JPH0541707B2 - - Google Patents
Info
- Publication number
- JPH0541707B2 JPH0541707B2 JP33275987A JP33275987A JPH0541707B2 JP H0541707 B2 JPH0541707 B2 JP H0541707B2 JP 33275987 A JP33275987 A JP 33275987A JP 33275987 A JP33275987 A JP 33275987A JP H0541707 B2 JPH0541707 B2 JP H0541707B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- organic resin
- phosphoric acid
- chromic anhydride
- colloidal silica
- 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.)
- Expired - Fee Related
Links
- 239000011347 resin Substances 0.000 claims description 84
- 229920005989 resin Polymers 0.000 claims description 84
- 229910000831 Steel Inorganic materials 0.000 claims description 30
- 239000010959 steel Substances 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 22
- 229910052725 zinc Inorganic materials 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 88
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 87
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 40
- 239000003973 paint Substances 0.000 description 37
- 239000008119 colloidal silica Substances 0.000 description 36
- 239000011651 chromium Substances 0.000 description 31
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 30
- 238000005260 corrosion Methods 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 10
- 230000003666 anti-fingerprint Effects 0.000 description 6
- 238000005246 galvanizing Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 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
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 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
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/33—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also phosphates
Description
〔産業上の利用分野〕
本発明は亜鉛めつき、または亜鉛系合金めつき
鋼板上にクロメート皮膜を生成させた、表面処理
鋼板に関するものである。
〔従来の技術とその問題点〕
従来、亜鉛めつき鋼板のクロメート処理として
クロムを主成分として、Si，Ｐ、有機樹脂を含む
皮膜を生成させることは既知である。
例えば、Siとしてシリカを添加したものとして
特公昭61−58552号公報、特公昭61−1508号公報、
特開昭60−13079号公報、特公昭61−54880号公報
記載のものなどがある。またＰとしてりん酸を添
加したものとして、特公昭53−41621号公報、ま
たSiとＰの双方を添加したものとして特公昭60−
18751号公報記載のものがある。これらは従来の
Crのみのクロメート皮膜の耐食性を更に向上さ
せる他、塗料との密着性を付与することを目的と
したものである。
一方、近年家電製品、事務機器などに用いられ
る鋼板は、亜鉛または亜鉛系合金めつき鋼板を塗
装せずに、または塗装して使用される。すなわち
鋼板に必要な特性は、無塗装での耐食性や外観
（色調、色むら）、製品製作中および使用中に於い
て指紋の付きにくいこと、更に塗装した時の塗料
の密着性等々である。
古くからクロム酸処理によるクロメート皮膜
は、単に耐食性を付与するものであつたが、上記
の種々の特性が要求されるに及んで、Si，Ｐ、金
属イオンが処理液に添加されるようになり、更に
耐指紋性の向上のためには、特開昭61−207579号
公報、特開昭59−140050号公報などに示されるよ
うに、有機樹脂が添加されるようになつた。
しかしながら、いずれも、要求される全ての性
能を完全に満たすことは出来ず、いくつかの性能
のバランスをとることで対応しているに過ぎな
い。
（発明が解決しようとする問題点）
本発明は上記の点に鑑み、亜鉛めつきおよび亜
鉛系合金めつき鋼板上のクロメート皮膜の耐食
