JP2000263695A - Organic composite coated steel panel - Google Patents
Organic composite coated steel panelInfo
- Publication number
- JP2000263695A JP2000263695A JP7640299A JP7640299A JP2000263695A JP 2000263695 A JP2000263695 A JP 2000263695A JP 7640299 A JP7640299 A JP 7640299A JP 7640299 A JP7640299 A JP 7640299A JP 2000263695 A JP2000263695 A JP 2000263695A
- Authority
- JP
- Japan
- Prior art keywords
- film
- steel sheet
- coated steel
- resin
- organic composite
- 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.)
- Granted
Links
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- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (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、自動車、家電、建
材といった用途に適当な、亜鉛系めっき鋼板 (亜鉛めっ
き鋼板および亜鉛合金めっき鋼板を含む) 、特に溶融亜
鉛系めっき鋼板を母材とする表面処理鋼板に関する。The present invention relates to a base material of a zinc-coated steel sheet (including a zinc-coated steel sheet and a zinc alloy-coated steel sheet), particularly a hot-dip galvanized steel sheet, which is suitable for use in automobiles, home appliances, and building materials. It relates to a surface-treated steel sheet.
【０００２】[0002]
【従来の技術】亜鉛系めっき鋼板の防錆処理としては、
従来よりクロメート処理が広く用いられてきた。しか
し、６価クロムが人体に有害であることが問題視される
ようになってきた。特に近年では、地球環境問題から６
価クロムを規制する動きが加速されているため、６価ク
ロムフリー、さらには完全にクロムフリーの防錆処理の
開発が望まれている。2. Description of the Related Art Rust prevention treatment of galvanized steel sheet is as follows.
Conventionally, chromate treatment has been widely used. However, it has been recognized that hexavalent chromium is harmful to the human body. Especially in recent years, 6
Since the movement to regulate chromium (VI) is being accelerated, there is a demand for the development of hexavalent chromium-free and further completely chromium-free rust prevention treatment.
【０００３】この要請に対し、従来からクロムフリーの
防錆処理の開発例があるが、特に近年は、樹脂を主成分
とし、必要により他の有機もしくは無機成分を添加した
皮膜を形成する有機複合被覆鋼板の開発例が多い。[0003] In response to this demand, there has been a development example of a chromium-free rust preventive treatment. There are many examples of the development of coated steel sheets.
【０００４】例えば、特開平８−232076号、同８−2320
77号、同10−251864号、同10−251865号各公報に記載の
珪酸エステルとアルミニウム塩とその他成分からなる皮
膜を形成する方法や、特開平５−195244号公報、同７−
145486号公報記載のフッ化物、リン酸、金属イオン、樹
脂等からなる皮膜を被覆する方法、特開平８−73775号
公報記載のシランカップリング剤から形成される皮膜を
被覆する方法、特開平10−251509号公報記載の樹脂、ポ
リアニリン、無機酸化物からなる皮膜を被覆する方法、
特開平10−337530号公報記載の樹脂と希土類化合物とを
含む皮膜を形成する方法がある。For example, Japanese Patent Application Laid-Open Nos. 8-232076 and 8-2320
No. 77, No. 10-251864, No. 10-251865, a method for forming a film comprising a silicate ester, an aluminum salt and other components, and JP-A-5-195244,
No. 145486, a method of coating a film composed of fluoride, phosphoric acid, metal ions, resin, etc., a method of coating a film formed from a silane coupling agent described in JP-A-8-73775, No. 251509, resin, polyaniline, a method of coating a film made of inorganic oxide,
There is a method for forming a film containing a resin and a rare earth compound described in JP-A-10-337530.
【０００５】[0005]
【発明が解決しようとする課題】ところで、クロメート
処理を施した溶融亜鉛めっき鋼板の課題として、高温多
湿環境に保持された場合、特にコイルのように、めっき
表面が密着した状況において、めっき表面が黒く変色す
る現象 (以下、黒変という) があり、商品価値が著しく
低下することがある。本発明者らが、種々のクロムフリ
ー処理について検討したところ、有機複合皮膜を形成し
た場合にも、同様な黒変が発生することが認められた。
ところが、上記の従来技術においては、耐黒変性につい
ては何ら検討されていない。One of the problems with the hot-dip galvanized steel sheet subjected to chromate treatment is that, when it is held in a high-temperature and high-humidity environment, especially when the plating surface is in close contact like a coil, the plating surface is There is a phenomenon of black discoloration (hereinafter referred to as black discoloration), and the commercial value may be significantly reduced. The present inventors have examined various chromium-free treatments and found that similar blackening occurs even when an organic composite film is formed.
However, in the above-mentioned prior art, no consideration has been given to blackening resistance.
【０００６】この黒変現象を抑制する技術としては、ク
ロメート処理の場合には、特開昭51−177381号公報記載
の、めっき後にNi、Coを薄くめっきしてからクロメート
処理を施すという技術がある。しかし、析出したNi、Co
は、めっき皮膜のZnと局部電池を形成するため、耐食性
(耐白錆性) の劣化を生ずる傾向がある。クロメート皮
膜の場合、皮膜の持つ優れた自己修復性能性により、耐
食性劣化を最小限度におさえることが可能だが、クロム
フリーの有機複合被覆鋼板では、耐食性劣化が大きく、
実用に供することができなかった。As a technique for suppressing this blackening phenomenon, in the case of chromate treatment, a technique described in JP-A-51-177381, in which Ni and Co are plated thinly after plating and then subjected to chromate treatment. is there. However, deposited Ni, Co
Is used to form a local battery with the plating film Zn,
(White rust resistance). In the case of a chromate film, the excellent self-healing performance of the film makes it possible to minimize the corrosion resistance deterioration.However, the chromium-free organic composite coated steel sheet has a large corrosion resistance deterioration,
It could not be put to practical use.
