JPH02209464A - Article showing bronzy color - Google Patents
Article showing bronzy colorInfo
- Publication number
- JPH02209464A JPH02209464A JP2756389A JP2756389A JPH02209464A JP H02209464 A JPH02209464 A JP H02209464A JP 2756389 A JP2756389 A JP 2756389A JP 2756389 A JP2756389 A JP 2756389A JP H02209464 A JPH02209464 A JP H02209464A
- Authority
- JP
- Japan
- Prior art keywords
- film
- color
- titanium
- aluminum
- bronzy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 150000004767 nitrides Chemical class 0.000 claims abstract description 14
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 14
- 229910000906 Bronze Inorganic materials 0.000 claims description 11
- 239000010974 bronze Substances 0.000 claims description 11
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 10
- 230000001747 exhibiting effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 14
- -1 TiN Chemical class 0.000 abstract description 8
- 239000006104 solid solution Substances 0.000 abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000007733 ion plating Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910001069 Ti alloy Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、時計などの外装部品、建材部品、自動車部品
、眼鏡の縁、文房具、アクセサリ−などに、表面の装飾
および保護を目的としてセラミック被膜を被覆したブロ
ンズ色を呈する物品に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention applies ceramics to exterior parts such as watches, building material parts, automobile parts, eyeglass rims, stationery, accessories, etc. for the purpose of surface decoration and protection. The invention relates to an article coated with a film that exhibits a bronze color.
［従来の技術］
従来より、窒化チタン、窒化ジルコニウム、窒化ハフニ
ウムなどの窒化物が金色を呈することが知られており、
それらの被膜を素材上に被覆することにより装飾の他に
保護膜の目的として各種装飾品や外装ケースに利用され
始めている。[Prior Art] It has been known that nitrides such as titanium nitride, zirconium nitride, and hafnium nitride exhibit a golden color.
By coating these films on materials, they are beginning to be used for various decorative items and exterior cases not only for decoration but also as a protective film.
また、窒化物以外にも炭化物、酸化物あるいは炭窒化物
、酸窒化物、炭酸化物、炭酸窒化物などを金色以外の色
、例えば黒色、銀黒色、銀白色、ピンク色、茶色などの
被膜として被覆することが行われている。In addition to nitrides, carbides, oxides, carbonitrides, oxynitrides, carbonates, and carbonitrides can be used as coatings in colors other than gold, such as black, silver-black, silver-white, pink, and brown. Covering is being done.
これらの被膜は、チタニウム、ジルコニウム、あるいは
ハフニウムなどを窒素雰囲気中にて蒸着またはスパッタ
リングまたはイオンブレーティングし、対象素材上にチ
タニウム、ジルコニウムあるいはハフニウムの窒化物を
コーティングするものであった。また金色以外の色を出
すためには、窒素の他に、酸素、あるいは炭素を供給す
るメタン、アセチレンなどを単独であるいはそれらの混
合ガスとして窒化物以外の炭化物、酸化物あるいは炭窒
化物、酸窒化物、炭酸化物、炭酸窒化物をコーティング
するものであった。These films were made by depositing titanium, zirconium, hafnium, etc. in a nitrogen atmosphere by vapor deposition, sputtering, or ion blasting to coat the target material with nitride of titanium, zirconium, or hafnium. In addition, in order to produce a color other than gold, in addition to nitrogen, oxygen, or methane, acetylene, etc. that supply carbon, may be used alone or as a mixture of these gases to produce carbides, oxides, carbonitrides, and oxidants other than nitrides. It was a coating of nitride, carbonate, and carbonitride.