性、塗料密着性、耐指紋性、色むらの全てを向上
させたクロメート皮膜構造を有する化成処理鋼板
を提供することを目的とする。
（問題点を解決するための手段）
上記目的は下記に示す構成の皮膜を亜鉛または
亜鉛系合金めつき鋼板上に形成させることによつ
て有利に達成出来る。すなわち、本発明の要旨と
するところは下記のとおりである。
(1) 亜鉛または亜鉛系合金めつき鋼板の表面に第
一層として、Cr／Ｐ＝0.1〜10、Cr＋Ｐ≧５
mg／m2の範囲でCrおよびＰを含む第一層皮膜
を有し、その上にＰ，Siのうち少なくとも１種
と有機樹脂（水溶性または水分散性）を含有
し、有機樹脂＋Si＋Ｐ≧１mg／m2、有機樹脂／
（Si＋Ｐ）≧0.05、Siを含むときは有機樹脂／Si
＝0.05〜10、Ｐを含むときは有機樹脂／Ｐ＝
0.05〜20の範囲にある第二層皮膜を有すること
を特徴とするクロメート処理鋼板。
(2) 亜鉛または亜鉛系合金めつき鋼板の表面に第
一層として、Cr／（Ｐ＋Si）＝0.1〜10、Cr＋Ｐ
＋Si≧５mg／m2の範囲でCr，ＰおよびSiを含む
第一層皮膜を有し、その上にＰ，Siのうち少な
くとも１種と有機樹脂（水溶性または水分散
性）を含有し、有機樹脂＋Si＋Ｐ≧１mg／m2、
有機樹脂／（Si＋Ｐ）≧0.05、Siを含むときは
有機樹脂／Si＝0.05〜10、Ｐを含むときは有機
樹脂／Ｐ＝0.05〜20の範囲にある第二層皮膜を
有することを特徴とするクロメート処理鋼板。
また、第一層中にSiをCr／（Ｐ＋Si）＝0.1〜
10，Cr＋Ｐ＋Si≧５mg／m2の範囲で含有するこ
とも有効である。さらに第一層中にSiを含む場
合、含まない場合のいずれについても、第二層中
にCrをCr／（Ｐ＋Si＋有機樹脂）≦0.2の範囲で含
有することも有効である。
また、さらに必要に応じて、以上すべての場合
について第一層皮膜中に水溶性または水分散性の
有機樹脂を含有させることも有効である。
本発明の構成に当り、発明者らは上記の諸性能
が皮膜構成成分によつて如何なる影響を受けるか
に関する詳細な検討を行つた。その結果Crは耐
食性に有効だが色むらの原因になり易く、外観を
損い、また塗料密着性、耐指紋性に不利であり、
Siは特に塗料一次密着性に有効だが、塗料二次密
着性および耐指紋性に不利であり、またＰは耐食
性と耐指紋性に有利だが塗料一次密着性に不利で
あることが判明した。塗料一次密着性とは、塗料
を塗布した直後の鋼板表面と、塗料との密着性を
意味し、塗膜にナイフで１mmのゴバン目100ケ
（10×10）の切込みを入れ、接着テープで剥離し
たときの剥離したゴバン目の数で評価したもので
ある。（ゴバン目テープ法）塗料二次密着性とは、
塗装した鋼板をある環境下で経時させた後の塗料
密着性を示し、本発明では、100％の湿気槽内に
１週間保持した後、ゴバン目テープ法にて評価し
たものである。
ここで諸性能の内容をよく考えてみると、耐食
性、色むらなどはクロメート皮膜全体の性能であ
るのに対し塗料密着性や耐指紋性は皮膜の最表層
部分が示す性能であると考えられる。つまり、最
表層は塗料密着性と耐指紋性に有利な構成とし、
内層は耐食性にすぐれた構成にすれば塗料密着
性、耐指紋性、耐食性の全てを充たすことが可能
となるはずである。また色むらの原因となり易い
Cr成分を第一層のみに止めることによりまたは
第二層の含有量を極微量に止めることにより外観
上の問題を解決できることになる。
本発明はこのような考え方に基き、第一層（内
層）をCrの含有を必須とする耐食性を確保する
層、第二層（外層）をCrを全く含まないか、ま
たは均一皮覆性のために極微量のみ含み、塗料一
次密着性、塗料二次密着性、耐指紋性を保持する
ための層と位置づけて、従来のクロメート処理鋼
板の有していた問題点を全て解決したものであ
る。
第一層（内層）は耐食性を保持するための層で
あるからCrの存在は必須であり、更に耐食性に
有効なＰの同時存在が望ましい。Cr／Ｐが0.1未
満となると耐食性が低下する。Cr／Ｐが10を超
えると、耐食性がわずかに低下する他、第二層
（外層）の存在にも拘らず色むらが発生し易くな
り外観を損う。Cr＋Ｐは５mg／m2未満では耐食
性が不足するので５mg／m2以上必要である。第一
層皮膜中にSiを添加することも可能であるがこの
場合も上記と同様の理由によりCr／（Ｐ＋Si）
は0.1〜10、Cr＋Ｐ＋Siは５mg／m2以上が必要で
ある。
また第一層形成処理液に水溶性または水分散性
有機樹脂を添加することにより、第一層皮膜中に
有機樹脂を添加することは、耐食性を更に向上さ
せる効果がある。
第二層（外層）は塗料一次密着性、塗料二次密
着性、耐指紋性を向上させ、更に第一層の色む
ら、色調を均一化、無色化することを目的とする
層である。樹脂、SiおよびＰが持つ、これらの性
能に対する効果は以下の通りである。Siは塗料一
次密着性を向上させるが、塗料二次密着性および
耐指紋性を低下させる。Ｐは塗料一次密着性を低
下させるが、塗料二次密着性の保持に役立ち、耐
指紋性の向上および第一層の色むら、色調の均一
化、無色化に効果を表わす。有機樹脂は塗料一
次、二次密着性の保持に役立ち、耐指紋性につい
ては添加量が一定以上になると向上効果を表わ
す。
樹脂をSiまたはＰと混合して第二層皮膜を形成
した場合、Siのもつ塗料二次密着性の低下効果、
Ｐの持つ塗料一次密着性の低下効果が樹脂の添加
により緩和されるが、そのために必要な添加量は
Siと混合する場合には有機樹脂／Si≧0.05、Ｐと
混合する場合には有機樹脂／Ｐ≧0.05であること
が必要でそれ未満では効果がない。一方、Siの塗
料一次密着性向上効果、Ｐの塗料二次密着性の保
持効果は、有機樹脂を多く混合しすぎると損わ
れ、その限界値は、Siと混合する場合には有機樹
脂／Si≦10、Ｐと混合する場合には有機樹脂／Ｐ
≦20である。耐指紋性を保つためには有機樹脂を