【０００７】従来文献 [例えば、内田ほか、日新製鋼技
報、51、p.29(1984)] によると、上記の黒変現象は、め
っき表層の亜鉛の酸欠錆と関連があり、表面の酸化皮膜
は黒変に影響せず、めっき皮膜中のAlの表層への拡散が
黒変に悪影響を及ぼすと報告されている。According to the conventional literature [for example, Uchida et al., Nisshin Steel Technical Report, 51, p. 29 (1984)], the blackening phenomenon described above is related to oxygen deficiency rust of zinc on the surface layer of the plating. It has been reported that the oxide film does not affect blackening, and the diffusion of Al in the plating film to the surface layer has an adverse effect on blackening.
【０００８】但し、めっき表面を完全に酸化してしまう
と、上層皮膜との密着性が劣化する、あるいは処理液そ
のものをはじいてしまうことが経験的に知られている。
本発明は、亜鉛系めっき鋼板、特に溶融亜鉛系めっき鋼
板を母材として、耐食性、密着性、耐黒変性を兼ね備え
たクロムフリーの有機複合被覆鋼板を開発することを課
題とする。However, it is empirically known that if the plating surface is completely oxidized, the adhesion to the upper layer film is deteriorated or the treatment liquid itself is repelled.
An object of the present invention is to develop a chromium-free organic composite coated steel sheet having both corrosion resistance, adhesion, and blackening resistance using a zinc-based coated steel sheet, particularly a hot-dip galvanized steel sheet as a base material.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、クロムフ
リー処理を施す際に、耐食性を確保できる皮膜であるこ
とを前提として、さらにめっき表面の酸化状態を抑制
し、かつ処理皮膜成分をめっきとの密着性を向上させる
ような成分構成とすることにより、上記課題を解決すべ
く検討を重ねた結果、シリカ質成分と有機樹脂を主成分
とするシリカ−有機樹脂複合皮膜に少量のリン酸類およ
びフッ化物類を含有させることが有効であることを知
り、本発明に至った。Means for Solving the Problems The inventors of the present invention presuppose that a film capable of ensuring corrosion resistance when performing a chromium-free treatment further suppresses the oxidized state of the plating surface and reduces the components of the treated film. As a result of repeated investigations to solve the above-mentioned problems by adopting a component composition that improves adhesion to plating, a small amount of phosphorous was added to a silica-organic resin composite coating mainly composed of a siliceous component and an organic resin. The inventors have found that it is effective to contain acids and fluorides, and have reached the present invention.
【００１０】本発明は、亜鉛系めっき鋼板の表面に、フ
ッ素を 0.5〜５at％、リンを 0.5〜５at％含有する、シ
リカ−有機樹脂複合皮膜を 0.2〜1.5 g/m2の付着量で設
けたことを特徴とする、耐食性、皮膜密着性、耐黒変性
に優れた有機複合被覆鋼板である。According to the present invention, a silica-organic resin composite film containing 0.5 to 5 at% of fluorine and 0.5 to 5 at% of phosphorus is provided on the surface of a galvanized steel sheet at an adhesion amount of 0.2 to 1.5 g / m 2. This is an organic composite coated steel sheet having excellent corrosion resistance, film adhesion, and blackening resistance.
【００１１】[0011]
【発明の実施の形態】亜鉛系めっき鋼板 本発明の有機複合被覆鋼板の母材は、任意の亜鉛系めっ
き鋼板、即ち、亜鉛めっき鋼板または亜鉛合金めっき鋼
板でよく、めっき方法は電気めっきと溶融めっきのいず
れでもよい。BEST MODE FOR CARRYING OUT THE INVENTION The base material of the organic composite coated steel sheet of the present invention may be any zinc-coated steel sheet, that is, a zinc-coated steel sheet or a zinc alloy-coated steel sheet. Any of plating may be used.
【００１２】しかし、本発明の主目的として、溶融亜鉛
めっき鋼板で顕著な黒変現象を抑制することがある。こ
の目的からは、特に黒変現象が顕著に見られる、めっき
皮膜中のAl含有量が0.05〜10重量％の溶融亜鉛系めっき
鋼板に本発明を適用することが有利である。具体的に
は、めっき浴中の有効Al濃度 (＝ [浴中Al濃度] − [浴
中Fe濃度])が0.08〜0.20％の条件で製造される溶融亜鉛
めっき鋼板、これを熱処理して合金化した合金化溶融亜
鉛めっき鋼板、さらにはAlを約５％含む溶融５％アルミ
ニウム−亜鉛合金めっき鋼板が母材鋼板として好まし
い。However, the main object of the present invention is to suppress a remarkable blackening phenomenon in a galvanized steel sheet. For this purpose, it is advantageous to apply the present invention to a hot-dip galvanized steel sheet having an Al content of 0.05 to 10% by weight in a plating film, in which a blackening phenomenon is particularly noticeable. Specifically, a hot-dip galvanized steel sheet manufactured under the condition that the effective Al concentration in the plating bath (= [Al concentration in the bath] − [Fe concentration in the bath]) is 0.08 to 0.20%. An alloyed hot-dip galvanized steel sheet and a hot-dip 5% aluminum-zinc alloy-coated steel sheet containing about 5% Al are preferable as the base steel sheet.
