JP6568770B2 - Colored titanium material - Google Patents
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- JP6568770B2 JP6568770B2 JP2015213076A JP2015213076A JP6568770B2 JP 6568770 B2 JP6568770 B2 JP 6568770B2 JP 2015213076 A JP2015213076 A JP 2015213076A JP 2015213076 A JP2015213076 A JP 2015213076A JP 6568770 B2 JP6568770 B2 JP 6568770B2
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- 239000010936 titanium Substances 0.000 title claims description 95
- 239000000463 material Substances 0.000 title claims description 93
- 229910052719 titanium Inorganic materials 0.000 title claims description 85
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 82
- 239000010410 layer Substances 0.000 claims description 163
- 239000011247 coating layer Substances 0.000 claims description 66
- 239000012535 impurity Substances 0.000 claims description 16
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 11
- 239000002023 wood Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 51
- 239000007789 gas Substances 0.000 description 23
- 238000002845 discoloration Methods 0.000 description 21
- 238000007733 ion plating Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000004040 coloring Methods 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000000137 annealing Methods 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000010891 electric arc Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- -1 argon ions Chemical class 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Description
本発明は、純チタン又はチタン合金（総称してチタンという場合がある）からなる基材の表面に被覆層を有し、黒色の外観を呈する発色チタン材に関するものである。 The present invention relates to a colored titanium material having a coating layer on the surface of a substrate made of pure titanium or a titanium alloy (sometimes collectively referred to as titanium) and exhibiting a black appearance.
チタンは、軽量で、耐食性に優れた材料であり、航空機、化学プラント、建築物の外装材、装飾品、民生品など、様々な用途に使用されている。また、チタンは、陽極酸化法やイオンプレーティング法によって表面に被覆層を形成することで、発色チタン材とすることが可能である。しかし、発色チタン材は、意匠性が求められる建築物の屋根材に適用する場合、酸性雨などの影響によって経時的に色調が変化する、いわゆる変色という問題があった。 Titanium is a lightweight material with excellent corrosion resistance, and is used in various applications such as aircraft, chemical plants, building exterior materials, ornaments, and consumer products. Titanium can be made into a coloring titanium material by forming a coating layer on the surface by an anodic oxidation method or ion plating method. However, when the colored titanium material is applied to a roof material of a building that requires design properties, there is a problem of so-called discoloration in which the color tone changes with time due to the influence of acid rain or the like.
このような問題に対し、チタンの表面にイオンプレーティング法によって窒化チタン被膜を形成した後、酸素と窒素との混合雰囲気中で加熱して透明な酸化チタン被膜を形成し、色調の安定化を図る方法が提案されている（例えば、特許文献１、参照）。
また、本発明者らは、基材となるチタンの表面の炭素濃度を制御することにより、イオンプレーティングによって基材の表面に形成される窒化チタン層の変色を抑制する方法を提案している（例えば、特許文献２及び３、参照）。
To solve this problem, after forming a titanium nitride film on the surface of titanium by ion plating, heat in a mixed atmosphere of oxygen and nitrogen to form a transparent titanium oxide film to stabilize the color tone. A method has been proposed (for example, see Patent Document 1).
In addition, the present inventors have proposed a method of suppressing discoloration of the titanium nitride layer formed on the surface of the base material by ion plating by controlling the carbon concentration on the surface of titanium serving as the base material. (See, for example, Patent Documents 2 and 3).
ところで、イオンプレーティング法によって、様々な色調を呈する発色チタン材の製造が可能であるが、意匠性の観点から、黒色の外観を呈する発色チタン材が求められることがある。このような要求に対して、金属の基材上に、灰色の中間層及び透光性を有する黒色の仕上げ層を形成した装飾部材が提案されている（例えば、特許文献４、参照）。特許文献４には、中間層の色彩測定値が示されているが、実際の外観の色調は不明である。 By the way, although the coloring titanium material which exhibits various colors by the ion plating method is possible, the coloring titanium material which exhibits a black external appearance may be calculated | required from a design viewpoint. In response to such a demand, a decorative member has been proposed in which a gray intermediate layer and a translucent black finish layer are formed on a metal substrate (see, for example, Patent Document 4). In Patent Document 4, although the color measurement value of the intermediate layer is shown, the actual color tone of the appearance is unknown.
発色チタン材は、建材や自動車部品に適用する際に、プレス加工などによって成形される場合がある。発色チタン材の表面に形成されている被覆層は、成形加工によって割れが生じてもよいが、被覆層が基材から剥離すると、意匠性が損なわれる。したがって、発色チタン材の被覆層には、基材との密着性が要求される。
本発明は、このような実情に鑑みてなされたものであり、黒色の外観を呈し、基材と被覆層との密着性に優れ、変色しにくい、発色チタン材を提供するものである。
When applied to building materials and automobile parts, the colored titanium material may be formed by pressing or the like. Although the coating layer formed on the surface of the colored titanium material may be cracked by molding, the design properties are impaired when the coating layer is peeled off from the substrate. Therefore, the coating layer of the coloring titanium material is required to have adhesiveness with the base material.
The present invention has been made in view of such circumstances, and provides a colored titanium material that exhibits a black appearance, is excellent in adhesion between a base material and a coating layer, and hardly discolors.
本発明は、基材の表面に、Ｔｉ、Ｃ、Ｎ、Ｏ及びＨを含む被覆層を有し、前記被覆層が、基材側から、Ｎ（窒素）濃度が高く厚みの薄い内層、Ｃ（炭素）濃度が高く厚みの厚い中間層、Ｏ（酸素）濃度が高く厚みの薄い外層、の順に形成したものである発色チタン材であり、その要旨は、以下のとおりである。 The present invention has a coating layer containing Ti, C, N, O, and H on the surface of the substrate, and the coating layer has an N (nitrogen) concentration and a thin inner layer from the substrate side, C This is a colored titanium material formed in the order of an intermediate layer having a high (carbon) concentration and a thick thickness and an outer layer having a high O (oxygen) concentration and a small thickness, and the gist thereof is as follows.
［１］ 純チタン又はチタン合金からなる基材の表面に、前記基材側から内層、中間層、外層の順に形成されてなる被覆層を有し、前記被覆層と前記基材との界面から前記基材側に１００ｎｍまでの領域におけるＣ濃度が２０．００原子％以下であり、
前記内層は、厚みが０．０１０〜０．１００μｍであり、
Ｃ濃度が１８．００原子％以下、
Ｎ濃度が１５．００〜４０．００原子％、
Ｏ濃度が１０．００〜３５．００原子％、
Ｈ濃度が１０．００原子％以下、
残部Ｔｉ及び不可避的不純物であり、
前記中間層は、厚みが０．１００〜０．９００μｍであり、
Ｃ濃度が４０．００〜６０．００原子％、
Ｎ濃度が１５．００〜３５．００原子％、
Ｏ濃度が５．００〜２５．００原子％、
Ｈ濃度が１５．００原子％以下、
残部Ｔｉ及び不可避的不純物であり、
前記外層は、厚みが０．０１０〜０．１００μｍであり、
Ｃ濃度が２０．００〜５０．００原子％、
Ｎ濃度が２５．００原子％以下、
Ｏ濃度が１５．００〜６０．００原子％かつ前記中間層のＯ濃度よりも高く、
Ｈ濃度が２０．００原子％以下、
残部Ｔｉ及び不可避的不純物であり、
外観のＬ＊ａ＊ｂ＊表色系で表される色空間が、Ｌ＊：１０〜４３、ａ＊：−３〜４、ｂ＊：−３〜６であることを特徴とする発色チタン材。
[1] On the surface of a substrate made of pure titanium or a titanium alloy, a coating layer formed in the order of an inner layer, an intermediate layer, and an outer layer from the substrate side is provided, and from the interface between the coating layer and the substrate. C concentration in the region up to 100 nm on the substrate side is 20.00 atomic% or less,
The inner layer has a thickness of 0.010 to 0.100 μm,
C concentration is 18.00 atomic% or less,
N concentration is 15.00-40.00 atomic%,
O concentration is 10.00 to 35.00 atomic%,
H concentration is 10.00 atomic% or less,
Remaining Ti and inevitable impurities,
The intermediate layer has a thickness of 0.100 to 0.900 μm,
C concentration is 40.00 to 60.00 atomic%,
N concentration is 15.00-35.00 atomic%,
O concentration is 5.00 to 25.00 atomic%,
H concentration is 15.00 atomic% or less,
Remaining Ti and inevitable impurities,
The outer layer has a thickness of 0.010 to 0.100 μm,
C concentration is 20.00-50.00 atomic%,
N concentration is 25.00 atomic% or less,
O concentration is 15.00-60.00 atomic% and higher than the O concentration of the intermediate layer,
H concentration is 20.00 atomic% or less,
Remaining Ti and inevitable impurities,
Colored titanium characterized in that the color space represented by the L * a * b * color system of the appearance is L * : 10-43, a * : -3-4, b * : -3-6 Wood.
