JP2002235179A - Pretreatment solution for coating for coated steel sheet and treated steel sheet - Google Patents
Pretreatment solution for coating for coated steel sheet and treated steel sheetInfo
- Publication number
- JP2002235179A JP2002235179A JP2001028474A JP2001028474A JP2002235179A JP 2002235179 A JP2002235179 A JP 2002235179A JP 2001028474 A JP2001028474 A JP 2001028474A JP 2001028474 A JP2001028474 A JP 2001028474A JP 2002235179 A JP2002235179 A JP 2002235179A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- coating
- mass
- coated steel
- polyvinyl alcohol
- 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.)
- Withdrawn
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 238000000576 coating method Methods 0.000 title claims abstract description 51
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 30
- 239000010959 steel Substances 0.000 title claims abstract description 30
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 21
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 21
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 21
- 229940033123 tannic acid Drugs 0.000 claims abstract description 21
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 21
- 229920002258 tannic acid Polymers 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 21
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- JZDMNWBZPLJKBT-UHFFFAOYSA-N F.[Zr] Chemical compound F.[Zr] JZDMNWBZPLJKBT-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 34
- 238000005260 corrosion Methods 0.000 abstract description 34
- 239000011651 chromium Substances 0.000 abstract description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052804 chromium Inorganic materials 0.000 abstract description 14
- LGBZAKBGIHHRLI-UHFFFAOYSA-N zirconium hydrofluoride Chemical compound [Zr].F.[Zr] LGBZAKBGIHHRLI-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000002411 adverse Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 238000007747 plating Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002987 primer (paints) Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- -1 furthermore Chemical compound 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、塗膜密着性および耐食
性に優れた塗装鋼板を得るための塗装前処理液および前
処理鋼板に関する。より詳しくは、クロムを含むことな
く、クロム含有前処理液と同等の性能を有する塗装前処
理液に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating pretreatment liquid and a pretreated steel sheet for obtaining a coated steel sheet having excellent coating film adhesion and corrosion resistance. More specifically, the present invention relates to a coating pretreatment liquid having the same performance as a chromium-containing pretreatment liquid without containing chromium.
【0002】[0002]
【従来の技術】従来、塗装鋼板は、亜鉛系、または亜鉛
−アルミニウム系のめっき鋼板に、塗布型クロメート処
理あるいはクロムを含む処理液中に浸漬、乾燥する等の
塗装前処理を施し、その上に下地と密着性に優れた下塗
り塗膜を設け、さらに着色顔料等を添加した、外観や耐
候性に優れた上塗り塗膜を設けた塗装鋼板が主流であっ
た。しかし、近年、クロムの有害性が指摘されはじめ、
家電製品や内装機器等を中心に、クロムを含まない塗装
鋼板の要求が高まっている。2. Description of the Related Art Conventionally, a coated steel sheet is subjected to a coating pretreatment such as coating type chromate treatment or immersion in a treatment solution containing chromium and drying, etc., on a zinc-based or zinc-aluminum-based plated steel sheet. The mainstream was a coated steel sheet provided with an undercoating film having excellent adhesion to a base, and further provided with a topcoating film having excellent appearance and weather resistance by further adding a coloring pigment and the like. However, in recent years, the harmfulness of chromium has begun to be pointed out,
There is a growing demand for chromium-free coated steel sheets, mainly for home appliances and interior equipment.