しかしながら、これらの公知技術において金色以外の色
を出すため、窒化物、炭化物、酸化物あるいは炭窒化物
、酸窒化物、炭酸化物、炭酸窒化物を形成する際、反応
ガスの圧力やガスの混合比が、これら被膜の色調を大き
く左右させる。このため一定の色調を再現性よく得るた
めには、反応ガスの分圧や混合比を高精度に管理するこ
とが要求される。しかしそれは、工業的に大量生産する
場合、非常に困難なことである。However, in order to produce colors other than gold in these known techniques, when forming nitrides, carbides, oxides, carbonitrides, oxynitrides, carbonates, and carbonitrides, the pressure of the reaction gas and the mixture of gases must be adjusted. The ratio greatly influences the color tone of these coatings. Therefore, in order to obtain a constant color tone with good reproducibility, it is required to control the partial pressure and mixing ratio of the reaction gases with high precision. However, this is extremely difficult in industrial mass production.
［発明が解決しようとする課題］
そこで本発明の目的は、コーティング時の反応ガスを供
給する際の操業条件を厳格にすることなく、再現性よく
同一色調を得ることが可能なブロンズ色を呈する物品を
提供することにある。[Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide a bronze color that can obtain the same color tone with good reproducibility without making the operating conditions strict when supplying a reaction gas during coating. The goal is to provide goods.
［課題を解決するための手段］
上記目的を解決する手段として本発明は、チタン、ジル
コニウム、ハフニウムから選ばれる少なくとも１つの金
属窒化物中にアルミニウムを固溶させてなる被膜が、表
面に形成されている点に特徴がある。[Means for Solving the Problems] As a means for solving the above-mentioned objects, the present invention provides a method in which a coating formed by solidly dissolving aluminum in at least one metal nitride selected from titanium, zirconium, and hafnium is formed on the surface. It is distinctive in that it is
［作 用］
チタン、ジルコニウム、ハフニウムから選ばれる少なく
とも１つの金属の窒化物、例えば窒化チタン中にアルミ
ニウムを固溶させ、Ｔｉ−βｂＨの構造を持ち、かつａ
＋ｂ＝１となる被膜は、アルミニウムの濃度すが増える
にしたがって、窒化チタンの金色に次第に赤みがかかる
、オレンジ色に近くなる。さらにｂ ＝ ０．６になる
と、それに紫色が混じってくることから、赤紫色に近い
色合いの被膜が得られる。[Function] A solid solution of aluminum in a nitride of at least one metal selected from titanium, zirconium, and hafnium, such as titanium nitride, having a structure of Ti-βbH, and a
The film where +b=1 becomes almost orange in color, with the gold color of titanium nitride gradually becoming reddish as the aluminum concentration increases. Furthermore, when b = 0.6, purple is mixed into it, so a film with a hue close to reddish-purple can be obtained.
この色合いの変化をＪＩＳ Ｚ８７０１に規定され、国
際照明委員会（略称ＣＩＥ）により推奨されたＸ７２表
色系を用いて表現すると次のようになる。This change in hue is expressed as follows using the X72 color system specified by JIS Z8701 and recommended by the Commission Internationale de l'Eclairage (CIE).
窒化チタンの金色は、色度図（ＣＩ Ｅクロマトシティ
ダイヤグラム）中のオレンジないしはオレンジピンク領
域に相当するが、被膜の持つ光沢のため、金色に見える
。また、該ＪＩＳ規格で規定されている色度座標ｘ、ｙ
ではＸが約０．５及びｙが約０．４付近となるが、この
色度座標を厳密に特定することは困難である。なぜなら
ば、同じ組成の被膜であっても測定対象の表面の光沢（
表面の粗さ）により値が変化するためである。The gold color of titanium nitride corresponds to the orange or orange-pink region in the chromaticity diagram (CIE chromatography diagram), but it appears golden due to the luster of the film. In addition, the chromaticity coordinates x, y specified in the JIS standard
In this case, X is approximately 0.5 and y is approximately 0.4, but it is difficult to specify these chromaticity coordinates exactly. This is because even if the coating has the same composition, the gloss of the surface to be measured (
This is because the value changes depending on the roughness of the surface.
アルミニウムの濃度すを次第に増やしてゆくと、赤みが
ましくｙが減少し）、さらに濃度が増えてｂ ＝ ０．
６になると紫色に近いものとなる（ｘ、 ｙ共に減少す
る）。これは、色度座標のｘ ＝ ０．４及びｙ ＝
０．３付近の領域に相当する。As the concentration of aluminum is gradually increased, y becomes reddish (y decreases), and the concentration increases further until b = 0.