［２］ 前記被覆層の厚みが合計で０．２００〜１．０００μｍであることを特徴とする上記［１］に記載の発色チタン材。
[2] The colored titanium material as described in [1] above, wherein the total thickness of the coating layer is 0.200 to 1.000 μm .
本発明によれば、黒色の外観を呈し、基材と被覆層との密着性に優れ、変色しにくい発色チタン材の提供が可能になり、本発明は、産業上の貢献が極めて顕著である。 According to the present invention, it is possible to provide a colored titanium material that exhibits a black appearance, is excellent in adhesion between the base material and the coating layer, and is difficult to discolor, and the present invention has an extremely significant industrial contribution. .
本発明の発色チタン材は、図１に模式的に示すように、基材１の表面に、被覆層５を有する。基材１は、純チタン又はチタン合金である。被覆層５は、Ｔｉ、Ｃ、Ｎ、Ｏ及びＨを含み、イオンプレーティング法を用いて形成させることができる。被覆層５は、基材１に近い側から順に形成された内層２、中間層３、外層４の三層からなる。
本発明の発色チタン材は、図１に示す三層の被覆層５によって、黒色の外観を呈する。
The coloring titanium material of the present invention has a coating layer 5 on the surface of a substrate 1 as schematically shown in FIG. The substrate 1 is pure titanium or a titanium alloy. The coating layer 5 contains Ti, C, N, O, and H, and can be formed using an ion plating method. The covering layer 5 includes three layers, an inner layer 2, an intermediate layer 3, and an outer layer 4, which are formed in order from the side close to the base material 1.
The colored titanium material of the present invention exhibits a black appearance due to the three coating layers 5 shown in FIG.
「基材（純チタン又はチタン合金）」
発色チタン材の基材１には、純チタン又はチタン合金を用いる。加工性が要求される場合は、不純物を低減したＪＩＳ１種（たとえば、ＪＩＳ Ｈ ４６００）の工業用純チタンが好適である。また、強度が必要とされる場合は、ＪＩＳ２種〜４種の工業用純チタンも適用できる。チタン合金としては、例えば、耐食性を向上させるために、微量の貴金属系の元素（パラジウム、白金、ルテニウム等）を添加したＪＩＳ１１種から２３種等が挙げられる。また、基材１は、ＪＩＳ Ｈ ４６００の板及び条に限らず、管や棒線を使用してもよい。
"Base material (pure titanium or titanium alloy)"
Pure titanium or a titanium alloy is used for the base material 1 of the coloring titanium material. When workability is required, industrially pure titanium of JIS type 1 (for example, JIS H 4600) with reduced impurities is suitable. Moreover, when intensity | strength is required, JIS 2-4 types of industrial pure titanium can also be applied. Examples of the titanium alloy include JIS 11 to 23 kinds to which a trace amount of noble metal elements (palladium, platinum, ruthenium, etc.) are added in order to improve corrosion resistance. Moreover, the base material 1 may use not only the board and strip | line of JIS H4600 but a pipe | tube and a bar wire.
ただし、基材１が、Ｔｉ−６Ａｌ−４Ｖ系合金のように、アルミニウムを多量に含有する場合、耐食性が劣化し、耐変色性に悪影響を及ぼす場合がある。そのため、チタン合金に本発明の被覆層５を形成する場合、予め、合金元素の影響を調査し、基材１の組成に応じて、各層の組成、厚みを適宜調整することが推奨される。 However, when the base material 1 contains a large amount of aluminum like a Ti-6Al-4V alloy, the corrosion resistance may be deteriorated, and the discoloration resistance may be adversely affected. Therefore, when the coating layer 5 of the present invention is formed on a titanium alloy, it is recommended to investigate the influence of the alloy elements in advance and appropriately adjust the composition and thickness of each layer according to the composition of the substrate 1.
「基材表面のＣ濃度」
基材１と被覆層５との界面（図１では基材１と内層２との界面）から、基材１側の炭素濃度が高いと、発色チタン材の耐変色性が劣化する。この理由は必ずしも明らかではないが、チタン炭化物（ＴｉＣ）の形成が被覆層５の安定性に悪影響を及ぼしているのではないかと考えられる。
“C concentration on substrate surface”
If the carbon concentration on the base material 1 side is high from the interface between the base material 1 and the coating layer 5 (the interface between the base material 1 and the inner layer 2 in FIG. 1), the discoloration resistance of the colored titanium material deteriorates. The reason for this is not necessarily clear, but it is considered that the formation of titanium carbide (TiC) has an adverse effect on the stability of the coating layer 5.
被覆層５と基材１との界面から基材１側に１００ｎｍまでの領域におけるＣ濃度（基材表面のＣ濃度）を２０．００原子％以下に制限することにより、発色チタン材の耐変色性を飛躍的に向上させることができる。基材１表面のＣ濃度の上限は１０．００原子％以下が好ましい。基材表面の炭素濃度は、冷間圧延の潤滑油の脱脂の強化や、真空焼鈍の条件の調整によって低減させることができる。基材表面の炭素濃度の下限は規定せず、０．００原子％でもよいが、１．００原子％未満にするには製造コストの大幅な増加を招き、また耐変色性を向上させる効果も飽和することから炭素濃度の下限値は１．００原子％でもよい。 By limiting the C concentration in the region from the interface between the coating layer 5 and the substrate 1 to 100 nm on the substrate 1 side (C concentration on the substrate surface) to 20.00 atomic percent or less, the color change resistance of the colored titanium material The sex can be improved dramatically. The upper limit of the C concentration on the surface of the substrate 1 is preferably 10.00 atomic% or less. The carbon concentration on the substrate surface can be reduced by enhancing the degreasing of the cold rolling lubricating oil or adjusting the conditions of vacuum annealing. The lower limit of the carbon concentration on the surface of the substrate is not specified, and may be 0.00 atomic%. However, if it is less than 1.00 atomic%, the manufacturing cost is greatly increased, and the effect of improving discoloration resistance is also achieved. Because of saturation, the lower limit of the carbon concentration may be 1.00 atomic%.
