JPH0149783B2 - - Google Patents
Info
- Publication number
- JPH0149783B2 JPH0149783B2 JP55057243A JP5724380A JPH0149783B2 JP H0149783 B2 JPH0149783 B2 JP H0149783B2 JP 55057243 A JP55057243 A JP 55057243A JP 5724380 A JP5724380 A JP 5724380A JP H0149783 B2 JPH0149783 B2 JP H0149783B2
- Authority
- JP
- Japan
- Prior art keywords
- corrosion resistance
- alloy
- mesh
- band
- less
- 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.)
- Expired
Links
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 239000011651 chromium Substances 0.000 claims description 15
- 239000010955 niobium Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 description 25
- 238000005260 corrosion Methods 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000009940 knitting Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 4
- 210000004243 sweat Anatomy 0.000 description 4
- -1 chlorine ions Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 101150062705 Wipf3 gene Proteins 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は機械的性質および耐食性を改善した腕
時計など携帯時計用外装部品特に腕時計用メツシ
ユバンドに関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an exterior part for a portable timepiece such as a wristwatch that has improved mechanical properties and corrosion resistance, and particularly to a mesh band for a wristwatch.
従来、腕時計用外装部品は、素材が黄銅もしく
は洋白で、それにニツケルメツキし、金、パラジ
ウム、ロジウムあるいはこれら合金のメツキを施
すものが主流であつた。あるいはオーステナイト
系ステンレス鋼、例えば180r−8Niステンレス鋼
を素材とし、表面研磨仕上げをして腕時計用外装
部品として供していた。しかし、腕時計用外装部
品の場合、複雑な形状をしているため携帯中に間
〓部分に汗、海水等が作用して腐食を生じ、商品
の価値を著しく低下させる事例があつた。特にメ
ツシユバンドは上記の現象がはなはだしかつた。 Conventionally, exterior parts for wristwatches have been mainly made of brass or nickel silver, plated with nickel, and plated with gold, palladium, rhodium, or an alloy thereof. Alternatively, they were made of austenitic stainless steel, such as 180r-8Ni stainless steel, and were used as exterior parts for wristwatches with a polished surface. However, in the case of wristwatch exterior parts, because they have a complex shape, there have been cases where sweat, seawater, etc. interact with the outer parts while the watch is being carried, causing corrosion, which significantly reduces the value of the product. The above phenomenon was particularly noticeable in the Metsuyu band.
また近年の腕時計の薄型化、小型化により、外
装部品素材として耐食性に優れ、かつ機械的性
質、とりわけ強度面で優れる材料が望まれてい
る。 In addition, as wristwatches have become thinner and smaller in recent years, there has been a demand for materials that have excellent corrosion resistance and mechanical properties, especially strength, as materials for exterior parts.
先行技術として類似のものとして、特開昭53−
90120に示されるように、Ni−Cr−Mo−Nbの合
金が開示されているが、この組成ではメツシユバ
ンド用としては、脆くてメツシユ編機への適性が
少なく、ヘリツクスの折損や、編むのに困難をと
もなつていた。 As a similar prior art, Japanese Patent Application Laid-Open No. 1983-
90120, an alloy of Ni-Cr-Mo-Nb has been disclosed, but this composition is brittle for mesh bands and is not suitable for mesh knitting machines, resulting in breakage of helices and difficulty in knitting. It was fraught with difficulties.
本発明は上記欠点を除去し、更に腕時計の薄型
化、小型化を促すためになされたものである。す
なわち、それ自体で耐食性の優れるNiをベース
に酸化性条件において耐食性の優れるCrと塩素
イオンを含む非酸化性条件下において耐食性に優
れるMoを加え、更に、Nbによつて機械的強度の
向上を図ることにより、従来のオーステナイト系
ステンレス鋼の如きCrによつて耐食性を維持す
る合金に替る高耐食、高強度の腕時計用メツシユ
バンドを提供するものである。 The present invention has been made in order to eliminate the above-mentioned drawbacks and to encourage wristwatches to be made thinner and smaller. In other words, based on Ni, which itself has excellent corrosion resistance, Cr, which has excellent corrosion resistance under oxidizing conditions, and Mo, which contains chlorine ions and has excellent corrosion resistance under non-oxidizing conditions, are added, and Nb improves mechanical strength. By doing so, it is possible to provide a highly corrosion-resistant and high-strength mesh band for wristwatches that can be used as an alternative to conventional alloys such as austenitic stainless steels, which maintain corrosion resistance through Cr.