【0003】[0003]
【発明が解決しようとする課題】従来、塗装前処理とし
ては、クロムとして可溶性の高い6価クロム、難溶性の
3価クロム、さらにはシリカ、有機物から処方された処
理液が主に使用されてきた。そして、今のところクロム
を含まずにかつクロム系と同等の充分な性能を有する塗
装前処理液として使用できるものはなかった。非クロム
系の前処理液が使用できなかった理由として、充分な密
着性が得られないこと、また塗装後の耐食性においても
端面部で塗膜のフクレ進行が早いことが挙げられてい
る。本発明は、このような問題を解消すべく案出された
ものであり、クロムと同等の強いインヒビター的作用を
有する元素を探索し、優れた塗膜密着性と耐食性を有す
る塗装鋼板を得るための非クロム系前処理液を提供する
ことを目的とする。Heretofore, as a pretreatment for coating, a treatment liquid formulated from hexavalent chromium, which is highly soluble as chromium, hardly soluble trivalent chromium, furthermore, silica and organic substances has been mainly used. Was. At the present time, there has been no liquid that does not contain chromium and has sufficient performance equivalent to that of a chromium-based material and can be used as a coating pretreatment liquid. The reason that a non-chromium-based pretreatment liquid could not be used is that sufficient adhesion cannot be obtained, and that the swelling of the coating film at the end face is fast in the corrosion resistance after coating. The present invention has been devised to solve such a problem, to search for an element having a strong inhibitory action equivalent to chromium, and to obtain a coated steel sheet having excellent coating film adhesion and corrosion resistance. And a non-chromium pretreatment liquid.
【0004】[0004]
【課題を解決するための手段】本発明の塗装鋼板用塗装
前処理液およびその液で処理した塗装用鋼板は、その目
的を達成するため、その処理液として、ポリビニールア
ルコール、タンニン酸、チタンフッ化水素酸、ジルコニ
ウムフッ化水素酸、シリカからなり、ポリビニールアル
コール100質量部に対して2〜15質量部のタンニン
酸を含み、さらに乾燥質量換算でポリビニールアルコー
ルとタンニン酸の合計量に対して1.6〜1.8倍の無
機物を含むように調整したものである。The coating pretreatment liquid of the present invention and the steel sheet for coating treated with the liquid according to the present invention include polyvinyl alcohol, tannic acid, titanium fluoride and the like as the processing liquid in order to achieve the object. It consists of hydrofluoric acid, zirconium hydrofluoric acid, and silica, and contains 2 to 15 parts by mass of tannic acid with respect to 100 parts by mass of polyvinyl alcohol, and further contains a total amount of polyvinyl alcohol and tannic acid in terms of dry mass. It was adjusted to contain 1.6 to 1.8 times the amount of inorganic material.
【0005】無機物の内、金属元素の割合が全金属元素
の中でチタンが70質量%以上、ジルコニウムが20質
量%以下、シリコンが3〜20質量%からなるように調
整すると、耐食性がさらに優れたものとなる。またこの
ような塗装鋼板用塗装前処理液を、乾燥後の処理皮膜と
して80〜300mg/m2を塗布すると、その後塗装
する塗膜として密着性の優れたものが得られる。[0005] When the proportion of the metal element among the inorganic substances is adjusted to be 70% by mass or more of titanium, 20% by mass or less of zirconium, and 3 to 20% by mass of silicon, the corrosion resistance is further improved. It will be. Further, when such a coating pretreatment liquid for a coated steel sheet is applied as a treatment film after drying at 80 to 300 mg / m 2 , a coating film to be applied thereafter has excellent adhesion.
【0006】[0006]
【作用】塗装鋼板に使用される原板としては、一般的に
は亜鉛系めっき鋼板、あるいは亜鉛−アルミニウム系め
っき鋼板である。アルミニウムの含有量がごく少量であ
っても、これらのめっき鋼板の表層は、アルミニウム系
酸化物で薄く覆われている。良好な塗膜密着性を得るた
めには、この最外表層皮膜を除去し、ついでクロメート
皮膜を設けることが一般的であった。The original sheet used for the coated steel sheet is generally a zinc-based plated steel sheet or a zinc-aluminum-based plated steel sheet. Even if the content of aluminum is very small, the surface layers of these plated steel sheets are thinly covered with an aluminum-based oxide. In order to obtain good coating adhesion, it was common to remove the outermost surface coating and then provide a chromate coating.
