JP2001049453A - Surface treating agent for metallic material excellent in corrosion resistance and surface treating method for metallic material - Google Patents
Surface treating agent for metallic material excellent in corrosion resistance and surface treating method for metallic materialInfo
- Publication number
- JP2001049453A JP2001049453A JP11230094A JP23009499A JP2001049453A JP 2001049453 A JP2001049453 A JP 2001049453A JP 11230094 A JP11230094 A JP 11230094A JP 23009499 A JP23009499 A JP 23009499A JP 2001049453 A JP2001049453 A JP 2001049453A
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- weight
- corrosion resistance
- surface treatment
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
-
- 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
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also 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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- 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
- C23C22/46—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 oxalates
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鋼、亜鉛系めっき
鋼板、アルミニウム板、等の金属材料の表面に優れた耐
食性および上塗り塗装密着性を付与する皮膜を形成する
ための表面処理剤およびそれを用いた金属材料の表面処
理方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for forming a film which imparts excellent corrosion resistance and topcoat adhesion to the surface of a metal material such as steel, galvanized steel sheet, aluminum sheet and the like. The present invention relates to a method for treating a surface of a metal material using the same.
【０００２】[0002]
【従来の技術】金属材料、その中でも亜鉛系めっき鋼板
は、自動車、家電、建材など様々な分野で使用されてい
るが、大気中で腐食して白錆と呼ばれる腐食生成物を形
成すると言う欠点を有している。そこで、従来技術では
耐食性を改善する目的で、亜鉛系めっき鋼板の表面にク
ロム酸水溶液を含む処理液を用いて６価クロムと３価ク
ロムを含む皮膜層を形成させるクロメート処理と言われ
る方法が一般的に行われている。2. Description of the Related Art Metal materials, in particular, galvanized steel sheets, are used in various fields such as automobiles, home appliances and building materials, but have the disadvantage that they corrode in the atmosphere to form a corrosion product called white rust. have. Therefore, in the prior art, for the purpose of improving corrosion resistance, there is a method called chromate treatment in which a coating layer containing hexavalent chromium and trivalent chromium is formed on the surface of a galvanized steel sheet using a treatment solution containing a chromic acid aqueous solution. Generally done.
【０００３】しかしながら、このクロメート処理に用い
る水溶液は人体に有害な６価クロムを有しているため、
排水処理は水質汚濁防止法に規定されている特別な処理
を施す必要がある。このため、近年地球的環境保全への
意識の高揚に伴い、出来る限り人体に有害な化合物の使
用を控えるという動きが強くなってきている。However, since the aqueous solution used for the chromate treatment has hexavalent chromium harmful to the human body,
Wastewater treatment requires special treatment specified in the Water Pollution Control Law. For this reason, in recent years, with an increase in awareness of global environmental conservation, there has been a strong movement to refrain from using compounds harmful to the human body as much as possible.
【０００４】一方、クロメート処理以外の表面処理方法
としては、タンニン酸を含む表面処理剤による処理方法
が良く知られている。タンニン酸の水溶液を用いて処理
すると、タンニン酸と金属材料との反応によって形成さ
れる保護皮膜が腐食物質の侵入を防ぐため、耐食性が向
上すると考えられる。しかしながら、この皮膜では、近
年の製品の高品質化（耐食性、塗装密着性）に対しての
対応は難しい。On the other hand, as a surface treatment method other than the chromate treatment, a treatment method using a surface treatment agent containing tannic acid is well known. It is considered that when the treatment is performed using an aqueous solution of tannic acid, the protective film formed by the reaction between the tannic acid and the metal material prevents invasion of corrosive substances, so that corrosion resistance is improved. However, with this film, it is difficult to respond to the recent demand for higher quality products (corrosion resistance, paint adhesion).
【０００５】クロメート皮膜以外の皮膜を用いる方法と
しては、特開昭５３−１２１０３４号公報、特開昭５７
−４４７５１号公報および特開平１−１７７３８０号公
報などに開示されている。As a method of using a film other than the chromate film, Japanese Patent Application Laid-Open Nos.
No. 4,475,751 and JP-A-1-177380.
【０００６】特開昭５３−１２１０３４号公報に開示さ
れている技術は、水分散性シリカと、アルキッド樹脂
と、トリアルコキシシラン化合物とを含む水溶液を金属
表面に塗布し、乾燥して皮膜を形成する方法である。し
かしながら、この方法によって得られた皮膜では我々が
目的とする耐食性を得ることができなかった。[0006] The technique disclosed in Japanese Patent Application Laid-Open No. 53-121034 discloses a method in which an aqueous solution containing water-dispersible silica, an alkyd resin, and a trialkoxysilane compound is applied to a metal surface and dried to form a film. How to However, the coatings obtained by this method could not achieve the corrosion resistance we intended.
【０００７】特開昭５７−４４７５１号公報に開示され
ている技術はヒドロキシピロン化合物誘導体からなる水
溶性樹脂、特開平１−１７７３８０号公報に開示されて
いる技術はヒドロキシスチレン化合物の水溶液または水
分散性重合体をそれぞれ用いる方法であるが、何れの方
法でも我々が目的とする耐食性を得ることができなかっ
た。[0007] The technique disclosed in JP-A-57-47451 is a water-soluble resin comprising a hydroxypyrone compound derivative, and the technique disclosed in JP-A-1-177380 is an aqueous solution or aqueous dispersion of a hydroxystyrene compound. In this method, the desired corrosion resistance could not be obtained by any method.
【０００８】この様に、何れの方法でもクロメート皮膜
の代替として使用できるような優れた耐食性を付与する
皮膜を得られていないのが現状である。[0008] As described above, at present, no film has been obtained which has excellent corrosion resistance and can be used as a substitute for a chromate film by any of the methods.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、従来技術の
有する前記課題点を解決して、耐食性と塗装密着性とが
優れた皮膜を金属材料（特に亜鉛系めっき鋼板）の表面
に形成することができる金属材料用表面処理剤およびそ
れを用いたその表面処理方法を提供することを目的とす
るものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and forms a film having excellent corrosion resistance and coating adhesion on the surface of a metal material (particularly a galvanized steel sheet). It is an object of the present invention to provide a surface treatment agent for a metal material that can be used and a surface treatment method using the same.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、これらの
従来技術の抱える問題点を解決すべく鋭意検討を重ねて
きた結果、１分子中に特定の官能基を２個以上有する化
合物と特定の酸または化合物を有する水性薬剤を用いて
金属材料の表面を処理することにより、耐食性、塗装密
着性に優れた皮膜を形成できることを新たに見出し、本
発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the problems of the prior art, and as a result, have found that a compound having two or more specific functional groups in one molecule can be obtained. The inventors have newly found that a film having excellent corrosion resistance and coating adhesion can be formed by treating the surface of a metal material with an aqueous chemical having a specific acid or compound, and have completed the present invention.
【００１１】即ち、本発明の耐食性に優れた金属材料用
表面処理剤は、（ａ）成分として１分子中に下記式
（Ｉ）で表される官能基を２個以上有する化合物と、
（ｂ）成分として有機酸、リン酸および錯弗化物からな
る群から選ばれる少なくとも１種の化合物とを含有し、
かつ、（ａ）成分中の前記官能基１個あたりの分子量
（平均分子量／官能基数）が１００〜３００００の範囲
にあることを特徴とする。That is, the surface treatment agent for a metal material having excellent corrosion resistance according to the present invention comprises, as a component (a), a compound having two or more functional groups represented by the following formula (I) in one molecule:
(B) as a component, at least one compound selected from the group consisting of organic acids, phosphoric acids and complex fluorides,
In addition, the molecular weight (average molecular weight / number of functional groups) per functional group in the component (a) is in the range of 100 to 30,000.
【化２】 Embedded image
【００１２】本発明の処理剤は、更に、（ｃ）成分とし
て骨格中に３級アミノ基あるいは４級アミノ基からなる
群から選ばれる少なくとも１種の官能基を有する樹脂を
含有することが好ましい。It is preferable that the treating agent of the present invention further contains a resin having at least one functional group selected from the group consisting of a tertiary amino group and a quaternary amino group in the skeleton as the component (c). .
【００１３】本発明の処理剤は、前記（ａ）成分と
（ｃ）成分の固形分重量比（ａ）／（ｃ）が１／９〜９
／１の範囲にあることが好ましい。The treating agent of the present invention has a solid content ratio (a) / (c) of component (a) / component (c) of 1/9 to 9
/ 1 is preferable.
【００１４】本発明の処理剤は、更に、（ｄ）成分とし
てコバルト、タングステン、バナジウム、マグネシウ
ム、アルミニウム、マンガン、チタン、３価クロムおよ
びモリブデンからなる群から選ばれる少なくとも１種の
金属のフッ素化合物、有機酸塩およびリン酸塩からなる
群から選ばれる少なくとも１種の化合物を（ａ）成分１
００重量％に対して０．０１〜１００重量％含有するこ
とが好ましい。The treating agent of the present invention further comprises, as the component (d), a fluorine compound of at least one metal selected from the group consisting of cobalt, tungsten, vanadium, magnesium, aluminum, manganese, titanium, trivalent chromium and molybdenum. And at least one compound selected from the group consisting of organic acid salts and phosphates,
It is preferably contained in an amount of 0.01 to 100% by weight based on 00% by weight.
