JPH05117869A - Metallic surface treating agent for forming composite film - Google Patents

Metallic surface treating agent for forming composite film

Info

Publication number
JPH05117869A
JPH05117869A JP3308227A JP30822791A JPH05117869A JP H05117869 A JPH05117869 A JP H05117869A JP 3308227 A JP3308227 A JP 3308227A JP 30822791 A JP30822791 A JP 30822791A JP H05117869 A JPH05117869 A JP H05117869A
Authority
JP
Japan
Prior art keywords
phosphate
film
coating
surface treating
composite film
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
Application number
JP3308227A
Other languages
Japanese (ja)
Other versions
JP3139795B2 (en
Inventor
Osamu Furuyama
治 古山
Ryoji Morita
良治 森田
Hitoshi Ishii
均 石井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nihon Parkerizing Co Ltd
Original Assignee
Nihon Parkerizing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=36791816&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=JPH05117869(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Priority to JP03308227A priority Critical patent/JP3139795B2/en
Priority to RU94019948/02A priority patent/RU94019948A/en
Priority to PCT/US1992/008811 priority patent/WO1993009265A1/en
Priority to CA002121486A priority patent/CA2121486A1/en
Priority to AU28841/92A priority patent/AU2884192A/en
Priority to KR1019940701427A priority patent/KR940702949A/en
Priority to BR9206685A priority patent/BR9206685A/en
Priority to EP92922276A priority patent/EP0610315A1/en
Priority to MX9206223A priority patent/MX9206223A/en
Priority to NZ244928A priority patent/NZ244928A/en
Priority to ZA928377A priority patent/ZA928377B/en
Priority to CN92112560A priority patent/CN1086269A/en
Priority to TW081109516A priority patent/TW245739B/zh
Publication of JPH05117869A publication Critical patent/JPH05117869A/en
Publication of JP3139795B2 publication Critical patent/JP3139795B2/en
Application granted granted Critical
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C23C22/07—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 phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2301/00—Inorganic additives or organic salts thereof
    • B05D2301/10—Phosphates, phosphoric acid or organic salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating

Abstract

PURPOSE:To provide the surface treating agent for forming a composite film which improves the corrosion resistance of metallic surfaces of iron, zinc, aluminum, etc., and is also excellent as a substrate for coating. CONSTITUTION:This metallic surface treating agent for the composite film consists of a phosphate surface treating liquid contg. a cationic org. high- polymer compd. contg. >=1 pieces of cationic nitrogen atoms and having 1000 to 1000000 mol.wt. or the salt thereof. The composite film is the film in the state in which the resin consisting of the cationic org. compd. or the salt thereof intrudes into the grain boundaries between the crystals of the phosphate and the resin form the composite. The metals treated with this metallic surface treating agent for forming the composite film are greatly improved in the corrosion resistance and the adhesion of the coating film as compared with the metals treated by the phosphate treatment. Further, the metals treated with this surface treating agent exhibit the performance nearly equal to the performance of the metals formed with the phosphate film subjected to primer coating.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、鉄、亜鉛、アルミニウ
ム等の金属表面の耐食性に優れ、かつ塗装下地としても
優れた複合皮膜を形成させる新規な表面処理剤に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel surface treating agent which forms a composite film which is excellent in corrosion resistance on the surface of metals such as iron, zinc and aluminum and which is also excellent as a coating base.

【０００２】[0002]

【従来の技術】現在、自動車ボデーや建材のような塗装
物は、従来にもまして、高度な耐食性が要求されてい
る。従来、金属の表面処理として、リン酸塩処理やクロ
メート処理等が行われているが、従来の金属表面処理剤
は高度な耐食性や塗膜密着性を必ずしも十分満足するも
のではない。2. Description of the Related Art At present, coated articles such as automobile bodies and building materials are required to have higher corrosion resistance than ever before. Conventionally, phosphate treatment, chromate treatment and the like have been performed as a metal surface treatment, but conventional metal surface treatment agents do not always sufficiently satisfy high corrosion resistance and coating film adhesion.

