JPH09241859A - Organic clad coating steel excellent in chromium eluting resistance and blister resistance - Google Patents
Organic clad coating steel excellent in chromium eluting resistance and blister resistanceInfo
- Publication number
- JPH09241859A JPH09241859A JP5295196A JP5295196A JPH09241859A JP H09241859 A JPH09241859 A JP H09241859A JP 5295196 A JP5295196 A JP 5295196A JP 5295196 A JP5295196 A JP 5295196A JP H09241859 A JPH09241859 A JP H09241859A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- chromate
- resistance
- weight ratio
- regulated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
-
- 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
- C23C22/34—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 fluorides or complex fluorides
- C23C22/37—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 fluorides or complex fluorides containing also hexavalent chromium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、主に自動車車体用
鋼板として、特に耐クロム溶出性および耐ブリスター性
に優れた有機複合被覆鋼板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic composite coated steel sheet having excellent chromium elution resistance and blister resistance, mainly as a steel sheet for automobile bodies.
【０００２】[0002]
【従来の技術】クロメート層と亜鉛または亜鉛系合金め
っき鋼板との密着性向上のために、クロメート処理液中
に、クロム（Ｃｒ3+、Ｃｒ6+）以外に、シリカ、リン
酸、樹脂、およびフッ素化合物を添加する方法が、特開
平０２−２４３７７２号公報および特開平０４−３５８
０８０号公報に記載されている。2. Description of the Related Art In order to improve the adhesion between a chromate layer and a zinc- or zinc-based alloy plated steel sheet, silica, phosphoric acid, resin, other than chromium (Cr 3+ , Cr 6+ ) is added to the chromate treatment liquid. And a method of adding a fluorine compound are disclosed in JP-A-02-243772 and JP-A-04-358.
No. 080 gazette.
【０００３】特開平０２−２４３７７２号公報は、クロ
メート液中に、クロム以外にシリカ、樹脂、フッ素化合
物を添加する方法を開示している。該公報は、純亜鉛め
っきの耐指紋性向上のみを目的とするもので、該公報で
得られるクロメート鋼板は、主として家電用であると考
えられ、自動車用途用鋼板とは、その使用背景、目的を
異にすることは明らかであり、本願発明の目的とする自
動車用鋼板としての耐クロム溶出性、耐ブリスター性を
向上させることはできない。Japanese Unexamined Patent Publication No. 02-243772 discloses a method of adding silica, a resin and a fluorine compound in addition to chromium to a chromate solution. This publication is intended only for improving the fingerprint resistance of pure zinc plating, and the chromate steel sheet obtained in this publication is considered to be mainly for home appliances. It is obvious that they are different from each other, and it is not possible to improve the chromium elution resistance and the blister resistance of the steel sheet for automobiles, which is the object of the present invention.
【０００４】特開平０４−３５８０８０号公報にも、ク
ロメート液中に、クロム以外に、シリカ、リン酸、樹
脂、フッ素化合物を添加する方法が開示されている。し
かしながら、該公報も家電用クロメート処理を念頭にお
いているものと考えられ、自動車用途として必要な耐ク
ロム溶出、耐ブリスター性の向上は得られない。Japanese Patent Application Laid-Open No. 04-358080 also discloses a method of adding silica, phosphoric acid, a resin and a fluorine compound to the chromate solution in addition to chromium. However, it is considered that this publication also bears the chromate treatment for home appliances in mind, and the improvement of chromium elution resistance and blister resistance required for automobile applications cannot be obtained.
【０００５】[0005]
【発明が解決しようとする課題】本発明は主として自動
車車体鋼板として、表面にクロメートおよび有機樹脂層
を有する有機複合被覆鋼板において、特に主として自動
車用途として用いるときに必要な、耐クロム溶出性およ
び耐ブリスター性の向上を図ることを目的とする。DISCLOSURE OF THE INVENTION The present invention is mainly used as an automobile body steel sheet, in an organic composite coated steel sheet having a chromate and an organic resin layer on the surface thereof, and particularly when it is mainly used for automobiles, the chromium elution resistance and the corrosion resistance are required. The purpose is to improve the blister property.
【０００６】[0006]
【課題を解決するための手段】上記問題を解決するため
に、亜鉛めっきまたは亜鉛系合金めっき鋼板表面上にＣ
ｒ6+量が、全Ｃｒに対して、重量比で２５〜６０ｗｔ
％、シリカが、密に充填可能な二組の粒径分布を有する
親水性気相シリカであり、その量が、全Ｃｒに対して、
重量比で０．５〜３．０、リン酸が、全Ｃｒに対して、
重量比で０．０１〜２．０、フッ素化合物量がフッ素と
して、全Ｃｒに対して、重量比で０．０２〜２．０、多
価フェノール性多糖類、蔗糖、麦芽糖、乳糖、果糖から
選ばれる一種類以上の有機化合物が、全Ｃｒに対して、
モル比で０．０５〜５．０、クロメート付着量が全Ｃｒ
換算で１０〜２００ｍｇ／ｍ2 であるクロメート被膜を
有し、該クロメート被膜の上層に、主として樹脂とシリ
カからなる有機樹脂層を有することを特徴とする、耐ク
ロム溶出性および耐ブリスター性に優れた有機複合被覆
鋼板。ここで、クロメート層中のシリカが、一次粒子径
が０．０５ｎｍ以上１０ｎｍ未満の親水性気相シリカに
対して、１０ｎｍ以上１００ｎｍ以下の親水性気相シリ
カを重量比で１〜１０含有する混合系であることが好適
である。[Means for Solving the Problems] In order to solve the above problems, C is formed on the surface of a galvanized or zinc-based alloy-plated steel sheet.
The amount of r 6+ is 25 to 60 wt% with respect to the total Cr.
%, Silica is a hydrophilic vapor phase silica having two sets of particle size distribution that can be densely packed, and its amount is relative to total Cr.
