JPH05140759A - Underlayer for coating and its formation - Google Patents
Underlayer for coating and its formationInfo
- Publication number
- JPH05140759A JPH05140759A JP32826691A JP32826691A JPH05140759A JP H05140759 A JPH05140759 A JP H05140759A JP 32826691 A JP32826691 A JP 32826691A JP 32826691 A JP32826691 A JP 32826691A JP H05140759 A JPH05140759 A JP H05140759A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- layer
- zinc
- film
- hemimorphite
- 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
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 229910052864 hemimorphite Inorganic materials 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 7
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 7
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- 239000002585 base Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 2
- 230000032683 aging Effects 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 239000007769 metal material Substances 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000011787 zinc oxide Substances 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 13
- 239000003973 paint Substances 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011282 treatment Methods 0.000 description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000272814 Anser sp. Species 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 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
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- -1 silicon alkoxide Chemical class 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【産業上の利用分野】本発明は、金属その他の基材上に
耐食性塗装を施すための下地形成技術に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base forming technique for applying a corrosion resistant coating on a metal or other substrate.
【従来の技術】従来から、亜鉛めっき鋼板の防食塗料と
して、特開昭５９−２１２２５６号公報、特公昭５３−
３７２５５号公報等に開示されているように、亜鉛粉末
と有機系あるいは無機系の珪酸塩を主体としたジンクリ
ッチペイントが用いられている。ところが、ジンクリッ
チペイント自体は、耐候性に優れてはいるものの、基本
的な組成が亜鉛粒子と珪酸塩との混合物であるために素
地との付着強度に難点があり、塗布に際しての均一性が
悪いという欠点がある。その塗装に際しての欠点を補う
ために、従来から、金属基材よりは塗料に対してなじみ
性が良く、しかも、それ自体が耐食性を有する下地層を
形成するために、りん酸またはクロム酸により化成処理
を施すことが行われている。さらに、近年、塗装鋼板の
耐久性を増すために、これよりも密着性と耐食性が優れ
た下地層として、例えば、特開昭５４−１３４２９号公
報および１９８７年に発行された「金属表面技術（ｖｏ
ｌ．３８．Ｎｏ．１２．ｐ．１２）」には、塗装下地層
として母材にアルカリ珪酸塩溶液と共にシリカゲルの塗
布層を形成することや、亜鉛とシリカゲルを共析めっき
することが開示されている。2. Description of the Related Art Conventionally, as an anticorrosive paint for galvanized steel sheets, JP-A-59-212256 and JP-B-53-
As disclosed in Japanese Patent No. 37255 and the like, a zinc rich paint mainly composed of zinc powder and an organic or inorganic silicate is used. However, although the zinc rich paint itself has excellent weather resistance, it has a difficulty in adhesion strength with the base material because the basic composition is a mixture of zinc particles and a silicate, and the uniformity during application is poor. It has the drawback of being bad. In order to make up for the drawbacks during coating, it has hitherto been formed with phosphoric acid or chromic acid in order to form an underlayer that has better compatibility with paints than metal base materials, and that itself has corrosion resistance. It is being processed. Furthermore, in recent years, in order to increase the durability of a coated steel sheet, as an underlayer having excellent adhesion and corrosion resistance, a metal surface technology (Japanese Patent Laid-Open No. 54-13429 and 1987 (for example, vo
l. 38. No. 12. p. 12) ”discloses forming a silica gel coating layer together with an alkali silicate solution on a base material as a coating base layer, and performing eutectoid plating of zinc and silica gel.
【発明が解決しようとする課題】本発明の目的は、これ
らの従来の塗装下地よりも、それ自体が水道水や雨水等
の雰囲気に対して耐食性においても、また、塗料に対す
る付着性にも優れ、充分に耐食塗料の機能を発揮させる
ことができる下地層を提供することにある。The object of the present invention is that it is superior in corrosion resistance to an atmosphere such as tap water or rainwater, and in its adhesiveness to a paint, as compared with these conventional coating substrates. The purpose of the present invention is to provide an underlayer capable of sufficiently exhibiting the function of a corrosion-resistant paint.