【０００３】通常、鉄、亜鉛、アルミニウム等の金属表
面に塗料、接着剤等の有機皮膜を塗布する場合、前処理
として金属表面にりん塩皮膜を形成させる方法は公知で
ある。リン酸塩皮膜を金属表面に形成させた後、塗料に
代表される有機皮膜を塗布すれば、耐食性、塗膜密着性
が向上する。さらに耐食性を求める場合は、リン酸塩処
理後クロム酸シーリング等による後処理を行った後又は
プライマー塗料を塗布後塗装される。しかしながらクロ
酸シーリング等の後処理の効果は小さく、又プライマー
塗料の塗布は塗装性能を向上させるが、塗布工程の増加
により著しく作業性を劣化させる。Usually, when an organic film such as a paint or an adhesive is applied to the surface of a metal such as iron, zinc or aluminum, a method of forming a phosphorus salt film on the surface of the metal is known as a pretreatment. If a phosphate film is formed on the metal surface and then an organic film typified by paint is applied, corrosion resistance and coating film adhesion are improved. Further, when corrosion resistance is required, it is applied after a phosphate treatment, after-treatment such as chromic acid sealing, or after applying a primer coating. However, the effect of the post-treatment such as chloric acid sealing is small, and the application of the primer coating improves the coating performance, but the workability is significantly deteriorated due to the increase in the coating process.

【０００４】現在、自動車ボデーや建材のような塗装物
は、プライマー塗装が必須なものとなる。自動車ボデー
の場合リン酸亜鉛皮膜を金属表面に生成させた後、水系
塗料に浸漬して電着塗装が行われる。この塗装は一種の
プライマー塗装であり、塗装面の耐食性の向上させるこ
と及び上塗り塗装を施し難い自動車ボデーの内面等の耐
食性を確保することを目的とする。建材も同様で、耐食
性向上を目的とし上塗り塗装前にプライマー塗装が施さ
れる。Presently, primer coating is indispensable for painted articles such as automobile bodies and building materials. In the case of automobile bodies, a zinc phosphate film is formed on a metal surface and then immersed in a water-based paint for electrodeposition coating. This coating is a kind of primer coating, and its purpose is to improve the corrosion resistance of the coated surface and to secure the corrosion resistance of the inner surface of an automobile body which is difficult to apply the top coating. The same applies to building materials, where primer coating is applied prior to top coating in order to improve corrosion resistance.

【０００５】塗装工程における作業性向上及びコスト低
減を目的として工程短縮が要求されているが、いまだそ
の目的対応し得る技術は開発されていない。すなわちリ
ン酸塩皮膜だけでは耐食性が乏しく、塗装のみでは耐食
性や塗装密着性で要求を満たさない。同様に、高度な耐
食性を要求される場合においては、リン酸塩皮膜とさら
にプライマー塗装が不可欠ある。このため塗装コストが
高くなりかつ作業面積を多くとるといった課題を有して
おり高度な耐食性や塗装密着性を有する金属表面処理剤
が要求され、またプライマー塗装が省略できる表面処理
剤も要望されている。Although a shortening of the process is required for the purpose of improving workability and cost reduction in the coating process, a technique capable of meeting the purpose has not been developed yet. In other words, the phosphate coating alone has poor corrosion resistance, and the coating alone does not meet the requirements for corrosion resistance and coating adhesion. Similarly, when a high degree of corrosion resistance is required, a phosphate coating and further primer coating are essential. Therefore, there is a problem that the coating cost is high and the work area is large, and therefore a metal surface treatment agent having high corrosion resistance and coating adhesion is required, and a surface treatment agent that can omit the primer coating is also required. There is.

【０００６】[0006]

【発明が解決しようとする課題】本発明は前記課題への
対応手段として、鉄、亜鉛、アルミニウム等のリン酸塩
皮膜処理できうる金属（以下金属という）に、高度な耐
食性及び塗膜密着性を付与できる金属表面処理剤及び、
現状の耐食性水準を維持してプライマー塗装が省略でき
る金属表面処理剤をも提供することを目的とするもので
ある。SUMMARY OF THE INVENTION As a means for solving the above problems, the present invention provides a metal (hereinafter referred to as a metal) which can be treated with a phosphate film such as iron, zinc and aluminum, with a high degree of corrosion resistance and coating adhesion. A metal surface treatment agent capable of imparting,
It is an object of the present invention to provide a metal surface treatment agent which can maintain the current level of corrosion resistance and omit the primer coating.

【０００７】[0007]

【課題を解決するための手段】前述の問題点を解決する
ために検討を重ねた結果、特定な性質を有する有機高分
子化合物又はその塩を含むリン酸塩処理液にて皮膜形成
させると、高度な耐食性及び塗装密着性が得られること
を見いだし本発明を完成した。Means for Solving the Problems As a result of repeated studies for solving the above-mentioned problems, when a film is formed with a phosphating solution containing an organic polymer compound having a specific property or a salt thereof, The inventors have found that high corrosion resistance and coating adhesion can be obtained, and completed the present invention.