有機樹脂／（Ｐ＋Si）≧0.05の範囲で添加する必
要があり、それ未満では効果がない。また（有機
樹脂＋Si＋Ｐ）の量は１mg／m2以上であることが
必要で、それ未満では第１層の影響を受け、第２
層として充分機能しない。
Siはシリカ粉、コロイダルシリカ、シランカツ
プリング剤、各種ケイ酸塩を水に溶解または分散
させることにより、またＰはりん酸、ポリリン
酸、りん酸塩を水に添加することにより容易に第
二層形成処理液の作成が可能である。
有機樹脂としては水溶性または水分散性であれ
ば全て適用が可能である。一般的には分子鎖に水
酸基、カルボキシル基を結合させることで水との
親和性を大きくし、水溶性または水分散性にする
ことが多い。特許例としてポリビニルアルコール
などを用いた特公昭61−28751号公報、カルボキ
シル化ポリエチレンを使用した特公昭60−33192
号公報、特公昭60−149789号公報、カルボキシル
化ポリオレフインを用いた特開昭62−50479号公
報、無水マレイン酸またはマレイン酸共重合体を
用いた特公昭50−6417号公報記載のものなどがあ
る。これらはいずれも加熱、乾燥後に化学的に安
定な硬い皮膜となり、指紋が付着しにくくなるも
のである。
第二層皮膜の均一塗布性のためにはCrの添加
が有効であるが、塗料密着性、耐指紋性を保つた
めにはその添加量は第二層皮膜中にＰ＋Si＋有機
樹脂に対して1/10以下、すなわちCr／（Ｐ＋Si
＋有機樹脂）≦0.2でなければならない。
Crは前記特許公報にも記述されているように
無水クロム酸、クロム酸塩、重クロム酸塩を水に
溶解することで容易に第一層または第二層形成処
理液に含有させ、従つて第一層皮膜中に含有させ
ることが可能である。この際Crを３価に還元す
るために還元剤を添加し、第一層または第二層皮
膜中の６価Crに対する３価Crの割合を増大する
ことも何ら支障はない。
鋼板上への皮膜形成は浸漬−ロール絞り−加熱
乾燥、ロールコーテイング、スプレーコーテイン
グ等通常の塗布クロメートのあらゆる皮膜形成方
法が適用できる。但し第一層皮膜形成後、第二層
皮膜形成までの間に第一層皮膜を乾燥することが
より望ましい。
本発明の化成処理は最表層が亜鉛または亜鉛系
合金めつきである全ての鋼板に適用できる。亜鉛
めつきとは電気亜鉛めつき、溶融亜鉛めつき、真
空蒸着による亜鉛めつきなど全てを含む。亜鉛系
合金めつきとは、亜鉛−ニツケル、亜鉛−鉄、亜
鉛−アルミなど亜鉛と他の金属１種以上を含むあ
らゆる合金めつき、および、ケイ素、チタン、ア
ルミ、クロムなどの金属酸化物をめつき層中に分
散させたもの全てを含むものである。複数層のめ
つき層を有する場合も最上層が上記亜鉛を含有す
るめつき層であれば適用が可能である。また、片
面めつき、樹脂を間に有する複合鋼板などへも同
様に適用が可能である。
〔実施例 １〕
電気亜鉛めつき鋼板（亜鉛付着量20ｇ／m2）を
(1) 無水クロム酸 ５ｇ／、
(2) 無水クロム酸 10ｇ／
(3) 無水クロム酸 ５ｇ／、りん酸 ５ｇ／
(4) 無水クロム酸 ５ｇ／、りん酸 ８ｇ／
(5) 無水クロム酸 ５ｇ／、りん酸 30ｇ／
(6) 無水クロム酸 ５ｇ／、りん酸 60ｇ／
(7) 無水クロム酸 ５ｇ／、りん酸 80ｇ／
(8) 無水クロム酸 10ｇ／、りん酸 0.5ｇ／
(9) 無水クロム酸 10ｇ／、りん酸 1.3ｇ／
(10) 無水クロム酸 10ｇ／、りん酸 2.6ｇ／
(11) 無水クロム酸 10ｇ／、りん酸 50ｇ／
(12) 無水クロム酸 10ｇ／、りん酸 130ｇ／
(13) 無水クロム酸 10ｇ／、りん酸 140ｇ／
(14) 無水クロム酸 ５ｇ／、アクリルアミド樹
脂10ｇ／
(15) 無水クロム酸 10ｇ／、アクリルアミド樹
脂10ｇ／
(16) 無水クロム酸 ５ｇ／、りん酸 ５ｇ／
、アクリルアミド樹脂 10ｇ／
(17) 無水クロム酸 ５ｇ／、りん酸 ８ｇ／
、アクリルアミド樹脂 10ｇ／
を含む第１層形成処理液で処理し、乾燥後りん酸
２ｇ／、コロイダルシリカ３ｇ／、アクリル
アミド樹脂５ｇ／を含む第２層形成処理液で処
理、乾燥した試料の性能評価を第１表に示す。こ
れより耐食性を保つためには第１層中のCrおよ
びＰの量は、Cr＋Ｐ≧５mg／m2、Cr／Ｐ＝0.1〜
10の範囲が良いことがわかる。
〔実施例 ２〕
電気亜鉛めつき鋼板（亜鉛めつき付着量20ｇ／
m2）を
(18) 無水クロム酸 ５ｇ／、コロイダルシリカ
５ｇ／
(19) 無水クロム酸 ５ｇ／、コロイダルシリカ
８ｇ／
(20) 無水クロム酸 ５ｇ／、コロイダルシリカ
５ｇ／、りん酸 2.5ｇ／
(21) 無水クロム酸 ５ｇ／、コロイダルシリ
カ2.5ｇ／、りん酸 ５ｇ／
(22) 無水クロム酸 ５ｇ／、コロイダルシリ
カ５ｇ／、りん酸 26ｇ／
(23) 無水クロム酸 ５ｇ／、コロイダルシリ
カ36ｇ／、りん酸 26ｇ／
(24) 無水クロム酸 ５ｇ／、コロイダルシリ
カ36ｇ／、りん酸 40ｇ／
(25) 無水クロム酸 10ｇ／、コロイダルシリ
カ0.5ｇ／
(26) 無水クロム酸 10ｇ／、コロイダルシリ
カ0.5ｇ／、りん酸 0.5ｇ／
(27) 無水クロム酸 10ｇ／、コロイダルシリ
カ1.3ｇ／、りん酸 1.3ｇ／
(28) 無水クロム酸 10ｇ／、コロイダルシリ
カ38ｇ／、りん酸 26ｇ／
(29) 無水クロム酸 10ｇ／、コロイダルシリ
カ77ｇ／、りん酸 50ｇ／
(30) 無水クロム酸 10ｇ／、コロイダルシリ
カ38ｇ／、りん酸 100ｇ／
(31) 無水クロム酸 10ｇ／、コロイダルシリ
カ115ｇ／、りん酸 26ｇ／
(32) 無水クロム酸 ５ｇ／、コロイダルシリ
カ５ｇ／、アクリルアミド樹脂 10ｇ／
(33) 無水クロム酸 ５ｇ／、コロイダルシリ
カ８ｇ／、アクリルアミド樹脂 10ｇ／
(34) 無水クロム酸 ５ｇ／、コロイダルシリ
カ2.5ｇ／、りん酸 ５ｇ／、
アクリルアミド樹脂 10ｇ／