【００１５】本発明の処理剤は、更に、（ｅ）成分とし
て１分子中にＣ＝Ｏ基、Ｃ＝Ｃ基、Ｃ≡Ｃ基、Ｃ＝Ｎ
基、Ｃ≡Ｎ基およびＮ＝Ｎ基から選ばれる少なくとも１
種の不飽和基あるいはＮ−Ｎ基、Ｓ原子を含む官能基か
らなる群から選ばれる少なくとも１種の官能基を有する
化合物を（ａ）成分１００重量％に対して０．１〜１０
０重量％含有することが好ましい。The treating agent of the present invention further comprises, as component (e), C ＝ O, C ＝ C, C≡C, C 、 N
At least one group selected from a group, a C N group and an N ＝ N group
A compound having at least one functional group selected from the group consisting of a kind of unsaturated group or a functional group containing an NN group and an S atom is used in an amount of 0.1 to 10 with respect to 100% by weight of the component (a).
It is preferably contained at 0% by weight.
【００１６】また、本発明の金属材料の表面処理方法
は、前記の金属材料用表面処理剤を金属材料の表面に塗
布し直ちに乾燥させ、前記表面に皮膜量として０．１〜
３．０ｇ／ｍ2 の皮膜を形成することを特徴とする。Further, in the surface treatment method for a metal material according to the present invention, the surface treatment agent for a metal material is applied to the surface of the metal material and immediately dried, and the surface has a coating amount of 0.1 to 0.1%.
It is characterized by forming a film of 3.0 g / m 2 .
【００１７】以下に、本発明の内容を詳細に説明する。
本発明の表面処理剤は、（ａ）成分と（ｂ）成分が重要
な成分である。本発明の表面処理剤は、（ａ）成分とし
て１分子中に下記式（Ｉ）で表される官能基を２個以上
有する化合物を用いることである。この化合物は、前記
官能基１個あたりの分子量（平均分子量／官能基数）が
１００〜３００００の範囲にあることが好ましく、より
好ましくは１２０〜１００００の範囲である。前記官能
基１個あたりの分子量が１００未満の場合は、化合物の
合成が難しく、一方、３００００を超える場合は、前記
官能基の特徴である金属材料表面に対する密着性が低下
するため好ましくない。尚、前記化合物の骨格として
は、特に限定するものではないが、エステル結合、エー
テル結合、酸アミド結合、ウレタン結合、ウレア結合、
ビニル結合などの結合を有していることが好ましい。Hereinafter, the contents of the present invention will be described in detail.
In the surface treatment agent of the present invention, the components (a) and (b) are important components. The surface treating agent of the present invention uses a compound having two or more functional groups represented by the following formula (I) in one molecule as the component (a). This compound preferably has a molecular weight (average molecular weight / number of functional groups) per functional group in the range of 100 to 30,000, more preferably 120 to 10,000. If the molecular weight per functional group is less than 100, it is difficult to synthesize the compound. On the other hand, if it exceeds 30,000, the adhesiveness to the metal material surface, which is a feature of the functional group, is undesirably reduced. The skeleton of the compound is not particularly limited, but may be an ester bond, an ether bond, an acid amide bond, a urethane bond, a urea bond,
It preferably has a bond such as a vinyl bond.
【００１８】また、化合物の製造方法についても、特に
限定するものではないが、活性水素を持つ２つ以上の官
能基を有する化合物とクロロシランとの反応により得る
方法、２種類以上のシランカップリング剤の反応により
得る方法、シランカップリング剤の有機官能基と反応し
得る官能基を持つ化合物との反応により得る方法、ビニ
ル基を持つシランカップリング剤と共重合可能なビニル
化合物との反応により得る方法、などが挙げられる。
尚、１分子中に前記官能基を１個しか含まない化合物の
場合、金属材料表面に対する密着力が低下するため好ま
しくない。The method for producing the compound is also not particularly limited, but a method for obtaining the compound by reacting a compound having two or more functional groups having active hydrogen with chlorosilane, two or more silane coupling agents , A method of reacting with a compound having a functional group capable of reacting with the organic functional group of the silane coupling agent, and a method of reacting with a vinyl compound copolymerizable with a silane coupling agent having a vinyl group. Method, and the like.
In addition, a compound containing only one of the functional groups in one molecule is not preferable because the adhesion to the metal material surface is reduced.
【００１９】[0019]
【化３】 Embedded image
【００２０】本発明の表面処理剤に用いる（ｂ）成分
は、有機酸、リン酸および錯弗化物からなる群から選ば
れる少なくとも１種の化合物である。有機酸は酸の中で
は比較的酸性度の低い酸であるため、亜鉛系めっき鋼板
を強力にエッチングすることなく、めっきの表面にある
極薄い酸化膜のみを取り除くので耐食性が向上する。一
方、これ以外の酸、例えば、硫酸、塩酸、硝酸のような
強酸では亜鉛系めっきに対するエッチング力が強すぎ、
耐食性が低下するので好ましくない。ここで言う有機酸
としては、例えば、蟻酸、酢酸、酪酸、蓚酸、琥珀酸、
乳酸、Ｌ−アスコルビン酸、酒石酸、クエン酸、ＤＬ−
リンゴ酸、マロン酸、マレイン酸、フタル酸、などが挙
げられる。The component (b) used in the surface treating agent of the present invention is at least one compound selected from the group consisting of organic acids, phosphoric acids and complex fluorides. The organic acid is an acid having a relatively low acidity among the acids, so that only the ultra-thin oxide film on the plating surface is removed without strongly etching the zinc-based plated steel sheet, so that the corrosion resistance is improved. On the other hand, other acids, for example, strong acids such as sulfuric acid, hydrochloric acid and nitric acid have too strong an etching power for zinc-based plating,
It is not preferable because the corrosion resistance is reduced. Examples of the organic acids mentioned here include formic acid, acetic acid, butyric acid, oxalic acid, succinic acid,
Lactic acid, L-ascorbic acid, tartaric acid, citric acid, DL-
Malic acid, malonic acid, maleic acid, phthalic acid and the like can be mentioned.
【００２１】また、リン酸は亜鉛系めっき表面に極僅か
であるがリン酸亜鉛系化成皮膜を形成するため耐食性が
向上する。ここで言うリン酸としては、メタリン酸、ピ
ロリン酸、オルトリン酸、三リン酸、四リン酸、および
これらのアンモニウム塩、アルミニウム塩、マグネシウ
ム塩、などが使用できる。錯弗化物はフッ素によるエッ
チング効果の他に錯弗化物に使用されている金属による
キレート作用のために耐食性が向上する。ここで言う錯
弗化物としては、ジルコニウムフッ化水素酸、チタンフ
ッ化水素酸、珪フッ化水素酸、およびこれらのアンモニ
ウム塩、フッ化水素酸などが挙げられる。Although the phosphoric acid forms a zinc phosphate-based chemical conversion film on the surface of the zinc-based plating, the corrosion resistance is improved. As the phosphoric acid mentioned here, metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, tetraphosphoric acid, and their ammonium salts, aluminum salts, magnesium salts, and the like can be used. The complex fluoride improves the corrosion resistance due to the chelating action of the metal used for the complex fluoride, in addition to the etching effect of fluorine. Examples of the complex fluoride include zirconium hydrofluoric acid, titanium hydrofluoric acid, hydrofluoric acid, and ammonium salts and hydrofluoric acid thereof.
【００２２】尚、これらの化合物の薬剤中の配合量とし
ては、（ａ）成分の固形分１００重量％に対して、有機
酸の場合は０．０１〜３００重量％、好ましくは０．０
５〜２００重量％、リン酸の場合は０．０１〜２００重
量％、好ましくは０．１〜１００重量％、錯弗化物の場
合は０．０１〜１００重量％、好ましくは０．０２〜５
０重量％の範囲である。これらの範囲未満の場合は、
（ｂ）成分の配合効果が乏しく、逆に範囲を超える場合
はその効果が飽和するので経済的でない。The compounding amount of these compounds in the medicine is 0.01 to 300% by weight, preferably 0.0%, in the case of an organic acid, based on 100% by weight of the solid content of the component (a).
5 to 200% by weight, 0.01 to 200% by weight, preferably 0.1 to 100% by weight for phosphoric acid, 0.01 to 100% by weight, preferably 0.02 to 5% for complex fluoride.
The range is 0% by weight. If it is below these ranges,
If the compounding effect of the component (b) is poor, and if it exceeds the range, the effect is saturated and it is not economical.
