JPH01135568A - Production of resin coated steel plate superior in corrosion resistance - Google Patents
Production of resin coated steel plate superior in corrosion resistanceInfo
- Publication number
- JPH01135568A JPH01135568A JP29466587A JP29466587A JPH01135568A JP H01135568 A JPH01135568 A JP H01135568A JP 29466587 A JP29466587 A JP 29466587A JP 29466587 A JP29466587 A JP 29466587A JP H01135568 A JPH01135568 A JP H01135568A
- Authority
- JP
- Japan
- Prior art keywords
- steel plate
- coated steel
- corrosion resistance
- resin coated
- monomer
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 27
- 239000010959 steel Substances 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 21
- 230000007797 corrosion Effects 0.000 title claims abstract description 13
- 238000005260 corrosion Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 238000010894 electron beam technology Methods 0.000 claims abstract description 8
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 7
- 230000001678 irradiating effect Effects 0.000 claims abstract 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- USSIQXCVUWKGNF-UHFFFAOYSA-N 6-(dimethylamino)-4,4-diphenylheptan-3-one Chemical compound C=1C=CC=CC=1C(CC(C)N(C)C)(C(=O)CC)C1=CC=CC=C1 USSIQXCVUWKGNF-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、樹脂被膜表面にイオン交換能を有するモノマ
ーをグラフト重合させて耐食性を向上させた樹脂被覆鋼
板の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a resin-coated steel sheet in which corrosion resistance is improved by graft polymerizing a monomer having ion exchange ability onto the surface of a resin coating.
（従来技術）
塗装鋼板やラミネート鋼板などの樹脂被覆鋼板は、めっ
ト鋼板にクロメート処理やリン酸塩処理などの化成処理
を施した後、防錆顔料を含有する下塗り塗料もしくは接
着剤を塗装し、その上に上塗り塗装もしくはフィルムを
ラミネートして製造している。(Prior technology) Resin-coated steel sheets such as painted steel sheets and laminated steel sheets are made by applying a chemical conversion treatment such as chromate treatment or phosphate treatment to a galvanized steel sheet, and then applying an undercoat or adhesive containing a rust-preventing pigment. It is then manufactured by laminating a top coat or film on top of it.
（発明が解決しようとする問題点）
この樹脂被覆鋼板は、施工や加工のとき、被膜に傷を付
けないように細心の注意を払うが、若干の傷を付けるの
は避けられない。この傷が鋼素地に達するような深い傷
の場合、めっき金属、化成処理層、防錆顔料などが鋼板
に対して腐食抑制効果を発揮している間、鋼板の腐食は
進行しないが、腐食抑制効果が小さくなったり、消滅し
たりすると、鋼板は腐食され、錆が被膜表面にまで達し
、外観を低下させる。この外観低下を防止するには、め
っき付着量や下塗り塗”膜中の防錆顔料量を増加させれ
ばよいのであるが、めつｌ＆層や塗膜の物性の関係で限
界がある。(Problems to be Solved by the Invention) When constructing or processing this resin-coated steel sheet, great care is taken not to damage the coating, but some damage is unavoidable. If this scratch is deep enough to reach the steel base, the corrosion of the steel plate will not progress while the plated metal, chemical conversion layer, anti-rust pigment, etc. exert a corrosion inhibiting effect on the steel plate, but corrosion will be suppressed. When the effect diminishes or disappears, the steel plate corrodes and rust reaches the surface of the coating, deteriorating its appearance. In order to prevent this deterioration in appearance, it is possible to increase the amount of plating deposited or the amount of rust preventive pigment in the undercoat film, but there is a limit due to the physical properties of the metal layer and the paint film.
そこで、本発明は、めっき層や塗膜の物性を低下させる
ことなく耐食性を向上させることができる樹脂被覆鋼板
の製造方法□を提供するものである。Therefore, the present invention provides a method for producing a resin-coated steel sheet that can improve corrosion resistance without reducing the physical properties of the plating layer or coating film.
