JP2021001372A - Metal surface treatment liquid, and metal surface treatment method - Google Patents

Metal surface treatment liquid, and metal surface treatment method Download PDF

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JP2021001372A
JP2021001372A JP2019115615A JP2019115615A JP2021001372A JP 2021001372 A JP2021001372 A JP 2021001372A JP 2019115615 A JP2019115615 A JP 2019115615A JP 2019115615 A JP2019115615 A JP 2019115615A JP 2021001372 A JP2021001372 A JP 2021001372A
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acid
metal surface
surface treatment
treatment liquid
salt
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JP7347751B2 (en
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壮平 長沢
Sohei Nagasawa
壮平 長沢
香取　光臣
Mitsuomi Katori
光臣 香取
美沙子 保坂
Misako Hosaka
美沙子 保坂
侑己 瓜田
Yuki Urita
侑己 瓜田
亮多 荒
Ryota Ara
亮多 荒
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Nippon Hyomen Kagaku KK
YKK Corp
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Nippon Hyomen Kagaku KK
YKK Corp
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Priority to CN202010326951.3A priority patent/CN112111736A/en
Priority to EP20171700.6A priority patent/EP3754048A1/en
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Priority to JP2023139242A priority patent/JP2023155377A/en
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    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
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    • 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
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    • 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
    • C23C22/52—Treatment of copper or alloys based thereon
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    • 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
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    • 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
    • C23C22/56—Treatment of aluminium or alloys based thereon
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    • 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
    • C23C22/57—Treatment of magnesium or alloys based thereon
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    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper 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
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  • Chemical Treatment Of Metals (AREA)

Abstract

To provide a metal surface treatment liquid and a metal surface treatment method capable of coloring a metal surface a grayish tint at a high treatment efficiency.SOLUTION: A metal surface treatment liquid contains tellurium, a tellurium compound or a salt thereof. The tellurium, the tellurium compound or the salt thereof are tellurium monoxide, tellurium dioxide, tellurium trioxide, tellurous acid, telluric acid, tellurium tetrachloride, dimethyl telluride, or a salt thereof, or a combination thereof. The total content of these substances is 0.5-100 g/L.SELECTED DRAWING: None

Description

本発明は、金属表面処理液及び金属表面処理方法に関する。 The present invention relates to a metal surface treatment liquid and a metal surface treatment method.

従来、種々の金属、特にアルミニウム又はアルミニウム合金の着色において、灰色系の色調を得るには陽極酸化や陽極酸化皮膜に染料を吸着させる方法が一般的である。 Conventionally, in coloring various metals, particularly aluminum or aluminum alloys, a method of adsorbing a dye on an anodized or anodized film is generally used to obtain a grayish color tone.

例えば、特許文献１には、アルミニウム又はアルミニウム合金の素地表面に形成した電解発色又は自然発色による発色被膜を、電解着色可能な皮膜構造とした後、電解着色を行って、色を重ね合わせて新たな色調の皮膜を得ることを特徴とするアルミニウム及びアルミニウム合金の電解着色方法が開示されている。そして、このような構成によれば、従来の電解着色方法では得られない様々な中間色を含む種々の色調を得ることができる電解着色方法を提供することができる、と記載されている。 For example, in Patent Document 1, a color-developing film formed on the surface of an aluminum or aluminum alloy base material by electrolytic coloring or natural coloring is formed into a film structure capable of electrolytic coloring, and then electrolytic coloring is performed to superimpose the colors. A method for electrolytically coloring aluminum and an aluminum alloy, which comprises obtaining a film having a different color tone, is disclosed. Then, it is described that according to such a configuration, it is possible to provide an electrolytic coloring method capable of obtaining various color tones including various neutral colors which cannot be obtained by the conventional electrolytic coloring method.

特開昭６０−１１０８９５号公報Japanese Unexamined Patent Publication No. 60-110895

しかしながら、従来、金属表面を灰色系の色調に着色するには、例えば、アルミニウム又はアルミニウム合金であればアルマイトを利用する必要があった。すなわち、金属表面を灰色系の色調に着色するには、酸化膜を表面に有する金属を利用する必要があり、処理工程が多く、処理効率の改善が望まれている。 However, conventionally, in order to color the metal surface to a grayish color, it has been necessary to use alumite, for example, in the case of aluminum or an aluminum alloy. That is, in order to color the metal surface to a grayish color tone, it is necessary to use a metal having an oxide film on the surface, and there are many treatment steps, and improvement in treatment efficiency is desired.

本発明は、このような問題に鑑み、良好な処理効率で金属表面を灰色系の色調に着色することが可能な金属表面処理液及び金属表面処理方法を提供することを目的とする。 In view of such a problem, an object of the present invention is to provide a metal surface treatment liquid and a metal surface treatment method capable of coloring a metal surface in a grayish color tone with good treatment efficiency.

本発明者らは上記課題を解決するために鋭意検討した結果、テルル若しくはテルル化合物、又はこれらの塩を含む金属表面処理液により処理を行うことで、良好な処理効率で金属表面を灰色系の色調に着色することが可能となることを見出した。 As a result of diligent studies to solve the above problems, the present inventors have made the metal surface grayish with good treatment efficiency by treating with a metal surface treatment solution containing tellurium or tellurium compounds or salts thereof. We have found that it is possible to color tones.

以上の知見を基礎として完成した本発明は一側面において、テルル若しくはテルル化合物、又はこれらの塩を含む金属表面処理液である。 The present invention completed on the basis of the above findings is, in one aspect, a metal surface treatment liquid containing tellurium or tellurium compounds, or salts thereof.

本発明の金属表面処理液は一実施形態において、前記テルル若しくはテルル化合物、又はこれらの塩が、一酸化テルル、二酸化テルル、三酸化テルル、亜テルル酸、テルル酸、四塩化テルル、テルル化ジメチル、若しくはこれらの塩、又はこれらの組み合わせである。 In one embodiment, the metal surface treatment liquid of the present invention contains the tellurium or tellurium compound, or a salt thereof, containing tellurium monoxide, tellurium dioxide, tellurium trioxide, tellurous acid, telluric acid, tellurium tetrachloride, or dimethyl telluride. , Or salts thereof, or a combination thereof.

本発明の金属表面処理液は別の一実施形態において、前記テルル若しくはテルル化合物、又はこれらの塩の合計含有量が、０．５〜１００ｇ／Ｌである。 In another embodiment, the metal surface treatment liquid of the present invention has a total content of the tellurium or tellurium compound, or salts thereof, of 0.5 to 100 g / L.

本発明の金属表面処理液は更に別の一実施形態において、更に、無機酸若しくはその塩を含む。 In yet another embodiment, the metal surface treatment liquid of the present invention further contains an inorganic acid or a salt thereof.

本発明の金属表面処理液は更に別の一実施形態において、前記無機酸若しくはその塩が、硫酸、硝酸、塩酸、リン酸、若しくはこれらの塩、又はこれらの組み合わせである。 In still another embodiment, the metal surface treatment liquid of the present invention is such that the inorganic acid or a salt thereof is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, or a salt thereof, or a combination thereof.

本発明の金属表面処理液は更に別の一実施形態において、前記無機酸若しくはその塩の合計含有量が、１〜２００ｇ／Ｌである。 In still another embodiment, the metal surface treatment liquid of the present invention has a total content of the inorganic acid or a salt thereof of 1 to 200 g / L.