0.5 to 3.0 by weight ratio, phosphoric acid is based on all Cr,
From 0.01 to 2.0 in weight ratio and 0.02 to 2.0 in weight ratio with respect to the total Cr as a fluorine compound amount as fluorine, from polyhydric phenolic polysaccharides, sucrose, maltose, lactose and fructose One or more kinds of organic compounds selected are all Cr,
The molar ratio is 0.05 to 5.0, and the amount of chromate deposited is total Cr.
Excellent chromate elution resistance and blistering resistance, characterized by having a chromate film of 10 to 200 mg / m 2 in terms of conversion, and having an organic resin layer mainly composed of resin and silica on the upper layer of the chromate film. Organic composite coated steel sheet. Here, the silica in the chromate layer is a mixture containing hydrophilic gas phase silica having a primary particle diameter of 0.05 nm or more and less than 10 nm and hydrophilic gas phase silica of 10 nm or more and 100 nm or less in a weight ratio of 1 to 10 It is preferably a system.
【０００７】以下、本発明に関し、具体的に説明する。
本発明の下地鋼板としては、亜鉛または亜鉛系合金めっ
き鋼板を用いる。亜鉛または亜鉛系合金めっきには、純
亜鉛めっき、ＺｎＮｉ合金めっき、ＺｎＦｅ合金めっ
き、ＺｎＣｒ合金めっき等の二元系めっき、ZnNiCrめっ
き、ZnCoCrめっきなどの三元系めっき、ZnSiO2めっき、
ZnCoCrAl2O3 めっき等の複合分散めっき等種々のものが
あるが、本願発明における下地鋼板としては、ＺｎＮｉ
合金めっき、ＺｎＦｅ合金めっき、ＺｎＣｒ合金めっ
き、ZnNiCr合金めっき、ZnCoCrAl2O3めっきが、本願発
明の有機複合被覆鋼板下地として好ましく、その中で
も、Ｎｉ含有率が９〜１６ｗｔ％であるＺｎＮｉ合金め
っきが、特に好ましい。これらのめっきは、電気めっき
法、溶融めっき法、または気相めっき法によって施され
る。The present invention will be described in detail below.
A zinc or zinc-based alloy plated steel sheet is used as the base steel sheet of the present invention. Zinc or zinc alloy plating includes pure zinc plating, binary plating such as ZnNi alloy plating, ZnFe alloy plating and ZnCr alloy plating, ternary plating such as ZnNiCr plating and ZnCoCr plating, ZnSiO 2 plating,
There are various types such as composite dispersion plating such as ZnCoCrAl 2 O 3 plating, but as the base steel sheet in the present invention, ZnNi
Alloy plating, ZnFe alloy plating, ZnCr alloy plating, ZnNiCr alloy plating, ZnCoCrAl 2 O 3 plating are preferred as the organic composite coated steel sheet substrate of the present invention, among which ZnNi alloy plating having a Ni content of 9 to 16 wt% is preferable. , Particularly preferred. These platings are performed by electroplating, hot dipping, or vapor plating.
【０００８】これらの亜鉛または亜鉛系合金めっき鋼板
上に、後述の有機高分子樹脂層との密着性向上、耐食性
を付与しかつ、耐クロム溶出性および耐ブリスター性の
向上等を目的として、シリカ、リン酸、フッ素化合物、
多価フェノール性糖類、蔗糖等の糖類を添加したクロメ
ート液を用いて、クロメート被膜を形成する。On these zinc- or zinc-based alloy-plated steel sheets, silica is used for the purpose of improving adhesion to the organic polymer resin layer described later, imparting corrosion resistance, and improving chromium elution resistance and blister resistance. , Phosphoric acid, fluorine compounds,
A chromate film is formed using a chromate solution to which saccharides such as polyhydric phenol saccharides and sucrose are added.
【０００９】クロメート付着量として、Ｃｒ換算で１０
〜２００ｍｇ／ｍ2 、好ましくは２０〜１５０ｍｇ／ｍ
2 、さらに好ましくは４５〜１５０ｍｇ／ｍ2 の範囲と
する。Ｃｒ付着量が１０ｍｇ／ｍ2 未満では、耐食性が
不十分であるばかりでなく、樹脂層との密着性も劣るた
め好ましくない。２００ｍｇ／ｍ2 を超えた場合、耐ク
ロム溶出性が低下するばかりでなく、被膜の絶縁抵抗が
高まり、スポット溶接性および電着塗装性を損なうので
好ましくない。The amount of chromate deposited is 10 in terms of Cr.
~ 200 mg / m 2 , preferably 20-150 mg / m
2 , more preferably 45 to 150 mg / m 2 . When the amount of deposited Cr is less than 10 mg / m 2 , not only the corrosion resistance is insufficient, but also the adhesion to the resin layer is poor, which is not preferable. When it exceeds 200 mg / m 2 , not only the chromium elution resistance is lowered, but also the insulation resistance of the coating film is increased and the spot weldability and electrodeposition coatability are impaired, which is not preferable.
【００１０】クロメート層のＣｒ6+量は、全Ｃｒに対し
て２５〜６０％、好ましくは３０〜４０％とする。Ｃｒ
6+量が２５％未満であると、Ｃｒ6+による自己修復作用
が望めず、耐食性に劣る被膜しか得られない。逆に、Ｃ
ｒ6+量が６０％を超えると、アルカリ脱脂時にクロメー
ト層中のＣｒ6+の溶出が起こりやすくなるため、好まし
くない。The amount of Cr 6+ in the chromate layer is 25 to 60%, preferably 30 to 40%, based on the total Cr. Cr
If the amount of 6+ is less than 25%, the self-repairing action of Cr 6+ cannot be expected, and only a coating having poor corrosion resistance can be obtained. Conversely, C
If the amount of r 6+ exceeds 60%, Cr 6+ in the chromate layer is likely to be eluted during alkaline degreasing, which is not preferable.
