JP4446233B2 - Covalent friction coefficient reducing agent for trivalent chromate treatment solution, trivalent chromate treatment solution and production method thereof, trivalent chromate coating with reduced overall friction coefficient and production method thereof - Google Patents

Covalent friction coefficient reducing agent for trivalent chromate treatment solution, trivalent chromate treatment solution and production method thereof, trivalent chromate coating with reduced overall friction coefficient and production method thereof Download PDF

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JP4446233B2
JP4446233B2 JP2004058857A JP2004058857A JP4446233B2 JP 4446233 B2 JP4446233 B2 JP 4446233B2 JP 2004058857 A JP2004058857 A JP 2004058857A JP 2004058857 A JP2004058857 A JP 2004058857A JP 4446233 B2 JP4446233 B2 JP 4446233B2
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treatment solution
trivalent chromate
trivalent
zinc
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JP2005248233A (en
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富孝 山本
道正 吉田
郷司 島宗
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Dipsol Chemicals Co Ltd
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Priority to CN200580014275XA priority patent/CN1950544B/en
Priority to EP05719901A priority patent/EP1734152A4/en
Priority to PCT/JP2005/003597 priority patent/WO2005085497A1/en
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    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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
    • 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
    • C23C22/47—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 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • 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
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Treatment Of Metals (AREA)

Description

本発明は、締め付け性を要求される亜鉛及び亜鉛合金めっき上の６価クロムフリー防錆３価クロメート皮膜における総合摩擦係数を低減するための技術に関するものである。より詳細には、本発明は、３価クロメート処理溶液用の皮膜総合摩擦係数低減剤、３価クロメート皮膜における総合摩擦係数を低減するための３価クロメート処理溶液及びその製造方法、並びに総合摩擦係数が低減した３価クロメート皮膜及びその製造方法に関する。   The present invention relates to a technique for reducing an overall friction coefficient in a hexavalent chromium-free rust-proof trivalent chromate film on zinc and zinc alloy plating that requires tightening properties. More specifically, the present invention relates to a coating total friction coefficient reducing agent for a trivalent chromate treatment solution, a trivalent chromate treatment solution for reducing the total friction coefficient in a trivalent chromate coating, a manufacturing method thereof, and a total friction coefficient. The present invention relates to a trivalent chromate film having a reduced content and a production method thereof.

金属表面の防食方法として、亜鉛及び亜鉛合金めっき上に６価クロムを含むクロメート処理が産業界で採用されてきた。近年、環境とヒトに対して有害性のある物質の規制強化が進み、発癌性等が指摘される６価クロムもその対象となり、６価クロムを処理液及び皮膜に含有しない３価クロメート代替技術が大成されつつある。
亜鉛及び亜鉛合金めっき上で６価クロムを含有しない３価クロム主体の処理溶液に接することで得られる皮膜であって、従来の６価クロムを主成分とするクロメート処理の皮膜と同等の耐食性を有し、更に加熱耐食性では従来の６価クロムを主成分とする皮膜をはるかに上回る耐食性を有する皮膜、その処理用液、及びその形成方法が提案されている（例えば、特許文献１〜３参照）。しかしながら、現在３価クロメート処理の１工程で得られる皮膜は、総じて従来の６価クロメート皮膜より高い総合摩擦係数となり、自動車業界などで締め付け性能が要求されるボルト、ナット類に対しては、安全上の問題から３価クロメート処理後のオーバーコート等で対応を図っているのが実情である。 As a corrosion protection method for metal surfaces, chromate treatment containing hexavalent chromium on zinc and zinc alloy plating has been adopted in the industry. In recent years, regulations on substances harmful to the environment and humans have been tightened, and hexavalent chromium, which is pointed out to be carcinogenic, has also been targeted. Alternative technology for trivalent chromate that does not contain hexavalent chromium in the treatment liquid and coating. Is being completed.
It is a coating obtained by contacting a treatment solution mainly composed of trivalent chromium that does not contain hexavalent chromium on zinc and zinc alloy plating, and has the same corrosion resistance as a chromate-treated coating mainly composed of hexavalent chromium. In addition, with respect to heat corrosion resistance, a film having corrosion resistance far exceeding that of a film mainly composed of hexavalent chromium as a main component, a treatment solution thereof, and a method for forming the same have been proposed (for example, see Patent Documents 1 to 3). ). However, the film currently obtained in one process of trivalent chromate treatment generally has a higher overall coefficient of friction than the conventional hexavalent chromate film, and it is safe for bolts and nuts that require tightening performance in the automobile industry. From the above problem, the actual situation is that the overcoat after the trivalent chromate treatment is used.

特許第３３３２３７３号公報Japanese Patent No. 3332373 特許第３３３２３７４号公報Japanese Patent No. 3332374 特開２００３−２６８５６２号公報JP 2003-268562 A

本発明は、亜鉛及び亜鉛合金めっき上で６価クロムを含有しない３価クロム主体の処理溶液に接することで得られる皮膜が、従来の６価クロムを主成分とするクロメート処理の皮膜の耐食性と同等であること、更には、従来の６価クロメート皮膜と同等以下の総合摩擦係数となる皮膜を提供することを目的とする。   The present invention provides a coating obtained by contacting a treatment solution mainly composed of trivalent chromium containing no hexavalent chromium on zinc and zinc alloy plating, and the corrosion resistance of a conventional chromate-treated coating mainly composed of hexavalent chromium. Another object of the present invention is to provide a film having the same coefficient of friction as that of a conventional hexavalent chromate film.

本発明は、亜鉛又は亜鉛合金めっき上に、キノリン系化合物又はその誘導体を含有させた処理溶液を用いて３価クロメート処理を行うことにより、上記課題を効率的に解決できるとの知見に基づいてなされたものである。
すなわち、本発明は、キノリン系化合物又はその誘導体を含有することを特徴とする、３価クロメート処理溶液用の皮膜総合摩擦係数低減剤を提供する。
また、本発明は、３価クロメート皮膜の総合摩擦係数を低減するためのキノリン系化合物又はその誘導体の使用を提供する。
さらに、本発明は、３価クロメート処理溶液にキノリン系化合物又はその誘導体を添加することを特徴とする、総合摩擦係数が低減した皮膜を形成するための３価クロメート処理溶液の製造方法を提供する。
さらに、本発明は、キノリン系化合物又はその誘導体を０．１〜２５ｇ／Ｌ含有することを特徴とする、３価クロメート処理溶液を提供する。
さらに、亜鉛又は亜鉛合金めっきを本発明の処理溶液に接触させることを特徴とする、３価クロメート皮膜の形成方法を提供する。
さらに、キノリン系化合物又はその誘導体を含有することを特徴とする、３価クロメート皮膜を提供する。 The present invention is based on the knowledge that the above problems can be efficiently solved by performing trivalent chromate treatment on a zinc or zinc alloy plating using a treatment solution containing a quinoline compound or a derivative thereof. It was made.
That is, the present invention provides a film total friction coefficient reducing agent for a trivalent chromate treatment solution characterized by containing a quinoline compound or a derivative thereof.
The present invention also provides the use of a quinoline compound or a derivative thereof for reducing the overall friction coefficient of a trivalent chromate film.
Furthermore, the present invention provides a method for producing a trivalent chromate treatment solution for forming a film having a reduced overall friction coefficient, which comprises adding a quinoline compound or a derivative thereof to the trivalent chromate treatment solution. .
Furthermore, the present invention provides a trivalent chromate treatment solution characterized by containing 0.1 to 25 g / L of a quinoline compound or a derivative thereof.
Furthermore, the present invention provides a method for forming a trivalent chromate film, wherein zinc or zinc alloy plating is brought into contact with the treatment solution of the present invention.
Furthermore, a trivalent chromate film characterized by containing a quinoline compound or a derivative thereof is provided.