【００２３】本発明では、（ｃ）成分として骨格中に３
級アミノ基または４級アミノ基からなる群から選ばれる
少なくとも１種を有する樹脂を更に配合することによ
り、さらに耐食性を向上させることができる。樹脂の種
類としては特に限定するものではないが、汎用的に使用
することができるアクリル樹脂、エポキシ樹脂、ウレタ
ン樹脂、エステル樹脂、などが好ましい。また、３級ア
ミノ基または４級アミノ基の導入方法としては特に限定
するものではないが、樹脂合成段階でアミノ基を持つ化
合物を用いる方法、樹脂合成段階でニトロ基あるいはニ
トリル基を持つ化合物を用いてこの官能基を還元する方
法、炭素に結合している水素を直接アミノ基に置換する
方法、などが挙げられ、何れの方法でも適用可能であ
る。In the present invention, as the component (c), 3
By further blending a resin having at least one selected from the group consisting of a quaternary amino group or a quaternary amino group, the corrosion resistance can be further improved. The type of the resin is not particularly limited, but an acrylic resin, an epoxy resin, a urethane resin, an ester resin, or the like that can be used for general purposes is preferable. The method for introducing a tertiary amino group or a quaternary amino group is not particularly limited, but a method using a compound having an amino group in the resin synthesis step, a method using a compound having a nitro group or a nitrile group in the resin synthesis step, and the like. And a method of directly substituting hydrogen bonded to carbon with an amino group, and the like, and any method is applicable.
【００２４】（ｃ）成分の配合量としては、（ａ）成分
と（ｃ）成分の固形分重量比（ａ）／（ｃ）で１／９〜
９／１、好ましくは２／８〜８／２の範囲内である。
（ａ）／（ｃ）の範囲が１／９未満では（ａ）成分の配
合効果が乏しく、耐食性が低下するため好ましくない。
一方、９／１を越える場合は、（ｃ）成分の配合効果が
乏しいため経済的ではない。The amount of the component (c) is from 1/9 to (a) / (c) in terms of the solid content weight ratio of the component (a) and the component (c).
9/1, preferably within the range of 2/8 to 8/2.
When the range of (a) / (c) is less than 1/9, the effect of blending the component (a) is poor, and the corrosion resistance is undesirably reduced.
On the other hand, if it exceeds 9/1, the effect of blending the component (c) is poor, so that it is not economical.
【００２５】本発明では、（ｄ）成分として、更に、コ
バルト、タングステン、バナジウム、マグネシウム、ア
ルミニウム、マンガン、チタン、３価クロムおよびモリ
ブデンから成る群から選ばれる少なくとも１種の金属の
弗化物、有機酸塩、リン酸塩からなる群から選ばれる少
なくとも１種の化合物を配合することにより、さらに耐
食性を向上させることができる。In the present invention, as the component (d), a fluoride of at least one metal selected from the group consisting of cobalt, tungsten, vanadium, magnesium, aluminum, manganese, titanium, trivalent chromium, and molybdenum; By adding at least one compound selected from the group consisting of acid salts and phosphates, the corrosion resistance can be further improved.
【００２６】これらの金属は、（ｂ）成分である有機
酸、リン酸および錯弗化物からなる群から選ばれる化合
物と難溶性の塩を作り、腐食環境下での亜鉛系めっきの
腐食電位をコントロールするために耐食性が向上すると
考えられる。これらの配合量としては、（ａ）成分の固
形分１００重量％に対して０．０１〜１００重量％、好
ましくは０．０５〜５０重量％の範囲である。（ｄ）成
分の配合量が０．０１重量％未満の場合は耐食性の向上
効果が乏しく、一方、１００重量％を超える場合はその
効果が飽和するため経済的ではない。These metals form a sparingly soluble salt with a compound selected from the group consisting of component (b), an organic acid, phosphoric acid and complex fluoride, and reduce the corrosion potential of zinc-based plating in a corrosive environment. It is thought that the corrosion resistance is improved for control. The amount of these components is in the range of 0.01 to 100% by weight, preferably 0.05 to 50% by weight, based on 100% by weight of the solid content of the component (a). When the amount of the component (d) is less than 0.01% by weight, the effect of improving the corrosion resistance is poor. On the other hand, when the amount exceeds 100% by weight, the effect is saturated, which is not economical.
【００２７】本発明では、（ｅ）成分として、更に、１
分子中にＣ＝Ｏ基、Ｃ＝Ｃ基、Ｃ≡Ｃ基、Ｃ＝Ｎ基、Ｃ
≡Ｎ基およびＮ＝Ｎ基から成る群から選ばれる少なくと
も１種の不飽和基、Ｎ−Ｎ基あるいはＳ元素を有する官
能基からなる群から選ばれる少なくとも１種の官能基を
有する化合物を配合することにより、さらに耐食性を向
上させることができる。これらの官能基を有する化合物
としては、特に限定するものではないが、ホルムアルデ
ヒド、アセトアルデヒドなどのアルデヒド類、アセト
ン、メチルエチルケトンなどのケトン類などのＣ＝Ｏ基
含有化合物、ベンゼンおよびその誘導体、ナフタレンお
よびその誘導体、アクリル酸およびメタクリル酸および
その誘導体、アルキルカルボン酸エステル、アルキルア
ルデヒドなどのＣ＝Ｃ基含有化合物、アセチレンアルコ
ールやアセチレン誘導体などのＣ≡Ｃ基含有化合物、ア
ジン、トリアジン、オサゾン染料、トリフェニルメタン
染料、クニジン、ピリミジン、ピラゾール、イミダゾー
ル、ピリジニウムおよびキノリニウム化合物などのＣ＝
Ｎ基含有化合物、エチレンシアンヒドリンなどのＣ≡Ｎ
含有化合物、ヒドラジン化合物およびその誘導体などの
Ｎ−Ｎ基含有化合物、アゾ染料などのＮ＝Ｎ基含有化合
物、スルホン酸、スルフォネート、スルフォアミド、チ
オ尿素および環状チオ尿素などのＳ元素含有化合物、な
どが挙げられる。In the present invention, as the component (e), 1
C = O group, C = C group, C 、 C group, C = N group, C
Compounding a compound having at least one unsaturated group selected from the group consisting of N groups and N = N groups, and at least one functional group selected from the group consisting of functional groups having an NN group or an S element. By doing so, the corrosion resistance can be further improved. Compounds having these functional groups are not particularly limited, but include aldehydes such as formaldehyde and acetaldehyde, C ＝ O group-containing compounds such as ketones such as acetone and methyl ethyl ketone, benzene and its derivatives, naphthalene and its derivatives. Derivatives, acrylic acid and methacrylic acid and derivatives thereof, C ＝ C group-containing compounds such as alkyl carboxylic acid esters and alkyl aldehydes, C≡C group-containing compounds such as acetylene alcohol and acetylene derivatives, azines, triazines, osazone dyes, triphenyl C = such as methane dye, kunidine, pyrimidine, pyrazole, imidazole, pyridinium and quinolinium compounds
C≡N such as N-group-containing compounds and ethylene cyanohydrin
Compounds, N-N group-containing compounds such as hydrazine compounds and derivatives thereof, N = N group-containing compounds such as azo dyes, and S element-containing compounds such as sulfonic acid, sulfonate, sulfamide, thiourea and cyclic thiourea. No.
【００２８】これらの化合物を配合すると、亜鉛系めっ
き鋼板の表面に吸着し、亜鉛系めっきの腐食電位を緩和
するために耐食性が向上すると考えられる。（ｅ）成分
の配合量としては、（ａ）成分の固形分１００重量％に
対して、０．１〜１００重量％、好ましくは０．５〜５
０％の範囲である。（ｅ）成分の配合量が０．１重量％
未満の場合は耐食性向上効果が乏しく、一方、１００重
量％を超える場合は塗装密着性が低下するため好ましく
ない。It is considered that when these compounds are blended, they are adsorbed on the surface of the galvanized steel sheet and the corrosion resistance is improved in order to reduce the corrosion potential of the galvanized steel sheet. The amount of the component (e) is 0.1 to 100% by weight, preferably 0.5 to 5%, based on 100% by weight of the solid content of the component (a).
The range is 0%. (E) 0.1% by weight of component
When the amount is less than 100%, the effect of improving the corrosion resistance is poor. On the other hand, when the amount is more than 100% by weight, the coating adhesion decreases, which is not preferable.
【００２９】尚、本発明の表面処理剤には、被塗面に均
一な皮膜を得るための濡れ性向上剤と呼ばれる界面活性
剤や増粘剤、溶接性向上のための導電性向上剤、意匠性
向上のための着色顔料、造膜性向上のための造膜助剤な
ども添加することもできる。The surface treating agent of the present invention includes a surfactant or a thickener called a wettability improver for obtaining a uniform film on the surface to be coated, a conductivity improver for improving weldability, A coloring pigment for improving the design property, a film forming aid for improving the film forming property, and the like can also be added.
【００３０】本発明の表面処理剤を塗布する素材として
は、鋼、例えば、冷延鋼板、熱延酸洗板など、亜鉛系め
っき鋼板、例えば、電気亜鉛めっき鋼板、溶融亜鉛めっ
き鋼板、合金化亜鉛めっき鋼板、アルミニウム含有亜鉛
めっき鋼板、亜鉛ニッケルめっき鋼板、亜鉛コバルトめ
っき鋼板、蒸着亜鉛めっき鋼板など、アルミニウム板な
どが好ましい。The material to which the surface treating agent of the present invention is applied may be steel, for example, a cold-rolled steel sheet, a hot-rolled pickled plate, or the like, a galvanized steel sheet, for example, an electro-galvanized steel sheet, a hot-dip galvanized steel sheet, or an alloyed steel sheet. Preferred are aluminum plates, such as galvanized steel plates, aluminum-containing galvanized steel plates, zinc-nickel-plated steel plates, zinc-cobalt-plated steel plates, and vapor-deposited galvanized steel plates.