【０００８】すなはち、陽イオン性窒素原子を一個以上
含み、分子量が１０００〜１００００００である陽イオ
ン性有機高分子化合物又はその塩を含有するリン酸塩表
面処理液からなることを特徴とする複合皮膜形成用金属
表面処理剤で金属表面を処理することによって上述した
優れた性能を有する複合皮膜を形成できる。なお本発明
での複合皮膜とは、リン酸塩の結晶と結晶の粒界に陽イ
オン性有機化合物又はその塩からなる樹脂が入り込み、
リン酸塩の結晶と樹脂が複合物を形成した状態の皮膜で
ある。That is, it is characterized in that it comprises a phosphate surface treatment liquid containing one or more cationic nitrogen atoms and a cationic organic polymer compound having a molecular weight of 1,000 to 1,000,000 or a salt thereof. By treating the metal surface with the metal surface treating agent for forming a composite film, the composite film having the above-described excellent performance can be formed. Incidentally, the composite film in the present invention, a resin consisting of a cationic organic compound or a salt thereof enters the crystal grain of the phosphate and the grain boundary of the crystal,
This is a film in which the phosphate crystals and the resin form a composite.

【０００９】本発明の表面処理剤とはリン酸塩処理液に
陽イオン性有機高分子化合物又はその塩を溶解又は安定
分散したものである。リン酸塩処理液とは、鉄、亜鉛、
アルミニウム等の金属表面にそれぞれ又はそれらの金属
の２種以上を同時に、リン酸塩皮膜を形成しうる表面処
理液であって通常亜鉛イオン、リン酸イオンが必須成分
であり、必要に応じて硝酸イオン、ニッケルイオン、マ
ンガンイオン、カルシウムイオン等の金属イオンフッ化
物、各種酸化剤等が添加されたものである。但し本発明
において特に限定するものでなく、公知のリン酸塩処理
液であれば良い。The surface treatment agent of the present invention is a solution obtained by dissolving or stably dispersing a cationic organic polymer compound or a salt thereof in a phosphate treatment solution. The phosphating solution is iron, zinc,
A surface treatment solution capable of simultaneously forming a phosphate film on the surface of a metal such as aluminum or two or more of these metals, and zinc ions and phosphate ions are usually essential components, and nitric acid may be added as necessary. Ion, nickel ion, manganese ion, calcium ion, and other metal ion fluorides, various oxidizing agents, etc. are added. However, the present invention is not particularly limited, and any known phosphate treatment liquid may be used.

【００１０】陽イオン性有機高分子化合物とは、陽イオ
ン性窒素原子を一個以上含み、分子量が１０００〜１０
０００００のものであって、その構造は特定するもので
はないが、より好ましくは次のいずれかの有機高分子を
挙げることができる。すなわちエポキシ系樹脂、ウレタ
ン系樹脂、ポリブタジエン系樹脂、アクリル系樹脂、無
水マレイン化樹脂の一種又は２種以上の樹脂骨格を有
し、これらの樹脂に陽イオン性窒素を含む基を導入した
もの。The cationic organic polymer compound contains at least one cationic nitrogen atom and has a molecular weight of 1000 to 10
00000 and its structure is not specified, but more preferably, any of the following organic polymers can be mentioned. That is, it has one or more kinds of resin skeletons of an epoxy resin, a urethane resin, a polybutadiene resin, an acrylic resin, and a maleic anhydride resin, and a group containing a cationic nitrogen is introduced into these resins.

【００１１】陽イオン性有機高分子化合物塩とは上述し
た陽イオン性有機高分子化合物のリン酸塩、硝酸塩、硫
酸塩等の無機酸塩又は酢酸塩、プロピオン酸塩、グリコ
ン酸塩等の有機酸塩である。これらの陽イオン性有機高
分子化合物又はその塩は一種又は二種以上で使用されて
もかまわない。分子量が１０００未満では耐食性向上効
果が乏しく、１００００００以上ではリン酸亜鉛浴への
溶解又は安定分散が困難となる。The cationic organic polymer compound salt is an inorganic acid salt such as phosphate, nitrate or sulfate of the above-mentioned cationic organic polymer compound or organic salt such as acetate, propionate or glyconate. It is an acid salt. These cationic organic polymer compounds or salts thereof may be used alone or in combination of two or more. If the molecular weight is less than 1000, the effect of improving corrosion resistance is poor, and if it is 1,000,000 or more, dissolution or stable dispersion in a zinc phosphate bath becomes difficult.