本発明によれば、亜鉛又は亜鉛合金めっき上に総合摩擦係数を低減した６価クロムフリー防錆３価クロメート皮膜を生成することができる。この方法により得られた皮膜により、亜鉛又は亜鉛合金めっき自体の耐食性に加え、更に３価クロメート皮膜の有する優れた耐食性を付与する。さらに皮膜の総合摩擦係数が、従来の６価クロメートと同等、または同等以下であるため、ボルト、ナット類の設計上、安全な締め付け性を有する。さらに、従来の６価クロメート処理で使用されている装置、及び工程をそのまま使用することができるために、生産性を維持することができる。
また、６価クロメートでは、めっき浴種（硫酸浴、塩化アンモン浴、カリ浴などの酸性浴、アルカリノーシアン浴、アルカリシアン浴等のアルカリ浴）に依存して総合摩擦係数に差が生じていたが、本発明によれば、異なるめっき浴種であっても同じ値の総合摩擦係数に調整することが可能であり、今後、部材締結における締め付け設計時に、安全性と経済性の両面で貢献できることが期待できる。 ADVANTAGE OF THE INVENTION According to this invention, the hexavalent chromium free rust prevention trivalent chromate film | membrane which reduced the overall friction coefficient on zinc or zinc alloy plating can be produced | generated. The film obtained by this method gives excellent corrosion resistance of the trivalent chromate film in addition to the corrosion resistance of zinc or zinc alloy plating itself. Furthermore, since the overall friction coefficient of the film is equal to or less than that of conventional hexavalent chromate, it has a safe tightening property in terms of bolt and nut design. Furthermore, since the apparatus and process currently used by the conventional hexavalent chromate process can be used as it is, productivity can be maintained.
For hexavalent chromate, there is a difference in the overall friction coefficient depending on the type of plating bath (acid bath such as sulfuric acid bath, ammonium chloride bath, potash bath, alkali bath such as alkali nocyan bath, alkali cyan bath, etc.). However, according to the present invention, it is possible to adjust the overall friction coefficient to the same value even with different plating bath types, and in the future, it will contribute to both safety and economics when designing tightening in member fastening. I can expect to do it.

本発明の３価クロメート処理溶液用の皮膜総合摩擦係数低減剤はキノリン系化合物又はその誘導体を含有する。キノリン系化合物又はその誘導体としては、例えばキノリンから誘導される１価又は２価の置換基（７種の異性構造がある）を有する酸若しくはそれらの塩（例えば、ナトリウム、カリウム、アンモニウム等の塩）が挙げられる。好ましくは、水溶性のキノリン系化合物又はその誘導体であり、−ＳＯ3Ｈ、−ＣＯＯＨ、−ＯＨ、−ＣＨＯ、−ＣＨ2ＣＯＯＨ、−ＮＨ2、−Ｃ8Ｈ4Ｏ3（−Ｃ2Ｏ3・Ｃ6Ｈ4）、−Ｃ8Ｈ5Ｏ2（−ＣＨ＝ＣＯ2・Ｃ6Ｈ4）等の置換基を有する酸又はそれらのナトリウム、カリウム、アンモニウム等の塩が好ましい。具体的には、キノリンスルホン酸、キナルジン酸、キノフタロン、キノリル酢酸が好ましく、特にキノリンスルホン酸が好ましい。本発明において、キノリン系化合物又はその誘導体は、１種又は２種以上を組み合わせて使用することができる。
本発明の前記低減剤はいずれの３価クロメート処理溶液に対しても使用できる。３価クロメート処理溶液に添加する前記低減剤の量は、３価クロメート処理溶液中のキノリン系化合物又はその誘導体の濃度が０．１〜２５ｇ／Ｌとなるような量であるのが好ましく、より好ましくは０．２〜１５ｇ／Ｌとなるような量である。キノリン系化合物又はその誘導体の濃度を上記範囲とすることで、総合摩擦係数が低減した皮膜を形成するのに適した３価クロメート処理溶液を得ることができる。
キノリン系化合物又はその誘導体を含む総合摩擦係数が低減した皮膜を形成するための３価クロメート処理溶液としては、例えば以下の処理溶液が挙げられ、各処理溶液中のキノリン系化合物又はその誘導体の濃度は、好ましくは０．１〜２５ｇ／Ｌであり、より好ましくは０．２〜１５ｇ／Ｌである：
［３価クロメート処理溶液（１）］
３価クロムイオンとシュウ酸イオンとを０．５〜１．５モル比で含有し、
３価クロムがシュウ酸との水溶性錯体の形態で存在し、
コバルトイオンがシュウ酸と難溶性の金属塩を形成して沈殿することなしに、３価クロメート処理溶液中に安定に存在する前記処理溶液であって、
亜鉛又は亜鉛合金めっきを該処理溶液に接触させたときに、亜鉛と反応して、亜鉛とクロムとコバルトとシュウ酸とキノリン系化合物又はその誘導体とを含む３価クロメート皮膜を亜鉛又は亜鉛合金めっき上に形成する前記処理溶液；
［３価クロメート処理溶液（２）］
３価クロムイオン、
Ａｌイオン、Ｓｉイオン、Ｔｉイオン、Ｍｎイオン、Ｆｅイオン、Ｃｏイオン、Ｎｉイオン、Ｚｎイオン及びその組み合わせからなる群より選ばれるイオン、及び
塩素イオン、硝酸イオン、硫酸イオン、燐酸イオン及びその組み合わせからなる群より選ばれる無機酸イオンを含有する３価クロメート処理溶液；及び
［３価クロメート処理溶液（３）］
３価クロムイオン、
Ａｌイオン、Ｓｉイオン、Ｔｉイオン、Ｍｎイオン、Ｆｅイオン、Ｃｏイオン、Ｎｉイオン、Ｚｎイオン及びその組み合わせからなる群より選ばれるイオン、
塩素イオン、硝酸イオン、硫酸イオン、燐酸イオン及びその組み合わせからなる群より選ばれる無機酸イオン、及び
３価クロムイオンと水溶性錯体を形成する有機酸を含有する３価クロメート処理溶液。 The film total friction coefficient reducing agent for a trivalent chromate treatment solution of the present invention contains a quinoline compound or a derivative thereof. Examples of quinoline compounds or derivatives thereof include acids having a monovalent or divalent substituent (seven isomer structures) derived from quinoline or salts thereof (for example, salts of sodium, potassium, ammonium, etc.) ). Preferably, a water-soluble quinoline compound or a derivative thereof, -SO 3 H, -COOH, -OH , -CHO, -CH 2 COOH, -NH 2, -C 8 H 4 O 3 (-C 2 O 3 · C 6 H 4 ), —C 8 H 5 O 2 (—CH═CO 2 · C 6 H 4 ) or the like, or a salt thereof such as sodium, potassium or ammonium is preferred. Specifically, quinoline sulfonic acid, quinaldic acid, quinophthalone, and quinolyl acetic acid are preferable, and quinoline sulfonic acid is particularly preferable. In the present invention, the quinoline compound or derivative thereof can be used alone or in combination of two or more.
The reducing agent of the present invention can be used for any trivalent chromate treatment solution. The amount of the reducing agent added to the trivalent chromate treatment solution is preferably such an amount that the concentration of the quinoline compound or its derivative in the trivalent chromate treatment solution is 0.1 to 25 g / L. The amount is preferably 0.2 to 15 g / L. By setting the concentration of the quinoline compound or derivative thereof within the above range, a trivalent chromate treatment solution suitable for forming a film having a reduced overall friction coefficient can be obtained.
Examples of the trivalent chromate treatment solution for forming a film containing a quinoline compound or a derivative thereof with a reduced overall friction coefficient include the following treatment solutions, and the concentration of the quinoline compound or the derivative thereof in each treatment solution: Is preferably 0.1 to 25 g / L, more preferably 0.2 to 15 g / L:
[Trivalent chromate treatment solution (1)]
Containing trivalent chromium ions and oxalate ions in a molar ratio of 0.5 to 1.5,
Trivalent chromium exists in the form of a water-soluble complex with oxalic acid,
The treatment solution is present stably in the trivalent chromate treatment solution without precipitation of cobalt ions forming a slightly soluble metal salt with oxalic acid,
When zinc or a zinc alloy plating is brought into contact with the treatment solution, a trivalent chromate film containing zinc, chromium, cobalt, oxalic acid, a quinoline-based compound or a derivative thereof reacts with zinc and is plated with zinc or a zinc alloy Said treatment solution formed on;
[Trivalent chromate treatment solution (2)]
Trivalent chromium ion,
From ions selected from the group consisting of Al ions, Si ions, Ti ions, Mn ions, Fe ions, Co ions, Ni ions, Zn ions and combinations thereof, and chloride ions, nitrate ions, sulfate ions, phosphate ions and combinations thereof A trivalent chromate treatment solution containing an inorganic acid ion selected from the group consisting of; and [trivalent chromate treatment solution (3)]
Trivalent chromium ion,
Ions selected from the group consisting of Al ions, Si ions, Ti ions, Mn ions, Fe ions, Co ions, Ni ions, Zn ions and combinations thereof,
A trivalent chromate treatment solution containing an inorganic acid ion selected from the group consisting of chlorine ions, nitrate ions, sulfate ions, phosphate ions, and combinations thereof, and an organic acid that forms a water-soluble complex with trivalent chromium ions.

