JPH11124686A - Chromate treated zinc base plated steel sheet having excellent black denaturation resistance, corrosion resistance, coating material adhesion property and lubricity and its production - Google Patents

Chromate treated zinc base plated steel sheet having excellent black denaturation resistance, corrosion resistance, coating material adhesion property and lubricity and its production

Info

Publication number
JPH11124686A
JPH11124686A JP10237993A JP23799398A JPH11124686A JP H11124686 A JPH11124686 A JP H11124686A JP 10237993 A JP10237993 A JP 10237993A JP 23799398 A JP23799398 A JP 23799398A JP H11124686 A JPH11124686 A JP H11124686A
Authority
JP
Japan
Prior art keywords
ion
chromium ion
surfactant
component
steel sheet
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
Application number
JP10237993A
Other languages
Japanese (ja)
Inventor
Tatsuya Miyoshi
達也 三好
Takahiro Kubota
隆広 窪田
Masaru Sagiyama
勝 鷺山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Engineering Corp
Original Assignee
NKK Corp
Nippon Kokan Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NKK Corp, Nippon Kokan Ltd filed Critical NKK Corp
Priority to JP10237993A priority Critical patent/JPH11124686A/en
Publication of JPH11124686A publication Critical patent/JPH11124686A/en
Pending legal-status Critical Current

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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—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
    • C23C22/30—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 trivalent chromium
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer

Abstract

PROBLEM TO BE SOLVED: To impart excellent white rust resistance, black denaturation resistance and coating material adhesion property by treating steel sheet surfaces by using an aq. resin-contg. chromate treating liquid contg. inorg. components of specific compsns. and resin emulsion components and specifying a pH value and Cr coating weight. SOLUTION: The inorg. components are of 1/10-3/10 in the weight ratio of tervalant Cr ions to the total of hexavalent and tervalent Cr ions and are of 1.0-3.0, 0.05-0.5, 0.05-0.5 respectively in the ratios of the respective ions of nitric acid, phosphoric acid and Co to the total Cr ions. The resin emulsion components are the resin emulsion of 10/100-20/100 in the weight ratio of the solid contents of an aq. resin emulsion surfactant of an acrylic copolymer subjected to emulsification polymn. in the presence of a nonionic reaction type surfactant having a C=C bond in a hydrophobic group and having a polyethylene oxide group as a hydrophilic group and an acrylic copolymer. The pH value of the chromate treating liquid is <=3 and the Cr coating weight 5-50 mg/m<3> .

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明が属する技術分野】本発明は、所謂フラッシュ処
理のような前処理を施すことなく一工程処理により製造
できる、耐黒変性、耐食性（耐白錆性）、塗料密着性お
よび潤滑性に優れたクロメート処理亜鉛系めっき鋼板と
その製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in blackening resistance, corrosion resistance (white rust resistance), paint adhesion and lubricity, which can be produced by one-step processing without performing pretreatment such as so-called flash processing. And a method for producing the same.

【０００２】[0002]

【従来の技術】鋼板の亜鉛めっきによる犠牲防食は最も
効果的で且つ経済的であるため、現在、例えば日本の年
間粗鋼生産量（約１億トン）の約１０％に当たる１００
０万トンが亜鉛系めっき鋼板として生産され、建材、自
動車、家電等の広い分野で使用されている。亜鉛による
犠牲防食機構は、亜鉛と鉄という２つの金属が接触した
状況下で電池が形成され、より卑な金属である亜鉛が陽
極となり、鉄を陰極化して鉄単独の場合の局部電池形成
による陽極溶解を抑止し、鉄の腐食を防止するものであ
る。このような防錆作用は鉄と接触している亜鉛が消失
した時点で終わるため、その作用効果を長期間持続させ
るためには亜鉛層の腐食を抑制することが必要であり、
その対策としてめっき後にクロメート処理を施すことが
広く行われている。BACKGROUND OF THE INVENTION Since sacrificial corrosion protection by galvanizing steel sheets is the most effective and economical, at present, for example, about 10% of Japan's annual crude steel production (about 100 million tons) is 100%.
100,000 tons are produced as galvanized steel sheets and are used in a wide range of fields such as building materials, automobiles and home appliances. The sacrificial corrosion protection mechanism using zinc is based on the formation of a battery in a situation where two metals, zinc and iron, are in contact with each other. It suppresses anode dissolution and prevents corrosion of iron. Since such rust prevention action ends when zinc in contact with iron disappears, it is necessary to suppress corrosion of the zinc layer in order to maintain the action effect for a long time,
As a countermeasure, chromate treatment is widely performed after plating.

【０００３】ところが、亜鉛めっき鋼板をクロメート処
理すると耐食性（耐白錆性）は顕著に改善されるもの
の、逆に保管中や輸送中、さらには使用後において鋼板
の外観性を大きく損なう黒変現象が発生するという問題
がある。[0003] However, when a galvanized steel sheet is subjected to chromate treatment, the corrosion resistance (white rust resistance) is remarkably improved, but on the contrary, the blackening phenomenon which greatly impairs the appearance of the steel sheet during storage, transportation and after use. There is a problem that occurs.

【０００４】このようなクロメート処理後の黒変を防止
する方法として、特開昭５９−１７７３８１号公報に示
されるようなＮｉイオンまたはＣｏイオン含有水溶液に
よるフラッシュ処理（化学的に極微量の金属を析出させ
る処理）が有効であることが知られている。この特開昭
５９−１７７３８１号公報に開示された方法は、亜鉛ま
たは亜鉛合金めっき鋼板のクロメート処理に先立ち、ｐ
Ｈが１〜４または１１〜１３．５で、且つＮｉイオン、
Ｃｏイオンの１種または２種を含む水溶液で鋼板の表面
をフラッシュ処理し、この処理によって前記金属イオン
を金属または酸化物の形で鋼板表面に析出させた後、水
洗し、しかる後クロメート皮膜を形成させるものであ
る。[0004] As a method of preventing such blackening after the chromate treatment, a flash treatment with an aqueous solution containing Ni ions or Co ions as disclosed in JP-A-59-177381 (a method of removing a trace amount of metal chemically) is disclosed. (Precipitation treatment) is known to be effective. The method disclosed in Japanese Unexamined Patent Publication No. Sho 59-177381 discloses a method in which p
H is 1-4 or 11-13.5, and Ni ion;
The surface of the steel sheet is subjected to flash treatment with an aqueous solution containing one or two types of Co ions, and the metal ions are precipitated on the surface of the steel sheet in the form of a metal or an oxide by this treatment, washed with water, and then a chromate film is formed. It is formed.

【０００５】しかしながら、このようなフラッシュ処理
をクロメート処理に先立って実施した場合、黒変の発生
は抑制されるが白錆はむしろ発生し易くなり、クロメー
ト処理本来の目的が失われてしまうという問題がある。
これは、フラッシュ処理が、めっきされた金属亜鉛に対
してより貴な金属であるＮｉやＣｏをめっき表面に金属
状態で置換析出させる処理であることから、亜鉛とこれ
らの貴な金属との間で局部電池が形成されるためである
と考えられる。However, when such a flash treatment is performed prior to the chromate treatment, blackening is suppressed, but white rust is more likely to occur, and the original purpose of the chromate treatment is lost. There is.
This is because the flash treatment is a treatment in which Ni and Co, which are more noble metals with respect to the plated metal zinc, are substituted and precipitated on the plating surface in a metal state. It is considered that this is because a local battery is formed in this case.

【０００６】このような問題をフラッシュ処理を行うこ
となく一工程処理により解決するための方法として、特
開平５−３３１６５９号公報や特開平７−５４１５６号
公報には、特定のアニオンやカチオンを適量配合したク
ロメート処理液で処理する方法が開示されており、この
方法によれば耐白錆性と耐黒変性をバランスよく向上で
きるとしている。しかし、これらの方法では十分に満足
できる耐食性が得られない。As a method for solving such a problem by one-step processing without performing flash processing, JP-A-5-331659 and JP-A-7-54156 disclose an appropriate amount of a specific anion or cation. A method of treating with a blended chromate treatment liquid is disclosed, and according to this method, white rust resistance and blackening resistance can be improved in a well-balanced manner. However, these methods do not provide sufficiently satisfactory corrosion resistance.

【０００７】一方、亜鉛系めっき鋼板を基材とした従来
の表面処理鋼板としては、上記のような一時的な防錆を
目的としたクロメート処理鋼板の他に、さらに高耐食性
を付与した表面処理鋼板があり、従来、このような表面
処理鋼板としては亜鉛めっき表面にクロメート処理を施
した後に、さらに有機樹脂皮膜を被覆するという二工程
処理を経て製造されるものが主流となってきたが、最近
では、表面処理の省プロセス化という観点から、一工程
処理（樹脂含有クロメート処理）により高耐食性の表面
処理鋼板を得るための技術も種々提案される。On the other hand, as conventional surface-treated steel sheets based on galvanized steel sheets, there are not only the above-mentioned chromate-treated steel sheets for the purpose of temporary rust prevention, but also surface treatments further imparted with high corrosion resistance. There is a steel sheet, and conventionally, as such a surface-treated steel sheet, after being subjected to a chromate treatment on a galvanized surface, those manufactured through a two-step treatment of further coating an organic resin film have become mainstream, Recently, from the viewpoint of saving the surface treatment, various techniques for obtaining a surface-treated steel sheet having high corrosion resistance by one-step treatment (resin-containing chromate treatment) have been proposed.

【０００８】このような一工程処理に関する技術とし
て、例えば、(1)特公平７−６０７０号公報、(2)特開平
３−２１９０８６号公報、(3)特開平５−２７９８６７
号公報、(4)特開平６−１９２８５０号公報、(5)特開平
６−９３４６１号公報、(6)特開平９−３６５７号公
報、(7)特開平７−１１４５３号公報、(8)特開平５−２
８７５４８号公報等が提案されている。Techniques relating to such a one-step process include, for example, (1) Japanese Patent Publication No. 7-6070, (2) Japanese Patent Application Laid-Open No. Hei 3-219086, and (3) Japanese Patent Application Laid-Open No. Hei 5-27967.
JP, JP-A-6-192850, (5) JP-A-6-93461, (6) JP-A-9-3657, (7) JP-A-7-11453, (8) JP-A-5-2
No. 87548 has been proposed.

【０００９】[0009]

【発明が解決しようとする課題】これらの従来技術のう
ち(1)〜(7)のものは、クロメート成分と樹脂成分とノニ
オン系界面活性剤を主成分とした樹脂含有水性クロメー
ト処理組成物に関するものであるが、このようなクロメ
ート処理組成物による処理によって製造された表面処理
亜鉛系めっき鋼板は耐白錆性や耐指紋性には優れるもの
の、耐黒変性は全く不十分なものであり、また塗装性も
劣ったものとなる。Among these prior arts, (1) to (7) relate to a resin-containing aqueous chromate treatment composition containing a chromate component, a resin component and a nonionic surfactant as main components. Although, the surface-treated galvanized steel sheet manufactured by the treatment with such a chromate treatment composition is excellent in white rust resistance and fingerprint resistance, but blackening resistance is completely insufficient, Also, the paintability is poor.

【００１０】また、(8)の従来技術は、クロメート成分
とアニオン系乳化剤を用いて重合された水性樹脂および
水溶性高分子ポリオールとを主成分とするクロメート処
理組成物に関するものであるが、この組成物は実質的に
ノニオン系乳化剤を含まないためにクロム酸の酸化力に
対するエマルジョンの安定性が悪く、このためポットラ
イフが不十分であり、実用性に劣る問題がある。また、
この組成物により形成されたクロメート皮膜は厳しい条
件下での耐黒変性に劣る欠点があり、さらに組成物中に
含まれる高分子ポリオールは塗装性を劣化させる原因と
なる。以上のように、従来技術では一工程処理により耐
白錆性、耐黒変性および塗装密着性のいずれにも優れた
表面処理亜鉛系めっき鋼板を工業的に安定して製造する
ことは難しかった。The prior art (8) relates to a chromate treatment composition containing, as main components, an aqueous resin and a water-soluble polymer polyol polymerized using a chromate component and an anionic emulsifier. Since the composition does not substantially contain a nonionic emulsifier, the stability of the emulsion to the oxidizing power of chromic acid is poor, so that the pot life is insufficient and there is a problem of poor practicality. Also,
The chromate film formed by this composition has a drawback of poor blackening resistance under severe conditions, and the high molecular polyol contained in the composition causes deterioration of coating properties. As described above, according to the conventional technology, it is difficult to industrially stably produce a surface-treated galvanized steel sheet which is excellent in all of white rust resistance, blackening resistance and paint adhesion by one-step treatment.

【００１１】したがって本発明の目的は、このような従
来技術の課題を解決し、一工程処理により工業的に安定
して製造でき、しかも耐白錆性、耐黒変性および塗装密
着性のいずれにも優れた表面処理亜鉛系めっき鋼板とそ
の製造方法を提供することにある。Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, to achieve industrially stable production by one-step treatment, and to improve white rust resistance, black discoloration resistance and paint adhesion. Another object of the present invention is to provide an excellent surface-treated galvanized steel sheet and a method for producing the same.

