JP2866168B2 - Surface treatment material with excellent coating film adhesion and corrosion resistance after painting - Google Patents
Surface treatment material with excellent coating film adhesion and corrosion resistance after paintingInfo
- Publication number
- JP2866168B2 JP2866168B2 JP22164890A JP22164890A JP2866168B2 JP 2866168 B2 JP2866168 B2 JP 2866168B2 JP 22164890 A JP22164890 A JP 22164890A JP 22164890 A JP22164890 A JP 22164890A JP 2866168 B2 JP2866168 B2 JP 2866168B2
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- Prior art keywords
- coating film
- plating
- corrosion resistance
- film adhesion
- surface treatment
- 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.)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は耐食性、塗装性、加工性等に優れた高機能め
っき層を有する表面処理材に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a surface treatment material having a highly functional plating layer excellent in corrosion resistance, paintability, workability and the like.
［従来の技術］ 鋼板に代表される金属材料は、耐食性や意匠性等の向
上を目的としてめっきを施して使用されることが多く、
そのような表面処理材料は自動車や家庭電化製品、建材
等の幅広い分野で利用されている。しかし技術の一層の
向上に伴って耐食性等のめっき機能に対する要求は更に
高くなっており、めっき付着量を増加させる、Zn−
Ni或はZn−Fe等のZn系合金めっきを使用する等の対策が
行なわれている。[Prior art] Metal materials represented by steel sheets are often plated and used for the purpose of improving corrosion resistance and design properties.
Such surface treatment materials are used in a wide range of fields such as automobiles, home appliances, and building materials. However, with the further improvement of technology, the demand for plating functions such as corrosion resistance has been further increased, and Zn-
Countermeasures such as using a Zn-based alloy plating such as Ni or Zn-Fe are taken.
また前記分野においては塗装を施して使用することが
一般的であり、塗膜密着性の良いことも必要である。し
かしZn系めっきでは塗膜密着性が十分ではないので、リ
ン酸塩やクロム酸塩等を用いた前処理が行なわれてい
る。In the above-mentioned field, it is common to use the composition after applying a coating, and it is necessary that the coating film has good adhesion. However, Zn-based plating does not have sufficient coating film adhesion, and thus pretreatment using a phosphate, a chromate, or the like is performed.
しかしながら上記，の方法ではプレス成形の際に
めっき層が剥離するいわゆるフレーキングやパウダリン
グと呼ばれる現象を引き起こし、トラブルの原因となっ
ている。また塗装前処理は工程の煩雑化を招き、コスト
アップの原因となっている。However, in the above methods, a phenomenon called flaking or powdering in which a plating layer peels off during press molding is caused, which is a cause of trouble. In addition, the pre-coating treatment complicates the process and causes an increase in cost.
上記問題を解決するために有機質化合物や無機質化合
物を基材表面或はめっき層中に分散させることも行なわ
れ、かなりの成果をあげているが、十分な塗膜密着性や
塗装後耐食性を得るには至っていない。In order to solve the above problems, dispersion of an organic compound or an inorganic compound on the surface of the base material or in the plating layer has also been performed, and although considerable results have been obtained, sufficient coating film adhesion and corrosion resistance after coating are obtained. Has not been reached.
［発明が解決しようとする課題］ 本発明は以上のような状況に鑑みてなされたものであ
って、塗装後も劣化しにくく、しかも塗膜密着性および
加工性に優れた表面処理材料を提供しようとするもので
ある。[Problems to be Solved by the Invention] The present invention has been made in view of the above situation, and provides a surface treatment material that is hardly deteriorated even after coating and has excellent coating film adhesion and workability. What you want to do.