本発明の腕時計用メツシユバンドは、いずれも
重量比にてCr（クロム）16％以上25％以下、Mo
（モリブデン）５％をこえて30％以下、Nb（ニオ
ブ）２％をこえて５％以下、Fe（鉄）５％以上25
％以下、Ｃ（炭素）0.08％以下で残部Niおよび不
可避的不純物よりなる合金線材を用いたことを特
徴とする。 The mesh band for wristwatches of the present invention has a weight ratio of Cr (chromium) of 16% to 25%, Mo.
(Molybdenum) More than 5% and less than 30%, Nb (niobium) More than 2% and less than 5%, Fe (Iron) More than 5%25
% or less, C (carbon) is 0.08% or less, and the balance is Ni and unavoidable impurities.
このような組成とすることにより、腕時計用メ
ツシユバンドの如き複雑な部品の耐食性及び強度
向上を図ることが可能である。 With such a composition, it is possible to improve the corrosion resistance and strength of complex parts such as mesh bands for wristwatches.
次に各成分の添加効果と組成範囲の限定理由を
述べる。 Next, the effect of adding each component and the reason for limiting the composition range will be described.
Niは耐食性が非常に優れており、Cr、Mo、
Niを十分に固溶し、合金強化と耐食性向上に大
きな特徴を有する有用なベース金属である。 Ni has very good corrosion resistance, and Cr, Mo,
It is a useful base metal that contains a sufficient amount of Ni as a solid solution, and has the major characteristics of strengthening the alloy and improving corrosion resistance.
Crは、合金の強度を向上し、耐食性を著しく
向上する元素であり、Niベースで後述のMo添加
の場合において十分な耐食性を維持するためには
16％が必要である。しかし、25％を越えて加える
と合金の脆化が見られ、材料の伸びが減少し線材
とした場合、メツシユバンドの加工が困難とな
り、メツシユ編み機械に止まることが起こり、30
％を越えると線材の折損が起こるのでCrの添加
範囲は16〜25％に定める。 Cr is an element that improves the strength of the alloy and significantly improves its corrosion resistance. Cr is an element that improves the strength of the alloy and significantly improves its corrosion resistance. Cr is an element that increases the strength of the alloy and significantly improves its corrosion resistance.
16% is required. However, if more than 25% is added, the alloy becomes brittle, the elongation of the material decreases, and when made into a wire rod, it becomes difficult to process the mesh band, and the mesh knitting machine stops working.
%, the wire rod will break, so the addition range of Cr is set at 16 to 25%.
Moは、合金強度の向上とともに、海水のよう
な塩素イオンを含む腐食環境に対して、優れた耐
食性を示す元素であり、耐食性に対しては５％を
こえてからその効果が著しく顕著になる。本合金
のベースに対するMoの固溶限はほぼ30％であ
り、これを越えるとメツシユ編みの加工性が困難
となり、メツシユ編みした時に線材が折れやすく
なる。また、原料を作るときにも溶解が非常に困
難になるため５％をこえて30％の範囲まで限定す
る。 Mo is an element that not only improves alloy strength, but also exhibits excellent corrosion resistance in corrosive environments containing chlorine ions, such as seawater, and its effect on corrosion resistance becomes particularly noticeable when it exceeds 5%. . The solid solubility limit of Mo in the base of this alloy is approximately 30%, and if this limit is exceeded, the workability of mesh weaving becomes difficult, and the wire rod tends to break when mesh knitted. Also, when making raw materials, it becomes extremely difficult to dissolve, so the content is limited to more than 5% and 30%.