【００３１】本発明の表面処理剤を金属材料の表面に、
ロールコーター法、浸漬法、静電塗布法、などの方法に
より塗布した後、到達板温度６０〜２５０℃、好ましく
は８０〜２２０℃の範囲になるように熱風あるいは誘導
加熱で乾燥し、皮膜量として０．１〜３．０ｇ／ｍ2 の
範囲の皮膜を形成させるのが好ましい。到達板温度が６
０℃未満の場合は、得られる皮膜の性能が不十分である
ため好ましくなく、一方、２５０℃を超える場合は皮膜
の熱劣化が起こるため好ましくない。また、皮膜量が
０．１ｇ／ｍ2 未満の場合は得られる皮膜の性能が不十
分であるため好ましくなく、３．０ｇ／ｍ2 を超える場
合は皮膜性能が飽和するため経済的でない。The surface treatment agent of the present invention is applied to the surface of a metal material.
After coating by a method such as a roll coater method, a dipping method, or an electrostatic coating method, the coated plate is dried with hot air or induction heating so that the reached plate temperature is in the range of 60 to 250 ° C, preferably 80 to 220 ° C. It is preferable to form a film in the range of 0.1 to 3.0 g / m 2 as. Ultimate plate temperature is 6
If the temperature is lower than 0 ° C., it is not preferable because the performance of the obtained film is insufficient. On the other hand, if it exceeds 250 ° C., thermal deterioration of the film occurs, which is not preferable. On the other hand, if the amount of the coating is less than 0.1 g / m 2, the performance of the obtained coating is insufficient, and if it exceeds 3.0 g / m 2 , the coating performance is saturated and it is not economical.
【００３２】尚、本発明の表面処理剤の固形分濃度は１
〜５０％の範囲にあることが好ましい。固形分濃度が１
％未満の場合は、表面処理剤が水系であるために乾燥ま
での時間が長くなるので好ましくない。一方、固形分濃
度が５０％を超える場合は、薬剤の分散安定性の低下や
粘度上昇などの不具合が生じるため好ましくない。The surface treatment agent of the present invention has a solid content of 1%.
It is preferably in the range of ５０50%. Solid content concentration is 1
% Is not preferable because the surface treatment agent is water-based and the time until drying becomes long. On the other hand, if the solid content exceeds 50%, problems such as a decrease in the dispersion stability of the drug and an increase in the viscosity occur, which is not preferable.
【００３３】[0033]
【実施例】以下に本発明の実施例を比較例と共に挙げ、
本発明を具体的に説明する。尚、本発明の範囲はこれら
の実施例により限定されるものではない。下記に実施例
および比較例に用いられる試験片、その脱脂処理および
金属材料用表面処理剤の塗布の方法について説明する。EXAMPLES Examples of the present invention will be described below together with comparative examples.
The present invention will be specifically described. The scope of the present invention is not limited by these examples. The test pieces used in the examples and comparative examples, their degreasing treatment and the method of applying the surface treatment agent for metal materials are described below.
【００３４】１．試験片の作製 （１−１）供試材 下記に示した市販の素材を供試材として使用した。 ・電気亜鉛めっき鋼板（ＥＧ） 板厚＝０．８ｍｍ、目付量＝２０／２０（ｇ／ｍ2 ） ・５％アルミニウム含有溶融亜鉛めっき鋼板（ＧＦ） 板厚＝０．８ｍｍ、目付量＝９０／９０（ｇ／ｍ2 ） ・亜鉛ニッケル合金めっき鋼板（Ｚｎ／Ｎｉ） 板厚＝０．８ｍｍ、目付量＝２０／２０（ｇ／ｍ2 ） ・溶融亜鉛めっき鋼板（ＧＩ） 板厚＝０．８ｍｍ、目付量＝９０／９０（ｇ／ｍ2 ） ・溶融５５％亜鉛合金めっき鋼板（ＧＬ） 板厚＝０．８ｍｍ、目付量＝９０／９０（ｇ／ｍ2 ） ・合金化（Ｚｎ−Ｆｅ）溶融亜鉛めっき鋼板（ＧＡ） 板厚＝０．８ｍｍ、目付量＝６０／６０（ｇ／ｍ2 ） ・Ａ−１１００系アルミニウム板（ＡＬ） 板厚＝０．８ｍｍ1. Preparation of test piece (1-1) Test material The following commercially available materials were used as test materials.・ Electro-galvanized steel sheet (EG) Sheet thickness = 0.8 mm, basis weight = 20/20 (g / m 2 ) ・ 5% aluminum-containing hot-dip galvanized steel sheet (GF) Sheet thickness = 0.8 mm, basis weight = 90 / 90 (g / m 2 ) ・ Zinc-nickel alloy plated steel sheet (Zn / Ni) Sheet thickness = 0.8 mm, basis weight = 20/20 (g / m 2 ) ・ Hot-dip galvanized steel sheet (GI) Sheet thickness = 0 .8Mm, basis weight = 90/90 (g / m 2) · molten 55% zinc alloy-plated steel sheet (GL) thickness = 0.8 mm, basis weight = 90/90 (g / m 2) · alloying (Zn -fe) galvanized steel sheets (GA) thickness = 0.8 mm, basis weight = 60/60 (g / m 2) · A-1100 series aluminum plate (AL) thickness = 0.8 mm
【００３５】（１−２）脱脂処理 供試材をシリケート系アルカリ脱脂剤のファインクリー
ナー４３３６（登録商標：日本パーカライジング（株）
製）を用いて、濃度２０ｇ／Ｌ、温度６０℃の条件で２
分間スプレー処理を行い、純水で３０秒間水洗したのち
に乾燥した。(1-2) Degreasing treatment The test material was a fine silicate alkaline degreasing agent, Fine Cleaner 4336 (registered trademark: Nippon Parkerizing Co., Ltd.).
Under the conditions of a concentration of 20 g / L and a temperature of 60 ° C.
Spraying for 30 minutes, washing with pure water for 30 seconds, and drying.
【００３６】（１−３）金属材料用表面処理剤の塗布 ００２９に示す金属材料用表面処理剤をバーコーターで
塗布し、３００℃の雰囲気温度で乾燥した。(1-3) Application of Surface Treatment Agent for Metal Material The surface treatment agent for metal material shown in 0029 was applied by a bar coater and dried at an ambient temperature of 300 ° C.
【００３７】２．塗装板性能試験 （２−１）平面部耐食性 ＪＩＳ−Ｚ−２３７１による塩水噴霧試験を１２０時間
行い、白錆発生状況を観察した。 ＜評価基準＞ ◎＝錆発生が全面積の３％未満 ○＝錆発生が全面積の３％以上１０％未満 △＝錆発生が全面積の１０％以上３０％未満 ×＝錆発生が全面積の３０％以上2. Painted plate performance test (2-1) Plane portion corrosion resistance A salt spray test according to JIS-Z-2371 was performed for 120 hours, and the occurrence of white rust was observed. <Evaluation Criteria> ◎ = Rust generation is less than 3% of the entire area ○ = Rust generation is 3% or more and less than 10% of the entire area △ = Rust generation is 10% or more and less than 30% of the entire area × = Rust generation is the whole area 30% or more of
【００３８】（２−２）加工部耐食性 ＪＩＳ−Ｚ−２２４７によるエリクセン試験（７ｍｍ押
し出し）を行った後、ＪＩＳ−Ｚ−２３７１による塩水
噴霧試験を７２時間行い、白錆発生状況を観察した。 ＜評価基準＞ ◎＝錆発生が全面積の１０％未満 ○＝錆発生が全面積の１０％以上２０％未満 △＝錆発生が全面積の２０％以上３０％未満 ×＝錆発生が全面積の３０％以上(2-2) Corrosion Resistance of Processed Parts After performing an Erichsen test (extrusion 7 mm) according to JIS-Z-2247, a salt spray test according to JIS-Z-2371 was performed for 72 hours, and the occurrence of white rust was observed. <Evaluation Criteria> ◎ = Rust generation is less than 10% of the entire area ○ = Rust generation is 10% or more and less than 20% of the entire area △ = Rust generation is 20% or more and less than 30% of the entire area × = Rust occurrence is the whole area 30% or more of
【００３９】（２−３）上塗り塗装密着性 メラミンアルキッド系塗料（アミラック＃１０００、登
録商標：関西ペイント（株）製）を焼き付け乾燥後の膜
厚が２５μｍになるように塗布して、１２５℃で２０分
間焼き付け、１次試験（２４時間放置後）および２次試
験（２４時間放置後に２時間沸騰水浸漬を行い、さらに
２４時間放置後）の評価を行った。評価方法は、ＮＴカ
ッターで１ｍｍ間隔で１００個碁盤目を作り、その碁盤
目部分をエリクセン試験機で７ｍｍ押し出した後にセロ
テープ剥離を行い、塗膜の剥離状況で評価を行った。 ＜評価基準＞ ◎＝塗膜剥離個数、０個 ○＝塗膜剥離個数、１個 △＝塗膜剥離個数、２〜１０個 ×＝塗膜剥離個数、１１〜１００個(2-3) Topcoat Coating Adhesion A melamine alkyd paint (Amirac # 1000, registered trademark: manufactured by Kansai Paint Co., Ltd.) was applied so that the film thickness after drying was 25 μm, and was applied at 125 ° C. And a secondary test (after standing for 24 hours, immersing in boiling water for 2 hours, and then standing for 24 hours) was performed. As an evaluation method, 100 cross-cuts were made at 1 mm intervals with an NT cutter, and the cross-cut portions were extruded by 7 mm with an Erichsen tester, and then the cellophane tape was peeled off, and the evaluation was made on the peeling state of the coating film. <Evaluation criteria> ◎ = number of peeled coatings, 0 ○ = number of peeled coatings, 1 △ = number of peeled coatings, 2-10 × = number of peeled coatings, 11-100
【００４０】３．金属材料用表面処理剤 ＜処理液Ａ＞ （ａ）ヘキサメチレンジアミン１モルとγ−グリシドキ
シプロピルトリメトキシシラン２モルをエタノール中で
反応させるにより得られた化合物１００重量％に対し
て、（ｂ）リン酸二水素一アンモニウム５重量％を添加
し、固形分濃度５％になるように脱イオン水で希釈し
た。尚、（ａ）成分中の官能基数は２個、官能基当量は
約２９４である。3. Surface treatment agent for metal material <Treatment liquid A> (a) With respect to 100% by weight of a compound obtained by reacting 1 mol of hexamethylenediamine and 2 mol of γ-glycidoxypropyltrimethoxysilane in ethanol, b) 5% by weight of monoammonium dihydrogen phosphate was added and diluted with deionized water to a solid concentration of 5%. The number of functional groups in the component (a) is 2, and the functional group equivalent is about 294.
