JPH01136738A - Laminated steel plate for can excellent in corrosion resistance - Google Patents
Laminated steel plate for can excellent in corrosion resistanceInfo
- Publication number
- JPH01136738A JPH01136738A JP29504087A JP29504087A JPH01136738A JP H01136738 A JPH01136738 A JP H01136738A JP 29504087 A JP29504087 A JP 29504087A JP 29504087 A JP29504087 A JP 29504087A JP H01136738 A JPH01136738 A JP H01136738A
- Authority
- JP
- Japan
- Prior art keywords
- film
- chromium
- steel plate
- chrome
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 15
- 230000007797 corrosion Effects 0.000 title claims abstract description 14
- 229910000576 Laminated steel Inorganic materials 0.000 title claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 24
- 239000010959 steel Substances 0.000 claims abstract description 24
- 229920001225 polyester resin Polymers 0.000 claims abstract description 20
- 239000004645 polyester resin Substances 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 18
- 239000011651 chromium Substances 0.000 claims description 29
- 229910052804 chromium Inorganic materials 0.000 claims description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 22
- 238000007747 plating Methods 0.000 claims description 19
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 235000013405 beer Nutrition 0.000 description 4
- -1 fluorine ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 235000014171 carbonated beverage Nutrition 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010409 ironing Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 235000011496 sports drink Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は耐食性の優れた缶用鋼板に関するもので、ビー
ル、炭酸飲料等の内圧缶あるいは一般食缶等に利用され
る。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a steel plate for cans with excellent corrosion resistance, and is used for internal pressure cans for beer, carbonated drinks, etc., general food cans, and the like.
（従来の技術）
周知の如く、ビール、炭酸飲料を内容物とする内圧缶は
、近年絞りとしごき加工を組合せて成形したいわゆるＤ
Ｉ缶（Ｄｒａｗｎ ＆ Ｉ ｒｏｎｅｄ缶）が主流で
あり、アルミニウム合金あるいはぶつきが素材として使
用されている。一方、魚介類、各種スープの缶等は減圧
充填されることが多（、缶強度の高い絞り缶が使用され
、その素材としては塩化ビニル樹脂をコーティングした
塗装ＴＦＳ （ティン７リースチール）が使用されで
いる。(Prior Art) As is well known, internal pressure cans containing beer and carbonated beverages are manufactured using the so-called D
I cans (Drawn & I roned cans) are the mainstream, and aluminum alloy or butsuki is used as the material. On the other hand, cans of seafood and various soups are often filled under reduced pressure (high-strength squeeze cans are used, and the material used is painted TFS (tin7ly steel) coated with vinyl chloride resin. It's been done.
よりさあるいはＴＦＳの場合、そのめっき厚みは通常１
μ以下と非常に薄く、ＤＩ加工あるいは絞り加工により
錫あるいはクロム等の金属皮膜は破壊されるため、その
上層に存在する有機皮膜に防食性能を期待している。In the case of stranded or TFS, the plating thickness is usually 1
It is extremely thin, less than μ, and metal coatings such as tin or chromium are destroyed by DI processing or drawing processing, so anti-corrosion performance is expected from the organic coating present on top of it.
ＤＩ缶の場合、成形加工後脱脂・塗装下地処理を施した
のち内容物に対する耐食性を確保するため（塗装−焼付
け）→（塗装−焼付け）と２ｒｊｊＪの缶内面塗装を行
い、塗膜欠陥を完全になくすようにしでいる。＊た、１
回あるいは多数回の絞り加工により成形される絞り缶の
場合、成形前に加工性の良い塩化ビニル系塗料を１０〜
１３μの厚みで塗装し、絞り加工においても塗膜欠陥の
発生しない様工夫されている。In the case of DI cans, after the molding process, degreasing and surface treatment for painting are performed, and in order to ensure corrosion resistance for the contents, the inside of the can is painted (painting-baking) → (painting-baking) to completely eliminate paint film defects. I try to get rid of it. *Ta, 1
In the case of drawn cans that are formed by drawing several times or many times, a polyvinyl chloride paint with good workability is applied to the can before forming.