【００１２】[0012]

【課題を解決するための手段】本発明者らは、上記の課
題を解決するための手段について鋭意検討を重ねた結
果、特定組成の無機成分と樹脂エマルジョン成分とを含
む水系樹脂含有クロメート処理液を用いて亜鉛系めっき
鋼板の表面を処理することにより、耐白錆性、耐黒変
性、塗装密着性および潤滑性のいずれにも優れた表面処
理亜鉛系めっき鋼板を工業的に安定して製造できること
を新たに見い出した。本発明はこのような知見に基づき
なされたもので、その特徴は以下の通りである。Means for Solving the Problems The present inventors have made intensive studies on means for solving the above-mentioned problems, and as a result, have found that a chromate treatment solution containing an aqueous resin containing an inorganic component having a specific composition and a resin emulsion component. The surface of galvanized steel sheet is treated by using to produce industrially stable galvanized steel sheet with excellent white rust resistance, blackening resistance, paint adhesion and lubricity. I found something new. The present invention has been made based on such findings, and the features thereof are as follows.

【００１３】[1] 亜鉛系めっき鋼板の表面に、下記の成
分〔１〕および成分〔２〕を含有し、且つ下記成分
〔１〕に含まれる６価クロムイオンおよび３価クロムイ
オンと、下記成分〔２〕に含まれる界面活性剤〔Ａ〕お
よびアクリル系共重合体〔Ｂ〕の固形分での重量比
［（〔Ａ〕＋〔Ｂ〕）／（６価クロムイオン＋３価クロ
ムイオン）］が２０／１〜５０／１で、且つｐＨ３以下
の水系樹脂含有クロメート処理液を塗布して形成され
た、金属クロム換算のクロム付着量が５〜５０ｍｇ／ｍ
2のクロメート皮膜を有することを特徴とする、耐黒変
性、耐食性、塗料密着性および潤滑性に優れたクロメー
ト処理亜鉛系めっき鋼板。 成分〔１〕：６価クロムイオンと３価クロムイオンを
［３価クロムイオン／（６価クロムイオン＋３価クロム
イオン）］の重量比で１／１０〜３／１０の割合で含
み、さらに、硝酸イオン、リン酸イオンおよびコバルト
イオンを全クロムイオン（６価クロムイオン＋３価クロ
ムイオン）に対するモル比で下記の割合で含む無機成分 硝酸イオン／全クロムイオン：１．０〜３．０ リン酸イオン／全クロムイオン：０．０５〜０．５ コバルトイオン／全クロムイオン：０．０５〜０．５ 成分〔２〕：疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有
し、且つ親水基としてポリエチレンオキサイド基を有す
る非イオン性反応型界面活性剤が固形分の重量％で５０
％以上含まれる界面活性剤〔Ａ〕の存在下で乳化重合さ
れたアクリル系共重合体〔Ｂ〕の水系樹脂エマルジョン
であって、界面活性剤〔Ａ〕とアクリル系共重合体
〔Ｂ〕の固形分での重量比〔Ａ〕／〔Ｂ〕が１０／１０
０〜２０／１００である樹脂エマルジョン[1] The surface of a galvanized steel sheet contains the following component [1] and component [2], and contains hexavalent chromium ion and trivalent chromium ion contained in the following component [1]; Weight ratio [([A] + [B]) / (hexavalent chromium ion + trivalent chromium ion) of the surfactant [A] and the acrylic copolymer [B] contained in the component [2] at the solid content. Is from 20/1 to 50/1, and has a chromium equivalent of 5 to 50 mg / m in terms of chromium metal formed by applying an aqueous resin-containing chromate treatment solution having a pH of 3 or less.
A chromate-treated galvanized steel sheet that is excellent in blackening resistance, corrosion resistance, paint adhesion and lubricity, characterized by having a chromate film of 2 . Component [1]: contains hexavalent chromium ion and trivalent chromium ion in a weight ratio of [trivalent chromium ion / (hexavalent chromium ion + trivalent chromium ion)] of 1/10 to 3/10; Inorganic component containing nitrate ion, phosphate ion and cobalt ion in the following ratio with respect to total chromium ion (hexavalent chromium ion + trivalent chromium ion) in the following ratio: nitrate ion / total chromium ion: 1.0 to 3.0 phosphoric acid Ion / total chromium ion: 0.05 to 0.5 cobalt ion / total chromium ion: 0.05 to 0.5 Component [2]: having a carbon-carbon double bond (C = C) in a hydrophobic group, The nonionic reactive surfactant having a polyethylene oxide group as a hydrophilic group contains 50% by weight of the solid content.
% Of an acrylic copolymer [B] emulsion-polymerized in the presence of a surfactant [A] contained in an amount of at least 10% by weight of the surfactant [A] and the acrylic copolymer [B]. The weight ratio [A] / [B] in solid content is 10/10
0-20 / 100 resin emulsion

【００１４】[2] 上記[1]のクロメート処理亜鉛系めっ
き鋼板において、成分〔２〕が、疎水基中に炭素間二重
結合（Ｃ＝Ｃ）を有し、且つ親水基としてポリエチレン
オキサイド基を有する非イオン性反応型界面活性剤から
なる界面活性剤〔Ａ〕の存在下で乳化重合されたアクリ
ル系共重合体〔Ｂ〕の水系樹脂エマルジョンであって、
界面活性剤〔Ａ〕とアクリル系共重合体〔Ｂ〕の固形分
での重量比〔Ａ〕／〔Ｂ〕が１０／１００〜２０／１０
０である樹脂エマルジョンであることを特徴とする耐黒
変性、耐食性、塗料密着性および潤滑性に優れたクロメ
ート処理亜鉛系めっき鋼板。[2] In the chromated zinc-coated steel sheet of the above [1], the component [2] has a carbon-carbon double bond (C = C) in a hydrophobic group and a polyethylene oxide group as a hydrophilic group. An aqueous resin emulsion of an acrylic copolymer [B] emulsion-polymerized in the presence of a surfactant [A] comprising a nonionic reactive surfactant having
The weight ratio [A] / [B] of the surfactant [A] and the acrylic copolymer [B] at the solid content is from 10/100 to 20/10.
A chromate-treated galvanized steel sheet excellent in blackening resistance, corrosion resistance, paint adhesion and lubricity, characterized by being a resin emulsion of 0.

【００１５】[3] 亜鉛系めっき鋼板の表面に、下記の成
分〔１〕および成分〔２〕を含有し、且つ下記成分
〔１〕に含まれる６価クロムイオンおよび３価クロムイ
オンと、下記成分〔２〕に含まれる界面活性剤〔Ａ〕お
よびアクリル系共重合体〔Ｂ〕の固形分での重量比
［（〔Ａ〕＋〔Ｂ〕）／（６価クロムイオン＋３価クロ
ムイオン）］が２０／１〜５０／１で、且つｐＨ３以下
の水系樹脂含有クロメート処理液を塗布して形成され
た、金属クロム換算のクロム付着量が５〜５０ｍｇ／ｍ
2のクロメート皮膜を有することを特徴とする、耐黒変
性、耐食性、塗料密着性および潤滑性に優れたクロメー
ト処理亜鉛系めっき鋼板。 成分〔１〕：６価クロムイオンと３価クロムイオンを
［３価クロムイオン／（６価クロムイオン＋３価クロム
イオン）］の重量比で１／１０〜３／１０の割合で含
み、さらに、硝酸イオン、リン酸イオンおよびコバルト
イオンを全クロムイオン（６価クロムイオン＋３価クロ
ムイオン）に対するモル比で下記の割合で含む無機成分 硝酸イオン／全クロムイオン：１．０〜３．０ リン酸イオン／全クロムイオン：０．０５〜０．５ コバルトイオン／全クロムイオン：０．０５〜０．５ 成分〔２〕：疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有
し、且つ親水基としてポリエチレンオキサイド基を有す
る非イオン性反応型界面活性剤〔ａ1〕と疎水基中に炭
素間二重結合（Ｃ＝Ｃ）を有し、且つ親水基としてポリ
エチレンオキサイド基を有する非イオン−アニオン性複
合反応型界面活性剤〔ａ2〕とからなり、非イオン性反
応型界面活性剤〔ａ1〕と非イオン−アニオン性複合反
応型界面活性剤〔ａ2〕の固形分の重量比〔ａ1〕／〔ａ
2〕が１／２以上である界面活性剤〔Ａ〕の存在下で乳
化重合されたアクリル系共重合体〔Ｂ〕の水系樹脂エマ
ルジョンであって、界面活性剤〔Ａ〕とアクリル系共重
合体〔Ｂ〕の固形分での重量比〔Ａ〕／〔Ｂ〕が１０／
１００〜２０／１００である樹脂エマルジョン[3] The surface of a galvanized steel sheet contains the following components [1] and [2], and contains hexavalent chromium ions and trivalent chromium ions contained in the following component [1]: Weight ratio [([A] + [B]) / (hexavalent chromium ion + trivalent chromium ion) of the surfactant [A] and the acrylic copolymer [B] contained in the component [2] at the solid content. Is from 20/1 to 50/1, and has a chromium equivalent of 5 to 50 mg / m in terms of chromium metal formed by applying an aqueous resin-containing chromate treatment solution having a pH of 3 or less.
A chromate-treated galvanized steel sheet that is excellent in blackening resistance, corrosion resistance, paint adhesion and lubricity, characterized by having a chromate film of 2 . Component [1]: contains hexavalent chromium ion and trivalent chromium ion in a weight ratio of [trivalent chromium ion / (hexavalent chromium ion + trivalent chromium ion)] of 1/10 to 3/10; Inorganic component containing nitrate ion, phosphate ion and cobalt ion in the following ratio with respect to total chromium ion (hexavalent chromium ion + trivalent chromium ion) in the following ratio: nitrate ion / total chromium ion: 1.0 to 3.0 phosphoric acid Ion / total chromium ion: 0.05 to 0.5 cobalt ion / total chromium ion: 0.05 to 0.5 Component [2]: having a carbon-carbon double bond (C = C) in a hydrophobic group, And a nonionic reactive surfactant [a 1 ] having a polyethylene oxide group as a hydrophilic group and a non-ionic surfactant having a carbon-carbon double bond (C = C) in a hydrophobic group and having a polyethylene oxide group as a hydrophilic group. I On - made from anionic complex reactive surfactant and [a 2], the non-ionic reactive surfactant [a 1] and nonionic - anionic complex reactive surfactant of solids [a 2] Weight ratio [a 1 ] / [a
2 ] is an aqueous resin emulsion of an acrylic copolymer [B] emulsion-polymerized in the presence of a surfactant [A] in which the amount of the surfactant [A] is at least 界面. The weight ratio [A] / [B] at the solid content of the combined [B] is 10 /
100-20 / 100 resin emulsion

【００１６】[4] 亜鉛系めっき鋼板の表面に、下記の成
分〔１〕および成分〔２〕を含有し、且つ下記成分
〔１〕に含まれる６価クロムイオンおよび３価クロムイ
オンと、下記成分〔２〕に含まれる界面活性剤〔Ａ〕お
よびアクリル系共重合体〔Ｂ〕の固形分での重量比
［（〔Ａ〕＋〔Ｂ〕）／（６価クロムイオン＋３価クロ
ムイオン）］が２０／１〜５０／１で、且つｐＨ３以下
の水系樹脂含有クロメート処理液を、金属クロム換算の
クロム付着量が５〜５０ｍｇ／ｍ2となるよう塗布した
後、５０〜２００℃で乾燥することを特徴とする、耐黒
変性、耐食性、塗料密着性および潤滑性に優れたクロメ
ート処理亜鉛系めっき鋼板の製造方法。 成分〔１〕：６価クロムイオンと３価クロムイオンを
［３価クロムイオン／（６価クロムイオン＋３価クロム
イオン）］の重量比で１／１０〜３／１０の割合で含
み、さらに、硝酸イオン、リン酸イオンおよびコバルト
イオンを全クロムイオン（６価クロムイオン＋３価クロ
ムイオン）に対するモル比で下記の割合で含む無機成分 硝酸イオン／全クロムイオン：１．０〜３．０ リン酸イオン／全クロムイオン：０．０５〜０．５ コバルトイオン／全クロムイオン：０．０５〜０．５ 成分〔２〕：疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有
し、且つ親水基としてポリエチレンオキサイド基を有す
る非イオン性反応型界面活性剤が固形分の重量％で５０
％以上含まれる界面活性剤〔Ａ〕の存在下で乳化重合さ
れたアクリル系共重合体〔Ｂ〕の水系樹脂エマルジョン
であって、界面活性剤〔Ａ〕とアクリル系共重合体
〔Ｂ〕の固形分での重量比〔Ａ〕／〔Ｂ〕が１０／１０
０〜２０／１００である樹脂エマルジョン[4] The surface of a galvanized steel sheet contains the following components [1] and [2], and contains hexavalent chromium ions and trivalent chromium ions contained in the following component [1]: Weight ratio [([A] + [B]) / (hexavalent chromium ion + trivalent chromium ion) of the surfactant [A] and the acrylic copolymer [B] contained in the component [2] at the solid content. ] Is applied at a pH of 20/1 to 50/1 and an aqueous resin-containing chromate treatment solution having a pH of 3 or less so that the chromium equivalent in terms of chromium metal becomes 5 to 50 mg / m 2, and then dried at 50 to 200 ° C. A method for producing a chromate-treated galvanized steel sheet having excellent blackening resistance, corrosion resistance, paint adhesion, and lubricity. Component [1]: contains hexavalent chromium ion and trivalent chromium ion in a weight ratio of [trivalent chromium ion / (hexavalent chromium ion + trivalent chromium ion)] of 1/10 to 3/10; Inorganic component containing nitrate ion, phosphate ion and cobalt ion in the following ratio with respect to total chromium ion (hexavalent chromium ion + trivalent chromium ion) in the following ratio: nitrate ion / total chromium ion: 1.0 to 3.0 phosphoric acid Ion / total chromium ion: 0.05 to 0.5 cobalt ion / total chromium ion: 0.05 to 0.5 Component [2]: having a carbon-carbon double bond (C = C) in a hydrophobic group, The nonionic reactive surfactant having a polyethylene oxide group as a hydrophilic group contains 50% by weight of the solid content.
% Of an acrylic copolymer [B] emulsion-polymerized in the presence of a surfactant [A] contained in an amount of at least 10% by weight of the surfactant [A] and the acrylic copolymer [B]. The weight ratio [A] / [B] in solid content is 10/10
0-20 / 100 resin emulsion