（問題点を解決するための手段）
本発明は、イオン交換能を有するモノマーを樹薄被膜表
面にグラフト重合させて、被膜表面に出できた金属イオ
ンを捕獲させ、金属イオンが表面で錆にならないように
した。すなわち、本発明は、有機樹脂被覆鋼板の表面に
カルボキシル基、スルフォン基、−ｃｏ、ｃｏ−結合の
うちの少な（とも１種と、エチレン性不飽和二重結合と
を有するモノマーを塗布した後、電子線を照射してグラ
フト重合させることにより耐食性を向上させた。(Means for Solving the Problems) The present invention graft-polymerizes a monomer having ion exchange ability onto the surface of a thin resin coating to capture the metal ions released on the coating surface, and the metal ions rust on the surface. I tried to prevent it from happening. That is, the present invention provides a method for applying a monomer having at least one of carboxyl groups, sulfone groups, -co, and co- bonds and an ethylenically unsaturated double bond to the surface of an organic resin-coated steel sheet. , the corrosion resistance was improved by graft polymerization by irradiation with electron beams.
上記モアマーはエチレン性不飽和二重結合を有している
ので、有機樹脂被覆鋼板に塗布して電子線を照射すると
、モノマーは、樹ｍ被膜にグラフト重合する。しかして
、このグラフＦ鎖は、イオン交換能を有するカルボキシ
ル基、スルフォン基または−ｃｏｚｃｏ−結合の少なく
とも１種を有するので、めっ！層やａ素地より溶出して
きた金属イオンが被膜表面に達したと務、金属イオンを
次のように捕獲し、被膜表面での錆や腐食生成物の生成
を抑制する。Since the above moamer has ethylenically unsaturated double bonds, when it is applied to an organic resin-coated steel sheet and irradiated with an electron beam, the monomer graft-polymerizes to the resin coating. Therefore, this graph F chain has at least one of a carboxyl group, a sulfone group, or a -cozco- bond that has ion exchange ability, so! When the metal ions eluted from the layer or substrate reach the coating surface, the metal ions are captured in the following manner to suppress the formation of rust and corrosion products on the coating surface.
−Ｃ０ＯＨ，−ＳＯ，Ｈ＋ Ｈ，＋→−ＣＯＯＨ＋ １
ＳＯＪ＋ ＋ ８”−ＣＯ□ＣＯ−＋２８＋＋→２（−
ＣＯ，Ｎ、）＋２）Ｊ＋（ただし、Ｈ９、Ｍ２は金属）
鋼板表面に塗布するモノマーとして、カルボキシル基を
有するものを使用する場合は、アクリル酸、メタクリル
酸、マレイン酸などを、また、スルフォン基を有するも
のを使用する場合は、スチレンスルフォン酸などを使用
すればよい。-C0OH, -SO, H+ H, +→-COOH+ 1
SOJ+ + 8”-CO□CO-+28++→2(-
CO, N, ) + 2) J + (However, H9 and M2 are metal) When using a monomer with a carboxyl group to coat the steel sheet surface, acrylic acid, methacrylic acid, maleic acid, etc. When using one having a group, styrene sulfonic acid or the like may be used.
さらに、−ＣＯ□Ｃ〇−結合を有するモノマーを使用す
る場合には無水マレイン酸などを使用すればよい。Furthermore, when using a monomer having a -CO□C〇- bond, maleic anhydride or the like may be used.
上記モノマーは、混合使用してもよく、また、モール塩
などの重合禁止剤を添加したものでもよい。The above monomers may be used as a mixture, or may be added with a polymerization inhibitor such as Mohr's salt.