【課題を解決するための手段】本発明は、天然組成に近
い鉱物組成を有する合成ヘミモルファイト皮膜を塗装下
地とすることによってその目的を達成した。合成ヘミモ
ルファイト皮膜は、基本的にはＺｎ4 （ＯＨ）2 Ｓｉ2
Ｏ7 ・Ｈ2 Ｏの化学式を有し、天然のヘミモルファイト
に近い結晶組織を有する。この合成ヘミモルファイトの
形成には、母材の上に１０μｍ以上の厚さの亜鉛層を形
成したのち、亜鉛または亜鉛合金層を少なくとも表面に
有する基材を、空気中で１００〜４００℃の加熱温度で
１〜３時間保持する予備酸化処理、またはｐＨ７〜１３
の水酸化ナトリウム溶液中で８０〜９５℃で１〜６０分
間煮沸処理して水酸化処理を行って、表面に活性酸化亜
鉛（ＺｎＯ）層、または活性水酸化亜鉛（Ｚｎ（ＯＨ）
2 ）層あるいはその混合層を形成したのち、珪酸または
珪酸塩水溶液中に浸漬または塗布して水または水蒸気存
在下で加熱する方法を採用できる。予備酸化あるいは水
酸化処理によって形成された活性酸化亜鉛層は、ヘミモ
ルファイト層の生成を容易にし、また亜鉛層との結合を
強固にするためであって、厚さは０．１〜２０μｍが適
当であるが、もっと厚くてもよい。また、合成ヘミモル
ファイトの皮膜の形成は、予備酸化あるいは水酸化処理
をした基材を５０〜１５０００ｐｐｍ濃度の珪酸または
珪酸塩水溶液中に浸漬または塗布し、１１０〜２１０
℃、１時間以上で飽和蒸気圧力以上の条件下での水熱合
成を行う。また、合成ヘミモルファイト皮膜は、電解等
の電気化学的な手法で基材表面の亜鉛含有層の亜鉛をア
ルカリ珪酸塩溶液中で溶出させ、表面に亜鉛と珪酸と水
からなる不定型の複合化合物を生成し、その後温水中で
熱成させることにより形成することもできる。さらに、
合成ヘミモルファイト皮膜の別の形成方法として、亜鉛
及び珪素のアルコキシドを有機溶媒に溶かして得た溶液
に、水蒸気を含む不活性気体を通気しながら攪拌して、
溶液内に水酸化亜鉛及び珪酸を共沈させた後、過剰の水
分を除去し、溶媒を揮発させて得たゲル状の白色沈澱物
（ヘミモルファイトの前駆物質）をアルカリ珪酸塩溶液
で希釈して、金属基材面に塗布し、その後温水中で熟成
させる方法を採用することも可能である。また、下地層
としての合成ヘミモルファイトの皮膜は、その上に塗布
する塗料との馴染みを考慮すると、必ずしも緻密な皮膜
である必要はなく、多孔質であっても良く、また、完全
に結晶化された状態のものでなくとも、厚さは０．５μ
ｍ以上であれば塗装の下地としての機能を充分に発揮で
きる。しかし、厚過ぎると加工応力や熱応力により割れ
を生じるので、５０μｍ以下とすべきである。さらに、
珪酸または珪酸塩の原料としては、Ｍを１価のアルカリ
金属類であるＬｉ，Ｎａ，Ｋ，Ｃｓ、あるいは、アンモ
ニウムまたはアミンとしたとき、Ｍ2 Ｏ／ＳｉＯ2 の比
が２以下である珪酸、珪酸塩類を使用することができ
る。この合成ヘミモルファイト下地層の生成に際して、
基材としては表面に亜鉛を有する層を形成したものであ
れば、亜鉛めっき鋼板に限らず、如何なる基材にも適用
できる。The present invention has achieved its object by using a synthetic hemimorphite coating having a mineral composition close to a natural composition as a coating base. The synthetic hemimorphite film is basically composed of Zn 4 (OH) 2 Si 2
It has a chemical formula of O 7 · H 2 O and has a crystal structure close to that of natural hemimorphite. In order to form this synthetic hemimorphite, a zinc layer having a thickness of 10 μm or more is formed on a base material, and a base material having a zinc or zinc alloy layer on at least the surface thereof is heated in air at 100 to 400 ° C. Pre-oxidation treatment for 1 to 3 hours at heating temperature, or pH 7 to 13
In a sodium hydroxide solution of 80 to 95 ° C. for 1 to 60 minutes to perform a hydroxylation treatment, and the surface is treated with an active zinc oxide (ZnO) layer or an active zinc hydroxide (Zn (OH) 2
After forming the layer 2 ) or a mixed layer thereof, a method of immersing or coating in a silicic acid or silicate aqueous solution and heating in the presence of water or steam can be adopted. The active zinc oxide layer formed by the pre-oxidation or hydroxylation treatment is for facilitating the formation of the hemimorphite layer and strengthening the bond with the zinc layer, and the thickness is 0.1 to 20 μm. Appropriate, but can be thicker. Further, formation of a film of synthetic hemimorphite is carried out by immersing or coating a pre-oxidized or hydroxylated base material in an aqueous solution of silicic acid or silicate having a concentration of 50 to 15,000 ppm and applying 110 to 210