The coating is applied to a thickness of 13μ, and measures have been taken to ensure that no coating defects occur during the drawing process.
（発明が解決しようとする問題点）
このようにぶりきあるいはＴＦＳをＤＩ缶あるいは絞り
缶に使用する場合、完全な塗膜欠陥のない有機塗装を行
う必要があり、高度の塗装技術と＾価な塗装置の負担は
避けられないものであった。(Problem to be Solved by the Invention) When tinplate or TFS is used for DI cans or squeeze cans, it is necessary to apply an organic coating that is completely free from coating defects, and requires advanced coating technology and high quality. The burden of additional painting equipment was unavoidable.
本発明はこれらの従来の問題点を解決し、缶用鋼板とし
て耐食性が優れ、缶内面塗装の簡略化が可能で経済性の
良い缶用鋼板を提供する。The present invention solves these conventional problems and provides a steel plate for cans that has excellent corrosion resistance, allows for simple can inner coating, and is economically efficient.
（問題点を解決するための手段）
本発明は、薄鋼板の片面に１〜１５ｇ／■２の錫めっき
皮膜を有し、他の面には金属クロムとして３〜１５０論
ｇ／霞２．水和酸化クロムとして２〜５０−ｇ／霞２（
クロム換算）の金属クロムおよび水和酸化りａム皮膜を
クロム付着量として合計５〜２００ｍｇ／ｍ２と、その
上層に融点（Ｔ−）が１８０℃≦Ｔｍ≦２３０℃である
１０〜１００μｍの厚みのポリエステル系樹脂皮膜とを
有することを特徴とする耐食性の優れた缶用積層鋼板、
および、薄鋼板の片面に１〜１５ｇ／ｍ”の錫めっき皮
膜を有し、他の面には錫めっき皮膜と、その上層に金属
クロムとして３〜１５０ ｍｇ／論２、水利酸化クロム
として２〜５０−ｇ／鋤２（クロム換算）の金属クロム
および水和酸化クロム皮膜をクロム付着量として合計５
〜２００ ｍｇ／曽２と、さらにその上層に融点（Ｔ謹
）が１８０℃≦Ｔｍ≦２３０℃である１０〜１００μｍ
の厚みのポリエステル系樹脂皮膜とを有することを特徴
とする耐食性の優れた缶用積層鋼板である。(Means for Solving the Problems) The present invention has a tin plating film of 1 to 15 g/2.2 on one side of a thin steel plate, and a tin plating film of 3 to 150 g/2.2 as metallic chromium on the other side. 2 to 50-g/haze 2 (as hydrated chromium oxide)
A total of 5 to 200 mg/m2 of metallic chromium (in terms of chromium) and hydrated sulfur oxide film as the amount of chromium deposited, and a thickness of 10 to 100 μm with a melting point (T-) of 180°C≦Tm≦230°C on the upper layer. A laminated steel sheet for cans with excellent corrosion resistance, characterized by having a polyester resin film of
And, one side of the thin steel plate has a tin plating film of 1 to 15 g/m'', and the other side has a tin plating film, and the upper layer has a tin plating film of 3 to 150 mg/2 as metallic chromium, and 2 as water-use chromium oxide. ~50-g/plow2 (chromium equivalent) of metallic chromium and hydrated chromium oxide film for a total chromium deposition amount of 5.
~200 mg/so2, and further above that 10 to 100 μm with a melting point (T) of 180°C≦Tm≦230°C
This is a laminated steel sheet for cans with excellent corrosion resistance, characterized by having a polyester resin film with a thickness of .
（作用）
薄鋼板の片面に施される錫めっき皮膜は製缶時に外面に
用いるとＤＩ成形時の潤滑剤となる。錫は非常に有効な
固体潤滑剤であり、その量は１〜１５ｇ／ｍ”の範囲に
限定される。１ｇ／ｍ”未満では有効な潤滑作用がなく
、かじり等の発生により連続製缶が不能となる。１５ｇ
／論２超ではコスト面で不利になると共に品質的な向上
も望めない。(Function) When the tin plating film applied to one side of a thin steel plate is used on the outer surface during can manufacturing, it becomes a lubricant during DI forming. Tin is a very effective solid lubricant, and its amount is limited to a range of 1 to 15 g/m". If it is less than 1 g/m", it has no effective lubricating effect, and continuous can making becomes impossible due to occurrence of galling, etc. It becomes impossible. 15g
If the value exceeds 2, it will be disadvantageous in terms of cost and no improvement in quality can be expected.