本発明の金属表面処理液は更に別の一実施形態において、更に、有機硫黄化合物若しくはその塩を含む。 In yet another embodiment, the metal surface treatment liquid of the present invention further contains an organic sulfur compound or a salt thereof.

本発明の金属表面処理液は更に別の一実施形態において、前記有機硫黄化合物若しくはその塩が、チオ尿素、二酸化チオ尿素、チオジグリコール、ジメチルチオ尿素、チオリンゴ酸、ジチオジグリコール酸、ジメチルスルホキシド、メタンスルホン酸、ｐ−トルエンスルホン酸、ｐ−フェノールスルホン酸、チオシアン酸、システイン、メチオニン、若しくはこれらの塩、又はこれらの組み合わせである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the organic sulfur compound or a salt thereof contains thiourea, thiourea dioxide, thiodiglycol, dimethylthiourea, thiocyanic acid, dithiodiglycolic acid, dimethylsulfoxide, and the like. Methanesulfonic acid, p-toluenesulfonic acid, p-phenolsulfonic acid, thiocyanic acid, cysteine, methionine, or salts thereof, or a combination thereof.

本発明の金属表面処理液は更に別の一実施形態において、前記有機硫黄化合物若しくはその塩の合計含有量が、０．１〜５０ｇ／Ｌである。 In yet another embodiment, the metal surface treatment liquid of the present invention has a total content of the organic sulfur compound or a salt thereof of 0.1 to 50 g / L.

本発明の金属表面処理液は更に別の一実施形態において、更に、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩を含む。 In yet another embodiment, the metal surface treatment liquid of the present invention further contains a carboxylic acid or a hydroxycarboxylic acid, or a salt thereof.

本発明の金属表面処理液は更に別の一実施形態において、前記カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩が、ギ酸、酢酸、プロピオン酸、乳酸、リンゴ酸、クエン酸、シュウ酸、グルコン酸、マロン酸、コハク酸、安息香酸、ピルビン酸、グリオキシル酸、ニトリロ三酢酸、エチレンジアミン四酢酸、若しくはこれらの塩、又はこれらの組み合わせである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the carboxylic acid or hydroxycarboxylic acid, or a salt thereof, is formic acid, acetic acid, propionic acid, lactic acid, malic acid, citric acid, oxalic acid, gluconic acid. , Malic acid, succinic acid, oxalic acid, pyruvate, formic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, or salts thereof, or a combination thereof.

本発明の金属表面処理液は更に別の一実施形態において、前記カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量が、０．５〜１００ｇ／Ｌである。 In yet another embodiment, the metal surface treatment liquid of the present invention has a total content of the carboxylic acid or hydroxycarboxylic acid, or a salt thereof, of 0.5 to 100 g / L.

本発明の金属表面処理液は更に別の一実施形態において、更に、オキソ酸若しくはその塩を含む。 In yet another embodiment, the metal surface treatment liquid of the present invention further contains an oxo acid or a salt thereof.

本発明の金属表面処理液は更に別の一実施形態において、前記オキソ酸若しくはその塩が、過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭素酸、炭酸、ホウ酸、若しくはこれらの塩、又はこれらの組み合わせである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the oxo acid or a salt thereof is perchloric acid, chloric acid, chloric acid, hypochlorous acid, bromic acid, carbonic acid, boric acid, or these. Salt, or a combination thereof.

本発明の金属表面処理液は更に別の一実施形態において、前記オキソ酸若しくはその塩の合計含有量が、０．５〜１００ｇ／Ｌである。 In still another embodiment, the metal surface treatment liquid of the present invention has a total content of the oxo acid or a salt thereof of 0.5 to 100 g / L.

本発明の金属表面処理液は更に別の一実施形態において、処理対象の金属が、アルミニウム、アルミニウム合金、銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金、ニッケル、ニッケル合金、マグネシウム、及びマグネシウム合金からなる群から選択される少なくとも１種である。 In yet another embodiment of the metal surface treatment liquid of the present invention, the metals to be treated are aluminum, aluminum alloy, copper, copper alloy, iron, iron alloy, zinc, zinc alloy, nickel, nickel alloy, magnesium, and At least one selected from the group consisting of magnesium alloys.

本発明は別の一側面において、本発明の金属表面処理液を使用して、金属に対して着色を行う工程を含む金属表面処理方法である。 In another aspect, the present invention is a metal surface treatment method comprising a step of coloring a metal using the metal surface treatment liquid of the present invention.

本発明の金属表面処理方法は一実施形態において、前記金属に対して着色を行う工程において、前記金属を前記金属表面処理液に１０℃〜８０℃で１０秒〜２０分間浸漬することで前記金属を着色する。 In one embodiment, the metal surface treatment method of the present invention comprises immersing the metal in the metal surface treatment liquid at 10 ° C. to 80 ° C. for 10 seconds to 20 minutes in a step of coloring the metal. To color.

本発明によれば、良好な処理効率で金属表面を灰色系の色調に着色することが可能な金属表面処理液及び金属表面処理方法を提供することができる。 According to the present invention, it is possible to provide a metal surface treatment liquid and a metal surface treatment method capable of coloring a metal surface in a grayish color tone with good treatment efficiency.

以下、本発明の金属表面処理液及び金属表面処理方法の実施形態について説明するが、本発明は、これに限定されて解釈されるものではなく、本発明の範囲を逸脱しない限りにおいて、当業者の知識に基づいて、種々の変更、修正、改良を加え得るものである。 Hereinafter, embodiments of the metal surface treatment liquid and the metal surface treatment method of the present invention will be described, but the present invention will not be construed as being limited thereto, and those skilled in the art will be skilled in the art as long as they do not deviate from the scope of the present invention. Various changes, modifications and improvements can be made based on the knowledge of.

〔金属表面処理液〕
本発明の実施形態に係る金属表面処理液は、テルル若しくはテルル化合物、又はこれらの塩を含む。テルル若しくはテルル化合物、又はこれらの塩を含む金属表面処理液を用いることで、処理対象の金属を当該金属表面処理液に浸漬するだけで、金属表面に皮膜（着色皮膜）を形成することができ、これにより灰色系の色調に着色することができる。このため、金属表面を灰色系の色調に着色する際に、当該金属の表面に酸化膜を形成しておく必要もなく、電解によって着色する必要もなくなり、処理効率が良好となる。また、本発明の実施形態に係る金属表面処理液によれば、金属表面に形成する皮膜（着色皮膜）の密着性も良好となる。 [Metal surface treatment liquid]
The metal surface treatment liquid according to the embodiment of the present invention contains tellurium or tellurium compounds, or salts thereof. By using a metal surface treatment solution containing tellurium or a tellurium compound, or a salt thereof, a film (colored film) can be formed on the metal surface simply by immersing the metal to be treated in the metal surface treatment solution. As a result, it is possible to color a grayish color tone. Therefore, when the metal surface is colored in a grayish color tone, it is not necessary to form an oxide film on the surface of the metal, and it is not necessary to color the metal surface by electrolysis, so that the treatment efficiency is improved. Further, according to the metal surface treatment liquid according to the embodiment of the present invention, the adhesion of the film (colored film) formed on the metal surface is also good.

