JP7432355B2 - Base material with film - Google Patents
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- JP7432355B2 JP7432355B2 JP2019230207A JP2019230207A JP7432355B2 JP 7432355 B2 JP7432355 B2 JP 7432355B2 JP 2019230207 A JP2019230207 A JP 2019230207A JP 2019230207 A JP2019230207 A JP 2019230207A JP 7432355 B2 JP7432355 B2 JP 7432355B2
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- 239000000463 material Substances 0.000 title claims description 67
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 9
- 125000004437 phosphorous atom Chemical group 0.000 claims description 9
- 239000002344 surface layer Substances 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 38
- 239000003795 chemical substances by application Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 238000000576 coating method Methods 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 101001108245 Cavia porcellus Neuronal pentraxin-2 Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
特許法第３０条第２項適用 日本マグネシウム協会第１９回表面処理分科会例会、マグネシウム合金の表面処理の技術動向 開催日 平成３０年１２月２１日Application of Article 30, Paragraph 2 of the Patent Act Japan Magnesium Association 19th Surface Treatment Subcommittee Regular Meeting, Technical Trends in Magnesium Alloy Surface Treatment Date held: December 21, 2018
本発明は、表層にマグネシウム合金を含む基材の表面又は表面上にアルミニウム原子、マグネシウム原子及びりん原子を含む皮膜を有する基材に関する。 The present invention relates to a substrate having a surface layer containing a magnesium alloy or a coating containing aluminum atoms, magnesium atoms, and phosphorus atoms on the surface of the substrate.
耐食性が劣ることで知られているマグネシウム合金部材には、従来、化成処理による化成皮膜を設けて、耐食性を付与することが行われている。
例えば特許文献１には、リン酸イオンとフッ化物イオンとを含有するマグネシウム合金用黒色化成処理液が開示されており、当該マグネシウム合金用黒色化成処理液を用いることにより、裸耐食性、塗装密着性、塗装耐食性に優れ、均一に黒色の化成皮膜をマグネシウム合金の表面に形成することができる、と記載されている。
Magnesium alloy members known to have poor corrosion resistance have conventionally been provided with a chemical conversion coating by chemical conversion treatment to impart corrosion resistance.
For example, Patent Document 1 discloses a black chemical conversion treatment liquid for magnesium alloys containing phosphate ions and fluoride ions, and by using the black chemical conversion treatment liquid for magnesium alloys, bare corrosion resistance and paint adhesion are improved. , it is described that the coating has excellent corrosion resistance and can form a uniform black chemical conversion film on the surface of the magnesium alloy.
一方、特許文献２には、マグネシウム合金材の表面皮膜中のＡｌ原子数／（Ｍｇ原子数＋Ａｌ原子数）を０．１５以上とすることで表面導電性を向上できることが開示されている。 On the other hand, Patent Document 2 discloses that surface conductivity can be improved by setting the number of Al atoms/(number of Mg atoms+number of Al atoms) in the surface film of a magnesium alloy material to 0.15 or more.
マグネシウム合金材を適用する場面によっては、光反射を伴うムラのある外観が問題になる場合がある。例えばカメラ鏡筒やヘッドアップディスプレイなどの光学部材では、黒色化成皮膜であっても色ムラがあることや光反射があることで、ゴースト現象が発生する場合や、画像の質の劣化を引き起こす場合など、があった。
本発明は、色ムラがなく、光反射が抑えられた良好な外観を呈し、且つ耐食性に優れた皮膜を有する基材を提供するものである。
Depending on the application of the magnesium alloy material, uneven appearance accompanied by light reflection may become a problem. For example, in optical components such as camera barrels and head-up displays, even with black chemical conversion coatings, there may be color unevenness or light reflection, which may cause ghost phenomena or deterioration of image quality. And so on.
The present invention provides a substrate having a film that is free from color unevenness, exhibits a good appearance with suppressed light reflection, and has excellent corrosion resistance.