この付着量は錫合金層を含めた錫付着量の合計であり、
必要に応じて錫めっき時に溶鍋処理を施し、光沢等を付
与しても良いが、その際に生成する錫−鉄合金は潤滑性
の面からは出来るだけ少なく （たとえば０ 、８ ｇ
／ ｍ”以下）することが望ましい、また、錫の表面に
は長期貯蔵時の錫酸化物の成長を避ける意味で軽度のり
四メート処理（Ｃｒ量として１０ｍｇ／曽２以下）を行
うことが望ましい。This adhesion amount is the total amount of tin adhesion including the tin alloy layer,
If necessary, a molten pot treatment may be applied during tin plating to impart shine, etc., but the tin-iron alloy produced at this time should be kept as small as possible from the viewpoint of lubricity (for example, 0.8 g
/ m" or less), and it is also desirable to perform a light adhesive treatment (Cr content of 10 mg/so2 or less) on the surface of the tin to avoid the growth of tin oxide during long-term storage. .
他の面に施す積層皮膜の構成であるが、成形缶の内面側
においては缶内容物に対する耐食性が重要である。した
がって、最上層に存在するポリエステル系樹脂皮膜が偏
成形加工後にも十分健全な膜としで存在することが重要
であり、下地との密着性が必要とされる。したがって、
樹脂皮膜と直接接する下地面には金属りａムおよび水和
酸化クロム皮膜の存在は不可欠であり、金属クロムとし
ては３〜１５０ ｔａｇ／ ｍ”、水利酸化クロムとし
ては２〜５０−ｇ／−２、クロム付着量の合計として５
〜２００ ｍｇｌ曽２の皮膜を形成する。このような皮
膜はクロム酸を主成分とし、少量の硫酸根および／虫た
は少量のフッ素イオンを含む水溶液中にて鋼板を陰極電
解することにより得ることができる。Although the laminated film is applied to other surfaces, corrosion resistance against the contents of the can is important on the inner surface of the molded can. Therefore, it is important that the polyester resin film present in the uppermost layer remains as a sufficiently sound film even after uneven molding processing, and adhesion to the base is required. therefore,
The presence of metal laminate and hydrated chromium oxide film on the base surface that is in direct contact with the resin film is essential, and the amount of metal chromium is 3 to 150 tag/m", and the water-use chromium oxide is 2 to 50 g/m". 2.5 as the total amount of chromium deposited
Forms a film of ~200 mgl so2. Such a film can be obtained by cathodically electrolyzing a steel plate in an aqueous solution containing chromic acid as a main component and a small amount of sulfuric acid and/or fluorine ions.
このクロム系皮膜は有機物との密着性に極めて優れてい
るが、皮膜そのものの加工性は必ずしも良くない、した
がって、成形後の耐食性の保持という面からは更にその
下層に錫系の皮膜を有するほうが有利である。すなわち
、クロム皮膜の下層に錫めっき皮ＩＫ（好ましくは１５
ｇ／ｍ２以下）を設けることによって一段と高度の耐食
性を付与することが可能である。この場合にもＤＩ成形
性に不利となる合金層の形成は出来るだけ避けたほうが
良い。Although this chromium-based film has extremely good adhesion to organic matter, the workability of the film itself is not necessarily good.Therefore, in terms of maintaining corrosion resistance after molding, it is better to have a tin-based film further below. It's advantageous. That is, a tin plating layer IK (preferably 15
g/m2 or less), it is possible to provide even higher corrosion resistance. In this case as well, it is better to avoid forming an alloy layer that is disadvantageous to DI formability as much as possible.