Nbは、Ni−Crマトリツクス中で優れた硬化能
を示し、本合金の機械的性質向上に大きく寄与す
る元素である。また、炭素を安定化し、クロム炭
化物の析出による耐食性低下をも妨げる元素であ
る。上記二点の効果はNbの添加量が２％をこえ
ると顕著になり添加量の増大とともにその効果を
増すが５％をこえるとメツシユ編み時の加工性が
低下するのでNbの添加量は２％をこえ５％以下
に定める。 Nb is an element that exhibits excellent hardenability in the Ni-Cr matrix and greatly contributes to improving the mechanical properties of the present alloy. It is also an element that stabilizes carbon and prevents corrosion resistance from decreasing due to precipitation of chromium carbide. The above two effects become noticeable when the amount of Nb added exceeds 2%, and the effects increase as the amount added increases, but when it exceeds 5%, the workability during mesh knitting decreases, so the amount of Nb added is 2%. % to 5% or less.
FeはCrを溶解する際のフエロアロイとして扱
うために５％位は入り込むが、また５％以上入つ
ていないと、伸びがよくならない。 Approximately 5% Fe is included to treat it as a ferroalloy when dissolving Cr, but unless it is included at least 5%, elongation will not improve.
また腕時計用外装部品としては、低コストで製
造できることが必須条件であり、本合金において
はCr、Moをバランスよく添加することによりFe
を25％まで添加しても耐食性を損なうことがな
く、伸びも充分に確保できるので、メツシユ編み
時に折損をすることもない。また、素材の製造コ
ストも低減させるものである。 In addition, as an exterior part for a wristwatch, it is essential that it can be manufactured at low cost, and this alloy has a well-balanced addition of Cr and Mo.
Even if up to 25% is added, corrosion resistance is not impaired and sufficient elongation is ensured, so there is no breakage during mesh knitting. It also reduces the manufacturing cost of the material.
Ｃは、固溶体を強化し、強度を向上するが、
800℃前後の使用においてCrと炭化物を形成し耐
食性と強度を劣化させるので極力減少すべく努力
が払われるべきである。しかし、0.08％以下の範
囲であれば前述のNbの添加効果により固定され
るので、0.08以下に限定する。 C strengthens the solid solution and improves the strength, but
When used at temperatures around 800°C, carbides are formed with Cr, which deteriorates corrosion resistance and strength, so efforts should be made to reduce this as much as possible. However, if it is in the range of 0.08% or less, it will be fixed by the effect of the addition of Nb mentioned above, so it is limited to 0.08% or less.
次に本発明の実施例を示す。 Next, examples of the present invention will be shown.
実施例 １
重量比にて、Cr16％、Mo5.5％、Nb2.5％、
Fe5％、C0.03％、残部Niおよび不可避的不純物
からなる合金を0.6mmφの線材を原料として、こ
れより腕時計用メツシユバンドを作成した。この
バンドおよび17Cr−15Ni、0.02％Ｃの低カーボ
ンオーステナイト系ステンレス鋼を素材としたバ
ンドで人工浸漬、５％食塩水溶液浸漬７日間の耐
食性試験を実施したところ、ステンレス鋼を素材
としたバンドの場合にはバンド全面に顕著な赤錆
が発生した。しかし本発明で得られたバンドは発
錆もほとんど見られなかつた。Example 1 Weight ratio: Cr16%, Mo5.5%, Nb2.5%,
A mesh band for a wristwatch was made from an alloy consisting of 5% Fe, 0.03% C, the balance Ni, and unavoidable impurities using a 0.6 mmφ wire as a raw material. When this band and a band made of low carbon austenitic stainless steel with 17Cr-15Ni and 0.02% C were artificially immersed and immersed in a 5% saline solution for 7 days, a corrosion resistance test was conducted. Significant red rust appeared on the entire surface of the band. However, in the band obtained according to the present invention, almost no rust was observed.
尚、機械的性質においては、引張強度81Kg／
mm2、伸び40％とすぐれた性質を示した。 In terms of mechanical properties, the tensile strength is 81Kg/
It showed excellent properties with mm 2 and elongation of 40%.