「基材の製造方法」
基材１として用いる純チタン及びチタン合金は、常法によって製造できる。基材１は、表面（被覆層５と基材１との界面から基材１側に１００ｎｍまでの領域）のＣ濃度を低減させるために、冷間圧延後の洗浄によって潤滑油を除去すること、および／または、焼鈍温度や焼鈍時間などの焼鈍条件を最適化することが必要である。また、基材１には、意匠性の観点から、鏡面仕上げ、酸洗仕上げ、ダル仕上げ、ヘアライン仕上げ、ブラスト仕上げ等の各種の表面仕上げを適用することができる。
"Method of manufacturing substrate"
Pure titanium and a titanium alloy used as the substrate 1 can be manufactured by a conventional method. In order to reduce the C concentration of the base material 1 (region from the interface between the coating layer 5 and the base material 1 to the base material 1 side up to 100 nm), the lubricating oil is removed by washing after cold rolling. It is necessary to optimize the annealing conditions such as the annealing temperature and the annealing time. In addition, various surface finishes such as mirror finish, pickling finish, dull finish, hairline finish, and blast finish can be applied to the substrate 1 from the viewpoint of design.
「内層の厚みと組成」
内層２は、厚みが０．０１０〜０．１００μｍであり、Ｃ濃度が１８．００原子％以下、Ｎ濃度が１５．００〜４０．００原子％、Ｏ濃度が１０．００〜３５．００原子％、Ｈ濃度が１０．００原子％以下、残部Ｔｉ及び不可避的不純物である。
内層２は、基材１と被覆層５との密着性、及び、外観上の色調に影響を及ぼす。内層２の厚みは中間層３に比べて相対的に薄い。内層２に含まれるＣ、Ｎ、Ｏ及びＨのうち、Ｎ濃度が最も高いことが好ましい。内層２は、中間層３に比べて軟質であるため、密着性の向上に寄与し、中間層３と色調が異なるため、発色チタン材の色調にも影響を及ぼす。
"Inner layer thickness and composition"
The inner layer 2 has a thickness of 0.010 to 0.100 μm, a C concentration of 18.00 atomic% or less, an N concentration of 15.00 to 40.00 atomic%, and an O concentration of 10.00 to 35.00 atoms. %, H concentration is 10.00 atomic% or less, remaining Ti and inevitable impurities.
The inner layer 2 affects the adhesion between the substrate 1 and the coating layer 5 and the color tone on the appearance. The inner layer 2 is relatively thinner than the intermediate layer 3. Of the C, N, O and H contained in the inner layer 2, the N concentration is preferably the highest. Since the inner layer 2 is softer than the intermediate layer 3, the inner layer 2 contributes to the improvement of adhesion, and since the color tone is different from that of the intermediate layer 3, the color tone of the coloring titanium material is also affected.
内層２の厚みは、基材１との密着性を向上させ、黒色の外観を得るために、０．０１０〜０．１００μｍとすることが必要である。内層２の厚みが０．０１０μｍ未満であると、基材１の表面の一部が内層２によって被覆されない可能性があり、基材１と被覆層５との密着性が部分的に劣化する。被覆層５は延性が低いため、発色チタン材の加工に伴う基材１の変形に追従し、細かく割れた状態になる。細かく割れた状態の被覆層５のうち、内層２に被覆されていない基材１上に形成された被覆層５は、基材１から容易に剥離する。このため、発色チタン材の表面に基材１が露出して、黒色の外観が得られなくなる場合がある。内層２の厚みは０．０１５μｍ以上であることが好ましい。一方、内層２の厚みが０．１００μｍを超えると、発色チタン材の加工を行っても被覆層５が細かく割れた状態になりにくくなる。このため、加工に起因する応力によって広い面積で被覆層５が基材１から剥離し、発色チタン材の表面に基材１が露出する場合がある。内層２の厚みは０．０５０μｍ以下であることが好ましい。 The thickness of the inner layer 2 is required to be 0.010 to 0.100 μm in order to improve the adhesion with the substrate 1 and obtain a black appearance. When the thickness of the inner layer 2 is less than 0.010 μm, a part of the surface of the substrate 1 may not be covered with the inner layer 2, and the adhesion between the substrate 1 and the coating layer 5 is partially deteriorated. Since the coating layer 5 has low ductility, the coating layer 5 follows the deformation of the base material 1 accompanying the processing of the coloring titanium material, and is finely cracked. Of the coating layer 5 in a finely broken state, the coating layer 5 formed on the substrate 1 that is not coated with the inner layer 2 is easily peeled off from the substrate 1. For this reason, the base material 1 may be exposed on the surface of the colored titanium material, and a black appearance may not be obtained. The thickness of the inner layer 2 is preferably 0.015 μm or more. On the other hand, when the thickness of the inner layer 2 exceeds 0.100 μm, the coating layer 5 is unlikely to be finely cracked even if the coloring titanium material is processed. For this reason, the coating layer 5 may peel from the base material 1 over a wide area due to stress resulting from the processing, and the base material 1 may be exposed on the surface of the colored titanium material. The thickness of the inner layer 2 is preferably 0.050 μm or less.
内層２の密着性を高めるには、Ｎ濃度及びＯ濃度を高め、Ｃ濃度及びＨ濃度を低減することが必要である。内層２のＮ濃度及びＯ濃度は、内層２を軟質にして密着性を高めるために、それぞれ、１５．００原子％以上及び１０．００原子％以上とすることが必要である。内層２のＮ濃度は２０．００原子％以上であることが好ましい。一方、内層２のＮ濃度及びＯ濃度は、多過ぎると内層２が硬化して密着性が低下することから、それぞれ、４０．００原子％以下及び３５．００原子％以下とすることが必要である。内層２のＮ濃度は３０．００原子％以下であることが好ましい。 In order to improve the adhesion of the inner layer 2, it is necessary to increase the N concentration and the O concentration and reduce the C concentration and the H concentration. The N concentration and O concentration of the inner layer 2 are required to be 15.00 atomic% or more and 10.00 atomic% or more, respectively, in order to soften the inner layer 2 and improve adhesion. The N concentration in the inner layer 2 is preferably 20.00 atomic% or more. On the other hand, if the N concentration and O concentration of the inner layer 2 are too large, the inner layer 2 is cured and the adhesiveness is lowered, so that it is necessary to set it to 40.00 atomic% or less and 35.00 atomic% or less, respectively. is there. The N concentration of the inner layer 2 is preferably 30.00 atomic% or less.
内層２に含まれる炭素と水素は、被覆層５の密着性を低下させることから制限することが好ましく、内層２のＣ濃度は１８．００原子％以下、Ｈ濃度は１０．００原子％以下とする。内層２のＣ濃度は１０．００原子％以下が好ましい。内層２のＣ濃度及びＨ濃度の下限は規定せず、０．００原子％でもよい。炭素及び水素は、内層２をイオンプレーティング法で形成する場合に使用するガスに混入することがあるため、内層２のＣ濃度およびＨ濃度の下限値は１．００原子％でもよい。
内層２に含まれる不可避的不純物は、イオンプレーティング法で使用されるガスや、アーク放電でイオン化するチタンに含まれる不純物であり、例えば、Ｆｅなどが挙げられる。
Carbon and hydrogen contained in the inner layer 2 are preferably limited because they reduce the adhesion of the coating layer 5. The C concentration of the inner layer 2 is 18.00 atomic% or less, and the H concentration is 10.00 atomic% or less. To do. The C concentration of the inner layer 2 is preferably 10.00 atomic% or less. The lower limits of the C concentration and H concentration of the inner layer 2 are not defined, and may be 0.00 atomic%. Since carbon and hydrogen may be mixed in a gas used when the inner layer 2 is formed by the ion plating method, the lower limit values of the C concentration and the H concentration of the inner layer 2 may be 1.00 atomic%.
The inevitable impurities contained in the inner layer 2 are impurities contained in a gas used in the ion plating method or titanium ionized by arc discharge, and examples thereof include Fe.