最上層に存在させるポリエステル系樹脂皮膜は１食性、
成形性、塗装性に優れたものである必要があり、！造技
術上および実用品質特性上その樹脂の融点（Ｔ−）は１
８０℃≦Ｔ１１≦２３０℃、望ましくは２１０℃≦Ｔｍ
≦２２５℃とする。The polyester resin film present on the top layer is mono-edible,
It must have excellent moldability and paintability! Due to manufacturing technology and practical quality characteristics, the melting point (T-) of the resin is 1.
80℃≦T11≦230℃, preferably 210℃≦Tm
The temperature shall be ≦225°C.
本発明に係る鋼板はＤＩ成形後、炭酸飲料あるいはビー
ル等を内容物として充填されるが、コーラ系飲料あるい
は塩素イオンを多量に含むスポーツ飲料等の用途には成
形時に発生する微小欠陥の補修のため熱硬化性の保護塗
膜を適用する二とが望ましい、この保護用の熱硬化性樹
脂としてはエボキン樹脂、フェノール樹脂、尿素樹脂、
ビニル樹脂等が使用されるが、２代らの樹脂は通常１７
０〜２１０℃の温度にて焼成される。したがって、これ
ら内面保護塗装が適用される場合、鋼板表面に予め存在
するポリエステル系樹脂が軟化、溶融すると補修塗膜の
形成が不均一になり、保護作用が消失することとなる。After DI forming, the steel sheet according to the present invention is filled with carbonated drinks or beer. However, for applications such as cola drinks or sports drinks containing large amounts of chlorine ions, it is necessary to repair minute defects that occur during forming. Therefore, it is desirable to apply a thermosetting protective coating. Examples of thermosetting resins for this protection include Evokin resin, phenolic resin, urea resin,
Vinyl resin etc. are used, but the second generation resin is usually 17
It is fired at a temperature of 0 to 210°C. Therefore, when these inner surface protective coatings are applied, if the polyester resin preexisting on the surface of the steel sheet softens and melts, the repair coating will be formed unevenly and the protective effect will disappear.
そのため、少な（とも１８０℃以上の融点を有するポリ
エステル系樹脂を用いる必要がある。尚、ＤＩ成形ほか
な９胃酷な冷開加工であり、たとえば０．３０ｍ−の軟
鋼板が瞬時に０．１０ｍｍ以下にまでしご訃加工により
伸ばされる。Therefore, it is necessary to use a polyester resin with a melting point of 180°C or higher.It is necessary to use a polyester resin with a melting point of 180°C or higher.In addition, DI molding and other harsh cold-opening processes are required, and for example, a 0.30m-thick mild steel plate can be instantly melted to 0.3m. It is stretched to 10mm or less by ladder processing.
この際、素材自体がかなりの発熱を起こし、上記の成形
の場合、約２００℃前後にまで温度上昇が起こる。した
がって、それ以下の融点の樹脂の場合、成形パンチへの
樹脂のビルドアップあるいはパンチよりの抜は不良等の
問題が起こる。そのため好本しくは２１０℃以上の融点
を有するポリエステル系樹脂を用いる。At this time, the material itself generates considerable heat, and in the case of the above molding, the temperature rises to around 200°C. Therefore, in the case of a resin having a melting point lower than that, problems such as build-up of the resin on the molding punch or poor removal from the punch occur. Therefore, preferably a polyester resin having a melting point of 210° C. or higher is used.
一方、上限温度の２３０℃は共存する金属錫の融点によ
るものである。このポリエステル系樹脂皮膜は素材を適
当な温度まで加熱し、熱圧着により積層されるものであ
る。熱圧着温度が２３０℃を越える場合、下層のあるい
は反対側の面（Ｄ Ｉ成形時の缶外面）の錫が溶融し、
合金層の生成によるＤＩ成形性の劣化をもたらすと共に
、フミネート作業に多大の支障が生じることとなる。す
なわち、ポリエステル系樹脂自体ゴムロール等で圧着す
ることにより接着されるため、反対面における錫の溶融
はロールへの錨巻き等を起こす。On the other hand, the upper limit temperature of 230° C. is due to the melting point of coexisting metal tin. This polyester resin film is laminated by heating the materials to an appropriate temperature and bonding them under heat. If the thermocompression bonding temperature exceeds 230°C, the tin in the lower layer or on the opposite side (outer surface of the can during DI molding) will melt.