【００１３】めっき付着量は特に制限されず、従来と同
様でよい。溶融亜鉛系めっき鋼板の場合、めっき付着量
は片面当たり40〜150 g/m2の範囲が一般的である。な
お、めっきは片面めっきであってもよいが、一般的には
両面めっきである。[0013] The amount of plating is not particularly limited, and may be the same as the conventional one. In the case of a hot-dip galvanized steel sheet, the coating weight is generally in the range of 40 to 150 g / m 2 per side. The plating may be single-sided plating, but is generally double-sided plating.
【００１４】本発明によれば、この母材の表面、即ち、
亜鉛系めっき皮膜の上にじかに、シリカ質成分と有機樹
脂を主成分とし、少量のフッ素とリンを含有するシリカ
−有機樹脂複合皮膜 (以下、シリカ−有機複合皮膜とい
う) を形成する。もちろん、その前に、母材の亜鉛系め
っき鋼板に、クロメート処理またはリン酸亜鉛処理とい
った適当な下地化成処理を施すことも可能であるが、本
発明では、このような処理、特にクロメート処理を行わ
ずに亜鉛系めっき鋼板の防錆能を高めることが主目的で
あるためである。According to the present invention, the surface of the base material, that is,
A silica-organic resin composite film (hereinafter, referred to as silica-organic composite film) mainly containing a siliceous component and an organic resin and containing a small amount of fluorine and phosphorus is formed directly on the zinc-based plating film. Of course, before that, it is also possible to subject the zinc-plated steel sheet of the base material to a suitable base chemical conversion treatment such as a chromate treatment or a zinc phosphate treatment, but in the present invention, such a treatment, particularly the chromate treatment, is performed. This is because the main purpose is to increase the rust prevention ability of the galvanized steel sheet without performing it.
【００１５】本発明に係るシリカ−有機複合皮膜は、有
機樹脂とそれ以外の成分の供給源を含有する処理液を母
材に塗布し、そのまま塗膜を焼付けて乾燥することによ
り形成される。次にこれらの成分について説明する。The silica-organic composite film according to the present invention is formed by applying a treatment liquid containing a supply source of an organic resin and other components to a base material, and baking and drying the coating film as it is. Next, these components will be described.
【００１６】有機樹脂 有機樹脂は上記複合皮膜の主成分である。樹脂種は、焼
付け硬化型であれば特に制限されない。例えば、アクリ
ル系、エポキシ系、ポリエステル系、ウレタン系、フェ
ノール系等が使用できる。樹脂液は、例えば、アルコー
ル等の水混和性有機溶剤を用いた有機系とすることも可
能であるが、水性系の樹脂液 (水溶性樹脂または水分散
性もしくはエマルジョン型樹脂を使用) とする方が好ま
しい。 Organic resin The organic resin is the main component of the composite film. The resin type is not particularly limited as long as it is a bake hardening type. For example, acrylic, epoxy, polyester, urethane, phenol and the like can be used. The resin liquid may be, for example, an organic resin liquid using a water-miscible organic solvent such as alcohol, but an aqueous resin liquid (using a water-soluble resin or a water-dispersible or emulsion-type resin). Is more preferred.
【００１７】シリカ質成分 シリカ質成分は、樹脂に次ぐ皮膜の主成分であり、樹脂
とシリカ質成分とでめっき皮膜の表面に、これを周囲環
境から遮断するバリア皮膜を形成する。シリカ質成分
は、乾燥後にシリカ質皮膜を形成できる任意の珪酸化合
物および関連化合物から誘導することができる。即ち、
このような化合物を処理液に添加すればよい。一般にシ
リカ質皮膜を形成できる材料は、Si−Ｏ結合を介して樹
脂およびシリカ質成分同士と結合することで、皮膜を強
化し、かつめっき皮膜との密着性を高めるので、従来よ
り鋼板の表面処理液に使用されてきた。The siliceous component The siliceous component is the main component of the film next to the resin. The resin and the siliceous component form a barrier film on the surface of the plating film, which shields the plating film from the surrounding environment. The siliceous component can be derived from any silicate compound and related compounds that can form a siliceous film after drying. That is,
Such a compound may be added to the treatment liquid. In general, materials that can form a siliceous film are bonded to the resin and siliceous components via Si-O bonds to strengthen the film and increase the adhesion to the plating film. It has been used in processing solutions.
【００１８】この種の材料の具体例として、コロイダル
シリカ（湿式シリカ、シリカゾル）、乾式シリカ（気相
シリカ、フュームドシリカ）、シランカップリング剤、
珪酸金属塩 (例、珪酸リチウム、珪酸ナトリウム等) 、
珪酸エステル (例、エチルシリケート) などが挙げられ
る。また、樹脂としてシリカ変性またはシリコーン変性
された樹脂を用いる場合には、この樹脂の変性部分をシ
リカ質成分として利用できる。即ち、この場合の樹脂
は、樹脂成分とシリカ質成分を兼ねる。Specific examples of this type of material include colloidal silica (wet silica, silica sol), dry silica (gas phase silica, fumed silica), silane coupling agent,
Metal silicates (eg, lithium silicate, sodium silicate, etc.),
Silicate esters (eg, ethyl silicate) and the like. When a silica-modified or silicone-modified resin is used as the resin, a modified portion of the resin can be used as a siliceous component. That is, the resin in this case serves both as a resin component and a siliceous component.