【００４１】＜処理液Ｂ＞ （ａ）＃８２８タイプのビスフェノールＡ型エポキシ樹
脂１モルとγ−アミノプロピルトリエトキシシラン２モ
ルをＮ−メチル−２−ピロリドン中で反応させることに
より得られた化合物１００重量％に対して、（ｂ）蓚酸
５重量％を添加し、固形分濃度５％になるように脱イオ
ン水で希釈した。尚、（ａ）成分の官能基数は２個、官
能基当量は約４１１である。<Treatment Solution B> (a) Compound obtained by reacting 1 mol of # 828 type bisphenol A epoxy resin with 2 mol of γ-aminopropyltriethoxysilane in N-methyl-2-pyrrolidone To 100% by weight, (b) 5% by weight of oxalic acid was added and diluted with deionized water so as to have a solid concentration of 5%. The component (a) has two functional groups and a functional group equivalent of about 411.
【００４２】＜処理液Ｃ＞ （ａ）アクリル酸１モルとブチルアクリレート５モルと
メチルメタクリレート５モルとγ−メタクリロキシプロ
ピルトリエトキシシラン３モルとを脱イオン水の中で乳
化重合することにより得られた化合物１００重量％に対
して、（ｂ）珪フッ化アンモニウム１０重量％を添加
し、固形分濃度５％になるように脱イオン水で希釈し
た。尚、（ａ）成分の官能基数は３個、官能基当量は約
６９４である。<Treatment Solution C> (a) Emulsion polymerization of 1 mol of acrylic acid, 5 mol of butyl acrylate, 5 mol of methyl methacrylate and 3 mol of γ-methacryloxypropyltriethoxysilane in deionized water. To 100% by weight of the obtained compound, (b) 10% by weight of ammonium silicofluoride was added, and the mixture was diluted with deionized water to a solid concentration of 5%. The component (a) has three functional groups and a functional group equivalent of about 694.
【００４３】＜処理液Ｄ＞処理液Ａに更に、（ｃ）アク
リル酸１モルとメチルメタクリレート５モルと２−ヒド
ロキシエチルメタクリレート３モルとジメチルアミノエ
チルメタクリレート２モルとを脱イオン水の中で乳化重
合することにより得られた化合物２０重量％を配合し、
固形分濃度５％になるように脱イオン水で希釈した。
尚、（ａ）成分の官能基数は２個、官能基当量は約２９
４、（ａ）成分と（ｃ）成分の固形分重量比（ａ）／
（ｃ）は５／１である。<Treatment Solution D> Further, (c) 1 mol of acrylic acid, 5 mol of methyl methacrylate, 3 mol of 2-hydroxyethyl methacrylate, and 2 mol of dimethylaminoethyl methacrylate were emulsified in treatment water A in deionized water. Compounding 20% by weight of the compound obtained by polymerization,
Diluted with deionized water to a solids concentration of 5%.
The component (a) has two functional groups and a functional group equivalent of about 29.
4, the solid content weight ratio of the component (a) and the component (c) (a) /
(C) is 5/1.
【００４４】＜処理液Ｅ＞処理液Ｂに更に、（ｃ）＃８
２８タイプのエポキシ樹脂１モルとジメチルエタノール
アミン２モルとを反応させた後に酢酸を加えてｐＨ４．
５に調整した化合物１００重量％を配合し、固形分濃度
５％になるように脱イオン水で希釈した。尚、（ａ）成
分の官能基数は２個、官能基当量は約４１１、（ａ）成
分と（ｃ）成分の固形分重量比（ａ）／（ｃ）は１／１
である。<Treatment Solution E> In addition to the treatment solution B, (c) # 8
After reacting 1 mol of 28 type epoxy resin with 2 mol of dimethylethanolamine, acetic acid was added to adjust the pH to 4.
The compound adjusted to 5 was blended with 100% by weight, and diluted with deionized water to a solid content concentration of 5%. The number of functional groups of the component (a) is 2, the functional group equivalent is about 411, and the weight ratio (a) / (c) of the solid content of the components (a) and (c) is 1/1.
It is.
【００４５】＜処理液Ｆ＞処理液Ｃに更に、（ｃ）３級
および４級アミノ基を持つ水系ウレタン樹脂（アデカボ
ンタイターＨＵＸ−６７０、登録商標：旭電化工業
（株）製）５００重量％を配合し、固形分濃度５％にな
るように脱イオン水で希釈した。尚、（ａ）成分の官能
基数は３個、官能基当量は約６９４、（ａ）成分と
（ｃ）成分の固形分重量比（ａ）／（ｃ）は１／５であ
る。<Treatment Solution F> The treatment solution C further contains (c) an aqueous urethane resin having tertiary and quaternary amino groups (Adekabon Titer HUX-670, registered trademark: Asahi Denka Kogyo KK) 500 weight % And diluted with deionized water to a solids concentration of 5%. The number of functional groups of the component (a) is 3, the functional group equivalent is about 694, and the weight ratio (a) / (c) of the solid content of the components (a) and (c) is 1/5.
【００４６】＜処理液Ｇ＞処理液Ａに更に、（ｄ）酢酸
マグネシウム（（ＣＨ3 ＣＯＯ）2 Ｍｇ）１０重量％を
配合し、固形分濃度５％になるように脱イオン水で希釈
した。尚、（ａ）成分の官能基当量は約２９４、（ａ）
成分に対する（ｄ）成分の配合量は１０重量％である。<Treatment Solution G> The treatment solution A was further mixed with (d) 10% by weight of magnesium acetate ((CH 3 COO) 2 Mg), and diluted with deionized water to a solid content concentration of 5%. . Incidentally, the functional group equivalent of the component (a) is about 294, (a)
The blending amount of the component (d) with respect to the component is 10% by weight.
【００４７】＜処理液Ｈ＞処理液Ｂに更に、（ｄ）メタ
バナジン酸アンモニウム（ＮＨ4 ＶＯ3 ）２０重量％を
配合し、固形分濃度５％になるように脱イオン水で希釈
した。尚、（ａ）成分の官能基数は２個、官能基当量は
約４１１、（ａ）成分に対する（ｄ）成分の配合量は２
０重量％である。<Treatment Solution H> The treatment solution B was further mixed with (d) 20% by weight of ammonium metavanadate (NH 4 VO 3 ), and diluted with deionized water to a solid content concentration of 5%. The number of functional groups of the component (a) is 2, the functional group equivalent is about 411, and the blending amount of the component (d) with respect to the component (a) is 2
0% by weight.
【００４８】＜処理液Ｉ＞処理液Ｃに更に、（ｄ）リン
酸アルミニウム（ＡｌＰＯ3 ）３０重量％を配合し、固
形分濃度５％になるように脱イオン水で希釈した。尚、
（ａ）成分の官能基数は３個、官能基当量は約６９４、
（ａ）成分に対する（ｄ）成分の配合量は３０重量％で
ある。<Treatment Solution I> The treatment solution C was further mixed with (d) 30% by weight of aluminum phosphate (AlPO 3 ), and diluted with deionized water to a solid content concentration of 5%. still,
The number of functional groups of the component (a) is 3, the functional group equivalent is about 694,
The blending amount of the component (d) with respect to the component (a) is 30% by weight.
【００４９】＜処理液Ｊ＞処理液Ａに更に、（ｅ）２−
ブチン−１，４−ジオール（ＨＯＣＨ2Ｃ≡ＣＣＨ2Ｏ
Ｈ）１０重量％を配合し、固形分濃度５％になるように
脱イオン水で希釈した。尚、（ａ）成分の官能基数は２
個、官能基当量は約２９４、（ａ）成分に対する（ｅ）
成分の配合量は１０重量％である。<Treatment Liquid J> The treatment liquid A was further added with (e) 2-
Butyne-1,4-diol (HOCH 2 C≡CCH 2 O
H) 10 wt% was blended and diluted with deionized water to a solids concentration of 5%. The number of functional groups of the component (a) is 2
And the functional group equivalent is about 294, (e) based on the component (a)
The amount of the components is 10% by weight.