This results in deterioration of DI formability due to the formation of an alloy layer, and also causes a great deal of trouble in the fuminate work. That is, since the polyester resin itself is adhered by being pressed with a rubber roll or the like, melting of tin on the opposite side causes anchoring on the roll.
本発明に用いるポリエステル系樹脂は二塩基酸成分とし
てテレフタル酸、イソフタル酸、７タル酸、セバシン酸
、アジピン酸等を、ノオール成分としてはエチレングリ
コール、ジエチレングリ５−ル、Ｆリエチレングリコー
ル、プタンノオールを含み、その含有比により１８０〜
２３０℃の融点に１１１ｇされる。The polyester resin used in the present invention contains terephthalic acid, isophthalic acid, 7-thalic acid, sebacic acid, adipic acid, etc. as a dibasic acid component, and ethylene glycol, diethylene glycol, F-lyethylene glycol, butanol as a nol component. Contains, depending on the content ratio, 180 ~
111 g with a melting point of 230°C.
この融点が１８０〜２３０℃にｇ４整された飽和ポリエ
ステル系樹脂は１０〜１００μの厚みに準備され、通電
加熱、誘導加熱あるいは輻射加熱等により予め加熱され
たクロム皮膜を有する鋼板表面に熱圧着により積層され
る。熱圧着の方法としでは、樹脂の融点以下１０〜６０
℃で第１大圧着し、その後鋼板温度を上昇させることに
より密着性の向上をはかり、必要に応じて樹脂が完全に
溶融するまで鋼板温度を上昇させる。This saturated polyester resin whose melting point has been adjusted to 180 to 230℃ is prepared to a thickness of 10 to 100μ, and is bonded by thermocompression to the surface of a steel plate with a chromium film that has been preheated by electrical heating, induction heating, or radiation heating. Laminated. For thermocompression bonding, the melting point of the resin is 10 to 60
The first large pressure bonding is carried out at .degree. C., and then the temperature of the steel sheet is increased to improve adhesion, and if necessary, the temperature of the steel sheet is increased until the resin is completely melted.
このような方法により得られた片面にポリエステル系樹
脂皮膜を有する鋼板は、ＤＩ缶のみならず絞り成形によ
り製缶されるＤＲＤ缶あるいは各種の缶壺等の用途にも
有効に使用される。A steel plate having a polyester resin film on one side obtained by such a method is effectively used not only for DI cans but also for DRD cans made by drawing or various can pots.
（実施例）
［実施例１］
０．５１の板厚を有する薄鋼板の片面に２．８６／ｍ”
のＳｎめっきを行った後、もう一方の面に金属クロムと
しで１０８曽ｇ／ＩＩ２、その上に水利酸化クロム皮膜
をＣｒ１ｉとして１８ ｍｇ／ ｍ”、合計Ｃｒｆｉ１
２６−ｇ／論２形成させた。このクロム皮膜上に通電加
熱により１７０″Ｃまで加熱した段階でポリエチレンテ
レフタレート／イソ７タレーシより成る融点２１５℃の
ポリエステルＭ樹脂皮ｉ！（２５μ）をロールで圧着し
、更に温度を上昇させ、最終到達温度２３０℃に達した
時点で冷却した。(Example) [Example 1] 2.86/m" on one side of a thin steel plate with a thickness of 0.51
After performing Sn plating on the other side, the other side was coated with 108 g/II2 of metallic chromium, and on top of that, a water-conserving chromium oxide film with Cr1i of 18 mg/m'', total Crfi1.
26-g/2 hours were formed. At the stage where the chromium film was heated to 170"C by electrical heating, a polyester M resin film i! (25μ) made of polyethylene terephthalate/iso7 thalais with a melting point of 215°C was pressed with a roll, the temperature was further raised, and the final When the final temperature reached 230°C, it was cooled.
この鋼板からプフンク径１１４ｍ−φの円形ブランクを
打抜き、錫めっき面を缶外面として２段の絞り成形で４
０φのカップに成形し、更に２段のしごき加工により板
厚０．２０ｍｍにまでＤＩ成形した。A circular blank with a Pfunk diameter of 114 m-φ was punched out from this steel plate, and the tin-plated surface was used as the outer surface of the can and was drawn in two stages.
