JP2008144225A - Metal blackening liquid, treatment method for blackening metal with the use of the metal blackening liquid, and product blackened with the treatment method for blackening metal - Google Patents
Metal blackening liquid, treatment method for blackening metal with the use of the metal blackening liquid, and product blackened with the treatment method for blackening metal Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 171
- 239000002184 metal Substances 0.000 title claims abstract description 170
- 239000007788 liquid Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 50
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010949 copper Substances 0.000 claims description 88
- 229910052802 copper Inorganic materials 0.000 claims description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- 239000010409 thin film Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 230000003667 anti-reflective effect Effects 0.000 abstract 1
- 229920002799 BoPET Polymers 0.000 description 44
- 239000000243 solution Substances 0.000 description 29
- 238000011156 evaluation Methods 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000002390 adhesive tape Substances 0.000 description 9
- 230000008021 deposition Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- VXLPBEHPTWIBJR-UHFFFAOYSA-N chloro tellurohypochlorite Chemical compound Cl[Te]Cl VXLPBEHPTWIBJR-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- -1 methanesulfonic acid Chemical class 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002531 CuTe Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010947 jewellery metal Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 150000003497 tellurium Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Abstract
Description
本発明は、金属表面を黒化するための処理液、当該処理液を用いた金属表面の黒化処理方法、及び当該黒化処理方法を用いて製造した黒化処理品に関するものである。 The present invention relates to a treatment liquid for blackening a metal surface, a blackening treatment method for a metal surface using the treatment liquid, and a blackening treatment product manufactured using the blackening treatment method.
カメラ、ソーラーパネル、ディスプレイ用電磁波遮蔽フィルタ等の部品や日用品に使用される金属には、しばしば金属表面での光の反射を防止することを目的として、金属の表面に黒化層が形成される。
当該黒化層を形成するための黒化処理方法としては、黒ニッケルメッキ、すず−ニッケル合金メッキ、黒クロムメッキなどのメッキ法や、薬品で黒化する化成処理法が挙げられる。
電解メッキ法は電解する必要があり、経済性、薬品の使用量、処理時間などに問題があり、また、電解メッキ法により形成された黒化層は表面が金属光沢を有するため、反射防止性能が不十分なおそれがある。一方、化成処理法は電解する必要がなく、短時間で簡便に行うことができるという長所がある。
Metals used in parts such as cameras, solar panels, electromagnetic wave shielding filters for displays, and daily necessities often have a blackened layer on the metal surface to prevent light reflection on the metal surface. .
Examples of the blackening treatment method for forming the blackening layer include plating methods such as black nickel plating, tin-nickel alloy plating, and black chrome plating, and chemical conversion treatment methods for blackening with chemicals.
The electroplating method requires electrolysis, and there are problems in economic efficiency, chemical usage, processing time, etc. Also, the blackened layer formed by the electroplating method has a metallic luster, so antireflection performance May be insufficient. On the other hand, the chemical conversion treatment method has the advantage that it does not need to be electrolyzed and can be carried out easily in a short time.
化成処理に用いる金属黒化処理液としては、例えば、特許文献１に、テルルが溶解された塩酸溶液であり、該塩酸溶液中におけるテルルの濃度（酸化物換算濃度）が０．５〜１６重量％の範囲内にあり、塩酸濃度が９．５〜３６重量％の範囲内にあることを特徴とする銀、銅、金及びこれらの合金を黒化するための金属黒化処理液が開示されている。
特許文献１に開示されている黒化処理液は、宝飾品の金属の黒化処理用であり、一液性で、操作が簡単で、かつ安定である。
An example of the metal blackening treatment solution used for the chemical conversion treatment is a hydrochloric acid solution in which tellurium is dissolved in Patent Document 1, and the concentration of tellurium (oxide equivalent concentration) in the hydrochloric acid solution is 0.5 to 16 wt. %, And a blackening treatment liquid for blackening silver, copper, gold and alloys thereof characterized in that the hydrochloric acid concentration is in the range of 9.5 to 36% by weight. ing.
The blackening treatment liquid disclosed in Patent Document 1 is for the blackening treatment of jewelry metal, and is one-component, easy to operate, and stable.
しかし、本発明者らは特許文献１に開示されている黒化処理液について検討した結果、得られる黒化処理品の金属−黒化層間の密着性が十分でなく、更に黒化層が厚いために剥離しやすい場合があり、また、樹脂やガラス等の支持体上に直接積層された金属薄膜を処理する場合には、支持体−金属薄膜間の浸食（アンダーカット）が問題となる場合があるという知見を得た。更に、特許文献１に開示されている黒化処理液により形成された黒化層は、用途によっては光沢過剰であり、反射防止性能が不十分な場合がある。また、塩酸の濃度が高いため、作業環境が悪いという問題がある。
また、化成処理にアルカリ水溶液を用いる場合においても同様に、アンダーカットの問題が生じる場合がある。
However, as a result of examining the blackening treatment liquid disclosed in Patent Document 1, the present inventors have found that the resulting blackening treatment product has insufficient adhesion between the metal and the blackening layer, and the blackening layer is thicker. When the metal thin film directly laminated on the support such as resin or glass is processed, the erosion (undercut) between the support and the metal thin film becomes a problem. I got the knowledge that there is. Furthermore, the blackening layer formed by the blackening treatment liquid disclosed in Patent Document 1 is excessively glossy depending on the application, and the antireflection performance may be insufficient. Moreover, since the concentration of hydrochloric acid is high, there is a problem that the working environment is bad.
Similarly, when an alkaline aqueous solution is used for the chemical conversion treatment, an undercut problem may occur.
本発明は上記問題点を解消するためになされたものであり、金属表面に対して、短時間で容易に反射防止性能を有する黒化層を形成することが可能な黒化処理液、当該黒化処理液を用いた黒化処理方法、及び当該黒化処理方法を用いた黒化層の密着性に優れる黒化処理品を提供することを目的とする。 The present invention has been made to solve the above problems, and a blackening treatment liquid capable of forming a blackening layer having antireflection performance easily on a metal surface in a short time, the blackening treatment liquid. It is an object of the present invention to provide a blackening treatment method using a blackening treatment liquid and a blackening treatment product having excellent adhesion of a blackening layer using the blackening treatment method.
本発明者は、上記目的を達成すべく鋭意検討した結果、特定のテルル濃度及び塩酸濃度の金属黒化処理液を用いて金属の表面を処理することにより、上記目的を達成できることを見出し、本発明を完成させるに至った。
すなわち、本発明に係る金属黒化処理液は、テルルが溶解された塩酸溶液であり、該塩酸溶液中におけるテルルの濃度（酸化物換算濃度）が０．０１〜０．４５重量％であり、塩酸濃度が０．０５〜８重量％であることを特徴とする。
As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by treating a metal surface with a metal blackening solution having a specific tellurium concentration and hydrochloric acid concentration. The invention has been completed.
That is, the metal blackening treatment liquid according to the present invention is a hydrochloric acid solution in which tellurium is dissolved, and the concentration of tellurium (oxide equivalent concentration) in the hydrochloric acid solution is 0.01 to 0.45% by weight, The hydrochloric acid concentration is 0.05 to 8% by weight.
上記本発明の金属黒化処理液によれば、テルル濃度及び塩酸濃度が従来の処理液よりも低いため、従来の金属黒化処理液に比べて穏やかな条件で、かつ短時間に金属表面に黒化層を堆積させることができる。
上記本発明の金属黒化処理液を用いることにより、金属表面に黒化層が形成された黒化処理品は、黒化層の厚さが薄く、金属−黒化層間の密着性が高い。また、優れた反射防止性能を発揮する。
According to the above-described metal blackening treatment liquid of the present invention, the tellurium concentration and hydrochloric acid concentration are lower than those of the conventional treatment liquid. A blackening layer can be deposited.