を含む第一層形成処理液で処理し、乾燥後りん酸
２ｇ／、コロイダルシリカ３ｇ／、アクリル
アミド樹脂５ｇ／を含む第二層形成処理液で処
理、乾燥した試料の性能評価を第２表に示す。こ
れより、耐食性を保つためには、第一層中のCr，
SiおよびＰの量は
Cr＋Si＋Ｐ≧５mg／m2，Cr／（Ｐ＋Si）＝0.1〜10
の範囲が良いことがわかる。
〔実施例 ３〕
電気亜鉛めつき鋼板（亜鉛めつき付着量20ｇ／
m2）を無水クロム酸40ｇ／、りん酸26ｇ／、
コロイダルシリカ77ｇ／を含む第一層形成処理
液で処理、乾燥した後、
(35) りん酸 １ｇ／、アクリルアミド樹脂0.5
ｇ／
(36) コロイダルシリカ １ｇ／、アクリルア
ミド樹脂 0.5ｇ／
(37) りん酸 1.3ｇ／、アクリルアミド樹脂
0.5ｇ／
(38) コロイダルシリカ 1.3ｇ／、アクリルア
ミド樹脂 0.5ｇ／
(39) アクリルアミド樹脂 １ｇ／
を含む第二層形成処理液で処理、乾燥した試料の
性能を第３表に示す。これより、塗料一次密着
性、塗料二次密着性、耐指紋性を確保するために
は、
（Ｐ＋Si＋有機樹脂）≧１mg／m2
となる必要があることがわかる。
〔実施例 ４〕
電気亜鉛めつき鋼板（亜鉛付着量20ｇ／m2）を
無水クロム酸40ｇ／、りん酸26ｇ／、コロイ
ダルシリカ77ｇ／を含む第一層形成処理液で処
理、乾燥した後、
(40) りん酸 26ｇ／、アクリルアミド樹脂0.4
ｇ／
(41) りん酸 26ｇ／、アクリルアミド樹脂0.5
ｇ／
(42) りん酸 26ｇ／、アクリルアミド樹脂10
ｇ／
(43) りん酸 26ｇ／、アクリルアミド樹脂
200ｇ／
(44) りん酸 26ｇ／、アクリルアミド樹脂
210ｇ／
(45) コロイダルシリカ26ｇ／、アクリルアミ
ド樹脂 0.4ｇ／
(46) コロイダルシリカ26ｇ／、アクリルアミ
ド樹脂 0.5ｇ／
(47) コロイダルシリカ26ｇ／、アクリルアミ
ド樹脂 10ｇ／
(48) コロイダルシリカ26ｇ／、アクリルアミ
ド樹脂 100ｇ／
(49) コロイダルシリカ26ｇ／、アクリルアミ
ド樹脂 110ｇ／
(50) りん酸 2.6ｇ／、コロイダルシリカ640
ｇ／、アクリルアミド樹脂10ｇ／
(51) りん酸 2.6ｇ／、コロイダルシリカ2.3
ｇ／、アクリルアミド樹脂10ｇ／
(52) りん酸 2.6ｇ／、コロイダルシリカ５
ｇ／、アクリルアミド樹脂10ｇ／
(53) りん酸 640ｇ／、コロイダルシリカ５
ｇ／、アクリルアミド樹脂10ｇ／
(54) りん酸 2.3ｇ／、コロイダルシリカ５
ｇ／、アクリルアミド樹脂10ｇ／
を含む第二層形成処理液で処理、乾燥した試料の
性能を第４表に示す。
これより塗料一次密着性、塗料二次密着性、耐
指紋性をすべて良好にするためには、第二層皮膜
中の成分として
Siと有機樹脂を同時に含むときには
有機樹脂／Si＝0.05〜10
Ｐと有機樹脂を同時に含むときには
有機樹脂／Ｐ＝0.05〜20
の範囲が良く、またSi，Ｐ、有機樹脂の量の間に
有機樹脂／（Ｐ＋Si）≧0.05
が成り立つ範囲が良いことがわかる。
〔実施例 ５〕
電気亜鉛めつき鋼板（亜鉛付着量20ｇ／m2）を
無水クロム酸40ｇ／、りん酸26ｇ／、コロイ
ダルシリカ77ｇ／を含む第一層形成処理液で処
理、乾燥した後、第二層形成処理液として
(55) りん酸40ｇ／、コロイダルシリカ40ｇ／
、アクリルアミド樹脂20ｇ／
(56) (55)に無水クロム酸2.4ｇ／を加えたもの
(57) (55)に無水クロム酸10.4ｇ／を加えたも
の
(58) (55)に無水クロム酸14.4ｇ／を加えたも
の
(59) (55)に無水クロム酸20.8ｇ／を加えたも
の
(60) (55)に無水クロム酸26ｇ／を加えたもの
で処理、乾燥した試料の性能を第５表に示す。こ
れより、第二層皮膜中のCr量が
Cr／（Ｐ＋Si＋有機樹脂）≦0.20
であれば、塗料一次密着性、塗料二次密着性、耐
指紋性のいずれも良好であることがわかる。
[Industrial Application Field] The present invention relates to a surface-treated steel sheet in which a chromate film is formed on a galvanized or zinc alloy-plated steel sheet. [Prior art and its problems] Conventionally, it has been known to produce a film containing chromium as a main component and containing Si, P, and an organic resin as a chromate treatment of galvanized steel sheets. For example, Japanese Patent Publication No. 61-58552, Japanese Patent Publication No. 61-1508, which contain silica as Si,
There are those described in Japanese Patent Application Laid-Open No. 60-13079 and Japanese Patent Publication No. 61-54880. Furthermore, as P, phosphoric acid is added, as published in Japanese Patent Publication No. 53-41621, and as added with both Si and P, published in Japanese Patent Publication No. 60-41621.