「中間層の厚みと組成」
中間層３は、内層２の表面に形成され、厚みが０．１００〜０．９００μｍであり、Ｃ濃度が４０．００〜６０．００原子％、Ｎ濃度が１５．００〜３５．００原子％、Ｏ濃度が５．００〜２５．００原子％、Ｈ濃度が１５．００原子％以下、残部Ｔｉ及び不可避的不純物である。そして、本発明の発色チタン材は、外観を黒色の色調とするために、中間層３のＣ濃度が内層２のＣ濃度よりも多くなっている。
"Thickness and composition of the intermediate layer"
The intermediate layer 3 is formed on the surface of the inner layer 2, has a thickness of 0.100 to 0.900 μm, a C concentration of 40.00 to 60.00 atomic%, and an N concentration of 15.00 to 35.00 atomic%. , O concentration is 5.00 to 25.00 atomic%, H concentration is 15.00 atomic% or less, the remainder is Ti and inevitable impurities. In the color developing titanium material of the present invention, the C concentration of the intermediate layer 3 is higher than the C concentration of the inner layer 2 so that the appearance is black.
中間層３の厚みは、黒色の外観を得るために、０．１００μｍ以上にすることが必要である。中間層３の厚みが０．１００μｍ未満であると、外観の色調における内層２の影響が大きくなり、黒色の色調の外観が得られない。中間層３の厚みは０．１５０μｍ以上であることが好ましい。一方、中間層３の厚みが０．９００μｍを超えると、被覆層５の密着性が低下し、発色チタン材の加工によって基材１から被覆層５が剥離することがある。中間層３の厚みは０．４００μｍ以下であることが好ましい。 The thickness of the intermediate layer 3 needs to be 0.100 μm or more in order to obtain a black appearance. When the thickness of the intermediate layer 3 is less than 0.100 μm, the influence of the inner layer 2 on the appearance color tone becomes large, and the appearance of black color tone cannot be obtained. The thickness of the intermediate layer 3 is preferably 0.150 μm or more. On the other hand, when the thickness of the intermediate layer 3 exceeds 0.900 μm, the adhesiveness of the coating layer 5 is lowered, and the coating layer 5 may be peeled off from the base material 1 by processing the coloring titanium material. The thickness of the intermediate layer 3 is preferably 0.400 μm or less.
発色チタン材の外観を黒色にするには、中間層３のＣ濃度を４０．００原子％以上とし、Ｎ濃度を３５．００原子％以下、Ｏ濃度を２５．００原子％以下にすることが必要である。中間層３のＣ濃度は、４５．００原子％以上が好ましい。中間層３のＯ濃度は、２０．００原子％以下が好ましい。一方、耐変色性を高めるには、中間層３のＣ濃度を６０．０％以下とすることが必要であり、５５．００原子％以下とすることが好ましい。また、密着性及び耐変色性を高めるには、中間層３のＮ濃度を１５．００原子％以上にすることが必要である。中間層３のＯ濃度が５．００原子％未満の場合、外層４のＯ濃度との差が大きくなって密着性が低下するため、Ｏ濃度を５．００原子％以上とする。中間層のＯ濃度は、７．００原子％以上が好ましい。中間層３に含まれるＨは密着性を低下させるため、Ｈ濃度を１５．００％以下とする。中間層３のＨ濃度の下限は規定せず、０．００原子％でもよい。水素は、中間層３をイオンプレーティング法で形成する場合に使用するガスに混入することがあるため、下限値は１．００原子％でもよい。
中間層３に含まれる不可避的不純物は、イオンプレーティング法で使用されるガスや、アーク放電でイオン化するチタンに含まれる不純物であり、例えば、Ｆｅなどが挙げられる。
In order to make the appearance of the colored titanium material black, the C concentration of the intermediate layer 3 should be 40.00 atomic% or more, the N concentration should be 35.00 atomic% or less, and the O concentration should be 25.00 atomic% or less. is necessary. The C concentration of the intermediate layer 3 is preferably 45.00 atomic% or more. The O concentration of the intermediate layer 3 is preferably 20.00 atomic% or less. On the other hand, in order to improve discoloration resistance, the C concentration of the intermediate layer 3 needs to be 60.0% or less, and is preferably 55.00 atomic% or less. Moreover, in order to improve adhesiveness and discoloration resistance, the N concentration of the intermediate layer 3 needs to be 15.00 atomic% or more. When the O concentration of the intermediate layer 3 is less than 5.00 atomic%, the difference from the O concentration of the outer layer 4 becomes large and the adhesiveness decreases, so the O concentration is set to 5.00 atomic% or more. The O concentration in the intermediate layer is preferably 7.00 atomic% or more. Since H contained in the intermediate layer 3 decreases the adhesion, the H concentration is set to 15.00% or less. The lower limit of the H concentration of the intermediate layer 3 is not defined and may be 0.00 atomic%. Since hydrogen may be mixed into a gas used when the intermediate layer 3 is formed by the ion plating method, the lower limit may be 1.00 atomic%.
The inevitable impurities contained in the intermediate layer 3 are impurities contained in a gas used in the ion plating method or titanium ionized by arc discharge, and examples thereof include Fe.
「外層の厚みと組成」
外層４は、中間層３の外側に形成され、被覆層５の最外面に位置する。外層４は、厚みが０．０１０〜０．１００μｍであり、Ｃ濃度が２０．００〜５０．００原子％、Ｎ濃度が２５．００原子％以下、Ｏ濃度が１５．００〜６０．００原子％、Ｈ濃度が２０．００原子％以下、残部Ｔｉ及び不可避的不純物である。そして、本発明の発色チタン材は、耐変色性を高めるために、外層４のＯ濃度が中間層３のＯ濃度よりも多くなっている。
“Outer layer thickness and composition”
The outer layer 4 is formed outside the intermediate layer 3 and is located on the outermost surface of the covering layer 5. The outer layer 4 has a thickness of 0.010 to 0.100 μm, a C concentration of 20.00 to 50.00 atomic percent, an N concentration of 25.00 atomic percent or less, and an O concentration of 15.00 to 60.00 atomic percent. %, H concentration is 20.00 atomic% or less, the remainder is Ti and inevitable impurities. In the color developing titanium material of the present invention, the O concentration of the outer layer 4 is higher than the O concentration of the intermediate layer 3 in order to improve the discoloration resistance.
外層４の厚みは、発色チタン材の黒色の外観に悪影響を及ぼさないように、０．１００μｍ以下にすることが必要であり、０．０６０μｍ以下であることが好ましい。一方、外層４の厚みが０．０１０μｍ未満であると、耐変色性が不十分になることがある。このため、外層４の厚みは０．０１０μｍ以上とし、０．０３０μｍ以上であることが好ましい。 The thickness of the outer layer 4 needs to be 0.100 μm or less and preferably 0.060 μm or less so as not to adversely affect the black appearance of the color developing titanium material. On the other hand, when the thickness of the outer layer 4 is less than 0.010 μm, discoloration resistance may be insufficient. For this reason, the thickness of the outer layer 4 is 0.010 μm or more, and preferably 0.030 μm or more.