It was molded into a 0φ cup, and further DI molded to a plate thickness of 0.20 mm by two steps of ironing.
その際、２段のしごき成形完了に至るまで缶内面側のポ
リエステル系樹脂の剥離は全くなく、優代な成形性を示
した。溶剤洗浄および缶外面印刷後、内面皮膜の健全性
を評価した（１％ＮａＣｌ＋活性剤、６ＶＸ１０秒、缶
を陽極とした場合の通電量）ところ、１鎗Ａ以下の良好
な値を示した。At that time, there was no peeling of the polyester resin on the inner surface of the can until the two-stage ironing process was completed, demonstrating excellent moldability. After solvent cleaning and printing on the outer surface of the can, the integrity of the inner surface film was evaluated (1% NaCl + activator, 6V x 10 seconds, amount of current applied when the can was used as an anode), and it showed a good value of 1 yen A or less.
［実施例２１
０．３０ｍｍの板厚を有する薄鋼板の両面に２．８ｇ／
ｌ１２のＳ ｎめっきを行った後、片方の面のＳｎめつ
き上に金属クロムとして３２ ｗｒｇ／ ｍ”と水和酸
化クロム皮膜としてクロム換算で１４−ｇ／輸２、合計
４６Ｂ／ｅａ”のクロム皮膜を形成した。このクロム皮
膜上に実施例１と同様の方法でポリエステル系樹脂皮膜
を積層した。[Example 21 2.8 g/g on both sides of a thin steel plate having a thickness of 0.30 mm
After performing Sn plating on one side, 32 wrg/m" of metallic chromium and 14-g/w2 of chromium as a hydrated chromium oxide film, totaling 46 B/ea", were applied to the Sn plating on one side. A chrome film was formed. A polyester resin film was laminated on this chromium film in the same manner as in Example 1.
この鋼板からブランク径１３９１φの円°形ブランクを
打抜き、ポリエステル系樹脂皮膜面を缶内面となるよう
にして２段の絞りと３段のしごき加工により最も板厚の
薄い所で０．０９０輪論０側壁厚みを有するビール缶を
成形した。脱脂後、缶外面印刷を行い、更に缶内面塗装
として３５〜５０ｍｇ／ｄａ”の付着量でエポキシフェ
ノール系熱硬化塗料を１回塗布後、実施例１と同様の方
法で内面皮膜の健全性を評価したところ、０．１霞Ａ以
下の優れた特性を示した。A circular blank with a blank diameter of 1391φ was punched out from this steel plate, and with the polyester resin coating surface facing the inner surface of the can, it was drawn in two stages and ironed in three stages to form a 0.090 mm diameter blank at the thinnest point. A beer can with zero sidewall thickness was molded. After degreasing, the outer surface of the can was printed, and the inner surface of the can was coated with epoxy phenol thermosetting paint at a coating amount of 35 to 50 mg/da. When evaluated, it showed excellent characteristics of 0.1 haze A or less.
［比較例１］
０．３０ｓ＋−の板厚を有する薄鋼板を実施例２と同様
の方法で両面にＳｎめっきし１．その片面にＣｒめっき
後、融点２６５℃を有するポリエチレンテレフタレート
皮膜を積層した。この場合、１次圧着温度を２４５℃と
し、最終到達板温２８０℃虫で加熱し、冷却した。その
後実施例２と同様に０．０９０−一までのしごき加工を
行い、加工性を判定したところ、連続成形で１５０缶を
越えるところで外面に線状のかじり疵が発生し、実用性
能として問題を生じた１缶外面側の合金層量を測定した
ところ、１．０５ｇ／ｍ”の錫が合金化しでいた。[Comparative Example 1] A thin steel plate having a thickness of 0.30s+- was plated with Sn on both sides in the same manner as in Example 2.1. After Cr plating on one side, a polyethylene terephthalate film having a melting point of 265°C was laminated. In this case, the primary pressure bonding temperature was 245° C., and the plate was heated to a final plate temperature of 280° C. and cooled. After that, ironing was carried out to 0.090-1 in the same manner as in Example 2, and when the workability was judged, linear galling defects occurred on the outer surface when more than 150 cans were continuously molded, which caused problems in terms of practical performance. When the amount of alloy layer formed on the outer surface of one can was measured, 1.05 g/m'' of tin had been alloyed.