【００１９】本発明においては、めっき皮膜との密着性
を向上させる目的で、珪酸化合物の一部または全部とし
てシランカップリング剤を使用することが好ましい。特
に好ましいシランカップリング剤は、使用する樹脂と反
応性の官能基を有するものである。反応の種類は、重合
反応、縮合反応、付加反応等でよく、特に制限されな
い。例えば、樹脂とシランカップリング剤の一方がカル
ボキシル基を有し、他方がアミノ基を有していると、縮
合反応により形成されたアミド結合を介して樹脂とシラ
ンカップリング剤が強固に結合し、皮膜がより強化され
ると共に、めっき皮膜との密着性も高まる。このような
互いに反応性の官能基の組合わせは、アミノ基、水酸基
および／もしくはカルボキシル基とエポキシ基との組合
わせ、水酸基および／もしくはスルホ基とカルボキシル
基との組合わせ、ビニル基同士の組合わせ等、他にも可
能である。従って、樹脂中の官能基に応じて、これと反
応性の適当な官能基を持つシランカップリング剤を選択
すればよい。In the present invention, it is preferable to use a silane coupling agent as part or all of the silicate compound for the purpose of improving the adhesion to the plating film. Particularly preferred silane coupling agents are those having a functional group reactive with the resin used. The type of the reaction may be a polymerization reaction, a condensation reaction, an addition reaction, or the like, and is not particularly limited. For example, when one of the resin and the silane coupling agent has a carboxyl group and the other has an amino group, the resin and the silane coupling agent are strongly bonded via an amide bond formed by a condensation reaction. As a result, the film is further strengthened and the adhesion to the plating film is increased. Such a combination of mutually reactive functional groups includes a combination of an amino group, a hydroxyl group and / or a carboxyl group and an epoxy group, a combination of a hydroxyl group and / or a sulfo group and a carboxyl group, and a combination of vinyl groups. Other methods such as matching are also possible. Therefore, a silane coupling agent having an appropriate functional group reactive with the functional group in the resin may be selected.
【００２０】具体例を示すと、ビニル基を有するアクリ
ル系樹脂に対しては、同じビニル基を有するビニルトリ
メトキシシランといったシランカップリング剤が反応性
を有する。また、アクリル系樹脂がカルボン酸基を有す
る (酸価を有する) ものである場合には、アミノ基を有
するシランカップリング剤も反応性がある。フェノール
樹脂や一部のアクリル系樹脂、ポリエステル樹脂等のよ
うに水酸基を有する樹脂に対しては、例えば、エポキシ
基を有するシランカップリング剤が反応性がある。To be specific, a silane coupling agent such as vinyltrimethoxysilane having the same vinyl group has reactivity with an acrylic resin having a vinyl group. When the acrylic resin has a carboxylic acid group (has an acid value), the silane coupling agent having an amino group is also reactive. For example, a silane coupling agent having an epoxy group is reactive with a resin having a hydroxyl group such as a phenol resin and some acrylic resins and polyester resins.
【００２１】シリカ質成分の皮膜中の含有量は、SiO2換
算で10〜30wt％の範囲が好ましく、より好ましくは10〜
25wt％である。なお、樹脂がシリカもしくはシリコーン
変性樹脂の場合には、樹脂中の変性部分のシリカ換算含
有量もこの量に含める。シリカ質成分の含有量が10wt％
未満または30wt％超であると、耐食性が劣化する傾向が
あり、また10wt％未満では皮膜密着性も低下する。The content of the siliceous component in the coating is preferably in the range of 10 to 30 wt% in terms of SiO 2 , more preferably 10 to 30 wt%.
25 wt%. When the resin is silica or a silicone-modified resin, the content in terms of silica of the modified portion in the resin is also included in this amount. Silica content is 10wt%
If it is less than 30% by weight or more than 30% by weight, the corrosion resistance tends to deteriorate, and if it is less than 10% by weight, the adhesion of the film decreases.
【００２２】シリカ質成分が、例えば気相シリカのよう
に、水性系では分散させにくいものである場合には、必
要に応じて、予めアルコール等の水混和性有機溶媒に分
散させてから加えることができる。この場合、皮膜中に
有機溶媒が残存しないように、できるだけ低沸点の溶媒
を使用することが好ましい。If the siliceous component is difficult to disperse in an aqueous system such as, for example, gas-phase silica, it may be added, if necessary, after dispersing in a water-miscible organic solvent such as alcohol. Can be. In this case, it is preferable to use a solvent having a boiling point as low as possible so that no organic solvent remains in the film.
【００２３】リン リンは、各種リン酸またはその塩を処理液に添加するこ
とにより、皮膜中に存在させることが好ましい。リン酸
は、オルトリン酸のほか、メタリン酸、ポリリン酸、亜
リン酸 (ホスホン酸) 、次亜リン酸 (ホスフィン酸) な
どでもよい。[0023] Phosphorus phosphorus by adding various phosphoric acid or its salt in the treatment liquid, it is preferably present in the coating. The phosphoric acid may be orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, phosphorous acid (phosphonic acid), hypophosphorous acid (phosphinic acid), or the like.