【００１２】さらに、必要に応じて顔料等の塗料添加物
や他種の樹脂、活性剤等の添加を拒むものではない。本
発明の金属表面処理方法としては、スプレー又は浸漬に
よる化成処理及び電解処理の何れの方法も可能であり、
本発明処理剤は処理方法は限定されるものではない。Furthermore, addition of paint additives such as pigments, other types of resins, activators and the like, if necessary, is not prohibited. As the metal surface treatment method of the present invention, any method of chemical conversion treatment by spraying or dipping and electrolytic treatment is possible,
The treating method of the treating agent of the present invention is not limited.

【００１３】[0013]

【作用】リン酸塩皮膜は公知のごとく、被処理金属の溶
出により金属界面におけるリン酸塩処理液のｐＨが上昇
することによって折出形成される。また陽イオン性有機
高分子化合物は陽イオン性で水中に溶解又は分散してい
るため、ｐＨ上昇は陽イオン性有機高分子化合物の溶解
性又は分散性を低下させ折出を促すのである。このため
本発明の表面処理剤で金属を処理すると、リン酸塩と有
機高分子化合物が同時に折出して複合皮膜が形成される
のである。As is well known, the phosphate film is formed by the elution of the metal to be treated and the pH of the phosphate treatment liquid at the metal interface rising. Further, since the cationic organic polymer compound is cationic and is dissolved or dispersed in water, an increase in pH lowers the solubility or dispersibility of the cationic organic polymer compound and promotes the protrusion. Therefore, when the metal is treated with the surface treating agent of the present invention, the phosphate and the organic polymer compound are simultaneously projected to form a composite film.

【００１４】リン酸塩皮膜はポーラスであり皮膜のみで
は耐食性への寄与は比較的小さい。本発明の表面処理剤
にて形成した複合皮膜が耐食性が良好なのは、有機高分
子化合物がリン酸塩皮膜のポーラス性をカバーするから
である。更に本発明の表面処理剤で形成された皮膜は、
リン酸亜鉛皮膜が有機高分子に保護されるため、例えば
塗装時にリン酸塩皮膜を塗料中に一部溶解し塗料密着を
劣化する現象を防止でき、あるいはリン酸塩皮膜処理工
程後次の塗装工程までの中間工程における錆発生を防止
できる等の作用があるThe phosphate coating is porous, and the contribution to the corrosion resistance is relatively small if the coating alone is used. The reason why the composite film formed by the surface treatment agent of the present invention has good corrosion resistance is that the organic polymer compound covers the porous property of the phosphate film. Further, the film formed by the surface treatment agent of the present invention,
Since the zinc phosphate film is protected by organic polymer, it is possible to prevent the phenomenon that the phosphate film is partially dissolved in the paint during coating and deteriorates the adhesion of the paint, or the next coating after the phosphate film treatment process. Has the effect of preventing rust generation in the intermediate process up to the process

【００１５】なお本発明は、陽イオン性有機高分子化合
物又はその塩を含有するリン酸塩処理液を用いることに
特徴がある。例えば、リン酸塩処理液で金属表面処理し
た後に、陽イオン性有機高分子化合物又はその塩を含む
溶液で処理しても効果がない。これは複合皮膜が形成さ
れずにリン酸塩処理皮膜の上に樹脂皮膜が覆うにすぎ
ず、皮膜が剥離しやすく強固でないからである。また、
本発明の複合皮膜により高度の耐食性及び塗膜密着性が
保持されることは実施例でも示す従来より苛酷な試験方
法により確認される。The present invention is characterized by using a phosphate treatment liquid containing a cationic organic polymer compound or a salt thereof. For example, there is no effect even if the metal surface is treated with a phosphate treatment solution and then treated with a solution containing a cationic organic polymer compound or a salt thereof. This is because the composite film is not formed and only the resin film covers the phosphate treatment film, and the film is easily peeled off and not strong. Also,
The fact that the composite coating of the present invention retains a high degree of corrosion resistance and coating adhesion is confirmed by the more rigorous test methods shown in the examples.

【００１６】陽イオン性有機高分子化合物の替わりにア
ニオン性有機高分子化合物またはノニオン性有機高分子
化合物を用いたのでは、ｐＨの上昇によって折出させ皮
膜を形成するのは困難である。When an anionic organic polymer compound or a nonionic organic polymer compound is used instead of the cationic organic polymer compound, it is difficult to form a film by causing the polymer to stick out due to an increase in pH.

【００１７】[0017]

【実施例】次に実施例を示し本発明の効果を詳述する
が、本発明はこれらの実施例に限定されるものではな
く、通常のリン酸塩塗装前処理及び通常の塗装システム
の一例として示したものである。EXAMPLES Next, the effects of the present invention will be described in detail by showing examples, but the present invention is not limited to these examples, and examples of ordinary phosphate pretreatment and ordinary coating system It is shown as.