When it reaches 6, it becomes almost purple (both x and y decrease). This corresponds to the chromaticity coordinates x = 0.4 and y =
This corresponds to an area around 0.3.
Ｍ３＾ＡｂＮの構造を持ち、ａ＋ｂ＝１で固溶されるア
ルミニウムの原子濃度すがＱ＜ｂ≦０．６の範囲である
被膜の色は、色度図中のオレンジ、ピンク及び紫がかっ
たピンクの領域に相当するが、該被膜は光沢を持ってい
るため、見た目にはいわゆるブロンズ色を呈するものと
なる。The color of the film, which has the structure M3^AbN and has an atomic concentration of aluminum dissolved in solid solution with a+b=1, is in the range of Q<b≦0.6, and is orange, pink, and purplish in the chromaticity diagram. Although it corresponds to a pink area, since the film has a gloss, it appears to have a so-called bronze color.
該被膜は、反応ガスの混合比等をコントロールして作製
するのではなく、固溶させるアルミニウムの濃度を変え
ることによって色合いをコントロールしているため、複
数の蒸発源を使用したり、あるいは蒸発源の金属中のア
ルミニウムの濃度を予め定めておけば、再現性よく同一
色調のブロンズ色を得ることが可能である。特に後者の
アルミニウムの濃度を予め定めた合金蒸発源を用いれば
、大量生産時の工程管理を大幅に簡略化することができ
る。The coating is not produced by controlling the mixing ratio of reaction gases, but rather by changing the concentration of solid-dissolved aluminum, so it is necessary to use multiple evaporation sources or If the concentration of aluminum in the metal is determined in advance, it is possible to obtain a bronze color of the same tone with good reproducibility. In particular, if an alloy evaporation source with a predetermined aluminum concentration is used, process control during mass production can be greatly simplified.
また、アルミニウムの濃度すが０．６以上の被膜ではさ
らに紫色の濃さが増し、黒色に近いものが得られる。し
かしながら、もしｂが０．６を越えると、アルミニウム
が窒化チタン中に完全に固溶せず、窒化チタンとは異な
る結晶構造となる。そのため被膜の機械的特性が劣化し
、硬質膜としての性質が摂なわれることが考えられるの
で不都合である。Further, in a coating having an aluminum concentration of 0.6 or more, the purple color becomes even more intense, and a coating close to black can be obtained. However, if b exceeds 0.6, aluminum will not be completely dissolved in titanium nitride, resulting in a crystal structure different from that of titanium nitride. This is disadvantageous because the mechanical properties of the coating may deteriorate and the properties of a hard film may be lost.
本発明の被膜は、イオンブレーティング法、蒸着法、ス
パッタリング法などの公知の方法を用いて製膜しても良
いが、特に強固な付着力を要求される被膜に対しては、
イオンブレーティング法が望ましい。The film of the present invention may be formed using a known method such as an ion blasting method, a vapor deposition method, or a sputtering method, but for a film that requires particularly strong adhesion,
Ion blating method is preferred.
該被膜をイオンブレーティング法で製膜する際、蒸発源
としてチタン、ジルコニウム、ハフニウムから選ばれる
少くとも１種、例えばチタンおよび金属アルミニウムの
２つを用いるが、該金属アルミニウムのかわりにアルミ
ニウムの原子濃度が５０％以下のチタン、ジルコニウム
、ハフニウムから選ばれる少くとも１種の元素金属とア
ルミニウムの合金を用いても良い。金属の蒸発およびイ
オン化の方法は特に制限されず、金属を蒸発させる方法
は、イオンブレーティング装置に備わった公知の抵抗加
熱や電子銃加熱などのどれでも良く、蒸発した金属のイ
オン化も公知のアーク放電、グロー放電、高周波放電な
どのいずれでも良い。When forming the film by the ion-blating method, at least one kind selected from titanium, zirconium, and hafnium is used as an evaporation source, for example, two of titanium and metal aluminum, but aluminum atoms are used instead of the metal aluminum. An alloy of aluminum and at least one elemental metal selected from titanium, zirconium, and hafnium with a concentration of 50% or less may be used. The method of evaporating and ionizing the metal is not particularly limited, and the method of evaporating the metal may be any known resistance heating or electron gun heating provided in the ion blating device, and the ionization of the evaporated metal can also be performed using a known arc. Any of discharge, glow discharge, high frequency discharge, etc. may be used.