【００１１】クロメート層へ添加するシリカは、親水性
気相シリカが好適に使用できる。親水性気相シリカは、
ハロゲン化珪素の酸水素焔中での高温加水分解により合
成されるもの、石英から精製される電気アーク法により
合成されるものがあり表面にはシラノール基を有する。
シリカの添加は、クロメート液塗布後の乾燥−成膜時
に、シリカとクロム間で強固な三次元ネットワークを形
成させるために必要である。すなわち、比表面積を大き
くし、その結果、上層樹脂層との相互作用に関与するシ
ラノール基量が多くなり、樹脂の密着性向上に効果的な
ためである。シリカゾル（液相シリカ）は、気相シリカ
に比べて比表面積を大きくする効果は小さいため、その
ままでは本願発明の目的とする用途に使用できない。た
だし、一次粒子を二次凝集させて比表面積を増大させた
ものは、気相シリカより三次元ネットワーク形成の性能
はかなり劣るが、使用できないわけではない。従来は、
特開平２−２４３７７２号公報、特開平４−３５８０８
０号公報のように、シリカゾルの規定を全く行わずにク
ロメート液中に添加する方法が開示されているが、その
方法では、本願発明に記載されたクロメート液組成で
は、全く効果がないのである。As the silica added to the chromate layer, hydrophilic gas phase silica can be preferably used. The hydrophilic vapor phase silica is
Some are synthesized by high-temperature hydrolysis of silicon halide in oxyhydrogen flame, others are synthesized by electric arc method refined from quartz, and have silanol groups on the surface.
The addition of silica is necessary in order to form a strong three-dimensional network between silica and chromium during the drying-film formation after coating the chromate solution. That is, the specific surface area is increased, and as a result, the amount of silanol groups involved in the interaction with the upper resin layer is increased, which is effective in improving the adhesiveness of the resin. Since silica sol (liquid phase silica) has a smaller effect of increasing the specific surface area than vapor phase silica, it cannot be used as it is for the intended purpose of the present invention. However, the one obtained by secondary-aggregating the primary particles to increase the specific surface area is considerably inferior to the vapor phase silica in the performance of forming a three-dimensional network, but is not unusable. conventionally,
JP-A-2-243772, JP-A-4-35808
A method of adding silica sol to a chromate solution without defining the silica sol is disclosed, as in JP-A-0, but the method has no effect at all in the chromate solution composition described in the present invention. .
【００１２】シリカの粒径は、ＢＥＴ法による測定を行
い、一次粒子径０．０５ｎｍ以上１０ｎｍ未満、好まし
くは４〜１０ｎｍの親水性気相シリカに対して、一次粒
子径１０ｎｍ以上１００ｎｍ以下、好ましくは２０〜５
０ｎｍの親水性気相シリカを重量比で１〜１０含有する
混合系であることが好ましい。このような二組の粒径分
布を有するシリカを用いることによって、単一の粒径分
布を有するシリカに比べて密に充填させることが可能と
なり、また、クロムとシリカのより強固なネットワーク
を形成できるため、クロメート被膜中のＣｒ6+の溶出を
抑制でき、耐食性の向上にも有効なためである。さらに
後述する有機化合物との併用により、Ｃｒ6+の溶出をさ
らに効果的に抑制できる。The particle size of silica is measured by the BET method, and the primary particle size is 10 nm or more and 100 nm or less, preferably 4 nm to 10 nm with respect to hydrophilic gas phase silica having a primary particle size of 0.05 nm or more and less than 10 nm. Is 20-5
A mixed system containing 1 to 10 by weight of 0 nm hydrophilic vapor phase silica is preferable. By using silica having such two sets of particle size distribution, it is possible to make packing more dense than silica having a single particle size distribution, and to form a stronger network of chromium and silica. Since it is possible to suppress the elution of Cr 6+ in the chromate film, it is also effective for improving the corrosion resistance. Further, the combined use with an organic compound described later can more effectively suppress the elution of Cr 6+ .
【００１３】一次粒子径０．０５ｎｍ以上１０ｎｍ未満
のシリカよりも粒径が小さいシリカを用いることは、ク
ロメート液中での均一分散を行わせ難く、最密充填効果
を最大限に利用することができず、Ｃｒ6+の溶出抑制効
果が小さくなるため好ましくない。逆に一次粒子径１０
ｎｍ以上１００ｎｍ以下の粒径範囲よりも大粒径のシリ
カを使用すれば、大粒子径シリカ間の空隙が大きくなり
すぎ、最密充填を行うためには小粒径のシリカ添加量を
限度以上に添加する必要がある。その結果、クロメート
被膜の粘度上昇に伴う成膜性の低下や、塗膜密着性の低
下が生じるためシリカ粒径が規定を超えることは好まし
くない。なお、このような二つの粒径分布を有するシリ
カを用いることにより、クロメート被膜の成膜時の焼き
付け温度は、８０℃〜１８０℃、好ましくは１００℃〜
１４５℃で十分である。これは、本願に引用した特開平
０２−２４３７７２号公報の焼き付け温度１５０℃〜２
５０℃を大幅に下まわるものであり、本願発明のクロメ
ート層成膜の容易さが証明される。The use of silica having a particle size smaller than that of silica having a primary particle size of 0.05 nm or more and less than 10 nm makes it difficult to uniformly disperse in the chromate solution and maximizes the close packing effect. This is not preferable because the effect of suppressing the elution of Cr 6+ is reduced. Conversely, the primary particle size is 10
If silica having a particle size larger than the particle size range of 100 nm or more and 100 nm or less is used, the voids between the silica particles having a large particle size become too large, and in order to perform the closest packing, the addition amount of the silica having a small particle size is over Need to be added to. As a result, the film-forming property and the coating film adhesion decrease as the viscosity of the chromate film increases, so that it is not preferable that the silica particle size exceeds the specified value. By using silica having such two particle size distributions, the baking temperature during the formation of the chromate film is 80 ° C to 180 ° C, preferably 100 ° C to
145 ° C is sufficient. This is a baking temperature of 150 ° C. to 2 of Japanese Patent Application Laid-Open No. 02-243772 cited in the present application.
This is much lower than 50 ° C., which proves the ease of forming the chromate layer of the present invention.