There is one described in Publication No. 18751. These are traditional
The purpose is to further improve the corrosion resistance of a chromate film made only of Cr, as well as to provide better adhesion to paint. On the other hand, in recent years, steel sheets used for home appliances, office equipment, etc. are zinc or zinc-based alloy coated steel sheets, either unpainted or coated. In other words, the properties required for a steel plate include corrosion resistance and appearance (color tone, color unevenness) without painting, resistance to fingerprints during product manufacturing and use, and adhesion of paint when painted. For a long time, chromate films formed by chromic acid treatment simply provided corrosion resistance, but as the various properties mentioned above became required, Si, P, and metal ions were added to the treatment solution. Furthermore, in order to improve the fingerprint resistance, organic resins have been added as shown in Japanese Patent Application Laid-Open No. 61-207579 and Japanese Patent Application Laid-Open No. 59-140050. However, none of these methods can completely satisfy all of the performance requirements, and only achieve this by balancing some of the performances. (Problems to be Solved by the Invention) In view of the above points, the present invention improves all of the corrosion resistance, paint adhesion, fingerprint resistance, and color unevenness of the chromate film on galvanized and zinc-based alloy coated steel sheets. The object of the present invention is to provide a chemical conversion treated steel sheet having a chromate film structure. (Means for Solving the Problems) The above object can be advantageously achieved by forming a film having the structure shown below on a zinc or zinc-based alloy coated steel sheet. That is, the gist of the present invention is as follows. (1) Cr/P=0.1~10, Cr+P≧5 as the first layer on the surface of zinc or zinc-based alloy coated steel sheet
It has a first layer film containing Cr and P in the range of mg/ m2 , and contains at least one of P and Si and an organic resin (water-soluble or water-dispersible), organic resin + Si + P≧ 1mg/m 2 , organic resin/
(Si+P)≧0.05, organic resin/Si when containing Si
=0.05~10, organic resin/P= when containing P
A chromate-treated steel sheet characterized by having a second layer coating in the range of 0.05 to 20. (2) Cr/(P+Si)=0.1~10, Cr+P as the first layer on the surface of zinc or zinc-based alloy coated steel sheet.
It has a first layer film containing Cr, P and Si in the range of +Si≧5mg/ m2 , and further contains at least one of P and Si and an organic resin (water-soluble or water-dispersible), Organic resin + Si + P≧1mg/m 2 ,
It is characterized by having a second layer film in which organic resin/(Si+P)≧0.05, organic resin/Si=0.05 to 10 when it contains Si, and organic resin/P=0.05 to 20 when it contains P. chromate treated steel sheet. In addition, Si is added in the first layer to Cr/(P+Si)=0.1~
It is also effective to contain 10, Cr+P+Si≧5mg/m 2 . Furthermore, whether or not the first layer contains Si, it is also effective to contain Cr in the second layer in the range of Cr/(P+Si+organic resin)≦0.2. Furthermore, if necessary, it is also effective to include a water-soluble or water-dispersible organic resin in the first layer film in all of the above cases. In constructing the present invention, the inventors conducted detailed studies on how the above-mentioned performances are affected by the film constituents. As a result, although Cr is effective for corrosion resistance, it tends to cause uneven color, impairs the appearance, and is disadvantageous in terms of paint adhesion and fingerprint resistance.
It has been found that Si is particularly effective for primary paint adhesion, but is disadvantageous for secondary paint adhesion and anti-fingerprint properties, and P is advantageous for corrosion resistance and anti-fingerprint properties, but is disadvantageous for primary adhesion of paint. Primary paint adhesion refers to the adhesion between the paint and the steel plate surface immediately after it has been applied. The evaluation was based on the number of peeled gobbles when peeled off. (Goban tape method) What is secondary paint adhesion?
This shows the paint adhesion of a painted steel plate after aging in a certain environment, and in the present invention, it is evaluated using the cross-cut tape method after being kept in a 100% humidity chamber for one week. If we consider the various performance details here, we can see that corrosion resistance, color unevenness, etc. are the performance of the entire chromate film, while paint adhesion and fingerprint resistance are the performance of the outermost layer of the film. . In other words, the outermost layer has a structure that is advantageous for paint adhesion and fingerprint resistance.
If the inner layer has a structure with excellent corrosion resistance, it should be possible to satisfy all of the requirements of paint adhesion, fingerprint resistance, and corrosion resistance. It also tends to cause uneven coloring.