発色チタン材の耐変色性を高めるには、外層４のＯ濃度を１５．００原子％以上とし、Ｃ濃度を５０．００原子％以下にすることが必要である。外層４のＯ濃度は、１７．００原子％以上が好ましい。一方、密着性を高めるには、外層４のＯ濃度は６０．００原子％以下であればよく、５５．００原子％以下とすることが好ましい。また、外層４のＣ濃度が２０．００原子％未満の場合、中間層３とのＣ濃度の差が大きくなって密着性が低下するため、外層４のＣ濃度を２０．００原子％以上とする。外層４に含まれるＮ及びＨは、密着性及び耐変色性を低下させるため、Ｎ濃度を２５．００原子％以下、Ｈ濃度を２０．００原子％以下とする。Ｎ濃度及びＨ濃度の下限は規定せず、０．００原子％でもよい。水素は、外層４をイオンプレーティング法で形成する場合に使用するガスに混入することがあるため、Ｈ濃度の下限値は１．００原子％でもよい。
外層４に含まれる不可避的不純物は、イオンプレーティング法で使用されるガスや、アーク放電でイオン化するチタンに含まれる不純物であり、例えば、Ｆｅなどが挙げられる。
In order to improve the color fastness of the color developing titanium material, it is necessary to set the O concentration of the outer layer 4 to 15.00 atomic% or more and the C concentration to 50.00 atomic% or less. The O concentration of the outer layer 4 is preferably 17.00 atomic% or more. On the other hand, in order to improve adhesion, the O concentration of the outer layer 4 may be 60.00 atomic% or less, and is preferably 55.00 atomic% or less. In addition, when the C concentration of the outer layer 4 is less than 20.00 atomic%, the difference in C concentration with the intermediate layer 3 becomes large and the adhesion decreases, so the C concentration of the outer layer 4 is 20.00 atomic% or more. To do. N and H contained in the outer layer 4 have an N concentration of 25.00 atomic% or less and an H concentration of 20.00 atomic% or less in order to reduce adhesion and discoloration resistance. The lower limits of N concentration and H concentration are not defined, and may be 0.00 atomic%. Since hydrogen may be mixed into a gas used when the outer layer 4 is formed by the ion plating method, the lower limit value of the H concentration may be 1.00 atomic%.
The inevitable impurities contained in the outer layer 4 are impurities contained in the gas used in the ion plating method or titanium ionized by arc discharge, and examples thereof include Fe.
「被覆層の厚み」
内層２、中間層３、外層４からなる被覆層５の合計の厚みは、０．２００μｍ〜１．０００μｍが好ましい。被覆層５の厚みを０．２００μｍ未満にすると、内層２、中間層３、外層４の各層の厚みが薄くなる。このため、基材１の面積が広くなると、表面全体を均一な色調にすることが難しくなることがある。また、被覆層５の厚みが１．０００μｍを超えると、厳しい加工を施した際に、基材１に対する被覆層５の密着性が劣化する場合がある。被覆層５の厚みは０．４００μｍ以下であることがより好ましい。
“Thickness of coating layer”
The total thickness of the coating layer 5 composed of the inner layer 2, the intermediate layer 3, and the outer layer 4 is preferably 0.200 μm to 1.000 μm. When the thickness of the coating layer 5 is less than 0.200 μm, the thicknesses of the inner layer 2, the intermediate layer 3, and the outer layer 4 are reduced. For this reason, when the area of the base material 1 becomes large, it may become difficult to make the whole surface into a uniform color tone. Moreover, when the thickness of the coating layer 5 exceeds 1.000 μm, the adhesiveness of the coating layer 5 to the substrate 1 may deteriorate when severe processing is performed. The thickness of the coating layer 5 is more preferably 0.400 μm or less.
「被覆層の形成方法」
基材１の表面に被覆層５を形成する方法としては、イオンプレーティング法、ＣＶＤ（ｃｈｅｍｉｃａｌ ｖａｐｏｒ ｄｅｐｏｓｉｔｉｏｎ）法、ＰＶＤ（ｐｈｙｓｉｃａｌ ｖａｐｏｒ ｄｅｐｏｓｉｔｉｏｎ）法などを用いることができる。ただし、ＣＶＤでは、基材１を高温に加熱する必要があり、基材の機械的性質に影響を及ぼす場合がある。また、ＣＶＤやスパッタリングによるＰＶＤは、基材と被覆層との密着性に問題が生じることが多い。また、電子ビームによるＰＶＤは、被覆層を形成できる基材の大きさに制限がある。
したがって、基材１の表面に被覆層５を形成させる際には、イオンプレーティング法を採用することが好ましい。イオンプレーティング法では、内層２、中間層３、外層４の各層に含まれる各元素の濃度及び厚みの制御が容易であり、基材１である純チタン又はチタン合金の表面が活性化するため被覆層５の密着性が向上し、また、厚みの分布が均一な被膜層５が得られる。
"Method of forming coating layer"
As a method of forming the coating layer 5 on the surface of the substrate 1, an ion plating method, a CVD (chemical vapor deposition) method, a PVD (physical vapor deposition) method, or the like can be used. However, in CVD, it is necessary to heat the base material 1 to a high temperature, which may affect the mechanical properties of the base material. Moreover, PVD by CVD or sputtering often causes a problem in the adhesion between the base material and the coating layer. Moreover, PVD by an electron beam has a restriction | limiting in the magnitude | size of the base material which can form a coating layer.
Therefore, when the coating layer 5 is formed on the surface of the substrate 1, it is preferable to employ an ion plating method. In the ion plating method, it is easy to control the concentration and thickness of each element contained in each of the inner layer 2, the intermediate layer 3, and the outer layer 4, and the surface of pure titanium or a titanium alloy as the substrate 1 is activated. The adhesion of the coating layer 5 is improved, and the coating layer 5 having a uniform thickness distribution is obtained.
イオンプレーティング法では、真空炉内で基材１を加熱し、組成を調整したガスを導入しながら、蒸発源である純チタンをアーク放電によってイオン化させて、陰極とした基材１の表面に、順次、内層２、中間層３、外層４を形成する。内層２を形成する前に、アルゴンイオンによるクリーニングを行って基材１の表面を活性化させてもよい。内層２、中間層３、外層４の各層の厚みは、イオンプレーティング処理時間（純チタンを加熱蒸発、イオン化させている時間）によって制御することができる。 In the ion plating method, while heating the substrate 1 in a vacuum furnace and introducing a gas whose composition has been adjusted, pure titanium as an evaporation source is ionized by arc discharge to form a cathode on the surface of the substrate 1. The inner layer 2, the intermediate layer 3, and the outer layer 4 are sequentially formed. Before forming the inner layer 2, the surface of the substrate 1 may be activated by cleaning with argon ions. The thicknesses of the inner layer 2, the intermediate layer 3, and the outer layer 4 can be controlled by the ion plating processing time (the time during which pure titanium is heated and evaporated and ionized).
内層２は、アンモニアガス分解ガス、窒素、窒素と水素の混合ガスなどを導入して、ガスの組成を制御して形成する。内層２を形成した後、内層２を形成する際に使用したガスとともに、メタン、二酸化炭素、アセチレン等を導入して、中間層３を形成する。中間層３を形成した後、酸素のみを導入して、外層４を形成する。 The inner layer 2 is formed by introducing ammonia gas decomposition gas, nitrogen, a mixed gas of nitrogen and hydrogen, and the like, and controlling the gas composition. After the inner layer 2 is formed, the intermediate layer 3 is formed by introducing methane, carbon dioxide, acetylene, and the like together with the gas used when the inner layer 2 is formed. After forming the intermediate layer 3, only oxygen is introduced to form the outer layer 4.
イオンプレーティング法によって基材１の表面に被覆層５を形成させるためには、各層の形成時において、使用するガスの濃度および基材１の温度を均一に制御することが好ましい。形成時の雰囲気中のガス濃度および基材１の温度が不均一であると、内層２、中間層３、外層４の各層の厚みが不均一になり、外観に色調のばらつきが生じ易くなる。各層の形成時における雰囲気中の各種ガス濃度、基材の温度、処理時間は特に規定するものではなく、要求される被覆層の性状および組成に応じて、適宜設定すれば良い。 In order to form the coating layer 5 on the surface of the substrate 1 by the ion plating method, it is preferable to uniformly control the concentration of the gas used and the temperature of the substrate 1 during the formation of each layer. If the gas concentration in the atmosphere at the time of formation and the temperature of the substrate 1 are non-uniform, the thicknesses of the inner layer 2, the intermediate layer 3, and the outer layer 4 become non-uniform, and the color tone tends to vary in appearance. Various gas concentrations in the atmosphere at the time of forming each layer, the temperature of the substrate, and the treatment time are not particularly defined, and may be appropriately set according to the required properties and composition of the coating layer.