【0007】水和酸化クロム主体のクロメート皮膜は下
塗り塗膜中に含有されるOH基と同じ基を含有してお
り、塗膜焼き付け時に脱水反応を生じ、下塗りと強固に
密着する。また同時にクロメート皮膜中に含有されてい
るシリカの最外表層も一般的にはOH基を持っていると
され、これも密着性に有効に作用している。さらにシリ
カは硬い性質を有しているため、塗膜の耐傷付き性にも
プラスに作用する。このOH基に着目し、耐食性に寄与
できそうな元素を検討したところ、金属元素として、チ
タン、ジルコニウムのOH基を有するものとシリコンを
一定の割合で存在させれば、クロムに代わり得ることが
明らかになった。また、有機物としてポリビニールアル
コールとタンニン酸が一定の割合で含有される時、各種
の性能が満足されることを見出したものである。The chromate film mainly composed of hydrated chromium oxide contains the same group as the OH group contained in the undercoat film, and causes a dehydration reaction at the time of baking the film, and firmly adheres to the undercoat film. At the same time, the outermost surface layer of silica contained in the chromate film is generally considered to have an OH group, and this also effectively acts on the adhesion. Further, since silica has a hard property, it has a positive effect on the scratch resistance of the coating film. Focusing on this OH group and examining elements that are likely to contribute to corrosion resistance, titanium and zirconium having an OH group and silicon as metal elements can be substituted for chromium if a certain ratio is present. It was revealed. Further, they have found that various performances are satisfied when polyvinyl alcohol and tannic acid are contained as organic substances at a certain ratio.
【0008】チタン、ジルコニウムのOH基を有するも
のとして、チタンあるいはジルコニウムのフッ化水素酸
を使用する。チタンフッ化水素酸はpHが低く、めっき
鋼板表面で亜鉛と反応し、薄膜状の含チタン亜鉛フッ化
物を鋼板表面に形成して耐食性の向上に寄与する。また
反応生成物の一部は若干の溶解成分を残存したまま乾燥
され、塗膜樹脂中にトラップされて、水分が侵入してき
た時に腐食抑制因子として作用するものと考えられる。
ジルコニウムもチタンと同様に作用すると考えられる。
チタンとジルコニウムの割合については、チタンの方
が、耐食性に寄与する効果が大きいため、チタンの量を
70%以上としないと、密着性とのバランスをとること
が困難となる。[0008] Titanium or zirconium hydrofluoric acid having titanium or zirconium OH groups is used. Titanium hydrofluoric acid has a low pH and reacts with zinc on the surface of a plated steel sheet to form a thin film of titanium-containing zinc fluoride on the surface of the steel sheet, thereby contributing to improvement of corrosion resistance. It is also considered that a part of the reaction product is dried with some dissolved components remaining, trapped in the coating resin, and acts as a corrosion inhibitor when moisture invades.
It is thought that zirconium acts similarly to titanium.
Regarding the ratio of titanium and zirconium, titanium has a greater effect of contributing to corrosion resistance. Therefore, unless the amount of titanium is set to 70% or more, it becomes difficult to balance the adhesion with titanium.
【0009】シリコンは塗膜下で硬い皮膜を形成するこ
とで塗膜密着性に寄与し、また腐食促進因子のトラップ
に有効であると考えられ、ある程度の量は必要である
が、この量が多すぎると樹脂の柔軟性が損なわれ、逆に
塗膜密着性に悪影響がでるものと考えられる。このた
め、量的には全金属元素中の3質量%以上20質量%以
下にするべきである。なお、添加するシリコンの形態に
ついては、とくに限定されるものではなく、シリカゾル
でも気相シリカでも同等の効果が得られる。Silicon is considered to contribute to the adhesion of the coating film by forming a hard film under the coating film, and is also effective for trapping corrosion promoting factors. If the amount is too large, it is considered that the flexibility of the resin is impaired, and conversely, the adhesion of the coating film is adversely affected. For this reason, the amount should be 3% by mass or more and 20% by mass or less of all the metal elements. The form of silicon to be added is not particularly limited, and the same effect can be obtained by using silica sol or gas-phase silica.