本発明者らは、上記課題を解決すべく研究をすすめ、表層にマグネシウム合金を含む基材の表面又は表面上にアルミニウム原子、マグネシウム原子及びりん原子を含む化成皮膜を形成し、化成皮膜中のカルシウム量、アルミニウム量、及びマグネシウム量を特定の範囲内とすることで、色ムラがなく、光反射が抑えられた良好な外観を呈し、且つ耐食性に優れた皮膜を有する基材を提供できることを見出した。 The present inventors conducted research to solve the above problems, and formed a chemical conversion film containing aluminum atoms, magnesium atoms, and phosphorus atoms on the surface of a base material containing a magnesium alloy in the surface layer, and By setting the amount of calcium, aluminum, and magnesium within specific ranges, it is possible to provide a base material that has a good appearance with no uneven color, suppressed light reflection, and a film with excellent corrosion resistance. I found it.
本発明は、表層にマグネシウム合金を含む基材の表面又は表面上にアルミニウム原子、マグネシウム原子及びりん原子を含む皮膜を有し、前記皮膜におけるカルシウムの含有率は０．５原子％以下であり、アルミニウム原子数／（マグネシウム原子数＋アルミニウム原子数）が０．３０以上０．９０以下の範囲内である、皮膜を有する基材である。
また、前記皮膜は、マンガンを０．３原子％以上３．０原子％以下の範囲内で含んでいてもよい。
The present invention has a coating containing aluminum atoms, magnesium atoms, and phosphorus atoms on the surface of a base material containing a magnesium alloy in the surface layer, and the content of calcium in the coating is 0.5 at% or less, The base material has a film in which the number of aluminum atoms/(the number of magnesium atoms+the number of aluminum atoms) is within the range of 0.30 or more and 0.90 or less.
Further, the film may contain manganese in a range of 0.3 atomic % or more and 3.0 atomic % or less.
本発明により、色ムラがなく、光反射が抑えられた良好な外観を呈し、且つ耐食性に優れた皮膜を有する基材が提供される。 ADVANTAGE OF THE INVENTION The present invention provides a base material that has a film that is free from color unevenness, exhibits a good appearance with suppressed light reflection, and has excellent corrosion resistance.
≪皮膜を有する基材≫
本発明の一実施形態は、皮膜を有する基材である。本実施形態の皮膜を有する基材は、表層にマグネシウム合金を含む基材の表面又は表面上にアルミニウム原子、マグネシウム原子及びりん原子を含む皮膜を有し、前記皮膜におけるカルシウムの含有率が０．５原子％以下であり、アルミニウム原子数／（マグネシウム原子数＋アルミニウム原子数）が０．３０以上０．９０以下の範囲内である。上記基材における皮膜は、色ムラがなく、光反射が抑えられた良好な外観を有し、且つ耐食性に優れる。
≪Base material with film≫
One embodiment of the invention is a substrate with a coating. The base material having a film of the present embodiment has a film containing aluminum atoms, magnesium atoms, and phosphorus atoms on the surface of the base material containing a magnesium alloy in its surface layer, or a film containing aluminum atoms, magnesium atoms, and phosphorus atoms, and the content of calcium in the film is 0. It is 5 atomic % or less, and the number of aluminum atoms/(number of magnesium atoms + number of aluminum atoms) is within the range of 0.30 or more and 0.90 or less. The film on the base material has a good appearance with no uneven color, suppressed light reflection, and excellent corrosion resistance.
皮膜を有する基材は、表層にマグネシウム合金を含む基材の表面又は表面上に皮膜を有する。基材の表層に存在するマグネシウム合金の表面又は表面上に皮膜が設けられていればよく、該マグネシウム合金の表面又は表面上の一部に皮膜が設けられていても、該マグネシウム合金の表面又は表面上の全部に皮膜が設けられていてもよい。 A base material having a film has a film on the surface of or on the surface of a base material containing a magnesium alloy in the surface layer. It is sufficient that a film is provided on the surface or surface of the magnesium alloy present in the surface layer of the base material, and even if a film is provided on the surface or a part of the surface of the magnesium alloy, A coating may be provided over the entire surface.
＜基材＞
基材は、その表層にマグネシウム合金を含む基材であればよく、基材全体がマグネシウム合金からなる形態であってもよく、コア金属をマグネシウム合金のシェルで覆うコアシェル形態であってもよい。
基材の形状は特に限定されるものではなく、板状であってよく、棒状であってよく、帯状であってよく、管状であってよく、柱状であってよく、中空状であってよい。また、必要に応じ、切削、研削、ブラスト、研磨、穴あけ等の加工がされていてもよい。
基材の製造方法は特に限定されず、鋳造により製造されてもよく、ダイカストにより製造されてもよいが、ダイカストにより製造された基材であることが好ましい。
<Base material>
The base material may be any base material as long as its surface layer contains a magnesium alloy, and the entire base material may be made of a magnesium alloy, or may be of a core-shell type in which a core metal is covered with a shell of a magnesium alloy.