【００２４】シリカ−有機複合皮膜が、このようなリン
酸類から誘導されたリンを含有することにより、皮膜の
バリア効果がより高まり、耐食性が改善される。そのた
めには、皮膜中のＰ含有量が 0.5〜５at％の範囲となる
ようにリン酸類を添加する。これより少量では上記の効
果が不足し、多すぎると耐黒変性の低下が認められる。
好ましいＰ含有量は１〜４at％である。なお、皮膜中の
各元素の含有量は、皮膜をＸＰＳ (Ｘ線光電子分光法、
ESCA) で分析することにより決定できる。When the silica-organic composite coating contains such phosphorus derived from phosphoric acids, the barrier effect of the coating is further enhanced, and the corrosion resistance is improved. For this purpose, phosphoric acids are added so that the P content in the film is in the range of 0.5 to 5 at%. If the amount is smaller than this, the above effect is insufficient, and if it is too large, a decrease in blackening resistance is recognized.
The preferred P content is 1-4 at%. The content of each element in the film was determined by measuring the film by XPS (X-ray photoelectron spectroscopy,
It can be determined by analyzing with ESCA).
【００２５】フッ素 フッ化物が処理液中に存在していると、処理中にめっき
皮膜の表面がエッチングされ、めっき皮膜との密着性が
増し、耐食性が向上する。フッ化物は、皮膜中のＦが
0.5〜５at％となる範囲で添加する。これより少量では
効果がほとんどなく、過添加では、耐黒変性および耐食
性が劣化する。好ましいＦ含有量は１〜４at％である。When the fluorine fluoride is present in the processing solution, the surface of the plating film is etched during the processing, the adhesion to the plating film is increased, and the corrosion resistance is improved. Fluoride, F in the film
It is added in a range of 0.5 to 5 at%. If the amount is smaller than this, there is almost no effect, and if it is excessively added, blackening resistance and corrosion resistance deteriorate. The preferred F content is 1 to 4 at%.
【００２６】フッ化物としては、フッ酸 (またはその
塩) のほか、フッ化チタン酸、フッ化ジルコン酸 (また
はその塩) 、ケイフッ酸などの錯フッ化物が挙げられ
る。Examples of the fluoride include complex fluorides such as hydrofluoric acid (or a salt thereof), fluorinated titanic acid, fluorinated zirconic acid (or a salt thereof), and silicic hydrofluoric acid.
【００２７】その他の成分 本発明の有機複合被覆鋼板の性能、特に耐食性や耐黒変
性に顕著な劣化を生じない限り、他の任意の添加剤をシ
リカ−有機複合皮膜中に存在させることができる。この
ような添加剤の例には、消泡剤、乳化剤、防錆剤等があ
る。また、ワックス等の固形潤滑剤を添加して、潤滑性
を付与することもできる。さらに、シランカップリング
剤の一部に代えて、チタネートカップリング剤やアルミ
ニウムアルコキシド等を使用すると、コスト高になり、
処理液寿命にも問題を生ずるものの、耐食性は向上す
る。なお、珪酸塩、リン酸塩、フッ化物塩などとして金
属元素が皮膜中に導入される場合があるが、これも耐食
性や耐黒変性に対し悪影響を及ぼさない限り許容され
る。 Other Ingredients Other optional additives can be present in the silica-organic composite coating as long as the performance of the organic composite coated steel sheet of the present invention, in particular, corrosion resistance and blackening resistance do not significantly deteriorate. . Examples of such additives include defoamers, emulsifiers, rust inhibitors and the like. Further, a lubricating property can be imparted by adding a solid lubricant such as wax. Furthermore, when a titanate coupling agent or aluminum alkoxide is used instead of a part of the silane coupling agent, the cost increases,
Although there is a problem in the life of the processing solution, the corrosion resistance is improved. In some cases, metal elements such as silicates, phosphates, and fluoride salts are introduced into the film, but these are also acceptable as long as they do not adversely affect corrosion resistance and blackening resistance.
【００２８】以上の成分を溶媒に溶解または分散させて
処理液を調製する。各成分とも１種もしくは２種以上を
使用できる。得られた処理液を母材の亜鉛系めっき鋼板
のめっき皮膜上に塗布し、直ちに焼付け・乾燥すると、
本発明の有機複合被覆鋼板が得られる。処理液中の各成
分の配合割合や焼付け温度等は、当業者であれば容易に
決定できる。塗布方法も特に制限されないが、工業的に
はロール塗布、噴霧、浸漬等が一般的である。The above components are dissolved or dispersed in a solvent to prepare a treatment liquid. One or more of each component can be used. The obtained treatment liquid is applied on the plating film of the zinc-based plated steel sheet of the base material, and immediately baked and dried,
The organic composite coated steel sheet of the present invention is obtained. Those skilled in the art can easily determine the mixing ratio of each component in the treatment liquid, the baking temperature, and the like. The coating method is not particularly limited, but roll coating, spraying, dipping, and the like are generally used industrially.