（処理対象の金属）
本発明の実施形態に係る金属表面処理液で表面を着色する対象となる金属（処理対象の金属）としては、アルミニウム、アルミニウム合金、銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金、ニッケル、ニッケル合金、マグネシウム、及びマグネシウム合金からなる群から選択される少なくとも１種が挙げられる。処理対象の金属は、当該金属自体であってもよく、例えば、鉄系材料や鉄系部品などの金属基材の表面に形成された、当該金属のメッキであってもよい。 (Metal to be processed)
Examples of the metal (metal to be treated) for coloring the surface with the metal surface treatment liquid according to the embodiment of the present invention include aluminum, aluminum alloy, copper, copper alloy, iron, iron alloy, zinc, zinc alloy, and nickel. , At least one selected from the group consisting of nickel alloys, magnesium, and magnesium alloys. The metal to be treated may be the metal itself, or may be, for example, plating of the metal formed on the surface of a metal base material such as an iron-based material or an iron-based component.

（テルル若しくはテルル化合物、又はこれらの塩）
テルル若しくはテルル化合物、又はこれらの塩は、一酸化テルル、二酸化テルル、三酸化テルル、亜テルル酸、テルル酸、四塩化テルル、テルル化ジメチル、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。一酸化テルル、二酸化テルル、三酸化テルル、亜テルル酸、テルル酸、四塩化テルル、テルル化ジメチルの塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。 (Tellurium or tellurium compounds, or salts thereof)
Tellurium or tellurium compounds, or salts thereof, are tellurium monoxide, tellurium dioxide, tellurium trioxide, tellurous acid, telluric acid, tellurium tetrachloride, dimethyl telluride, or salts thereof, or a combination thereof. preferable. As the salts of tellurium monoxide, tellurium dioxide, tellurium trioxide, tellurous acid, telluric acid, tellurium tetrachloride, and dimethyl telluride, these metal salts, ammonium salts, and the like can be used.

本発明の実施形態に係る金属表面処理液におけるテルル若しくはテルル化合物、又はこれらの塩の合計含有量は、処理対象の金属の種類、及び、どの程度の灰色系の色調に着色するかによるが、例えば、テルル若しくはテルル化合物、又はこれらの塩の合計含有量は、０．５〜１００ｇ／Ｌとすることができる。基本的には、テルル若しくはテルル化合物、又はこれらの塩の合計含有量が少ないほど、金属表面を薄い灰色系の色調に着色することができる。また、テルル若しくはテルル化合物、又はこれらの塩の合計含有量が多いほど、金属表面を濃い灰色系の色調に着色することができる。テルル若しくはテルル化合物、又はこれらの塩の合計含有量は、１〜５０ｇ／Ｌであることがより好ましく、２〜２０ｇ／Ｌであることがより好ましい。 The total content of tellurium or tellurium compounds, or salts thereof in the metal surface treatment liquid according to the embodiment of the present invention depends on the type of metal to be treated and the degree of grayish color tones. For example, the total content of tellurium or tellurium compounds, or salts thereof, can be 0.5-100 g / L. Basically, the smaller the total content of tellurium or tellurium compounds, or salts thereof, the lighter the gray color of the metal surface can be colored. Further, the larger the total content of tellurium or tellurium compound, or salts thereof, the darker the gray color of the metal surface can be colored. The total content of tellurium or tellurium compounds, or salts thereof, is more preferably 1 to 50 g / L, more preferably 2 to 20 g / L.

本発明の実施形態に係る金属表面処理液は、後述のように、無機酸若しくはその塩、有機硫黄化合物若しくはその塩、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩、オキソ酸若しくはその塩等を含んでもよいが、これらの成分を含まない金属表面処理液の場合、特にアルミニウム、アルミニウム合金などの金属表面を、より美観に優れた灰色系の色調に着色することができる。 As described later, the metal surface treatment liquid according to the embodiment of the present invention contains an inorganic acid or a salt thereof, an organic sulfur compound or a salt thereof, a carboxylic acid or a hydroxycarboxylic acid, or a salt thereof, an oxo acid or a salt thereof, or the like. Although it may be contained, in the case of a metal surface treatment liquid which does not contain these components, it is possible to color a metal surface such as aluminum or an aluminum alloy in a more aesthetically pleasing grayish color.

（無機酸若しくはその塩）
本発明の実施形態に係る金属表面処理液は、更に、無機酸若しくはその塩を含んでもよい。本発明の実施形態に係る金属表面処理液は、無機酸若しくはその塩を含んでも、良好な処理効率で前述の処理対象の金属表面を灰色系の色調に着色することができる。また、本発明の実施形態に係る金属表面処理液は、無機酸若しくはその塩を含むことにより、金属溶解が促進し金属表面のｐＨが上昇することで着色皮膜が形成される反応が促進されるため、特に銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金、ニッケル、ニッケル合金、マグネシウム、マグネシウム合金などの金属の表面を、より美観に優れた灰色系の色調に着色することができる。 (Inorganic acid or salt thereof)
The metal surface treatment liquid according to the embodiment of the present invention may further contain an inorganic acid or a salt thereof. Even if the metal surface treatment liquid according to the embodiment of the present invention contains an inorganic acid or a salt thereof, the metal surface to be treated can be colored in a grayish color with good treatment efficiency. Further, when the metal surface treatment liquid according to the embodiment of the present invention contains an inorganic acid or a salt thereof, metal dissolution is promoted and the pH of the metal surface is raised to promote a reaction in which a colored film is formed. Therefore, it is possible to color the surface of a metal such as copper, copper alloy, iron, iron alloy, zinc, zinc alloy, nickel, nickel alloy, magnesium, magnesium alloy, etc. in a more aesthetically pleasing grayish color.

無機酸若しくはその塩が、硫酸、硝酸、塩酸、リン酸、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。硫酸、硝酸、塩酸、リン酸の塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。 It is preferable that the inorganic acid or a salt thereof is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, or a salt thereof, or a combination thereof. As the salts of sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid, these metal salts, ammonium salts, and the like can be used.

本発明の実施形態に係る金属表面処理液における無機酸若しくはその塩の合計含有量は、１〜２００ｇ／Ｌとすることができる。基本的には、無機酸若しくはその塩の合計含有量が少ないほど、金属表面を薄い灰色系の色調に着色することができる。また、無機酸若しくはその塩の合計含有量が多いほど、金属表面を濃い灰色系の色調に着色することができる。無機酸若しくはその塩の合計含有量は、１０〜１５０ｇ／Ｌであることがより好ましく、７０〜１２０ｇ／Ｌであることがより好ましい。 The total content of the inorganic acid or a salt thereof in the metal surface treatment liquid according to the embodiment of the present invention can be 1 to 200 g / L. Basically, the smaller the total content of the inorganic acid or its salt, the lighter the gray color of the metal surface can be colored. Further, the larger the total content of the inorganic acid or a salt thereof, the darker the gray color of the metal surface can be colored. The total content of the inorganic acid or a salt thereof is more preferably 10 to 150 g / L, and more preferably 70 to 120 g / L.

（有機硫黄化合物若しくはその塩）
本発明の実施形態に係る金属表面処理液は、更に、有機硫黄化合物若しくはその塩を含んでもよい。本発明の実施形態に係る金属表面処理液は、有機硫黄化合物若しくはその塩を含んでも、良好な処理効率で前述の処理対象の金属表面を灰色系の色調に着色することができる。また、本発明の実施形態に係る金属表面処理液は、有機硫黄化合物若しくはその塩を含むことにより、有機硫黄化合物によって金属溶解が促進し金属表面のｐＨが上昇することで着色皮膜が形成される反応が促進される。このため、特に銅、銅合金、ニッケル、ニッケル合金などの金属の表面を、より美観に優れた灰色系の色調に着色することができる。 (Organosulfur compounds or salts thereof)
The metal surface treatment liquid according to the embodiment of the present invention may further contain an organic sulfur compound or a salt thereof. Even if the metal surface treatment liquid according to the embodiment of the present invention contains an organic sulfur compound or a salt thereof, the metal surface to be treated can be colored in a grayish color with good treatment efficiency. Further, when the metal surface treatment liquid according to the embodiment of the present invention contains an organic sulfur compound or a salt thereof, the organic sulfur compound promotes metal dissolution and raises the pH of the metal surface to form a colored film. The reaction is promoted. Therefore, it is possible to color the surface of a metal such as copper, a copper alloy, nickel, or a nickel alloy in a more aesthetically pleasing grayish color tone.