異なる色調のブロンズ色を出すためにチタン、ジルコニ
ウム、ハフニウムから選ばれる少くとも１種の元素の金
属とアルミニウムの組成比を任意に制御する方法は、２
つの蒸発源の蒸発量を変化させても良いし、シャッター
などの遮蔽物の開閉による方法を用いても良い。A method of arbitrarily controlling the composition ratio of at least one metal element selected from titanium, zirconium, and hafnium and aluminum in order to produce bronze colors of different tones is as follows:
The amount of evaporation from one evaporation source may be changed, or a method of opening and closing a shield such as a shutter may be used.
反応性ガスとしては、窒化物を生成させるための反応性
ガスで、窒素あるいはアンモニアまたはこれらの混合ガ
スを用いればよく、該反応性ガスを反応容器中に導入す
る。The reactive gas is a reactive gas for producing nitrides, and nitrogen, ammonia, or a mixture thereof may be used, and the reactive gas is introduced into the reaction vessel.
被覆させる素材は、合成樹脂、金属またはセラミック等
何でも良く、この素材上にめっきまたはコーティング処
理によって、ニッケル、クロム等の金属被膜や、金属の
窒化物、酸化物、炭化物またはそれらの複合物の被膜が
下地として形成されていてもさしつかえない。The material to be coated may be any material such as synthetic resin, metal, or ceramic, and by plating or coating on this material, a metal film such as nickel, chromium, or a film of metal nitride, oxide, carbide, or a composite thereof can be formed. There is no problem even if it is formed as a base.
被覆する対象物が金属のように導電性を持つものであれ
ば、基材に負のバイアス電圧を印加し、チタン、ジルコ
ニウム、ハフニウムから選ばれる少くとも１種の元素の
金属アルミニウムの組成比を上記方法により制御して本
発明の被膜を製膜する。また基材が導電性の無い合成樹
脂あるいはセラミックなどのようなものの場合は、基材
に高周波（ＲＦ）を印加して製膜を行うか、予め基材表
面にめっきあるいは蒸着あるいはスパッタリングによっ
てニッケル、クロム等の金属被膜や、導電性を持つセラ
ミンク等を被覆してから製膜する。If the object to be coated is electrically conductive, such as a metal, a negative bias voltage is applied to the base material, and the composition ratio of metallic aluminum of at least one element selected from titanium, zirconium, and hafnium is adjusted. The film of the present invention is formed by controlling the method described above. In addition, if the base material is made of non-conductive synthetic resin or ceramic, the film may be formed by applying radio frequency (RF) to the base material, or by plating, vapor deposition, or sputtering on the surface of the base material in advance. The film is formed after being coated with a metal film such as chromium or a conductive ceramic film.
これら金属被膜や、金属の窒化物、酸化物、炭化物また
はそらの複合物が下地として被覆されていると、耐食性
や、耐衝撃性を向上させる意味においても非常に有効で
ある。Coating with these metal films, metal nitrides, oxides, carbides, or composites thereof as a base is very effective in improving corrosion resistance and impact resistance.
以下に実施例を示し、本発明を更に説明する。The present invention will be further explained with reference to Examples below.
［実施例１］
１７ｍ角、厚み２鶴のステンレスｍ （Ｓ［ｌ５３０４
）基板を鏡面にまで研磨し、有機溶剤で洗浄した後、真
空アーク放電型イオンブレーティング装置に取付けた。[Example 1] Stainless steel m (S [l5304
) After polishing the substrate to a mirror surface and cleaning it with an organic solvent, it was installed in a vacuum arc discharge type ion blating device.