【００２９】母材が両面めっき鋼板の場合、この複合皮
膜を両面に形成することが防食効果の点からは好ましい
が、片面だけに形成し、他面はめっき皮膜のままか、別
の防食皮膜を形成することも可能である。When the base material is a double-sided plated steel sheet, it is preferable to form this composite film on both surfaces from the viewpoint of the anticorrosion effect, but it is formed on only one surface and the other surface is a plated film or another anticorrosion film. It is also possible to form
【００３０】シリカ−有機複合皮膜の付着量は、要求さ
れる性能レベル (主に耐食性) により異なるため一概に
決められないが、 0.2〜1.5 g/m2の範囲内が適当であ
る。薄すぎると、十分な耐食性が得られず、厚すぎる
と、性能が飽和してコスト高につながる上、導電性の低
下により抵抗溶接性が低下する。仮にこの皮膜の比重を
１とすれば、上記の付着量は膜厚 0.2〜1.5 μｍに相当
し、非常に薄膜であるが、本発明の皮膜が非常に緻密で
あるので、このような薄膜でも高いバリア効果を示すこ
とができる。好ましい付着量は 0.3〜1.0 g/m2である。The amount of the silica-organic composite film to be deposited cannot be unconditionally determined because it varies depending on the required performance level (mainly corrosion resistance), but is suitably in the range of 0.2 to 1.5 g / m 2 . If the thickness is too small, sufficient corrosion resistance cannot be obtained. If the thickness is too large, the performance is saturated, leading to an increase in cost. Assuming that the specific gravity of this film is 1, the above-mentioned amount of adhesion is equivalent to a film thickness of 0.2 to 1.5 μm, which is a very thin film. However, since the film of the present invention is very dense, even such a thin film can be used. A high barrier effect can be exhibited. Preferred coating weight is 0.3~1.0 g / m 2.
【００３１】本発明の有機複合被覆鋼板は、上記のよう
に耐食性と耐黒変性に優れている上、シリカ−有機複合
皮膜の膜厚が非常に薄いので、溶接性も良好であり、ま
たこの皮膜の密着性が高いので加工性も良好である。こ
の有機複合被覆鋼板は、そのまま無塗装で使用すること
ができるが、所望により塗装を施してもよい。その場
合、リン酸亜鉛処理などの適当な塗装前処理を施しても
よい。本発明の有機複合被覆鋼板は塗料との密着性にも
優れており、高い塗膜密着性を与えることができる。以
上より、本発明の有機複合被覆鋼板は、自動車、家電、
建材といった各種用途に有用であることは明らかであ
る。The organic composite coated steel sheet of the present invention is excellent in corrosion resistance and blackening resistance as described above, and has a very thin silica-organic composite film, so that it has good weldability. Workability is also good due to the high adhesion of the film. The organic composite coated steel sheet can be used as it is without coating, but may be coated if desired. In that case, an appropriate pre-coating treatment such as a zinc phosphate treatment may be performed. The organic composite coated steel sheet of the present invention also has excellent adhesion to paint, and can provide high coating film adhesion. As described above, the organic composite coated steel sheet of the present invention is used for automobiles, home appliances,
Obviously, it is useful for various uses such as building materials.
【００３２】[0032]
【実施例】母材として、両面溶融亜鉛めっき鋼板 (浴中
有効Al濃度＝0.12％、めっき皮膜中Al含有量＝0.6 ％、
片面当たりめっき付着量＝110 g/m2、以下ＧＩ) および
両面溶融５％Al−Znめっき鋼板 (片面当たりめっき付着
量＝110 g/m2、以下ＧＦ)を用いた。[Example] As a base material, a double-sided hot-dip galvanized steel sheet (effective Al concentration in bath = 0.12%, Al content in plating film = 0.6%,
A coating weight per one side = 110 g / m 2 (hereinafter referred to as GI) and a double-sided 5% Al-Zn plated steel sheet (a coating weight per side = 110 g / m 2 , hereinafter GF) were used.
【００３３】母材めっき鋼板を弱アルカリ性脱脂液で脱
脂した後、その両面に、表１に示す割合の樹脂 (アクリ
ル系またはフェノール系) とシリカ質成分化合物 (シリ
カ、シランカップリング剤、珪酸塩) 、およびオルトリ
ン酸とフッ酸を含有する水性処理液をバーコーターにて
塗布し、最高到達温度が100 ℃となるように焼付け、シ
リカ−有機複合皮膜を形成した。使用したアクリル系樹
脂はカルボキシル基と水酸基を官能基として含有する
が、一部ではアミノ変性したアクリル系樹脂を使用し
た。同様に、フェノール系樹脂は水酸基を官能基として
含有するが、一部ではさらにスルホ基またはアミノ基を
含有するように変性したフェノール系樹脂を使用した。After the base metal-plated steel sheet is degreased with a weak alkaline degreasing solution, a resin (acrylic or phenolic) and a siliceous component compound (silica, silane coupling agent, silicate, ) And an aqueous treatment liquid containing orthophosphoric acid and hydrofluoric acid were applied by a bar coater and baked so that the maximum temperature reached 100 ° C. to form a silica-organic composite film. The acrylic resin used contains a carboxyl group and a hydroxyl group as functional groups, but partially used an amino-modified acrylic resin. Similarly, a phenolic resin containing a hydroxyl group as a functional group was used, but a phenolic resin modified to partially contain a sulfo group or an amino group was used.