本発明の３価クロメート処理溶液で処理される基体としては、鉄、ニッケル、銅などの各種金属、及びこれらの合金、あるいは亜鉛置換処理を施したアルミニウムなどの金属や合金の板状物、直方体、円柱、円筒、球状物など種々の形状のものが挙げられる。
上記基体は、常法により亜鉛又は亜鉛合金めっきが施される。基体上に亜鉛めっきを析出させるには、硫酸浴、アンモン浴、カリ浴などの酸性浴、アルカリノーシアン浴、アルカリシアン浴等のアルカリ浴のいずれでもよい。基体上に析出する亜鉛めっきの厚みは任意とすることができるが、１μｍ以上、好ましくは５〜２５μｍ厚とするのがよい。
また、亜鉛合金めっきとしては、亜鉛−鉄合金めっき、ニッケル供析率５〜２０質量％の亜鉛−ニッケル合金めっき、亜鉛―コバルト合金めっき、錫―亜鉛合金めっき等が挙げられる。基体上に析出する亜鉛及び亜鉛合金めっきの厚みは任意とすることができるが、１μｍ以上、好ましくは５〜２５μｍ厚とするのがよい。
本発明では、このようにして基体上に亜鉛及び亜鉛合金めっきを析出させた後、例えば必要な場合には水洗し、本発明の３価クロメート皮膜を形成するための処理溶液に接触、例えばこの処理溶液を用いて浸漬処理を行う。 As the substrate to be treated with the trivalent chromate treatment solution of the present invention, various metals such as iron, nickel and copper, and alloys thereof, or a metal or alloy plate such as aluminum subjected to zinc substitution treatment, a rectangular parallelepiped , Cylinders, spheres, and other various shapes.
The base is plated with zinc or a zinc alloy by a conventional method. In order to deposit galvanizing on the substrate, any of an acidic bath such as a sulfuric acid bath, an ammon bath, and a potassium bath, an alkaline bath such as an alkali non-cyan bath, and an alkali cyan bath may be used. The thickness of the galvanizing deposited on the substrate can be arbitrary, but it is 1 μm or more, preferably 5 to 25 μm.
Examples of the zinc alloy plating include zinc-iron alloy plating, zinc-nickel alloy plating with a nickel deposition rate of 5 to 20% by mass, zinc-cobalt alloy plating, and tin-zinc alloy plating. The thickness of the zinc and zinc alloy plating deposited on the substrate can be arbitrary, but it is 1 μm or more, preferably 5 to 25 μm.
In the present invention, after depositing zinc and zinc alloy plating on the substrate in this way, for example, if necessary, it is washed with water and contacted with a treatment solution for forming the trivalent chromate film of the present invention, for example, this Immersion treatment is performed using the treatment solution.

本発明の３価クロメート処理溶液（１）において、３価クロムイオンの供給源としては３価クロムを含むいずれのクロム化合物も使用することができるが、好ましくは、塩化クロム、硫酸クロム、硝酸クロム、リン酸クロム、酢酸クロム等の３価クロム塩を使用し、又はクロム酸や重クロム酸塩等の６価クロムを、還元剤にて３価に還元することもできる。上記３価クロムの供給源は、１種あるいは２種以上を使用することができる。処理溶液中の３価クロムの濃度は、排水処理性の観点からすると、できるだけ低濃度とするのが好ましいが、耐食性を考慮して、０．２〜１０ｇ／Ｌが好ましく、１〜５ｇ／Ｌがもっとも好ましい濃度である。本発明においてこの低濃度範囲で３価クロムを用いると、排水処理、経済的にも有利である。
又、シュウ酸としては、酸あるいはそれらの塩（例えばナトリウム、カリウム、アンモニウム等の塩）の１種又は２種以上を使用することができる。シュウ酸の濃度は０．２〜１３ｇ／Ｌであるのが好ましく、より好ましくは２〜１１ｇ／Ｌである。
又、コバルトイオンの供給源としては、２価コバルトを含むいずれのコバルト化合物も使用することができるが、好ましくは、硝酸コバルト、硫酸コバルト、塩化コバルトを使用する。コバルトイオンの濃度は０．２〜１０ｇ／Ｌであるのが好ましく、より好ましくは０．５〜８ｇ／Ｌである。特に耐熱耐食性を向上させるためには２．０ｇ／Ｌ以上であるのがよい。皮膜中のコバルトの量は処理溶液中のコバルトイオン濃度の増加に従って増え、それに比例して耐食性も向上する。
処理溶液中の３価クロムとシュウ酸とのモル比は、０．５〜１．５であるのが好ましく、より好ましくは０．８〜１．３である。 In the trivalent chromate treatment solution (1) of the present invention, any chromium compound containing trivalent chromium can be used as a source of trivalent chromium ions, but preferably chromium chloride, chromium sulfate, chromium nitrate. Further, trivalent chromium salts such as chromium phosphate and chromium acetate can be used, or hexavalent chromium such as chromic acid and dichromate can be reduced to trivalent with a reducing agent. The said trivalent chromium supply source can use 1 type (s) or 2 or more types. The concentration of trivalent chromium in the treatment solution is preferably as low as possible from the viewpoint of wastewater treatment properties, but considering the corrosion resistance, it is preferably 0.2 to 10 g / L, and preferably 1 to 5 g / L. Is the most preferred concentration. In the present invention, when trivalent chromium is used in this low concentration range, it is advantageous from the viewpoint of wastewater treatment and economy.
As oxalic acid, one or more of acids or salts thereof (for example, salts of sodium, potassium, ammonium, etc.) can be used. The concentration of oxalic acid is preferably 0.2 to 13 g / L, more preferably 2 to 11 g / L.
Moreover, as a supply source of cobalt ions, any cobalt compound containing divalent cobalt can be used, but cobalt nitrate, cobalt sulfate, and cobalt chloride are preferably used. The concentration of cobalt ions is preferably 0.2 to 10 g / L, and more preferably 0.5 to 8 g / L. In particular, it is preferably 2.0 g / L or more in order to improve the heat and corrosion resistance. The amount of cobalt in the film increases as the cobalt ion concentration in the treatment solution increases, and the corrosion resistance increases in proportion thereto.
The molar ratio of trivalent chromium to oxalic acid in the treatment solution is preferably 0.5 to 1.5, more preferably 0.8 to 1.3.