【００５０】＜処理液Ｋ＞処理液Ｂに更に （ｅ）チオ
尿素（Ｈ2ＮＣＳＮＨ2 ）１０重量％を配合し、固形分
濃度で５％になるように脱イオン水で希釈した。尚、
（ａ）成分の官能基数は２個、官能基当量は約４１１、
（ａ）成分に対する（ｅ）成分の配合量は１０重量％で
ある。<Treatment Solution K> The treatment solution B was further mixed with (e) 10% by weight of thiourea (H 2 NCSNH 2 ) and diluted with deionized water so as to have a solid content of 5%. still,
The number of functional groups of the component (a) is 2, the functional group equivalent is about 411,
The blending amount of the component (e) with respect to the component (a) is 10% by weight.
【００５１】＜処理液Ｌ＞処理液Ｄに更に、（ｄ）酢酸
マグネシウム（（ＣＨ3 ＣＯＯ）2 Ｍｇ）２０重量％を
配合し、固形分濃度５％になるように脱イオン水で希釈
した。尚、（ａ）成分の官能基数は２個、官能基当量は
約２９４、（ａ）成分と（ｃ）成分の固形分重量比
（ａ）／（ｃ）は５／１、（ａ）成分に対する（ｄ）成
分の配合量は２０重量％である。<Treatment Solution L> 20% by weight of (d) magnesium acetate ((CH 3 COO) 2 Mg) was further blended with the treatment solution D, and diluted with deionized water so as to have a solid content concentration of 5%. . The number of functional groups in the component (a) is 2, the functional group equivalent is about 294, the solid content weight ratio (a) / (c) of the component (a) to the component (c) is 5/1, and the component (a) The amount of the component (d) is 20% by weight.
【００５２】＜処理液Ｍ＞処理液Ｅに更に、（ｄ）メタ
バナジン酸アンモニウム（ＮＨ4 ＶＯ3 ）２０重量％と
リン酸アルミニウム（ＡｌＰＯ3 ）３０重量％を配合
し、固形分濃度５％になるように脱イオン水で希釈し
た。尚、（ａ）成分の官能基数は２個、官能基当量は約
４１１、（ａ）成分と（ｃ）成分の固形分重量比（ａ）
／（ｃ）は１／１、（ａ）成分に対する（ｄ）成分の配
合量は４０重量％である。<Treatment Liquid M> Further, (d) 20% by weight of ammonium metavanadate (NH 4 VO 3 ) and 30% by weight of aluminum phosphate (AlPO 3 ) were added to the treatment liquid E, and the solid content was adjusted to 5%. Diluted with deionized water. The number of functional groups in the component (a) is 2, the functional group equivalent is about 411, and the solid content weight ratio of the components (a) and (c) is (a).
/ (C) is 1/1, and the blending amount of the component (d) with respect to the component (a) is 40% by weight.
【００５３】＜処理液Ｎ＞処理液Ｆに更に、（ｄ）酢酸
マグネシウム（（ＣＨ3 ＣＯＯ）2 Ｍｇ）２０重量％
と、（ｅ）チオ尿素（Ｈ2ＮＣＳＮＨ2 ）１０重量％を
配合し、固形分濃度５％になるように脱イオン水で希釈
した。尚、（ａ）成分の官能基数は３個、官能基当量は
約６９４、（ａ）成分と（ｃ）成分の固形分比率（ａ）
／（ｃ）は１／５、（ａ）成分に対する（ｄ）成分の配
合量は２０重量％、（ａ）成分に対する（ｅ）成分に配
合量は１０重量％である。<Treatment Solution N> The treatment solution F further contains (d) 20% by weight of magnesium acetate ((CH 3 COO) 2 Mg).
And (e) 10% by weight of thiourea (H 2 NCSNH 2 ), and diluted with deionized water to a solid content concentration of 5%. The component (a) has three functional groups, the functional group equivalent is about 694, and the solid content ratio between the components (a) and (c) is (a)
/ (C) is 1/5, the blending amount of the component (d) with respect to the component (a) is 20% by weight, and the blending amount of the component (e) with respect to the component (a) is 10% by weight.
【００５４】＜処理液Ｏ＞ （ａ）ヘキサメチレンジアミン１モルとγ−グリシドキ
シプロピルトリメトキシシラン２モルをエタノール中で
反応させるにより得られた化合物１００重量％に対し
て、（ｂ）リン酸二水素一アンモニウム５重量％と珪フ
ッ化アンモニウム１０重量％を添加し、固形分濃度５％
になるように脱イオン水で希釈した。尚、（ａ）成分の
官能基数は２個、官能基当量は約２９４である。<Treatment Solution O> (a) 100 mol% of a compound obtained by reacting 1 mol of hexamethylenediamine and 2 mol of γ-glycidoxypropyltrimethoxysilane in ethanol was added to (b) phosphorus Add 5% by weight of monoammonium dihydrogenate and 10% by weight of ammonium silicofluoride to give a solid concentration of 5%
And diluted with deionized water. The component (a) has two functional groups and a functional group equivalent of about 294.
【００５５】＜処理液Ｐ＞ （ａ）ビス（トリメトキシシリルプロピル）アミン（日
本ユニカー（株）製、製品名Ａ−１１７０）１００重量
％に対して、（ｂ）リン酸二水素一アンモニウム５重量
％と珪フッ化アンモニウム１０重量％を添加し、（ｃ）
３級および４級アミノ基を持つ水系ウレタン樹脂（登録
商標：アデカボンタイターＨＵＸ−７６０、旭電化工業
（株）製）２００重量％を配合し、固形分濃度５％にな
るように脱イオン水で希釈した。尚、（ａ）成分の官能
基数は２個、官能基当量は約１７１、（ａ）成分と
（ｃ）成分の固形分重量比（ａ）／（ｃ）は１／２であ
る。<Treatment Solution P> (a) 100% by weight of bis (trimethoxysilylpropyl) amine (manufactured by Nippon Unicar Co., Ltd., product name A-1170), and (b) monoammonium dihydrogen phosphate 5 % By weight and 10% by weight of ammonium silicofluoride, and (c)
200% by weight of an aqueous urethane resin having tertiary and quaternary amino groups (registered trademark: Adecabon Titer HUX-760, manufactured by Asahi Denka Kogyo Co., Ltd.) and deionized water so as to have a solid concentration of 5% Diluted. The component (a) has two functional groups, the functional group equivalent is about 171, and the weight ratio (a) / (c) of the solid content of the components (a) and (c) is 1/2.
【００５６】＜比較処理液Ｑ＞ （ａ）アクリル酸５０モルとブチルアクリレート１００
モルとメチルメタクリレート１００モルと２−ヒドロキ
シエチルメタクリレート１００モルとγ−メタクリロキ
シプロピルトリエトキシシラン１モルとを脱イオン水の
中で乳化重合することにより得られた化合物（平均分子
量約４００００）１００重量％に対して、（ｂ）珪フッ
化アンモニウム１０重量％を添加し、固形分濃度５％に
なるように希釈した。尚、本処理液中の（ａ）成分の官
能基数は１個、官能基当量は約４００００であり、本発
明の（ａ）成分の官能基当量の範囲外である。<Comparative treatment liquid Q> (a) 50 mol of acrylic acid and 100 parts of butyl acrylate
100 moles of a compound (average molecular weight of about 40,000) obtained by emulsion polymerization of 100 moles of methyl, 100 moles of methyl methacrylate, 100 moles of 2-hydroxyethyl methacrylate and 1 mole of γ-methacryloxypropyltriethoxysilane in deionized water. (B) 10% by weight of ammonium silicofluoride was added to the mixture, and the mixture was diluted to a solid concentration of 5%. In addition, the number of functional groups of the component (a) in the treatment liquid is 1 and the functional group equivalent is about 40,000, which is outside the range of the functional group equivalent of the component (a) of the present invention.
【００５７】＜比較処理液Ｒ＞ （ａ）ヘキサメチレンジアミン１モルとγ−グリシドキ
シプロピルトリメトキシシラン２モルをエタノール中で
反応させることにより得られた化合物１００重量％に対
して、硫酸１重量％を添加し、固形分濃度５％になるよ
うに脱イオン水で希釈した。尚、本処理液中の（ａ）成
分の官能基数は２個、官能基当量は約２９４であるが、
本処理液中には（ｂ）成分に該当する化合物は配合され
ていない。<Comparative treatment solution R> (a) 100 mol% of a compound obtained by reacting 1 mol of hexamethylenediamine and 2 mol of γ-glycidoxypropyltrimethoxysilane in ethanol was added to sulfuric acid. % By weight and diluted with deionized water to a solids concentration of 5%. Although the number of functional groups of the component (a) in the treatment liquid is 2 and the functional group equivalent is about 294,
The compound corresponding to the component (b) is not contained in the treatment liquid.