【００１８】（供試板） 冷延鋼板 電気めっき鋼板（亜鉛目付け２０ｇ／ｍ2） アルミニウム板（ＪＩＳ−５０５２）(Sample plate) Cold rolled steel plate Electroplated steel plate (Zinc basis weight 20 g / m 2 ) Aluminum plate (JIS-5052)

【００１９】（供試表面処理剤）実施例に用いた陽イオ
ン性有機高分子化合物並びに比較例に用いた高分子化合
物を表１に示す。有機高分子化合物を除くリン酸塩表面
処理液は代表的なものとしてパルボンドＬ３０２０（日
本パーカライジング社製）の自動車用表面処理剤からな
るリン酸塩表面処理液を用いた。(Test Surface Treatment Agent) Table 1 shows the cationic organic polymer compounds used in the examples and the polymer compounds used in the comparative examples. As the phosphate surface treatment liquid excluding the organic polymer compound, a phosphate surface treatment liquid containing Palbond L3020 (manufactured by Nippon Parkerizing Co., Ltd.), which is an automobile surface treatment agent, was used as a representative.

【００２０】（処理方法） １）脱脂 ファインクリーナーＬ４４６０（日本パーカライジング
社製）の２％液４２℃１２０秒スプレー ２）水洗 常温 ３０秒 スプレー ３）表面調整 パーコレンＺＮ（日本パーカライジング社製）の０．１
％液 常温 ２０秒 スプレー 実施例、比較例共１）〜３）の前処理をおこなった。 ４）本発明表面処理 本発明表面処理剤、比較例における表面処理剤共に下記
条件で処理した。 ４２℃ １２０秒 浸漬 ５）水洗 常温 ３０秒 スプレー ６）脱イオン水洗（電導度；０．２μｓ／ｃｍ） 常温 ２０秒 スプレー 実施例、比較例共に同様に行った。(Treatment method) 1) Degreasing Fine cleaner L4460 (manufactured by Nippon Parkerizing Co., Ltd.) 2% solution 42 ° C. 120 seconds spray 2) Washing at room temperature 30 seconds spray 3) Surface adjustment Percollene ZN (manufactured by Nippon Parkerizing Co., Ltd.) 1
% Liquid, normal temperature, 20 seconds, spray The pretreatment of 1) to 3) was performed for both Examples and Comparative Examples. 4) Surface Treatment of the Present Invention Both the surface treatment agent of the present invention and the surface treatment agent of Comparative Example were treated under the following conditions. 42 ° C. 120 seconds immersion 5) Water washing at room temperature for 30 seconds Spray 6) Deionized water washing (electrical conductivity; 0.2 μs / cm) Room temperature for 20 seconds Spray Example and Comparative Example were carried out in the same manner.

【００２１】（塗装）実施例、比較例共に同様に以下の
工程で塗装した。 １）プライマー塗装 電着塗装（エレクロン９４１０；関西ペイント社製） 膜厚２０μｍ 焼付け１７５℃ ３０分 ２）中塗り塗装 ＫＰＸ３６（関西ペイント社製） 膜厚３０μｍ 焼付け１４０℃ ３０分 ３）上塗り塗装 ルーガベークＢ５３１（関西ペイント社製） 膜厚４０μｍ 焼付け１４０℃ ３０分(Coating) Coating was carried out in the following steps in the same manner for both the examples and comparative examples. 1) Primer coating Electrodeposition coating (Electron 9410; manufactured by Kansai Paint Co., Ltd.) Film thickness 20 μm baking 175 ° C. 30 minutes 2) Intermediate coating KPX36 (Kansai Paint Co.) Film thickness 30 μm baking 140 ° C. 30 minutes 3) Top coating Lugabak B531 (Manufactured by Kansai Paint Co., Ltd.) Film thickness 40 μm Baking 140 ° C. 30 minutes

【００２２】（性能評価） １）耐水二次密着性 塗装板を４０℃脱イオン水に２４０時間浸漬後、鋭利な
カッターで素地に達するように２ｍｍ角のゴバン目を１
００個切り、セロテープ剥離を行っ た後のゴバン
目剥離個数を評価した。剥離個数の少ない程良好。 ２）複合サイクルテスト 塗装板に鋭利なカッターで素地に達するするようにクロ
ススクラッチを入れ、下記Ｔ1→Ｔ2のサイクルを１４サ
イクル繰り返し、試験後のクロススクラッチからの片側
最大塗膜膨れ幅を測定し評価した。 Ｔ1；塩水噴霧試験（ＪＩＳ−Ｚ２３７１）：２４時間 Ｔ2；湿潤試験（５０℃、７０％ＲＨ）：２１６時間(Performance Evaluation) 1) Secondary Adhesion to Water Resistance After immersing a coated plate in deionized water at 40 ° C. for 240 hours, a sharp edged cutter is used to make a square edge of 2 mm square to reach the base.
The piece was cut into 00 pieces, and the number of peeled pieces after peeling the cellophane tape was evaluated. The smaller the number of peeled pieces, the better. 2) Combined cycle test Insert a cross scratch on the coated plate with a sharp cutter to reach the substrate, and repeat the following cycle of T 1 → T 2 for 14 cycles to determine the maximum coating swell width on one side from the cross scratch after the test. It was measured and evaluated. T 1 ; Salt spray test (JIS-Z2371): 24 hours T 2 ; Wet test (50 ° C., 70% RH): 216 hours