また、前記処理溶液（１）は硝酸、硫酸、塩酸及びその組み合わせからなる群から選択される無機酸の塩を含んでもよい。無機酸（塩酸、硫酸、硝酸）イオンの濃度は、１〜５０ｇ／Ｌであるのが好ましく、より好ましくは、５〜２０ｇ／Ｌである。
上記の他に、リン酸、亜リン酸等のリンの酸素酸、及びそれらのアルカリ塩等から選ばれる１種以上を添加してもよい。その濃度は０．１〜５０ｇ／Ｌであるのが好ましく、より好ましくは０．５〜２０ｇ／Ｌである。
さらにマロン酸、コハク酸のジカルボン酸、クエン酸、酒石酸、リンゴ酸等のオキシカルボン酸、トリカルバリル酸等の多価カルボン酸をさらに加えてもよい。その濃度は１〜３０ｇ／Ｌ含有させるのが好ましい。
本発明の処理溶液のｐＨは０．５〜４にするのが好ましい。より好ましくは２〜２．５である。この範囲にｐＨを調整するために、前記無機酸イオンを用いてもよく、又水酸化アルカリ、アンモニア水などのアルカリ剤を用いてもよい。
処理溶液中、三価クロムとシュウ酸は下記一般式の構造を有するものと推察される安定な水溶性錯体を形成して存在し、コバルトイオンは、シュウ酸と難溶性の金属塩を形成して沈殿することなしに、安定に存在する必要がある。例えば、上記の安定なクロム錯体が形成されない場合、または、過剰のシュウ酸イオンを処理溶液中に含有する場合は、コバルトイオンが、処理溶液中のフリーシュウ酸と反応し、シュウ酸コバルトの沈殿を生じる。その結果、耐食性の良い化成皮膜を得ることはできない。
〔(Cr)l ・ (C2O4)m ・ (H2O)n〕+(n-3)
（Crとシュウ酸のモル比：0.5＜m/l＜1.5、
n=6-2m/l 、
対イオンの限定はない。）
亜鉛又は亜鉛合金めっきを本発明の前記処理溶液（１）に接触させた場合、特許第３３３２３７３号公報おいて推察されるように亜鉛と反応して、亜鉛とクロムとコバルトとシュウ酸とキノリン系化合物又はその誘導体とを含む六価クロムフリー防錆三価クロメート皮膜を亜鉛及び亜鉛合金めっき上に形成する。 The treatment solution (1) may contain a salt of an inorganic acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid and combinations thereof. The concentration of inorganic acid (hydrochloric acid, sulfuric acid, nitric acid) ions is preferably 1 to 50 g / L, and more preferably 5 to 20 g / L.
In addition to the above, one or more selected from phosphorus oxyacids such as phosphoric acid and phosphorous acid, and alkali salts thereof may be added. The concentration is preferably 0.1 to 50 g / L, more preferably 0.5 to 20 g / L.
Further, malonic acid, dicarboxylic acid of succinic acid, oxycarboxylic acid such as citric acid, tartaric acid and malic acid, and polyvalent carboxylic acid such as tricarbaryl acid may be further added. The concentration is preferably 1 to 30 g / L.
The pH of the treatment solution of the present invention is preferably 0.5-4. More preferably, it is 2-2.5. In order to adjust the pH within this range, the inorganic acid ion may be used, or an alkali agent such as alkali hydroxide or aqueous ammonia may be used.
In the treatment solution, trivalent chromium and oxalic acid exist in the form of a stable water-soluble complex presumed to have the structure of the following general formula, and cobalt ions form a sparingly soluble metal salt with oxalic acid. It must exist stably without precipitation. For example, when the above stable chromium complex is not formed, or when excessive oxalate ions are contained in the treatment solution, cobalt ions react with free oxalic acid in the treatment solution to precipitate cobalt oxalate. Produce. As a result, a chemical conversion film with good corrosion resistance cannot be obtained.
[(Cr) l・ (C 2 O 4 ) m・ (H 2 O) n ] + (n-3)
(Molar ratio of Cr to oxalic acid: 0.5 <m / l <1.5,
n = 6-2m / l,
There is no limitation on the counter ion. )
When zinc or zinc alloy plating is brought into contact with the treatment solution (1) of the present invention, it reacts with zinc as inferred in Japanese Patent No. 3332373, and zinc, chromium, cobalt, oxalic acid and quinoline series A hexavalent chromium-free rust-proof trivalent chromate film containing a compound or a derivative thereof is formed on zinc and zinc alloy plating.

本発明の３価クロメート処理溶液（２）において、３価クロムイオンの供給源は上記処理溶液（１）と同様である。処理溶液中の３価クロムの濃度は、排水処理性の観点からすると、できるだけ低濃度とするのが好ましいが、耐食性を考慮して、０．２〜１０ｇ／Ｌが好ましく、１〜５ｇ／Ｌがもっとも好ましい濃度である。本発明においてこの低濃度範囲で３価クロムを用いると、排水処理、経済的にも有利である。
Ａｌイオン、Ｓｉイオン、Ｔｉイオン、Ｍｎイオン、Ｆｅイオン、Ｃｏイオン、Ｎｉイオン、Ｚｎイオン及びその組み合わせからなる群より選ばれるイオンの供給源としては、それらを含むいずれの化合物も使用できるが、水溶液中でイオン化し易い硝酸塩、硫酸塩、塩化塩等の無機酸塩が好ましい。これらのイオンの処理溶液中の濃度は、合計で０．２〜１０ｇ／Ｌであるのが好ましく、より好ましくは０．５〜８ｇ／Ｌである。特に耐食性を向上させるためには２．０ｇ／Ｌ以上であるのがよい。これらのイオンの皮膜中の含有量は処理溶液中の濃度の増加に従って増え、それに比例して皮膜の耐食性も向上する。
塩酸イオン、硝酸イオン、硫酸イオン、燐酸イオン及びその組み合わせからなる群より選ばれる無機酸イオンの処理溶液中の濃度は、合計で１〜５０ｇ／Ｌであるのが好ましく、より好ましくは、５〜２０ｇ／Ｌである。
本発明の前記処理溶液（２）のｐＨは０．５〜４にするのが好ましい。より好ましくは１〜３である。この範囲にｐＨを調整するために、前記無機酸イオンを用いてもよく、又水酸化アルカリ、アンモニア水などのアルカリ剤を用いてもよい。 In the trivalent chromate treatment solution (2) of the present invention, the source of trivalent chromium ions is the same as that of the treatment solution (1). The concentration of trivalent chromium in the treatment solution is preferably as low as possible from the viewpoint of wastewater treatment properties, but considering the corrosion resistance, it is preferably 0.2 to 10 g / L, and preferably 1 to 5 g / L. Is the most preferred concentration. In the present invention, when trivalent chromium is used in this low concentration range, it is advantageous from the viewpoint of wastewater treatment and economy.
As a source of ions selected from the group consisting of Al ions, Si ions, Ti ions, Mn ions, Fe ions, Co ions, Ni ions, Zn ions and combinations thereof, any compound containing them can be used. Inorganic acid salts such as nitrates, sulfates and chlorides that are easily ionized in an aqueous solution are preferred. The total concentration of these ions in the treatment solution is preferably 0.2 to 10 g / L, and more preferably 0.5 to 8 g / L. In particular, in order to improve corrosion resistance, it is good that it is 2.0 g / L or more. The content of these ions in the film increases as the concentration in the treatment solution increases, and the corrosion resistance of the film also increases in proportion thereto.
The concentration of inorganic acid ions selected from the group consisting of hydrochloric acid ions, nitrate ions, sulfate ions, phosphate ions and combinations thereof in the treatment solution is preferably 1 to 50 g / L in total, more preferably 5 to 5 g / L. 20 g / L.
The pH of the treatment solution (2) of the present invention is preferably 0.5-4. More preferably, it is 1-3. In order to adjust the pH within this range, the inorganic acid ion may be used, or an alkali agent such as alkali hydroxide or aqueous ammonia may be used.