［課題を解決するための手段］ 本発明の表面処理材料は ［但しＡはCn H2n:nは０または正の整数、R1,R2は同一
又は異なってＨあるいはアルキル基］で表わされる官能
基に、エポキシ基を有する化合物が付加された基 を有する（メタ）アクリルアミド系モノマー単位が、全
繰り返し単位の5mol％以上である（メタ）アクリル系ポ
リマーをＣ量として0.001〜10重量％含有し、且つ残部
がZn或はZn合金からなるZn系めっき層が基材表面に形成
されたものである点に要旨がある。[Means for Solving the Problems] The surface treatment material of the present invention [Where A is C n H 2n : n is 0 or a positive integer, and R 1 and R 2 are the same or different and are H or an alkyl group] and a group obtained by adding a compound having an epoxy group to a functional group represented by Zn-based plating in which the (meth) acrylamide-based monomer unit contains 0.001 to 10% by weight of a (meth) acryl-based polymer having a C content of 5 mol% or more of the total repeating units and the balance is Zn or a Zn alloy The point is that the layer is formed on the surface of the base material.
［作用］ まず本発明者らは、上記各特性を得るためには夫々ど
のような性質がめっき添加剤に必要であるかを検討した
結果、以下のような知見を得た。[Operation] First, the present inventors have studied what kind of properties are necessary for the plating additive in order to obtain each of the above properties, and have obtained the following knowledge.
塗膜密着性及び塗装後の耐食性： 添加剤がめっき皮膜中に共析して塗装時に塗料成分と
の間で結合を形成することと、その結合が腐食環境下に
おいても劣化しないことが望ましい。Coating film adhesion and corrosion resistance after coating: It is desirable that the additive be codeposited in the plating film to form a bond with the paint component at the time of coating, and that the bond does not deteriorate even in a corrosive environment.
加工性（プレス成形性）： めっき皮膜がある程度の硬さと潤滑性を有することが
望ましい。Workability (press formability): It is desirable that the plating film has a certain degree of hardness and lubricity.
上記知見に基づいて鋭意研究を重ねた結果、優れた機
能を有する本発明の表面処理材を完成させるに至った。
以下にその内容を説明する。As a result of intensive studies based on the above findings, the present inventors have completed the surface treatment material of the present invention having excellent functions.
The details will be described below.
本発明ではめっき層表面に極性を付与することを目的
として、特定の有機質化合物をめっき層中に分散共析さ
せた。該有機質化合物とは、前記式（Ｉ）で示される官
能基に、エポキシ基を有する化合物が付加された基を有
する（メタ）アクリルアミド系モノマー単位が、全繰り
返し単位の5mol％以上である（メタ）アクリル系ポリマ
ーである。In the present invention, a specific organic compound is dispersed and eutectoid in the plating layer for the purpose of imparting polarity to the plating layer surface. The organic compound means that the (meth) acrylamide-based monomer unit having a group in which a compound having an epoxy group is added to the functional group represented by the formula (I) is 5 mol% or more of all repeating units (meth) ) An acrylic polymer.
まず上記定義中の−Cn H2n−（ｎは正の整数）および
アルキル基について説明する。First -C n H 2n in the definition - (n is a positive integer) will be explained and an alkyl group.
−Cn H2n−は、直鎖状又は分岐状の如何を問わず、代
表的なものとしてはメチレン、エチレン、トリメチレ
ン、テトラメチレン、ペンタメチレン、ヘキサメチレ
ン、プロピレン、エチルエチレン等が掲げられ、特に好
ましいのはｎが６以下のものである。-C n H 2n- , whether linear or branched, typical examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, propylene, ethylethylene, and the like, Particularly preferably, n is 6 or less.
アルキル基も直鎖状又は分岐状の如何を問わず、代表
的なものとしては、メチル、エチル、プロピル、イソプ
ロピル、ブチル、第３級ブチル、ペンチル、ヘキシル等
が掲げられ、特に好ましいのは低級アルキル基である。The alkyl group may be linear or branched, and typical examples include methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl, hexyl, and the like. It is an alkyl group.