有機硫黄化合物若しくはその塩が、チオ尿素、二酸化チオ尿素、チオジグリコール、ジメチルチオ尿素、チオリンゴ酸、ジチオジグリコール酸、ジメチルスルホキシド、メタンスルホン酸、ｐ−トルエンスルホン酸、ｐ−フェノールスルホン酸、チオシアン酸、システイン、メチオニン、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。チオ尿素、二酸化チオ尿素、チオジグリコール、ジメチルチオ尿素、チオリンゴ酸、ジチオジグリコール酸、ジメチルスルホキシド、メタンスルホン酸、ｐ−トルエンスルホン酸、ｐ−フェノールスルホン酸、チオシアン酸、システイン、メチオニンの塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。 Organosulfur compounds or salts thereof are thiourea, thiourea dioxide, thiodiglycol, dimethylthiourea, thioapple acid, dithiodiglycolic acid, dimethylsulfoxide, methanesulfonic acid, p-toluenesulfonic acid, p-phenolsulfonic acid, thiocyanate. Acids, cysteines, methionines, or salts thereof, or combinations thereof are preferred. As salts of thiourea, thiourea dioxide, thiodiglycol, dimethylthiourea, thioapple acid, dithiodiglycolic acid, dimethylsulfoxide, methanesulfonic acid, p-toluenesulfonic acid, p-phenolsulfonic acid, thiocyanic acid, cysteine, methionine Can use these metal salts, ammonium salts, and the like.

本発明の実施形態に係る金属表面処理液における有機硫黄化合物若しくはその塩の合計含有量は、０．１〜５０ｇ／Ｌとすることができる。基本的には、有機硫黄化合物若しくはその塩の合計含有量が少ないほど、金属表面を薄い灰色系の色調に着色することができる。また、有機硫黄化合物若しくはその塩の合計含有量が多いほど、金属表面を濃い灰色系の色調に着色することができる。有機硫黄化合物若しくはその塩の合計含有量は、１〜３０ｇ／Ｌであることがより好ましく、５〜１５ｇ／Ｌであることがより好ましい。 The total content of the organic sulfur compound or a salt thereof in the metal surface treatment liquid according to the embodiment of the present invention can be 0.1 to 50 g / L. Basically, the smaller the total content of the organic sulfur compound or its salt, the lighter the gray color of the metal surface can be colored. Further, the larger the total content of the organic sulfur compound or a salt thereof, the darker the grayish color of the metal surface can be colored. The total content of the organic sulfur compound or a salt thereof is more preferably 1 to 30 g / L, and more preferably 5 to 15 g / L.

（カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩）
本発明の実施形態に係る金属表面処理液は、更に、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩を含んでもよい。本発明の実施形態に係る金属表面処理液は、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩を含んでも、良好な処理効率で前述の処理対象の金属表面を灰色系の色調に着色することができる。また、本発明の実施形態に係る金属表面処理液は、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩を含むことにより、カルボン酸若しくはヒドロキシカルボン酸がテルルとキレートすることで着色反応が抑制され緻密な皮膜が形成されやすくなる。このため、特に銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金などの金属の表面を、より美観に優れた灰色系の色調に着色することができる。 (Carboxylic acid or hydroxycarboxylic acid, or salts thereof)
The metal surface treatment liquid according to the embodiment of the present invention may further contain a carboxylic acid, a hydroxycarboxylic acid, or a salt thereof. Even if the metal surface treatment liquid according to the embodiment of the present invention contains carboxylic acid, hydroxycarboxylic acid, or salts thereof, the metal surface to be treated can be colored in a grayish color with good treatment efficiency. it can. Further, the metal surface treatment liquid according to the embodiment of the present invention contains a carboxylic acid or a hydroxycarboxylic acid, or a salt thereof, so that the carboxylic acid or the hydroxycarboxylic acid chelate with tellurium, thereby suppressing the coloring reaction and making it dense. Film is likely to be formed. Therefore, the surface of a metal such as copper, copper alloy, iron, iron alloy, zinc, and zinc alloy can be colored in a more aesthetically pleasing grayish color.

カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩が、ギ酸、酢酸、プロピオン酸、乳酸、リンゴ酸、クエン酸、シュウ酸、グルコン酸、マロン酸、コハク酸、安息香酸、ピルビン酸、グリオキシル酸、ニトリロ三酢酸、エチレンジアミン四酢酸、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。ギ酸、酢酸、プロピオン酸、乳酸、リンゴ酸、クエン酸、シュウ酸、グルコン酸、マロン酸、コハク酸、安息香酸、ピルビン酸、グリオキシル酸、ニトリロ三酢酸、エチレンジアミン四酢酸の塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。 Carboxylic acid or hydroxycarboxylic acid, or salts thereof, are formic acid, acetic acid, propionic acid, lactic acid, malic acid, citric acid, oxalic acid, gluconic acid, malonic acid, succinic acid, benzoic acid, pyruvate, glyoxylic acid, nitrilo. It is preferably triacetic acid, ethylenediaminetetraacetic acid, salts thereof, or a combination thereof. As salts of formic acid, acetic acid, propionic acid, lactic acid, malic acid, citric acid, oxalic acid, gluconic acid, malonic acid, succinic acid, benzoic acid, pyruvic acid, glyoxylic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid, these A metal salt, an ammonium salt, or the like can be used.

本発明の実施形態に係る金属表面処理液におけるカルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量は、０．５〜１００ｇ／Ｌとすることができる。基本的には、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量が少ないほど、金属表面を濃い灰色系の色調に着色することができる。また、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量が多いほど、金属表面を薄い灰色系の色調に着色することができる。カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量は、１〜５０ｇ／Ｌであることがより好ましく、１０〜３０ｇ／Ｌであることがより好ましい。 The total content of the carboxylic acid or hydroxycarboxylic acid, or salts thereof in the metal surface treatment liquid according to the embodiment of the present invention can be 0.5 to 100 g / L. Basically, the smaller the total content of carboxylic acid or hydroxycarboxylic acid, or salts thereof, the darker the gray color of the metal surface can be colored. Further, the larger the total content of carboxylic acid, hydroxycarboxylic acid, or salts thereof, the lighter the gray color of the metal surface can be colored. The total content of the carboxylic acid or hydroxycarboxylic acid, or salts thereof, is more preferably 1 to 50 g / L, more preferably 10 to 30 g / L.