Hydrothermal synthesis is performed at a temperature of 1 hour or more at a saturated steam pressure or higher. In addition, the synthetic hemimorphite coating is an atypical complex consisting of zinc, silicic acid, and water on the surface of which zinc in the zinc-containing layer on the substrate surface is eluted by an electrochemical method such as electrolysis. It can also be formed by forming the compound and then thermally accelerating it in warm water. further,
As another method for forming a synthetic hemimorphite film, a solution obtained by dissolving zinc and silicon alkoxide in an organic solvent is stirred while aerating an inert gas containing water vapor,
After coprecipitating zinc hydroxide and silicic acid in the solution, remove excess water and evaporate the solvent to dilute the gel-like white precipitate (precursor of hemimorphite) with the alkali silicate solution. Then, it is also possible to adopt a method in which it is applied to the surface of the metal substrate and then aged in warm water. Also, the film of synthetic hemimorphite as the underlayer does not necessarily have to be a dense film, considering the compatibility with the coating material to be applied thereon, may be porous, and may be completely crystalline. Even if it is not in a solidified state, the thickness is 0.5μ
If it is m or more, the function as a base for coating can be sufficiently exhibited. However, if it is too thick, cracking will occur due to processing stress or thermal stress, so it should be 50 μm or less. further,
As a raw material for silicic acid or silicate, when M is Li, Na, K, Cs which is a monovalent alkali metal, or when ammonium or amine is used, silicic acid having a ratio of M 2 O / SiO 2 of 2 or less. , Silicates can be used. In producing this synthetic hemimorphite underlayer,
The base material is not limited to a galvanized steel sheet, and any base material can be applied as long as it has a layer having zinc on its surface.
【作用】本発明にいう合成ヘミモルファイト層は、酸化
亜鉛または水酸化亜鉛の層を介して基材との結晶構造上
の連結によって充分な結合性を有するとともに、それ自
体が板状あるいは柱状の結晶が立体的に配向した形状を
しており、その表面に形成される塗膜に対し十分なアン
カー作用を奏し、塗料との馴染み性がきわめて良好であ
る。The synthetic hemimorphite layer referred to in the present invention has sufficient bondability due to the crystal structure connection with the base material through the zinc oxide or zinc hydroxide layer, and is itself plate-like or columnar. Crystals have a three-dimensionally oriented shape, exert a sufficient anchoring action on the coating film formed on the surface thereof, and have very good compatibility with the coating material.