【0010】クロメート皮膜の場合には、クロムの腐食
抑制作用が強く、また樹脂が含有されていなくてもプラ
イマーとの密着性は満足されていたが、クロムを含まな
い処理膜の場合、樹脂等有機物の役割は重要で、この含
有量によって密着性や耐食性が大きく影響されることが
わかった。前処理皮膜中の樹脂は、耐食性に寄与する成
分を包み込み、その成分の溶出を抑制、適正化し、長期
にわたって耐食性を維持させる機能を有している。ポリ
ビニールアルコールはOH基を有しており、これがプラ
イマーとの密着性の向上に大きく寄与している。しか
し、ポリビニールアルコール自身の耐食性への寄与は、
膜厚にもよるが、水分や腐食促進因子に対してバリアー
的作用を有することによると推察される。In the case of a chromate film, the effect of inhibiting the corrosion of chromium was strong, and the adhesion to the primer was satisfied even if no resin was contained. It was found that the role of the organic matter is important, and that the content greatly affects the adhesion and corrosion resistance. The resin in the pretreatment film has a function of wrapping a component that contributes to corrosion resistance, suppressing and optimizing the elution of the component, and maintaining the corrosion resistance for a long period of time. Polyvinyl alcohol has an OH group, which greatly contributes to improving the adhesion to the primer. However, the contribution of polyvinyl alcohol itself to corrosion resistance is
Although it depends on the film thickness, it is presumed to have a barrier action against moisture and corrosion promoting factors.
【0011】耐食性を向上させるためにタンニン酸を添
加する。有機物であるタンニン酸は亜鉛系めっき鋼板表
面の亜鉛と反応し、亜鉛と結合した錯体のような化合物
膜を鋼板表面に均一に形成する。無機物がめっき成分と
反応する場合、電位的に卑な部分と最初に反応するため
に、反応部位が不均一になり易く、したがって反応生成
がめっき面全面に均一に覆うものではない。しかしなが
ら、上記タンニン酸とめっき成分との反応は、電気化学
的な反応とは異なり、全面的に反応するので、反応生成
物はめっき面全面的に均一に形成され、耐食性に有効に
作用する。To improve the corrosion resistance, tannic acid is added. Tannic acid, which is an organic substance, reacts with zinc on the surface of a galvanized steel sheet to form a uniform compound film such as a complex bonded with zinc on the steel sheet surface. When the inorganic substance reacts with the plating component, the reaction site tends to be non-uniform because it reacts first with a potential-negative part, so that the reaction product does not uniformly cover the entire plating surface. However, the reaction between the tannic acid and the plating component is totally different from the electrochemical reaction, so that the reaction product is uniformly formed on the entire plating surface, and effectively acts on the corrosion resistance.
【0012】塗膜密着性と耐食性をバランスさせて具備
させるためには、上記ポリビニールアルコールとタンニ
ン酸の配合比率を、ポリビニールアルコール100質量
部に対してタンニン酸を2〜15質量部の範囲で調整す
る必要がある。タンニン酸の量については、この量より
も多すぎても、少なすぎても、塗膜密着性に悪影響がで
る。In order to provide a good balance between coating film adhesion and corrosion resistance, the mixing ratio of the above-mentioned polyvinyl alcohol and tannic acid should be in the range of 2 to 15 parts by mass of tannic acid with respect to 100 parts by mass of polyvinyl alcohol. Need to be adjusted. If the amount of tannic acid is too large or too small, the adhesion of the coating film will be adversely affected.
【0013】全体としては、耐食性は無機系の元素の担
うところが大きいが、無機系の添加材には塗膜密着性に
寄与するところがない。場合によっては、無機物には柔
軟性がなく、また酸化作用に乏しい等のため、密着性を
阻害する要因ともなる。長期の耐食性が要求される場合
には無機物の割合を増やしたいが、この場合有機物の割
合が小さくなり、この状態で厚く塗布することによっ
て、耐食性の要求を満たすと、無機物の層が形成される
ことによって密着性に悪影響がでる。逆に有機物を多く
してこの弊害を取り除こうとすると、耐食性に寄与する
無機物を有機物が取り囲むこととなり、その徐放性が損
なわれ耐食性が劣ることになる。したがって、耐食性と
密着性のバランスをとるために無機物と有機物の割合を
適正な範囲に調整する必要がある。具体的には、乾燥重
量換算で重量として、無機物/有機物比は1.6〜1.