式（Ｉ）で示される官能基を有し、且つエポキシ基を
有する化合物が付加される前の（メタ）アクリル系アミ
ドとしては、例えばジメチルアミノエチルアクリルアミ
ドやメチルエチルアミノエチルアクリルアミド、ジプロ
ピルアミノプロピルアクリルアミド、ジメチルアミノプ
ロピルメタクリルアミド、ジエチルアミノエチルメタク
リルアミド、ジメチルアミノエチルメタクリルアミド、
アクリル酸ジメチルヒドラジド等がある。例示したもの
は末端アミノ基が３級アミノ基のものであるが、１級ア
ミノ基やメチルアミノ、エチルアミノ等の２級アミノ基
であるものも本発明に含まれる。Examples of the (meth) acrylic amide before the addition of the compound having the functional group represented by the formula (I) and having an epoxy group include dimethylaminoethylacrylamide, methylethylaminoethylacrylamide, dipropylaminopropyl Acrylamide, dimethylaminopropyl methacrylamide, diethylaminoethyl methacrylamide, dimethylaminoethyl methacrylamide,
Acrylic acid dimethyl hydrazide and the like. Those exemplified are those having a terminal amino group of a tertiary amino group, but those having a primary amino group or a secondary amino group such as methylamino or ethylamino are also included in the present invention.
そして上記例示された様な（メタ）アクリル系のアミ
ドまたはヒドラジドに付加される、エポキシ基を有する
化合物としては、例えばビスフェノールＡグリシジルエ
ーテル、エピクロルヒドリン、アリルグリシジルエーテ
ル、スチレンオキサイド、フェニルグリシジルエーテ
ル、グリシジルアセテート挙がある。これらの付加を行
なうときの組合せは特に限定されるものではない。Compounds having an epoxy group added to the (meth) acrylic amide or hydrazide as exemplified above include, for example, bisphenol A glycidyl ether, epichlorohydrin, allyl glycidyl ether, styrene oxide, phenyl glycidyl ether, glycidyl acetate There is a feat. Combinations for performing these additions are not particularly limited.
本発明の（メタ）アクリル系ポリマーは上記の様にし
て製造される化合物を先に述べるようにモノマー単位と
して5mol％以上を含むものであり、該モノマー単位が10
0mol％である場合を包含するが、希望に応じて上記化合
物以外の共重合性化合物をモノマー単位として構成単位
中に含んでいても良い。この様なモノマー成分として
は、例えばアクリルアミドやメタクリルアミド、アクリ
ル酸メチル、メタクリル酸メチル等の（メタ）アクリル
系アミドやエステル化合物が挙げられる。The (meth) acrylic polymer of the present invention contains the compound produced as described above in an amount of 5 mol% or more as a monomer unit as described above, and the monomer unit has a content of 10 mol%.
The case where the content is 0 mol% is included, but a copolymerizable compound other than the above compound may be contained in the structural unit as a monomer unit as desired. Examples of such a monomer component include (meth) acrylic amides and ester compounds such as acrylamide, methacrylamide, methyl acrylate, and methyl methacrylate.
ところでエポキシ基を有する化合物を付加させる反応
は、重合に先立って行なっても良いが、もっとも一般的
には例えば上記モノマー類を単独重合又は共重合させる
ことによってポリマーを形成した後エポキシ系の化合物
を反応させる方法等が推奨される。付加によりアミノ系
の官能基は４級化されるものと考えられる。Incidentally, the reaction of adding the compound having an epoxy group may be performed prior to the polymerization, but most commonly, for example, after forming a polymer by homopolymerizing or copolymerizing the above monomers, an epoxy compound is used. A reaction method is recommended. It is considered that the amino group is quaternized by the addition.
上記付加反応において、エポキシ基を有する化合物が
付加されたモノマー単位をポリマー中に5mol％以上、好
ましくは10mol％以上存在させることによって本発明の
効果が得られる。第１図にエポキシ系モノマー単位の変
性率と塗膜剥離幅（塗装後耐食性）の関係を示した。変
性率が5mol％以下の場合には十分な効果が得られなかっ
た。尚塗膜剥離幅は実施例に示される方法で測定した。In the above addition reaction, the effect of the present invention can be obtained by causing the monomer unit to which the compound having an epoxy group is added to be present in the polymer in an amount of 5 mol% or more, preferably 10 mol% or more. FIG. 1 shows the relationship between the modification ratio of the epoxy monomer unit and the coating peeling width (corrosion resistance after coating). When the denaturation rate was 5 mol% or less, a sufficient effect was not obtained. In addition, the coating film peeling width was measured by the method shown in the examples.