The shape of the base material is not particularly limited, and may be plate-shaped, rod-shaped, band-shaped, tubular, columnar, or hollow. . Moreover, processing such as cutting, grinding, blasting, polishing, and drilling may be performed as necessary.
The manufacturing method of the base material is not particularly limited, and the base material may be manufactured by casting or die casting, but it is preferable that the base material is manufactured by die casting.
基材の表層に含まれるマグネシウム合金は、マグネシウムを含む合金であれば特に限定されず、マグネシウムが主成分であること、すなわち合金中にマグネシウムを５０質量％以上含むことが好ましい。マグネシウムとともに合金を構成するその他金属成分としては、アルミニウム、亜鉛、ジルコニウム、マンガン、ケイ素、銅、ニッケル、鉄等が挙げられる。マグネシウム合金を構成するその他金属成分の含有量は特段限定されないが、アルミニウムを含む場合には１．０質量％以上であってよく、３．０質量％以上であってよく、５．０質量％以上であってよく、７．０質量％以上であってよく、９．０質量％以上含むことが好ましい。上限は特に限定されず、通常１５質量％以下である。また亜鉛を含む場合には０．５質量％以上含むことが好ましく、１５質量％以下含むことが好ましい。
マグネシウム合金の具体例としては、ＡＺ９２、ＡＺ９１、ＡＺ８０、ＡＺ６３、ＡＺ６１、ＡＺ３１、ＡＭ１００、ＡＭ６０、ＡＭ５０、ＡＭ２０、ＡＳ４１、ＡＳ２１、ＡＥ４２などが挙げられる。
The magnesium alloy contained in the surface layer of the base material is not particularly limited as long as it is an alloy containing magnesium, and it is preferable that magnesium is the main component, that is, the alloy contains 50% by mass or more of magnesium. Other metal components constituting the alloy with magnesium include aluminum, zinc, zirconium, manganese, silicon, copper, nickel, iron, and the like. The content of other metal components constituting the magnesium alloy is not particularly limited, but when aluminum is included, it may be 1.0% by mass or more, 3.0% by mass or more, and 5.0% by mass. The content may be 7.0% by mass or more, and preferably 9.0% by mass or more. The upper limit is not particularly limited and is usually 15% by mass or less. When zinc is contained, it is preferably contained at 0.5% by mass or more, and preferably at most 15% by mass.
Specific examples of magnesium alloys include AZ92, AZ91, AZ80, AZ63, AZ61, AZ31, AM100, AM60, AM50, AM20, AS41, AS21, AE42, and the like.
＜皮膜＞
皮膜は、アルミニウム原子、マグネシウム原子及びりん原子を含む。
皮膜中に含まれるアルミニウム原子及びマグネシウム原子は、アルミニウム原子数／（マグネシウム原子数＋アルミニウム原子数）が０．３０以上０．９０以下の範囲内であり、下限が０．３５以上であってよく、０．４０以上であってよい。また上限は０．８５以下であってよく、０．８０以下であってよい。
皮膜中のＡｌ及びＭｇの総含有率の下限値は、５％であってもよく、１０％であってもよく、１５％であってもよい。また、該含有率の上限値は、５０％であってもよく、４５％であってもよく、４０％であってもよく、３５％であってもよく、３０％であってもよく、２５％であってもよく、２０％であってもよい。
<Film>
The film contains aluminum atoms, magnesium atoms, and phosphorus atoms.
The aluminum atoms and magnesium atoms contained in the film have the number of aluminum atoms/(number of magnesium atoms + number of aluminum atoms) in a range of 0.30 or more and 0.90 or less, and the lower limit may be 0.35 or more. , 0.40 or more. Moreover, the upper limit may be 0.85 or less, and may be 0.80 or less.
The lower limit of the total content of Al and Mg in the film may be 5%, 10%, or 15%. Further, the upper limit of the content may be 50%, 45%, 40%, 35%, 30%, It may be 25% or 20%.