本発明の３価クロメート処理溶液（３）は、上記処理溶液（２）に３価クロムイオンと水溶性錯体を形成する有機酸を加える。前記有機酸としては、シュウ酸等のカルボン酸若しくはそれらの塩（例えばナトリウム、カリウム、アンモニウム等の塩）が挙げられ、これらの有機酸は１種又は２種以上を組み合わせて使用することができる。有機酸の濃度は０．２〜１３ｇ／Ｌであるのが好ましく、より好ましくは２〜１１ｇ／Ｌである。処理溶液中の三価クロムと有機酸とのモル比は、０．５〜１．５であるのが好ましく、より好ましくは０．８〜１．３である。
本発明の上記処理溶液（１）〜（３）における上記必須成分の残分は水である。 In the trivalent chromate treatment solution (3) of the present invention, an organic acid that forms a water-soluble complex with trivalent chromium ions is added to the treatment solution (2). Examples of the organic acid include carboxylic acids such as oxalic acid or salts thereof (for example, salts of sodium, potassium, ammonium, etc.), and these organic acids can be used alone or in combination of two or more. . The concentration of the organic acid is preferably 0.2 to 13 g / L, more preferably 2 to 11 g / L. The molar ratio of trivalent chromium and organic acid in the treatment solution is preferably 0.5 to 1.5, more preferably 0.8 to 1.3.
The remainder of the essential component in the treatment solutions (1) to (3) of the present invention is water.

亜鉛又は亜鉛合金めっきを本発明の前記処理溶液に接触させることによって、キノリン系化合物又はその誘導体を含有する３価クロメート皮膜を亜鉛又は亜鉛合金めっき上に形成することができる。３価クロメート皮膜中のキノリン系化合物又はその誘導体の濃度は、好ましくは０．１〜１５ｍｇ／ｄｍ2であり、より好ましくは０．２〜１０ｍｇ／ｄｍ2である。
亜鉛又は亜鉛合金めっきを本発明の前記処理溶液に接触させる方法としては、上記処理溶液に亜鉛又は亜鉛合金めっきした物を浸漬するのが一般的である。例えば１０〜５０℃、より好ましくは２０〜４０℃の液温で５〜６００秒間浸漬するのが好ましく、より好ましくは２０〜６０秒間浸漬する。
なお、亜鉛めっきではクロメート皮膜の光沢を増すために、通常、クロメート処理前に被処理物を希硝酸溶液に浸漬させることが行われるが、本発明ではこのような前処理を用いてもよいし、用いなくともよい。
また上記皮膜の形成方法は、さらに、前記処理溶液の一部を取り出して、取り出した処理溶液に本発明の低減剤を添加して前記処理溶液に戻すことにより３価クロメート処理溶液を調製する工程を含んでもよい。この工程により処理溶液中のキノリン系化合物又はその誘導体の濃度を一定に保つことが容易にできる。特に、キノリン系化合物又はその誘導体が粉末状又は油状である場合には、その溶解性及び均一化の点で直接、処理槽中の処理溶液に添加する方法等よりも有利である。なお、キノリン系化合物等を水溶液の形で補給することも可能であるが、補給量によっては処理溶液全量が増加してしまう。３価クロメート処理溶液の一部を取り出す方法としては、例えば処理槽からオーバーフロー液として取り出す方法や処理槽からポンプを用いて取り出す方法等が挙げられる。処理溶液に戻すときに濾過することが好ましい。
上記以外の条件や処理操作は、従来のクロメート処理方法に準じて行うことができる。 By bringing zinc or zinc alloy plating into contact with the treatment solution of the present invention, a trivalent chromate film containing a quinoline compound or a derivative thereof can be formed on zinc or zinc alloy plating. The concentration of the quinoline compound or derivative thereof in the trivalent chromate film is preferably 0.1 to 15 mg / dm 2 , more preferably 0.2 to 10 mg / dm 2 .
As a method of bringing zinc or zinc alloy plating into contact with the treatment solution of the present invention, it is common to immerse a zinc or zinc alloy plated product in the treatment solution. For example, it is preferable to immerse at a liquid temperature of 10 to 50 ° C., more preferably 20 to 40 ° C. for 5 to 600 seconds, and more preferably 20 to 60 seconds.
In galvanization, in order to increase the gloss of the chromate film, the object to be treated is usually immersed in a dilute nitric acid solution before the chromate treatment. In the present invention, such pretreatment may be used. It is not necessary to use it.
The method for forming a film further comprises a step of preparing a trivalent chromate treatment solution by taking out a part of the treatment solution, adding the reducing agent of the present invention to the taken treatment solution, and returning the solution to the treatment solution. May be included. This step makes it easy to keep the concentration of the quinoline compound or derivative thereof in the treatment solution constant. In particular, when the quinoline-based compound or derivative thereof is in the form of powder or oil, it is more advantageous than the method of adding it directly to the treatment solution in the treatment tank in terms of its solubility and homogenization. Although it is possible to replenish quinoline compounds in the form of an aqueous solution, the total amount of the treatment solution increases depending on the amount of replenishment. Examples of a method for removing a part of the trivalent chromate treatment solution include a method for removing the trivalent chromate solution from the treatment tank as an overflow liquid and a method for removing the trivalent chromate treatment solution from the treatment tank using a pump. It is preferable to filter when returning to the treatment solution.
Conditions and processing operations other than those described above can be performed in accordance with conventional chromate processing methods.

（実施例１〜１８）
Ｍ６ボルト（Ｓ４５Ｃ材、強度区分８．８）に各種Ｚｎめっき（ジンケート浴（ディップソール（株）社製ＮＺ−８７）、シアン浴（ディップソール（株）社製Ｌ−８００）、塩化浴（ディップソール（株）社製ＥＺ−９８８））を厚さ８μｍに施したものを、表１及び表２に示す３価クロメート処理溶液に浸漬し、次いで水洗いした。















(Examples 1-18)
Various types of Zn plating (zincate bath (NZ-87 made by Dipsol Co., Ltd.)), cyan bath (L-800 made by Dipsol Co., Ltd.), chloride bath (M6 bolt (S45C material, strength category 8.8)) A product obtained by applying EZ-988) manufactured by Dipsol Co., Ltd. to a thickness of 8 μm was immersed in the trivalent chromate treatment solutions shown in Tables 1 and 2, and then washed with water.