またポリマー自身の大きさは特に限定されるものでは
ないが、分子量として1000〜100万の間にあることが望
ましい。この大きさの物質がめっき皮膜中に共析するこ
とによって、めっき層に内部応力を発生させ、めっき層
の硬さを向上させることができる。更に有機化合物であ
るので、ある程度の潤滑性を有しており、作製しためっ
き皮膜のプレス成形性も大幅に向上させることができ
る。The size of the polymer itself is not particularly limited, but it is desirable that the molecular weight be between 1,000 and 100,000. When a substance of this size is eutectoid in the plating film, internal stress is generated in the plating layer, and the hardness of the plating layer can be improved. Further, since it is an organic compound, it has a certain degree of lubricity, and can greatly improve the press formability of the produced plating film.
以上のような構成を有する本発明による有機質化合物
は、エポキシ基やアミノ基によって極性が高められてい
るので、pH1〜４の酸性のめっき液中でも安定且つ均一
に分散し、その特性はめっき層中に共析した後も維持さ
れる。特に本発明においてはアミド基にエポキシ系官能
基が付加されたアミノ系官能基を有する構造をとってい
るので、金属イオンが多量に存在する溶液中においても
有機質化合物の塩析による劣化を抑制し、長期間に亘る
連続的な電解操業をも可能にしている。更に該有機質化
合物は電解によるめっき皮膜形成時、特に高電流密度の
条件下においては、基板の凹凸等に起因する局部的な電
流の集中を抑制し、均一な表面処理層の製造に寄与する
ので、均一光沢外観を得ることもできる。Since the polarity of the organic compound according to the present invention having the above-described structure is enhanced by an epoxy group or an amino group, the organic compound is stably and uniformly dispersed even in an acidic plating solution having a pH of 1 to 4, and its characteristics are in the plating layer. It is maintained after eutectoid. In particular, in the present invention, since it has a structure having an amino functional group in which an epoxy functional group is added to an amide group, it suppresses deterioration due to salting out of an organic compound even in a solution containing a large amount of metal ions. In addition, continuous electrolysis operation over a long period of time is enabled. Further, the organic compound suppresses local concentration of current due to unevenness of the substrate when forming a plating film by electrolysis, particularly under conditions of high current density, and contributes to the production of a uniform surface treatment layer. , Uniform gloss appearance can be obtained.
また得られためっき層は、めっき層中に存在するエポ
キシ基やエポキシ基の付加によって形成された水酸基が
塗装焼付け時（80℃以上）に塗料との間で架橋結合を形
成するので、塗膜密着性が高い。しかも該めっき層は本
発明のエポキシ系化合物を付加された（メタ）アクリレ
ート系ポリマーを含有しているので優れた塗装後耐食性
を示す。更に、ポリマーをめっき層中に共析させること
によって、前述のようにめっき層にある程度の硬さを持
たせることができると同時に、添加剤自身の潤滑性を付
与することができる。従ってめっき層のプレス成形性が
大幅に向上する。In addition, the resulting plating layer forms a cross-link between the epoxy group present in the plating layer and the hydroxyl group formed by the addition of the epoxy group during paint baking (80 ° C or higher) with the paint. High adhesion. Moreover, since the plating layer contains the (meth) acrylate polymer to which the epoxy compound of the present invention has been added, it exhibits excellent corrosion resistance after painting. Further, by causing the polymer to be eutectoid in the plating layer, the plating layer can have a certain degree of hardness as described above, and at the same time, the additive itself can be provided with lubricity. Therefore, the press formability of the plating layer is greatly improved.