皮膜中に含まれるりん原子の含有率は特に限定されないが、５原子％以上１５原子％以
下の範囲内であることが好ましく、７原子％以上１０原子％以下の範囲内であることがより好ましい。
皮膜中にはカルシウムが含まれてもよいが、カルシウムの含有率は０．５原子％以下であり、０．１原子％以下であることが好ましく、カルシウムが含まれないことがより好ましい。
皮膜中にはマンガンが含まれてもよく、マンガンが含まれる場合その含有率は特に限定されないが、０．３原子％以上３．０原子％以下の範囲内であることが好ましく、０．５原子％以上２．５原子％以下の範囲内であることがより好ましい。
なお、皮膜中の元素分析は、皮膜を有する基材の断面を作製し、走査型電子顕微鏡／エネルギー分散型Ｘ線分光分析によって実施できる。元素分析の結果から、上記皮膜中に含まれる原子の含有率を算出できる。
The content of phosphorus atoms contained in the film is not particularly limited, but it is preferably within the range of 5 at % or more and 15 at % or less, and more preferably within the range of 7 at % or more and 10 at % or less. .
Although calcium may be contained in the film, the content of calcium is 0.5 atomic % or less, preferably 0.1 atomic % or less, and more preferably no calcium is contained.
Manganese may be included in the film, and if manganese is included, its content is not particularly limited, but it is preferably within the range of 0.3 atomic % or more and 3.0 atomic % or less, and 0.5 atomic % or less. More preferably, the content is in the range of at least 2.5 at %.
Note that elemental analysis in the film can be carried out by preparing a cross section of the base material having the film and performing scanning electron microscopy/energy dispersive X-ray spectroscopy. From the results of elemental analysis, the content of atoms contained in the film can be calculated.
皮膜中におけるアルミニウム原子、マグネシウム原子、リン原子等の形態は特に限定されず、塩の形態であってよく、酸化物の形態であってよく、金属錯体の形態であってもよい。
また、基材と皮膜との間に、マグネシウム合金に含まれる元素の、酸化物又は水酸化物の皮膜を有してもよく、有さなくてもよい。
The forms of aluminum atoms, magnesium atoms, phosphorus atoms, etc. in the film are not particularly limited, and may be in the form of salts, oxides, or metal complexes.
Furthermore, a film of an oxide or hydroxide of an element contained in the magnesium alloy may or may not be present between the base material and the film.
＜皮膜を有する基材の製造方法＞
基材の表面又は表面上に皮膜を形成する方法は特に限定されないが、基材と化成処理剤とを接触させることで、皮膜を基材の表面又は表面上に形成することができる。化成処理剤は、基材の表面又は表面上に所望の皮膜を形成できるものであれば特に限定されず、例えばミリオン化学株式会社製のグランダーＭＣ－５０００建浴剤を用い、常法に従って基材と接触させることで、本実施形態の皮膜を有する基材を得ることができる。なお、上記、アルミニウム原子数／（マグネシウム原子数＋アルミニウム原子数）は、上記化成処理剤と基材とを接触させる時間を調整すること、基材と接触させる上記化成処理剤の濃度を調整すること、などにより所望の範囲内とすることができる。
<Method for manufacturing base material with film>
Although the method of forming a film on or on the surface of a base material is not particularly limited, a film can be formed on or on the surface of a base material by bringing the base material into contact with a chemical conversion treatment agent. The chemical conversion treatment agent is not particularly limited as long as it can form a desired film on or on the surface of the base material. For example, using Grander MC-5000 bath building agent manufactured by Million Chemical Co., Ltd. A base material having a film of this embodiment can be obtained by contacting with the film. In addition, the above-mentioned number of aluminum atoms/(number of magnesium atoms + number of aluminum atoms) is determined by adjusting the time for which the chemical conversion treatment agent is brought into contact with the base material, and by adjusting the concentration of the chemical conversion treatment agent that is brought into contact with the base material. It can be set within a desired range by, for example,
＜皮膜を有する基材の物性＞
本実施形態の皮膜を有する基材は、光反射が抑えられた基材である。具体的には、以下の分光反射率測定において、測定波長３００～１０００ｎｍの全領域で分光反射率が５％以下であることが好ましく、４％以下であることがより好ましい。
分光反射率測定は、株式会社島津製作所製紫外可視赤外分光光度計ＳｏｌｉｄＳｐｅｃ－３７００ＤＵＶを用いて実施できる。入射光は８°とし、拡散反射率と正反射率を加算して測定することができる。
<Physical properties of base material with film>
The base material having the film of this embodiment is a base material with suppressed light reflection. Specifically, in the following spectral reflectance measurement, the spectral reflectance is preferably 5% or less, more preferably 4% or less over the entire measurement wavelength range of 300 to 1000 nm.