【００２３】[0023]

【表１】 [Table 1]

【００２４】（実施例）冷延鋼板を用いて評価した結果
を表２に示す。電気亜鉛めっき鋼板を用いて評価した結
果をを表３に示す。(Example) Table 2 shows the results of evaluation using a cold rolled steel sheet. Table 3 shows the results of evaluation using an electrogalvanized steel sheet.

【００２５】（比較例）本発明品以外の有機高分子化合
物を使用した場合又は陽イオン有機高分子か使用しなか
った場合の例を実施例と同様に処理し評価した。Comparative Example An example in which an organic polymer compound other than the product of the present invention was used or when no cationic organic polymer was used was treated and evaluated in the same manner as in Examples.

【００２６】[0026]

【表２】 [Table 2]

【００２７】[0027]

【表３】 [Table 3]

【００２８】[0028]

【表４】 [Table 4]

【００２９】[0029]

【発明の効果】表２、３、４はそれぞれ冷延鋼板、電気
亜鉛めっき鋼板、アンモニウム板に表面処理を行った皮
膜の塗膜密着性及び耐食性を比較例とともに示したもの
である。 本発明の複合皮膜形成用金属表面処理剤で処
理したものは、耐食性、塗膜密着性がリン酸塩処理に比
べ著しく向上するのが解る。さらにプライマー塗装を省
略した場合においても本発明は、リン酸塩皮膜にプライ
マー塗装をしたものと同等に近い性能を示す。本発明に
含まれない有機高分子化合物を用いた場合、全く効果が
ないか逆に性能を劣化させることが解る。この様に本発
明の複合皮膜形成用金属表面処理剤は耐食性及び塗膜密
着性を向上させ、さらにプライマー塗装の省略を可能と
する。EFFECTS OF THE INVENTION Tables 2, 3 and 4 show the coating film adhesion and corrosion resistance of cold-rolled steel sheets, electrogalvanized steel sheets, and ammonium sheets, which were surface-treated, together with comparative examples. It can be seen that those treated with the metal surface treating agent for forming a composite film of the present invention have significantly improved corrosion resistance and coating film adhesion as compared with the phosphate treatment. Further, even when the primer coating is omitted, the present invention exhibits a performance close to that obtained by applying the primer coating to the phosphate film. It can be seen that when an organic polymer compound not included in the present invention is used, there is no effect or conversely the performance is deteriorated. As described above, the metal surface treating agent for forming a composite film of the present invention improves the corrosion resistance and the adhesion of the coating film, and further allows the primer coating to be omitted.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 133/06 ＰＦＹ 7921−4Ｊ 163/00 ＰＪＭ 8416−4Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location C09D 133/06 PFY 7921-4J 163/00 PJM 8416-4J