By limiting the Cr component to only the first layer or by keeping the content of the second layer to an extremely small amount, the problem in appearance can be solved. The present invention is based on this idea, and the first layer (inner layer) is a layer that ensures corrosion resistance by containing Cr, and the second layer (outer layer) is a layer that does not contain Cr at all or has a uniform coating. Therefore, it contains only a very small amount and is positioned as a layer to maintain primary paint adhesion, secondary paint adhesion, and anti-fingerprint properties, solving all the problems that conventional chromate-treated steel sheets had. . Since the first layer (inner layer) is a layer for maintaining corrosion resistance, the presence of Cr is essential, and the simultaneous presence of P, which is effective for corrosion resistance, is also desirable. When Cr/P is less than 0.1, corrosion resistance decreases. When Cr/P exceeds 10, corrosion resistance slightly decreases, and color unevenness tends to occur despite the presence of the second layer (outer layer), impairing the appearance. If Cr+P is less than 5 mg/m 2 , corrosion resistance is insufficient, so 5 mg/m 2 or more is required. It is also possible to add Si to the first layer film, but in this case as well, for the same reason as above, Cr/(P+Si)
is required to be 0.1 to 10, and Cr+P+Si is required to be 5 mg/m2 or more . Further, by adding a water-soluble or water-dispersible organic resin to the first layer forming treatment liquid, the organic resin is added to the first layer film, which has the effect of further improving corrosion resistance. The second layer (outer layer) is a layer whose purpose is to improve the primary paint adhesion, secondary paint adhesion, and fingerprint resistance, as well as to make the color unevenness and tone of the first layer uniform and colorless. The effects of resin, Si, and P on these performances are as follows. Although Si improves the primary adhesion of the paint, it reduces the secondary adhesion of the paint and fingerprint resistance. Although P reduces the primary adhesion of the paint, it helps maintain the secondary adhesion of the paint, and is effective in improving fingerprint resistance, reducing color unevenness in the first layer, making the color tone uniform, and making it colorless. The organic resin helps maintain the primary and secondary adhesion of the paint, and exhibits an improvement effect on fingerprint resistance when the amount added exceeds a certain level. When a second layer film is formed by mixing resin with Si or P, the effect of Si on reducing secondary paint adhesion,
The effect of P on reducing the primary adhesion of paint can be alleviated by adding resin, but the amount required for this is
When mixed with Si, it is necessary that organic resin/Si≧0.05, and when mixed with P, it is necessary that organic resin/P≧0.05, and if it is less than that, there is no effect. On the other hand, the effect of Si on improving the primary adhesion of the paint and the effect of P on maintaining the secondary adhesion of the paint are impaired if too much organic resin is mixed, and the limit value is the organic resin/Si when mixed with Si. ≦10, organic resin/P when mixed with P
≦20. In order to maintain anti-fingerprint properties, it is necessary to add an organic resin within the range of organic resin/(P+Si)≧0.05, and if it is less than that, there is no effect. In addition, the amount of (organic resin + Si + P) must be 1 mg/m 2 or more; if it is less than that, it will be affected by the first layer and the second layer will be affected.
Does not function well as a layer. Si can be easily obtained by dissolving or dispersing silica powder, colloidal silica, silane coupling agents, and various silicates in water, and P can be easily obtained by adding phosphoric acid, polyphosphoric acid, or phosphates to water. It is possible to create a layer forming treatment solution. Any organic resin that is water-soluble or water-dispersible can be used. In general, hydroxyl or carboxyl groups are bonded to the molecular chain to increase affinity with water and often make it water-soluble or water-dispersible. Examples of patents include Japanese Patent Publication No. 61-28751, which uses polyvinyl alcohol, etc., and Japanese Patent Publication No. 60-33192, which uses carboxylated polyethylene.
JP-A-60-149789, JP-A-62-50479 using carboxylated polyolefin, and JP-A-50-6417 using maleic anhydride or maleic acid copolymer. be. All of these become chemically stable hard films after heating and drying, making it difficult for fingerprints to adhere to them. Adding Cr is effective for uniform coating of the second layer film, but in order to maintain paint adhesion and fingerprint resistance, the amount of Cr added should be 1 to P + Si + organic resin in the second layer film. /10 or less, that is, Cr/(P+Si
+ organic resin) ≦0.2. As described in the above-mentioned patent publication, Cr can be easily incorporated into the first or second layer forming treatment solution by dissolving chromic anhydride, chromate, or dichromate in water. It is possible to include it in the first layer film. At this time, there is no problem in adding a reducing agent to reduce Cr to trivalent and increasing the ratio of trivalent Cr to hexavalent Cr in the first layer or second layer film. For forming a film on a steel plate, any film forming method commonly used for coated chromates can be applied, such as dipping-roll drawing-heat drying, roll coating, and spray coating. However, it is more desirable to dry the first layer film after forming the first layer film and before forming the second layer film. The chemical conversion treatment of the present invention can be applied to all steel sheets whose outermost layer is plated with zinc or zinc-based alloy. Galvanizing includes all galvanizing methods such as electrolytic galvanizing, hot-dip galvanizing, and vacuum evaporation galvanizing. Zinc-based alloy plating refers to all alloy plating containing zinc and one or more other metals, such as zinc-nickel, zinc-iron, and zinc-aluminum, as well as metal oxide plating such as silicon, titanium, aluminum, and chromium. This includes everything dispersed in the plating layer. Even in the case of having a plurality of plated layers, it is possible to apply the plated layer as long as the uppermost layer is the plated layer containing the above-mentioned zinc. Furthermore, it can be similarly applied to composite steel plates that are plated on one side or have a resin between them. [Example 1] Electrogalvanized steel sheet (zinc coating amount 20 g/m 2 ) was coated with (1) chromic anhydride 5 g/, (2) chromic anhydride 10 g/ (3) chromic anhydride 5 g/, phosphoric acid 5 g/ (4) Chromic anhydride 5g/, phosphoric acid 8g/ (5) chromic anhydride 5g/, phosphoric acid 30g/ (6) chromic anhydride 5g/, phosphoric acid 60g/ (7) chromic anhydride 5g/, phosphoric acid 80g/ (8) Chromic anhydride 10g/, phosphoric acid 0.5g/