（オキソ酸若しくはその塩）
本発明の実施形態に係る金属表面処理液は、更に、オキソ酸若しくはその塩を含んでもよい。本発明の実施形態に係る金属表面処理液は、オキソ酸若しくはその塩を含んでも、良好な処理効率で前述の処理対象の金属表面を灰色系の色調に着色することができる。また、本発明の実施形態に係る金属表面処理液は、オキソ酸若しくはその塩を含むことにより、特に銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金などの金属の表面を、より美観に優れた灰色系の色調に着色することができる。 (Oxyacid or its salt)
The metal surface treatment liquid according to the embodiment of the present invention may further contain an oxo acid or a salt thereof. Even if the metal surface treatment liquid according to the embodiment of the present invention contains an oxo acid or a salt thereof, the metal surface to be treated can be colored in a grayish color with good treatment efficiency. Further, the metal surface treatment liquid according to the embodiment of the present invention contains oxo acid or a salt thereof to make the surface of metals such as copper, copper alloys, iron, iron alloys, zinc and zinc alloys more aesthetically pleasing. It can be colored with an excellent grayish hue.

オキソ酸若しくはその塩が、過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭素酸、炭酸、ホウ酸、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭素酸、炭酸、ホウ酸の塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。 It is preferable that the oxo acid or a salt thereof is perchloric acid, chloric acid, chloric acid, hypochlorous acid, bromic acid, carbonic acid, boric acid, or a salt thereof, or a combination thereof. As the salts of perchloric acid, chloric acid, chloric acid, hypochlorous acid, bromic acid, carbonic acid, and boric acid, these metal salts, ammonium salts, and the like can be used.

本発明の実施形態に係る金属表面処理液におけるオキソ酸若しくはその塩の合計含有量は、０．５〜１００ｇ／Ｌとすることができる。基本的には、オキソ酸若しくはその塩の合計含有量が少ないほど、金属表面を薄い灰色系の色調に着色することができる。また、オキソ酸若しくはその塩の合計含有量が多いほど、金属表面を濃い灰色系の色調に着色することができる。オキソ酸若しくはその塩の合計含有量は、１〜５０ｇ／Ｌであることがより好ましく、１０〜３０ｇ／Ｌであることがより好ましい。 The total content of the oxo acid or a salt thereof in the metal surface treatment liquid according to the embodiment of the present invention can be 0.5 to 100 g / L. Basically, the smaller the total content of oxoacid or a salt thereof, the lighter the grayish color of the metal surface can be colored. Further, the larger the total content of the oxo acid or the salt thereof, the darker the gray color of the metal surface can be colored. The total content of the oxo acid or a salt thereof is more preferably 1 to 50 g / L, and more preferably 10 to 30 g / L.

（水性媒体）
本発明の実施形態に係る金属表面処理液は、前述の各種成分に、水性媒体を混合したものであってもよい。水性媒体は、水を主成分とする媒体を示す。水性媒体としては、例えば、水を主成分とし、水と混和可能なアルコール等の有機溶媒を含む媒体が挙げられる。水性媒体は、本発明の実施形態に係る金属表面処理液の調製の際、金属表面処理液の保存の際、又は金属表面を着色した後において、当該金属の着色表面の何らかの特性向上のために有利に作用する各種の成分、又は本発明の効果を実質的に阻害しない各種成分を、必要に応じて含むことができる。例えばｐＨ調整剤、保存安定剤等は、そのような成分の具体例である。 (Aqueous medium)
The metal surface treatment liquid according to the embodiment of the present invention may be a mixture of the above-mentioned various components and an aqueous medium. Aqueous medium refers to a medium containing water as a main component. Examples of the aqueous medium include a medium containing water as a main component and containing an organic solvent such as alcohol which is miscible with water. The aqueous medium is used for preparing the metal surface treatment liquid according to the embodiment of the present invention, storing the metal surface treatment liquid, or after coloring the metal surface, in order to improve some properties of the colored surface of the metal. Various components that act advantageously or various components that do not substantially impair the effects of the present invention can be contained, if necessary. For example, pH adjusters, storage stabilizers and the like are specific examples of such components.

〔金属表面処理方法〕
次に、本発明の実施形態に係る金属表面処理方法について詳述する。まず、本発明の実施形態に係る金属表面処理液が入った浴槽を準備する。次に、浴槽中の金属表面処理液の温度を制御しながら、処理対象の金属を金属表面処理液に浸漬する。所定時間経過後、浴槽から処理対象の金属を引き上げることで、金属表面が灰色系の色調に着色された金属を得る。このように、本発明の実施形態に係る金属表面処理方法によれば、処理対象の金属を金属表面処理液に浸漬するだけで、灰色系の色調に着色することができる。このため、金属表面を灰色系の色調に着色する際に、当該金属の表面に酸化膜を形成しておく必要もなく、電解によって着色する必要もなくなり、処理効率が良好となる。 [Metal surface treatment method]
Next, the metal surface treatment method according to the embodiment of the present invention will be described in detail. First, a bathtub containing the metal surface treatment liquid according to the embodiment of the present invention is prepared. Next, the metal to be treated is immersed in the metal surface treatment liquid while controlling the temperature of the metal surface treatment liquid in the bathtub. After a lapse of a predetermined time, the metal to be treated is pulled up from the bathtub to obtain a metal whose metal surface is colored in a grayish color. As described above, according to the metal surface treatment method according to the embodiment of the present invention, the metal to be treated can be colored in a grayish color simply by immersing it in the metal surface treatment liquid. Therefore, when the metal surface is colored in a grayish color tone, it is not necessary to form an oxide film on the surface of the metal, and it is not necessary to color the metal surface by electrolysis, so that the treatment efficiency is improved.

また、本発明の実施形態に係る金属表面処理方法において、処理対象の金属を金属表面処理液に浸漬する以外に、例えば、金属表面処理液を用いた吹き付け工程によって、処理対象の金属の表面に金属表面処理液を接触させて、処理対象の金属の表面を着色してもよい。 Further, in the metal surface treatment method according to the embodiment of the present invention, in addition to immersing the metal to be treated in the metal surface treatment liquid, for example, a spraying step using the metal surface treatment liquid is performed on the surface of the metal to be treated. The surface of the metal to be treated may be colored by contacting the metal surface treatment liquid.

金属表面処理液による処理温度は、１０〜８０℃の範囲が好ましく、１０〜６０℃の範囲がより好ましく、３０〜６０℃の範囲が更により好ましい。処理温度が１０℃以上であると表面処理の反応速度が増し、８０℃以下であると蒸発による金属表面処理液の液面の低下を抑制することができる。 The treatment temperature with the metal surface treatment liquid is preferably in the range of 10 to 80 ° C, more preferably in the range of 10 to 60 ° C, and even more preferably in the range of 30 to 60 ° C. When the treatment temperature is 10 ° C. or higher, the reaction rate of the surface treatment is increased, and when the treatment temperature is 80 ° C. or lower, the decrease in the liquid level of the metal surface treatment liquid due to evaporation can be suppressed.

金属表面処理液による処理時間は、１０秒〜２０分間の範囲が好ましく、３０秒〜２０分間の範囲がより好ましく、１分〜１０分間の範囲が更により好ましい。基本的には、処理時間が短いほど、金属表面を薄い灰色系の色調に着色することができる。また、処理時間が長いほど、金属表面を濃い灰色系の色調に着色することができる。 The treatment time with the metal surface treatment liquid is preferably in the range of 10 seconds to 20 minutes, more preferably in the range of 30 seconds to 20 minutes, and even more preferably in the range of 1 minute to 10 minutes. Basically, the shorter the treatment time, the lighter the grayish color of the metal surface can be colored. Further, the longer the treatment time, the darker the grayish color of the metal surface can be colored.