［比較例２１
板厚０．３０ｍｍの薄鋼板の両面に２．８ｇ／ｍ２の錫
めっ軽後、クロム皮膜をつけずに実施例１の方法と同じ
方法でポリエステルＭ樹脂を積層した。その後実施例２
の方法と同じく板厚０．３０ｍｍより０．０９０閣論に
までしご軽加工を行い、脱脂、洗浄を行ったところ、苗
土端部切り口からの皮膜ｆＭＲが認められた。Comparative Example 21 After plating both sides of a thin steel plate with a thickness of 0.30 mm at 2.8 g/m2, polyester M resin was laminated in the same manner as in Example 1 without applying a chromium film. Then Example 2
Similar to the method described above, light ladder processing was performed from 0.30 mm to 0.090 mm thickness, and when degreasing and cleaning were performed, film fMR was observed from the cut end of the seedling soil.
（発明の効果）
本発明の缶用積層鋼板は、缶成形時の加工性が優れ、か
つ加工後の缶内面側の耐食性が優れた缶を安価に製造す
ることができる。(Effects of the Invention) The laminated steel sheet for cans of the present invention has excellent workability during can forming, and cans with excellent corrosion resistance on the inner surface of the can after processing can be manufactured at low cost.
Claims (2)
皮膜を有し、他の面には金属クロムとして３〜１５０ｍ
ｇ／ｍ＾２、水和酸化クロムとして２〜５０ｍｇ／ｍ＾
２（クロム換算）の金属クロムおよび水和酸化クロム皮
膜をクロム付着量として合計５〜２００ｍｇ／ｍ＾２と
、その上層に融点（Ｔ＿ｍ）が１８０℃≦Ｔ＿ｍ≦２３
０℃である１０〜１００μｍの厚みのポリエステル系樹
脂皮膜とを有することを特徴とする耐食性の優れた缶用
積層鋼板。(1) One side of the thin steel plate has a tin plating film of 1 to 15 g/mm^2, and the other side has a tin plating film of 3 to 150 m as metallic chromium.
g/m^2, 2 to 50 mg/m^ as hydrated chromium oxide
2 (chromium equivalent) and a hydrated chromium oxide film with a total chromium adhesion amount of 5 to 200 mg/m^2, and the upper layer has a melting point (T_m) of 180°C≦T_m≦23.
A laminated steel sheet for cans having excellent corrosion resistance, characterized by having a polyester resin film having a thickness of 10 to 100 μm at 0°C.
膜を有し、他の面には錫めっき皮膜と、その上層に金属
クロムとして３〜１５０ｍｇ／ｍ＾２、水和酸化クロム
として２〜５０ｍｇ／ｍ＾２（クロム換算）の金属クロ
ムおよび水和酸化クロム皮膜をクロム付着量として合計
５〜２００ｍｇ／ｍ＾２と、さらにその上層に融点（Ｔ
＿ｍ）が１８０℃≦Ｔ＿ｍ≦２３０℃である１０〜１０
０μｍの厚みのポリエステル系樹脂皮膜とを有すること
を特徴とする耐食性の優れた缶用積層鋼板。(2) One side of the thin steel plate has a tin plating film of 1 to 15 g/m^2, the other side has a tin plating film, and the upper layer has a tin plating film of 3 to 150 mg/m^2 as metallic chromium, and hydrated oxidation. The total amount of chromium deposited is 2 to 50 mg/m^2 (chromium equivalent) of metallic chromium and a hydrated chromium oxide film with a total amount of 5 to 200 mg/m^2 of chromium, and the melting point (T
_m) is 180℃≦T_m≦230℃, 10 to 10
A laminated steel sheet for cans having excellent corrosion resistance, characterized by having a polyester resin film with a thickness of 0 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29504087A JPH01136738A (en) | 1987-11-25 | 1987-11-25 | Laminated steel plate for can excellent in corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29504087A JPH01136738A (en) | 1987-11-25 | 1987-11-25 | Laminated steel plate for can excellent in corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01136738A true JPH01136738A (en) | 1989-05-30 |
Family
ID=17815544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29504087A Pending JPH01136738A (en) | 1987-11-25 | 1987-11-25 | Laminated steel plate for can excellent in corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01136738A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0398844A (en) * | 1989-09-11 | 1991-04-24 | Toyo Seikan Kaisha Ltd | Contracted or contracted-stroked can of laminated material and manufacture thereof |