By using the metal blackening treatment liquid of the present invention, a blackened product having a blackened layer formed on the metal surface has a thin blackened layer and high adhesion between the metal and blackened layer. In addition, it exhibits excellent antireflection performance.
上記本発明の金属黒化処理液は、更に、硫酸を含み、硫酸濃度が９０重量％以下であることが、黒濃度が高い黒化層を形成することができる点から好ましい。 The metal blackening treatment liquid of the present invention further contains sulfuric acid, and the sulfuric acid concentration is preferably 90% by weight or less from the viewpoint that a blackening layer having a high black concentration can be formed.
本発明に係る金属黒化処理方法は、上記金属黒化処理液に、金属の表面を接触させて黒化層を形成する工程を含むことを特徴とする。
上記本発明の金属黒化処理方法によれば、テルル濃度及び塩酸濃度が従来の処理液よりも低いため、従来の金属黒化処理液に比べて穏やかな条件で黒化層を金属表面に堆積させることができる。
上記本発明の金属黒化処理方法により得られる黒化処理品は、黒化層の厚さが薄く、金属−黒化層間の密着性が高い。また黒化処理面の反射防止性能に優れる。
The metal blackening treatment method according to the present invention includes a step of forming a blackening layer by bringing the metal surface into contact with the metal blackening treatment liquid.
According to the metal blackening treatment method of the present invention, since the tellurium concentration and the hydrochloric acid concentration are lower than those of the conventional treatment liquid, the blackening layer is deposited on the metal surface under mild conditions as compared with the conventional metal blackening treatment liquid. Can be made.
The blackened product obtained by the metal blackening treatment method of the present invention has a thin blackened layer and high adhesion between the metal and blackened layers. Moreover, it is excellent in the antireflection performance of the blackened surface.
前記金属は、イオン化傾向が銅と同等又はそれより大きい金属元素を含んでなることが、黒化処理後、金属表面の黒色外観が良好になり、処理面内で黒色の色調がムラなく安定化し、金属−黒化層の密着性が向上する点から好ましい。 The metal contains a metal element having an ionization tendency equal to or greater than that of copper. After the blackening treatment, the black appearance of the metal surface is improved, and the black color tone is stabilized uniformly in the treated surface. From the viewpoint of improving the adhesion of the metal-blackening layer.
本発明の金属黒化処理方法は、前記金属が薄膜である場合において、薄膜の支持体と薄膜との間の密着性に優れる点から特に好ましい。
本発明に係る黒化処理品は、上記金属黒化処理方法を用いて製造したものである。上記本発明の処理方法を用いて製造された黒化処理品は、従来の金属黒化処理方法よりも穏やかな条件で黒化層を堆積させることができるため、黒化層の厚さが薄く、金属−黒化層間の密着性が高い。また、黒化処理面の反射防止性能に優れる。
本発明に係る黒化処理品の黒化層には主に塩化テルルを含む。
The metal blackening treatment method of the present invention is particularly preferable because the adhesion between the thin film support and the thin film is excellent when the metal is a thin film.
The blackening treatment product according to the present invention is manufactured using the metal blackening treatment method. Since the blackened product manufactured using the processing method of the present invention can deposit the blackened layer under milder conditions than the conventional metal blackened method, the thickness of the blackened layer is thin. High adhesion between metal and blackened layer. Moreover, it is excellent in the antireflection performance of the blackened surface.
The blackened layer of the blackened product according to the present invention mainly contains tellurium chloride.
本発明によれば、テルル濃度及び塩酸濃度が従来の処理液よりも低いため、従来の金属黒化処理液に比べて穏やかな条件で、かつ短時間に金属表面に黒化層を堆積させることが可能な金属黒化処理液、及び当該黒化処理液を用いた金属黒化処理方法を提供することができる。
また、本発明によれば、上記金属黒化処理液及び金属黒化処理方法を用いて、厚さが薄く、金属−黒化層間の密着性が高く、また、優れた反射防止性能を有する黒化層が金属表面に形成された黒化処理品を提供することができる。
According to the present invention, since the tellurium concentration and hydrochloric acid concentration are lower than those of the conventional processing solution, the blackening layer is deposited on the metal surface in a short time under mild conditions as compared with the conventional metal blacking processing solution. And a metal blackening treatment method using the blackening treatment liquid can be provided.
Further, according to the present invention, the above-described metal blackening treatment liquid and metal blackening treatment method are used to reduce the thickness, provide high adhesion between the metal-blackening layers, and have excellent antireflection performance. It is possible to provide a blackening-treated product in which the blackening layer is formed on the metal surface.
１．黒化処理液
本発明にかかる金属黒化処理液は、テルルが溶解された塩酸溶液であり、該塩酸溶液中におけるテルルの濃度（酸化物換算濃度）が０．０１〜０．４５重量％であり、塩酸濃度が０．０５〜８重量％であることを特徴とする。
1. Blackening treatment liquid The metal blackening treatment liquid according to the present invention is a hydrochloric acid solution in which tellurium is dissolved, and the concentration of tellurium (oxide equivalent concentration) in the hydrochloric acid solution is 0.01 to 0.45% by weight. Yes, the hydrochloric acid concentration is 0.05 to 8% by weight.
以下、本発明に係る金属黒化処理液について、具体的に説明する。
本発明に係る金属黒化処理液は、テルルが溶解された塩酸溶液であり、このテルルの供給源として、酸化テルルを用いることが好ましい。本発明でテルル供給源として使用される酸化テルルは、ＴｅＯ2で表すことができる。
本発明の金属黒化処理液（１００重量％）中には、テルルは、酸化物換算で、０．０１〜０．４５重量％の範囲内の量、好ましくは０．０５〜０．４０重量％の量で含有されている。上記量のテルルを配合する。本発明の処理液は従来の処理液よりもテルル濃度が低いため、黒化層の堆積速度が小さくなり、薄く、金属−黒化層間の密着性が高い黒化層を堆積させることができる。
Hereinafter, the metal blackening treatment liquid according to the present invention will be specifically described.
The metal blackening treatment liquid according to the present invention is a hydrochloric acid solution in which tellurium is dissolved, and it is preferable to use tellurium oxide as a source of this tellurium. Tellurium oxide is used as tellurium source in the present invention can be represented by TeO 2.
In the metal blackening solution (100% by weight) of the present invention, tellurium is an amount in the range of 0.01 to 0.45% by weight, preferably 0.05 to 0.40% by weight in terms of oxide. % Content. Blend the above amount of tellurium. Since the treatment liquid of the present invention has a tellurium concentration lower than that of the conventional treatment liquid, the deposition rate of the blackened layer is reduced, and a blackened layer having a low adhesion and high adhesion between the metal-blackened layers can be deposited.
また、本発明では、テルルは塩酸に溶解した状態で処理液中に存在し、大変安定性がよく、金属黒化処理液を長時間放置した場合であっても配合物が析出しにくい。したがって、本発明の金属黒化処理液を一液型の処理剤とすることができる。更に、この一液型金属黒化処理液は、処理金属と接触させた後も、その安定性が低下しないので、繰り返し使用することができる。
テルルの配合量が０．４５重量％を超える場合は、黒化層の堆積速度が大きすぎて、金属表面に堆積する黒化層にはひびが入り、黒化層−金属間の密着性が不十分になるおそれがある。一方、テルルの配合量が０．０１重量％未満の場合は、黒化層−金属間の密着性は十分だが堆積速度が小さく、処理効率に劣るおそれがある。
本発明の金属黒化処理液に使用される酸化テルルとしては、工業的に提供される酸化テルルを使用することができるが、酸化テルルの純度が高いものを使用することが好ましく、純度９９〜１００％の酸化テルルを使用することが特に好ましい。
In the present invention, tellurium is present in the treatment liquid in a state dissolved in hydrochloric acid, has very good stability, and even when the metal blackening treatment liquid is allowed to stand for a long time, the compound is hardly precipitated. Therefore, the metal blackening treatment liquid of the present invention can be used as a one-pack type treatment agent. Furthermore, since the stability of the one-pack type metal blackening treatment liquid does not deteriorate even after being brought into contact with the treated metal, it can be used repeatedly.