Figure 0004446233
Figure 0004446233























Figure 0004446233
表中、Ｃｒ3+源としてはＣｒＣｌ3（実施例１、３、５、８、１０、１５及び１８）及びＣｒ（ＮＯ3）3（実施例２、４、６、７、９、１１〜１４、１６及び１７）を使用した。シュウ酸は２水塩を使用した。Ｃｏ源としてはＣｏ（ＮＯ3）2を使用した。Ｓｉ源としてはコロイダルシリカを使用した。Ｖ源としてはＶＯＳＯ4を使用した。Ｎｉ源としてはＮｉＳＯ4を使用した。ＮＯ3-源としてはＨＮＯ3（実施例２、３、４、９〜１１、１４、１５及び１８）及びＮａＮＯ3（実施例１、５〜７、１２、１３、１６及び１７）を添加した。Ｃｌ-源としてはＮａＣｌを添加した。ＰＯ4 -源としてはＮａＨ2ＰＯ4を添加した。残部は水である。また、ｐＨはＮａＯＨで調整した。
Figure 0004446233
 In the table, Cr 3+ sources include CrCl 3 (Examples 1, 3, 5, 8, 10, 15 and 18) and Cr (NO 3 ) 3 (Examples 2, 4, 6, 7, 9, 11-11). 14, 16 and 17) were used. As the oxalic acid, dihydrate was used. Co (NO 3 ) 2 was used as the Co source. Colloidal silica was used as the Si source. VOSO 4 was used as the V source. NiSO 4 was used as the Ni source. HNO 3 (Examples 2, 3, 4, 9-11, 14, 15 and 18) and NaNO 3 (Examples 1, 5-7, 12, 13, 16 and 17) were added as NO 3 sources. . Cl - The source was added NaCl. PO 4 - as the source was added NaH 2 PO 4. The balance is water. The pH was adjusted with NaOH.

（実施例１９〜２２）
Ｍ６ボルト（Ｓ４５Ｃ材、強度区分８．８）にアルカリ亜鉛ニッケル合金めっき（ディップソール（株）社製ＩＺ−２６２（Ｎｉ：７％）、ディップソール（株）社製ＩＺ−２５２（Ｎｉ：１４％））を厚さ８μｍに施したものを、表３に示す３価クロメート処理溶液に浸漬し、次いで水洗いした。









(Examples 19 to 22)
Alkaline zinc nickel alloy plating (IZ-262 (Ni: 7%) manufactured by Dipsol Co., Ltd.), IZ-252 (Ni: 14 manufactured by Dipsol Co., Ltd.) on M6 bolt (S45C material, strength category 8.8) %)) To a thickness of 8 μm was immersed in a trivalent chromate treatment solution shown in Table 3 and then washed with water.









Figure 0004446233
表中、Ｃｒ3+源としてはＣｒ（ＮＯ3）3（実施例１５及び１７）及びＣｒＣｌ3（実施例１６及び１８）を使用した。シュウ酸は２水塩を使用した。Ｃｏ源としてはＣｏ（ＮＯ3）2を使用した。Ｓｉ源としてはコロイダルシリカを使用した。Ｎｉ源としてはＮｉＳＯ4を使用した。ＮＯ3-源としてはＮａＮＯ3を添加した。Ｃｌ-源としてはＮａＣｌを添加した。ＰＯ4 -源としてはＮａＨ2ＰＯ4を添加した。残部は水である。また、ｐＨはＮａＯＨで調整した。
Figure 0004446233
 In the table, Cr (NO 3 ) 3 (Examples 15 and 17) and CrCl 3 (Examples 16 and 18) were used as Cr 3+ sources. As the oxalic acid, dihydrate was used. Co (NO 3 ) 2 was used as the Co source. Colloidal silica was used as the Si source. NiSO 4 was used as the Ni source. NaNO 3 was added as a NO 3- source. Cl - The source was added NaCl. PO 4 - as the source was added NaH 2 PO 4. The balance is water. The pH was adjusted with NaOH.

（比較例１）
Ｍ６ボルト（Ｓ４５Ｃ材、強度区分８．８）に各種Ｚｎめっき（ジンケート浴（ディップソール（株）社製ＮＺ−８７）、シアン浴（ディップソール（株）社製Ｌ−８００）、塩化浴（ディップソール（株）社製ＥＺ−９８８））を８μｍ施したものに６価クロメート処理を行った。６価クロメートはディップソール（株）製Ｚ−４９３（１０ｍＬ／Ｌ、処理条件は、３０℃−４０秒）を使用した。 (Comparative Example 1)
Various types of Zn plating (zincate bath (NZ-87 made by Dipsol Co., Ltd.)), cyan bath (L-800 made by Dipsol Co., Ltd.), chloride bath (M6 bolt (S45C material, strength category 8.8)) A 6-valent chromate treatment was performed on 8 μm of EZ-988) manufactured by Dipsol Co., Ltd. As the hexavalent chromate, Z-493 (10 mL / L, treatment conditions: 30 ° C.-40 seconds) manufactured by Dipsol Co., Ltd. was used.

（比較例２）
Ｍ６ボルト（Ｓ４５Ｃ材、強度区分８．８）に各種Ｚｎめっき（ジンケート浴（ディップソール（株）社製ＮＺ−８７）、シアン浴（ディップソール（株）社製Ｌ−８００）、塩化浴（ディップソール（株）社製ＥＺ−９８８））を８μｍ施したものに特許第３３３２３７３号の実施例に記載された下記の組成で３価クロメートを行った（処理条件は、３０℃−４０秒）。
Ｃｒ（ＮＯ3）3 １４ｇ／Ｌ（Ｃｒ3+として３ｇ／Ｌ）
ＮａＮＯ3 ７ｇ／Ｌ
シュウ酸２水塩 ８ｇ／Ｌ
Ｃｏ（ＮＯ3）2 ３ｇ／Ｌ（Ｃｏとして１ｇ／Ｌ）
ｐＨ ２．０（ＮａＯＨで調整） (Comparative Example 2)
Various types of Zn plating (zincate bath (NZ-87 made by Dipsol Co., Ltd.)), cyan bath (L-800 made by Dipsol Co., Ltd.), chloride bath (M6 bolt (S45C material, strength category 8.8)) Trivalent chromate was performed with the following composition described in the example of Japanese Patent No. 3332373 on EZ-988) produced by Dipsol Co., Ltd. (process conditions were 30 ° C. to 40 seconds). .
Cr (NO 3 ) 3 14 g / L ( 3 g / L as Cr 3+ )
NaNO 3 7g / L
Oxalic acid dihydrate 8g / L
Co (NO 3 ) 2 3 g / L (1 g / L as Co)
pH 2.0 (adjusted with NaOH)

（比較例３）
Ｍ６ボルト（Ｓ４５Ｃ材、強度区分８．８）に各種Ｚｎめっき（ジンケート浴（ディップソール（株）社製ＮＺ−８７）、シアン浴（ディップソール（株）社製Ｌ−８００）、塩化浴（ディップソール（株）社製ＥＺ−９８８））を８μｍ施したものに、特開２００３−３１３６７５の実施例７に記載された下記の組成で３価クロメートを行った（処理条件は、３０℃−３０秒）。
Ｃｒ（ＮＯ3）3 ７ｇ／Ｌ（Ｃｒ3+として１．５ｇ／Ｌ）
尿素 １ｇ／Ｌ
硫酸 ２ｇ／Ｌ
ヴァナジン酸アンモン ５ｇ／Ｌ（Ｖとして２．２ｇ／Ｌ）
Ｃｏ（ＮＯ3）2 ３ｇ／Ｌ（Ｃｏとして１ｇ／Ｌ）
コロイダルシリカ ２０ｇ／Ｌ（Ｓｉとして４ｇ／Ｌ）
ｐＨ ２．０（ＮａＯＨで調整） (Comparative Example 3)
Various types of Zn plating (zincate bath (NZ-87 made by Dipsol Co., Ltd.)), cyan bath (L-800 made by Dipsol Co., Ltd.), chloride bath (M6 bolt (S45C material, strength category 8.8)) A trivalent chromate having the following composition described in Example 7 of JP-A-2003-313675 was performed on EZ-988) manufactured by Dipsol Co., Ltd. for 8 μm. 30 seconds).
Cr (NO 3 ) 3 7 g / L (1.5 g / L as Cr 3+ )
Urea 1g / L
Sulfuric acid 2g / L
Ammon Vanadate 5g / L (2.2g / L as V)
Co (NO 3 ) 2 3 g / L (1 g / L as Co)
Colloidal silica 20g / L (4g / L as Si)
pH 2.0 (adjusted with NaOH)