【実施例】５０ｍｍ×３０ｍｍ×１ｍｍの試料片の表面
をアセトン脱脂後、１５０℃の空気中で２時間酸化処
理し、亜鉛の酸化物の皮膜を、または、ｐＨ９．７の
水酸化ナトリウム水溶液中で３０分間煮沸して、亜鉛の
水酸化物の皮膜をそれぞれ形成した。次いで、この亜鉛
めっき鋼板をＳｉＯ2 濃度３００ｐｐｍまたは１０００
ｐｐｍのメタケイ酸ナトリウム水溶液１２５ｍｌ中に浸
漬した後、１８０℃のオートクレーブ中で６時間または
２０時間水熱処理を行った。図１は、ヘミモルファイト
合成皮膜を走査型電子顕微鏡で観察した表面形態を示
す。基材表面が板状のヘミモルファイト結晶で覆われて
いる様子がわかる。図２は、Ｘ線回折による合成皮膜生
成物の同定結果を天然ヘミモルファイトと合わせて示
す。これらの本発明鋼材の一次耐食性、二次耐食性、一
次塗料密着性及び二次塗料密着性を試験した。その結果
を表１に示す。一次耐食性としては、各本発明鋼材に対
してＪＩＳ−Ｚ−２３７１による塩水噴霧試験を行っ
て、白錆発生までの時間を測定した。二次耐食性として
は、各本発明鋼材に対して塗料塗装後、塗装面にクロス
カットを入れ、ＪＩＳ−Ｚ−２３７１の塩水噴霧試験を
１００時間行い、クロスカット部に発生する塗料の剥離
幅を測定した。一次塗料密着性としては、各本発明鋼材
に対してＪＩＳ−Ｋ−５４００によるゴバン目試験を行
い、塗膜面の損傷状況を判定した。各本発明鋼材に塗料
を塗装後、１ｍｍ間隔にして１００個のゴバン目を塗膜
面に刻み、セロハンテープをこのゴバン目に密着させて
から剥がすことによって行った。二次塗料密着性として
は、各本発明鋼材に対して塗料を塗装後、沸騰水中に３
時間浸漬させ、一次塗料密着性と同様にゴバン目試験を
行った。密着性は、共に次の評価基準に基づいて判定を
行った。 評価点 １０：全く異常なし 〃 ８： １〜 ５個の塗膜剥離を起こしている。 〃 ６： ６〜１５個の塗膜剥離を起こしている。 〃 ４：１６〜３５個の塗膜剥離を起こしている。 〃 ２：３６〜６５個の塗膜剥離を起こしている。 〃 ０： ６６個以上の塗膜剥離を起こしている。EXAMPLE The surface of a sample piece of 50 mm × 30 mm × 1 mm was degreased with acetone and then oxidized in air at 150 ° C. for 2 hours to form a zinc oxide film or in a sodium hydroxide aqueous solution having a pH of 9.7. And boiled for 30 minutes to form a zinc hydroxide film. Then, the galvanized steel sheet is treated with a SiO 2 concentration of 300 ppm or 1000
After immersing in 125 ml of a ppm aqueous solution of sodium metasilicate, hydrothermal treatment was carried out in an autoclave at 180 ° C. for 6 hours or 20 hours. FIG. 1 shows the surface morphology of the hemimorphite synthetic film observed by a scanning electron microscope. It can be seen that the substrate surface is covered with plate-like hemimorphite crystals. FIG. 2 shows the identification results of the synthetic film product by X-ray diffraction, together with the natural hemimorphite. These steel materials of the present invention were tested for primary corrosion resistance, secondary corrosion resistance, primary paint adhesion and secondary paint adhesion. The results are shown in Table 1. As the primary corrosion resistance, a salt water spray test according to JIS-Z-2371 was performed on each steel material of the present invention, and the time until the occurrence of white rust was measured. As the secondary corrosion resistance, after each steel material of the present invention is coated with a paint, a crosscut is put on the coated surface, and a salt spray test of JIS-Z-2371 is performed for 100 hours to determine the peeling width of the paint generated in the crosscut portion. It was measured. As for the primary coating adhesion, a steel sheet material of the present invention was subjected to a goose stitch test according to JIS-K-5400 to determine the damage state of the coating film surface. After each steel material of the present invention was coated with a coating material, 100 goggles were cut at 1 mm intervals on the coating film surface, and cellophane tape was adhered to the gobangs and then peeled off. The secondary coating adhesion was 3 in boiling water after coating each steel material of the present invention with the coating material.
After being immersed for a period of time, a goose-eye test was conducted in the same manner as the primary paint adhesion. The adhesiveness was determined based on the following evaluation criteria. Evaluation point 10: No abnormality at all 〃 8: 1 to 5 peeling of the coating film occurred. 〃 6: 6 to 15 peeling of the coating film has occurred. 〃 4: 16 to 35 coating film peeling occurred. 〃 2: 36 to 65 pieces of coating film peeled off. 〃 0: 66 or more peeled coating films have occurred.