When the amount of tellurium exceeds 0.45% by weight, the deposition rate of the blackened layer is too high, the blackened layer deposited on the metal surface is cracked, and the adhesion between the blackened layer and the metal is poor. May be insufficient. On the other hand, when the blending amount of tellurium is less than 0.01% by weight, the adhesion between the blackened layer and the metal is sufficient, but the deposition rate is small and the processing efficiency may be inferior.
As the tellurium oxide used in the metal blackening treatment liquid of the present invention, industrially provided tellurium oxide can be used, but it is preferable to use a tellurium oxide having a high purity, and a purity of 99 to It is particularly preferred to use 100% tellurium oxide.
酸化テルルを溶解する塩酸水溶液は、通常は３５％（以下、単に塩酸とも呼称する。）塩酸に水を配合することにより調製される。この塩酸水溶液中のＨＣｌ（塩化水素）濃度は、０．０５〜８重量％の範囲内にあり、好ましくは０．１〜２重量％、さらに好ましくは０．３〜１重量％である。このような濃度の塩酸水溶液を使用することにより、上記酸化テルルを完全に溶解することができる。また、処理する金属が支持体に直接積層された金属薄膜の場合には、支持体−金属薄膜間の浸食（アンダーカット）が発生することなく、十分な密着性を有する。
また、上記ＨＣｌ濃度の黒化処理液によれば、得られる黒化処理品は反射防止性能に優れる。本発明の黒化処理液のほうが、従来のＨＣｌ濃度が高い黒化処理液よりも処理後の金属の表面粗さは小さくなり、金属表面の粗面効果による反射防止性能が劣ると推測されたが、実際には本発明の黒化処理液により得られる黒化層の方が反射防止性能に優れている。この原因は明らかではないが、形成された黒化層の形状及び原子配列が異なることに起因するものと推測される。
An aqueous hydrochloric acid solution that dissolves tellurium oxide is usually prepared by blending water with 35% (hereinafter, simply referred to as hydrochloric acid) hydrochloric acid. The concentration of HCl (hydrogen chloride) in the aqueous hydrochloric acid solution is in the range of 0.05 to 8% by weight, preferably 0.1 to 2% by weight, and more preferably 0.3 to 1% by weight. By using an aqueous hydrochloric acid solution having such a concentration, the tellurium oxide can be completely dissolved. Further, when the metal to be treated is a metal thin film directly laminated on a support, there is sufficient adhesion without causing erosion (undercut) between the support and the metal thin film.
Further, according to the blackening treatment liquid having the HCl concentration, the obtained blackening treatment product is excellent in antireflection performance. It was speculated that the blackening treatment liquid of the present invention had a lower surface roughness of the metal after the treatment than the conventional blackening treatment liquid having a high HCl concentration, and the antireflection performance due to the rough surface effect of the metal surface was inferior. However, the blackening layer obtained by the blackening treatment liquid of the present invention is actually superior in antireflection performance. The cause of this is not clear, but is presumed to be due to the difference in the shape and atomic arrangement of the formed blackened layer.
塩酸水溶液中のＨＣｌ濃度が８重量％を超える場合は、支持体−金属薄膜間の密着性に劣り、アンダーカットが発生するおそれがある。特に、処理する金属が支持体に直接積層された金属薄膜の場合には、アンダーカットが発生しやすい。また、反射防止性能に劣る場合がある。
また、ＨＣｌ濃度が０．０５重量％未満の場合には酸化テルルを完全に溶解させることができないおそれがあり、その結果、金属表面における黒化層の堆積速度が小さくなり、処理効率に劣る場合がある。
When the HCl concentration in the hydrochloric acid aqueous solution exceeds 8% by weight, the adhesion between the support and the metal thin film is inferior and undercutting may occur. In particular, in the case of a metal thin film in which the metal to be treated is directly laminated on a support, undercut is likely to occur. Moreover, the antireflection performance may be inferior.
Also, if the HCl concentration is less than 0.05% by weight, tellurium oxide may not be completely dissolved. As a result, the deposition rate of the blackened layer on the metal surface is reduced, resulting in poor processing efficiency. There is.
尚、上記のような塩酸水溶液の他に、任意の無機酸及び有機酸を添加してもよい。
上記本発明の金属黒化処理液は、無機酸として硫酸を含有し、当該硫酸濃度が９０重量％以下であることが、黒濃度が高い黒化層を形成することができる点から好ましい。
硫酸濃度が９０重量％を超える場合、処理する金属が支持体に直接積層された金属薄膜の場合には、支持体−金属薄膜間の密着性に劣り、アンダーカットが発生するおそれがある。
上記硫酸濃度は、更に１０〜４５重量％、特に１５〜３０重量％であることが、処理時間を短くすることができ、また得られる黒化層の黒濃度に優れる点から好ましい。
In addition to the hydrochloric acid aqueous solution as described above, an arbitrary inorganic acid and organic acid may be added.
The metal blackening treatment liquid of the present invention preferably contains sulfuric acid as an inorganic acid, and the sulfuric acid concentration is preferably 90% by weight or less from the viewpoint that a blackening layer having a high black concentration can be formed.
When the sulfuric acid concentration exceeds 90% by weight, when the metal to be treated is a metal thin film directly laminated on a support, the adhesion between the support and the metal thin film is inferior, and undercutting may occur.
The sulfuric acid concentration is preferably 10 to 45% by weight, more preferably 15 to 30% by weight, because the treatment time can be shortened and the black density of the resulting blackened layer is excellent.
無機酸としては、上記硫酸の他、硝酸、リン酸等を用いることができる。また、有機酸としては、酢酸、蟻酸、プロピオン酸、蓚酸、安息香酸等の有機カルボン酸、メタンスルホン酸等の有機スルホン酸等を用いることができる。本発明の金属黒化処理液に上記塩酸及び硫酸以外の無機酸及び有機酸を含有させる場合は、必要に応じて０〜９０重量％程度含有させることができる。
また、本発明の金属黒化処理液には、テルルの溶解性を高めるための第三成分を添加してもよい。
As the inorganic acid, nitric acid, phosphoric acid and the like can be used in addition to the sulfuric acid. As the organic acid, organic carboxylic acids such as acetic acid, formic acid, propionic acid, succinic acid, and benzoic acid, organic sulfonic acids such as methanesulfonic acid, and the like can be used. When the metal blackening treatment liquid of the present invention contains an inorganic acid and an organic acid other than the hydrochloric acid and sulfuric acid, it can be contained in an amount of about 0 to 90% by weight as necessary.
Moreover, you may add the 3rd component for improving the solubility of tellurium to the metal blackening process liquid of this invention.
本発明の金属黒化処理液は、塩酸と水とを混合して塩酸水溶液を調製し、この塩酸水溶液に酸化テルルを配合して、酸化テルルを塩酸水溶液に完全に溶解させることにより調製することができる。 The metal blackening treatment solution of the present invention is prepared by mixing hydrochloric acid and water to prepare an aqueous hydrochloric acid solution, blending tellurium oxide with the aqueous hydrochloric acid solution, and completely dissolving the tellurium oxide in the aqueous hydrochloric acid solution. Can do.