【００３４】複合皮膜中のシリカ質成分の含有量 (SiO2
換算量) は、処理液への添加量から、樹脂との合計量に
基づいて算出した。複合皮膜の付着量は、蛍光Ｘ線装置
にて皮膜中のSi強度を測定し、この測定値と上記のシリ
カ質成分の含有量とから求めた。また、皮膜中フッ素お
よびリンは、表面のＸＰＳ分析結果から求めた。以上の
結果を表１に示す。The content of the siliceous component in the composite coating (SiO 2
(Converted amount) was calculated from the amount added to the treatment liquid based on the total amount with the resin. The adhesion amount of the composite film was determined by measuring the Si intensity in the film with a fluorescent X-ray apparatus and using the measured value and the content of the above-mentioned siliceous component. Fluorine and phosphorus in the film were determined from the results of XPS analysis of the surface. Table 1 shows the above results.
【００３５】得られた有機複合被覆鋼板の各サンプルの
耐食性、耐黒変性、導電性を以下の方法で調査した。比
較のために、母材がＧＩ＋Niめっき (ＧＩをNi2+水溶液
に浸漬して、Niを約１g/m2の付着量で置換析出させたも
の) であるもの (これに上記のと同様にシリカ−有機複
合被覆を形成したもの) 、およびＧＩのクロメート処理
品 (ＧＩを市販の反応型クロメート (酢酸クロメート)
液にて処理し、Cr換算で10 mg/m2のクロメート皮膜を形
成したもの) についても、同様に調査を行った。これら
の試験結果も表１に併せて示す。The corrosion resistance, blackening resistance, and conductivity of each sample of the obtained organic composite coated steel sheet were examined by the following methods. For comparison, the base material was GI + Ni plating (GI was immersed in an aqueous solution of Ni 2+ to replace and deposit Ni at an adhesion amount of about 1 g / m 2 ). A silica-organic composite coating formed), and a chromate-treated product of GI (GI is commercially available reactive chromate (chromate acetate))
The solution was treated with a liquid to form a chromate film of 10 mg / m 2 in terms of Cr)). These test results are also shown in Table 1.
【００３６】耐食性 有機複合被覆鋼板のサンプルの端面をポリエステルテー
プで被覆した後、塩水噴霧試験 (JIS Z2371 に準拠) に
72時間供し、サンプル表面の白錆発生面積率で評価し
た。Corrosion resistance After coating the end face of the sample of the organic composite coated steel sheet with a polyester tape, the sample was subjected to a salt spray test (based on JIS Z2371).
The sample was provided for 72 hours and evaluated by the area ratio of white rust on the sample surface.
【００３７】耐黒変性 有機複合被覆鋼板のサンプル表面を、厚さ約20μｍの透
明なポリエステルテープで被覆し、予め表面の明度 (JI
S-Z8370 に規定されるL*) を測定した。このサンプル
を、恒温恒湿器 (60℃、85％RH) に１週間保持したの
ち、再びL*を測定した。このときのΔL* [ L*(試験後)
−L* (試験前)]で評価した。こうして求めたΔL*が−８
以下になると、目視でも明らかに黒変していた。The sample surface of the blackened organic composite coated steel sheet was coated with a transparent polyester tape having a thickness of about 20 μm, and the surface brightness (JI
L *) specified in S-Z8370 was measured. After keeping this sample in a thermo-hygrostat (60 ° C., 85% RH) for one week, L * was measured again. ΔL * at this time [L * (after test)
−L * (before test)]. ΔL * thus obtained is -8
Below, it was apparently blackened visually.
【００３８】導電性 ＳＱメータ (荷重300 g)を用いて、表面の電気抵抗値を
測定した。この電気抵抗値が1000Ωを超えると、実用上
スポット溶接が困難である。Using a conductive SQ meter (300 g load), the electric resistance of the surface was measured. When the electric resistance exceeds 1000Ω, spot welding is practically difficult.
【００３９】[0039]
【表１−１】 [Table 1-1]
【００４０】[0040]
【表１−２】 [Table 1-2]
【００４１】この表からわかるように、本発明の有機複
合被覆鋼板は、耐食性に関して反応型クロメート皮膜を
形成した場合と同レベル (塩水噴霧72時間で白錆20％)
またはそれ以上の性能を示す。特に、シリカ質成分の少
なくとも一部を、樹脂と反応性の官能基を有するシラン
カップリング剤から形成したときに、非常に優れた耐食
性 (塩水噴霧72時間で白錆５％以下) を示すことがわか
った。耐黒変性に関しては、本発明の有機複合被覆鋼板
は、若干の明度低下( ｜L*｜＝５前後またはそれ以下)
が認められるが、十分実用に耐えうるレベルであった。As can be seen from the table, the organic composite coated steel sheet of the present invention has the same level of corrosion resistance as that obtained when the reactive chromate film was formed (white rust 20% after 72 hours of salt water spray).
Or better performance. In particular, when at least a part of the siliceous component is formed from a silane coupling agent having a functional group reactive with a resin, it exhibits excellent corrosion resistance (5% or less of white rust after 72 hours of salt spray). I understood. Regarding blackening resistance, the organic composite coated steel sheet of the present invention has a slight decrease in lightness (| L * | = about 5 or less)
However, the level was sufficiently practical.