【００１７】[5] 上記[4]の製造方法において、成分
〔２〕が、疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有
し、且つ親水基としてポリエチレンオキサイド基を有す
る非イオン性反応型界面活性剤からなる界面活性剤
〔Ａ〕の存在下で乳化重合されたアクリル系共重合体
〔Ｂ〕の水系樹脂エマルジョンであって、界面活性剤
〔Ａ〕とアクリル系共重合体〔Ｂ〕の固形分での重量比
〔Ａ〕／〔Ｂ〕が１０／１００〜２０／１００である樹
脂エマルジョンであることを特徴とする耐黒変性、耐食
性、塗料密着性および潤滑性に優れたクロメート処理亜
鉛系めっき鋼板の製造方法。[5] In the method of the above-mentioned [4], the component [2] is a non-ionic compound having a carbon-carbon double bond (C = C) in a hydrophobic group and a polyethylene oxide group as a hydrophilic group. An aqueous resin emulsion of an acrylic copolymer [B] emulsion-polymerized in the presence of a surfactant [A] comprising a surfactant [A], comprising a surfactant [A] and an acrylic copolymer It is a resin emulsion having a weight ratio [A] / [B] in solid content of [B] of 10/100 to 20/100, and is excellent in blackening resistance, corrosion resistance, paint adhesion and lubricity. Method for producing a chromate-treated galvanized steel sheet.

【００１８】[6] 亜鉛系めっき鋼板の表面に、下記の成
分〔１〕および成分〔２〕を含有し、且つ下記成分
〔１〕に含まれる６価クロムイオンおよび３価クロムイ
オンと、下記成分〔２〕に含まれる界面活性剤〔Ａ〕お
よびアクリル系共重合体〔Ｂ〕の固形分での重量比
［（〔Ａ〕＋〔Ｂ〕）／（６価クロムイオン＋３価クロ
ムイオン）］が２０／１〜５０／１で、且つｐＨ３以下
の水系樹脂含有クロメート処理液を、金属クロム換算の
クロム付着量が５〜５０ｍｇ／ｍ2となるよう塗布した
後、５０〜２００℃で乾燥することを特徴とする、耐黒
変性、耐食性、塗料密着性および潤滑性に優れたクロメ
ート処理亜鉛系めっき鋼板の製造方法。 成分〔１〕：６価クロムイオンと３価クロムイオンを
［３価クロムイオン／（６価クロムイオン＋３価クロム
イオン）］の重量比で１／１０〜３／１０の割合で含
み、さらに、硝酸イオン、リン酸イオンおよびコバルト
イオンを全クロムイオン（６価クロムイオン＋３価クロ
ムイオン）に対するモル比で下記の割合で含む無機成分 硝酸イオン／全クロムイオン：１．０〜３．０ リン酸イオン／全クロムイオン：０．０５〜０．５ コバルトイオン／全クロムイオン：０．０５〜０．５ 成分〔２〕：疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有
し、且つ親水基としてポリエチレンオキサイド基を有す
る非イオン性反応型界面活性剤〔ａ1〕と疎水基中に炭
素間二重結合（Ｃ＝Ｃ）を有し、且つ親水基としてポリ
エチレンオキサイド基を有する非イオン−アニオン性複
合反応型界面活性剤〔ａ2〕とからなり、非イオン性反
応型界面活性剤〔ａ1〕と非イオン−アニオン性複合反
応型界面活性剤〔ａ2〕の固形分の重量比〔ａ1〕／〔ａ
2〕が１／２以上である界面活性剤〔Ａ〕の存在下で乳
化重合されたアクリル系共重合体〔Ｂ〕の水系樹脂エマ
ルジョンであって、界面活性剤〔Ａ〕とアクリル系共重
合体〔Ｂ〕の固形分での重量比〔Ａ〕／〔Ｂ〕が１０／
１００〜２０／１００である樹脂エマルジョン[6] The surface of a galvanized steel sheet contains the following components [1] and [2], and contains hexavalent chromium ions and trivalent chromium ions contained in the following component [1]: Weight ratio [([A] + [B]) / (hexavalent chromium ion + trivalent chromium ion) of the surfactant [A] and the acrylic copolymer [B] contained in the component [2] at the solid content. ] Is applied at a pH of 20/1 to 50/1 and an aqueous resin-containing chromate treatment solution having a pH of 3 or less so that the chromium equivalent in terms of chromium metal becomes 5 to 50 mg / m 2, and then dried at 50 to 200 ° C. A method for producing a chromate-treated galvanized steel sheet having excellent blackening resistance, corrosion resistance, paint adhesion, and lubricity. Component [1]: contains hexavalent chromium ion and trivalent chromium ion in a weight ratio of [trivalent chromium ion / (hexavalent chromium ion + trivalent chromium ion)] of 1/10 to 3/10; Inorganic component containing nitrate ion, phosphate ion and cobalt ion in the following ratio with respect to total chromium ion (hexavalent chromium ion + trivalent chromium ion) in the following ratio: nitrate ion / total chromium ion: 1.0 to 3.0 phosphoric acid Ion / total chromium ion: 0.05 to 0.5 cobalt ion / total chromium ion: 0.05 to 0.5 Component [2]: having a carbon-carbon double bond (C = C) in a hydrophobic group, And a nonionic reactive surfactant [a 1 ] having a polyethylene oxide group as a hydrophilic group and a non-ionic surfactant having a carbon-carbon double bond (C = C) in a hydrophobic group and having a polyethylene oxide group as a hydrophilic group. I On - made from anionic complex reactive surfactant and [a 2], the non-ionic reactive surfactant [a 1] and nonionic - anionic complex reactive surfactant of solids [a 2] Weight ratio [a 1 ] / [a
2 ] is an aqueous resin emulsion of an acrylic copolymer [B] emulsion-polymerized in the presence of a surfactant [A] in which the amount of the surfactant [A] is at least 界面. The weight ratio [A] / [B] at the solid content of the combined [B] is 10 /
100-20 / 100 resin emulsion

【００１９】[0019]

【発明の実施の形態】以下、本発明の詳細をその限定理
由とともに説明する。本発明の表面処理亜鉛系めっき鋼
板は、亜鉛系めっき鋼板の表面に、無機成分である下記
成分〔１〕と樹脂エマルジョン成分である下記成分
〔２〕を所定の割合で含有する水系樹脂含有クロメート
処理組成物（処理液）を塗布して形成されたクロメート
皮膜を有する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below together with the reasons for limiting the same. The surface-treated galvanized steel sheet of the present invention is a water-based resin-containing chromate containing the following components [1] as an inorganic component and the following component [2] as a resin emulsion component at a predetermined ratio on the surface of the galvanized steel sheet. It has a chromate film formed by applying a treatment composition (treatment solution).

【００２０】まず、無機成分である成分〔１〕について
説明すると、この無機成分は６価クロムイオンおよび３
価クロムイオンとを含み、さらに硝酸イオン、リン酸イ
オンおよびコバルトイオンを含む。６価クロムイオンと
３価クロムイオンの割合は、［３価クロムイオン／（６
価クロムイオン＋３価クロムイオン）］の重量比で１／
１０〜３／１０とする。この重量比が１／１０未満では
クロメート皮膜の骨格を担う３価クロム成分が少ないた
めにクロムが溶出しやすく、長期間にわたる耐食性の低
下や環境汚染を招き、また耐黒変性も劣化するため好ま
しくない。一方、重量比が３／１０を超えると、６価ク
ロムイオンが少ないため耐食性が不十分となり、また処
理液安定性も低下するため好ましくない。First, the component [1], which is an inorganic component, will be described.
Valent chromium ions, and further includes nitrate ions, phosphate ions and cobalt ions. The ratio of hexavalent chromium ion to trivalent chromium ion is [trivalent chromium ion / (6
(Chromium ion + trivalent chromium ion)]
10/3/10. When the weight ratio is less than 1/10, chromium is easily eluted due to a small amount of trivalent chromium component serving as a skeleton of the chromate film, leading to deterioration of corrosion resistance and environmental pollution over a long period of time, and deterioration of blackening resistance. Absent. On the other hand, if the weight ratio exceeds 3/10, the corrosion resistance becomes insufficient due to a small amount of hexavalent chromium ions, and the stability of the processing solution is undesirably reduced.

【００２１】また、硝酸イオン、リン酸イオンおよびコ
バルトイオンの配合比は、全クロムイオン（６価クロム
イオン＋３価クロムイオン）対するモル比で下記の割合
とする。 硝酸イオン／全クロムイオン：１．０〜３．０ リン酸イオン／全クロムイオン：０．０５〜０．５ コバルトイオン／全クロムイオン：０．０５〜０．５The mixing ratio of the nitrate ion, the phosphate ion and the cobalt ion is as follows in terms of molar ratio to all chromium ions (hexavalent chromium ion + trivalent chromium ion). Nitrate ion / total chromium ion: 1.0 to 3.0 Phosphate ion / total chromium ion: 0.05 to 0.5 Cobalt ion / total chromium ion: 0.05 to 0.5

【００２２】ここで、硝酸イオン／全クロムイオンのモ
ル比が１．０未満では耐黒変性向上効果が小さく、また
処理液安定性も低下するため好ましくない。一方、モル
比が３．０を超えると硝酸イオンによる耐黒変性向上効
果が飽和するため経済的に不利であるばかりでなく、処
理液安定性も低下するため好ましくない。リン酸イオン
／全クロムイオンのモル比が０．０５未満では耐食性向
上効果が不十分であり、一方、モル比が０．５を超える
と耐黒変性が低下し、また処理液安定性も低下するため
好ましくない。なお、硝酸イオンやリン酸イオンは通
常、硝酸やリン酸の形で添加するが、これらの酸を含む
金属塩を添加してもよい。Here, when the molar ratio of nitrate ion / total chromium ion is less than 1.0, the effect of improving blackening resistance is small and the stability of the processing solution is undesirably reduced. On the other hand, if the molar ratio exceeds 3.0, the effect of improving the blackening resistance due to nitrate ions is saturated, which is not only economically disadvantageous but also lowers the stability of the processing solution, which is not preferable. If the molar ratio of phosphate ion / total chromium ion is less than 0.05, the effect of improving corrosion resistance is insufficient, while if the molar ratio exceeds 0.5, blackening resistance is reduced and the stability of the processing solution is also reduced. Is not preferred. The nitrate ion or phosphate ion is usually added in the form of nitric acid or phosphoric acid, but a metal salt containing these acids may be added.

【００２３】Ｃｏイオン／全クロムイオンのモル比が
０．０５未満では耐食性向上効果が小さく、一方、モル
比が０．５を超えると耐食性向上効果が飽和するため経
済性を損なうだけでなく、処理液の安定性が低下（沈殿
物の発生やゲル化）するため好ましくない。また、Ｃｏ
イオンの添加方法に特別な制約はないが、硝酸塩、クロ
ム酸塩、炭酸塩、水酸化物、酸化物などの無機酸塩を用
いるのが簡便で好ましい。If the molar ratio of Co ion / total chromium ion is less than 0.05, the effect of improving corrosion resistance is small, while if the molar ratio exceeds 0.5, the effect of improving corrosion resistance is saturated, which not only impairs economic efficiency but also impairs economic efficiency. It is not preferable because the stability of the treatment liquid is lowered (generation of a precipitate or gelation). Also, Co
Although there is no particular limitation on the method of adding ions, it is convenient and preferable to use an inorganic acid salt such as a nitrate, a chromate, a carbonate, a hydroxide, and an oxide.