蒸発源としてはチタンターゲットと、チタンとアルミニ
ウムの原子組成比が５０％ずつの合金ターゲットを用い
た。As the evaporation source, a titanium target and an alloy target with an atomic composition ratio of titanium and aluminum of 50% each were used.
まず真空度を１×１０″５Ｔｏｒｒ以下にした後、チタ
ンイオン衝撃により、基材の洗浄、加熱を行った。次に
反応ガスとして窒素ガスを導入して、装置内圧力を３０
ｍＴｏｒｒとした。First, the degree of vacuum was reduced to 1 x 10''5 Torr or less, and the substrate was cleaned and heated by titanium ion bombardment.Next, nitrogen gas was introduced as a reaction gas, and the pressure inside the device was reduced to 30
mTorr.
最も紫色に近い色調のブロンズ色の被膜を作るために、
まずチタン・アルミニウム比が５０原子％ずつのチタン
・アルミニウム合金ターゲットの電流値を９０Ａとして
、真空アーク放電でチタンイオンとアルミニウムイオン
を放出させて、−３００Ｖのバイアス電圧が印加された
基材上にＴｔＪ７！ｂＮを１５分間製膜した。To create a bronze-colored film with a tone closest to purple,
First, a titanium/aluminum alloy target with a titanium/aluminum ratio of 50 at % was set at a current value of 90 A, and titanium ions and aluminum ions were released by vacuum arc discharge onto a base material to which a bias voltage of -300 V was applied. TtJ7! bN was formed into a film for 15 minutes.
製膜した被膜のチタンとアルミニウムの組成比は、電子
線マイクロ分析装置（ＥＰＭＡ）により測定したところ
、ａ ： ｂ＝ｏ、６ ： ０．４であった。The composition ratio of titanium and aluminum in the formed film was measured using an electron beam microanalyzer (EPMA), and was found to be a:b=o, 6:0.4.
［実施例２］
チタン・ターゲットとチタン・アルミニウム合金ターゲ
ットの２つの蒸発源を使い、チタン・ターゲットの電流
値を４０Ａ、チタン・アルミニウム合金ターゲットの電
流値を８０Ａとした以外は、実施例１と同様に製膜した
。[Example 2] Same as Example 1 except that two evaporation sources, a titanium target and a titanium/aluminum alloy target, were used, and the current value of the titanium target was 40 A, and the current value of the titanium/aluminum alloy target was 80 A. A film was formed in the same manner.
製膜した被膜のチタンとアルミニウムの組成比は、ａ
： ｂ＝ｏ、７ ： ０．３であった。The composition ratio of titanium and aluminum in the formed film is a
: b=o, 7 : 0.3.
［実施例３〕
チタン・ターゲットの電流値を６ＯＡ、チタン・アルミ
ニウム合金ターゲットの電流値を６ＯＡとした以外は、
実施例２と同様に製膜した。[Example 3] Except that the current value of the titanium target was 6OA and the current value of the titanium/aluminum alloy target was 6OA,
A film was formed in the same manner as in Example 2.
製膜した被膜のチタンとアルミニウムの組成比は、ａ
： ｂ ＝ ０．８ ： ０．２ テアツタ。The composition ratio of titanium and aluminum in the formed film is a
: b = 0.8 : 0.2 Tea ivy.
［実施例４］
チタン・ターゲットの電流値を８０Ａ、チタン・アルミ
ニウム合金ターゲットの電流値を４０Ａとした以外は、
実施例２と同様に製膜した。[Example 4] Except that the current value of the titanium target was 80A and the current value of the titanium/aluminum alloy target was 40A,
A film was formed in the same manner as in Example 2.
製膜した被膜のチタンとアルミニウムの組成比は、ａ
： ｂ＝ｏ、８５ ： ０．１５Ｔニアツタ。The composition ratio of titanium and aluminum in the formed film is a
: b=o, 85: 0.15T near ivy.