次に本発明において上記有機化合物をめっき層中に共
析させる方法について説明する。めっき方法は特に限定
されるものではなく、電気めっき法等を必要に応じて採
用することができる。例えば前記有機化合物を0.01〜20
0g/の濃度で含有する酸性Zn或はZn系合金めっき液を
使用して電解を行なうことによって実施することができ
る。第２図にめっき液中の有機質化合物含有量と塗膜剥
離率の関係を、第３図にめっき液中の有機質化合物含有
量と布膜剥離量の関係を示した。めっき液中の有機化合
物の濃度が0.01g/よりも低いときは十分な効果が得ら
れにくく、一方200g/よりも高いときはめっき液の粘
度が上昇して被処理基材表面への金属イオンの供給が不
十分となると共に、有機化合物が過剰に被処理基材表面
に吸着されていることが、かえってめっき不良を引き起
こして外観を損なうばかりでなく、塗装性や塗装後耐食
性、更にはプレス成形性等へも悪影響を及ぼす。Next, a method of eutecting the above organic compound into the plating layer in the present invention will be described. The plating method is not particularly limited, and an electroplating method or the like can be employed as needed. For example, 0.01-20 of the organic compound
It can be carried out by performing electrolysis using an acidic Zn or Zn-based alloy plating solution containing 0 g / concentration. FIG. 2 shows the relationship between the content of the organic compound in the plating solution and the peeling rate of the coating film, and FIG. 3 shows the relationship between the content of the organic compound in the plating solution and the peeling amount of the cloth film. When the concentration of the organic compound in the plating solution is lower than 0.01 g /, it is difficult to obtain a sufficient effect. On the other hand, when the concentration is higher than 200 g /, the viscosity of the plating solution increases and metal ions on the surface of the substrate to be treated are increased. Insufficient supply of organic compounds and excessive adsorption of organic compounds to the surface of the substrate to be treated not only causes poor plating but also impairs the appearance, but also paintability, corrosion resistance after painting, and pressing. It also has an adverse effect on moldability and the like.
またこれらの効果を十分に発揮させるためには共析し
ている有機化合物は、めっき層中における炭素量で0.00
1〜10重量％、より望ましくは0.01〜５重量％含有され
ていることが必要である。第４図にめっき層中の炭素含
有量と塗膜剥離率の関係を、第５図にめっき層中の炭素
含有量とめっき剥離量の関係を示した。0.01重量％未満
であると十分な効果が得られにくく、この範囲を超える
とプレス成形時のめっき剥離の原因となる場合がある。Further, in order to sufficiently exhibit these effects, the eutectoid organic compound is required to have a carbon content in the plating layer of 0.00%.
It is necessary that the content be 1 to 10% by weight, more preferably 0.01 to 5% by weight. FIG. 4 shows the relationship between the carbon content in the plating layer and the coating film peeling rate, and FIG. 5 shows the relationship between the carbon content in the plating layer and the plating peeling amount. If the content is less than 0.01% by weight, it is difficult to obtain a sufficient effect, and if it exceeds this range, plating may be peeled off during press molding.
以下実施例について説明するが、本発明は下記の実施
例に限定されるものではなく、本発明の趣旨に基づいて
適宜設計変更を行なうことは、すべて本発明の範囲に含
まれる。EXAMPLES Hereinafter, examples will be described. However, the present invention is not limited to the following examples, and any appropriate design change based on the gist of the present invention is included in the scope of the present invention.
［実施例］ 脱脂酸洗の前処理を施した冷延鋼板及びそれぞれ適切
な前処理を施した電気めっき或は溶融めっき鋼板を基材
として、第１表に示されるめっきを施した。めっき処理
は基材を陰極とし電流密度100〜200A・dm6-2にて電解を
行なうことによって実施した。[Examples] Plating shown in Table 1 was applied to a cold-rolled steel sheet that had been subjected to a pretreatment for degreasing and pickling and an electroplated or hot-dip coated steel sheet that had been appropriately subjected to a pretreatment. The plating process was performed by performing electrolysis at a current density of 100 to 200 A · dm 6 -2 using the base material as a cathode.
得られためっき処理鋼板は塗膜密着性、塗装後耐食
性、プレス成形性について下記の方法により評価した。
尚本発明による添加剤としては、その代表例として、ジ
メチルアミノエチルメタクリルアミドにエピクロルヒド
リンを付与した化合物とアクリルアミドからなる分子量
30万の共重合体を用いた。The obtained plated steel sheet was evaluated for coating film adhesion, corrosion resistance after painting, and press formability by the following methods.
In addition, as a typical example of the additive according to the present invention, a molecular weight of a compound obtained by adding epichlorohydrin to dimethylaminoethyl methacrylamide and acrylamide
300,000 copolymers were used.
（評価方法） ・塗膜密着性 アルキド・メラミン系の塗料をめっきに
直接塗布し、碁盤目エリクセンテープ剥離試験を行な
い、塗膜剥離率にて評価した。(Evaluation method)-Coating film adhesion An alkyd / melamine-based paint was directly applied to the plating, and a cross-cut Ericksen tape peeling test was performed to evaluate the coating film peeling rate.