【００２４】次に、樹脂エマルジョンである成分〔２〕
について説明する。本発明で用いる樹脂エマルジョン
（水系樹脂成分）は、疎水基中に炭素間二重結合（Ｃ＝
Ｃ）を有し、且つ親水基としてポリエチレンオキサイド
基を有する非イオン性反応型界面活性剤が固形分の重量
％で５０％以上含まれる界面活性剤〔Ａ〕の存在下で乳
化重合されたアクリル系共重合体の水系樹脂エマルジョ
ンである。また、上記界面活性剤〔Ａ〕としては、疎水
基中に炭素間二重結合（Ｃ＝Ｃ）を有し、且つ親水基と
してポリエチレンオキサイド基を有する非イオン性反応
型界面活性剤〔ａ1〕と疎水基中に炭素間二重結合（Ｃ
＝Ｃ）を有し、且つ親水基としてポリエチレンオキサイ
ド基を有する非イオン−アニオン性複合反応型界面活性
剤〔ａ2〕とからなり、非イオン性反応型界面活性剤
〔ａ1〕と非イオン−アニオン性複合反応型界面活性剤
〔ａ2〕の固形分の重量比〔ａ1〕／〔ａ2〕が１／２以
上である界面活性剤を用いることができる。Next, component [2] which is a resin emulsion
Will be described. The resin emulsion (aqueous resin component) used in the present invention contains a carbon-carbon double bond (C =
Acrylic emulsion-polymerized in the presence of a surfactant [A] containing C) and containing a nonionic reactive surfactant having a polyethylene oxide group as a hydrophilic group in an amount of 50% or more by weight of solid content. It is an aqueous resin emulsion of a system copolymer. The surfactant [A] includes a nonionic reactive surfactant [a 1 ] having a carbon-carbon double bond (C = C) in a hydrophobic group and a polyethylene oxide group as a hydrophilic group. ] And a carbon-carbon double bond (C
= C) and a nonionic-anionic composite reactive surfactant [a 2 ] having a polyethylene oxide group as a hydrophilic group, comprising a nonionic reactive surfactant [a 1 ] and a nonionic - can be used the weight ratio of the solid content of the anionic complex reactive surfactant [a 2] [a 1] / [a 2] is 1/2 or more surfactants.

【００２５】この樹脂エマルジョンは、アクリル系モノ
マー、またはアクリル系モノマーとこれと共重合可能な
ビニル化合物とを乳化重合して得られるアクリル系共重
合体の樹脂エマルジョンであることが好ましい。アクリ
ル系モノマーと重合可能なビニル化合物の種類は特に限
定されないが、例えば、スチレン、ビニルトルエン、酢
酸ビニル等が挙げられる。アクリル系共重合体の水系樹
脂エマルジョンは、他の水系樹脂エマルジョンに比べ
て、非イオン性反応型界面活性剤との反応性および無機
成分と混和した場合の処理液安定性に優れているため好
ましい。The resin emulsion is preferably a resin emulsion of an acrylic monomer or an acrylic copolymer obtained by emulsion polymerization of an acrylic monomer and a vinyl compound copolymerizable therewith. The type of the vinyl compound that can be polymerized with the acrylic monomer is not particularly limited, and examples include styrene, vinyl toluene, and vinyl acetate. Aqueous resin emulsions of acrylic copolymers are preferred, as compared with other aqueous resin emulsions, because they have excellent reactivity with nonionic reactive surfactants and excellent treatment liquid stability when mixed with inorganic components. .

【００２６】上記アクリル系モノマーの種類に特に限定
はないが、例えば、アクリル酸、メタクリル酸、マレイ
ン酸、無水マレイン酸、フマル酸、クロトン酸、イタコ
ン酸、シトラコン酸、桂皮酸等のカルボキシル基を有す
るもの；メチルアクリレート、エチルアクリレート、イ
ソプロピルアクリレート、ｎ−ブチルアクリレート、ｉ
−ブチルアクリレート、ｎ−オクチルアクリレート、ｉ
−オクチルアクリレート、２−エチルヘキシルアクリレ
ート、ｎ−ノニルアクリレート、ｉ−ノニルアクリレー
ト、ｎ−デシルアクリレート、ｎ−ドデシルアクリレー
ト、２−ヒドロキシエチルアクリレート、ヒドロキシル
プロピルアクリレート等のアクリル酸のモノアルキルエ
ステル；エチレングリコールジアクリレート、グリセリ
ントリアクリレート等のアクリル酸の多価エステル；メ
チルメタクリレート、エチルメタクリレート、ｎ−ブチ
ルメタクリレート、２−エチルヘキシルメタクリレー
ト、ヒドロキシプロピルメタクリレート、グリシジルメ
タクリレート等のメタクリル酸のアルキルモノエステ
ル；アクリロニトリル、メタクリロニトリル等のニトロ
化合物；アクリルアミド、Ｎ−メチロールアクリルアミ
ド、Ｎ−メチルアクリルアミド、Ｎ−メトキシエチルア
クリルアミド、ジアセトンアクリルアミド等のアクリル
酸のアミド化合物等が挙げられる。The type of the acrylic monomer is not particularly limited. For example, carboxyl groups such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, and cinnamic acid are used. Having; methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, i
-Butyl acrylate, n-octyl acrylate, i
Monoalkyl esters of acrylic acid such as octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, i-nonyl acrylate, n-decyl acrylate, n-dodecyl acrylate, 2-hydroxyethyl acrylate and hydroxylpropyl acrylate; Polyacrylates of acrylic acid such as acrylate and glycerin triacrylate; alkyl monoesters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, hydroxypropyl methacrylate and glycidyl methacrylate; acrylonitrile and methacrylonitrile Nitro compounds such as acrylamide, N-methylolacrylamide, N-methylacryl Amide, N- methoxyethyl acrylamide, amide compounds of acrylic acid diacetone acrylamide, and the like.

【００２７】樹脂エマルジョンの乳化剤として用いる界
面活性剤は、疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有
し、且つ親水基としてポリエチレンオキサイド基を有す
る非イオン性反応型界面活性剤を、少なくとも固形分の
重量％で５０％以上含む必要がある。このような非イオ
ン性反応型界面活性剤は樹脂成分と反応して皮膜中で樹
脂骨格の一部となるため、一般の乳化剤（界面活性剤）
のように皮膜中に単独で残存して皮膜の耐水性や水に対
するバリヤー性を劣化させるようなことがなく、このた
め皮膜に高度な耐食性や塗装密着性を付与することがで
きる。The surfactant used as an emulsifier for the resin emulsion is a nonionic reactive surfactant having a carbon-carbon double bond (C = C) in a hydrophobic group and a polyethylene oxide group as a hydrophilic group. , At least 50% by weight of the solid content. Such a nonionic reactive surfactant reacts with the resin component to become a part of the resin skeleton in the film, so that a general emulsifier (surfactant) is used.
As described above, the film does not remain alone in the film and deteriorates the water resistance and barrier property against water, so that the film can be imparted with high corrosion resistance and coating adhesion.

【００２８】上記の非イオン性反応型界面活性剤の例と
しては、アルキル化フェノールのエチレンオキサイド付
加物の骨格構造に、−ＣＨ＝ＣＨＣＨ3基、または−Ｃ
Ｈ2ＯＣＨ2ＣＨ＝ＣＨ2基等の二重結合を有する基を付
加したもの、アクリル酸またはメタクリル酸モノマーと
ポリエチレングリコールまたはポリプロピレングリコー
ルとのエステル化合物、またはスチレンモノマー等の二
重結合を有する骨格にポリエチレングリコール基を付加
重合させたもの等が挙げられる。Examples of the above-mentioned nonionic reactive surfactant include a —CH ＝ CHCH 3 group or —C in the skeleton structure of an ethylene oxide adduct of an alkylated phenol.
H 2 OCH 2 CH ＝ CH 2 group or other double-bonded group, ester compound of acrylic acid or methacrylic acid monomer and polyethylene glycol or polypropylene glycol, or skeleton having double bond such as styrene monomer To which a polyethylene glycol group is subjected to addition polymerization.

【００２９】界面活性剤中に占める上記非イオン性反応
型界面活性剤の割合（固形分の割合）が５０重量％未満
では、酸性領域下における親水性が低下し、上記非イオ
ン性反応型界面活性剤を用いたことによる処理液安定性
および皮膜特性が十分に確保できない。したがって、界
面活性剤としては上記の非イオン性反応型界面活性剤の
みを用いることが最も好ましい。このように界面活性剤
として上記の非イオン性反応型界面活性剤のみを用いた
場合には、皮膜の耐水性や水に対するバリヤー性がより
向上し、特に優れた皮膜特性（耐水性、塗装密着性等）
を得ることができる。If the proportion (solid content) of the nonionic reactive surfactant in the surfactant is less than 50% by weight, the hydrophilicity in an acidic region is reduced, and the nonionic reactive surfactant is reduced. The use of the activator does not ensure sufficient treatment liquid stability and film properties. Therefore, it is most preferable to use only the nonionic reactive surfactant described above as the surfactant. As described above, when only the above-mentioned nonionic reactive surfactant is used as the surfactant, the water resistance of the film and the barrier property against water are further improved, and particularly excellent film characteristics (water resistance, paint adhesion, etc.) Sex)
Can be obtained.

【００３０】上記の非イオン性反応型界面活性剤と他の
界面活性剤を複合して用いる場合、非イオン性反応型界
面活性剤以外の界面活性剤の種類に特別な制限はない
が、特に非イオン性を部分的に有する反応型界面活性
剤、例えば、非イオン性反応型界面活性剤の骨格中に硫
酸、リン酸、炭酸などのうちの１種または２種以上の親
水性酸を付加して、アニオン部分となる硫酸エステル
（−ＯＳＯ3Ｈ）基、スルホン酸（−ＳＯ3Ｈ）基、リン
酸エステル（−ＯＰＯ3Ｈ）基、カルボン酸（−ＣＯＯ
Ｈ）基、或いはこれらの塩からなる基のうちの１種また
は２種以上を付加した非イオン−アニオン性複合反応型
界面活性剤が好適に利用できる。またそのなかでも、疎
水基中に炭素間二重結合（Ｃ＝Ｃ）を有し、且つ親水基
としてポリエチレンオキサイド基を有する非イオン−ア
ニオン性複合反応型界面活性剤が特に好適である。When the above-mentioned nonionic reactive surfactant is used in combination with another surfactant, there is no particular limitation on the type of surfactant other than the nonionic reactive surfactant. Addition of one or more hydrophilic acids of sulfuric acid, phosphoric acid, carbonic acid, etc. into the skeleton of a nonionic reactive surfactant, for example, a nonionic reactive surfactant Then, a sulfate (—OSO 3 H) group, a sulfonic acid (—SO 3 H) group, a phosphate (—OPO 3 H) group, and a carboxylic acid (—COO) serving as an anion portion
A nonionic-anionic complex reactive surfactant to which one or more of the H) group or a group consisting of these salts is added can be suitably used. Among them, a nonionic-anionic complex reactive surfactant having a carbon-carbon double bond (C = C) in a hydrophobic group and having a polyethylene oxide group as a hydrophilic group is particularly preferable.

【００３１】このように疎水基中に炭素間二重結合（Ｃ
＝Ｃ）を有し、且つ親水基としてポリエチレンオキサイ
ド基を有する非イオン性反応型界面活性剤〔ａ1〕と、
疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有し、且つ親水
基としてポリエチレンオキサイド基を有する非イオン−
アニオン性複合反応型界面活性剤〔ａ2〕とを複合して
用いる場合、非イオン性反応型界面活性剤〔ａ1〕と非
イオン−アニオン性複合反応型界面活性剤〔ａ2〕の固
形分の重量比〔ａ1〕／〔ａ2〕は１／２以上とする。こ
の重量比〔ａ1〕／〔ａ2〕が１／２未満では酸性領域下
における親水性が低下するため、処理液安定性や皮膜特
性が十分に確保できない。Thus, a carbon-carbon double bond (C
ＣC), and a nonionic reactive surfactant [a 1 ] having a polyethylene oxide group as a hydrophilic group;
Nonionic having a carbon-carbon double bond (C = C) in a hydrophobic group and a polyethylene oxide group as a hydrophilic group
When the anionic complex reactive surfactant [a 2 ] is used in combination, the solid content of the nonionic reactive surfactant [a 1 ] and the nonionic-anionic complex reactive surfactant [a 2 ] The weight ratio [a 1 ] / [a 2 ] is set to 1/2 or more. If the weight ratio [a 1 ] / [a 2 ] is less than ２, the hydrophilicity in the acidic region is reduced, so that the stability of the treatment liquid and the film properties cannot be sufficiently secured.

【００３２】界面活性剤〔Ａ〕は、アクリル系共重合体
〔Ｂ〕との固形分の重量比〔Ａ〕／〔Ｂ〕で、１０／１
００〜２０／１００の割合で添加することが好ましい。
この重量比が１０／１００未満では無機成分と混合した
ときの処理液安定性が不十分であり、一方、２０／１０
０を超えるとクロメート皮膜の耐水性が低下して耐食性
や塗装密着性の劣化を招き、また耐黒変性も低下する。The surfactant [A] is 10/1 in terms of the weight ratio [A] / [B] of the solid content with the acrylic copolymer [B].
It is preferable to add at a ratio of 00 to 20/100.
If the weight ratio is less than 10/100, the stability of the treatment liquid when mixed with the inorganic component is insufficient, while
If it exceeds 0, the water resistance of the chromate film decreases, causing deterioration in corrosion resistance and coating adhesion, and also lowers blackening resistance.