(9) Chromic anhydride 10g/, phosphoric acid 1.3g/
(10) Chromic anhydride 10g/, phosphoric acid 2.6g/
(11) Chromic anhydride 10g/, phosphoric acid 50g/ (12) Chromic anhydride 10g/, phosphoric acid 130g/
(13) Chromic anhydride 10g/, phosphoric acid 140g/
(14) Chromic anhydride 5g/, acrylamide resin 10g/ (15) chromic anhydride 10g/, acrylamide resin 10g/ (16) chromic anhydride 5g/, phosphoric acid 5g/
, Acrylamide resin 10g/ (17) Chromic anhydride 5g/, Phosphoric acid 8g/
Performance evaluation of samples treated with a first layer forming treatment liquid containing 10 g/acrylamide resin, dried, treated with a second layer forming treatment liquid containing 2 g/ phosphoric acid, 3 g/colloidal silica, and 5 g/acrylamide resin, and dried. are shown in Table 1. In order to maintain corrosion resistance, the amounts of Cr and P in the first layer should be Cr+P≧5mg/m 2 , Cr/P=0.1~
It turns out that a range of 10 is good. [Example 2] Electrogalvanized steel sheet (zinc coating amount 20g/
m 2 ) to (18) chromic anhydride 5g/, colloidal silica 5g/ (19) chromic anhydride 5g/, colloidal silica 8g/ (20) chromic anhydride 5g/, colloidal silica 5g/, phosphoric acid 2.5g/ ( 21) Chromic anhydride 5g/, colloidal silica 2.5g/, phosphoric acid 5g/ (22) chromic anhydride 5g/, colloidal silica 5g/, phosphoric acid 26g/ (23) chromic anhydride 5g/, colloidal silica 36g/, Phosphoric acid 26g/ (24) Chromic anhydride 5g/, colloidal silica 36g/, phosphoric acid 40g/ (25) chromic anhydride 10g/, colloidal silica 0.5g/ (26) chromic anhydride 10g/, colloidal silica 0.5g/ , phosphoric acid 0.5g/ (27) chromic anhydride 10g/, colloidal silica 1.3g/, phosphoric acid 1.3g/ (28) chromic anhydride 10g/, colloidal silica 38g/, phosphoric acid 26g/ (29) chromic anhydride 10g/, Colloidal Silica 77g/, Phosphoric Acid 50g/ (30) Chromic Anhydride 10g/, Colloidal Silica 38g/, Phosphoric Acid 100g/ (31) Chromic Anhydride 10g/, Colloidal Silica 115g/, Phosphoric Acid 26g/ (32 ) Chromic anhydride 5g/, colloidal silica 5g/, acrylamide resin 10g/ (33) chromic anhydride 5g/, colloidal silica 8g/, acrylamide resin 10g/ (34) chromic anhydride 5g/, colloidal silica 2.5g/, phosphorus A sample treated with a first layer forming treatment solution containing 5 g of acid, 10 g of acrylamide resin, and dried, treated with a second layer forming solution containing 2 g of phosphoric acid, 3 g of colloidal silica, and 5 g of acrylamide resin, and dried. The performance evaluation is shown in Table 2. From this, in order to maintain corrosion resistance, Cr in the first layer,
The amount of Si and P is Cr+Si+P≧5mg/m 2 , Cr/(P+Si)=0.1~10
It can be seen that the range of is good. [Example 3] Electrogalvanized steel sheet (zinc coating amount 20g/
m2 ) chromic anhydride 40g/, phosphoric acid 26g/,
After being treated with a first layer forming treatment solution containing 77 g/colloidal silica and dried, (35) phosphoric acid 1 g/, acrylamide resin 0.5
g/ (36) Colloidal silica 1g/, acrylamide resin 0.5g/ (37) Phosphoric acid 1.3g/, acrylamide resin
Table 3 shows the performance of the sample treated and dried with the second layer forming treatment solution containing 0.5g/(38) colloidal silica 1.3g/, and acrylamide resin 0.5g/(39) acrylamide resin 1g/. From this, it can be seen that in order to ensure primary paint adhesion, secondary paint adhesion, and anti-fingerprint properties, it is necessary that (P+Si+organic resin)≧1mg/m 2 . [Example 4] After treating an electrogalvanized steel sheet (zinc coating amount: 20 g/m 2 ) with a first layer forming treatment solution containing 40 g of chromic anhydride, 26 g of phosphoric acid, and 77 g of colloidal silica, and drying, (40) Phosphoric acid 26g/, acrylamide resin 0.4
g/ (41) Phosphoric acid 26g/, Acrylamide resin 0.5
g/ (42) phosphoric acid 26g/, acrylamide resin 10
g/ (43) phosphoric acid 26g/, acrylamide resin
200g/ (44) Phosphoric acid 26g/, acrylamide resin
210g/ (45) Colloidal silica 26g/, acrylamide resin 0.4g/ (46) Colloidal silica 26g/, acrylamide resin 0.5g/ (47) Colloidal silica 26g/, acrylamide resin 10g/ (48) Colloidal silica 26g/, acrylamide resin 100g/ (49) Colloidal silica 26g/, Acrylamide resin 110g/ (50) Phosphoric acid 2.6g/, Colloidal silica 640
g/, acrylamide resin 10g/ (51) phosphoric acid 2.6g/, colloidal silica 2.3
g/, acrylamide resin 10g/ (52) phosphoric acid 2.6g/, colloidal silica 5
g/, acrylamide resin 10g/ (53) phosphoric acid 640g/, colloidal silica 5
g/, acrylamide resin 10g/ (54) phosphoric acid 2.3g/, colloidal silica 5
Table 4 shows the performance of the samples treated and dried with the second layer forming treatment solution containing 10 g/g/ of acrylamide resin. From this, in order to improve primary paint adhesion, secondary paint adhesion, and anti-fingerprint properties, when the second layer film contains Si and organic resin at the same time, organic resin/Si = 0.05 to 10 P. It can be seen that when containing both organic resin and organic resin at the same time, the range of organic resin/P = 0.05 to 20 is good, and the range where organic resin/(P+Si)≧0.05 holds between the amounts of Si, P, and organic resin is good. [Example 5] An electrogalvanized steel sheet (zinc coating amount: 20 g/m 2 ) was treated with a first layer forming treatment solution containing 40 g of chromic anhydride, 26 g of phosphoric acid, and 77 g of colloidal silica, and then dried. As second layer forming treatment liquid (55) phosphoric acid 40g/, colloidal silica 40g/
, acrylamide resin 20g/ (56) (55) with chromic anhydride 2.4g/(57) (55) with chromic anhydride 10.4g/(58) (55) with chromic anhydride 14.4 (59) (55) plus 20.8 g/ of chromic anhydride (60) (55) plus 26 g/ of chromic anhydride Shown in the table. This shows that if the amount of Cr in the second layer film is Cr/(P+Si+organic resin)≦0.20, the primary paint adhesion, secondary paint adhesion, and fingerprint resistance are all good.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
（発明の効果）
本発明は耐食性を目的とする第一層と、塗料密
着性及び耐指紋性を目的とする第二層とに機能を
分離させることにより、耐食性、塗料密着性、耐
指紋性の全てに優れた性能を確保したのである。
特に、第一層にCrとＰを同時に含むことにより、
従来より高い耐食性を持ち、また第二層にSi，
Ｐ、有機樹脂のうち少なくとも二つを含むことに
より、原理的に相矛盾する塗料一次密着性、塗料
二次密着性、耐指紋性のすべてに優れたクロメー
ト処理鋼板を提供する。[Table] (Effects of the invention) The present invention provides corrosion resistance, paint adhesion, This ensures excellent performance in all areas including fingerprint resistance.