○：塗膜剥離率 ５％以下 △： 〃 ５〜30％ ×： 〃 30％以上 ・塗装後耐食性 アルキド・メラミン系の塗料をめっき
に直接塗布し、クロスカットSST24時間後にテープ剥離
試験を行ない、塗膜の剥離幅にて評価した。○: Peeling rate of coating film 5% or less △: ５〜 5-30% ×: 〃 30% or more ・ Corrosion resistance after coating Apply alkyd / melamine-based paint directly to plating, perform tape peeling test 24 hours after cross-cut SST, The evaluation was based on the peel width of the coating film.
○：塗膜剥離幅 1mm以下 △： 〃 １〜2mm ×： 〃 2mm以上 ・プレス成形性 ドロビード試験を行ない、めっきの剥
離量を調査した。：: coating film peel width 1 mm or less Δ: 〃 1-2 mm ×: 〃 2 mm or more-Press formability A Dlobroid test was conducted to examine the amount of plating peeling.
○：めっき剥離量0.2g/m2以下 △： 〃 02〜0.5g/m2 ×： 〃 0.5g/m2以上 結果を第１表に示す。○: Plating Peeling amount 0.2 g / m 2 or less △: 〃 02~0.5g / m 2 ×: 〃 0.5 g / m 2 or more The results are shown in Table 1.
第１表に示されるように、本発明による添加剤を使用
した実施例は、塗膜密着性、塗装後耐食性、プレス成形
性すべてにおいて優れている。一方、比較例であるNo.1
0は変性率が5mol％以下であり塗装後耐食性が悪く、No.
11は分子量が1000以下であるのでプレス成形性が悪く、
No.12は有機質化合物の含有量が低いので塗膜密着性及
び塗装後耐食性が悪く、No.14は有機質化合物の含有量
が高いので塗膜密着性及び塗装後耐食性が悪い。またN
o.13及び15は有機質化合物を含有しないので、No.16及
び17は本発明以外の有機質化合物を用いるので塗膜密着
性、塗装後耐食性及びプレス成形性が悪い。 As shown in Table 1, the examples using the additives according to the present invention are excellent in all of coating film adhesion, post-coating corrosion resistance and press moldability. On the other hand, the comparative example No. 1
No. 0 has a denaturation rate of 5 mol% or less, and has poor corrosion resistance after painting.
11 is poor in press moldability because the molecular weight is 1000 or less,
No. 12 has poor coating film adhesion and post-coating corrosion resistance due to low organic compound content, and No. 14 has poor coating film adhesion and post-coating corrosion resistance because of high organic compound content. Also N
Nos. 13 and 15 do not contain an organic compound, and Nos. 16 and 17 use an organic compound other than the present invention, so that the coating film adhesion, post-coating corrosion resistance and press moldability are poor.
［発明の効果］ 本発明は以上のように構成されており、本発明の表面
処理材料は塗装後耐食性、塗膜密着性、プレス成形性に
優れためっき層を有しているので塗装用表面処理材料と
してたいへん有用である。[Effects of the Invention] The present invention is configured as described above. Since the surface-treated material of the present invention has a plating layer having excellent corrosion resistance after coating, coating film adhesion, and press moldability, the coating surface Very useful as a processing material.
第１図は添加剤中のエポキシ系モノマー単位の変性率と
塗膜剥離幅の関係を示すグラフ、第２図はめっき液中の
有機質化合物含有量と塗膜剥離率の関係を示すグラフ、
第３図はめっき液中の有機質化合物含有量と塗膜剥離量
の関係を示すグラフ、第４図はめっき層中の炭素含有量
と塗膜剥離率の関係を示すグラフ、第５図はめっき層中
の炭素含有量とめっき剥離量の関係を示すグラフであ
る。FIG. 1 is a graph showing the relationship between the modification ratio of the epoxy monomer unit in the additive and the coating film peeling width, and FIG. 2 is a graph showing the relationship between the organic compound content in the plating solution and the coating film peeling ratio.