【００３３】本発明で用いる水系樹脂含有クロメート処
理液は、上述した無機成分（成分〔１〕）と樹脂エマル
ジョン（成分〔２〕）が、無機成分に含まれる６価クロ
ムイオンおよび３価クロムイオンと、樹脂エマルジョン
中に含まれる界面活性剤〔Ａ〕およびアクリル系共重合
体〔Ｂ〕の固形分での重量比［（〔Ａ〕＋〔Ｂ〕）／
（６価クロムイオン＋３価クロムイオン）］が２０／１
〜５０／１となるよう配合される。この重量比
［（〔Ａ〕＋〔Ｂ〕）／（６価クロムイオン＋３価クロ
ムイオン）］が２０／１未満では十分な耐食性や塗装密
着性が得られず、また耐黒変性、潤滑性、処理液安定性
も低下する。一方、重量比が５０／１を超えると樹脂エ
マルジョン添加による効果が飽和するため経済性を損な
うばかりでなく、クロメート成分の割合が減少するため
耐食性が低下する。The aqueous resin-containing chromate treatment solution used in the present invention comprises the above-mentioned inorganic component (component [1]) and a resin emulsion (component [2]) containing hexavalent chromium ions and trivalent chromium ions contained in the inorganic components. And the weight ratio of the surfactant [A] and the acrylic copolymer [B] contained in the resin emulsion at the solid content [([A] + [B]) /
(Hexavalent chromium ion + trivalent chromium ion)] is 20/1
５０50/1. If the weight ratio [([A] + [B]) / (hexavalent chromium ion + trivalent chromium ion)] is less than 20/1, sufficient corrosion resistance and coating adhesion cannot be obtained, and blackening resistance and lubricity In addition, the stability of the processing solution also decreases. On the other hand, if the weight ratio exceeds 50/1, the effect of the addition of the resin emulsion is saturated, which not only impairs economic efficiency, but also reduces the ratio of chromate components, thereby lowering the corrosion resistance.

【００３４】また、水系樹脂含有クロメート処理液のｐ
Ｈは３以下とする。これはクロメート成分中の３価クロ
ムイオンがカチオンであるために、ｐＨが３を超えると
処理液が不安定となり、沈殿物を形成したり、ゲル化す
るおそれがあるためである。In addition, p of the chromate treatment solution containing an aqueous resin
H is 3 or less. This is because, since the trivalent chromium ion in the chromate component is a cation, when the pH exceeds 3, the treatment liquid becomes unstable, and a precipitate may be formed or gelation may occur.

【００３５】次に、上述した水系樹脂含有クロメート処
理液により形成されるクロメート皮膜の作用効果につい
て説明する。本発明において亜鉛系めっき鋼板の表面に
クロメート皮膜を形成する水系樹脂含有クロメート処理
液は、亜鉛系めっき鋼板に対して基本的な耐食性を与え
るクロメート成分（３価クロムイオン、６価クロムイオ
ン）と、耐黒変性を向上させる無機成分（硝酸イオン）
と、耐食性をより向上させる無機成分（リン酸イオン、
コバルトイオン）と、さらに高度な耐食性および塗装密
着性を与える特定の界面活性剤を使用した樹脂エマルジ
ョン成分により構成され、無機成分に樹脂成分が安定に
分散し、且つｐＨ３以下に調整されたものである。Next, the function and effect of the chromate film formed by the above-mentioned aqueous resin-containing chromate treatment solution will be described. In the present invention, the aqueous resin-containing chromate treatment solution that forms a chromate film on the surface of a zinc-based plated steel sheet is composed of a chromate component (trivalent chromium ion, hexavalent chromium ion) that provides basic corrosion resistance to the zinc-based plated steel sheet. , An inorganic component that improves blackening resistance (nitrate ion)
And an inorganic component (phosphate ion,
(Cobalt ion) and a resin emulsion component that uses a specific surfactant that gives higher corrosion resistance and coating adhesion. The resin component is stably dispersed in the inorganic component, and the pH is adjusted to 3 or less. is there.

【００３６】このような水系樹脂含有クロメート処理液
で形成されるクロメート皮膜により優れた諸特性が得ら
れる機構は必ずしも明確ではないが、まず無機成分に関
しては以下のような基本的な作用が考えられる。クロメ
ート皮膜の有する白錆発生防止機構は、一般的には６価
クロムイオンによる亜鉛の腐食を抑制するインヒビター
効果と理解されており、さらに「材料と環境 41,244-24
5,1992」に見られるように、クロメート皮膜中から溶出
する６価クロムイオンが皮膜の破損部分を補修する自己
補修効果によるものであると考えられている。The mechanism by which the chromate film formed with such an aqueous resin-containing chromate treatment solution provides excellent properties is not necessarily clear, but first, the following basic actions can be considered for inorganic components. . The mechanism for preventing the formation of white rust in the chromate film is generally understood as an inhibitory effect that suppresses the corrosion of zinc by hexavalent chromium ions.
5,1992 ", it is believed that hexavalent chromium ions eluted from the chromate film are due to a self-repair effect of repairing a damaged portion of the film.

【００３７】さらに、水系樹脂含有クロメート処理液中
に添加された硝酸イオンは、亜鉛との塩を形成するこ
とにより酸素欠乏型の腐食生成物の形成（黒変性物）が
抑制されること、亜鉛系めっき表面に存在する鉛など
の不純物（但し有意に添加する場合もある）が硝酸添加
により選択的にエッチングされ、除去される結果、表面
の不純物残存量が減少し、腐食環境での局部電池形成が
抑制されること、また、エッチングされた鉛部と６価ク
ロムが反応し、亜鉛より貴な金属からクロム酸鉛等の化
合物へと変化することにより、腐食環境での局部電池形
成が抑制されること、酸化剤である硝酸が亜鉛めっき
の表面を緻密に酸化することにより、腐食環境における
それ以上の酸化が抑制されること、等の基本的な作用に
より特性改善に寄与し、その結果、耐食性、耐黒変性を
向上させるものと考えられる。さらに、水系樹脂含有ク
ロメート処理液中に添加されたリン酸は、エッチング反
応により溶出した亜鉛イオン、３価クロムイオン、コバ
ルトイオンと難溶性の塩を形成して皮膜のバリヤー性を
高め、耐食性を向上させるものと考えられる。Further, nitrate ions added to the aqueous resin-containing chromate treatment liquid form a salt with zinc, thereby suppressing the formation of oxygen-deficient corrosion products (black denatured products). Impurities (but may be significantly added) such as lead present on the surface of the system-based plating are selectively etched and removed by adding nitric acid. As a result, the residual amount of impurities on the surface is reduced, and the local battery in a corrosive environment is reduced. The formation is suppressed, and the etched lead and hexavalent chromium react with each other to change from a noble metal to a compound such as lead chromate, thereby suppressing the formation of a local battery in a corrosive environment. That the nitric acid, which is an oxidizing agent, oxidizes the surface of the zinc plating densely, thereby suppressing further oxidation in a corrosive environment. Results believed to enhance corrosion resistance, the resistance to blackening. Further, the phosphoric acid added to the aqueous resin-containing chromate treatment solution forms a hardly soluble salt with zinc ion, trivalent chromium ion, and cobalt ion eluted by the etching reaction to increase the barrier property of the film and improve the corrosion resistance. It is thought to improve.

【００３８】次に、上記無機成分と特定の樹脂エマルジ
ョンの複合添加による作用効果について述べる。一般的
に、親水性の樹脂粒子はアニオン性の官能基、または水
酸基、若しくはポリエチレングリコール基等の親水基を
樹脂骨格中に有することにより、自己乳化してエマルジ
ョン化し、また疎水性樹脂は界面活性剤で転層乳化して
エマルジョン化されるか、または反応性の界面活性剤で
乳化重合してエマルジョン化されており、これら樹脂エ
マルジョンは中性〜アルカリ性のｐＨ範囲で安定に分散
している。Next, the function and effect of the composite addition of the above-mentioned inorganic component and a specific resin emulsion will be described. Generally, hydrophilic resin particles have an anionic functional group, or a hydrophilic group such as a hydroxyl group or a polyethylene glycol group in a resin skeleton, thereby self-emulsifying and emulsifying, and a hydrophobic resin has a surfactant. The resin emulsion is emulsified by inversion emulsification with an emulsifier, or emulsified by emulsion polymerization with a reactive surfactant, and these resin emulsions are stably dispersed in a neutral to alkaline pH range.

【００３９】そして、これら樹脂エマルジョンを無機ク
ロメート成分と混合した場合を考えてみると、まず、３
価クロムイオンは多価のカチオンとして作用し、エマル
ジョン粒子の表面の電荷を中和する作用がある。一般に
粒子の表面電荷を中和すると、その粒子の分散は不安定
化し、凝集する傾向を生じる。このためアニオン性の官
能基を有し自己乳化したエマルジョンやアニオン性界面
活性剤は、３価クロムイオンにより中和され、イオン性
が低下するとともに親水性が低下するため、水中に安定
に分散できなくなってしまう。Considering the case where these resin emulsions are mixed with an inorganic chromate component,
The valent chromium ion acts as a polyvalent cation and has a function of neutralizing the charge on the surface of the emulsion particles. In general, neutralizing the surface charge of a particle destabilizes the particle's dispersion and tends to agglomerate. Therefore, self-emulsified emulsions and anionic surfactants having anionic functional groups are neutralized by trivalent chromium ions, and their ionicity and hydrophilicity are reduced, so that they can be stably dispersed in water. Will be gone.

【００４０】また同時に、無機クロメート成分中に存在
する６価クロムイオンは強力な酸化剤であり、処理液ｐ
Ｈが３．０以下に保持されるので、このような無機クロ
メート成分と樹脂成分とを混合すると、急激なｐＨ変化
により樹脂エマルジョンの表面のゼータ（ζ）電位も急
激に変化し、その分散安定性が低下するために凝集する
傾向を生じる。At the same time, hexavalent chromium ion present in the inorganic chromate component is a strong oxidizing agent,
Since H is kept at 3.0 or less, if such an inorganic chromate component and a resin component are mixed, the zeta (ζ) potential on the surface of the resin emulsion also changes rapidly due to a sudden pH change, and the dispersion stability A tendency to agglomerate due to reduced properties.

【００４１】このような状況下で樹脂成分の分散の不安
定化を防止し、安定な分散状態を保つためには、ノニオ
ン（非イオン）部分を含有する界面活性剤により安定に
水分散している樹脂成分を使用することが効果的であ
る。つまり、ノニオン部分によって樹脂成分が水中に安
定に分散するのに十分な親水性が与えられれば、３価ク
ロムイオンによる電荷の中和や、急激なｐＨ変化に伴う
表面電荷の変化による樹脂成分の凝集を防ぎ、無機クロ
メート成分と樹脂成分が安定化する１液型の組成物が得
られる。Under these circumstances, in order to prevent the dispersion of the resin component from becoming unstable and to maintain a stable dispersion state, the resin component is dispersed in water with a surfactant containing a nonionic (nonionic) portion. It is effective to use a resin component that is present. In other words, if the nonionic portion provides sufficient hydrophilicity to stably disperse the resin component in water, neutralization of the charge by trivalent chromium ions and the change of the resin component by a change in surface charge due to a rapid pH change A one-pack type composition is obtained in which aggregation is prevented and the inorganic chromate component and the resin component are stabilized.

【００４２】しかしながら、単純にノニオン系界面活性
剤により分散した樹脂エマルジョンよりも、本発明のよ
うに非イオン系の反応型界面活性剤を用いて樹脂エマル
ジョンを得るほうが、耐食性、塗装密着性の面で優れた
特性が得られる。これは、単純にノニオン系界面活性剤
でエマルジョン化された樹脂では、成膜時に乳化剤が皮
膜表面や皮膜と亜鉛系めっき面との界面に存在（偏析）
することにより、塗装密着性や耐食性が十分に得られな
くなるのに対し、本発明のように反応型界面活性剤を使
用した場合には界面活性剤が樹脂成分と反応して界面活
性剤も皮膜成分の一部となるため、そのような問題を生
じるおそれはなく、この結果、優れた耐食性、塗装密着
性が得られるものと考えられる。However, it is better to obtain a resin emulsion using a nonionic reactive surfactant as in the present invention than a resin emulsion simply dispersed with a nonionic surfactant in terms of corrosion resistance and coating adhesion. And excellent characteristics can be obtained. This is because in a resin simply emulsified with a nonionic surfactant, the emulsifier is present at the film surface or at the interface between the film and the zinc-based plating surface during film formation (segregation).
By doing so, coating adhesion and corrosion resistance can not be sufficiently obtained, whereas when a reactive surfactant is used as in the present invention, the surfactant reacts with the resin component and the surfactant also forms a film. Since it becomes a part of the components, there is no possibility that such a problem occurs. As a result, it is considered that excellent corrosion resistance and coating adhesion are obtained.

【００４３】本発明のクロメート処理亜鉛系めっき鋼板
は、以上のような水系樹脂含有クロメート処理液を亜鉛
系めっき鋼板の表面に塗布し、乾燥させてクロメート皮
膜を形成したものである。このクロメート皮膜のクロム
付着量は、金属クロム換算で５〜５０ｍｇ／ｍ2とす
る。クロム付着量が５ｍｇ／ｍ2未満では皮膜の耐食性
が不十分であり、また耐黒変性、二次塗装密着性、潤滑
性も低下する。一方、クロム付着量が５０ｍｇ／ｍ2を
超えると耐食性向上効果が飽和するため経済性を損なう
だけでなく、ロールフォーミング等の加工時に皮膜が剥
離しやすくなり、剥離粉がロール表面に転写される等の
問題を生じるため好ましくなく、また、クロム溶出量も
多くなるため、環境汚染の面からも好ましくない。The chromate-treated galvanized steel sheet of the present invention is obtained by applying a water-based resin-containing chromate treatment liquid as described above to the surface of a galvanized steel sheet and drying it to form a chromate film. The amount of chromium deposited on the chromate film is 5 to 50 mg / m 2 in terms of chromium metal. If the amount of chromium is less than 5 mg / m 2 , the corrosion resistance of the film is insufficient, and the blackening resistance, the adhesion to the secondary coating and the lubricity are also reduced. On the other hand, if the amount of chromium exceeds 50 mg / m 2 , the effect of improving corrosion resistance is saturated, which not only impairs economic efficiency, but also facilitates peeling of the film during processing such as roll forming, and peeling powder is transferred to the roll surface. It is not preferable because it causes problems such as the above, and the amount of chromium eluted is also large, which is not preferable from the viewpoint of environmental pollution.