【表１】 この結果から、本発明によって形成されたヘミモルファ
イト皮膜は、その処理を行わない場合（実施例５）や他
の塗装下地処理（実施例６，７）と比較して、どの実施
例（１〜４）においても耐食性及び塗料密着性に優れて
いることがわかる。[Table 1] From these results, the hemimorphite film formed according to the present invention was compared with the case where the treatment was not performed (Example 5) and other coating substrate treatments (Examples 6 and 7). It can be seen that also in ~ 4), the corrosion resistance and the paint adhesion are excellent.
【発明の効果】本発明によって以下の効果を奏すること
ができる。 （１） 亜鉛めっき等の亜鉛あるいは亜鉛含有表面上に
形成された合成ヘミモルファイト皮膜は、その表面の立
体構造から充分なアンカー効果が期待できるので、塗装
密着性に優れた下地が得られる。 （２） 基材上に形成された合成ヘミモルファイトの皮
膜は、湿性大気、塩水、あるいは、水道水、雨水と基材
との充分な遮断効果を有し、塗膜の下地として優れた耐
食性を有する。 （３） さらに、亜鉛めっき等の亜鉛あるいは亜鉛含有
表面を予備処理したＺｎＯ、またはＺｎ（ＯＨ）2 上に
連続して形成した合成ヘミモルファイトは、組織もＺｎ
Ｏ、またはＺｎ（ＯＨ）2 と連続した組織を有し基材と
の結合性が一層高くなる。According to the present invention, the following effects can be obtained. (1) A synthetic hemimorphite coating formed on zinc or a zinc-containing surface such as zinc plating can be expected to have a sufficient anchoring effect due to the three-dimensional structure of the surface, so that a base having excellent coating adhesion can be obtained. (2) The synthetic hemimorphite film formed on the base material has a sufficient effect of blocking the base material from wet air, salt water, tap water, or rainwater, and has excellent corrosion resistance as a base of the coating film. Have. (3) Furthermore, ZnO which has been pretreated with zinc or a zinc-containing surface such as zinc plating, or synthetic hemimorphite continuously formed on Zn (OH) 2 has a texture as well as Zn.
It has a structure continuous with O or Zn (OH) 2 and has higher bondability with the substrate.
【図１】 亜鉛めっき鋼板上に合成した皮膜の走査型電
子顕微鏡（ＳＥＭ）での結晶構造を示す。FIG. 1 shows a crystal structure of a coating synthesized on a galvanized steel sheet under a scanning electron microscope (SEM).
【図２】 Ｘ線回折による皮膜生成物の同定結果を示
す。FIG. 2 shows the results of identifying a film product by X-ray diffraction.
Claims (4)
Ｈ2 Ｏの化学式を有する合成ヘミモルファイト皮膜から
なる塗装用下地層。1. Basically, Zn 4 (OH) 2 Si 2 O 7
An undercoat layer for coating, which is composed of a synthetic hemimorphite film having a chemical formula of H 2 O.
活性酸化亜鉛（ＺｎＯ）層、または活性水酸化亜鉛（Ｚ
ｎ（ＯＨ）2 ）層あるいはその混合層を形成したのち、
珪酸または珪酸塩水溶液中で加熱熟成して合成ヘミモル
ファイト皮膜を形成する塗装用下地層の形成法。2. An active zinc oxide (ZnO) layer or an active zinc hydroxide (Z) is formed on the surface of a substrate having a zinc-containing layer on its surface.
After forming the n (OH) 2 ) layer or a mixed layer thereof,
A method for forming a base layer for coating which forms a synthetic hemimorphite film by heating and aging it in an aqueous solution of silicic acid or silicate.
リ珪酸塩溶液中で電解して、基材表面に亜鉛と水からな
る複合化合物を生成し、次いで、この複合化合物を温水
中で熟成して、基材表面に合成ヘミモルファイト皮膜を
形成する塗装用下地層の形成法。3. A base material having a zinc-containing layer on its surface is electrolyzed in an alkali silicate solution to produce a composite compound consisting of zinc and water on the surface of the base material, and then the composite compound is aged in warm water. Then, a method for forming an undercoat layer for coating, which forms a synthetic hemimorphite film on the surface of a substrate.