In particular, by simultaneously containing Cr and P in the first layer,
It has higher corrosion resistance than before, and the second layer contains Si,
By containing at least two of P and an organic resin, a chromate-treated steel sheet is provided which is excellent in primary paint adhesion, secondary paint adhesion, and fingerprint resistance, which are contradictory in principle.
Claims (1)
一層として、Cr／Ｐ＝0.1〜10、Cr＋Ｐ≧５mg／
m2の範囲でCrおよびＰを含む第一層皮膜を有し、
その上にＰ，Siのうち少なくとも１種と有機樹脂
（水溶性または水分散性）を含有し、有機樹脂＋
Si＋Ｐ≧１mg／m2、有機樹脂／（Si＋Ｐ）≧0.05、
Siを含むときは有機樹脂／Si＝0.05〜10、Ｐを含
むときは有機樹脂／Ｐ＝0.05〜20の範囲にある第
二層皮膜を有することを特徴とするクロメート処
理鋼板。 ２ 亜鉛または亜鉛系合金めつき鋼板の表面に第
一層として、Cr／（Ｐ＋Si）＝0.1〜10、Cr＋Ｐ＋
Si≧５mg／m2の範囲でCr，ＰおよびSiを含む第一
層皮膜を有し、その上にＰ，Siのうち少なくとも
１種と有機樹脂（水溶性または水分散性）を含有
し、有機樹脂＋Si＋Ｐ≧１mg／m2、有機樹脂／
（Si＋Ｐ）≧0.05、Siを含むときは有機樹脂／Si＝
0.05〜10、Ｐを含むときは有機樹脂／Ｐ＝0.05〜
20の範囲にある第二層皮膜を有することを特徴と
するクロメート処理鋼板。 ３ 第一層皮膜中に水溶性または水分散性有機樹
脂を含有せしめたことを特徴とする特許請求の範
囲第１項または第２項記載のクロメート処理鋼
板。 ４ 第二層皮膜中にCr／（Ｐ＋Si＋有機樹脂）≦
0.2の範囲でCrを含有せしめたことを特徴とする
特許請求の範囲第１項、第２項または第３項のい
ずれかに記載のクロメート処理鋼板。[Claims] 1. Cr/P=0.1 to 10, Cr+P≧5mg/
having a first layer film containing Cr and P in the range of m2 ,
It contains at least one of P and Si and an organic resin (water-soluble or water-dispersible), and the organic resin +
Si+P≧1mg/m 2 , organic resin/(Si+P)≧0.05,
A chromate-treated steel sheet characterized by having a second layer film in which the organic resin/Si ratio is in the range of 0.05 to 10 when it contains Si, and the organic resin/P ratio is in the range of 0.05 to 20 when it contains P. 2. Cr/(P+Si)=0.1~10, Cr+P+ as the first layer on the surface of zinc or zinc-based alloy coated steel sheet.
It has a first layer film containing Cr, P and Si in the range of Si≧5mg/ m2 , and contains at least one of P and Si and an organic resin (water-soluble or water-dispersible) thereon, Organic resin + Si + P≧1mg/m 2 , organic resin/
(Si+P)≧0.05, when containing Si, organic resin/Si=
0.05~10, when containing P, organic resin/P=0.05~
A chromate-treated steel sheet characterized by having a second layer coating in the range of 20 to 20. 3. The chromate-treated steel sheet according to claim 1 or 2, characterized in that the first layer film contains a water-soluble or water-dispersible organic resin. 4 Cr/(P+Si+organic resin)≦ in the second layer film
Chromate-treated steel sheet according to any one of claims 1, 2, and 3, characterized in that the steel sheet contains Cr in a range of 0.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33275987A JPH01177378A (en) | 1987-12-30 | 1987-12-30 | Chromated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33275987A JPH01177378A (en) | 1987-12-30 | 1987-12-30 | Chromated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01177378A JPH01177378A (en) | 1989-07-13 |
| JPH0541707B2 true JPH0541707B2 (en) | 1993-06-24 |
Family
ID=18258527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33275987A Granted JPH01177378A (en) | 1987-12-30 | 1987-12-30 | Chromated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01177378A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA3131809A1 (en) * | 2019-02-28 | 2020-09-03 | Atotech Deutschland Gmbh | Aqueous post treatment composition and method for corrosion protection |
-
1987
- 1987-12-30 JP JP33275987A patent/JPH01177378A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01177378A (en) | 1989-07-13 |
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