２．黒化処理方法
本発明に係る黒化処理方法は、上記金属黒化処理液に、金属の表面を接触させて黒化層を形成する工程を含むことを特徴とする。
上記本発明の金属黒化処理方法によれば、テルル濃度及び塩酸濃度が従来の処理液よりも低く、従来の金属黒化処理液に比べて穏やかな条件で黒化層を金属表面に堆積させることができる。
上記本発明の金属黒化処理方法により得られる黒化処理品は、黒化層の厚さが薄く、金属−黒化層間の密着性が高い。また、黒化処理面の反射防止性能に優れる。
2. Blackening treatment method The blackening treatment method according to the present invention includes a step of forming a blackened layer by bringing a metal surface into contact with the metal blackening treatment liquid.
According to the above-described metal blackening treatment method of the present invention, the tellurium concentration and hydrochloric acid concentration are lower than those of the conventional treatment liquid, and the blackening layer is deposited on the metal surface under milder conditions than the conventional metal blackening treatment liquid. be able to.
The blackened product obtained by the metal blackening treatment method of the present invention has a thin blackened layer and high adhesion between the metal and blackened layers. Moreover, it is excellent in the antireflection performance of the blackened surface.
（被処理金属表面）
本発明の黒化処理方法は、カメラ、ソーラーパネル、電磁波遮蔽フィルタ等の部品や日用品に使用される金属の表面を処理して黒化層を形成し、当該金属表面に優れた反射防止性能を付与する。
上記金属は特に限定されるものではなく、金属に含まれる元素の種類は1種類でも2種類以上でもよいが、上記金属が、イオン化傾向が銅と同等又はそれより大きい金属元素を含んでなることが、黒化処理後の金属表面の黒色外観が良好になり、処理面内で黒色の色調がムラなく安定化し、金属−黒化層の密着性を向上させる点から好ましい。
(Metal surface to be treated)
The blackening treatment method of the present invention forms a blackened layer by treating the surface of a metal used in parts such as cameras, solar panels, electromagnetic wave shielding filters and daily necessities, and has excellent antireflection performance on the metal surface. Give.
The metal is not particularly limited, and the element contained in the metal may be one type or two or more types, but the metal contains a metal element having an ionization tendency equal to or greater than that of copper. However, it is preferable from the viewpoint that the black appearance of the metal surface after the blackening treatment is improved, the black color tone is stabilized uniformly in the treated surface, and the adhesion of the metal-blackened layer is improved.
イオン化傾向が銅と同等又はそれより大きい金属元素には、Ｆｅ、Ｓｎ、Ｎｉ、Ｚｎ、Ｐｂ、Ｃｕ、Ｍｇ、Ａｌ、Ｃｄ、Ｃｏ、Ｃｒ等が挙げられるが、その中でもＦｅ、Ｓｎ、Ｎｉ、Ｚｎ、Ｐｂ、Ｃｕが好ましく、特にＳｎ、Ｎｉ、Ｃｕが、上記黒色外観、色調、密着性の他、耐食性、導電性の点から好ましい。 Examples of metal elements having an ionization tendency equal to or greater than that of copper include Fe, Sn, Ni, Zn, Pb, Cu, Mg, Al, Cd, Co, and Cr. Among them, Fe, Sn, Ni, Zn, Pb, and Cu are preferable. In particular, Sn, Ni, and Cu are preferable from the viewpoint of corrosion resistance and conductivity in addition to the black appearance, color tone, and adhesion.
上記金属が２種類以上からなる合金としては、例えば真鍮（黄銅）が挙げられ、特にＣｕを７０〜８０重量％、Ｚｎを２０〜３０重量％配合した真鍮を好ましく用いることができる。 As an alloy composed of two or more kinds of metals, for example, brass (brass) can be used, and in particular, brass containing 70 to 80% by weight of Cu and 20 to 30% by weight of Zn can be preferably used.
本発明の黒化処理方法における金属表面を有する被処理体は金属そのものであってもよいし、支持体上に金属薄膜を積層した積層体であってもよい。また、被処理体の形状は特に限定されるものではなく、任意の３次元形状を有するものであってもよいし、支持体上に金属薄膜を積層した平板状のものであってもよい。
本発明の黒化処理方法は、前記金属が支持体に直接積層された厚さ０．１〜５．０μｍ程度の金属薄膜である場合において、黒化処理中に金属薄膜−支持体間の侵食（アンダーカット）が発生せず、黒化処理品の金属薄膜−支持体間の密着性に優れる点から特に有効である。
The object to be treated having a metal surface in the blackening treatment method of the present invention may be a metal itself or a laminate in which a metal thin film is laminated on a support. Further, the shape of the object to be processed is not particularly limited, and may be an arbitrary three-dimensional shape, or may be a flat plate shape in which a metal thin film is laminated on a support.
In the blackening treatment method of the present invention, when the metal is a metal thin film having a thickness of about 0.1 to 5.0 μm directly laminated on a support, the erosion between the metal thin film and the support is performed during the blackening treatment. (Undercut) does not occur, and is particularly effective from the viewpoint of excellent adhesion between the metal thin film and the support of the blackened product.
尚、上記支持体の材質及び形状は、少なくとも機械的強度が弱い金属薄膜を補強することができ、本発明で使用する黒化処理液に対して腐食性を有していないものであればよく、黒化処理品の用途に応じて適当なものを選択して用いることができる。また、支持体−金属間は任意の接着剤を介して接着積層された金属薄膜の場合も、直接積層された金属薄膜と同様にアンダーカットが発生せず、密着性が優れる点から有効である。 The material and shape of the support may be any material as long as it can reinforce a metal thin film having a weak mechanical strength and does not have corrosiveness to the blackening treatment liquid used in the present invention. Depending on the application of the blackened product, an appropriate one can be selected and used. In addition, even in the case of a metal thin film bonded and laminated between the support and the metal via an arbitrary adhesive, undercut does not occur as in the case of the directly laminated metal thin film, and it is effective from the viewpoint of excellent adhesion. .
（接触）
上記金属黒化処理液と金属とが接触することによって、金属の表面に主に塩化テルル（ＴｅＣｌ２）からなる黒化層を形成することができる。接触中は、例えば金属として銅を使用する場合、接触界面で下記溶解反応（ｉ）〜（ｉｉｉ）、及び下記析出反応（ｉｖ）〜（ｖｉｉｉ）が起きていることが予想される。
(contact)
By bringing the metal blackening treatment liquid into contact with the metal, a blackened layer mainly made of tellurium chloride (TeCl 2 ) can be formed on the surface of the metal. During contact, for example, when copper is used as the metal, the following dissolution reactions (i) to (iii) and the following precipitation reactions (iv) to (viii) are expected to occur at the contact interface.