【００４４】本発明鋼板の下地となる亜鉛めっき系鋼板
としては、少なくともクロメート皮膜が形成する面に亜
鉛系めっき層を有するものであればよく、また、亜鉛系
めっき鋼板の種類としては、亜鉛めっき鋼板のほかに、
ニッケル、鉄、アルミニウム、マンガン、クロム、コバ
ルト、モリブデン、シリコン等の中から選ばれる１種以
上の元素を含有した亜鉛合金めっき層を有する亜鉛系合
金めっき鋼板、複数層の亜鉛めっき層および／または亜
鉛合金めっき層を有する複層亜鉛系めっき鋼板でもよ
い。具体的には、溶融亜鉛めっき鋼板、合金化溶融亜鉛
めっき鋼板、電気亜鉛めっき鋼板、溶融Ｚｎ−５５％Ａ
ｌ合金めっき鋼板、溶融Ｚｎ−５％Ａｌ合金めっき鋼
板、Ｚｎ−Ｎｉ合金めっき鋼板、Ｚｎ−Ｃｏ金めっき鋼
板、Ｚｎ−Ｃｒ合金めっき鋼板、複合亜鉛系めっき鋼板
（例えば、電気Ｚｎ−ＳｉＯ2分散めっき鋼板）等の各
種亜鉛系めっき鋼板を用いることができるThe zinc-coated steel sheet serving as the base of the steel sheet of the present invention may be any one having a zinc-based plating layer on at least the surface on which the chromate film is formed. In addition to steel plates,
A zinc-based alloy-plated steel sheet having a zinc alloy-plated layer containing at least one element selected from nickel, iron, aluminum, manganese, chromium, cobalt, molybdenum, silicon, etc .; A multi-layer zinc-coated steel sheet having a zinc alloy plating layer may be used. Specifically, hot-dip galvanized steel sheet, alloyed hot-dip galvanized steel sheet, electro-galvanized steel sheet, hot-dip Zn-55% A
l alloy plated steel sheet, molten Zn-5% Al alloy plated steel sheet, Zn-Ni alloy plated steel sheet, Zn-Co alloy plated steel sheet, Zn-Cr alloy plated steel sheet, a composite zinc-plated steel sheet (for example, electric Zn-SiO 2 dispersion Various zinc-based coated steel sheets such as coated steel sheets) can be used.

【００４５】次に、本発明のクロメート処理亜鉛系めっ
き鋼板の製造方法について説明する。本発明のクロメー
ト処理亜鉛系めっき鋼板は、上述した水系樹脂含有クロ
メート処理液を下地鋼板である亜鉛系めっき鋼板の表面
に上述したクロム付着量となるように塗布し、乾燥させ
ることにより製造される。この製造方法において処理液
の塗布方法および乾燥方法には特別な制約はない。処理
液の塗布には、通常用いられている方法、例えば浸漬
法、シャワー法、ロールコート法、スプレーコート法等
の任意の方法が適用できる。これらの方法を用いてめっ
き鋼板面に処理液を塗布する際、エアーブローやロール
絞り等により塗布量を調整してもよい。Next, the method for producing the chromate-treated galvanized steel sheet of the present invention will be described. The chromate-treated galvanized steel sheet of the present invention is manufactured by applying the above-mentioned aqueous resin-containing chromate treatment solution to the surface of the zinc-based plated steel sheet as the base steel sheet so as to have the above-mentioned chromium adhesion amount, and then drying it. . In this manufacturing method, there are no particular restrictions on the method of applying and drying the treatment liquid. For application of the treatment liquid, any method generally used, for example, an immersion method, a shower method, a roll coating method, a spray coating method, or the like can be applied. When the treatment liquid is applied to the surface of the plated steel sheet using these methods, the application amount may be adjusted by air blow, roll drawing, or the like.

【００４６】また、処理液をめっき鋼板面に塗布した後
の乾燥は、基本的には水分が蒸発するような乾燥であれ
ばよいが、好ましくは最高到達板温で５０〜２００℃の
範囲で乾燥することが望ましい。乾燥温度（板温）が５
０℃未満では水分蒸発が不十分なため、皮膜形成が十分
に行われない場合があり、耐食性、耐黒変性、塗料密着
性が低下する。一方、２００℃を超える乾燥温度では経
済性を損なうだけでなく、耐食性、塗料密着性も劣化す
る傾向にある。乾燥方法にも特別な制限はなく、用途、
生産性、経済性に応じて、熱風炉、高周波誘導加熱炉等
の乾燥方法を適宜選択して使用できる。The drying after the treatment liquid is applied to the surface of the plated steel sheet may be basically a drying method in which moisture is evaporated. Preferably, the drying is performed at a maximum temperature of 50 to 200 ° C. at the maximum sheet temperature. It is desirable to dry. Drying temperature (plate temperature) is 5
If the temperature is lower than 0 ° C., moisture may not be sufficiently evaporated, so that a film may not be sufficiently formed, and the corrosion resistance, blackening resistance and paint adhesion may be reduced. On the other hand, if the drying temperature exceeds 200 ° C., not only the economic efficiency is impaired, but also the corrosion resistance and the paint adhesion tend to deteriorate. There are no special restrictions on the drying method,
A drying method such as a hot blast stove or a high-frequency induction heating furnace can be appropriately selected and used depending on productivity and economy.

【００４７】[0047]

【実施例】下記の各亜鉛系めっき鋼板の両面をアルカリ
脱脂した後、めっき面に水性樹脂含有クロメート処理液
をロールコーティング法により塗布（クロム付着量はウ
ェット塗布量により調整）した後、これを炉温３００
℃、炉内風速２ｍ／ｓｅｃの熱風乾燥炉内において最高
到達板温４０〜２３０℃の範囲で乾燥させ、供試材を作
成した。EXAMPLE After zinc-coated zinc-coated steel sheets were alkali-degreased on both sides, an aqueous resin-containing chromate treatment solution was applied to the plated surfaces by a roll coating method (the amount of chromium adhering was adjusted by the wet application amount). Furnace temperature 300
The sample was dried in a hot air drying oven at a temperature of 40 ° C and a maximum temperature of 40 to 230 ° C in a hot air drying oven at an air velocity of 2 m / sec.

【００４８】(1) Ｐｂレスゼロスパングル溶融亜鉛めっ
き鋼板（板厚０．８ｍｍ、めっき付着量９０ｇ／ｍ2） (2) ０．１重量％Ｐｂ含有レギュラースパングル溶融亜
鉛めっき鋼板（板厚０．８ｍｍ、めっき付着量９０ｇ／
ｍ2） (3) 電気亜鉛めっき鋼板（板厚０．８ｍｍ、めっき付着
量２０ｇ／ｍ2） (4) 亜鉛−ニッケル合金めっき鋼板（板厚０．８ｍｍ、
めっき付着量２０ｇ／ｍ2） (5) 合金化溶融亜鉛めっき鋼板（板厚０．８ｍｍ、めっ
き付着量４５ｇ／ｍ2） (6) 溶融亜鉛−５％アルミニウム合金めっき鋼板（板厚
０．８ｍｍ、めっき付着量９０ｇ／ｍ2） (7) 溶融亜鉛−５５％アルミニウム合金めっき鋼板（板
厚０．８ｍｍ、めっき付着量７０ｇ／ｍ2）(1) Pb-less zero spangle hot-dip galvanized steel sheet (sheet thickness 0.8 mm, coating weight 90 g / m 2 ) (2) Regular spangle hot-dip galvanized steel sheet containing 0.1% by weight of Pb (sheet thickness 0. 8mm, 90g /
m 2 ) (3) Electro-galvanized steel sheet (sheet thickness 0.8 mm, coating weight 20 g / m 2 ) (4) Zinc-nickel alloy plated steel sheet (sheet thickness 0.8 mm,
Coating weight 20g / m 2) (5) galvannealed steel sheet (sheet thickness 0.8mm, coating weight 45g / m 2) (6) molten zinc -5% aluminum alloy plated steel sheet (sheet thickness 0.8mm , 90g / m 2 of coating weight) (7) Hot-dip zinc-55% aluminum alloy coated steel sheet (0.8mm thick, 70g / m 2 of coating weight)

【００４９】各供試材に使用したクロメート処理液の組
成をクロム付着量、皮膜乾燥板温ともに表１〜表４に示
す。使用したクロメート処理液について処理液安定性を
評価するとともに、得られた供試材について耐食性（耐
白錆性）、耐黒変性、塗装密着性および潤滑性を評価し
た。その結果を表５〜表７に示す。また、クロメート処
理液を構成する樹脂エマルジョンの組成を表８〜表１０
に示す。Tables 1 to 4 show the composition of the chromate treatment solution used for each sample, together with the amount of chromium deposited and the temperature of the dried film. The treatment liquid stability of the used chromate treatment liquid was evaluated, and the obtained test materials were evaluated for corrosion resistance (white rust resistance), blackening resistance, coating adhesion, and lubricity. The results are shown in Tables 5 to 7. Tables 8 to 10 show the compositions of the resin emulsions constituting the chromate treatment liquid.
Shown in

【００５０】クロメート処理液の調整方法と性能評価法
を以下に示す。 ［クロメート処理液の調整］ （1-1）クロメート成分の調整 表１〜表４に示した組成を有するクロメート成分を調整
した。各クロメート成分は、無水クロム酸２００ｇを純
水に溶かし、メタノールを加えて６価クロムの一部を還
元し、このメタノールの添加量により３価クロムイオン
／（３価クロムイオン＋６価クロムイオン）の重量比を
調整した。 （1-2）無機成分の調整 上記(1-1)で調整したクロメート成分に対して、無機酸
（硝酸、リン酸）および金属（塩基性炭酸コバルト）を
添加し、表１〜表４に示す組成となるように調整した。The method for preparing the chromate treatment solution and the method for evaluating its performance are described below. [Adjustment of Chromate Treatment Solution] (1-1) Adjustment of Chromate Component Chromate components having the compositions shown in Tables 1 to 4 were prepared. Each chromate component is prepared by dissolving 200 g of chromic anhydride in pure water, adding methanol to reduce a part of hexavalent chromium, and adjusting the amount of methanol to add trivalent chromium ion / (trivalent chromium ion + hexavalent chromium ion). Was adjusted. (1-2) Adjustment of Inorganic Component To the chromate component adjusted in the above (1-1), an inorganic acid (nitric acid, phosphoric acid) and a metal (basic cobalt carbonate) were added, and as shown in Tables 1 to 4, The composition was adjusted so as to have the composition shown.

【００５１】（1-3）樹脂エマルジョン 表８〜表１０に示す水系樹脂エマルジョンを用いた。 （1-4）クロメート処理液の調整 上記（1-3）の水系樹脂エマルジョンを撹拌していると
ころに、上記（1-2）で調整された無機成分を徐々に添
加し、表１〜表４に示した処理液組成に調整した。(1-3) Resin emulsion The aqueous resin emulsions shown in Tables 8 to 10 were used. (1-4) Preparation of chromate treatment solution While the aqueous resin emulsion of (1-3) was being stirred, the inorganic component adjusted in (1-2) was gradually added thereto. The composition of the processing solution shown in FIG.