| JPH03239538A (en) * | 1990-02-16 | 1991-10-25 | Toyo Kohan Co Ltd | Polyester resin film-laminated surface-treated steel sheet excellent in corrosion resistance and manufacture thereof |
| US5094924A (en) * | 1988-10-19 | 1992-03-10 | Kenzo Matsui | Polyester resin film laminated steel sheet for drawn and ironed can |
| JPH0531452A (en) * | 1991-07-29 | 1993-02-09 | Toyo Kohan Co Ltd | One side coated steel sheet for di can |
| JPH05177763A (en) * | 1991-12-27 | 1993-07-20 | Nkk Corp | Laminated steel plate for welded can |
| JPH07138786A (en) * | 1993-11-11 | 1995-05-30 | Toyo Kohan Co Ltd | Laminate steel sheet and its original sheet |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5582797A (en) * | 1978-12-14 | 1980-06-21 | Nippon Steel Corp | Preparation of high anticorrosive d and i can |
| JPS6039159A (en) * | 1983-07-06 | 1985-02-28 | ライボルト‐ヘレーウス・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Magnetron cathode for cathode sputtering device |
| JPS60168643A (en) * | 1984-02-14 | 1985-09-02 | 東洋製罐株式会社 | Coated steel plate for drawing die can and drawing die can |
| JPS62124296A (en) * | 1985-11-25 | 1987-06-05 | Toyo Kohan Co Ltd | Surface treated steel sheet having excellent seam weldability and paint adhesiveness and its production |
-
1987
- 1987-11-25 JP JP29504087A patent/JPH01136738A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5582797A (en) * | 1978-12-14 | 1980-06-21 | Nippon Steel Corp | Preparation of high anticorrosive d and i can |
| JPS6039159A (en) * | 1983-07-06 | 1985-02-28 | ライボルト‐ヘレーウス・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Magnetron cathode for cathode sputtering device |
| JPS60168643A (en) * | 1984-02-14 | 1985-09-02 | 東洋製罐株式会社 | Coated steel plate for drawing die can and drawing die can |
| JPS62124296A (en) * | 1985-11-25 | 1987-06-05 | Toyo Kohan Co Ltd | Surface treated steel sheet having excellent seam weldability and paint adhesiveness and its production |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5094924A (en) * | 1988-10-19 | 1992-03-10 | Kenzo Matsui | Polyester resin film laminated steel sheet for drawn and ironed can |
| JPH0398844A (en) * | 1989-09-11 | 1991-04-24 | Toyo Seikan Kaisha Ltd | Contracted or contracted-stroked can of laminated material and manufacture thereof |
| JPH06102464B2 (en) * | 1989-09-11 | 1994-12-14 | 東洋製罐株式会社 | Squeezing or squeezing from laminated material-ironing can and its manufacturing method |
| JPH03239538A (en) * | 1990-02-16 | 1991-10-25 | Toyo Kohan Co Ltd | Polyester resin film-laminated surface-treated steel sheet excellent in corrosion resistance and manufacture thereof |
| JPH0531452A (en) * | 1991-07-29 | 1993-02-09 | Toyo Kohan Co Ltd | One side coated steel sheet for di can |
| JPH05177763A (en) * | 1991-12-27 | 1993-07-20 | Nkk Corp | Laminated steel plate for welded can |
| JPH07138786A (en) * | 1993-11-11 | 1995-05-30 | Toyo Kohan Co Ltd | Laminate steel sheet and its original sheet |
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