ＴｅＯ２＋４ＨＣｌ → Ｔｅ４＋ ＋ ４Ｃｌ− ＋ ２Ｈ２Ｏ （ｉ） TeO 2 + 4HCl → Te 4+ + 4Cl − + 2H 2 O (i)
Ｔｅ４＋ ＋ ２Ｃｌ− ＋ ２ｅ− → ＴｅＣｌ２ （ｉｖ）
Ｔｅ４＋ ＋ ４ｅ− → Ｔｅ （ｖ）
Ｔｅ４＋ ＋ ４Ｃｌ− → ＴｅＣｌ４ （ｖｉ）
Ｃｕ２＋ ＋ ２Ｃｌ− → ＣｕＣｌ２ （ｖｉｉ）
Ｃｕ＋ ＋ Ｃｌ− → ＣｕＣｌ （ｖｉｉｉ）
Te 4+ + 2Cl − + 2e − → TeCl 2 (iv)
Te 4+ + 4e − → Te (v)
Te 4+ + 4Cl − → TeCl 4 (vi)
Cu 2+ + 2Cl − → CuCl 2 (vii)
Cu + + Cl − → CuCl (viii)
析出が予想される化合物の色は、ＴｅＣｌ２が黒色、Ｔｅが銀灰色〜灰色、ＴｅＣｌ４が黄色、ＣｕＣｌ２が白色、ＣｕＣｌが褐黄色である。黒化層の色調から、黒化層には主にＴｅＣｌ２が含まれていると推定されるが、条件によってはＴｅ、ＴｅＣｌ４、ＣｕＣｌ２、ＣｕＣｌのうち少なくとも一つが含まれる。更に空気中では、これらが酸化した化合物、即ちＴｅＯ２、ＣｕＯ、ＣｕＯ２、或いはＣｕ２Ｔｅ、ＣｕＴｅ及びこれらの酸化物なども含まれる可能性がある。 The color of the compound expected to precipitate is TeCl 2 is black, Te is silver gray to gray, TeCl 4 is yellow, CuCl 2 is white, and CuCl is brown yellow. From the color tone of the blackened layer, it is estimated that the blackened layer mainly contains TeCl 2, but at least one of Te, TeCl 4 , CuCl 2 , and CuCl is included depending on conditions. Further, in the air, compounds in which they are oxidized, that is, TeO 2 , CuO, CuO 2 , Cu 2 Te, CuTe, and oxides thereof may be included.
上記金属黒化処理液と金属との接触方法は特に限定されないが、例えば、ディッピング（浸漬）、カーテンコート、掛け流しなどの方法で、金属表面と接触する。
本発明における黒化処理液と金属表面との接触温度は常温でよく、好ましくは１０〜４０℃の範囲内の温度である。このように本発明の黒化処理液は、特に加熱する必要がなく、常温で金属表面と接触させることにより、金属の表面を安定に黒化処理することができる。
The method for contacting the metal blackening treatment liquid with the metal is not particularly limited. For example, the metal blackening solution is brought into contact with the metal surface by a method such as dipping (immersion), curtain coating, or pouring.
The contact temperature between the blackening treatment liquid and the metal surface in the present invention may be room temperature, and is preferably within the range of 10 to 40 ° C. As described above, the blackening treatment liquid of the present invention does not need to be particularly heated, and can be stably blackened on the metal surface by bringing it into contact with the metal surface at room temperature.
上記のような温度条件において、金属と黒化処理液との接触時間は、通常１５分以下、好ましくは１秒〜２分、特に好ましくは５秒〜３０秒である。このように本発明の金属黒化処理方法によれば、非常に短時間で金属の表面を黒化することができる。
なお、接触温度及び接触時間は上記範囲に限定されるものではなく、金属黒化処理液の濃度及び金属元素の組成に応じて、変更することができる。
Under the temperature conditions as described above, the contact time between the metal and the blackening treatment liquid is usually 15 minutes or less, preferably 1 second to 2 minutes, and particularly preferably 5 seconds to 30 seconds. Thus, according to the metal blackening treatment method of the present invention, the metal surface can be blackened in a very short time.
The contact temperature and contact time are not limited to the above ranges, and can be changed according to the concentration of the metal blackening solution and the composition of the metal element.
上記本発明の黒化処理により形成される黒化層は、主に塩化テルル（ＴｅＣｌ２）からなる。黒化層の詳細については、３．黒化処理品において説明する。 The blackening layer formed by the blackening treatment of the present invention is mainly composed of tellurium chloride (TeCl 2 ). For details of the blackened layer, see 3. This will be described in the blackened product.
３．黒化処理品
本発明に係る黒化処理品は、上記金属黒化処理方法を用いて製造したものである。
上記本発明の処理方法を用いて製造された黒化処理品は、従来の金属黒化処理方法よりも穏やかな条件で黒化層を堆積させることができるため、黒化層の厚さが薄く、金属−黒化層間の密着性が高く、黒化処理面の反射防止性能に優れる。
3. Blackening treatment product The blackening treatment product according to the present invention is manufactured using the metal blackening treatment method.
Since the blackened product manufactured using the processing method of the present invention can deposit the blackened layer under milder conditions than the conventional metal blackened method, the thickness of the blackened layer is thin. The adhesion between the metal and the blackening layer is high, and the antireflection performance of the blackened surface is excellent.
（黒化層）
黒化層は、外光を吸収させて金属表面の反射を防止することを目的として、上記金属黒化処理方法により金属の表面に形成される層であり、主に塩化テルル（ＴｅＣｌ２）からなる。
本発明の黒化処理品は、黒化層が金属の表面に積層されることにより、優れた反射防止性能を有する。この黒化層は典型的には一般的な膜状であるが、必ずしも連続する膜に限定されるものではなく、島状に分散した二次元配置を持つ不連続膜であってもよい。
(Blackening layer)
The blackening layer is a layer formed on the surface of the metal by the above-described metal blackening treatment method for the purpose of absorbing external light and preventing reflection of the metal surface, and is mainly made of tellurium chloride (TeCl 2 ). Become.
The blackened product of the present invention has excellent antireflection performance by the blackened layer being laminated on the metal surface. The blackening layer is typically a general film shape, but is not necessarily limited to a continuous film, and may be a discontinuous film having a two-dimensional arrangement dispersed in an island shape.
金属表面に積層される黒化層は主に塩化テルル（ＴｅＣｌ２）からなり、その色は通常黒色であるが、黒色には限定されず、反射防止機能を十分発揮できる暗色であればよい。黒化層の厚みは０．０５〜１μｍの範囲内であることが好ましい。
上記範囲を超える場合には、黒化層の強度及び密着性が不十分なおそれがあり、上記範囲未満の場合には、黒濃度や反射防止性能が不十分なおそれがある。
The blackened layer laminated on the metal surface is mainly made of tellurium chloride (TeCl 2 ), and its color is usually black, but it is not limited to black and may be any dark color that can sufficiently exhibit the antireflection function. The thickness of the blackening layer is preferably in the range of 0.05 to 1 μm.
When it exceeds the above range, the strength and adhesion of the blackened layer may be insufficient, and when it is less than the above range, the black density and antireflection performance may be insufficient.
以下、本発明について実施例を示して具体的に説明する。これらの記載により本発明を制限するものではない。尚、実施例中、部は特に特定しない限り重量部を表す。
〔性能評価方法〕
下記、各実施例及び比較例に対して、以下の点を評価した。
Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention. In the examples, parts represent parts by weight unless otherwise specified.
[Performance evaluation method]
The following points were evaluated for the following examples and comparative examples.
（１）金属板の黒化層の外観及び金属−黒化層間の密着性評価
下記実施例及び比較例の黒化処理を行った金属板（ハルセル板）について、黒濃度の確認のため目視にて黒濃度及び反射防止性能の点から黒化層の外観を確認した。反射防止性能については、蛍光灯を映り込ませ、光沢の程度を確認した。
また、実施例及び比較例の黒化処理を行い、1日放置したハルセル板の表面に、黒化層の表面に粘着テープ（ニチバン社製、商品名「ＣＴ４０５ＡＰ−１８」）を貼り、更に剥離した後の外観を目視にて確認し、金属−黒化層間の密着性を評価した。評価基準は下記の通りである。
(1) Appearance evaluation of blackened layer of metal plate and adhesion between metal and blackened layer About the metal plate (Hull cell plate) subjected to blackening treatment in the following examples and comparative examples, it was visually checked for confirmation of black density. The appearance of the blackened layer was confirmed from the viewpoint of black density and antireflection performance. Regarding the antireflection performance, a fluorescent lamp was reflected and the degree of gloss was confirmed.