金属表面処理を行う際、あらかじめ処理対象の金属の脱脂、活性化、表面調整を行うことで、処理対象の金属の外観、耐食性及び金属表面処理液との反応性を向上させることが可能である。 When performing metal surface treatment, it is possible to improve the appearance, corrosion resistance, and reactivity with the metal surface treatment liquid of the metal to be treated by degreasing, activating, and surface-adjusting the metal to be treated in advance. ..

金属表面処理後に、ケイ素、樹脂及びワックスからなる群のうちの１種以上を含有するコーティング剤にて後処理を行っても良い。所望の金属表面の色調に影響を与えない範囲において、これらコーティング剤に特に限定はなく、アクリル樹脂、オレフィン樹脂、アルキド樹脂、尿素樹脂、エポキシ樹脂、メラミン樹脂、フッ素樹脂、ポリエチレン、ポリ塩化ビニル、ポリスチレン、ポリプロピレン、メタクリル樹脂、フェノール樹脂、ポリエステル樹脂、ポリウレタン、ポリアミド、ポリカーボネート等の樹脂類やケイ酸塩、コロイダルシリカ等を成分とするコーティング剤を用いても良い。これらの樹脂濃度は、０．０１〜８００ｇ／Ｌが好ましいが、適切な濃度は樹脂の種類により異なる。コーティング剤としては、具体的には、コスマーコート（商品名、関西ペイント（株））、ハイシール２７２（商品名、日本表面化学（株））、ストロンＪＳコート（商品名、日本表面化学（株））、トライナーＴＲ−１７０（商品名、日本表面化学（株））、フィニガード（商品名、Coventya社）等が挙げられる。アクリル樹脂としては、具体的には、ヒロタイト（商品名、日立化成（株））、アロセット（商品名、（株）日本触媒）等があり、オレフィン樹脂については、フローセン（商品名、住友精化（株））、ＰＥＳ（商品名、日本ユニカー（株））、ケミパール（商品名、三井化学（株））、サンファイン（商品名、旭化成（株））等が挙げられる。 After the metal surface treatment, the post-treatment may be performed with a coating agent containing at least one of the group consisting of silicon, resin and wax. The coating agents are not particularly limited as long as they do not affect the desired color tone of the metal surface, and acrylic resin, olefin resin, alkyd resin, urea resin, epoxy resin, melamine resin, fluororesin, polyethylene, polyvinyl chloride, etc. Resins such as polystyrene, polypropylene, methacrylic resin, phenol resin, polyester resin, polyurethane, polyamide and polycarbonate, and coating agents containing silicate, colloidal silica and the like as components may be used. The concentration of these resins is preferably 0.01 to 800 g / L, but the appropriate concentration varies depending on the type of resin. Specific examples of the coating agent include Cosmer Coat (trade name, Kansai Paint Co., Ltd.), High Seal 272 (trade name, Nippon Surface Chemical Co., Ltd.), and Stron JS Coat (trade name, Nippon Surface Chemical Co., Ltd.). ), Triner TR-170 (trade name, Nippon Surface Chemical Co., Ltd.), Finigard (trade name, Coventya Co., Ltd.) and the like. Specific examples of acrylic resins include Hirotite (trade name, Hitachi Kasei Co., Ltd.), Arosett (trade name, Nippon Shokubai Co., Ltd.), and Frosen (trade name, Sumitomo Seika Co., Ltd.) for olefin resins. (Co., Ltd.), PES (trade name, Nippon Unicar Co., Ltd.), Chemipearl (trade name, Mitsui Kagaku Co., Ltd.), Sunfine (trade name, Asahi Kasei Co., Ltd.) and the like.

本発明の実施形態に係る金属表面処理液は、金属表面を、所望の色に着色させる、所望の美観を付与する、又は識別性を付与する等の目的で使用することができる。このような処理対象の金属の形態としては、あらゆるものを用いることができ、特に限定されないが、例えば、装飾品、ボタンやファスナー等のファスニング部材、車載用部品等を用いることができる。また、当該処理対象の金属の形状についても限定されず、あらゆる形状のものを用いることができる。 The metal surface treatment liquid according to the embodiment of the present invention can be used for the purpose of coloring the metal surface to a desired color, imparting a desired aesthetic appearance, imparting distinctiveness, and the like. Any form of the metal to be processed can be used, and the form is not particularly limited, and for example, ornaments, fastening members such as buttons and fasteners, in-vehicle parts, and the like can be used. Further, the shape of the metal to be treated is not limited, and any shape can be used.

以下、本発明の実施例を示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。 Hereinafter, examples of the present invention will be shown, but these are provided for a better understanding of the present invention, and are not intended to limit the present invention.

〔試験例１：アルミニウム、アルミニウム合金の着色試験〕
（実施例１〜３５、９２、９３）
試験片（処理対象の金属片）として、ＪＩＳ Ａ５０５２（アルミニウム−マグネシウム合金）、ＡＤＣ１２（アルミダイキャスト）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表１〜３、８に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表１〜３、８に示す温度に制御した状態で、試験片を浸漬した。表１〜３、８に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。 [Test Example 1: Coloring test of aluminum and aluminum alloy]
(Examples 1-35, 92, 93)
JIS A5052 (aluminum-magnesium alloy) and ADC12 (aluminum die-cast) were prepared as test pieces (metal pieces to be treated), and the surface of the test pieces was degreased and washed with water in this order.
Next, a bathtub containing the metal surface treatment liquid having the liquid compositions shown in Tables 1 to 8 was prepared. Pure water was used as the aqueous medium of the metal surface treatment liquid.
Next, the test piece was immersed in a state where the temperature of the metal surface treatment liquid in the bathtub was controlled to the temperatures shown in Tables 1 to 8. After immersing for the time shown in Tables 1 to 8, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.

なお、実施例９２及び９３については、浸漬により皮膜（着色皮膜）を形成した後の試験片を水洗し、コーティング処理を行い、乾燥した。実施例９２のコーティング処理にはストロンＪＳコート（日本表面化学（株）製コーティング剤）、実施例９３のコーティング処理にはＴＲ−１７０（日本表面化学（株）製コーティング剤）を使用した。 In Examples 92 and 93, the test piece after forming the film (colored film) by immersion was washed with water, coated, and dried. Stron JS Coat (coating agent manufactured by Nippon Surface Chemical Co., Ltd.) was used for the coating treatment of Example 92, and TR-170 (coating agent manufactured by Nippon Surface Chemical Co., Ltd.) was used for the coating treatment of Example 93.

〔試験例２：銅、銅合金の着色試験〕
（実施例３６〜５５）
試験片（処理対象の金属片）として、ＪＩＳ Ｃ２６００Ｐ（真鍮）、Ｃ１１００Ｐ（純銅）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表４〜５に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表４〜５に示す温度に制御した状態で、試験片を浸漬した。表４〜５に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。 [Test Example 2: Coloring test of copper and copper alloy]
(Examples 36 to 55)
JIS C2600P (brass) and C1100P (pure copper) were prepared as test pieces (metal pieces to be treated), and the surface of the test pieces was degreased and washed with water in this order.
Next, a bathtub containing the metal surface treatment liquid having the liquid compositions shown in Tables 4 to 5 was prepared. Pure water was used as the aqueous medium of the metal surface treatment liquid.
Next, the test piece was immersed in a state where the metal surface treatment liquid in the bathtub was controlled to the temperatures shown in Tables 4 to 5. After soaking for the time shown in Tables 4 to 5, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.