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 陽イオン性窒素原子を一個以上含み、分
子量が１０００〜１００００００である陽イオン性有機
高分子化合物又はその塩を含有するリン酸塩表面処理液
からなることを特徴とする複合皮膜形成用金属表面処理
剤。1. A composite film comprising a phosphate surface treatment liquid containing at least one cationic nitrogen atom and having a molecular weight of 1,000 to 1,000,000 or a cationic organic polymer compound or a salt thereof. Metal surface treatment agent for forming. 【請求項２】 陽イオン性有機高分子化合物がエポキシ
系樹脂、ウレタン系樹脂、ポリブタジエン系樹脂、アク
リル系樹脂、無水マレイン化樹脂の一種又は２種以上の
樹脂骨格を有する化合物である請求項１に記載の複合皮
膜形成用金属表面処理剤。2. A compound having a resin skeleton of one or more of an epoxy resin, a urethane resin, a polybutadiene resin, an acrylic resin, and a maleic anhydride resin, wherein the cationic organic polymer compound is a compound. The metal surface treating agent for forming a composite film as described in 1.
JP03308227A 1991-10-29 1991-10-29 Metal surface treatment agent for composite film formation Expired - Lifetime JP3139795B2 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
JP03308227A JP3139795B2 (en) 1991-10-29 1991-10-29 Metal surface treatment agent for composite film formation
RU94019948/02A RU94019948A (en) 1991-10-29 1992-10-22 Compound for treatment of phosphate coating, method for formation of protective coating of article
PCT/US1992/008811 WO1993009265A1 (en) 1991-10-29 1992-10-22 Treatment for the formation of a corrosion resistant film on metal surfaces
CA002121486A CA2121486A1 (en) 1991-10-29 1992-10-22 Treatment for the formation of a corrosion resistant film on metal surfaces
AU28841/92A AU2884192A (en) 1991-10-29 1992-10-22 Treatment for the formation of a corrosion resistant film on metal surfaces
KR1019940701427A KR940702949A (en) 1991-10-29 1992-10-22 TREATMENT FOR THE FORMATION OF A CORROSION RESISTANT FILM ON METAL SURFACES
BR9206685A BR9206685A (en) 1991-10-29 1992-10-22 Phosphate conversion coating treatment composition for metal surfaces, process for forming a protective coating on a metal, and manufactured product
EP92922276A EP0610315A1 (en) 1991-10-29 1992-10-22 Treatment for the formation of a corrosion resistant film on metal surfaces
MX9206223A MX9206223A (en) 1991-10-29 1992-10-28 TREATMENT FOR THE FORMATION OF A FILM RESISTANT TO CORROSION ON METAL SURFACES.
NZ244928A NZ244928A (en) 1991-10-29 1992-10-29 Phosphate conversion coatings for metal surfaces, containing an organic polymer which has cationic nitrogens; article of manufacture
ZA928377A ZA928377B (en) 1991-10-29 1992-10-29 Treatment for the formation of a corrosion resistant film on metal surfaces.
CN92112560A CN1086269A (en) 1991-10-29 1992-10-29 Form the treatment process of anti-corrosion film in the metallic surface
TW081109516A TW245739B (en) 1991-10-29 1992-11-27

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP03308227A JP3139795B2 (en) 1991-10-29 1991-10-29 Metal surface treatment agent for composite film formation
CN92112560A CN1086269A (en) 1991-10-29 1992-10-29 Form the treatment process of anti-corrosion film in the metallic surface

Publications (2)

Publication Number Publication Date
JPH05117869A true JPH05117869A (en) 1993-05-14
JP3139795B2 JP3139795B2 (en) 2001-03-05

Family

ID=36791816

Family Applications (1)

Application Number Title Priority Date Filing Date
JP03308227A Expired - Lifetime JP3139795B2 (en) 1991-10-29 1991-10-29 Metal surface treatment agent for composite film formation

Country Status (10)

Country Link
EP (1) EP0610315A1 (en)
JP (1) JP3139795B2 (en)
CN (1) CN1086269A (en)
AU (1) AU2884192A (en)
BR (1) BR9206685A (en)
CA (1) CA2121486A1 (en)
MX (1) MX9206223A (en)
NZ (1) NZ244928A (en)
WO (1) WO1993009265A1 (en)
ZA (1) ZA928377B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6146473A (en) * 1996-10-21 2000-11-14 Nippon Paint Co., Ltd. Metal surface treatment composition containing an acrylic resin comprising a n-heterocycle ring, treatment method, and treated metal material
US6388021B1 (en) 1996-10-21 2002-05-14 Nippon Paint Co., Ltd. Acrylic metal surface treatment composition with hydroxy and amino/ammonium functionality
JP2004218070A (en) * 2002-12-24 2004-08-05 Nippon Paint Co Ltd Pretreatment method for coating
JP2008057047A (en) * 2002-06-28 2008-03-13 Jfe Steel Kk Method for producing surface-treated zinc series metal plated steel sheet
US8075708B2 (en) 2002-12-24 2011-12-13 Nippon Paint Co., Ltd. Pretreatment method for coating