8に調整する必要がある。この範囲を外れると耐食性と
密着性のバランスが悪くなる。As a whole, the corrosion resistance largely depends on the inorganic elements, but the inorganic additives do not contribute to the coating film adhesion. In some cases, the inorganic substance is inflexible and has a poor oxidizing effect, and thus may be a factor inhibiting adhesion. When long-term corrosion resistance is required, it is desired to increase the proportion of the inorganic substance, but in this case, the proportion of the organic substance becomes small, and by applying thickly in this state, if the requirement of the corrosion resistance is satisfied, a layer of the inorganic substance is formed. This adversely affects the adhesion. On the other hand, if an attempt is made to remove this adverse effect by increasing the amount of organic substances, the organic substances will surround the inorganic substances that contribute to corrosion resistance, and the sustained release property will be impaired, resulting in poor corrosion resistance. Therefore, it is necessary to adjust the ratio of the inorganic substance and the organic substance to an appropriate range in order to balance the corrosion resistance and the adhesion. Specifically, the inorganic / organic ratio is 1.6 to 1.
It needs to be adjusted to 8. Outside of this range, the balance between corrosion resistance and adhesion is poor.
【0014】処理液濃度については、極端に薄い液を厚
く付けることは困難を伴うことから10g/l以上、ま
た、濃厚な液を極度に薄く付けることも困難であること
から実用上100g/l以下が好ましい。極端に濃度の
薄い液や濃度の高い液は取り扱い難く、現在実用されて
いる塗布装置では制御できない、あるいは乾燥に多大な
熱量が必要になる等、好ましくない。本処理液の場合に
は有機物の濃度が高いと液の粘性が上昇することから有
機物濃度としては50g/lが上限である。また、処理
被覆量については、80mg/m2より低すぎると、被
覆面積が充分でないため耐食性が劣っていた。また、3
00mg/m2を超えると膜の物性に悪影響が表れるた
めか、塗膜密着性が低下してしまう。このため、乾燥後
の処理皮膜量として80〜300mg/m2を塗布する
ことが好ましい。The concentration of the processing solution is 10 g / l or more because it is difficult to make an extremely thin solution thick, and it is practically 100 g / l because it is difficult to make a thick solution extremely thin. The following is preferred. Liquids with extremely low or high concentrations are difficult to handle, and cannot be controlled by a coating apparatus currently in practical use, or require a large amount of heat for drying. In the case of this treatment liquid, if the concentration of the organic substance is high, the viscosity of the liquid increases, so the upper limit of the organic substance concentration is 50 g / l. On the other hand, if the treatment coating amount was lower than 80 mg / m 2 , the coating area was not sufficient and the corrosion resistance was poor. Also, 3
If it exceeds 00 mg / m 2 , the adhesiveness of the coating film may be reduced, possibly due to an adverse effect on the physical properties of the film. For this reason, it is preferable to apply 80 to 300 mg / m 2 as the amount of the treated film after drying.
【0015】本発明の処理液で処理する前に、クロメー
ト処理等で通常行われているニッケルやコバルト析出型
の表面調整処理については、実施することが好ましい
が、表面状態によっては割愛することも可能である。Before the treatment with the treatment liquid of the present invention, it is preferable to carry out a surface conditioning treatment of a nickel or cobalt precipitation type which is usually carried out by a chromate treatment or the like, but may be omitted depending on the surface condition. It is possible.
【0016】[0016]
【実施例】以下に、本発明を実施例、比較例を示して詳
述する。4%Al−Znめっき鋼板(板厚:0.5m
m、片面めっき付着量135g/m2に、表面調整処理
を施して、湯洗、水洗により洗浄し、乾燥した。しかる
後、表1に示す処理液をロールコーターで塗布し、水洗
することなく100℃で乾燥させ、全乾燥皮膜量が80
〜300mg/m2の皮膜を形成した。EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. 4% Al-Zn plated steel sheet (sheet thickness: 0.5m
m, a surface conditioning treatment was applied to a coating weight of 135 g / m 2 on one side, and the resultant was washed with hot water and water, and dried. Thereafter, the treatment liquid shown in Table 1 was applied by a roll coater and dried at 100 ° C. without washing with water.