〔試験例３：亜鉛、亜鉛合金の着色試験〕
（実施例５６〜７５）
試験片（処理対象の金属片）として、ＪＩＳ ＺＤＣ２（亜鉛ダイキャスト）及び亜鉛めっき材を準備し、当該試験片の表面に、脱脂、水洗を順に行った。当該亜鉛めっき材は、ＪＩＳで規定されるＪＩＳ ＳＰＣＣ（圧延鋼板）を基材として、膜厚８μｍのジンケート亜鉛メッキを施したものである。また、当該ジンケート亜鉛メッキの光沢剤として、日本表面化学株式会社製９０００ＡＢＳを使用した。
次に、表６〜７に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表６〜７に示す温度に制御した状態で、試験片を浸漬した。表６〜７に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。 [Test Example 3: Coloring test of zinc and zinc alloy]
(Examples 56 to 75)
JIS ZDC2 (zinc die-cast) and a galvanized material were prepared as test pieces (metal pieces to be treated), and the surface of the test pieces was degreased and washed with water in this order. The galvanized material is a zinc-plated material having a thickness of 8 μm, using JIS SPCC (rolled steel sheet) specified by JIS as a base material. Further, 9000 ABS manufactured by Nippon Surface Chemical Co., Ltd. was used as the brightener for the zincate zinc plating.
Next, a bathtub containing the metal surface treatment liquid having the liquid compositions shown in Tables 6 to 7 was prepared. Pure water was used as the aqueous medium of the metal surface treatment liquid.
Next, the test piece was immersed in a state where the metal surface treatment liquid in the bathtub was controlled to the temperatures shown in Tables 6 to 7. After soaking for the time shown in Tables 6 to 7, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.

〔試験例４：鉄、鉄合金の着色試験〕
（実施例７６〜８０）
試験片（処理対象の金属片）として、ＪＩＳ ＳＰＣＣ（圧延鋼板）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表７に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表７に示す温度に制御した状態で、試験片を浸漬した。表７に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。 [Test Example 4: Coloring test of iron and iron alloy]
(Examples 76 to 80)
JIS SPCC (rolled steel sheet) was prepared as a test piece (metal piece to be treated), and the surface of the test piece was degreased and washed with water in this order.
Next, a bathtub containing the metal surface treatment liquid having the liquid composition shown in Table 7 was prepared. Pure water was used as the aqueous medium of the metal surface treatment liquid.
Next, the test piece was immersed in a state where the metal surface treatment liquid in the bathtub was controlled to the temperature shown in Table 7. After soaking for the time shown in Table 7, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.

〔試験例５：マグネシウム、マグネシウム合金の着色試験〕
（実施例８１〜８６）
試験片（処理対象の金属片）として、ＪＩＳ ＡＺ３１及びＪＩＳ ＡＺ９１（マグネシウム−亜鉛合金）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表８に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表８に示す温度に制御した状態で、試験片を浸漬した。表８に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。 [Test Example 5: Coloring test of magnesium and magnesium alloy]
(Examples 81-86)
JIS AZ31 and JIS AZ91 (magnesium-zinc alloy) were prepared as test pieces (metal pieces to be treated), and the surface of the test pieces was degreased and washed with water in this order.
Next, a bathtub containing the metal surface treatment liquid having the liquid composition shown in Table 8 was prepared. Pure water was used as the aqueous medium of the metal surface treatment liquid.
Next, the test piece was immersed in a state where the metal surface treatment liquid in the bathtub was controlled to the temperature shown in Table 8. After soaking for the time shown in Table 8, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.

〔試験例６：ニッケル、ニッケル合金の着色試験〕
（実施例８７〜９１）
試験片（処理対象の金属片）として、ＪＩＳ Ｎｉ２００（純ニッケル）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表８に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表８に示す温度に制御した状態で、試験片を浸漬した。表８に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。 [Test Example 6: Coloring test of nickel and nickel alloy]
(Examples 87 to 91)
JIS Ni200 (pure nickel) was prepared as a test piece (metal piece to be treated), and the surface of the test piece was degreased and washed with water in this order.
Next, a bathtub containing the metal surface treatment liquid having the liquid composition shown in Table 8 was prepared. Pure water was used as the aqueous medium of the metal surface treatment liquid.
Next, the test piece was immersed in a state where the metal surface treatment liquid in the bathtub was controlled to the temperature shown in Table 8. After soaking for the time shown in Table 8, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.

〔試験例７〕
（比較例１〜１０）
試験片（処理対象の金属片）として、表９に示す金属を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表９に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表９に示す温度に制御した状態で、試験片を浸漬した。表９に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。 [Test Example 7]
(Comparative Examples 1 to 10)
As a test piece (metal piece to be treated), the metal shown in Table 9 was prepared, and the surface of the test piece was degreased and washed with water in this order.
Next, a bathtub containing the metal surface treatment liquid having the liquid composition shown in Table 9 was prepared. Pure water was used as the aqueous medium of the metal surface treatment liquid.
Next, the test piece was immersed in a state where the metal surface treatment liquid in the bathtub was controlled to the temperature shown in Table 9. After soaking for the time shown in Table 9, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.

〔各種評価〕
実施例１〜９３及び比較例１〜１０で作製した試験片について、色調評価及び密着性評価を以下の通り行った。 [Various evaluations]
The test pieces prepared in Examples 1 to 93 and Comparative Examples 1 to 10 were evaluated for color tone and adhesion as follows.

（色調評価）
試験片の表面の色調は、目視により評価した。評価基準を以下に示す。
Ａ：均一で美観に優れた処理外観を有するアンティークグレー
Ｂ：均一で美観に優れた処理外観を有するＡよりも濃いアンティークグレー
Ｃ：均一で美観に優れた処理外観を有するＡよりも薄いアンティークグレー
Ｄ：着色せず (Color tone evaluation)
The color tone of the surface of the test piece was visually evaluated. The evaluation criteria are shown below.
A: Antique gray with uniform and aesthetically pleasing treated appearance B: Antique gray darker than A with uniform and aesthetically pleasing treated appearance C: Antique gray lighter than A with uniform and aesthetically pleasing treated appearance D: Not colored

（密着性評価）
試験片の表面に、カッターで１０×１０マス（合計１００マス）の切り込みを入れ、セロテープ（登録商標）を貼って剥がした際に、着色皮膜が剥がれなかったマス目の数をカウントした。１マス分のサイズは、縦×横＝１ｍｍ×１ｍｍであった。
各表には、（着色皮膜が剥がれなかったマス目の数）／１００で示しており、着色皮膜が剥がれなかったマス目の数が大きいほど着色皮膜の密着性が高いことを示している。 (Adhesion evaluation)
A notch of 10 × 10 squares (100 squares in total) was made on the surface of the test piece with a cutter, and the number of squares in which the colored film was not peeled off when the cellophane tape (registered trademark) was attached and peeled off was counted. The size of one square was length x width = 1 mm x 1 mm.
In each table, it is indicated by (the number of squares in which the colored film did not peel off) / 100, and it is shown that the larger the number of squares in which the colored film did not peel off, the higher the adhesion of the colored film.

実施例１〜９３及び比較例１〜１０について、試験条件及び評価結果を表１〜９に示す。 The test conditions and evaluation results for Examples 1 to 93 and Comparative Examples 1 to 10 are shown in Tables 1 to 9.