【００５８】＜比較処理液Ｓ＞ （ａ）γ−メルカプトプロピルトリメトキシシラン（信
越化学工業（株）製、製品名ＫＢＭ８０３）１００重量
％に対して、（ｂ）リン酸５重量％を添加し、固形分重
量５％になるように脱イオン水で希釈した。尚、（ａ）
成分は１分子中の官能基数が１個であり、本発明の範囲
外である。<Comparative treatment solution S> (a) 5% by weight of phosphoric acid (b) was added to 100% by weight of γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM803). And diluted with deionized water to a solids weight of 5%. (A)
The component has one functional group in one molecule and is outside the scope of the present invention.
【００５９】＜比較処理液Ｔ＞一時防錆用途の亜鉛めっ
き鋼板用クロメート処理薬剤ジンクロム３３６０Ｈ（登
録商標：日本パーカライジング（株）製）を適宜希釈し
て用いた。<Comparative treatment solution T> Zinchrome 3360H (registered trademark: manufactured by Nippon Parkerizing Co., Ltd.), a chromate treatment agent for galvanized steel sheet for temporary rust prevention, was appropriately diluted and used.
【００６０】＜比較処理液Ｕ＞中耐食用途の亜鉛めっき
鋼板用クロメート処理薬剤ジンクロム３３８３（登録商
標：日本パーカライジング（株）製）を適宜希釈して用
いた。<Comparative treatment solution U> Zinchrome 3383 (registered trademark: manufactured by Nippon Parkerizing Co., Ltd.), a chromate treatment agent for galvanized steel sheets for medium corrosion resistance, was appropriately diluted and used.
【００６１】４．試験結果 ［水準］の表１に金属材料用表面処理剤の試験水準の一
覧、［結果］の表２に金属材料用表面処理剤の塗装板性
能試験結果の一覧を示し、実施例と比較例を説明する。4. Test results Table 1 of [Level] shows a list of test levels of surface treatment agents for metal materials, and Table 2 of [Results] shows a list of test results of coated plate performance of surface treatment agents for metal materials. Examples and Comparative Examples Will be described.
【００６２】表２のＮｏ．１〜２５は、亜鉛系メッキ鋼
板に本発明の金属材料用表面処理剤（表１の実施例のＮ
ｏ．１〜２５）を塗布後乾燥して皮膜を形成させたもの
であり、平面部耐食性、加工部耐食性、上塗り塗装密着
性の各性能が何れも良好である。一方、本発明とは異な
る表１の比較例Ｎｏ．１〜５の処理薬剤を用いた表２の
Ｎｏ．２７〜３１では、平面部耐食性、加工部耐食性、
上塗り塗装密着性とも劣っている。No. 2 in Table 2. 1 to 25 are surface treatment agents for metal materials of the present invention (N in Examples of Table 1)
o. 1) to 25) are applied and dried to form a film, and all the properties of the corrosion resistance of the flat portion, the corrosion resistance of the processed portion, and the adhesion of the top coat are good. On the other hand, Comparative Example No. 1 in Table 1 different from the present invention. No. 1 in Table 2 using the treatment chemicals Nos. 1 to 5 27-31, flat part corrosion resistance, processed part corrosion resistance,
Poor topcoat paint adhesion.
【００６３】[0063]
【発明の効果】以上説明したように、本発明の金属材料
用表面処理剤を亜鉛系めっき鋼板の表面に塗布すること
により、平面部耐食性、加工部耐食性、上塗り塗装密着
性の優れた皮膜が得られるのである。As described above, by applying the surface treatment agent for a metal material of the present invention to the surface of a galvanized steel sheet, a film having excellent corrosion resistance in a flat portion, corrosion resistance in a processed portion, and adhesion to a top coat can be obtained. You get it.
【００６４】[0064]
【表１】 [Table 1]
【００６５】[0065]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 水野 賢輔 東京都中央区日本橋１−15−１ 日本パー カライジング株式会社内 Ｆターム(参考） 4K026 AA02 AA07 AA09 AA12 AA13 AA22 BA01 BB06 BB08 CA13 CA16 CA19 CA23 CA24 CA26 CA28 CA30 CA37 CA38 CA39 CA40 DA15 DA16 EA08 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kensuke Mizuno F-term (reference) 4K026 AA02 AA07 AA09 AA12 AA13 AA22 BA01 BB06 BB08 CA13 CA16 CA19 CA23 CA24 CA26 CA28 CA30 CA37 CA38 CA39 CA40 DA15 DA16 EA08
Claims (6)
（Ｉ）で表される官能基を２個以上有する化合物と、
（ｂ）成分として有機酸、リン酸および錯弗化物からな
る群から選ばれる少なくとも１種の化合物とを含有し、
かつ、（ａ）成分中の前記官能基１個あたりの分子量
（平均分子量／官能基数）が１００〜３００００の範囲
にあることを特徴とする耐食性に優れた金属材料用表面
処理剤。 【化１】 1. A compound having two or more functional groups represented by the following formula (I) in one molecule as a component (a):
(B) as a component, at least one compound selected from the group consisting of organic acids, phosphoric acids and complex fluorides,
Further, a surface treatment agent for a metal material excellent in corrosion resistance, wherein the molecular weight (average molecular weight / number of functional groups) per one functional group in the component (a) is in the range of 100 to 30,000. Embedded image
ミノ基および４級アミノ基からなる群から選ばれる少な
くとも１種の官能基を有する樹脂を含有するものである
請求項１に記載の耐食性に優れた金属材料用表面処理
剤。2. The composition according to claim 1, further comprising a resin having at least one functional group selected from the group consisting of a tertiary amino group and a quaternary amino group in the skeleton as the component (c). Surface treatment agent for metal materials with excellent corrosion resistance.
量比（ａ）／（ｃ）が１／９〜９／１の範囲内である請
求項２に記載の耐食性に優れた金属材料用表面処理剤。3. The corrosion resistance according to claim 2, wherein the weight ratio (a) / (c) of the solid components (a) and (c) is in the range of 1/9 to 9/1. Surface treatment agent for metal materials.
グステン、バナジウム、マグネシウム、アルミニウム、
マンガン、チタン、３価クロムおよびモリブデンから成
る群から選ばれる少なくとも１種の金属のフッ素化合
物、有機酸塩およびリン酸塩からなる群から選ばれる少
なくとも１種の化合物を（ａ）成分１００重量％に対し
て０．０１〜１００重量％含有するものである請求項１
〜３の何れか１項に記載の耐食性に優れた金属材料用表
面処理剤。4. Further, as component (d), cobalt, tungsten, vanadium, magnesium, aluminum,
100% by weight of component (a) at least one compound selected from the group consisting of a fluorine compound of at least one metal selected from the group consisting of manganese, titanium, trivalent chromium and molybdenum, and organic acid salts and phosphates 2. The composition according to claim 1, wherein the content is 0.01 to 100% by weight.
4. The surface treatment agent for a metal material having excellent corrosion resistance according to any one of items 1 to 3.
Ｏ基、Ｃ＝Ｃ基、Ｃ≡Ｃ基、Ｃ＝Ｎ基、Ｃ≡Ｎ基および
Ｎ＝Ｎ基から選ばれる少なくとも１種の不飽和基あるい
はＮ−Ｎ基、Ｓ原子を含む官能基からなる群から選ばれ
る少なくとも１種の官能基を有する化合物を（ａ）成分
１００重量％に対して０．１〜１００重量％含有するも
のである請求項１〜４の何れか１項に記載の耐食性に優
れた金属材料用表面処理剤。5. Further, as a component (e), C =
At least one unsaturated group selected from an O group, a C 基 C group, a C≡C group, a C ＝ N group, a C≡N group and an N ＝ N group, or a NN group or a functional group containing an S atom. The compound having at least one functional group selected from the group consisting of 0.1 to 100% by weight based on 100% by weight of the component (a). Surface treatment agent for metal materials with excellent corrosion resistance.