Spectral reflectance measurement can be performed using an ultraviolet-visible-infrared spectrophotometer SolidSpec-3700DUV manufactured by Shimadzu Corporation. The incident light is set at 8°, and the measurement can be performed by adding the diffuse reflectance and the specular reflectance.
＜用途＞
本実施形態の皮膜を有する基材は、カメラ鏡筒やヘッドアップディスプレイなどの光学部材に好ましく適用できるが、これらの用途に限られるわけではなく、その他マグネシウム合金を用いる用途に適用してもよい。
<Application>
The base material having the film of this embodiment can be preferably applied to optical members such as camera barrels and head-up displays, but is not limited to these uses, and may be applied to other uses using magnesium alloys. .
以下、本発明を具体的な実施例を用いて説明するが、本発明は以下の実施例によって限定されるものではない。 Hereinafter, the present invention will be explained using specific examples, but the present invention is not limited to the following examples.
基材として、矩形のＡＺ６１Ｄ材（７．５ｃｍ×１０ｃｍ×０．２ｃｍ）を用いた。基材に対し、アルカリ脱脂［グランダファイナーＭＧ－１５ＳＸ ミリオン化学株式会社製：１５０ｇ／Ｌ、及びグランダファイナー添加剤Ｆ２１：５ｇ／Ｌ、７０℃、浸漬時間５分］ののち、酸洗［グランダファイナーＭＧ－１０４ＳＸ ミリオン化学株式会社製、２８ｇ／Ｌ、６０℃、浸漬時間１分］を実施した。なお、アルカリ脱脂及び酸洗のそれぞれ
の工程後に水洗を実施した。その後、表１に示す化成処理剤に基材を３００秒間浸漬し、８０℃で１０分乾燥させて皮膜を有する基材を得た。なお、基材を浸漬した際の化成処理剤の温度は９０℃であった。また、表中のグランダー名の化成処理剤は、ミリオン化学株式会社製である。
A rectangular AZ61D material (7.5 cm x 10 cm x 0.2 cm) was used as the base material. After alkaline degreasing [Grandafiner MG-15SX manufactured by Million Kagaku Co., Ltd.: 150g/L and Grandafiner additive F21: 5g/L, 70°C, immersion time 5 minutes], the base material was pickled [Grandafiner MG-104SX, manufactured by Million Kagaku Co., Ltd., 28 g/L, 60° C., immersion time 1 minute]. Note that water washing was performed after each step of alkaline degreasing and pickling. Thereafter, the base material was immersed in the chemical conversion treatment agent shown in Table 1 for 300 seconds and dried at 80° C. for 10 minutes to obtain a base material having a film. Note that the temperature of the chemical conversion treatment agent when the base material was immersed was 90°C. In addition, the chemical conversion treatment agent named Grander in the table is manufactured by Million Chemical Co., Ltd.
基材及び化成処理剤に基材を浸漬する時間を変更した以外は、実施例１と同様の方法で、実施例２の皮膜を有する基材を製造した。具体的には、基材としてＡＺ９１Ｄ材を用いて、基材を１８０秒間化成処理剤に浸漬した。 A substrate having a film of Example 2 was produced in the same manner as in Example 1, except that the substrate and the time for immersing the substrate in the chemical conversion treatment agent were changed. Specifically, an AZ91D material was used as the base material, and the base material was immersed in the chemical conversion treatment agent for 180 seconds.
化成処理剤に基材を浸漬する時間を変更した以外は実施例２と同様の方法で、実施例３の皮膜を有する基材を製造した。具体的には、基材を３００秒間化成処理剤に浸漬した。 A substrate having the film of Example 3 was produced in the same manner as in Example 2, except that the time for immersing the substrate in the chemical conversion treatment agent was changed. Specifically, the base material was immersed in the chemical conversion treatment agent for 300 seconds.
化成処理剤に基材を浸漬する時間を変更した以外は実施例２と同様の方法で、実施例４の皮膜を有する基材を製造した。具体的には、基材を４２０秒間化成処理剤に浸漬した。 A substrate having the film of Example 4 was produced in the same manner as in Example 2 except that the time for immersing the substrate in the chemical conversion treatment agent was changed. Specifically, the base material was immersed in the chemical conversion treatment agent for 420 seconds.