A film of 300300 mg / m 2 was formed.
【0017】次いで、この皮膜の上に、カルシウム変性
シリカを樹脂の不揮発分に対して20重量%添加した乾
燥膜厚5μmのエポキシ樹脂系プライマー塗膜を215
℃で焼き付け、さらに、上塗り塗膜を着色顔料、体質顔
料等を樹脂の不揮発分に対して20重量%添加したポリ
エステル樹脂系塗料を15μm、215℃で焼き付け形
成した。Next, an epoxy resin-based primer coating film containing calcium-modified silica at 20% by weight with respect to the non-volatile content of the resin and having a dry film thickness of 5 μm was formed on the coating film.
C., and a top coating film was formed by baking at 15 ° C. and 215 ° C. a polyester resin-based coating in which a coloring pigment, an extender pigment and the like were added at 20% by weight based on the nonvolatile content of the resin.
【0018】比較のために、有機物量の低い処理液、あ
るいは高すぎる処理液、また、有機物量は適当であって
も含有される金属元素量の比率が適正でない溶液による
処理を行い、同様な塗装鋼板を作製した。これらの組成
を表2に示す。なお、表2中にあって、チタンフッ化水
素酸中のチタン分は29.26%であり、ジルコニウム
フッ化水素酸中のジルコニウム分は43.96%、シリ
カ中のシリコン分は46.66%であり、これによって
処理液中の金属元素の中のチタン、ジルコニウムおよび
シリコンの各含有%を求めている。For the purpose of comparison, a treatment liquid having a low organic substance content or a processing liquid having an excessively high organic substance content, or a solution having an appropriate organic substance content but an inappropriate ratio of the contained metal element was carried out. A coated steel plate was manufactured. Table 2 shows their compositions. In Table 2, the titanium content in titanium hydrofluoric acid is 29.26%, the zirconium content in zirconium hydrofluoric acid is 43.96%, and the silicon content in silica is 46.66%. Thus, the content percentages of titanium, zirconium, and silicon in the metal elements in the processing solution are determined.
【0019】 [0019]
【0020】 [0020]
【0021】このようにして得られた塗装鋼板に対して
下記の試験を行った。 (1) 塗膜密着性試験 1次塗膜密着性は塗装された鋼板を2t折り曲げし、そ
の曲げ部の塗膜の剥離面積が5%以下のものを◎、6〜
10%のものを○、11〜30%のものを△、30%を
超えるものを×で評価した。2次塗膜密着性は塗装され
た鋼板を2時間沸騰水に浸漬し、その後、20℃、相対
湿度60%の状態に24時間静置した後、1次塗膜密着
性と同様な試験および評価を行った。The following test was conducted on the coated steel sheet obtained in this manner. (1) Coating film adhesion test The primary coating film adhesion was evaluated by bending the coated steel plate by 2 tons and peeling the coating film at the bent portion to 5% or less.
10% was evaluated as ○, 11 to 30% was evaluated as Δ, and more than 30% was evaluated as ×. The secondary coating adhesion was determined by immersing the coated steel plate in boiling water for 2 hours, then leaving it to stand at 20 ° C. and a relative humidity of 60% for 24 hours. An evaluation was performed.