FIG. 3 is a graph showing the relationship between the organic compound content in the plating solution and the amount of coating film peeling, FIG. 4 is a graph showing the relationship between the carbon content in the plating layer and the coating film peeling ratio, and FIG. It is a graph which shows the relationship between the carbon content in a layer, and the plating peeling amount.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山村 なぎさ 兵庫県神戸市西区狩場台４―19―17 (56)参考文献 特開 昭61−127887（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C25D 3/00 - 3/64 C23C 2/00 - 2/40 C08F 20/00 - 22/40────────────────────────────────────────────────── ─── Continued on the front page (72) Nagisa Yamamura 4-19-17 Karibadai, Nishi-ku, Kobe-shi, Hyogo (56) References JP-A-61-127887 (JP, A) (58) Fields investigated (Int) .Cl. 6 , DB name) C25D 3/00-3/64 C23C 2/00-2/40 C08F 20/00-22/40
Claims (1)
又は異なってＨあるいはアルキル基］で表わされる官能
基に、エポキシ基を有する化合物が付加された基 を有する（メタ）アクリルアミド系モノマー単位が、全
繰り返し単位の5mol％以上である（メタ）アクリル系ポ
リマーをＣ量として0.001〜10重量％含有し、且つ残部
がZn或はZn合金からなるZn系めっき層が基材表面に形成
されたものであることを特徴とする塗膜密着性、塗装後
耐食性に優れた表面処理材料。(1) Wherein A is C n H 2n ; n is 0 or a positive integer, and R 1 and R 2 are the same or different and are H or an alkyl group, and a group obtained by adding a compound having an epoxy group to a functional group represented by Zn-based plating in which the (meth) acrylamide-based monomer unit contains 0.001 to 10% by weight of a (meth) acryl-based polymer having a C content of 5 mol% or more of the total repeating units and the balance is Zn or a Zn alloy A surface treatment material having excellent coating film adhesion and corrosion resistance after painting, characterized in that the layer is formed on the surface of the substrate.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22164890A JP2866168B2 (en) | 1990-08-22 | 1990-08-22 | Surface treatment material with excellent coating film adhesion and corrosion resistance after painting |
| US07/747,967 US5169726A (en) | 1990-08-22 | 1991-08-21 | Surface treated materials of excellent adhesion for painting layer, corrosion resistance after painting, and press formability, as well as a method of manufacturing them |
| DE1991618995 DE69118995T2 (en) | 1990-08-22 | 1991-08-22 | Surface treated materials with excellent adhesion to paint layers, corrosion resistance after painting and mechanical deformability as well as processes for their production |
| CA 2049736 CA2049736A1 (en) | 1990-08-22 | 1991-08-22 | Surface treated materials of excellent adhesion for painted layer, corrosion resistance after painting, and press formability, as well as a method of manufacturing them |
| EP19910114106 EP0472204B1 (en) | 1990-08-22 | 1991-08-22 | Surface treated materials of excellent adhesion for painting layer, corrosion resistance after painting, and press formability, as well as a method of manufacturing them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22164890A JP2866168B2 (en) | 1990-08-22 | 1990-08-22 | Surface treatment material with excellent coating film adhesion and corrosion resistance after painting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04103790A JPH04103790A (en) | 1992-04-06 |
| JP2866168B2 true JP2866168B2 (en) | 1999-03-08 |
Family
ID=16770074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22164890A Expired - Fee Related JP2866168B2 (en) | 1990-08-22 | 1990-08-22 | Surface treatment material with excellent coating film adhesion and corrosion resistance after painting |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2866168B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100321374B1 (en) * | 1997-07-18 | 2002-04-17 | 이구택 | METHOD FOR MANUFACTURING Zn/Fe ALLOY ELECTROPLATED STEEL SHEET EXCELLENT IN PLATING ADHESION, SURFACE ROUGHNESS AND APPEARANCE |
| KR100349149B1 (en) * | 1997-12-13 | 2002-11-18 | 주식회사 포스코 | Additive having superior addhesion and surface roughness and electro galvanizing solution containing it |
-
1990
- 1990-08-22 JP JP22164890A patent/JP2866168B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04103790A (en) | 1992-04-06 |
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