以上の結果から、実施例１〜９３のように、テルル若しくはテルル化合物、又はこれらの塩を含む金属表面処理液によれば、良好な処理効率で金属表面を灰色系の色調に着色することができることが確認された。
一方、比較例１〜１０のように、金属表面処理液がテルル若しくはテルル化合物、又はこれらの塩を含まないと、金属表面を灰色系の色調に着色することができないことが確認された。 From the above results, as in Examples 1 to 93, according to the tellurium or tellurium compound, or the metal surface treatment liquid containing salts thereof, the metal surface can be colored in a grayish color with good treatment efficiency. It was confirmed that it could be done.
On the other hand, as in Comparative Examples 1 to 10, it was confirmed that the metal surface could not be colored in a grayish color unless the metal surface treatment liquid contained tellurium, a tellurium compound, or a salt thereof.

Claims (18)

テルル若しくはテルル化合物、又はこれらの塩を含む金属表面処理液。 A metal surface treatment solution containing tellurium or tellurium compounds, or salts thereof. 前記テルル若しくはテルル化合物、又はこれらの塩が、一酸化テルル、二酸化テルル、三酸化テルル、亜テルル酸、テルル酸、四塩化テルル、テルル化ジメチル、若しくはこれらの塩、又はこれらの組み合わせである請求項１に記載の金属表面処理液。 Claims that the tellurium or tellurium compound, or salts thereof, are tellurium monoxide, tellurium dioxide, tellurium trioxide, tellurous acid, telluric acid, tellurium tetrachloride, dimethyl telluride, or salts thereof, or a combination thereof. Item 2. The metal surface treatment liquid according to Item 1. 前記テルル若しくはテルル化合物、又はこれらの塩の合計含有量が、０．５〜１００ｇ／Ｌである請求項１又は２に記載の金属表面処理液。 The metal surface treatment liquid according to claim 1 or 2, wherein the total content of the tellurium or the tellurium compound or a salt thereof is 0.5 to 100 g / L. 更に、無機酸若しくはその塩を含む請求項１〜３のいずれか一項に記載の金属表面処理液。 The metal surface treatment liquid according to any one of claims 1 to 3, further comprising an inorganic acid or a salt thereof. 前記無機酸若しくはその塩が、硫酸、硝酸、塩酸、リン酸、若しくはこれらの塩、又はこれらの組み合わせである請求項４に記載の金属表面処理液。 The metal surface treatment liquid according to claim 4, wherein the inorganic acid or a salt thereof is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, or a salt thereof, or a combination thereof. 前記無機酸若しくはその塩の合計含有量が、１〜２００ｇ／Ｌである請求項４又は５に記載の金属表面処理液。 The metal surface treatment liquid according to claim 4 or 5, wherein the total content of the inorganic acid or a salt thereof is 1 to 200 g / L. 更に、有機硫黄化合物若しくはその塩を含む請求項１〜６のいずれか一項に記載の金属表面処理液。 The metal surface treatment liquid according to any one of claims 1 to 6, further comprising an organic sulfur compound or a salt thereof. 前記有機硫黄化合物若しくはその塩が、チオ尿素、二酸化チオ尿素、チオジグリコール、ジメチルチオ尿素、チオリンゴ酸、ジチオジグリコール酸、ジメチルスルホキシド、メタンスルホン酸、ｐ−トルエンスルホン酸、ｐ−フェノールスルホン酸、チオシアン酸、システイン、メチオニン、若しくはこれらの塩、又はこれらの組み合わせである請求項７に記載の金属表面処理液。 The organic sulfur compound or a salt thereof is thiourea, thiourea dioxide, thiodiglycol, dimethylthiourea, thiocyanate, dithiodiglycolic acid, dimethylsulfoxide, methanesulfonic acid, p-toluenesulfonic acid, p-phenolsulfonic acid, The metal surface treatment liquid according to claim 7, which is a thiocyanic acid, cysteine, methionine, a salt thereof, or a combination thereof. 前記有機硫黄化合物若しくはその塩の合計含有量が、０．１〜５０ｇ／Ｌである請求項７又は８に記載の金属表面処理液。 The metal surface treatment liquid according to claim 7 or 8, wherein the total content of the organic sulfur compound or a salt thereof is 0.1 to 50 g / L. 更に、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩を含む請求項１〜９のいずれか一項に記載の金属表面処理液。 The metal surface treatment liquid according to any one of claims 1 to 9, further comprising a carboxylic acid, a hydroxycarboxylic acid, or a salt thereof. 前記カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩が、ギ酸、酢酸、プロピオン酸、乳酸、リンゴ酸、クエン酸、シュウ酸、グルコン酸、マロン酸、コハク酸、安息香酸、ピルビン酸、グリオキシル酸、ニトリロ三酢酸、エチレンジアミン四酢酸、若しくはこれらの塩、又はこれらの組み合わせである請求項１０に記載の金属表面処理液。 The carboxylic acid or hydroxycarboxylic acid, or salts thereof, are formic acid, acetic acid, propionic acid, lactic acid, malic acid, citric acid, oxalic acid, gluconic acid, malonic acid, succinic acid, benzoic acid, pyruvate, glyoxylic acid, The metal surface treatment solution according to claim 10, which is nitrilotriacetic acid, ethylenediaminetetraacetic acid, or a salt thereof, or a combination thereof. 前記カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量が、０．５〜１００ｇ／Ｌである請求項１０又は１１に記載の金属表面処理液。 The metal surface treatment liquid according to claim 10 or 11, wherein the total content of the carboxylic acid or hydroxycarboxylic acid, or a salt thereof is 0.5 to 100 g / L. 更に、オキソ酸若しくはその塩を含む請求項１〜１２のいずれか一項に記載の金属表面処理液。 The metal surface treatment liquid according to any one of claims 1 to 12, further comprising an oxo acid or a salt thereof. 前記オキソ酸若しくはその塩が、過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭素酸、炭酸、ホウ酸、若しくはこれらの塩、又はこれらの組み合わせである請求項１３に記載の金属表面処理液。 The metal according to claim 13, wherein the oxo acid or a salt thereof is perchloric acid, chloric acid, chloric acid, hypochlorous acid, bromic acid, carbonic acid, boric acid, or a salt thereof, or a combination thereof. Surface treatment liquid. 前記オキソ酸若しくはその塩の合計含有量が、０．５〜１００ｇ／Ｌである請求項１３又は１４に記載の金属表面処理液。 The metal surface treatment liquid according to claim 13 or 14, wherein the total content of the oxo acid or a salt thereof is 0.5 to 100 g / L. 処理対象の金属が、アルミニウム、アルミニウム合金、銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金、ニッケル、ニッケル合金、マグネシウム、及びマグネシウム合金からなる群から選択される少なくとも１種である請求項１〜１５のいずれか一項に記載の金属表面処理液。 Claim that the metal to be treated is at least one selected from the group consisting of aluminum, aluminum alloys, copper, copper alloys, iron, iron alloys, zinc, zinc alloys, nickel, nickel alloys, magnesium, and magnesium alloys. The metal surface treatment liquid according to any one of 1 to 15. 請求項１〜１６のいずれか一項に記載の金属表面処理液を使用して、金属に対して着色を行う工程を含む金属表面処理方法。 A metal surface treatment method comprising a step of coloring a metal using the metal surface treatment liquid according to any one of claims 1 to 16. 前記金属に対して着色を行う工程において、前記金属を前記金属表面処理液に１０℃〜８０℃で１０秒〜２０分間浸漬することで前記金属を着色する請求項１７に記載の金属表面処理方法。 The metal surface treatment method according to claim 17, wherein in the step of coloring the metal, the metal is colored by immersing the metal in the metal surface treatment liquid at 10 ° C. to 80 ° C. for 10 seconds to 20 minutes. ..
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