【００１４】クロメート層中のシリカ重量比は全Ｃｒ量
に対し０．５〜３．０でなければならない。シリカ重量
比が０．５未満では、耐水二次密着性が不十分になるた
めであり、３を超えても、それ以上の耐水二次密着性改
善効果が無く、絶縁物であるシリカによってスポット溶
接性と電着塗装性を損なわれるため好ましくない。The weight ratio of silica in the chromate layer should be 0.5 to 3.0 based on the total Cr content. If the weight ratio of silica is less than 0.5, the water-resistant secondary adhesion will be insufficient, and if it exceeds 3, there will be no further improvement in the water-resistant secondary adhesion, and silica as an insulator will not Weldability and electrodeposition coatability are impaired, which is not preferable.
【００１５】クロメート層のリン酸重量比は、全Ｃｒ量
に対し、０．０１〜２．０である必要がある。リン酸重
量比が０．０１未満であると、十分な亜鉛系めっきのエ
ッチング効果が無く、めっきとの密着性に劣り、クロメ
ート液の安定性も劣る。一方、リン酸重量比が２．０を
超えると、耐クロム溶出性に劣るクロメート層となる。The weight ratio of phosphoric acid in the chromate layer should be 0.01 to 2.0 with respect to the total amount of Cr. When the phosphoric acid weight ratio is less than 0.01, the zinc-based plating does not have a sufficient etching effect, the adhesion to the plating is poor, and the stability of the chromate solution is poor. On the other hand, when the phosphoric acid weight ratio exceeds 2.0, the chromate layer has poor chromium elution resistance.
【００１６】フッ素化合物は、クロメート層とめっきと
の密着性を向上させるために、フッ素として、全Ｃｒ量
に対し０．０１〜２．０、好ましくは０．０２〜０．
８、さらに好ましくは０．０２〜０．１９の範囲で添加
する。フッ素化合物が０．０２未満では、めっきとの密
着性向上効果が十分に得られないため好ましくない。逆
に、フッ素化合物が２．０を超えると、亜鉛または亜鉛
系めっきのエッチング量が多くなり、耐水二次密着性や
耐食性の低下をもたらすため好ましくない。ここでフッ
素化合物とはH2TiF6、H2ZrF6、H2SiF6、H2SrF6等が好適
に使用できる。これらは、単独で添加してもよいが、二
種以上を組み合わせて添加しても、好適な結果が得られ
る。フッ素化合物は、それ単独の添加でもめっき密着性
向上効果があるが、リン酸と併用することにより、他の
特性（耐クロム溶出性、耐ブリスター性等）を損なうこ
となく、めっき密着性をさらに向上することができる。
また、効果の向上は、フッ素化合物の添加量が、全Ｃｒ
量に関し、０．０２〜０．８、好ましくは０．０２〜
０．１９の範囲で最大になる。本願発明では、クロメー
ト液中の全Ｃｒ量に対するフッ素化合物比を比較的少な
くすることにより、密着性向上効果をもたらすことに成
功したものである。さらに、粒径分布の異なる気相シリ
カを使用し、三次元ネットワークの発達したクロメート
被膜構造としたことにより、前述のフッ素化合物および
リン酸添加効果が、より大きくなる。The fluorine compound is used as fluorine in an amount of 0.01 to 2.0, preferably 0.02 to 0.2, relative to the total amount of Cr in order to improve the adhesion between the chromate layer and the plating.
8, more preferably 0.02 to 0.19. If the amount of the fluorine compound is less than 0.02, the effect of improving the adhesion to plating cannot be sufficiently obtained, which is not preferable. On the other hand, if the fluorine compound content exceeds 2.0, the etching amount of zinc or zinc-based plating increases, resulting in a decrease in water-resistant secondary adhesion and corrosion resistance, which is not preferable. Here, as the fluorine compound, H 2 TiF 6 , H 2 ZrF 6 , H 2 SiF 6 , H 2 SrF 6 and the like can be preferably used. These may be added alone, or suitable results may be obtained by adding two or more kinds in combination. The fluorine compound has the effect of improving the plating adhesion even if added alone, but by using it in combination with phosphoric acid, the plating adhesion is further improved without impairing other properties (chromium elution resistance, blister resistance, etc.). Can be improved.
In addition, the effect is improved when the amount of fluorine compound added is
Regarding the amount, 0.02-0.8, preferably 0.02-
It becomes the maximum in the range of 0.19. The present invention succeeds in providing the effect of improving the adhesiveness by relatively reducing the ratio of the fluorine compound to the total amount of Cr in the chromate solution. Furthermore, by using a vapor phase silica having a different particle size distribution and having a chromate film structure with a developed three-dimensional network, the effect of adding the above-mentioned fluorine compound and phosphoric acid becomes greater.
【００１７】多価フェノール性多糖類、蔗糖、麦芽糖、
乳糖、果糖から選ばれる一種類以上の有機化合物は、ク
ロメート被膜の耐食性を大幅に向上すると同時に、特に
シリカを最密充填させて、クロムとシリカのより強固な
ネットワークを形成した状況下において、溶出しやすい
Ｃｒ（VI）を溶出しないＣｒ（III)へ還元することによ
り、耐クロム溶出性をより向上する。上記有機化合物の
添加量は、全Ｃｒに対して、０．０５〜５．０（モル
比）とする。好ましくは、０．０５〜２．５（モル
比）。クロメート中に添加される上記有機化合物量が
０．０５未満であれば、耐食性向上に効果が無いためで
あり、逆に５．０を超えると、耐Ｃｒ溶出性が低下する
ためである。Polyphenolic polysaccharides, sucrose, maltose,
One or more organic compounds selected from lactose and fructose significantly improve the corrosion resistance of the chromate coating, and at the same time, elute under the condition that silica is most closely packed to form a stronger network of chromium and silica. By reducing Cr (VI), which is easy to dissolve, to Cr (III) that does not elute, the chromium elution resistance is further improved. The amount of the organic compound added is 0.05 to 5.0 (molar ratio) with respect to the total Cr. Preferably, it is 0.05 to 2.5 (molar ratio). This is because if the amount of the organic compound added to the chromate is less than 0.05, there is no effect in improving the corrosion resistance, and conversely, if it exceeds 5.0, the Cr elution resistance decreases.