「黒色の外観」
本発明の発色チタン材は、図１に示す三層構造の被覆層５によって、黒色の外観を呈する。本発明では、発色チタン材の外観の測色をＪＩＳ Ｋ ５６００−４−５に準じて行う。本発明では、黒色を、ＪＩＳ Ｋ ５６００−４−４に準じて、Ｌ＊ａ＊ｂ＊表色系で表される色空間の数値範囲で定量的に定義し、Ｌ＊を１０．００〜４３．００、ａ＊を−３．００〜４．００、ｂ＊を−３．００〜６．００とする。Ｌ＊が４３．００を超えると、灰色の外観となるため、４３．００を上限とする。また、Ｌ＊の下限は、低いほど好ましいが、１０．００よりも低くすることは工業的に極めて困難であるため、１０．００を下限とする。また、ａ＊及びｂ＊が、それぞれ、−３．００〜４．００及び−３．００〜６．００の範囲外では黒色の外観を呈さない。例えば、ａ＊が高すぎると赤色系統、低すぎると緑色系統の色調が強くなる。ｂ＊が高すぎると黄色系統、低すぎると青色系統の色調が強くなることがある。
"Black appearance"
The colored titanium material of the present invention exhibits a black appearance by the coating layer 5 having a three-layer structure shown in FIG. In the present invention, the color appearance of the colored titanium material is measured according to JIS K 5600-4-5. In the present invention, black is quantitatively defined in the numerical range of the color space represented by the L * a * b * color system in accordance with JIS K 5600-4-4, and L * is 10.00 to 43.00, a * is -3.00 to 4.00, and b * is -3.00 to 6.00. If L * exceeds 43.00, a gray appearance is obtained, so 43.000 is the upper limit. Further, the lower limit of L * is preferably as low as possible. However, since it is extremely difficult industrially to make it lower than 10.00, 10.00 is set as the lower limit. Moreover, when a * and b * are outside the range of −3.00 to 4.00 and −3.00 to 6.00, respectively, no black appearance is exhibited. For example, if a * is too high, the color tone of the red color system becomes strong, and if it is too low, the color color of the green color system becomes strong. If b * is too high, the color tone of the yellow color system may become strong, and if it is too low, the color color of the blue color system may become strong.
「耐変色性の評価」
耐変色性は、酸性雨の影響を模擬した環境における発色チタン材のＬ＊ａ＊ｂ＊色空間の変化をＪＩＳ Ｋ ５６００−４−６に準拠し、色差で評価する。具体的には、発色チタン材をｐＨ３、温度６０℃の硫酸水溶液中に１４日間浸漬する浸漬試験を行い、試験前後の発色チタン材のＬ＊、ａ＊、ｂ＊色空間の差異から色差を求めて耐変色性を評価する。試験前後の色差（ΔＥ）は、以下の式によって算出する。色差の値の少ないものほど、耐変色性に優れ、ΔＥが４．０以下のものを耐変色性が良好と評価する。
"Evaluation of discoloration resistance"
The discoloration resistance is evaluated by a color difference in accordance with JIS K 5600-4-6 based on the change in L * a * b * color space of the colored titanium material in an environment simulating the influence of acid rain. Specifically, an immersion test is performed in which the colored titanium material is immersed in a sulfuric acid aqueous solution at pH 3 and a temperature of 60 ° C. for 14 days, and the color difference is determined from the difference in L * , a * , b * color space of the colored titanium material before and after the test. Obtain and evaluate discoloration resistance. The color difference (ΔE) before and after the test is calculated by the following formula. The smaller the color difference value, the better the resistance to discoloration, and the one having ΔE of 4.0 or less is evaluated as having good discoloration resistance.
ΔＥ＝｛（Ｌ＊ ２−Ｌ＊ １）２＋（ａ＊ ２−ａ＊ １）２＋（ｂ＊ ２−ｂ＊ １）２｝１／２
ここで、Ｌ＊ １、ａ＊ １、ｂ＊ １は浸漬試験前の色空間Ｌ＊ａ＊ｂ＊の測定値、Ｌ＊ ２、ａ＊ ２、ｂ＊ ２は浸漬試験後の色空間Ｌ＊ａ＊ｂ＊の測定値である。
ΔE = {(L * 2 -L * 1) 2 + (a * 2 -a * 1) 2 + (b * 2 -b * 1) 2} 1/2
Here, L * 1 , a * 1 , and b * 1 are measured values of the color space L * a * b * before the immersion test, and L * 2 , a * 2 , and b * 2 are the color space L after the immersion test. * Measured value of a * b * .
「各層の厚み及び組成、基材表面のＣ濃度の測定方法」
発色チタン材の外観の色調、被覆層５の密着性、耐変色性を制御するためには、基材１の表面（基材１と被覆層５（内層２）との界面から基材側）のＣ濃度、被覆層５の厚み及び組成が重要である。被覆層５の合計の厚み、内層２、中間層３、外層４の各層の厚みと、各層のＣ濃度、Ｎ濃度、Ｏ濃度及びＨ濃度、更に、基材１表面のＣ濃度は、グロー放電分光分析法（Ｇｌｏｗ Ｄｉｓｃｈａｒｇｅ Ｓｐｅｃｔｒｏｓｃｏｐｙ、ＧＤＳ）によって測定することができる。ＧＤＳは、指定した元素の深さ方向における濃度の変化を測定できる分析方法である。
"Method for measuring thickness and composition of each layer, C concentration on substrate surface"
In order to control the color tone of the appearance of the coloring titanium material, the adhesion of the coating layer 5, and the resistance to discoloration, the surface of the substrate 1 (from the interface between the substrate 1 and the coating layer 5 (inner layer 2) to the substrate side) C concentration, the thickness and composition of the coating layer 5 are important. The total thickness of the coating layer 5, the thicknesses of the inner layer 2, the intermediate layer 3 and the outer layer 4, the C concentration, the N concentration, the O concentration and the H concentration of each layer, and the C concentration on the surface of the substrate 1 are determined by glow discharge. It can be measured by spectroscopic analysis (Glow Discharge Spectroscopy, GDS). GDS is an analysis method that can measure changes in the concentration of a specified element in the depth direction.
ＧＤＳでは、Ｃ、Ｎ、Ｏ、Ｈ及びＴｉの分析を行い、Ｃ濃度、Ｎ濃度、Ｏ濃度及びＨ濃度の残部はＴｉ濃度となる。ＧＤＳによる測定では、深さ方向の元素分析を精度良く行うために、十分な分解能を備える装置を使用し、スパッタ速度及び測定時間を調整することが必要である。 In GDS, C, N, O, H, and Ti are analyzed, and the balance of C concentration, N concentration, O concentration, and H concentration is Ti concentration. In the measurement by GDS, it is necessary to use a device with sufficient resolution and adjust the sputtering rate and measurement time in order to perform elemental analysis in the depth direction with high accuracy.