［比較例］
比較例として、実施例と同じ装置を使い窒素チタンを作
製した。方法は、チタン・ターゲットを用いた他は、実
施例１と同様に製膜した。[Comparative Example] As a comparative example, nitrogen titanium was produced using the same apparatus as in the example. The film was formed in the same manner as in Example 1, except that a titanium target was used.
実施例１〜４で得られた被膜は、アルミニウムの原子濃
度すが増えるに従って赤みを帯びたブロンズ色から赤紫
色に近いブロンズ色を呈している。The coatings obtained in Examples 1 to 4 exhibit a reddish bronze color to a bronze color close to reddish-purple as the aluminum atomic concentration increases.
実施例１〜４および比較例の色を表示するために、ＪＩ
Ｓ Ｚ８７０１に規定されるＸ７２表色系における色度
座標ｘ、ｙを用いた。To display the colors of Examples 1-4 and comparative examples, JI
The chromaticity coordinates x and y in the X72 color system defined in SZ8701 were used.
該ＪＩＳ規格によるカラーテスターにより各試料の色度
座標ｘ、ｙを測定したところ、第１表の数値が得られた
。When the chromaticity coordinates x and y of each sample were measured using a color tester according to the JIS standard, the values shown in Table 1 were obtained.
求められた色度座標ｘ、ｙを該ＪＩＳ規格に付図されて
いる色度図にプロットしたものが、第１図である。図中
の黒丸１〜４が実施例１〜４に対応し、黒丸５が比較例
のＴｉＮを表す。FIG. 1 shows the obtained chromaticity coordinates x, y plotted on the chromaticity diagram attached to the JIS standard. Black circles 1 to 4 in the figure correspond to Examples 1 to 4, and black circle 5 represents TiN as a comparative example.
第１表
Ｕ発明の効果コ
以上のように本発明のブロンズ色を呈する物品は、コー
ティング時の混合ガスを供給する際の操業条件を厳格に
する必要はなく、再現性よく同一色調を得ることができ
、工業的に低コストで大量生産するのに極めて好適であ
る。Table 1 U Effects of the Invention As described above, the article exhibiting a bronze color of the present invention does not require strict operating conditions when supplying a mixed gas during coating, and can obtain the same color tone with good reproducibility. It is extremely suitable for industrial mass production at low cost.
しかも、その色調は被膜中に固溶させるアルミニウムの
濃度により決定することができ、その濃度をコントロー
ルすることは、蒸発源であるターゲット組成を変えれば
良いため、極めて容易である。Furthermore, the color tone can be determined by the concentration of aluminum solid-dissolved in the film, and controlling the concentration is extremely easy because it is only necessary to change the composition of the target, which is the evaporation source.
図面は、本発明の実施例に関するものであって、第１図
は、本発明の被膜のチタンとアルミニウムの濃度比を変
えた実施例１〜４と、比較例としての窒化チタンの色度
図である。これは、ＪＩＳ Ｚ８７０１に規定されてい
る色の表示方法である。
横軸及び縦軸は、色度座標ｘ、ｙである。波長目盛りの
付いている曲線は、スペクトル軌跡であって、スペクト
ル軌跡の両端を結ぶ直線は、純紫軌跡である。測定され
た光の波長により色が定められ、図中の表示は、赤、黄
、緑、青、紫等の主な色の領域の位置を示している。
なお、点Ａ、Ｂ、、Ｃ及びＤ６５は、標準の光Ａ１Ｂ、
Ｃ及びＤ６５ （ＪＩＳ ｚ８７２０） （７）色度座
標を表し、Ｄ６５は白色の色度座標である。The drawings relate to Examples of the present invention, and FIG. 1 is a chromaticity diagram of Examples 1 to 4 in which the concentration ratio of titanium and aluminum in the coating of the present invention was changed, and titanium nitride as a comparative example. It is. This is a color display method defined in JIS Z8701. The horizontal and vertical axes are the chromaticity coordinates x, y. The curve with a wavelength scale is a spectral locus, and the straight line connecting both ends of the spectral locus is a pure violet locus. The color is determined by the wavelength of the measured light, and the markings in the figure indicate the positions of the main color regions, such as red, yellow, green, blue, and violet. Note that points A, B, , C, and D65 are standard lights A1B,
C and D65 (JIS z8720) (7) Represents chromaticity coordinates, and D65 is the chromaticity coordinate of white.