【００１８】次に、本願発明の有機複合被覆鋼板の製造
方法の一例を説明する。クロメート層を亜鉛または亜鉛
系合金めっき鋼板上に形成する方法は、前述した所定の
組成物を所定の割合で混合して得られた処理液を用い、
ロールコーター等を用いる塗布型クロメート法によって
行うのが好ましいが、電解型クロメート法または反応型
クロメート法等の種々の方法によっても行ってもよい。
この場合、クロメート処理液の混合方法は、水にクロム
酸とリン酸を加え、所定の還元率とし、次に、多価フェ
ノール性多糖類、蔗糖、麦芽糖、乳糖、果糖から選ばれ
る一種以上の有機化合物を加える。その後、シリカ分散
液、フッ素化合物の順で加える。なお、本発明において
は、液の濡れ性が良好であるため、この場合に樹脂を加
える必要がない。めっき板をクロメート処理液で処理し
た後は、熱風乾燥等による乾燥工程を経てクロメート被
膜をめっき板の少なくとも一方の面に形成する。なお、
乾燥工程における加熱処理は、シリカの三次元ネットワ
ークが容易に形成できる組成であるため、６０℃〜１８
０℃、好ましくは１００℃〜１４５℃という低温で処理
が可能である。Next, an example of the method for producing the organic composite coated steel sheet of the present invention will be described. The method of forming the chromate layer on the zinc or zinc-based alloy plated steel sheet, using a treatment liquid obtained by mixing the above-mentioned predetermined composition in a predetermined ratio,
It is preferable to carry out by a coating type chromate method using a roll coater or the like, but it may be also carried out by various methods such as an electrolytic type chromate method or a reactive type chromate method.
In this case, the mixing method of the chromate treatment liquid is to add chromic acid and phosphoric acid to water to a predetermined reduction rate, and then one or more selected from polyhydric phenolic polysaccharides, sucrose, maltose, lactose and fructose. Add organic compound. Then, the silica dispersion and the fluorine compound are added in this order. In the present invention, since the wettability of the liquid is good, it is not necessary to add a resin in this case. After treating the plated plate with the chromate treatment liquid, a chromate film is formed on at least one surface of the plated plate through a drying step such as hot air drying. In addition,
The heat treatment in the drying step has a composition capable of easily forming a three-dimensional network of silica, and therefore 60 ° C to 18 ° C.
The treatment can be performed at a low temperature of 0 ° C, preferably 100 ° C to 145 ° C.
【００１９】このようなクロメート層の上層には、主と
して樹脂とシリカからなる有機樹脂層を形成する。ここ
で述べる樹脂とシリカは、環境保全の観点から、樹脂と
シリカが水中に分散した水性塗料であることが好まし
い。また、本発明におけるシリカ上塗り樹脂塗料には、
架橋剤が配合されていてもよい。上層樹脂層中に添加す
るシリカとしては、水分散液相均一シリカゾル、水分散
液相凝集形態シリカゾル、水分散液相鎖状シリカゾル、
親水性気相シリカゾル、気相シリカ等の各種のシリカを
使用することができるが、特に、水分散液相均一シリカ
ゾルと水分散液相鎖状シリカゾルが好ましい。また、上
層樹脂層中に添加するシリカ量は、有機樹脂１００重量
部に対して、１０〜１００重量部が好ましく、さらに好
ましくは、２０〜７０重量部である。上層樹脂層の有機
樹脂としては、カルボキシル基含有アニオン系ウレタン
樹脂、カルボキシル基含有アニオン系エポキシ樹脂、カ
ルボキシル基含有エポキシ変性ウレタン樹脂、カチオン
系ウレタン樹脂等の各種樹脂を使用することができる
が、中でも、カルボキシル基含有アニオン系エポキシ樹
脂、カルボキシル基含有アニオン系ウレタン樹脂が好ま
しい。On the upper layer of such a chromate layer, an organic resin layer mainly composed of resin and silica is formed. The resin and silica described here are preferably an aqueous paint in which the resin and silica are dispersed in water from the viewpoint of environmental protection. Further, the silica top coat resin coating material of the present invention,
A crosslinking agent may be blended. As the silica to be added to the upper resin layer, an aqueous dispersion liquid phase uniform silica sol, an aqueous dispersion liquid phase aggregate form silica sol, an aqueous dispersion liquid phase chain silica sol,
Various kinds of silica such as hydrophilic vapor phase silica sol and vapor phase silica can be used, and particularly, water dispersion liquid phase uniform silica sol and water dispersion liquid phase chain silica sol are preferable. Further, the amount of silica added to the upper resin layer is preferably 10 to 100 parts by weight, more preferably 20 to 70 parts by weight, based on 100 parts by weight of the organic resin. As the organic resin of the upper resin layer, various resins such as a carboxyl group-containing anionic urethane resin, a carboxyl group-containing anionic epoxy resin, a carboxyl group-containing epoxy-modified urethane resin, and a cationic urethane resin can be used. , A carboxyl group-containing anionic epoxy resin and a carboxyl group-containing anionic urethane resin are preferable.
【００２０】シリカ含有上塗り塗料の焼き付け条件後の
付着量としては、０．１〜３ｇ／ｍ 2 であることが好ま
しい。０．１ｇ／ｍ2 未満では、十分な耐食性が得られ
ず、また３ｇ／ｍ2 を超えると、被膜の絶縁抵抗が高ま
り、スポット溶接性、電着塗装性が低下するためであ
る。クロメート層とその上層有機樹脂被覆は、用途に応
じて両面、あるいは片面のみの被覆であってもよい。片
面のみの被覆の場合には、非被覆面が、亜鉛系めっき、
亜鉛系めっき上層にクロメート処理した面、あるいは冷
延面などである。After baking conditions for silica-containing topcoats
As adhesion amount, 0.1-3g / m TwoPreferably
New 0.1 g / mTwoBelow, sufficient corrosion resistance is obtained
No, again 3g / mTwoAbove, the insulation resistance of the coating will increase.
And the spot weldability and electrodeposition paintability are reduced.