発色チタン材の表面からＧＤＳによる測定を行う場合、まず、外層４の厚みは、最表面からＯ濃度が最表面のＯ濃度に対して半減する位置までの厚みとする。続いて、Ｏ濃度が半減した位置から深さ方向にＣ濃度がほぼ一定値を示した後、Ｃ濃度が半減する位置までの厚みを中間層３の厚みとする。更に、Ｃ濃度が半減した位置から深さ方向にＮ濃度がほぼ一定値を示した後、Ｎ濃度が半減する位置までの厚みを内層２の厚みとする。各元素の濃度は、各層の厚みでの平均値とする。Ｎ濃度がほぼ一定値を示した後、半減した位置は、基材１と被覆層５との界面であり、そのまま、ＧＤＳによる測定を継続して、１００ｎｍまでのＣ濃度を測定する。 When GDS measurement is performed from the surface of the coloring titanium material, first, the thickness of the outer layer 4 is a thickness from the outermost surface to a position where the O concentration is halved with respect to the O concentration of the outermost surface. Subsequently, the thickness from the position where the O concentration is halved to the position where the C concentration is halved after the C concentration is almost constant in the depth direction is defined as the thickness of the intermediate layer 3. Further, the thickness from the position at which the C concentration is reduced by half to the position at which the N concentration is reduced by half after the N concentration is almost constant in the depth direction is defined as the thickness of the inner layer 2. The concentration of each element is an average value in the thickness of each layer. After the N concentration shows a substantially constant value, the position where the N concentration is halved is the interface between the base material 1 and the coating layer 5, and the measurement by GDS is continued as it is to measure the C concentration up to 100 nm.
表１に示す種類及び表面仕上げの純チタン及びチタン合金を基材とし、イオンプレーティング法で被覆層を形成し、発色チタン材を得た。被覆層の形成は、アーク放電を用いたチタンのイオン化によるイオンプレーティングを実施して行った。 Using the types and surface finishes of pure titanium and titanium alloys shown in Table 1, a coating layer was formed by an ion plating method to obtain a colored titanium material. The coating layer was formed by performing ion plating by ionization of titanium using arc discharge.
表１では、純チタンの種類をＪＩＳ Ｈ ４６００に準じて、「純チタン１種」、「純チタン２種」、「純チタン３種」、「純チタン４種」と表記している。また、表面仕上げの「ＨＬ仕上げ」はヘアライン仕上げ、「ＶＡ」は真空焼鈍を意味する。
表１に示す基材においては、製造工程における焼鈍温度および焼鈍時間を調節することにより、被覆層と基材との界面から基材側に１００ｎｍまでの領域（基材表面）におけるＣ濃度が、表２に示す濃度となるようにした。なお、焼鈍後に表面仕上げとして酸洗および／または研磨を行った基材においては、酸洗および／または研磨により除去される厚みを調節することによっても、基材表面におけるＣ濃度を調節した。
In Table 1, according to JIS H 4600, the types of pure titanium are described as “Pure Titanium 1”, “Pure Titanium 2”, “Pure Titanium 3”, and “Pure Titanium 4”. The surface finish “HL finish” means hairline finish, and “VA” means vacuum annealing.
In the base material shown in Table 1, by adjusting the annealing temperature and annealing time in the manufacturing process, the C concentration in the region (base material surface) from the interface between the coating layer and the base material to the base material side up to 100 nm is The concentrations shown in Table 2 were used. In addition, in the base material which performed pickling and / or grinding | polishing as surface finishing after annealing, the C density | concentration in a base-material surface was also adjusted by adjusting the thickness removed by pickling and / or grinding | polishing.
基材の表面に被覆層を形成する前に、真空チャンバー内を真空（１０−２Ｐａ程度）にして、温度を上昇させ（１００℃程度）、アルゴンイオンを用いて基材の表面をクリーニングした。その後、真空度を高め、所定の真空度（１０−３〜１０−４Ｐａ程度）に到達した後、ガスを導入して基材の表面に被覆層を形成した。 Before forming the coating layer on the surface of the substrate, the inside of the vacuum chamber was evacuated (approximately 10 −2 Pa), the temperature was increased (approximately 100 ° C.), and the surface of the substrate was cleaned using argon ions. . Thereafter, the degree of vacuum was increased, and after reaching a predetermined degree of vacuum (about 10 −3 to 10 −4 Pa), a gas was introduced to form a coating layer on the surface of the substrate.
内層は、アンモニアガス分解ガス、窒素、窒素と水素の混合ガスを導入してガスの組成を調整して形成した。その後、内層を形成する際に使用したガスに、メタン、二酸化炭素、アセチレン等を加えてガスの組成を調整し、連続して中間層を形成した。中間層を形成した後、酸素のみを導入して連続して外層を形成し、発色チタン材を得た。内層、中間層、外層の各層の厚みは、イオンプレーティング処理時間によって制御した。なお、比較のため、一部の発色チタン材は、外層を形成する際に、酸素及び二酸化炭素を導入して製造した（Ｎｏ．３２）。また、一部の発色チタン材は、内層を形成せず、アンモニアガス分解ガス、窒素、窒素と水素の混合ガスに、メタン、二酸化炭素、アセチレン等を加えてガスの組成を調整し、中間層を形成した後、酸素のみを導入して連続して外層を形成して製造した（Ｎｏ．３１）。 The inner layer was formed by introducing ammonia gas decomposition gas, nitrogen, a mixed gas of nitrogen and hydrogen, and adjusting the gas composition. Then, methane, carbon dioxide, acetylene, etc. were added to the gas used when forming an inner layer, the composition of gas was adjusted, and the intermediate | middle layer was formed continuously. After forming the intermediate layer, only oxygen was introduced to continuously form the outer layer to obtain a colored titanium material. The thicknesses of the inner layer, intermediate layer, and outer layer were controlled by the ion plating treatment time. For comparison, some colored titanium materials were produced by introducing oxygen and carbon dioxide when forming the outer layer (No. 32). In addition, some colored titanium materials do not form an inner layer, and the gas composition is adjusted by adding methane, carbon dioxide, acetylene, etc. to a mixed gas of ammonia gas decomposition gas, nitrogen, nitrogen and hydrogen, and the intermediate layer After forming, the outer layer was continuously formed by introducing only oxygen (No. 31).
このようにして得られた各発色チタン材について、ＧＤＳによって上述した方法を用いて、被覆層の厚み、内層、中間層、外層の厚み及び組成、並びに、基材表面（被覆層と基材との界面から基材側に１００ｎｍまでの領域）のＣ濃度を測定した。その結果を表２に示す。 About each coloring titanium material obtained in this way, using the method described above by GDS, the thickness of the coating layer, the thickness and composition of the inner layer, the intermediate layer, the outer layer, and the substrate surface (the coating layer and the substrate) C concentration in the region from the interface to the substrate side up to 100 nm) was measured. The results are shown in Table 2.
表２に示す各発色チタン材から試料を採取し、ＪＩＳ Ｚ ５６００−４−５に準拠して外観の測色を行い、ＪＩＳ Ｋ ５６００−４−４に準じて、Ｌ＊ａ＊ｂ＊色空間の各座標（Ｌ＊、ａ＊、ｂ＊）を求めた。Ｌ＊ａ＊ｂ＊表色系で表される色空間が、Ｌ＊：１０．００〜４３．００、ａ＊：−３．００〜４．００、ｂ＊：−３．００〜６．００であるものを黒色と評価する。
更に、各発色チタン材をｐＨ３、温度６０℃の硫酸溶液中に１４日間浸漬する浸漬試験を行って、外観の測色を行った。その後、ＪＩＳ Ｋ５６００−４−６に準じて、浸漬試験前後の発色チタンの色差（ΔＥ）を測定した。なお、色差（ΔＥ）は、以下の式によって算出した。ΔＥが４．０以下のものを耐変色性が良好と評価する。
Samples were collected from each colored titanium material shown in Table 2, and the color of the appearance was measured according to JIS Z 5600-4-5. L * a * b * color according to JIS K 5600-4-4 Each coordinate (L * , a * , b * ) of space was calculated. The color space represented by the L * a * b * color system is L * : 10.00 to 43.00, a * : −3.00 to 4.00, b * : −3.00 to 6. A value of 00 is evaluated as black.