Also, the blackening treatment of the examples and comparative examples was performed, and the adhesive tape (trade name “CT405AP-18”, manufactured by Nichiban Co., Ltd.) was applied to the surface of the blackened layer on the surface of the Hull cell plate left for one day, and further peeled After the appearance, the appearance was visually confirmed, and the adhesion between the metal and the blackened layer was evaluated. The evaluation criteria are as follows.
［外観（黒濃度）評価基準］
○：黒色外観。
△：グレー外観。
×：黒色層の堆積が認められない。
[Appearance (black density) evaluation criteria]
○: Black appearance.
Δ: Gray appearance.
X: Black layer deposition is not recognized.
［外観（反射防止性能）評価基準］
○：半光沢〜光沢なし。
△：光沢あり。
×：黒色層の堆積が認められない。
[Appearance (Antireflection Performance) Evaluation Criteria]
○: Semi-gloss to no gloss.
Δ: Glossy.
X: Black layer deposition is not recognized.
［金属−黒化層間の密着性評価基準］
○：下地の金属が目視で確認されない。
×：下地の金属が目視で確認できる。
[Evaluation criteria for adhesion between metal and blackened layer]
○: The underlying metal is not visually confirmed.
X: Underlying metal can be confirmed visually.
（２）金属／ＰＥＴフィルム積層体のエッチング性（金属−ＰＥＴフィルム間の密着性）評価
下記実施例及び比較例の黒化処理を行った金属／ＰＥＴフィルム積層体について、金属−ＰＥＴフィルム間の密着性の確認のため、黒化層の外観を目視にて確認した。外観上問題が認められない積層体については、1日放置した後に、（１）と同様に黒化層表面に粘着テープを貼り、更に剥離した後の外観を目視で確認し、金属−ＰＥＴフィルム間の密着性を評価した。
(2) Etching property of metal / PET film laminate (adhesion between metal and PET film) Evaluation About metal / PET film laminate subjected to blackening treatment in the following examples and comparative examples, between metal and PET film For confirmation of adhesion, the appearance of the blackened layer was visually confirmed. For laminates that do not have any problems in appearance, after standing for 1 day, the adhesive tape is applied to the surface of the blackened layer in the same manner as in (1), and the appearance after peeling is visually confirmed, and the metal-PET film The adhesion between them was evaluated.
［金属−ＰＥＴフィルム間の密着性評価基準］
○：粘着テープを剥離した後に金属層側から見て、ＰＥＴフィルムが目視で確認されない。
×：粘着テープを剥離した後に金属層側から見て、ＰＥＴフィルムが目視で確認できる。
[Evaluation criteria for adhesion between metal and PET film]
○: The PET film is not visually confirmed when viewed from the metal layer side after the adhesive tape is peeled off.
X: After peeling off the adhesive tape, the PET film can be visually confirmed when viewed from the metal layer side.
＜実施例１＞
金属黒化処理液として、二酸化テルル０．２５重量％（テルル濃度として０．２重量％）、塩酸０．４５重量％の水溶液（温度：２５℃）を用い、当該処理液に銅板（（株）山本鍍金試験器製、商品名「ハルセル陰極板 銅板 Ｂ−６０−Ｐ０５」）、及びＣｕスパッタ処理したポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡製、商品名「Ａ４３００」）のＣｕスパッタ層上に、硫酸銅めっき（１．５Ａ／ｄｍ２、６．７分間、２５℃）により２μｍの銅層を堆積させた積層体（以下、Ｃｕ／ＰＥＴフィルム積層体と呼称する）を1５分間浸漬し、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
外観、金属−黒化層間の密着性及び金属−ＰＥＴフィルム間密着性の評価結果はいずれも良好だった。
<Example 1>
An aqueous solution (temperature: 25 ° C.) of 0.25% by weight of tellurium dioxide (0.2% by weight of tellurium) and 0.45% by weight of hydrochloric acid was used as the metal blackening treatment solution, and a copper plate ((stock) ) On the Cu sputtered layer of a polyethylene terephthalate (PET) film (trade name “A4300”, manufactured by Toyobo Co., Ltd.), manufactured by Yamamoto Kakin Tester, trade name “Hull Cell Cathode Plate Copper Plate B-60-P05”) A laminate in which a copper layer of 2 μm was deposited by copper sulfate plating (1.5 A / dm 2 , 6.7 minutes, 25 ° C.) (hereinafter referred to as a Cu / PET film laminate) was immersed for 15 minutes to obtain a copper plate A blackening layer was deposited on the surface and the copper surface of the Cu / PET film laminate, and further washed with water.
The evaluation results of the appearance, the adhesion between the metal-blackening layer and the adhesion between the metal and the PET film were all good.
＜実施例２＞
金属黒化処理液として、二酸化テルル０．２５重量％（テルル濃度として０．２重量％）、塩酸０．４５重量％、硫酸２０重量％の水溶液（温度：２５℃）を用い、当該処理液に実施例１と同様の銅板を３０秒間、Ｃｕ／ＰＥＴフィルム積層体を２分間浸漬し、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
外観、金属−黒化層間の密着性、及び金属−ＰＥＴフィルム間密着性の評価結果はいずれも良好だった。
図１（Ａ）に、黒化処理を施した銅板の、密着性評価後の黒化層の表面、及び密着性評価に用いた粘着テープを撮影した写真を示す。また、図２（Ｂ）に、実施例２の黒化処理を施したＣｕ／ＰＥＴフィルム積層体の銅表面の、密着性評価後の黒化層の表面を撮影した写真を示す。銅板表面及び積層体の銅表面に堆積した黒化層の剥離は認められず、粘着テープへの黒化層の付着も認められなかった。
<Example 2>
As the metal blackening treatment solution, an aqueous solution (temperature: 25 ° C.) containing 0.25% by weight of tellurium dioxide (0.2% by weight as tellurium concentration), 0.45% by weight of hydrochloric acid and 20% by weight of sulfuric acid was used. The copper plate similar to Example 1 was immersed for 30 seconds and the Cu / PET film laminate was immersed for 2 minutes to deposit a blackening layer on the copper plate surface and the copper surface of the Cu / PET film laminate, and further washed with water.
The evaluation results of the appearance, the adhesion between the metal-blackening layers, and the adhesion between the metal and the PET film were all good.
The photograph which image | photographed the adhesive tape used for the surface of the blackening layer after adhesive evaluation of the copper plate which performed the blackening process to FIG. 1 (A), and adhesive evaluation is shown. Moreover, the photograph which image | photographed the surface of the blackening layer after adhesive evaluation of the copper surface of the Cu / PET film laminated body which performed the blackening process of Example 2 in FIG.2 (B) is shown. No peeling of the blackened layer deposited on the copper plate surface and the copper surface of the laminate was observed, and no adhesion of the blackened layer to the adhesive tape was observed.
＜実施例３＞
金属黒化処理液として、二酸化テルル０．５重量％（テルル濃度として０．４重量％）、塩酸０．４５重量％、硫酸１５重量％の水溶液（温度：２５℃）を用い、当該処理液に実施例１と同様の銅板及びＣｕ／ＰＥＴフィルム積層体を1分間浸漬し、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
外観、金属−黒化層間の密着性、及び金属−ＰＥＴフィルム間密着性の評価結果はいずれも良好だった。
<Example 3>
As a metal blackening treatment solution, an aqueous solution (temperature: 25 ° C.) of 0.5% by weight of tellurium dioxide (0.4% by weight as tellurium concentration), 0.45% by weight of hydrochloric acid and 15% by weight of sulfuric acid was used. Then, the same copper plate and Cu / PET film laminate as in Example 1 were immersed for 1 minute to deposit a blackened layer on the copper plate surface and the copper surface of the Cu / PET film laminate, and further washed with water.