【００５２】［性能評価］ (1) 耐黒変性 各供試材から７０ｍｍ×１５０ｍｍの試験片を複数枚切
り出し、各試験片の供試面を対面させて一対としたもの
を５〜１０枚重ねてビニールコート紙にて梱包し、これ
を内側にアクリル板を貼付けた厚さ１０ｍｍの２枚のス
テンレス板の間に挾み、その四隅をボルト締めしてトル
クレンチで０．６７ｋｇｆ・ｃｍ2の荷重をかけ、７０
℃、９５％の相対湿度の湿潤箱内に２４０時間保持した
後、取り出し、重ね合わせ部の黒変状況を目視にて判定
した。その評価基準は下記の通りである。 ◎：黒変無し ○：極めて軽度に灰色化 △：黒変発生 ×：著しい黒変発生[Evaluation of Performance] (1) Blackening Resistance A plurality of test pieces of 70 mm × 150 mm were cut out from each test material, and 5 to 10 test pieces of each test piece were faced to form a pair. Packed with vinyl-coated paper, sandwiched between two stainless steel plates with a thickness of 10 mm with an acrylic plate adhered on the inside, tightened the four corners with bolts and applied a load of 0.67 kgf · cm 2 with a torque wrench. Over 70
After being kept in a humid box at a temperature of 95 ° C. and a relative humidity of 95% for 240 hours, it was taken out, and the blackening state of the overlapped portion was visually judged. The evaluation criteria are as follows. ◎: no blackening ○: extremely slight graying △: blackening occurred ×: remarkable blackening occurred

【００５３】(2) 耐食性 各供試材から７０ｍｍ×１５０ｍｍの試験片を複数枚切
り出し、これらの試験片にＪＩＳ Ｚ ２３７１に規定さ
れた塩水噴霧試験を実施し、４００時間後の白錆発生面
積を目視で判定した。その評価基準は下記の通りであ
る。 ◎：白錆発生無し ○：白錆発生面積率５％未満 △：白錆発生面積率５％以上、２５％未満 ×：白錆発生面積率２５％以上(2) Corrosion resistance A plurality of test pieces of 70 mm × 150 mm were cut out from each test material, and a salt spray test specified in JIS Z 2371 was performed on these test pieces. Was visually determined. The evaluation criteria are as follows. ：: No white rust generated ○: White rust generated area rate less than 5% △: White rust generated area rate 5% or more, less than 25% ×: White rust generated area rate 25% or more

【００５４】(3) 塗装密着性 各供試材から７０ｍｍ×１５０ｍｍの試験片を複数枚切
り出し、メラミンアルキド系塗料（大日本塗料（株）
製：デリコン♯７００）をスプレーにて膜厚３０μｍに
なるように塗装し、１３０℃で３０分間焼き付けたサン
プルについて、一次密着性としてＪＩＳ Ｋ ５４００に
規定された碁盤目試験（１ｍｍ×１００ケ）を実施し、
テープを貼着・剥離した後の塗膜の剥離状態により塗料
密着性を評価した。評価基準は以下の通りである。 ◎：剥離無し ○：剥離面積１０％未満 △：剥離面積１０％以上、５０％未満 ×：剥離面積５０％以上 また二次密着性として、一次密着性と同様のサンプルを
沸水に２時間浸漬した後に、同様に碁盤目試験（１ｍｍ
×１００ケ）を実施し、テープを貼着・剥離した後の塗
膜の剥離状態により塗料密着性を評価した。評価基準は
上記と同様である。(3) Coating Adhesion A plurality of test pieces of 70 mm × 150 mm were cut out from each test material, and a melamine alkyd paint (Dainippon Paint Co., Ltd.)
Manufactured by Delicon Co., Ltd. 700) by spraying to a film thickness of 30 μm and baked at 130 ° C. for 30 minutes. The cross-cut test (1 mm × 100 pieces) specified in JIS K 5400 as the primary adhesiveness of the sample. And implement
The paint adhesion was evaluated by the peeling state of the coating film after the tape was attached and peeled. The evaluation criteria are as follows. ：: No peeling ：: Peeling area less than 10% △: Peeling area 10% or more, less than 50% ×: Peeling area 50% or more Also, as secondary adhesion, a sample similar to the primary adhesion was immersed in boiling water for 2 hours. Later, similarly, a grid test (1 mm
× 100), and the paint adhesion was evaluated based on the peeling state of the coating film after the tape was attached and peeled off. Evaluation criteria are the same as above.

【００５５】(4) 潤滑性 引張試験機を使用した平板引き抜き法により、面圧：８
００ｋｇｆ／ｃｍ2、引き抜き速度：５００ｍｍ／ｍｉ
ｎの条件で引き抜き、その際の動摩擦係数を調べること
で潤滑性を評価した。評価基準は以下の通りである。 ○：動摩擦係数０．３以下 △：動摩擦係数０．３超、０．４以下 ×：動摩擦係数０．４超 また、摩擦摺動面について皮膜の損傷状態を目視で観察
し、潤滑性を評価した。評価基準は以下の通りである。 ○：皮膜の剥れ無し △：皮膜の剥れが軽微 ×：皮膜の剥れが著しい(4) Lubricity Surface pressure: 8 by a flat plate drawing method using a tensile tester.
00 kgf / cm 2 , drawing speed: 500 mm / mi
Under the condition of n, the lubricating property was evaluated by examining the dynamic friction coefficient at that time. The evaluation criteria are as follows. ：: Dynamic friction coefficient 0.3 or less △: Dynamic friction coefficient 0.3 or more, 0.4 or less ×: Dynamic friction coefficient more than 0.4 Further, the damage state of the coating on the friction sliding surface is visually observed to evaluate the lubricity. did. The evaluation criteria are as follows. ：: No peeling of film △: Minor peeling of film ×: Remarkable peeling of film

【００５６】(5) 水系樹脂含有クロメート処理液の安定
性 水系樹脂含有クロメート処理液１００ｍｌを栓付きのポ
リ瓶にとり、５０℃、３６０時間経時後の沈殿物発生の
状況を目視で観察した。評価基準は以下の通りである。 ○：沈殿物の発生無し △：沈殿物の発生が軽微 ×：沈殿物の発生が著しい(5) Stability of Chromate Treatment Solution Containing Aqueous Resin 100 ml of the chromate treatment solution containing an aqueous resin was placed in a stoppered plastic bottle, and the state of generation of a precipitate after elapse of 360 hours at 50 ° C. was visually observed. The evaluation criteria are as follows. ：: No sediment generated △: Slight sediment generated ×: Sediment generated remarkably

【００５７】表１〜表７によれば、本発明によるクロメ
ート処理亜鉛系めっき鋼板は、耐黒変性、耐食性、塗装
密着性および潤滑性のいずれにも優れており、また、使
用した水系樹脂含有クロメート処理液は処理液安定性に
優れている。これに対して、比較例は耐黒変性、耐食
性、塗装密着性、潤滑性、処理液の安定性の何れかに劣
っている。According to Tables 1 to 7, the chromate-treated galvanized steel sheet according to the present invention is excellent in all of blackening resistance, corrosion resistance, paint adhesion and lubricity, and contains the aqueous resin used. The chromate treatment liquid has excellent treatment liquid stability. On the other hand, the comparative example is inferior in any of blackening resistance, corrosion resistance, coating adhesion, lubricity, and stability of the processing solution.

【００５８】[0058]

【表１】 [Table 1]

【００５９】[0059]

【表２】 [Table 2]

【００６０】[0060]

【表３】 [Table 3]

【００６１】[0061]

【表４】 [Table 4]

【００６２】[0062]

【表５】 [Table 5]

【００６３】[0063]

【表６】 [Table 6]

【００６４】[0064]

【表７】 [Table 7]

【００６５】[0065]

【表８】 [Table 8]

【００６６】[0066]

【表９】 [Table 9]

【００６７】[0067]

【表１０】 [Table 10]

【００６８】[0068]

【発明の効果】以上述べたように本発明のクロメート処
理亜鉛系めっき鋼板は、Ｎｉ、Ｃｏ等のフラッシュ処理
を施すことなく一工程処理で製造でき、しかも耐黒変
性、耐食性、塗装密着性、潤滑性の何れにも優れた特性
を有している。また、本発明の製造方法によれば、この
ようなクロメート処理亜鉛系めっき鋼板を安定して製造
することができる。As described above, the chromate-treated galvanized steel sheet of the present invention can be manufactured in one step without flash treatment of Ni, Co, etc., and furthermore, the blackening resistance, corrosion resistance, coating adhesion, It has excellent lubricating properties. Moreover, according to the production method of the present invention, such a chromate-treated galvanized steel sheet can be produced stably.