You. The chromate layer and the overlying organic resin coating are
On the other hand, the coating may be on both sides or only on one side. Piece
In the case of coating only the surface, the non-coated surface is zinc-based plating,
Chromate-treated surface of zinc-based plating or cold
For example, a rolled surface.
【００２１】有機樹脂層をクロメート層上層に被覆する
方法は、所定の樹脂を水に分散させた後、シリカ分散液
を混合して均一とする。得られた混合物をロールコー
ト、スプレー、シャワーコート、エアナイフ等の公知の
方法によって所定の厚さになるように塗布し、乾燥させ
る。このとき、乾燥のための加熱処理の板温は、９０〜
２００℃が好ましく、１２０〜１８０℃がより好適であ
る。In the method of coating the organic resin layer on the upper layer of the chromate layer, a predetermined resin is dispersed in water, and then a silica dispersion is mixed to make it uniform. The obtained mixture is applied to a predetermined thickness by a known method such as roll coating, spraying, shower coating, and air knife, and dried. At this time, the plate temperature of the heat treatment for drying is 90 to
200 degreeC is preferable and 120-180 degreeC is more suitable.
【００２２】[0022]
【実施例】以下に、本発明を実施例に基づいて具体的に
説明する。各種の亜鉛めっき鋼板または亜鉛系合金めっ
き鋼板（板厚０．８ｍｍ）を、１５０×２３０ｍｍの大
きさに切断し、塗装前処理として、有機溶剤による超音
波脱脂（３０℃×１８０秒）、アルカリスプレー脱脂
（液ｐＨ＝１１、４０℃×６０秒）を行った。脱脂後の
めっき鋼板上に、ロールコーターで各種クロメート処理
を施した後、最高到達板温１２０℃で焼き付けた。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. Various zinc-plated steel sheets or zinc-based alloy-plated steel sheets (sheet thickness 0.8 mm) are cut into a size of 150 x 230 mm, and as a pretreatment for coating, ultrasonic degreasing with an organic solvent (30 ° C x 180 seconds), alkali Spray degreasing (liquid pH = 11, 40 ° C. × 60 seconds) was performed. The degreased plated steel sheet was subjected to various chromate treatments with a roll coater and then baked at a maximum reaching plate temperature of 120 ° C.
【００２３】次に、種々の水性樹脂と平均粒子径の異な
る各種シリカを混合することにより調製した塗料を、バ
ーコーターで塗布し、最高到達板温１５０℃で焼き付け
た。クロメート処理液に添加するシリカとして、日本エ
アロジル（株）製気相シリカを用いた。クロメート処理
液に添加したフッ素化合物は、H2TiF6、H2ZrF6、H2SiF6
およびH2SrF6である。多価フェノール性多糖類として、
タンニン酸、糖類として麦芽糖、蔗糖、乳糖を用いた。
また、クロメート液中にリン酸を添加した。Next, a coating material prepared by mixing various aqueous resins and various silicas having different average particle diameters was applied with a bar coater and baked at a maximum plate temperature of 150 ° C. As the silica added to the chromate treatment liquid, vapor phase silica manufactured by Nippon Aerosil Co., Ltd. was used. The fluorine compounds added to the chromate treatment solution are H 2 TiF 6 , H 2 ZrF 6 , and H 2 SiF 6
And H 2 SrF 6 . As a polyphenolic polysaccharide,
Tannic acid, maltose, sucrose, and lactose were used as sugars.
In addition, phosphoric acid was added to the chromate solution.
【００２４】上層樹脂層の、樹脂種は以下のとおりであ
る。 （Ａ）カルボキシル基含有アニオン系ウレタン樹脂（酸
価５０、重量平均分子量20000 ）のジエチルアミン中和
物 （Ｂ）カルボキシル基含有アニオン系エポキシ樹脂（酸
価４８、重量平均分子量15000 ）のトリエチルアミン中
和物 （Ｃ）ノニオン系アクリル樹脂（重量平均分子量28000
、ガラス転移温度１８℃） （Ｄ）カルボキシル基含有エポキシ変性ウレタン樹脂
（酸価６０、重量平均分子量38000 ）のジエチルアミン
中和物 （Ｅ）カチオン系ウレタン樹脂（アミン価４５、重量平
均分子量35000 ）の酢酸中和物The resin species of the upper resin layer are as follows. (A) Diethylamine neutralized product of carboxyl group-containing anionic urethane resin (acid value 50, weight average molecular weight 20000) (B) Triethylamine neutralized product of carboxyl group-containing anionic epoxy resin (acid value 48, weight average molecular weight 15000) (C) Nonionic acrylic resin (weight average molecular weight 28,000
, Glass transition temperature 18 ° C.) (D) Diethylamine neutralized product of carboxyl group-containing epoxy-modified urethane resin (acid value 60, weight average molecular weight 38000) (E) Cationic urethane resin (amine value 45, weight average molecular weight 35000) Acetic acid neutralized product
【００２５】上層樹脂中のシリカ種は次の通りである。 （Ａ）水分散液相均一シリカゾル（日産化学工業（株）
製） （Ｂ）水分散液相凝集形態シリカゾル（日産化学工業
（株）製） （Ｃ）水分散液相鎖状シリカゾル（日産化学工業（株）
製） （Ｄ）親水性気相シリカゾル（日本アエロジル（株）
製） （Ｅ）気相シリカ（日本アエロジル（株）製） 得られた有機複合被覆鋼板製品の性能評価のために、以
下の試験を行った。結果を表１、２に示す。The silica species in the upper layer resin are as follows. (A) Aqueous dispersion liquid phase homogeneous silica sol (Nissan Chemical Industry Co., Ltd.)
(B) Aqueous dispersion liquid phase aggregate form silica sol (manufactured by Nissan Chemical Industries, Ltd.) (C) Aqueous dispersion liquid phase chain silica sol (Nissan Chemical Industry Co., Ltd.)
(D) Hydrophilic gas phase silica sol (Nippon Aerosil Co., Ltd.)
