for producing chemical conversion treated steel sheet |
| JPWO2016056621A1 (en) * | 2014-10-09 | 2017-04-27 | 新日鐵住金株式会社 | Chemically treated steel sheet for acidic contents storage container and method for producing chemical treated steel sheet for acidic contents storage container |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11229156A (en) * | 1998-02-18 | 1999-08-24 | Nippon Parkerizing Co Ltd | Aluminum alloy treated can and its treatment |
| JPH11264075A (en) * | 1998-03-17 | 1999-09-28 | Nippon Parkerizing Co Ltd | Tin-plated steel surface treated can and surface treatment of tin-plated steel can |
| JP2000185735A (en) * | 1998-12-18 | 2000-07-04 | Daiwa Can Co Ltd | Film-stuck can and its manufacture |
-
2001
- 2001-08-23 JP JP2001253501A patent/JP4865163B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11229156A (en) * | 1998-02-18 | 1999-08-24 | Nippon Parkerizing Co Ltd | Aluminum alloy treated can and its treatment |
| JPH11264075A (en) * | 1998-03-17 | 1999-09-28 | Nippon Parkerizing Co Ltd | Tin-plated steel surface treated can and surface treatment of tin-plated steel can |
| JP2000185735A (en) * | 1998-12-18 | 2000-07-04 | Daiwa Can Co Ltd | Film-stuck can and its manufacture |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119866A (en) * | 2005-10-28 | 2007-05-17 | Jfe Steel Kk | Surface-treated metal plate, its production method, resin-coated metal plate, metal can and can cover |
| EP2071055A4 (en) * | 2006-09-08 | 2016-03-16 | Nippon Steel & Sumitomo Metal Corp | Steel plate for container, and method for production thereof |
| JP2012082515A (en) * | 2010-09-15 | 2012-04-26 | Jfe Steel Corp | Steel sheet for container and its manufacturing method |
| JPWO2016056621A1 (en) * | 2014-10-09 | 2017-04-27 | 新日鐵住金株式会社 | Chemically treated steel sheet for acidic contents storage container and method for producing chemical treated steel sheet for acidic contents storage container |
| KR20170031192A (en) * | 2014-10-09 | 2017-03-20 | 신닛테츠스미킨 카부시키카이샤 | Chemical conversion treated steel sheet, and method for producing chemical conversion treated steel sheet |
| JPWO2016056627A1 (en) * | 2014-10-09 | 2017-04-27 | 新日鐵住金株式会社 | Chemical conversion treated steel sheet and method for producing chemical conversion treated steel sheet |
| WO2016056627A1 (en) * | 2014-10-09 | 2016-04-14 | 新日鐵住金株式会社 | Chemical conversion treated steel sheet, and method for producing chemical conversion treated steel sheet |
| TWI580797B (en) * | 2014-10-09 | 2017-05-01 | 新日鐵住金股份有限公司 | Chemically-treated steel sheet, production method thereof, and metal container |
| TWI580798B (en) * | 2014-10-09 | 2017-05-01 | 新日鐵住金股份有限公司 | Chemically-treated steel sheet, production method thereof, and metal container |
| CN106661737A (en) * | 2014-10-09 | 2017-05-10 | 新日铁住金株式会社 | Chemical conversion treated steel sheet, and method for producing chemical conversion treated steel sheet |
| EP3205744A4 (en) * | 2014-10-09 | 2018-02-28 | Nippon Steel & Sumitomo Metal Corporation | Chemical conversion treated steel sheet, and method for producing chemical conversion treated steel sheet |
| KR101942202B1 (en) * | 2014-10-09 | 2019-01-24 | 신닛테츠스미킨 카부시키카이샤 | Chemical conversion treated steel sheet, and method for producing chemical conversion treated steel sheet |
| CN106661737B (en) * | 2014-10-09 | 2019-05-17 | 新日铁住金株式会社 | The manufacturing method of chemical conversion treatment steel plate and chemical conversion treatment steel plate |
| US10294577B2 (en) | 2014-10-09 | 2019-05-21 | Nippon Steel & Sumitomo Metal Corporation | Chemical treatment steel sheet, and method for producing chemical treatment steel sheet |
| US10301721B2 (en) | 2014-10-09 | 2019-05-28 | Nippon Steel & Sumitomo Metal Corporation | Chemical treatment steel sheet, and method for producing chemical treatment steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4865163B2 (en) | 2012-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5196035B2 (en) | Steel plate for container and method for producing the same | |
| JP4886811B2 (en) | Steel plate for containers excellent in organic film performance and method for producing the same | |
| TW539769B (en) | Surface treated tin-plated steel sheet and chemical treatment solution | |
| WO2005123991A1 (en) | Surface-treated metal material and surface treatment method therefor, resin-coated metal material, can and lid of can | |
| JP5672775B2 (en) | Steel plate for containers excellent in organic film performance and method for producing the same | |
| WO2011126137A1 (en) | Process for production of steel sheet for container material which has reduced load on environments, steel sheet for container material which has reduced load on environments, and laminate steel sheet for container material and coated precoat steel sheet for container material which are produced using the steel sheet | |
| TW201223752A (en) | Method for manufacturing steel sheet for container | |
| KR101431941B1 (en) | Steel sheet for vessel having excellent corrosion resistance | |
| JP4915068B2 (en) | Aluminum alloy can lid with excellent corrosion resistance and adhesion and method for producing the same | |
| JP2003063518A (en) | Steel di can | |
| JP5311266B2 (en) | Resin-coated seamless aluminum can with excellent corrosion resistance and adhesion | |
| JPH0649933B2 (en) | Plated steel plate for cans | |
| JP3742533B2 (en) | Steel sheet for laminated containers with excellent can-making processability | |
| JP2003119570A (en) | Pretreated aluminum material superior in coating adhesiveness and corrosion resistance | |
| JP2578532B2 (en) | Phosphate treated Sn plated steel sheet | |
| JP2002356785A (en) | Tinned steel sheet having excellent oxidation resistance and production method therefor | |
| JP2600218B2 (en) | Multi-layer plated steel sheet for cans | |
| JP5007482B2 (en) | Manufacturing method of aluminum DI can body | |
| JPS63168238A (en) | Pressure resistant can subjected to drawn ironing by using aluminum coated steel plate | |
| WO2001004380A1 (en) | Steel plate for laminated container, and method for producing can using the same and can | |
| JP6553936B2 (en) | Method for producing aluminum alloy sheet for packaging container | |
| JP2625499B2 (en) | Hot-dip aluminized steel sheet for container, manufacturing method and can body | |
| JPS6217199A (en) | Sn coated steel sheet for vessel having superior paintability and corrosion resistance and its manufacture | |
| JP6565308B2 (en) | Steel plate for container and method for producing steel plate for container | |
| JP2726008B2 (en) | High performance Sn-based multi-layer plated steel sheet with excellent corrosion resistance, weldability and paint adhesion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080812 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100521 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110309 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110419 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110617 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111108 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111110 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141118 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4865163 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| EXPY | Cancellation because of completion of term |