Claims (2)
少なくとも１つの金属の窒化物中にアルミニウムを固溶
させてなる被膜が、表面に形成されていることを特徴と
するブロンズ色を呈する物品。(1) An article exhibiting a bronze color, characterized in that a coating formed by solidly dissolving aluminum in a nitride of at least one metal selected from titanium, zirconium, and hafnium is formed on the surface.
ジルコニウム、ハフニウムから選ばれる少なくとも１つ
の金属を示す。）の構造を持ち、かつａ＋ｂ＝１となり
、固溶されるアルミニウムの原子濃度ｂが０＜ｂ≦０．
６の範囲にあることを特徴とする特許請求の範囲第１項
に記載のブロンズ色を呈する物品。(2) The above film is M_aAl_bN (M is titanium,
Indicates at least one metal selected from zirconium and hafnium. ), and a+b=1, and the atomic concentration b of solid-dissolved aluminum is 0<b≦0.
6. An article exhibiting a bronze color according to claim 1, characterized in that the bronze color is in the range of 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1027563A JP2716186B2 (en) | 1989-02-08 | 1989-02-08 | Articles with a bronze color |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1027563A JP2716186B2 (en) | 1989-02-08 | 1989-02-08 | Articles with a bronze color |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02209464A true JPH02209464A (en) | 1990-08-20 |
| JP2716186B2 JP2716186B2 (en) | 1998-02-18 |
Family
ID=12224501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1027563A Expired - Fee Related JP2716186B2 (en) | 1989-02-08 | 1989-02-08 | Articles with a bronze color |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2716186B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2699555A1 (en) * | 1992-12-23 | 1994-06-24 | Ebauchesfabrik Eta Ag | Object having a pinkish-colored coating. |
| JPH10102245A (en) * | 1996-07-31 | 1998-04-21 | Dr Ing H C F Porsche Ag | Gloss coating method for member, preferably, for member for vehicle, particularly, for wheel and member coated thereby |
| JP2007182630A (en) * | 2005-12-30 | 2007-07-19 | Meian Kokusai Gigyo Kofun Yugenkoshi | Method of giving multi-colored metallic performance to non-metallic article and non-metallic article having multi-color metallic appearance |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63266068A (en) * | 1987-04-23 | 1988-11-02 | Nisshin Steel Co Ltd | Method for coloring dry ceramic coating film |
-
1989
- 1989-02-08 JP JP1027563A patent/JP2716186B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63266068A (en) * | 1987-04-23 | 1988-11-02 | Nisshin Steel Co Ltd | Method for coloring dry ceramic coating film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2699555A1 (en) * | 1992-12-23 | 1994-06-24 | Ebauchesfabrik Eta Ag | Object having a pinkish-colored coating. |
| EP0603673A1 (en) * | 1992-12-23 | 1994-06-29 | Eta SA Fabriques d'Ebauches | Object having a pink coating |
| JPH10102245A (en) * | 1996-07-31 | 1998-04-21 | Dr Ing H C F Porsche Ag | Gloss coating method for member, preferably, for member for vehicle, particularly, for wheel and member coated thereby |
| JP4584366B2 (en) * | 1996-07-31 | 2010-11-17 | ドクトル イング ハー ツェー エフ ポルシェ アクチエンゲゼルシャフト | Glossy coating method for components, preferably vehicle components, in particular wheels, and components coated thereby |
| JP2007182630A (en) * | 2005-12-30 | 2007-07-19 | Meian Kokusai Gigyo Kofun Yugenkoshi | Method of giving multi-colored metallic performance to non-metallic article and non-metallic article having multi-color metallic appearance |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2716186B2 (en) | 1998-02-18 |
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