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 亜鉛系めっき鋼板の表面に、下記の成分
〔１〕および成分〔２〕を含有し、且つ下記成分〔１〕
に含まれる６価クロムイオンおよび３価クロムイオン
と、下記成分〔２〕に含まれる界面活性剤〔Ａ〕および
アクリル系共重合体〔Ｂ〕の固形分での重量比
［（〔Ａ〕＋〔Ｂ〕）／（６価クロムイオン＋３価クロ
ムイオン）］が２０／１〜５０／１で、且つｐＨ３以下
の水系樹脂含有クロメート処理液を塗布して形成され
た、金属クロム換算のクロム付着量が５〜５０ｍｇ／ｍ
2のクロメート皮膜を有することを特徴とする、耐黒変
性、耐食性、塗料密着性および潤滑性に優れたクロメー
ト処理亜鉛系めっき鋼板。 成分〔１〕：６価クロムイオンと３価クロムイオンを
［３価クロムイオン／（６価クロムイオン＋３価クロム
イオン）］の重量比で１／１０〜３／１０の割合で含
み、さらに、硝酸イオン、リン酸イオンおよびコバルト
イオンを全クロムイオン（６価クロムイオン＋３価クロ
ムイオン）に対するモル比で下記の割合で含む無機成分 硝酸イオン／全クロムイオン：１．０〜３．０ リン酸イオン／全クロムイオン：０．０５〜０．５ コバルトイオン／全クロムイオン：０．０５〜０．５ 成分〔２〕：疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有
し、且つ親水基としてポリエチレンオキサイド基を有す
る非イオン性反応型界面活性剤が固形分の重量％で５０
％以上含まれる界面活性剤〔Ａ〕の存在下で乳化重合さ
れたアクリル系共重合体〔Ｂ〕の水系樹脂エマルジョン
であって、界面活性剤〔Ａ〕とアクリル系共重合体
〔Ｂ〕の固形分での重量比〔Ａ〕／〔Ｂ〕が１０／１０
０〜２０／１００である樹脂エマルジョン1. The surface of a galvanized steel sheet contains the following components [1] and [2], and the following component [1]:
Weight ratio of the hexavalent chromium ion and trivalent chromium ion contained in the surfactant [A] and the acrylic copolymer [B] contained in the following component [2] at the solid content [([A] + [B]) / (hexavalent chromium ion + trivalent chromium ion)] is 20/1 to 50/1, and a chromium adhesion in terms of metal chromium formed by applying a chromate treatment solution containing an aqueous resin having a pH of 3 or less. The amount is 5-50mg / m
A chromate-treated galvanized steel sheet that is excellent in blackening resistance, corrosion resistance, paint adhesion and lubricity, characterized by having a chromate film of 2 . Component [1]: contains hexavalent chromium ion and trivalent chromium ion in a weight ratio of [trivalent chromium ion / (hexavalent chromium ion + trivalent chromium ion)] of 1/10 to 3/10; Inorganic component containing nitrate ion, phosphate ion and cobalt ion in the following ratio with respect to total chromium ion (hexavalent chromium ion + trivalent chromium ion) in the following ratio: nitrate ion / total chromium ion: 1.0 to 3.0 phosphoric acid Ion / total chromium ion: 0.05 to 0.5 cobalt ion / total chromium ion: 0.05 to 0.5 Component [2]: having a carbon-carbon double bond (C = C) in a hydrophobic group, The nonionic reactive surfactant having a polyethylene oxide group as a hydrophilic group contains 50% by weight of the solid content.
% Of an acrylic copolymer [B] emulsion-polymerized in the presence of a surfactant [A] contained in an amount of at least 10% by weight of the surfactant [A] and the acrylic copolymer [B]. The weight ratio [A] / [B] in solid content is 10/10
0-20 / 100 resin emulsion 【請求項２】 成分〔２〕が、疎水基中に炭素間二重結
合（Ｃ＝Ｃ）を有し、且つ親水基としてポリエチレンオ
キサイド基を有する非イオン性反応型界面活性剤からな
る界面活性剤〔Ａ〕の存在下で乳化重合されたアクリル
系共重合体〔Ｂ〕の水系樹脂エマルジョンであって、界
面活性剤〔Ａ〕とアクリル系共重合体〔Ｂ〕の固形分で
の重量比〔Ａ〕／〔Ｂ〕が１０／１００〜２０／１００
である樹脂エマルジョンであることを特徴とする請求項
１に記載の耐黒変性、耐食性、塗料密着性および潤滑性
に優れたクロメート処理亜鉛系めっき鋼板。2. A surfactant comprising a component [2] comprising a nonionic reactive surfactant having a carbon-carbon double bond (C = C) in a hydrophobic group and a polyethylene oxide group as a hydrophilic group. An aqueous resin emulsion of the acrylic copolymer [B] emulsion-polymerized in the presence of the agent [A], wherein the weight ratio of the surfactant [A] and the acrylic copolymer [B] at the solid content is [A] / [B] is from 10/100 to 20/100
The chromate-treated galvanized steel sheet according to claim 1, which is excellent in blackening resistance, corrosion resistance, paint adhesion, and lubricity. 【請求項３】 亜鉛系めっき鋼板の表面に、下記の成分
〔１〕および成分〔２〕を含有し、且つ下記成分〔１〕
に含まれる６価クロムイオンおよび３価クロムイオン
と、下記成分〔２〕に含まれる界面活性剤〔Ａ〕および
アクリル系共重合体〔Ｂ〕の固形分での重量比
［（〔Ａ〕＋〔Ｂ〕）／（６価クロムイオン＋３価クロ
ムイオン）］が２０／１〜５０／１で、且つｐＨ３以下
の水系樹脂含有クロメート処理液を塗布して形成され
た、金属クロム換算のクロム付着量が５〜５０ｍｇ／ｍ
2のクロメート皮膜を有することを特徴とする、耐黒変
性、耐食性、塗料密着性および潤滑性に優れたクロメー
ト処理亜鉛系めっき鋼板。 成分〔１〕：６価クロムイオンと３価クロムイオンを
［３価クロムイオン／（６価クロムイオン＋３価クロム
イオン）］の重量比で１／１０〜３／１０の割合で含
み、さらに、硝酸イオン、リン酸イオンおよびコバルト
イオンを全クロムイオン（６価クロムイオン＋３価クロ
ムイオン）に対するモル比で下記の割合で含む無機成分 硝酸イオン／全クロムイオン：１．０〜３．０ リン酸イオン／全クロムイオン：０．０５〜０．５ コバルトイオン／全クロムイオン：０．０５〜０．５ 成分〔２〕：疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有
し、且つ親水基としてポリエチレンオキサイド基を有す
る非イオン性反応型界面活性剤〔ａ1〕と疎水基中に炭
素間二重結合（Ｃ＝Ｃ）を有し、且つ親水基としてポリ
エチレンオキサイド基を有する非イオン−アニオン性複
合反応型界面活性剤〔ａ2〕とからなり、非イオン性反
応型界面活性剤〔ａ1〕と非イオン−アニオン性複合反
応型界面活性剤〔ａ2〕の固形分の重量比〔ａ1〕／〔ａ
2〕が１／２以上である界面活性剤〔Ａ〕の存在下で乳
化重合されたアクリル系共重合体〔Ｂ〕の水系樹脂エマ
ルジョンであって、界面活性剤〔Ａ〕とアクリル系共重
合体〔Ｂ〕の固形分での重量比〔Ａ〕／〔Ｂ〕が１０／
１００〜２０／１００である樹脂エマルジョン3. The surface of a galvanized steel sheet contains the following components [1] and [2] and the following component [1]:
Weight ratio of the hexavalent chromium ion and trivalent chromium ion contained in the surfactant [A] and the acrylic copolymer [B] contained in the following component [2] at the solid content [([A] + [B]) / (hexavalent chromium ion + trivalent chromium ion)] is 20/1 to 50/1, and a chromium adhesion in terms of metal chromium formed by applying a chromate treatment solution containing an aqueous resin having a pH of 3 or less. The amount is 5-50mg / m
A chromate-treated galvanized steel sheet that is excellent in blackening resistance, corrosion resistance, paint adhesion and lubricity, characterized by having a chromate film of 2 . Component [1]: contains hexavalent chromium ion and trivalent chromium ion in a weight ratio of [trivalent chromium ion / (hexavalent chromium ion + trivalent chromium ion)] of 1/10 to 3/10; Inorganic component containing nitrate ion, phosphate ion and cobalt ion in the following ratio with respect to total chromium ion (hexavalent chromium ion + trivalent chromium ion) in the following ratio: nitrate ion / total chromium ion: 1.0 to 3.0 phosphoric acid Ion / total chromium ion: 0.05 to 0.5 cobalt ion / total chromium ion: 0.05 to 0.5 Component [2]: having a carbon-carbon double bond (C = C) in a hydrophobic group, And a nonionic reactive surfactant [a 1 ] having a polyethylene oxide group as a hydrophilic group and a non-ionic surfactant having a carbon-carbon double bond (C = C) in a hydrophobic group and having a polyethylene oxide group as a hydrophilic group. I On - made from anionic complex reactive surfactant and [a 2], the non-ionic reactive surfactant [a 1] and nonionic - anionic complex reactive surfactant of solids [a 2] Weight ratio [a 1 ] / [a
2 ] is an aqueous resin emulsion of an acrylic copolymer [B] emulsion-polymerized in the presence of a surfactant [A] in which the amount of the surfactant [A] is at least 界面. The weight ratio [A] / [B] at the solid content of the combined [B] is 10 /
100-20 / 100 resin emulsion 【請求項４】 亜鉛系めっき鋼板の表面に、下記の成分
〔１〕および成分〔２〕を含有し、且つ下記成分〔１〕
に含まれる６価クロムイオンおよび３価クロムイオン
と、下記成分〔２〕に含まれる界面活性剤〔Ａ〕および
アクリル系共重合体〔Ｂ〕の固形分での重量比
［（〔Ａ〕＋〔Ｂ〕）／（６価クロムイオン＋３価クロ
ムイオン）］が２０／１〜５０／１で、且つｐＨ３以下
の水系樹脂含有クロメート処理液を、金属クロム換算の
クロム付着量が５〜５０ｍｇ／ｍ2となるよう塗布した
後、５０〜２００℃で乾燥することを特徴とする、耐黒
変性、耐食性、塗料密着性および潤滑性に優れたクロメ
ート処理亜鉛系めっき鋼板の製造方法。 成分〔１〕：６価クロムイオンと３価クロムイオンを
［３価クロムイオン／（６価クロムイオン＋３価クロム
イオン）］の重量比で１／１０〜３／１０の割合で含
み、さらに、硝酸イオン、リン酸イオンおよびコバルト
イオンを全クロムイオン（６価クロムイオン＋３価クロ
ムイオン）に対するモル比で下記の割合で含む無機成分 硝酸イオン／全クロムイオン：１．０〜３．０ リン酸イオン／全クロムイオン：０．０５〜０．５ コバルトイオン／全クロムイオン：０．０５〜０．５ 成分〔２〕：疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有
し、且つ親水基としてポリエチレンオキサイド基を有す
る非イオン性反応型界面活性剤が固形分の重量％で５０
％以上含まれる界面活性剤〔Ａ〕の存在下で乳化重合さ
れたアクリル系共重合体〔Ｂ〕の水系樹脂エマルジョン
であって、界面活性剤〔Ａ〕とアクリル系共重合体
〔Ｂ〕の固形分での重量比〔Ａ〕／〔Ｂ〕が１０／１０
０〜２０／１００である樹脂エマルジョン4. The surface of a galvanized steel sheet contains the following components [1] and [2], and the following components [1]:
Weight ratio of the hexavalent chromium ion and trivalent chromium ion contained in the surfactant [A] and the acrylic copolymer [B] contained in the following component [2] at the solid content [([A] + [B]) / (hexavalent chromium ion + trivalent chromium ion)] is 20/1 to 50/1 and the pH is 3 or less. after coating so as to be m 2, wherein the drying at 50 to 200 ° C., blackening, the corrosion resistance, the production method excellent chromated galvanized steel sheet in the paint adhesion and lubricating property. Component [1]: contains hexavalent chromium ion and trivalent chromium ion in a weight ratio of [trivalent chromium ion / (hexavalent chromium ion + trivalent chromium ion)] of 1/10 to 3/10; Inorganic component containing nitrate ion, phosphate ion and cobalt ion in the following ratio with respect to total chromium ion (hexavalent chromium ion + trivalent chromium ion) in the following ratio: nitrate ion / total chromium ion: 1.0 to 3.0 phosphoric acid Ion / total chromium ion: 0.05 to 0.5 cobalt ion / total chromium ion: 0.05 to 0.5 Component [2]: having a carbon-carbon double bond (C = C) in a hydrophobic group, The nonionic reactive surfactant having a polyethylene oxide group as a hydrophilic group contains 50% by weight of the solid content.
% Of an acrylic copolymer [B] emulsion-polymerized in the presence of a surfactant [A] contained in an amount of at least 10% by weight of the surfactant [A] and the acrylic copolymer [B]. The weight ratio [A] / [B] in solid content is 10/10
0-20 / 100 resin emulsion 【請求項５】 成分〔２〕が、疎水基中に炭素間二重結
合（Ｃ＝Ｃ）を有し、且つ親水基としてポリエチレンオ
キサイド基を有する非イオン性反応型界面活性剤からな
る界面活性剤〔Ａ〕の存在下で乳化重合されたアクリル
系共重合体〔Ｂ〕の水系樹脂エマルジョンであって、界
面活性剤〔Ａ〕とアクリル系共重合体〔Ｂ〕の固形分で
の重量比〔Ａ〕／〔Ｂ〕が１０／１００〜２０／１００
である樹脂エマルジョンであることを特徴とする請求項
４に記載の耐黒変性、耐食性、塗料密着性および潤滑性
に優れたクロメート処理亜鉛系めっき鋼板の製造方法。5. A surfactant comprising a nonionic reactive surfactant in which the component [2] has a carbon-carbon double bond (C = C) in a hydrophobic group and a polyethylene oxide group as a hydrophilic group. An aqueous resin emulsion of the acrylic copolymer [B] emulsion-polymerized in the presence of the agent [A], wherein the weight ratio of the surfactant [A] and the acrylic copolymer [B] at the solid content is [A] / [B] is from 10/100 to 20/100
The method for producing a chromate-treated galvanized steel sheet excellent in blackening resistance, corrosion resistance, paint adhesion, and lubricity according to claim 4, wherein the resin emulsion is a resin emulsion. 【請求項６】 亜鉛系めっき鋼板の表面に、下記の成分
〔１〕および成分〔２〕を含有し、且つ下記成分〔１〕
に含まれる６価クロムイオンおよび３価クロムイオン
と、下記成分〔２〕に含まれる界面活性剤〔Ａ〕および
アクリル系共重合体〔Ｂ〕の固形分での重量比
［（〔Ａ〕＋〔Ｂ〕）／（６価クロムイオン＋３価クロ
ムイオン）］が２０／１〜５０／１で、且つｐＨ３以下
の水系樹脂含有クロメート処理液を、金属クロム換算の
クロム付着量が５〜５０ｍｇ／ｍ2となるよう塗布した
後、５０〜２００℃で乾燥することを特徴とする、耐黒
変性、耐食性、塗料密着性および潤滑性に優れたクロメ
ート処理亜鉛系めっき鋼板の製造方法。 成分〔１〕：６価クロムイオンと３価クロムイオンを
［３価クロムイオン／（６価クロムイオン＋３価クロム
イオン）］の重量比で１／１０〜３／１０の割合で含
み、さらに、硝酸イオン、リン酸イオンおよびコバルト
イオンを全クロムイオン（６価クロムイオン＋３価クロ
ムイオン）に対するモル比で下記の割合で含む無機成分 硝酸イオン／全クロムイオン：１．０〜３．０ リン酸イオン／全クロムイオン：０．０５〜０．５ コバルトイオン／全クロムイオン：０．０５〜０．５ 成分〔２〕：疎水基中に炭素間二重結合（Ｃ＝Ｃ）を有
し、且つ親水基としてポリエチレンオキサイド基を有す
る非イオン性反応型界面活性剤〔ａ1〕と疎水基中に炭
素間二重結合（Ｃ＝Ｃ）を有し、且つ親水基としてポリ
エチレンオキサイド基を有する非イオン−アニオン性複
合反応型界面活性剤〔ａ2〕とからなり、非イオン性反
応型界面活性剤〔ａ1〕と非イオン−アニオン性複合反
応型界面活性剤〔ａ2〕の固形分の重量比〔ａ1〕／〔ａ
2〕が１／２以上である界面活性剤〔Ａ〕の存在下で乳
化重合されたアクリル系共重合体〔Ｂ〕の水系樹脂エマ
ルジョンであって、界面活性剤〔Ａ〕とアクリル系共重
合体〔Ｂ〕の固形分での重量比〔Ａ〕／〔Ｂ〕が１０／
１００〜２０／１００である樹脂エマルジョン6. The surface of a galvanized steel sheet contains the following components [1] and [2] and the following component [1]:
Weight ratio of the hexavalent chromium ion and trivalent chromium ion contained in the surfactant [A] and the acrylic copolymer [B] contained in the following component [2] at the solid content [([A] + [B]) / (hexavalent chromium ion + trivalent chromium ion)] is 20/1 to 50/1 and the pH is 3 or less. after coating so as to be m 2, wherein the drying at 50 to 200 ° C., blackening, the corrosion resistance, the production method excellent chromated galvanized steel sheet in the paint adhesion and lubricating property. Component [1]: contains hexavalent chromium ion and trivalent chromium ion in a weight ratio of [trivalent chromium ion / (hexavalent chromium ion + trivalent chromium ion)] of 1/10 to 3/10; Inorganic component containing nitrate ion, phosphate ion and cobalt ion in the following ratio with respect to total chromium ion (hexavalent chromium ion + trivalent chromium ion) in the following ratio: nitrate ion / total chromium ion: 1.0 to 3.0 phosphoric acid Ion / total chromium ion: 0.05 to 0.5 cobalt ion / total chromium ion: 0.05 to 0.5 Component [2]: having a carbon-carbon double bond (C = C) in a hydrophobic group, And a nonionic reactive surfactant [a 1 ] having a polyethylene oxide group as a hydrophilic group and a non-ionic surfactant having a carbon-carbon double bond (C = C) in a hydrophobic group and having a polyethylene oxide group as a hydrophilic group. I On - made from anionic complex reactive surfactant and [a 2], the non-ionic reactive surfactant [a 1] and nonionic - anionic complex reactive surfactant of solids [a 2] Weight ratio [a 1 ] / [a
2 ] is an aqueous resin emulsion of an acrylic copolymer [B] emulsion-polymerized in the presence of a surfactant [A] in which the amount of the surfactant [A] is at least 界面. The weight ratio [A] / [B] at the solid content of the combined [B] is 10 /
100-20 / 100 resin emulsion
JP10237993A 1997-08-13 1998-08-10 Chromate treated zinc base plated steel sheet having excellent black denaturation resistance, corrosion resistance, coating material adhesion property and lubricity and its production Pending JPH11124686A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10237993A JPH11124686A (en) 1997-08-13 1998-08-10 Chromate treated zinc base plated steel sheet having excellent black denaturation resistance, corrosion resistance, coating material adhesion property and lubricity and its production

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP9-230472 1997-08-13
JP23047297 1997-08-13
JP10237993A JPH11124686A (en) 1997-08-13 1998-08-10 Chromate treated zinc base plated steel sheet having excellent black denaturation resistance, corrosion resistance, coating material adhesion property and lubricity and its production

Publications (1)

Publication Number Publication Date
JPH11124686A true JPH11124686A (en) 1999-05-11

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100950127B1 (en) * 2001-10-18 2010-03-30 캐나디안 일렉트로닉 파우더스 코퍼레이션 Powder for laminated ceramic capacitor internal electrode

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100950127B1 (en) * 2001-10-18 2010-03-30 캐나디안 일렉트로닉 파우더스 코퍼레이션 Powder for laminated ceramic capacitor internal electrode

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