モノマーの塗布は、通常、スプレー、カーテン７０−、
ロールコート、モノマー中への浸漬ナト公知方法で行う
が、塗布後の電子線照射は、鋼板の樹脂被膜劣化を防止
するため、０．５〜２０Ｈｒａｄの純量にするのが好ま
しい、電子線を照射しても樹脂被膜に重合しないモノマ
ーやホモポリマーが残存するが、これらは水洗などで除
去する。The monomer is usually applied by spraying, curtain 70-,
Roll coating and immersion in monomer are known methods. However, electron beam irradiation after coating is preferably carried out in a pure amount of 0.5 to 20 Hrad in order to prevent deterioration of the resin coating on the steel plate. Monomers and homopolymers that do not polymerize remain in the resin film even after irradiation, but these are removed by washing with water.
本発明による錆や腐食生成物の生成抑制能力は、モノマ
ーのグラフト重合量と共に増大するので、抑制要求程度
に応じてグラフＦ量を調整すればよい、この調整は、鋼
板やモノマーの温度をｇ４９する方法によれば容易に実
施できる６例えば、鋼板温度を被膜樹脂の軟化点以上に
してグラフト重合させると、表層のみならず、内部にま
でグラフト重合させることができる。The ability to suppress the formation of rust and corrosion products according to the present invention increases with the amount of graft polymerization of the monomer, so the amount of graph F can be adjusted according to the degree of suppression required. For example, if the temperature of the steel sheet is raised to a temperature higher than the softening point of the coating resin and graft polymerization is carried out, it is possible to carry out graft polymerization not only in the surface layer but also in the interior.
本発明による耐食性向上は、原板がめつき鋼板以外の場
合にも適用でき、また、鋼板の樹脂被膜がポリ塩化ビニ
ル、ポリオレフィン、ポリエチレンテレ７グレートなど
のような熱可塑性樹脂、ポリエステル、ウレタン、エポ
キシ、７ツ素、７クリルなどの熱硬化性樹脂あるいは放
射線硬化性樹脂などであっても適用可能である。The improvement in corrosion resistance according to the present invention can be applied to cases other than plated steel sheets, and the resin coating of the steel sheet may be made of thermoplastic resin such as polyvinyl chloride, polyolefin, polyethylene Tele 7 grade, polyester, urethane, epoxy, etc. It is also possible to use thermosetting resins such as heptadone and heptacrylic, or radiation curing resins.
（実施例）
実施例１
板厚０．６１の溶融亜鉛めっき鋼板にアクリル変性エポ
キシ系プライマーを乾燥塗膜厚で５μ−になるように塗
装して焼付は乾燥した後、塩化ビニルゾル塗料を２００
μ−ｍ装して溶融造膜し、その表面にバーコーター＃１
０で表１に示すモノマーを塗布した。そして、塗布復電
子線を１０Ｍｒａｄ照 ゛射し、残存モノマーをエ
タノールまたは水で洗浄除去後乾燥した。(Example) Example 1 An acrylic-modified epoxy primer was applied to a hot-dip galvanized steel sheet with a thickness of 0.61 to a dry film thickness of 5μ, and after drying, a vinyl chloride sol paint was applied at a rate of 200 μm.
Melt film is formed using μ-m, and bar coater #1 is applied to the surface.
The monomers shown in Table 1 were applied at 0.0. Then, the coating was irradiated with a 10 Mrad electron beam, and the remaining monomer was removed by washing with ethanol or water, followed by drying.
次に、この鋼板にカッターナイフで鋼素地に達するりａ
Ｘカットを入れ、＃ｉＩＢを一部残してシールした後、
湿潤試験（相対湿度９８％、温度４９℃）、塩水噴霧試
験（相対湿度９８％、温度３５℃、５％ＮａＣｌ水溶液
噴霧）を施し、白錆や被膜膨れの発生状態を観察した０
表１にこの結果を示す。Next, use a utility knife to reach the steel base on this steel plate.
After making an X cut and sealing with some #iIB left,
A humidity test (98% relative humidity, temperature 49°C) and a salt spray test (98% relative humidity, temperature 35°C, 5% NaCl aqueous solution spray) were conducted, and the occurrence of white rust and coating blistering was observed.