化成処理剤に基材を浸漬する時間を変更した以外は実施例２と同様の方法で、実施例５の皮膜を有する基材を製造した。具体的には、基材を５４０秒間化成処理剤に浸漬した。 A substrate having the film of Example 5 was produced in the same manner as in Example 2, except that the time for immersing the substrate in the chemical conversion treatment agent was changed. Specifically, the base material was immersed in the chemical conversion treatment agent for 540 seconds.
化成処理剤に基材を浸漬する時間を変更した以外は実施例２と同様の方法で、実施例６の皮膜を有する基材を製造した。具体的には、基材を７２０秒間化成処理剤に浸漬した。 A substrate having the film of Example 6 was produced in the same manner as in Example 2, except that the time for immersing the substrate in the chemical conversion treatment agent was changed. Specifically, the base material was immersed in the chemical conversion treatment agent for 720 seconds.
化成処理剤を表１に示すとおり変更した以外は実施例２と同様の方法で、実施例７の皮膜を有する基材を製造した。 A base material having the film of Example 7 was produced in the same manner as in Example 2 except that the chemical conversion treatment agent was changed as shown in Table 1.
化成処理剤を表１に示すとおり変更した以外は実施例２と同様の方法で、実施例８の皮膜を有する基材を製造した。 A base material having the film of Example 8 was produced in the same manner as in Example 2 except that the chemical conversion treatment agent was changed as shown in Table 1.
化成処理剤を表１に示すとおり変更した以外は実施例２と同様の方法で、実施例９の皮膜を有する基材を製造した。 A base material having the film of Example 9 was produced in the same manner as in Example 2 except that the chemical conversion treatment agent was changed as shown in Table 1.
化成処理剤を表１に示すとおり変更した以外は実施例２と同様の方法で、実施例１０の皮膜を有する基材を製造した。 A base material having a film of Example 10 was produced in the same manner as in Example 2 except that the chemical conversion treatment agent was changed as shown in Table 1.
化成処理剤を表１に示すとおり変更した以外は実施例２と同様の方法で、実施例１１の皮膜を有する基材を製造した。 A base material having the film of Example 11 was produced in the same manner as in Example 2 except that the chemical conversion treatment agent was changed as shown in Table 1.
化成処理剤を表１に示すとおり変更した以外は実施例２と同様の方法で、比較例１の皮膜を有する基材を製造した。なお、基材を浸漬した際の化成処理剤の温度は３５℃であった。 A base material having a film of Comparative Example 1 was produced in the same manner as in Example 2 except that the chemical conversion treatment agent was changed as shown in Table 1. Note that the temperature of the chemical conversion treatment agent when the base material was immersed was 35°C.
化成処理剤を表１に示すとおり変更した以外は実施例２と同様の方法で、比較例２の皮膜を有する基材を製造した。 A base material having a film of Comparative Example 2 was produced in the same manner as in Example 2 except that the chemical conversion treatment agent was changed as shown in Table 1.
化成処理剤を表１に示すとおり変更し、乾燥工程を加えたこと以外は実施例２と同様の方法で、比較例３の皮膜を有する基材を製造した。具体的には、比較例３の１の化成処理剤を用いて、基材を１８０秒間浸漬（化成処理剤の温度は５０℃）したのち、水洗を実施した。次に、比較例３の２の化成処理剤を用いて、基材を７２００秒間浸漬（化成処理剤の温度は５０℃）したのち、水洗を実施した。さらに、比較例３の３の化成処理剤を用いて、基材を４５秒間浸漬（成処理剤の温度は２３℃）したのち、水洗を実施した。最後に、基材を１００℃、８５％ＲＨで１２００秒間乾燥することで、比較例３の皮膜を有する
基材を製造した。
A base material having a film of Comparative Example 3 was produced in the same manner as in Example 2 except that the chemical conversion treatment agent was changed as shown in Table 1 and a drying step was added. Specifically, the base material was immersed in the chemical conversion treatment agent 1 of Comparative Example 3 for 180 seconds (the temperature of the chemical conversion treatment agent was 50° C.), and then washed with water. Next, the base material was immersed in the chemical conversion treatment agent of Comparative Example 3-2 for 7200 seconds (the temperature of the chemical conversion treatment agent was 50° C.), and then washed with water. Furthermore, the base material was immersed for 45 seconds using the chemical conversion treatment agent 3 of Comparative Example 3 (temperature of the conversion treatment agent was 23° C.), and then washed with water. Finally, the base material was dried at 100° C. and 85% RH for 1200 seconds to produce a base material having the film of Comparative Example 3.