The evaluation results of the appearance, the adhesion between the metal-blackening layers, and the adhesion between the metal and the PET film were all good.
＜実施例４＞
実施例２の処理液の代わりに、二酸化テルル０．０２重量％（テルル濃度として０．０１６重量％）、塩酸０．４５重量％、硫酸２０重量％の水溶液（温度：２５℃）を用いたこと以外は実施例２と同様にして、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
外観、金属−黒化層間の密着性、及び金属−ＰＥＴフィルム間密着性の評価結果はいずれも良好だった。
<Example 4>
Instead of the treatment liquid of Example 2, an aqueous solution (temperature: 25 ° C.) of 0.02% by weight of tellurium dioxide (0.016% by weight as the tellurium concentration), 0.45% by weight of hydrochloric acid, and 20% by weight of sulfuric acid was used. Except for this, a blackening layer was deposited on the copper plate surface and the copper surface of the Cu / PET film laminate in the same manner as in Example 2, and further washed with water.
The evaluation results of the appearance, the adhesion between the metal-blackening layers, and the adhesion between the metal and the PET film were all good.
＜実施例５＞
実施例２の処理液の代わりに、二酸化テルル０．２５重量％（テルル濃度として０．２重量％）、塩酸５．０重量％、硫酸２０重量％の水溶液（温度：２５℃）を用いたこと以外は実施例２と同様にして、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
外観、金属−黒化層間の密着性、及び金属−ＰＥＴフィルム間密着性の評価結果はいずれも良好だった。
<Example 5>
Instead of the treatment liquid of Example 2, an aqueous solution (temperature: 25 ° C.) of 0.25 wt% tellurium dioxide (0.2 wt% tellurium concentration), 5.0 wt% hydrochloric acid and 20 wt% sulfuric acid was used. Except for this, a blackening layer was deposited on the copper plate surface and the copper surface of the Cu / PET film laminate in the same manner as in Example 2, and further washed with water.
The evaluation results of the appearance, the adhesion between the metal-blackening layers, and the adhesion between the metal and the PET film were all good.
＜実施例６＞
実施例２の処理液の代わりに、二酸化テルル０．２５重量％（テルル濃度として０．２重量％）、塩酸０．１重量％、硫酸２５重量％の水溶液（温度：２５℃）を用いたこと以外は実施例２と同様にして、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
外観、金属−黒化層間の密着性、及び金属−ＰＥＴフィルム間密着性の評価結果はいずれも良好だった。
<Example 6>
Instead of the treatment liquid of Example 2, an aqueous solution (temperature: 25 ° C.) containing 0.25 wt% tellurium dioxide (0.2 wt% tellurium concentration), 0.1 wt% hydrochloric acid, and 25 wt% sulfuric acid was used. Except for this, a blackening layer was deposited on the copper plate surface and the copper surface of the Cu / PET film laminate in the same manner as in Example 2, and further washed with water.
The evaluation results of the appearance, the adhesion between the metal-blackening layers, and the adhesion between the metal and the PET film were all good.
＜実施例７＞
実施例２の処理液の代わりに、二酸化テルル０．２５重量％（テルル濃度として０．２重量％）、塩酸０．４５重量％、硫酸７５重量％の水溶液（温度：２５℃）を用いたこと以外は実施例２と同様にして、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
外観、金属−黒化層間の密着性、及び金属−ＰＥＴフィルム間密着性の評価結果はいずれも良好だった。
<Example 7>
Instead of the treatment liquid of Example 2, an aqueous solution (temperature: 25 ° C.) of 0.25% by weight of tellurium dioxide (0.2% by weight as tellurium concentration), 0.45% by weight of hydrochloric acid, and 75% by weight of sulfuric acid was used. Except for this, a blackening layer was deposited on the copper plate surface and the copper surface of the Cu / PET film laminate in the same manner as in Example 2, and further washed with water.
The evaluation results of the appearance, the adhesion between the metal-blackening layers, and the adhesion between the metal and the PET film were all good.
＜比較例１＞
実施例２の処理液の代わりに、二酸化テルル０．５重量％（テルル濃度として０．４重量％）、塩酸９．５重量％、酢酸０．５重量％の水溶液（温度：２５℃）を用い、当該処理液に実施例２と同様の銅板を３０秒間、Ｃｕ／ＰＥＴフィルム積層体を２分間浸漬したこと以外は実施例２と同様にして、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
銅板表面の黒化層は水洗により一部剥離し、外観及び金属−黒化層間の密着性が不十分だった。また、金属−ＰＥＴフィルム間密着性は、下地ＰＥＴが観察され、不十分だった。
図２（Ａ）に、比較例１の黒化処理を施した銅板表面の黒化層の、密着性評価後の黒化層の表面、及び密着性評価に用いた粘着テープを撮影した写真を示す。銅板表面に堆積した黒化層の剥離が認められ、粘着テープへの黒化層の付着が認められた。
また、図２（Ｂ）に、比較例１の黒化処理を施したＣｕ／ＰＥＴフィルム積層体の黒化層側の表面を撮影した写真を示す。銅表面に堆積した黒化層は、水洗工程において剥離した。
<Comparative Example 1>
Instead of the treatment liquid of Example 2, an aqueous solution (temperature: 25 ° C.) of 0.5% by weight of tellurium dioxide (0.4% by weight as tellurium concentration), 9.5% by weight of hydrochloric acid, and 0.5% by weight of acetic acid. The copper plate surface and the copper of the Cu / PET film laminate were used in the same manner as in Example 2 except that the same copper plate as in Example 2 was immersed in the treatment solution for 30 seconds and the Cu / PET film laminate was immersed for 2 minutes. A blackened layer was deposited on the surface and further washed with water.
The blackened layer on the surface of the copper plate was partially peeled off by washing with water, and the appearance and the adhesion between the metal and blackened layers were insufficient. Moreover, the base PET was observed and the metal-PET film adhesion was insufficient.
The photograph which image | photographed the adhesive tape used for FIG. 2 (A) the surface of the blackening layer after the adhesive evaluation of the blackened layer of the copper plate surface which performed the blackening process of the comparative example 1, and adhesiveness evaluation. Show. Peeling of the blackened layer deposited on the copper plate surface was observed, and adhesion of the blackened layer to the adhesive tape was observed.
Moreover, the photograph which image | photographed the surface by the side of the blackening layer of the Cu / PET film laminated body which performed the blackening process of the comparative example 1 in FIG.2 (B) is shown. The blackened layer deposited on the copper surface was peeled off in the water washing step.
＜比較例２＞
実施例２の処理液の代わりに、二酸化テルル０．４８重量％（テルル濃度として重量０．３８４％）、塩酸０．４５重量％、硫酸２０重量％の水溶液（温度：２５℃）を用い、当該処理液に実施例２と同様の銅板を１分間、Ｃｕ／ＰＥＴフィルム積層体を２分間浸漬したこと以外は実施例２と同様にして、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
銅板表面の黒化層は水洗により一部剥離し、外観及び金属−黒化層間の密着性が不十分だった。また、エッチング性評価は、水洗後も下地ＰＥＴが観察されなかったが、テープを用いた密着性評価を行ったところ、金属−ＰＥＴフィルム間の密着性が不十分であった。
<Comparative example 2>
Instead of the treatment liquid of Example 2, an aqueous solution (temperature: 25 ° C.) of tellurium dioxide 0.48% by weight (tellurium concentration: 0.384%), hydrochloric acid 0.45% by weight, sulfuric acid 20% by weight, In the same manner as in Example 2 except that the same copper plate as in Example 2 was immersed in the treatment solution for 1 minute and the Cu / PET film laminate was immersed in 2 minutes on the copper plate surface and the copper surface of the Cu / PET film laminate. A blackened layer was deposited and further washed with water.