Further, an immersion test was conducted in which each colored titanium material was immersed in a sulfuric acid solution having a pH of 3 and a temperature of 60 ° C. for 14 days to measure the appearance. Thereafter, according to JIS K5600-4-6, the color difference (ΔE) of the colored titanium before and after the immersion test was measured. The color difference (ΔE) was calculated by the following formula. Those having ΔE of 4.0 or less are evaluated as having good discoloration resistance.
ΔＥ＝｛（Ｌ＊ ２−Ｌ＊ １）２＋（ａ＊ ２−ａ＊ １）２＋（ｂ＊ ２−ｂ＊ １）２｝１／２
ここで、Ｌ＊ １、ａ＊ １、ｂ＊ １は浸漬試験前の色空間Ｌ＊ａ＊ｂ＊の測定値、Ｌ＊ ２、ａ＊ ２、ｂ＊ ２は浸漬試験後の色空間Ｌ＊ａ＊ｂ＊の測定値である。
浸漬試験前のＬ＊ａ＊ｂ＊色空間の各座標（Ｌ＊、ａ＊、ｂ＊）および色差（ΔＥ）を表３に示す。
ΔE = {(L * 2 -L * 1) 2 + (a * 2 -a * 1) 2 + (b * 2 -b * 1) 2} 1/2
Here, L * 1 , a * 1 , and b * 1 are measured values of the color space L * a * b * before the immersion test, and L * 2 , a * 2 , and b * 2 are the color space L after the immersion test. * Measured value of a * b * .
Table 3 shows the coordinates (L * , a * , b * ) and color difference (ΔE) of the L * a * b * color space before the immersion test.
また、表２に示す各発色チタン材について、被覆層の密着性を、ＪＩＳ Ｋ ５６００−５−６に準拠して、クロスカット法で評価した。カットの間隔は１ｍｍとした。被覆層が全く剥離しなかったもの（試験結果の分類「０」）を○、剥離したもの（試験結果の分類「１」〜「５」）を×として評価した。その結果を表３に示す。 Moreover, about each color development titanium material shown in Table 2, the adhesiveness of the coating layer was evaluated by the cross-cut method based on JISK5600-5-6. The interval between cuts was 1 mm. The case where the coating layer did not peel at all (test result classification “0”) was evaluated as “○”, and the case where the coating layer was peeled off (test result classification “1” to “5”) was evaluated as “x”. The results are shown in Table 3.
表３に示すように、本発明例は、外観が黒色を呈し、かつ耐変色性及び密着性が良好であった。
これに対し、比較例は、外観が黒色でないか、耐変色性に劣るか、又は、密着性が劣位である。
As shown in Table 3, the examples of the present invention had a black appearance and good discoloration resistance and adhesion.
On the other hand, the comparative example is not black in appearance, inferior in discoloration resistance, or inferior in adhesion.
より詳細には、Ｎｏ．３１の発色チタン材は、内層がないため、明度が高く、灰色の外観となり、黒色の外観が得られなかった。また、Ｎｏ．３１の発色チタン材は、内層がないため、密着性が不十分であり、クロスカット法の評価が×になった。
Ｎｏ．３２の発色チタン材は、外層のＣ濃度が過剰であるため、耐変色性が不十分であり、色差（ΔＥ）が４．０超となった。
Ｎｏ．３３の発色チタン材は、中間層の厚みが不足しているため、灰色の外観となり、黒色の外観が得られなかった。
Ｎｏ．３４の発色チタン材は、基材表面のＣ濃度が高すぎるため、耐変色性が不十分であり、色差（ΔＥ）が４．０超となった。
Ｎｏ．３５の発色チタン材は、中間層のＣ濃度が不足しており、Ｎ濃度が高すぎるため、黄色系統の色調が強い外観となり、黒色の外観が得られなかった。
More specifically, no. Since the color-developing titanium material No. 31 had no inner layer, it had high brightness and a gray appearance, and a black appearance was not obtained. No. Since the coloring titanium material of 31 had no inner layer, the adhesion was insufficient, and the cross-cut method was evaluated as x.
No. In the 32 color developing titanium material, since the C concentration of the outer layer was excessive, the discoloration resistance was insufficient, and the color difference (ΔE) was more than 4.0.
No. The 33 color-developing titanium material had a gray appearance due to the insufficient thickness of the intermediate layer, and a black appearance was not obtained.
No. 34 colored titanium material had insufficient discoloration resistance because the C concentration on the surface of the substrate was too high, and the color difference (ΔE) exceeded 4.0.
No. In the 35 color developing titanium material, the C concentration of the intermediate layer was insufficient, and the N concentration was too high, so that the yellow color system had a strong color tone and a black appearance was not obtained.
１・・・ 基材
２・・・ 内層
３・・・ 中間層
４・・・ 外層
５・・・ 被覆層
DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Inner layer 3 ... Intermediate layer 4 ... Outer layer 5 ... Covering layer
Claims (2)
前記内層は、厚みが０．０１０〜０．１００μｍであり、
Ｃ濃度が１８．００原子％以下、
Ｎ濃度が１５．００〜４０．００原子％、
Ｏ濃度が１０．００〜３５．００原子％、
Ｈ濃度が１０．００原子％以下、
残部Ｔｉ及び不可避的不純物であり、
前記中間層は、厚みが０．１００〜０．９００μｍであり、
Ｃ濃度が４０．００〜６０．００原子％、
Ｎ濃度が１５．００〜３５．００原子％、
Ｏ濃度が５．００〜２５．００原子％、
Ｈ濃度が１５．００原子％以下、
残部Ｔｉ及び不可避的不純物であり、
前記外層は、厚みが０．０１０〜０．１００μｍであり、
Ｃ濃度が２０．００〜５０．００原子％、
Ｎ濃度が２５．００原子％以下、
Ｏ濃度が１５．００〜６０．００原子％かつ前記中間層のＯ濃度よりも高く、
Ｈ濃度が２０．００原子％以下、
残部Ｔｉ及び不可避的不純物であり、
外観のＬ＊ａ＊ｂ＊表色系で表される色空間が、Ｌ＊：１０〜４３、ａ＊：−３〜４、ｂ＊：−３〜６であることを特徴とする発色チタン材。 It has a coating layer formed in the order of an inner layer, an intermediate layer, and an outer layer from the base material side on the surface of the base material made of pure titanium or titanium alloy, and the base material from the interface between the coating layer and the base material C concentration in the region up to 100 nm on the side is 20.00 atomic% or less,
The inner layer has a thickness of 0.010 to 0.100 μm,
C concentration is 18.00 atomic% or less,
N concentration is 15.00-40.00 atomic%,
O concentration is 10.00 to 35.00 atomic%,
H concentration is 10.00 atomic% or less,
Remaining Ti and inevitable impurities,
The intermediate layer has a thickness of 0.100 to 0.900 μm,
C concentration is 40.00 to 60.00 atomic%,
N concentration is 15.00-35.00 atomic%,
O concentration is 5.00 to 25.00 atomic%,
H concentration is 15.00 atomic% or less,
Remaining Ti and inevitable impurities,
The outer layer has a thickness of 0.010 to 0.100 μm,
C concentration is 20.00-50.00 atomic%,
N concentration is 25.00 atomic% or less,
O concentration is 15.00-60.00 atomic% and higher than the O concentration of the intermediate layer,
H concentration is 20.00 atomic% or less,
Remaining Ti and inevitable impurities,
Colored titanium characterized in that the color space represented by the L * a * b * color system of the appearance is L * : 10-43, a * : -3-4, b * : -3-6 Wood.
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