化成処理剤を実施例１のとおり変更した以外は実施例２と同様の方法で、比較例４の皮膜を有する基材を製造した。 A base material having a film of Comparative Example 4 was produced in the same manner as in Example 2 except that the chemical conversion treatment agent was changed as in Example 1.
得られた実施例１～１１及び比較例１～５の皮膜を有する基材に対して、以下の測定及び評価を行った。その結果を表２に示す。 The following measurements and evaluations were performed on the obtained substrates having the films of Examples 1 to 11 and Comparative Examples 1 to 5. The results are shown in Table 2.
［皮膜の元素含有率測定］
実施例・比較例の皮膜を有する基材について、走査電子顕微鏡／エネルギー分散型Ｘ線分光分析によって皮膜の元素分析を実施した。元素分析は、日本電子株式会社製走査電子顕微鏡ＪＳＭ－ＩＴ１００とオックスフォード・インストゥルメンツ株式会社製エネルギー分散型Ｘ線分析装置Ｘ－ＭａｘＮ５０を用いて行った。皮膜を有する基材の断面を作製し、走査電子顕微鏡で加速電圧２０ｋＶの条件で観察し、皮膜の領域でエネルギー分散型Ｘ線分光分析を行った。得られたスペクトルからＺＡＦ補正によりアルミニウム（Ａｌ）、マグネシウム（Ｍｇ）、及びりん（Ｐ）の含有率を求めた。また、得られたアルミニウム、マグネシウムの含有率からアルミニウム原子数／（マグネシウム原子数＋アルミニウム原子数）を算出した。
[Measurement of elemental content of film]
Elemental analysis of the coatings was performed on the substrates having the coatings of Examples and Comparative Examples by scanning electron microscopy/energy dispersive X-ray spectroscopy. Elemental analysis was performed using a scanning electron microscope JSM-IT100 manufactured by JEOL Ltd. and an energy dispersive X-ray analyzer X-MaxN50 manufactured by Oxford Instruments Ltd. A cross section of the base material having the film was prepared and observed with a scanning electron microscope at an acceleration voltage of 20 kV, and energy dispersive X-ray spectroscopy was performed on the region of the film. The contents of aluminum (Al), magnesium (Mg), and phosphorus (P) were determined from the obtained spectrum by ZAF correction. Further, the number of aluminum atoms/(number of magnesium atoms+number of aluminum atoms) was calculated from the obtained aluminum and magnesium contents.
［外観観察］
実施例・比較例の皮膜を有する基材について、外観を目視で観察した。色調にムラが見られない場合を〇、ムラがやや見られる場合を△、ムラが顕著に見られる場合を×とした。このうち「〇」以上を合格とした。
[Exterior observation]
The appearance of the substrates having the films of Examples and Comparative Examples was visually observed. The case where no unevenness was observed in the color tone was rated as ○, the case where some unevenness was observed was rated △, and the case where unevenness was noticeable was rated ×. Of these, those with a score of ``〇'' or higher were considered to have passed.
［明度測定］
実施例・比較例の皮膜を有する基材について、ＪＩＳ Ｚ ８７２２：２００９に準じて明度を評価した。明度測定は、コニカミノルタ株式会社製色彩色差計ＣＲ－４００を用いて実施した。観察光源はＣとし、白色校正板ＣＲ－Ａ４３を用いて校正した。測定結果はＬ＊ａ＊ｂ＊表色系で表示し、明度Ｌ＊で黒色度を評価した。このうちＬ＊値が３０以下を合格とした。
[Brightness measurement]
The lightness of the substrates having the films of Examples and Comparative Examples was evaluated according to JIS Z 8722:2009. The brightness measurement was carried out using a color difference meter CR-400 manufactured by Konica Minolta, Inc. The observation light source was C, and it was calibrated using a white calibration plate CR-A43. The measurement results were expressed using the L * a * b * color system, and the degree of blackness was evaluated using the lightness L * . Among these, those with an L* value of 30 or less were considered to be acceptable.