に溶かして得た溶液に、水蒸気を含む不活性気体を通気
しながら攪拌して、溶液内に水酸化亜鉛及び珪酸を共沈
させた後、過剰の水分を除去し、溶媒を揮発させて得た
ゲル状の白色沈澱物をアルカリ珪酸塩溶液で希釈して金
属基材表面へ塗布し、その金属材料を温水中で熟成して
合成ヘミモルファイト皮膜を形成する塗装用下地層の形
成法。4. A solution obtained by dissolving an alkoxide of zinc and silicon in an organic solvent is stirred while aerating an inert gas containing water vapor, and zinc hydroxide and silicic acid are coprecipitated in the solution. A gel-like white precipitate obtained by removing excess water and volatilizing the solvent is diluted with an alkali silicate solution and applied to the surface of a metal substrate, and the metal material is aged in warm water to synthesize a synthetic hemi-mol. A method for forming an undercoat layer for painting that forms a fight film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32826691A JPH05140759A (en) | 1991-11-15 | 1991-11-15 | Underlayer for coating and its formation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32826691A JPH05140759A (en) | 1991-11-15 | 1991-11-15 | Underlayer for coating and its formation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05140759A true JPH05140759A (en) | 1993-06-08 |
Family
ID=18208308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32826691A Pending JPH05140759A (en) | 1991-11-15 | 1991-11-15 | Underlayer for coating and its formation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05140759A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021157745A1 (en) * | 2020-02-06 | 2021-08-12 | 株式会社オーアンドケー | Lubricant composition for forming hemimorphite-containing lubrication coating, method for forming said lubrication coating on surface of metal workpiece, and metal workpiece comprising said lubrication coating |
-
1991
- 1991-11-15 JP JP32826691A patent/JPH05140759A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021157745A1 (en) * | 2020-02-06 | 2021-08-12 | 株式会社オーアンドケー | Lubricant composition for forming hemimorphite-containing lubrication coating, method for forming said lubrication coating on surface of metal workpiece, and metal workpiece comprising said lubrication coating |
| US12319885B2 (en) | 2020-02-06 | 2025-06-03 | O&K Company | Lubricant composition for forming hemimorphite-containing lubrication coating, method for forming said lubrication coating on surface of metal workpiece, and metal workpiece comprising said lubrication coating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5196916B2 (en) | Method for surface modification treatment of hot-dip galvanized steel and surface-modified hot-dip metal-plated steel | |
| AU625900B2 (en) | Method and composition for surface treatment | |
| JP5203974B2 (en) | Corrosion-resistant substrate | |
| CN105247104A (en) | Aluminum-containing galvanized steel sheet and method for manufacturing aluminum-containing galvanized steel sheet | |
| US11999871B2 (en) | Titanium and magnesium compound for corrosion-resistant coatings | |
| JPH06506263A (en) | Phosphate treatment method for metal surfaces | |
| JP2010053424A (en) | Surface-treated metal plate having superior adhesiveness to coating, and method for producing the same | |
| JPS5928637B2 (en) | Method of forming a protective film on the surface of magnesium material | |
| JPH05140759A (en) | Underlayer for coating and its formation | |
| JP4415449B2 (en) | Method for producing surface-treated steel with excellent weather resistance | |
| JP4528149B2 (en) | Hot-dip plated steel and coated steel plate with excellent corrosion resistance | |
| JP2001164182A (en) | Rust prevention coating agent and rust prevention treatment method | |
| JP2004052056A (en) | Surface treatment method of zinc or zinc alloy plated material | |
| JPS5928638B2 (en) | Method of forming a colored protective film on the surface of magnesium material | |
| JP4176581B2 (en) | Surface-treated aluminum material and aluminum molded body | |
| JP3224034B2 (en) | Corrosion resistant film and its formation method | |
| JP2659616B2 (en) | Base treatment agent for forming organic resin layer on metal surface | |
| JP3776879B2 (en) | Corrosion resistant galvanized steel sheet | |
| JPS6233780A (en) | Surface treatment of metallic material | |
| JP2002060959A (en) | Galvanized steel sheet excellent in corrosion resistance and adhesive strength of coating, chemically treating solution and chemical conversion treating method | |
| JPS6216061Y2 (en) | ||
| JPH04333576A (en) | Production of surface-treated steel sheet having excellent adhesive property | |
| JPH03229880A (en) | Manufacturing method of surface-treated steel sheet for adhesive base | |
| JPH10147888A (en) | Corrosion resistant surface treated metal plate | |
| JPS596383A (en) | Production of corrosion protecting layer on aluminum parts without using electric current |