【0022】(2) 促進耐食性試験 SST35℃×500時間で促進耐食性試験を行い、下
バリ切断面の塗膜フクレ巾とクロスカット部の塗膜フク
レ巾(いずれも最大フクレ巾)を測定した。切断面に対
して塗膜フクレ巾が、2mm以下のものを◎、2.1〜
3mmのものを○、3.1〜5mmのものを△、5mm
を超えるものを×で評価した。クロスカット部に対して
塗膜フクレ巾が、0mmのものを◎、0.1〜2mmの
ものを○、2.1〜3mmのものを△、3mmを超える
ものを×で評価した。(2) Accelerated Corrosion Resistance Test An accelerated corrosion resistance test was performed at SST 35 ° C. × 500 hours, and the width of the blister on the cut surface of the lower burr and the width of the blister on the cross-cut portion were measured. When the coating blister width is 2 mm or less with respect to the cut surface,
○ for 3 mm, Δ for 3.1 to 5 mm, 5 mm
Those exceeding were evaluated with ×. With respect to the cross-cut portion, the evaluation was ク レ for the coating blister width of 0 mm, ○ for 0.1 to 2 mm, Δ for 2.1 to 3 mm, and x for those exceeding 3 mm.
【0023】本発明の要件を満たす実施例No.1〜1
5は塗膜密着性、耐食性ともに優れたものが得られてい
る。これに対して、比較例のNo.1は、ポリビニール
アルコールに対してタンニン酸の割合が規定する範囲よ
りも多く、また無機物/有機物比も規定値よりも大きい
ために、塗膜密着性、耐食性ともに全く不十分であっ
た。比較例No.2、3は、ポリビニールアルコールに
対してタンニン酸の割合が規定する範囲よりも多いた
め、塗膜密着性、耐食性ともに不十分であった。また、
比較例No.4、5、6はタンニン酸の配合量は適当で
あるが、無機物/有機物比が規定値を外れているため
に、塗膜密着性と耐食性のバランスが悪くなっている。
さらに、比較例No.7、8、9はタンニン酸の量が少
ないために、塗膜密着性が悪くなっている。The embodiment No. 1 satisfying the requirements of the present invention. 1 to 1
Sample No. 5 is excellent in both coating film adhesion and corrosion resistance. On the other hand, in Comparative Example No. In No. 1, since the ratio of tannic acid to polyvinyl alcohol was larger than the specified range, and the inorganic / organic ratio was larger than the specified values, both the coating film adhesion and the corrosion resistance were completely insufficient. Comparative Example No. In Nos. 2 and 3, since the ratio of tannic acid to polyvinyl alcohol was larger than the specified range, both the coating film adhesion and the corrosion resistance were insufficient. Also,
Comparative Example No. Nos. 4, 5, and 6 have appropriate amounts of tannic acid, but the inorganic / organic ratio is out of the specified value, so that the balance between coating film adhesion and corrosion resistance is poor.
Further, in Comparative Example No. In 7, 8, and 9, the adhesion of the coating film was poor because the amount of tannic acid was small.
【0024】 [0024]
【0025】[0025]
【発明の効果】以上に説明したように、塗装鋼板用塗層
前処理液としてポリビニールアルコール、タンニン酸、
チタンフッ化水素酸、ジルコニウムフッ化水素酸および
シリカを、それぞれの量を調整して組み合わせたものを
使用すれば、Crを含有した前処理液を使用しなくても
塗膜密着性、耐食性に優れた塗装鋼板を得ることができ
る。As described above, polyvinyl alcohol, tannic acid,
If titanium hydrofluoric acid, zirconium hydrofluoric acid and silica are used with their respective amounts adjusted and combined, excellent coating film adhesion and corrosion resistance can be obtained without using a pretreatment liquid containing Cr. A coated steel sheet can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松原 和美 千葉県市川市高谷新町7番1号 日新製鋼 株式会社技術研究所内 Fターム(参考) 4D075 BB76X CA13 CA33 DB05 DB07 EC01 EC54 4F100 AA00B AA02B AA05B AA20 AB03 AB03A AB10 AB18 AH02B AK21B BA02 BA03 BA04 EH46 EH46B EH71 EJ64B EJ65 GB08 GB48 JB02 JK06 YY00B 4K026 AA02 AA07 AA11 AA22 BA08 BB08 BB10 CA28 CA37 CA39 DA02 EA09 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazumi Matsubara 7-1 Takaya Shinmachi, Ichikawa City, Chiba Prefecture Nisshin Steel R & D Co., Ltd. F-term (reference) 4D075 BB76X CA13 CA33 DB05 DB07 EC01 EC54 4F100 AA00B AA02B AA05B AA20 AB03 AB03A AB10 AB18 AH02B AK21B BA02 BA03 BA04 EH46 EH46B EH71 EJ64B EJ65 GB08 GB48 JB02 JK06 YY00B 4K026 AA02 AA07 AA11 AA22 BA08 BB08 BB10 CA28 CA37 CA39 DA02 EA09