［分光反射率測定］
実施例・比較例の皮膜を有する基材について、分光反射率を評価した。分光反射率測定は、株式会社島津製作所製紫外可視赤外分光光度計ＳｏｌｉｄＳｐｅｃ－３７００ＤＵＶを用いて実施した。入射光は８°とし、拡散反射率と正反射率を加算した。測定波長３００～１０００ｎｍの全領域で分光反射率が５％以下の場合を〇、分光反射率が５％を超える波長が存在する場合を×とした。このうち「〇」以上を合格とした。
[Spectral reflectance measurement]
The spectral reflectance of the substrates having the films of Examples and Comparative Examples was evaluated. The spectral reflectance measurement was performed using an ultraviolet-visible-infrared spectrophotometer SolidSpec-3700DUV manufactured by Shimadzu Corporation. The incident light was set at 8°, and the diffuse reflectance and regular reflectance were added. A case where the spectral reflectance was 5% or less in the entire measurement wavelength range of 300 to 1000 nm was marked as ○, and a case where there was a wavelength where the spectral reflectance exceeded 5% was marked as ×. Of these, those with a score of ``〇'' or higher were considered to have passed.
［耐食性試験］
実施例・比較例の皮膜を有する基材について、ＪＩＳ Ｚ ２３７１：２０１５に準じて中性塩水噴霧試験を実施した。塩水噴霧時間は９６時間とし、塩水噴霧終了後の腐食発生状況を目視で評価した。腐食面積率が５％未満の場合を〇、５％以上１０％未満の場合を△、１０％以上の場合を×とした。このうち「△」以上を合格とした。
結果を表２に示す。
[Corrosion resistance test]
A neutral salt spray test was conducted on the substrates having the films of Examples and Comparative Examples in accordance with JIS Z 2371:2015. The salt water spraying time was 96 hours, and the occurrence of corrosion after the salt water spraying was visually evaluated. The case where the corrosion area ratio was less than 5% was rated ○, the case where it was 5% or more but less than 10% was rated △, and the case where it was 10% or more was rated ×. Among these, those with a rating of "△" or higher were considered to be passed.
The results are shown in Table 2.
Claims (2)
前記皮膜におけるカルシウムの含有率は０．５原子％以下であり、アルミニウム原子数／（マグネシウム原子数＋アルミニウム原子数）が０．４０以上０．９０以下の範囲内である、皮膜を有する基材。 having a film containing aluminum atoms, magnesium atoms and phosphorus atoms on the surface or surface of a base material containing a magnesium alloy in the surface layer;
The calcium content in the film is 0.5 at % or less, and the number of aluminum atoms/(number of magnesium atoms + number of aluminum atoms) is 0. 4. A base material having a film in the range of 0 or more and 0.90 or less.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003171776A (en) | 2001-12-07 | 2003-06-20 | Million Kagaku Kk | Surface treatment method for lithium based magnesium alloy material |
| JP2009114504A (en) | 2007-11-07 | 2009-05-28 | Shingijutsu Kenkyusho:Kk | Magnesium alloy article, magnesium alloy member, and method for manufacturing the same |
| JP2010084203A (en) | 2008-09-30 | 2010-04-15 | Nippon Kinzoku Co Ltd | Black chemical conversion treatment liquid for magnesium alloy, chemical conversion treatment method and chemically-conversion-treated member |
| CN105755455A (en) | 2016-03-22 | 2016-07-13 | 博罗县东明化工有限公司 | Magnesium alloy AZ31 blackening liquid and blackening method |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003171776A (en) | 2001-12-07 | 2003-06-20 | Million Kagaku Kk | Surface treatment method for lithium based magnesium alloy material |
| JP2009114504A (en) | 2007-11-07 | 2009-05-28 | Shingijutsu Kenkyusho:Kk | Magnesium alloy article, magnesium alloy member, and method for manufacturing the same |
| JP2010084203A (en) | 2008-09-30 | 2010-04-15 | Nippon Kinzoku Co Ltd | Black chemical conversion treatment liquid for magnesium alloy, chemical conversion treatment method and chemically-conversion-treated member |
| CN105755455A (en) | 2016-03-22 | 2016-07-13 | 博罗县东明化工有限公司 | Magnesium alloy AZ31 blackening liquid and blackening method |
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