Table 1 shows the results.
実施例２
板厚０．３５ｍｍの溶融亜鉛めっき鋼板にエポキシ系ま
たはポリエステル系のプライマーを乾燥塗膜厚で５μ論
になるように塗装して焼付は乾燥した後、ポリエステル
系上塗り塗料を乾燥塗膜厚で１２μ論になるように塗装
して焼付は乾燥した。Example 2 An epoxy or polyester primer was applied to a hot-dip galvanized steel plate with a thickness of 0.35 mm to a dry film thickness of 5 μm. After drying, a polyester top coat was applied to the dry film. I painted it to a thickness of 12 microns and let it dry.
次に、この鋼板の温度を８０℃に調整して、上塗り塗膜
の表面に表２に示すモノマーをパーコーター＃１０で塗
布し、その上にさらに２５μ醜厚のポリエステルフィル
ムを気泡が入らないようにラミネートした。この状態で
電子線を５８ｒａｄ照射し、モノマーをグラフト重合さ
せ、重合後フィルムをはがして、残存モノマーをエタノ
ールまたは水で洗浄除去後乾燥した。この鋼板に対する
実施例１と同様の試験結果を表２に示す。Next, the temperature of this steel plate was adjusted to 80°C, and the monomers shown in Table 2 were applied to the surface of the top coat using Percoater #10, and then a 25μ thick polyester film was further applied to prevent air bubbles from entering. Laminated on. In this state, 58 rad of electron beam was irradiated to graft-polymerize the monomers. After the polymerization, the film was peeled off, and the remaining monomers were removed by washing with ethanol or water, and then dried. Table 2 shows the test results for this steel plate similar to those in Example 1.
（発明の効果）
以上のように、本発明は、鋼板を被覆しているり（脂の
表面にイオン交換能を有するモノマーをグラフト重合さ
せて、溶出金属イオンを捕獲することにより外観が損な
われるのを抑制するのであるから、めっき層や塗膜の加
工性を低下させない。(Effects of the Invention) As described above, the present invention can prevent the appearance from being damaged by coating a steel plate (graft polymerizing a monomer having ion exchange ability on the surface of a fat and capturing eluted metal ions). Therefore, it does not reduce the workability of the plating layer or coating film.
Claims (1)
基、−ＣＯ＿２ＣＯ−結合のうちの少なくとも１種と、
エチレン性不飽和二重結合とを有するモノマーを塗布し
た後、電子線を照射してグラフト重合させることを特徴
とする耐食性に優れた樹脂被覆鋼板の製造方法。At least one of a carboxyl group, a sulfone group, and a -CO_2CO- bond on the surface of the organic resin-coated steel sheet,
A method for producing a resin-coated steel sheet with excellent corrosion resistance, which comprises applying a monomer having an ethylenically unsaturated double bond and then irradiating it with an electron beam to cause graft polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62294665A JP2540055B2 (en) | 1987-11-21 | 1987-11-21 | Method for producing resin-coated steel sheet with excellent corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62294665A JP2540055B2 (en) | 1987-11-21 | 1987-11-21 | Method for producing resin-coated steel sheet with excellent corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01135568A true JPH01135568A (en) | 1989-05-29 |
| JP2540055B2 JP2540055B2 (en) | 1996-10-02 |
Family
ID=17810717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62294665A Expired - Lifetime JP2540055B2 (en) | 1987-11-21 | 1987-11-21 | Method for producing resin-coated steel sheet with excellent corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2540055B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6411137A (en) * | 1987-07-04 | 1989-01-13 | Nisshin Steel Co Ltd | Surface modification of steel plate coated with polyvinyl chloride sol |
-
1987
- 1987-11-21 JP JP62294665A patent/JP2540055B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6411137A (en) * | 1987-07-04 | 1989-01-13 | Nisshin Steel Co Ltd | Surface modification of steel plate coated with polyvinyl chloride sol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2540055B2 (en) | 1996-10-02 |
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