（比較例４）
Ｍ６ボルト（Ｓ４５Ｃ材、強度区分８．８）に各種Ｚｎめっき（ジンケート浴（ディップソール（株）社製ＮＺ−８７）、シアン浴（ディップソール（株）社製Ｌ−８００）、塩化浴（ディップソール（株）社製ＥＺ−９８８））を８μｍ施したものに、特開２０００−５０９４３４の実施例２に記載された下記の組成で３価クロメートを行った（処理条件は、３０℃−４０秒）。
ＣｒＣｌ3・６Ｈ2Ｏ ５０ｇ／Ｌ（Ｃｒ3+として９．８ｇ／Ｌ）
Ｃｏ（ＮＯ3）2 ３ｇ／Ｌ（Ｃｏとして１．０ｇ／Ｌ）
ＮａＮＯ3 １００ｇ／Ｌ
マロン酸 ３１．２ｇ／Ｌ
ｐＨ ２．０（ＮａＯＨで調整） (Comparative Example 4)
Various types of Zn plating (zincate bath (NZ-87 made by Dipsol Co., Ltd.)), cyan bath (L-800 made by Dipsol Co., Ltd.), chloride bath (M6 bolt (S45C material, strength category 8.8)) A trivalent chromate having the following composition described in Example 2 of JP-A No. 2000-509434 was performed on 8 μm of EZ-988) manufactured by Dipsol Co., Ltd. (processing conditions were 30 ° C.- 40 seconds).
CrCl 3 .6H 2 O 50 g / L (9.8 g / L as Cr 3+ )
Co (NO 3 ) 2 3 g / L (1.0 g / L as Co)
NaNO 3 100 g / L
Malonic acid 31.2g / L
pH 2.0 (adjusted with NaOH)

（比較例５）
Ｍ６ボルト（Ｓ４５Ｃ材、強度区分８．８）にアルカリ亜鉛ニッケル合金めっき（ディップソール（株）社製ＩＺ−２６２（Ｎｉ：７％））を厚さ８μｍに施したものに６価クロメート処理を行った。６価クロメートはディップソール（株）製ＩＺ−２６８（３０ｍＬ／Ｌ、処理条件は、３０℃−３０秒）を使用した。 (Comparative Example 5)
Hexavalent chromate treatment was applied to M6 bolts (S45C material, strength category 8.8) coated with alkali zinc nickel alloy plating (IZ-262 (Ni: 7%) manufactured by Dipsol Co., Ltd.) to a thickness of 8 μm. went. As the hexavalent chromate, IZ-268 (30 mL / L, treatment condition: 30 ° C.-30 seconds) manufactured by Dipsol Co., Ltd. was used.

（比較例６）
Ｍ６ボルト（Ｓ４５Ｃ材、強度区分８．８）にアルカリ亜鉛ニッケル合金めっき（ディップソール（株）社製ＩＺ−２５２（Ｎｉ：１４％））を厚さ８μｍに施したものに６価クロメート処理を行った。６価クロメートはディップソール（株）製ＩＺ−２５８（Ｓ：２００ｍＬ／Ｌ、Ｅ：１０ｇ／Ｌ、処理条件は、３０℃−４０秒）を使用した。 (Comparative Example 6)
Hexavalent chromate treatment was applied to M6 bolts (S45C material, strength category 8.8) coated with alkali zinc nickel alloy plating (IZ-252 (Ni: 14%) manufactured by Dipsol Co., Ltd.) to a thickness of 8 μm. went. As the hexavalent chromate, IZ-258 (S: 200 mL / L, E: 10 g / L, treatment conditions: 30 ° C.-40 seconds) manufactured by Dipsol Co., Ltd. was used.

工程：
なお、上記処理工程は以下の通りである。
めっき→水洗→硝酸活性→水洗→クロメート処理→水洗→乾燥1
注１：乾燥は６０〜８０℃−１０分 Process:
In addition, the said process process is as follows.
Plating → Washing → Nitric acid activity → Washing → Chromate treatment → Washing → Drying 1
Note 1: Drying is 60-80 ° C for 10 minutes.

一般耐食性塩水噴霧試験：
実施例１〜２２及び比較例１〜４で得られたクロメート皮膜について、塩水噴霧試験（ＪＩＳ−Ｚ−２３７１）結果を表４及び５に示す。
締め付け性試験：
実施例１〜２２及び比較例１〜４で得られたクロメート皮膜について、締め付け性試験を行い、その結果から得られた総合摩擦係数の値を表４及び５に示す。総合摩擦係数の測定は、「ねじ部品の摩擦係数」（酒井智次）日本機械学会論文集（第３部）43-370（1977-6）p.2372-2381に記載の方法に準じて、ナット（対応する実施例又は比較例と同一の表面処理）、無処理の座金（Ｓ４５Ｃ材、硬さＨＲＣ−２５）にて、締め付け回転数４回転、評価トルク１１．８Ｎｍでの軸力測定から計算した。
表４及び５に示されるように、実施例１〜２２の皮膜の場合でも比較例１の従来の６価クロメート皮膜や比較例２〜４の３価クロメート皮膜と比較し同等以上の耐食性が得られた。また、実施例１〜２２の皮膜の場合は、比較例１の従来６価クロメート皮膜と同等、又はやや低めの総合摩擦係数値が得られ、比較例２〜４の皮膜と比較すると締め付け性が改善される総合摩擦係数の値が得られた。







































General corrosion resistance salt spray test:
Tables 4 and 5 show the results of the salt spray test (JIS-Z-2371) for the chromate films obtained in Examples 1 to 22 and Comparative Examples 1 to 4.
Tightness test:
The chromate coatings obtained in Examples 1 to 22 and Comparative Examples 1 to 4 were subjected to a tightening test, and the values of the overall friction coefficient obtained from the results are shown in Tables 4 and 5. The overall friction coefficient is measured according to the method described in “Friction Coefficient of Screw Parts” (Tomoji Sakai), Transactions of the Japan Society of Mechanical Engineers (Part 3) 43-370 (1977-6) p.2372-2381. From an axial force measurement with a nut (same surface treatment as in the corresponding example or comparative example) and an untreated washer (S45C material, hardness HRC-25) at a tightening rotation speed of 4 rotations and an evaluation torque of 11.8 Nm Calculated.
As shown in Tables 4 and 5, even in the case of the coatings of Examples 1 to 22, corrosion resistance equal to or higher than that of the conventional hexavalent chromate coating of Comparative Example 1 and the trivalent chromate coating of Comparative Examples 2 to 4 was obtained. It was. Moreover, in the case of the films of Examples 1 to 22, an overall friction coefficient value equivalent to or slightly lower than that of the conventional hexavalent chromate film of Comparative Example 1 is obtained. An improved overall coefficient of friction value was obtained.







































Figure 0004446233
Figure 0004446233

Figure 0004446233
Figure 0004446233

（実施例２３）
実施例１の３価クロメート処理溶液を用いてボルトに皮膜を形成する際に、オーバーフロー液を予備槽に移した。汲み出し速度は８００Ｌ／ｈｒとした。次いで、予備槽の処理溶液中の濃度が８ｇ／Ｌとなるようにキナルジン酸を添加し、濾過機（キザイ社製Ｋ−０５）を通して処理槽に戻した。処理槽の処理溶液中のキナルジン酸の濃度を一定に保つことができた。 (Example 23)
When forming a film on the bolt using the trivalent chromate treatment solution of Example 1, the overflow solution was transferred to a preliminary tank. The pumping speed was 800 L / hr. Subsequently, quinaldic acid was added so that the density | concentration in the processing solution of a preliminary tank might be 8 g / L, and it returned to the processing tank through the filter (Kisai K-05). The concentration of quinaldic acid in the treatment solution in the treatment tank could be kept constant.