(E) Vapor phase silica (manufactured by Nippon Aerosil Co., Ltd.) The following tests were performed to evaluate the performance of the obtained organic composite coated steel sheet product. The results are shown in Tables 1 and 2.
【００２６】耐ブリスター性および耐水二次密着性を評
価するために、日本ペイント（株）製サーフダイン２５
００で化成処理を行い、日本ペイント（株）製電着塗料
パワートップ Ｕ−２６００を２０〜３０μｍ電着し、
１６０℃で１０分間焼き付けを行った。その後、日本ペ
イント（株）製中塗り塗料ＯＰ−２クロを約４０μｍ厚
さになるようにスプレー塗装し、１４０℃で２０分間焼
き付けた。その後、日本ペイント（株）製上塗り塗料Ｏ
Ｓ−３０クロを約４０μｍ厚さにスプレー塗装し、１４
０℃で２０分間焼き付けを行った。これらの処理を行っ
た試料を５０℃の純水中に１０日間浸漬し、取り出して
から１時間後に２ｍｍ間隔の碁盤目クロスカットおよび
セロテープ剥離試験を行い、以下の評価基準に従って耐
水二次密着性を評価した。 ◎；剥離無し ○；剥離面積５％未満でかつ碁盤目の完全剥離が無いこ
と △；剥離面積５％以上〜３５％未満 ×；剥離面積３５％以上Surf Paint 25 manufactured by Nippon Paint Co., Ltd. for evaluating the blister resistance and the water resistant secondary adhesion.
Chemical conversion treatment at 00, electrodeposition paint Power Top U-2600 manufactured by Nippon Paint Co., Ltd. is electrodeposited for 20 to 30 μm,
Baking was performed at 160 ° C. for 10 minutes. Then, Nippon Paint Co., Ltd. intermediate coating paint OP-2 black was spray-coated to a thickness of about 40 μm and baked at 140 ° C. for 20 minutes. After that, top paint O made by Nippon Paint Co., Ltd.
Spray-paint S-30 black to a thickness of about 40 μm, and
Baking was performed at 0 ° C. for 20 minutes. The sample that has been subjected to these treatments is immersed in pure water at 50 ° C for 10 days, and 1 hour after being taken out, a cross-cut cross-cut and a cellophane tape peeling test are performed at intervals of 2 mm, and the water-resistant secondary adhesion is evaluated according to the following evaluation criteria. Was evaluated. ⊚: No peeling ◯: Peeling area less than 5% and no complete peeling of cross-cuts △: Peeling area 5% to less than 35% ×: Peeling area 35% or more
【００２７】耐ブリスター性については、上記のうち電
着塗料を電着し、１６０℃で１０分間焼き付けを行った
後に評価した。評価基準は、以下の通りである。 ○；ブリスター無し △；ブリスター発生５個未満 ×；ブリスター発生５個以上The blister resistance was evaluated after electrodeposition of the above-mentioned electrodeposition paint and baking at 160 ° C. for 10 minutes. The evaluation criteria are as follows. ○: No blisters △: Less than 5 blisters ×: 5 or more blisters
【００２８】加工後耐食性を評価するために、円筒絞り
試験（絞り比２．０、しわ押さえ圧１０００ｋｇ）を行
った試験片を、５％ＮａＣｌ水溶液噴霧（３５℃）４時
間、乾燥（６０℃）２時間 湿潤環境（ＲＨ９５％、５
０℃）２時間を１サイクルとする複合サイクル腐食試験
に供し、２００サイクル後の試験片側壁の赤錆発生状況
を調べた。評価基準を以下に示した。 ◎；赤錆発生無し ○；赤錆発生面積率１０％未満 △；赤錆発生面積率１０％〜２０％ ×；赤錆発生面積率２０％超In order to evaluate the corrosion resistance after processing, a test piece which was subjected to a cylindrical drawing test (drawing ratio 2.0, wrinkle pressing pressure 1000 kg) was sprayed with a 5% NaCl aqueous solution (35 ° C.) for 4 hours and dried (60 ° C.). ) 2 hours humid environment (RH 95%, 5
It was subjected to a combined cycle corrosion test in which one cycle was set to 0 ° C.) for 2 hours, and the occurrence of red rust on the sidewall of the test piece after 200 cycles was examined. The evaluation criteria are shown below. ◎: No red rust generation ○: Red rust generation area ratio less than 10% △: Red rust generation area ratio 10% to 20% ×; Red rust generation area ratio over 20%
【００２９】耐クロム溶出性を評価するために、脱脂、
水洗、表面調整、化成処理の４工程を行い、処理前後の
クロム付着量変化を、蛍光Ｘ線分析により調べた。評価
基準は以下の通りである。 ◎；クロム溶出量１％未満 ○；クロム溶出量１％〜２％ △；クロム溶出量２％〜５％ ×；クロム溶出量５％超 なお、クロム溶出量とは、（塗装後のクロム付着量−化
成処理工程終了後のクロム付着量）×１００／塗装後の
クロム付着量 であらわされるものである。In order to evaluate the chromium elution resistance, degreasing,
Four steps of washing with water, surface adjustment, and chemical conversion treatment were performed, and changes in the amount of chromium deposited before and after the treatment were examined by fluorescent X-ray analysis. The evaluation criteria are as follows. ◎: Chromium elution amount less than 1% ○; Chromium elution amount 1% to 2% △; Chromium elution amount 2% to 5% ×; Chromium elution amount over 5% In addition, chromium elution amount is (chromium adhesion after coating Amount-amount of chromium deposited after the chemical conversion treatment process) x 100 / amount of chromium deposited after painting.