The blackened layer on the surface of the copper plate was partially peeled off by washing with water, and the appearance and the adhesion between the metal and blackened layers were insufficient. In addition, in the evaluation of the etching property, the underlying PET was not observed even after washing with water. However, when the adhesion evaluation using a tape was performed, the adhesion between the metal and the PET film was insufficient.
＜比較例３＞
実施例２の処理液の代わりに、二酸化テルル０．００８重量％（テルル濃度として０．００６４重量％）、塩酸０．４５重量％、硫酸２０重量％の水溶液（温度：２５℃）を用い、当該処理液に実施例２と同様の銅板を１分間、Ｃｕ／ＰＥＴフィルム積層体を２分間浸漬したこと以外は実施例２と同様にして、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層の堆積を試みた。
銅板及びＣｕ／ＰＥＴフィルム積層体の銅表面への黒化層の堆積が認められなかった。
<Comparative Example 3>
Instead of the treatment liquid of Example 2, an aqueous solution (temperature: 25 ° C.) of 0.008% by weight of tellurium dioxide (0.0064% by weight as tellurium concentration), 0.45% by weight of hydrochloric acid, and 20% by weight of sulfuric acid was used. In the same manner as in Example 2 except that the same copper plate as in Example 2 was immersed in the treatment solution for 1 minute and the Cu / PET film laminate was immersed in 2 minutes on the copper plate surface and the copper surface of the Cu / PET film laminate. An attempt was made to deposit a blackened layer.
The deposition of the blackened layer on the copper surface of the copper plate and Cu / PET film laminate was not observed.
＜比較例４＞
実施例２の処理液の代わりに、二酸化テルル０．２５重量％（テルル濃度として０．２重量％）、塩酸８．５重量％、硫酸２０重量％の水溶液（温度：２５℃）を用い、当該処理液に実施例２と同様の銅板を１分間、Ｃｕ／ＰＥＴフィルム積層体を２分間浸漬したこと以外は実施例２と同様にして、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
銅板表面の黒化層は、金属−黒化層間の密着性は良好だったが、グレーの外観であり反射防止性能は不十分だった。また、金属−ＰＥＴフィルム間の密着性は良好だった。
<Comparative Example 4>
Instead of the treatment liquid of Example 2, an aqueous solution (temperature: 25 ° C.) of 0.25% by weight of tellurium dioxide (0.2% by weight as tellurium concentration), 8.5% by weight of hydrochloric acid, and 20% by weight of sulfuric acid was used. In the same manner as in Example 2 except that the same copper plate as in Example 2 was immersed in the treatment solution for 1 minute and the Cu / PET film laminate was immersed in 2 minutes on the copper plate surface and the copper surface of the Cu / PET film laminate. A blackened layer was deposited and further washed with water.
The blackened layer on the copper plate surface had good adhesion between the metal and blackened layer, but had a gray appearance and insufficient antireflection performance. Moreover, the adhesiveness between metal-PET films was good.
＜比較例５＞
実施例２の処理液の代わりに、二酸化テルル０．２５重量％（テルル濃度として０．２重量％）、塩酸０．０４重量％、硫酸２０重量％の水溶液（温度：２５℃）を用い、当該処理液に実施例２と同様の銅板を１分間、Ｃｕ／ＰＥＴフィルム積層体を２分間浸漬したこと以外は実施例２と同様にして、銅板表面及びＣｕ／ＰＥＴフィルム積層体の銅表面に黒化層を堆積させ、更に水洗を行った。
銅板表面の黒化層は、金属−黒化層間の密着性は良好だったが、黒色表面に色ムラが認められた。また、エッチング性評価は、金属−ＰＥＴフィルム間に一部剥離が認められ、密着性が不十分だった。
<Comparative Example 5>
Instead of the treatment liquid of Example 2, an aqueous solution (temperature: 25 ° C.) of 0.25% by weight of tellurium dioxide (0.2% by weight as the tellurium concentration), 0.04% by weight of hydrochloric acid, and 20% by weight of sulfuric acid was used. In the same manner as in Example 2 except that the same copper plate as in Example 2 was immersed in the treatment solution for 1 minute and the Cu / PET film laminate was immersed in 2 minutes on the copper plate surface and the copper surface of the Cu / PET film laminate. A blackened layer was deposited and further washed with water.
The blackened layer on the copper plate surface had good adhesion between the metal and blackened layer, but color unevenness was observed on the black surface. Further, in the evaluation of etching property, partial peeling was observed between the metal-PET films, and the adhesion was insufficient.
表１に、実施例及び比較例で得られた黒化処理物の性能評価結果をまとめて示す。 Table 1 summarizes the performance evaluation results of the blackened products obtained in the examples and comparative examples.
Claims (7)
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| JP2011082211A (en) * | 2009-10-02 | 2011-04-21 | Dainippon Printing Co Ltd | Transparent conductive material and method of manufacturing the same |
| CN105088209A (en) * | 2015-09-11 | 2015-11-25 | 江苏振宇环保科技有限公司 | Preparation method of inky and brown chromate-free passivation solution |
| KR20160114597A (en) * | 2014-01-31 | 2016-10-05 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive substrate, conductive substrate laminate, method for producing conductive substrate, and method for producing conductive substrate laminate |
| CN112111736A (en) * | 2019-06-21 | 2020-12-22 | 日本表面化学株式会社 | Metal surface treatment liquid and metal surface treatment method |
| US11807943B2 (en) | 2019-06-21 | 2023-11-07 | Ykk Corporation | Aluminum alloy fastening member and method for producing aluminum alloy fastening member |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011082211A (en) * | 2009-10-02 | 2011-04-21 | Dainippon Printing Co Ltd | Transparent conductive material and method of manufacturing the same |
| KR20160114597A (en) * | 2014-01-31 | 2016-10-05 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive substrate, conductive substrate laminate, method for producing conductive substrate, and method for producing conductive substrate laminate |
| KR102461565B1 (en) * | 2014-01-31 | 2022-10-31 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive substrate, conductive substrate laminate, method for producing conductive substrate, and method for producing conductive substrate laminate |
| CN105088209A (en) * | 2015-09-11 | 2015-11-25 | 江苏振宇环保科技有限公司 | Preparation method of inky and brown chromate-free passivation solution |
| CN105088209B (en) * | 2015-09-11 | 2017-06-30 | 南通亿能彩钢板有限公司 | A kind of preparation method of black brown chromium-free passivation liquid |
| CN112111736A (en) * | 2019-06-21 | 2020-12-22 | 日本表面化学株式会社 | Metal surface treatment liquid and metal surface treatment method |
| JP2021001372A (en) * | 2019-06-21 | 2021-01-07 | 日本表面化学株式会社 | Metal surface treatment liquid, and metal surface treatment method |
| JP7347751B2 (en) | 2019-06-21 | 2023-09-20 | 日本表面化学株式会社 | Metal surface treatment method |
| US11807943B2 (en) | 2019-06-21 | 2023-11-07 | Ykk Corporation | Aluminum alloy fastening member and method for producing aluminum alloy fastening member |
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