Claims (8)

キノリン系化合物又はその誘導体を含有することを特徴とする、３価クロメート処理溶液用の皮膜総合摩擦係数低減剤。   A film total friction coefficient reducing agent for a trivalent chromate treatment solution, comprising a quinoline compound or a derivative thereof. ３価クロメート皮膜の総合摩擦係数を低減するためのキノリン系化合物又はその誘導体の使用。   Use of a quinoline compound or a derivative thereof for reducing the overall friction coefficient of a trivalent chromate film. ３価クロメート処理溶液にキノリン系化合物又はその誘導体を添加することを特徴とする、総合摩擦係数が低減した皮膜を形成するための３価クロメート処理溶液の製造方法。   A method for producing a trivalent chromate treatment solution for forming a film having a reduced overall friction coefficient, which comprises adding a quinoline compound or a derivative thereof to the trivalent chromate treatment solution. キノリン系化合物又はその誘導体を０．１〜２５ｇ／Ｌ添加する、請求項３記載の製造方法。 Quinoline compounds or additives 0.1~25g / L derivatives thereof The method according to claim 3, wherein. ３価クロメート処理溶液が、
３価クロムイオンとシュウ酸イオンとを０．５〜１．５モル比で含有し、
３価クロムがシュウ酸との水溶性錯体の形態で存在し、
コバルトイオンがシュウ酸と難溶性の金属塩を形成して沈殿することなしに、３価クロメート処理溶液中に安定に存在する３価クロメート処理溶液であって、
亜鉛又は亜鉛合金めっきを該処理溶液に接触させたときに、亜鉛と反応して、亜鉛とクロムとコバルトとシュウ酸とキノリン系化合物又はその誘導体とを含む３価クロメート皮膜を亜鉛又は亜鉛合金めっき上に形成する処理溶液である、請求項３又は４記載の製造方法。 Trivalent chromate treatment solution
Containing trivalent chromium ions and oxalate ions in a molar ratio of 0.5 to 1.5,
Trivalent chromium exists in the form of a water-soluble complex with oxalic acid,
A trivalent chromate treatment solution that is stably present in the trivalent chromate treatment solution without precipitation of cobalt ions forming a slightly soluble metal salt with oxalic acid,
When zinc or a zinc alloy plating is brought into contact with the treatment solution, a trivalent chromate film containing zinc, chromium, cobalt, oxalic acid, a quinoline-based compound or a derivative thereof reacts with zinc and is plated with zinc or a zinc alloy The manufacturing method of Claim 3 or 4 which is a process solution formed on top. ３価クロメート処理溶液が、
３価クロムイオン、
Ａｌイオン、Ｓｉイオン、Ｔｉイオン、Ｍｎイオン、Ｆｅイオン、Ｃｏイオン、Ｎｉイオン、Ｚｎイオン及びその組み合わせからなる群より選ばれるイオン、及び
塩素イオン、硝酸イオン、硫酸イオン、燐酸イオン及びその組み合わせからなる群より選ばれる無機酸イオンを含有する、請求項３又は４記載の製造方法。 Trivalent chromate treatment solution
Trivalent chromium ion,
From ions selected from the group consisting of Al ions, Si ions, Ti ions, Mn ions, Fe ions, Co ions, Ni ions, Zn ions and combinations thereof, and chloride ions, nitrate ions, sulfate ions, phosphate ions and combinations thereof The manufacturing method of Claim 3 or 4 containing the inorganic acid ion chosen from consisting of. ３価クロメート処理溶液が、
３価クロムイオン、
Ａｌイオン、Ｓｉイオン、Ｔｉイオン、Ｍｎイオン、Ｆｅイオン、Ｃｏイオン、Ｎｉイオン、Ｚｎイオン及びその組み合わせからなる群より選ばれるイオン、
塩素イオン、硝酸イオン、硫酸イオン、燐酸イオン及びその組み合わせからなる群より選ばれる無機酸イオン、及び
３価クロムイオンと水溶性錯体を形成する有機酸を含有する、請求項３又は４記載の製造方法。 Trivalent chromate treatment solution
Trivalent chromium ion,
Ions selected from the group consisting of Al ions, Si ions, Ti ions, Mn ions, Fe ions, Co ions, Ni ions, Zn ions and combinations thereof,
The production according to claim 3 or 4, comprising an inorganic acid ion selected from the group consisting of chlorine ion, nitrate ion, sulfate ion, phosphate ion and combinations thereof, and an organic acid that forms a water-soluble complex with trivalent chromium ion. Way . 亜鉛又は亜鉛合金めっきを請求項３〜７のいずれか１項記載の製造方法により製造された処理溶液に接触させることを特徴とする、３価クロメート皮膜の形成方法であって、
さらに、前記処理溶液の一部を取り出し、取り出した処理溶液に請求項１に記載の低減剤を添加して前記処理溶液に戻すことにより３価クロメート処理溶液を調製する工程を含む形成方法。 A method for forming a trivalent chromate film, characterized in that zinc or zinc alloy plating is brought into contact with the treatment solution produced by the production method according to any one of claims 3 to 7 ,
Furthermore, a forming method comprising a step of preparing a trivalent chromate treatment solution by taking out a part of the treatment solution, adding the reducing agent according to claim 1 to the removed treatment solution, and returning the treated solution to the treatment solution .
JP2004058857A 2004-03-03 2004-03-03 Covalent friction coefficient reducing agent for trivalent chromate treatment solution, trivalent chromate treatment solution and production method thereof, trivalent chromate coating with reduced overall friction coefficient and production method thereof Expired - Fee Related JP4446233B2 (en)

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KR1020067018882A KR100799845B1 (en) 2004-03-03 2005-03-03 Agent for reducing conversion film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate conversion film reduced in overall friction coefficient and method for production thereof
CN200580014275XA CN1950544B (en) 2004-03-03 2005-03-03 Agent for reducing conversion film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate conversion film reduced in overall friction coefficient and method for production thereof
EP05719901A EP1734152A4 (en) 2004-03-03 2005-03-03 Agent for reducing coating film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate coating film reduced in overall friction coefficient and method for production thereof
PCT/JP2005/003597 WO2005085497A1 (en) 2004-03-03 2005-03-03 Agent for reducing coating film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate coating film reduced in overall friction coefficient and method for production thereof
US11/514,505 US20070023104A1 (en) 2004-03-03 2006-09-01 Agent for reducing conversion film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate conversion film reduced in overall friction coefficient and method for production thereof

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WO2005085497A1 (en) 2005-09-15
KR100799845B1 (en) 2008-01-31
EP1734152A1 (en) 2006-12-20
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