【００３０】スポット溶接性を評価するために、先端６
ｍｍφのＡｌ2 Ｏ3 分散銅合金製の溶接チップを用い、
加圧力２００ｋｇｆ、溶接電流９ＫＡ、溶接時間０．２
秒／回で連続溶接を行いナゲット径が基準値を下回るま
での連続溶接打点数を測定した。評価基準を、以下に示
した。 ◎；３０００点以上 ○；２０００〜３０００点 △；１０００〜２０００点 ×；１０００点未満 表１に、クロメート層、樹脂層被覆条件と評価結果をま
とめた。To evaluate spot weldability, the tip 6
Using a welding tip made of Al 2 O 3 dispersed copper alloy of mmφ,
Welding pressure 200kgf, welding current 9KA, welding time 0.2
Continuous welding was performed at a time of once per second, and the number of continuous welding points until the nugget diameter fell below the reference value was measured. The evaluation criteria are shown below. ⊚: 3000 points or more O: 2000 to 3000 points Δ: 1000 to 2000 points x: Less than 1000 points Table 1 summarizes the conditions for coating the chromate layer and the resin layer and the evaluation results.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【表４】 [Table 4]
【００３５】[0035]
【表５】 [Table 5]
【００３６】[0036]
【表６】 [Table 6]
【００３７】[0037]
【発明の効果】上述したように、本発明の有機複合被覆
鋼板は、耐クロム溶出性および耐ブリスター性に極めて
優れ、耐水二次密着性、平板裸耐食性、加工後耐食性、
高カチオン電着塗装性、および高スポット溶接性も良好
なことから、自動車車体をはじめとして、同様の品質特
性を期待される広範囲の用途に使用することができる。As described above, the organic composite coated steel sheet of the present invention is extremely excellent in chromium elution resistance and blister resistance, and has secondary resistance to water adhesion, bare plate corrosion resistance, post-processing corrosion resistance,
Since it has a high cationic electrodeposition coating property and a high spot weldability, it can be used in a wide range of applications where similar quality characteristics are expected, including automobile bodies.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ２３Ｃ 28/00 Ｃ２３Ｃ 28/00 Ｃ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location C23C 28/00 C23C 28/00 C
Claims (2)
面上に、 （Ａ）Ｃｒ6+量が、全Ｃｒに対して、２５〜６０ｗｔ％ （Ｂ）シリカが、密に充填可能な二組の粒径分布を有す
る親水性気相シリカであり、その量が、全Ｃｒに対し
て、重量比で０．５〜３．０ （Ｃ）リン酸が、全Ｃｒに対して、重量比で０．０１〜
２．０ （Ｄ）フッ素化合物量がフッ素として、全Ｃｒに対し
て、重量比で０．０２〜２．０ （Ｅ）多価フェノール性多糖類、蔗糖、麦芽糖、乳糖、
果糖から選ばれる一種類以上の有機化合物が、全Ｃｒに
対して、モル比で０．０５〜５．０ （Ｆ）クロメート付着量が全Ｃｒ換算で１０〜２００ｍ
ｇ／ｍ2 であるクロメート被膜を有し、該クロメート被膜の上層
に、主として樹脂とシリカからなる有機樹脂層を有する
ことを特徴とする、耐クロム溶出性および耐ブリスター
性に優れた有機複合被覆鋼板。1. A zinc-plated or zinc-based alloy-plated steel sheet surface comprising (A) Cr 6+ in an amount of 25 to 60 wt% with respect to the total Cr (B) silica. It is a hydrophilic vapor phase silica having a particle size distribution, and its amount is 0.5 to 3.0 (C) phosphoric acid in a weight ratio to the total Cr, and 0 in a weight ratio to the total Cr. .01-
2.0 (D) 0.02 to 2.0 (E) Polyhydric phenolic polysaccharide, sucrose, maltose, lactose in a weight ratio with respect to the total Cr, where the amount of fluorine compound is fluorine,
One or more kinds of organic compounds selected from fructose have a molar ratio of 0.05 to 5.0 (F) chromate adhesion to total Cr of 10 to 200 m in terms of total Cr.
An organic composite coating excellent in chromium elution resistance and blister resistance, characterized by having a chromate coating of g / m 2 and having an organic resin layer mainly composed of resin and silica on the chromate coating. steel sheet.
径が０．０５ｎｍ以上１０ｎｍ未満の親水性気相シリカ
に対して、１０ｎｍ以上１００ｎｍ以下の親水性気相シ
リカを重量比で１〜１０含有する混合系であることを特
徴とする、請求項１に記載の耐クロム溶出性および耐ブ
リスター性に優れた有機複合被覆鋼板。2. The hydrophilic silica in the chromate layer has a primary particle diameter of 0.05 nm or more and less than 10 nm and a hydrophilic gas phase silica of 10 nm to 100 nm in a weight ratio of 1 to 10. The organic composite-coated steel sheet having excellent chromium elution resistance and blister resistance according to claim 1, which is a mixed system containing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5295196A JPH09241859A (en) | 1996-03-11 | 1996-03-11 | Organic clad coating steel excellent in chromium eluting resistance and blister resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5295196A JPH09241859A (en) | 1996-03-11 | 1996-03-11 | Organic clad coating steel excellent in chromium eluting resistance and blister resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09241859A true JPH09241859A (en) | 1997-09-16 |
Family
ID=12929198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5295196A Withdrawn JPH09241859A (en) | 1996-03-11 | 1996-03-11 | Organic clad coating steel excellent in chromium eluting resistance and blister resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09241859A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011056737A (en) * | 2009-09-09 | 2011-03-24 | Jfe Steel Corp | Surface-treated steel material excellent in corrosion resistance |
| KR101271967B1 (en) * | 2011-12-20 | 2013-06-07 | 주식회사 포스코 | A method for manufacturing painted steel sheets blister |
| US20180251899A1 (en) * | 2015-09-02 | 2018-09-06 | Jfe Steel Corporation | Insulative coating processing liquid and method for manufacturing metal having insulative coating |
-
1996
- 1996-03-11 JP JP5295196A patent/JPH09241859A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011056737A (en) * | 2009-09-09 | 2011-03-24 | Jfe Steel Corp | Surface-treated steel material excellent in corrosion resistance |
| KR101271967B1 (en) * | 2011-12-20 | 2013-06-07 | 주식회사 포스코 | A method for manufacturing painted steel sheets blister |
| US20180251899A1 (en) * | 2015-09-02 | 2018-09-06 | Jfe Steel Corporation | Insulative coating processing liquid and method for manufacturing metal having insulative coating |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20030603 |