Claims (3)
チタンフッ化水素酸、ジルコニウムフッ化水素酸、シリ
カからなり、ポリビニールアルコール100質量部に対
して2〜15質量部のタンニン酸を含み、さらに乾燥質
量換算でポリビニールアルコールとタンニン酸の合計量
に対して1.6〜1.8倍の無機物を含むように調整し
たことを特徴とする塗装鋼板用塗装前処理液。1. Polyvinyl alcohol, tannic acid,
It is composed of titanium hydrofluoric acid, zirconium hydrofluoric acid, and silica, and contains 2 to 15 parts by mass of tannic acid with respect to 100 parts by mass of polyvinyl alcohol, and further contains a total amount of polyvinyl alcohol and tannic acid in terms of dry mass. A coating pretreatment liquid for a coated steel sheet, which is adjusted to contain 1.6 to 1.8 times the amount of an inorganic substance.
素の中でチタンが70質量%以上、ジルコニウムが20
質量%以下、シリコンが3〜20質量%からなる請求項
1に記載の塗装鋼板用塗装前処理液。2. Among the inorganic substances, the ratio of a metal element is 70% by mass or more and zirconium is 20% or more of all metal elements.
The coating pretreatment liquid for a coated steel sheet according to claim 1, wherein the silicon is 3% to 20% by mass, the mass being 3% by mass or less.
用塗装前処理液を、乾燥後の処理皮膜として80〜30
0mg/m2を塗布した塗装用鋼板。3. The coating pretreatment liquid for a coated steel sheet according to claim 1 or 2 as a treatment film after drying.
0 mg / m 2 coated steel sheet for painting.
Priority Applications (1)
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JP2001028474A JP2002235179A (en) | 2001-02-05 | 2001-02-05 | Pretreatment solution for coating for coated steel sheet and treated steel sheet |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP2001028474A JP2002235179A (en) | 2001-02-05 | 2001-02-05 | Pretreatment solution for coating for coated steel sheet and treated steel sheet |
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Publication Number | Publication Date |
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JP2002235179A true JP2002235179A (en) | 2002-08-23 |
Family
ID=18892973
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JP2001028474A Withdrawn JP2002235179A (en) | 2001-02-05 | 2001-02-05 | Pretreatment solution for coating for coated steel sheet and treated steel sheet |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100900639B1 (en) * | 2002-07-02 | 2009-06-02 | 주식회사 포스코 | Post Treatment Water Soluble Coating Composition for Galvanized Steel Sheet |
JP2009174010A (en) * | 2008-01-24 | 2009-08-06 | Nisshin Steel Co Ltd | Chemical conversion treated steel sheet |
US8557343B2 (en) | 2004-03-19 | 2013-10-15 | The Boeing Company | Activation method |
US9909020B2 (en) | 2005-01-21 | 2018-03-06 | The Boeing Company | Activation method using modifying agent |
-
2001
- 2001-02-05 JP JP2001028474A patent/JP2002235179A/en not_active Withdrawn
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100900639B1 (en) * | 2002-07-02 | 2009-06-02 | 주식회사 포스코 | Post Treatment Water Soluble Coating Composition for Galvanized Steel Sheet |
US8557343B2 (en) | 2004-03-19 | 2013-10-15 | The Boeing Company | Activation method |
US9909020B2 (en) | 2005-01-21 | 2018-03-06 | The Boeing Company | Activation method using modifying agent |
US10888896B2 (en) | 2005-01-21 | 2021-01-12 | The Boeing Company | Activation method using modifying agent |
JP2009174010A (en) * | 2008-01-24 | 2009-08-06 | Nisshin Steel Co Ltd | Chemical conversion treated steel sheet |
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