処理剤を金属材料の表面に塗布し直ちに乾燥させ、前記
表面に皮膜量として０．１〜３．０ｇ／ｍ2 の皮膜を形
成させることを特徴とする金属材料の表面処理方法。6. The surface treatment agent according to any one of claims 1 to 5, which is applied to the surface of a metal material and immediately dried, and the surface has a coating amount of 0.1 to 3.0 g / m 2 . A surface treatment method for a metal material, which comprises forming a film.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23009499A JP4113309B2 (en) | 1999-08-16 | 1999-08-16 | Surface treatment agent for metal material excellent in corrosion resistance and surface treatment method of metal material |
| KR1020000045222A KR100676602B1 (en) | 1999-08-16 | 2000-08-04 | Metal surface treatment chemical providing the metal with excellent corrosion resistance and method for surface treatment of metal using the chemical |
| EP00955557A EP1230422A1 (en) | 1999-08-16 | 2000-08-14 | Process and composition for treating metals |
| MXPA02001637A MXPA02001637A (en) | 1999-08-16 | 2000-08-14 | Process and composition for treating metals. |
| CA002383485A CA2383485A1 (en) | 1999-08-16 | 2000-08-14 | Process and composition for treating metals |
| PCT/US2000/022363 WO2001012876A1 (en) | 1999-08-16 | 2000-08-14 | Process and composition for treating metals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23009499A JP4113309B2 (en) | 1999-08-16 | 1999-08-16 | Surface treatment agent for metal material excellent in corrosion resistance and surface treatment method of metal material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001049453A true JP2001049453A (en) | 2001-02-20 |
| JP4113309B2 JP4113309B2 (en) | 2008-07-09 |
Family
ID=16902466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23009499A Expired - Fee Related JP4113309B2 (en) | 1999-08-16 | 1999-08-16 | Surface treatment agent for metal material excellent in corrosion resistance and surface treatment method of metal material |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1230422A1 (en) |
| JP (1) | JP4113309B2 (en) |
| KR (1) | KR100676602B1 (en) |
| CA (1) | CA2383485A1 (en) |
| MX (1) | MXPA02001637A (en) |
| WO (1) | WO2001012876A1 (en) |
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|---|---|---|---|---|
| JP2002363767A (en) * | 2001-06-06 | 2002-12-18 | Nisshin Steel Co Ltd | Welded steel pipe having excellent corrosion resistance |
| JP2004218070A (en) * | 2002-12-24 | 2004-08-05 | Nippon Paint Co Ltd | Pretreatment method for coating |
| JP2007177314A (en) * | 2005-12-28 | 2007-07-12 | Nippon Paint Co Ltd | Composition for metal surface treatment, metal surface treatment method and surface-treated galvanized steel sheet |
| JP2008133510A (en) * | 2006-11-28 | 2008-06-12 | Nippon Steel Corp | Surface treated metallic material |
| JPWO2006082951A1 (en) * | 2005-02-02 | 2008-06-26 | 日本パーカライジング株式会社 | Water-based metal material surface treatment agent, surface treatment method and surface treatment metal material |
| JPWO2006082946A1 (en) * | 2005-02-02 | 2008-06-26 | 日本パーカライジング株式会社 | Water-based metal material surface treatment agent, surface treatment method and surface treatment metal material |
| JP2008184690A (en) * | 2002-12-24 | 2008-08-14 | Nippon Paint Co Ltd | Pretreatment method for coating |
| JP2008223084A (en) * | 2007-03-13 | 2008-09-25 | Nippon Steel Corp | Al PLATED STEEL SHEET FOR HOT PRESSING |
| JP2009138234A (en) * | 2007-12-06 | 2009-06-25 | Asahi Kagaku Kogyo Co Ltd | Surface treatment agent, and steel sheet |
| JP2011063650A (en) * | 2009-09-15 | 2011-03-31 | Nippon Parkerizing Co Ltd | Surface treatment agent for metal material, surface treatment method, and surface treated metal material |
| JP2011518953A (en) * | 2008-04-25 | 2011-06-30 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Trivalent chromium passivator for treating galvanized steel |
| US8075708B2 (en) | 2002-12-24 | 2011-12-13 | Nippon Paint Co., Ltd. | Pretreatment method for coating |
| JP2014031556A (en) * | 2012-08-06 | 2014-02-20 | Shin Etsu Chem Co Ltd | Metal surface treatment agent, surface-treated steel and method for surface treatment of the same, and painted steel and method for producing the same |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5964781A (en) * | 1982-09-30 | 1984-04-12 | Nippon Parkerizing Co Ltd | Formation of film on metal surface |
| JPS60197773A (en) * | 1984-03-21 | 1985-10-07 | Kansai Paint Co Ltd | Composition for treating metal surface and method for treating metal surface therewith |
| JPS646036A (en) * | 1986-06-30 | 1989-01-10 | Dow Corning | Coupling agent composition |
| JPH0873775A (en) * | 1994-09-02 | 1996-03-19 | Nippon Parkerizing Co Ltd | Metal surface treating agent for forming coating film excellent in fingerprint resistance, corrosion resistance and adhesion of coating film and method of treating therewith |
| US5750197A (en) * | 1997-01-09 | 1998-05-12 | The University Of Cincinnati | Method of preventing corrosion of metals using silanes |
| JPH11106945A (en) * | 1997-10-03 | 1999-04-20 | Nippon Parkerizing Co Ltd | Surface treating agent composition for metallic material and treating method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5846342A (en) * | 1994-02-03 | 1998-12-08 | Henkel Corporation | Surface treatment agent for zinciferous-plated steel |
| US5711996A (en) * | 1995-09-28 | 1998-01-27 | Man-Gill Chemical Company | Aqueous coating compositions and coated metal surfaces |
| US6132808A (en) * | 1999-02-05 | 2000-10-17 | Brent International Plc | Method of treating metals using amino silanes and multi-silyl-functional silanes in admixture |
-
1999
- 1999-08-16 JP JP23009499A patent/JP4113309B2/en not_active Expired - Fee Related
-
2000
- 2000-08-04 KR KR1020000045222A patent/KR100676602B1/en active IP Right Grant
- 2000-08-14 CA CA002383485A patent/CA2383485A1/en not_active Abandoned
- 2000-08-14 WO PCT/US2000/022363 patent/WO2001012876A1/en not_active Application Discontinuation
- 2000-08-14 MX MXPA02001637A patent/MXPA02001637A/en unknown
- 2000-08-14 EP EP00955557A patent/EP1230422A1/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5964781A (en) * | 1982-09-30 | 1984-04-12 | Nippon Parkerizing Co Ltd | Formation of film on metal surface |
| JPS60197773A (en) * | 1984-03-21 | 1985-10-07 | Kansai Paint Co Ltd | Composition for treating metal surface and method for treating metal surface therewith |
| JPS646036A (en) * | 1986-06-30 | 1989-01-10 | Dow Corning | Coupling agent composition |
| JPH0873775A (en) * | 1994-09-02 | 1996-03-19 | Nippon Parkerizing Co Ltd | Metal surface treating agent for forming coating film excellent in fingerprint resistance, corrosion resistance and adhesion of coating film and method of treating therewith |
| US5750197A (en) * | 1997-01-09 | 1998-05-12 | The University Of Cincinnati | Method of preventing corrosion of metals using silanes |
| JPH11106945A (en) * | 1997-10-03 | 1999-04-20 | Nippon Parkerizing Co Ltd | Surface treating agent composition for metallic material and treating method |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002363767A (en) * | 2001-06-06 | 2002-12-18 | Nisshin Steel Co Ltd | Welded steel pipe having excellent corrosion resistance |
| JP4634650B2 (en) * | 2001-06-06 | 2011-02-16 | 日新製鋼株式会社 | Welded steel pipe with excellent corrosion resistance |
| JP2008184690A (en) * | 2002-12-24 | 2008-08-14 | Nippon Paint Co Ltd | Pretreatment method for coating |
| 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 |
| JP4683582B2 (en) * | 2005-02-02 | 2011-05-18 | 日本パーカライジング株式会社 | Water-based metal material surface treatment agent, surface treatment method and surface treatment metal material |
| JPWO2006082951A1 (en) * | 2005-02-02 | 2008-06-26 | 日本パーカライジング株式会社 | Water-based metal material surface treatment agent, surface treatment method and surface treatment metal material |
| JP4683581B2 (en) * | 2005-02-02 | 2011-05-18 | 日本パーカライジング株式会社 | Water-based metal material surface treatment agent, surface treatment method and surface treatment metal material |
| JPWO2006082946A1 (en) * | 2005-02-02 | 2008-06-26 | 日本パーカライジング株式会社 | Water-based metal material surface treatment agent, surface treatment method and surface treatment metal material |
| JP2007177314A (en) * | 2005-12-28 | 2007-07-12 | Nippon Paint Co Ltd | Composition for metal surface treatment, metal surface treatment method and surface-treated galvanized steel sheet |
| JP2008133510A (en) * | 2006-11-28 | 2008-06-12 | Nippon Steel Corp | Surface treated metallic material |
| JP4616854B2 (en) * | 2007-03-13 | 2011-01-19 | 新日本製鐵株式会社 | Al plated steel sheet for hot pressing |
| JP2008223084A (en) * | 2007-03-13 | 2008-09-25 | Nippon Steel Corp | Al PLATED STEEL SHEET FOR HOT PRESSING |
| JP2009138234A (en) * | 2007-12-06 | 2009-06-25 | Asahi Kagaku Kogyo Co Ltd | Surface treatment agent, and steel sheet |
| JP2011518953A (en) * | 2008-04-25 | 2011-06-30 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Trivalent chromium passivator for treating galvanized steel |
| JP2011063650A (en) * | 2009-09-15 | 2011-03-31 | Nippon Parkerizing Co Ltd | Surface treatment agent for metal material, surface treatment method, and surface treated metal material |
| JP2014031556A (en) * | 2012-08-06 | 2014-02-20 | Shin Etsu Chem Co Ltd | Metal surface treatment agent, surface-treated steel and method for surface treatment of the same, and painted steel and method for producing the same |
| KR20210129681A (en) | 2019-03-19 | 2021-10-28 | 닛폰세이테츠 가부시키가이샤 | surface treatment metal material |
| US11965249B2 (en) | 2019-03-19 | 2024-04-23 | Nippon Steel Corporation | Surface-treated metal material |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1230422A1 (en) | 2002-08-14 |
| KR100676602B1 (en) | 2007-01-30 |
| CA2383485A1 (en) | 2001-02-22 |
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| JP4113309B2 (en) | 2008-07-09 |
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