【００４２】一方、複合皮膜中のシリカ質成分、リン、
フッ素の少なくとも１成分が本発明の範囲外になると、
耐食性または耐黒変性のいずれかが劣った。この皮膜の
付着量が0.2 mg/m2 未満では耐食性に劣り、1.5 g/m2超
のとき表面の導電性に劣った。また黒変抑制技術である
下地Niめっき処理では、黒変性の改善効果はあるが、そ
の上に本発明と同様のシリカ−有機複合皮膜を形成して
も、耐食性の劣化が著しかった。これはNiめっき自体
が、前述したように局部電池作用により亜鉛系めっきの
耐食性を大きく低下させてしまうからである。On the other hand, the siliceous component, phosphorus,
When at least one component of fluorine is out of the range of the present invention,
Either corrosion resistance or blackening resistance was poor. When the coating amount of this film was less than 0.2 mg / m 2 , the corrosion resistance was poor, and when it exceeded 1.5 g / m 2 , the surface conductivity was poor. In addition, although the underlayer Ni plating treatment, which is a technique for suppressing blackening, has an effect of improving blackening, even if a silica-organic composite film similar to that of the present invention is formed thereon, the corrosion resistance is significantly deteriorated. This is because the Ni plating itself significantly reduces the corrosion resistance of the zinc-based plating due to the local battery action as described above.
【００４３】[0043]
【発明の効果】本発明により、耐食性と耐黒変性に優
れ、かつ環境への負荷の少ないクロムフリー有機複合被
覆鋼板が提供される。この有機複合被覆鋼板は、溶接可
能であり、塗装性も良好であるので、自動車、家電製
品、建材などをはじめとする各種用途に有用である。According to the present invention, there is provided a chromium-free organic composite coated steel sheet which is excellent in corrosion resistance and blackening resistance and has little environmental load. Since the organic composite coated steel sheet is weldable and has good paintability, it is useful for various applications including automobiles, home appliances, building materials, and the like.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D075 CA13 CA33 CA44 DB02 DB05 DC01 DC12 DC18 EC03 4F100 AA20H AB03A AB18A AH05H AK01B AK01C AK25 AK33 AL06 AL08B AL08C BA02 BA03 BA06 BA10B BA10C EH46 EH462 EJ42 EJ422 GB07 GB32 GB48 JB02 JL11 YY00A YY00B YY00C 4K044 AA02 AB02 BA10 BA14 BA19 BA20 BA21 BC02 BC05 CA11 CA53 CA62 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4D075 CA13 CA33 CA44 DB02 DB05 DC01 DC12 DC18 EC03 4F100 AA20H AB03A AB18A AH05H AK01B AK01C AK25 AK33 AL06 AL08B AL08C BA02 BA03 BA06 BA10B BA10C EH46 EH462 GB02J42Y42 GB02J42B YY00C 4K044 AA02 AB02 BA10 BA14 BA19 BA20 BA21 BC02 BC05 CA11 CA53 CA62
Claims (3)
0.5〜５at％、リンを0.5〜５at％含有する、シリカ−有
機樹脂複合皮膜を 0.2〜1.5 g/m2の付着量で設けたこと
を特徴とする、耐食性、皮膜密着性、耐黒変性に優れた
有機複合被覆鋼板。Claims 1. Fluorine is added to the surface of a galvanized steel sheet.
A silica-organic resin composite film containing 0.5 to 5 at% and phosphorus of 0.5 to 5 at% is provided with an adhesion amount of 0.2 to 1.5 g / m 2. Excellent organic composite coated steel sheet.
算で10〜30wt％の範囲である、請求項１記載の有機複合
被覆鋼板。2. The organic composite coated steel sheet according to claim 1, wherein the content of the siliceous component in the coating is in the range of 10 to 30 wt% in terms of SiO 2 .
有量が0.05〜10wt％である、請求項１または２記載の有
機複合被覆鋼板。3. The organic composite coated steel sheet according to claim 1, wherein the content of Al in the plating film of the zinc-based plated steel sheet is 0.05 to 10 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7640299A JP3405260B2 (en) | 1999-03-19 | 1999-03-19 | Organic composite coated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7640299A JP3405260B2 (en) | 1999-03-19 | 1999-03-19 | Organic composite coated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000263695A true JP2000263695A (en) | 2000-09-26 |
| JP3405260B2 JP3405260B2 (en) | 2003-05-12 |
Family
ID=13604292
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7640299A Expired - Fee Related JP3405260B2 (en) | 1999-03-19 | 1999-03-19 | Organic composite coated steel sheet |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004243310A (en) * | 2003-01-23 | 2004-09-02 | Sumitomo Metal Ind Ltd | Heat radiating surface-treated metal plate and case for electronic apparatus |
| JP2008023975A (en) * | 2006-06-22 | 2008-02-07 | Nippon Steel Corp | Zinc-based plated steel sheet for back cover of indicating device using thin display panel |
| US7608337B2 (en) | 2003-11-18 | 2009-10-27 | Nippon Steel Corporation | Chemical conversion-treated metal plate |
| US7875363B2 (en) | 2005-11-30 | 2011-01-25 | Jfe Steel Corporation | Surface-treated steel sheet |
-
1999
- 1999-03-19 JP JP7640299A patent/JP3405260B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004243310A (en) * | 2003-01-23 | 2004-09-02 | Sumitomo Metal Ind Ltd | Heat radiating surface-treated metal plate and case for electronic apparatus |
| US7608337B2 (en) | 2003-11-18 | 2009-10-27 | Nippon Steel Corporation | Chemical conversion-treated metal plate |
| US7875363B2 (en) | 2005-11-30 | 2011-01-25 | Jfe Steel Corporation | Surface-treated steel sheet |
| JP2008023975A (en) * | 2006-06-22 | 2008-02-07 | Nippon Steel Corp | Zinc-based plated steel sheet for back cover of indicating device using thin display panel |
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