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5306526A (en) * 1992-04-02 1994-04-26 Ppg Industries, Inc. Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method
JP3193798B2 (en) * 1993-01-13 2001-07-30 日本パーカライジング株式会社 Metal surface treatment liquid for forming composite film for cold working of metal and method for forming composite film
DE4341602A1 (en) * 1993-12-07 1995-06-08 Bayer Ag Use of a polyurethane dispersion as a penetration base and a process for the production of multicoat paint systems
JPH101782A (en) * 1996-06-13 1998-01-06 Nippon Paint Co Ltd Metallic surface treating agent, treatment and surface treated metallic material
JPH1046101A (en) * 1996-08-01 1998-02-17 Nippon Parkerizing Co Ltd Coated metallic material prepared by forming undercoat for film lamination on the surface of metallic material and its production
FR2769325B1 (en) * 1997-10-08 1999-12-03 Cfpi Ind ACID BATH FOR ZINC PHOSPHATATION OF METAL SUBSTRATES, CONCENTRATE FOR THE PREPARATION OF THE BATH AND PHOSPHATATION METHOD USING THE SAME
US5972433A (en) * 1997-12-05 1999-10-26 Calgon Corporation Method for treatment of metal substrates using Mannich-derived polyethers
FR2837209B1 (en) * 2002-03-13 2004-06-18 Rhodia Chimie Sa USE OF BLOCK COPOLYMERS CARRYING PHOSPHATE AND / OR PHOSPHONATE FUNCTIONS AS ADHESION PROMOTERS OR AS PROTECTIVE AGENTS AGAINST CORROSION OF A METAL SURFACE

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2159511B (en) * 1984-04-25 1988-09-21 Dearborn Chemicals Ltd A method of inhibiting corrosion in aqueous systems
US4978399A (en) * 1988-01-04 1990-12-18 Kao Corporation Metal surface treatment with an aqueous solution
DE3906898A1 (en) * 1989-03-03 1990-09-06 Henkel Kgaa ZINC-BARIUM PHOSPHATION OF METAL SURFACES
JPH04193957A (en) * 1990-11-28 1992-07-14 Nippon Parkerizing Co Ltd Chromating solution for substrate for clear coat

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6146473A (en) * 1996-10-21 2000-11-14 Nippon Paint Co., Ltd. Metal surface treatment composition containing an acrylic resin comprising a n-heterocycle ring, treatment method, and treated metal material
US6388021B1 (en) 1996-10-21 2002-05-14 Nippon Paint Co., Ltd. Acrylic metal surface treatment composition with hydroxy and amino/ammonium functionality
JP2008057047A (en) * 2002-06-28 2008-03-13 Jfe Steel Kk Method for producing surface-treated zinc series metal plated steel sheet
JP2004218070A (en) * 2002-12-24 2004-08-05 Nippon Paint Co Ltd Pretreatment method for coating
US8075708B2 (en) 2002-12-24 2011-12-13 Nippon Paint Co., Ltd. Pretreatment method for coating

Also Published As

Publication number Publication date
AU2884192A (en) 1993-06-07
ZA928377B (en) 1993-05-14
JP3139795B2 (en) 2001-03-05
BR9206685A (en) 1995-10-24
NZ244928A (en) 1994-10-26
MX9206223A (en) 1993-11-30
EP0610315A1 (en) 1994-08-17
CN1086269A (en) 1994-05-04
WO1993009265A1 (en) 1993-05-13
CA2121486A1 (en) 1993-05-13

Similar Documents

Publication Publication Date Title
US6436475B1 (en) Process of treating metallic surfaces
JP3221882B2 (en) A simplified method for producing a lacquer coating having good corrosion resistance and good adhesion and a workpiece obtained by the method
RU2482220C2 (en) Metallizing preliminary treatment of zinc surfaces
US6527841B2 (en) Post-treatment for metal coated substrates
US3053691A (en) Protective coating
JPS5811514B2 (en) How to protect metal surfaces
JPS5811513B2 (en) How to protect metal surfaces
JPS6136588B2 (en)
EP1433876A1 (en) Chemical conversion coating agent and surface-treated metal
JP4276530B2 (en) Chemical conversion treatment agent and surface treatment metal
JP3987633B2 (en) Metal protective film forming treatment agent and forming method
JPS5811515B2 (en) Composition for forming a zinc phosphate film on metal surfaces
JPS61174973A (en) Method of improving corrosion resistanceof self-migration coating resin coating
JP3139795B2 (en) Metal surface treatment agent for composite film formation
EP0119608B1 (en) Coating composite for extended corrosion resistance
JPH04276087A (en) Method for after-cleaning of formed layer
JPH10251509A (en) Metal surface treating solution and surface treated metal plate
JPH0361385A (en) Cleaning phosphate layer after passivation
US3720547A (en) Permanganate final rinse for metal coatings
WO1995027809A1 (en) Method of pre-treating metal substrates prior to painting
JPS62174385A (en) Pretreatment for painting by cationic electrodeposition
US5888315A (en) Composition and process for forming an underpaint coating on metals
US6569498B2 (en) Passification of zinc surfaces
JPS6141987B2 (en)
US3467589A (en) Method of forming a copper containing protective coating prior to electrodeposition of paint