実施例 ２
重量比にて、Cr25％、Mo30％、Nb5％、Fe25
％、C0.08％、残部Niおよび不可避的不純物より
なる合金を実施例１と同様の方法にて、腕時計メ
ツシユバンド作製後、このバンドおよびこれと同
様の方法で作製した20Cr−30Niのオーステナイ
ト系ステンレス鋼を素材としたバンドで人工汗、
５％食塩水浸漬７日間の耐食性試験を実施したと
ころ、前記同様、オーステナイト系ステンレス鋼
を素材としたバンドの場合は全面に赤錆が発生し
たが、本発明で得られたバンドは全く異状が認め
られなかつた。機械的性質においては、引張強さ
97Kg／mm2、伸び35％の値であつた。Example 2 Weight ratio: Cr25%, Mo30%, Nb5%, Fe25
%, C 0.08%, balance Ni and unavoidable impurities, a wristwatch mesh band was prepared in the same manner as in Example 1, and then this band and 20Cr-30Ni austenitic stainless steel made in the same manner as above were prepared. Artificial sweat with a band made of steel,
When a corrosion resistance test was carried out by immersion in 5% saline solution for 7 days, red rust occurred on the entire surface of the band made of austenitic stainless steel, as described above, but no abnormality was observed in the band obtained by the present invention. I couldn't help it. In terms of mechanical properties, tensile strength
The value was 97Kg/mm 2 and the elongation was 35%.
以上述べた様に、本発明によればMnを含むこ
となくNiベースにCr、Mo、Nb、Ｃを所定の範
囲にバランス良く加え、耐食性を維持しながら、
Feを５〜25％まで添加して腕時計用メツシユバ
ンドとすることにより、合金線材としても加工し
やすく、またこれでメツシユバンドを編む合金線
材として使用しても、伸びが35％〜40％、引張り
強さも80Kg／mm2をこえた強さもあることから適度
な柔軟性が確保できているので、合金線材の折損
を起こすこともなく、また、編み機のヘリツクス
にうまくマツチするので機械に余計な荷重をかけ
て機械を止めたり、ヘリツクスを折ることもな
く、さらには、合金線材が折損することもない低
コストで加工性のよい合金線材を得ることがでぎ
る。 As described above, according to the present invention, Cr, Mo, Nb, and C are added in a well-balanced manner to a Ni base in a predetermined range without including Mn, and while maintaining corrosion resistance,
By adding Fe up to 5-25% to make mesh bands for watches, it can be easily processed as an alloy wire material, and even when used as an alloy wire material for knitting mesh bands, the elongation is 35%-40%, and the tensile strength is 35%-40%. It also has a strength exceeding 80 kg/mm 2 , which ensures appropriate flexibility, so the alloy wire does not break, and it fits well with the helix of the knitting machine, so it does not place unnecessary loads on the machine. It is possible to obtain an alloy wire rod with good workability at a low cost without having to stop the machine or break the helix, and furthermore, the alloy wire rod does not break.
また、材料自体が耐食性にすぐれているのでメ
ツシユバンドの様に編んだものは、間隙が多くて
汗などがたまりやすく、その汗によつて間隙腐食
の起こりやすい部品であつても耐食性が確保でき
る安価な外装部品を得ることができる。 In addition, the material itself has excellent corrosion resistance, so woven items such as mesh bands have many gaps that allow sweat to accumulate, making it possible to ensure corrosion resistance even in parts that are prone to crevice corrosion due to sweat. It is possible to obtain beautiful exterior parts.
Claims (1)
％以下、Mo（モリブデン）５％をこえて30％以
下、Nb（ニオブ）２％をこえて５％以下、Fe
（鉄）５％以上25％以下、Ｃ（炭素）0.08％以下で
残部Niおよび不可避的不純物よりなる合金線材
を用いたことを特徴とする腕時計用メツシユバン
ド。1 All have a weight ratio of Cr (chromium) of 16% or more25
% or less, Mo (molybdenum) more than 5% and less than 30%, Nb (niobium) more than 2% and less than 5%, Fe
A mesh band for a wristwatch, characterized by using an alloy wire material consisting of 5% to 25% (iron), 0.08% or less C (carbon), and the balance being Ni and unavoidable impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5724380A JPS56152939A (en) | 1980-04-30 | 1980-04-30 | Exterior decorative parts for pocket watch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5724380A JPS56152939A (en) | 1980-04-30 | 1980-04-30 | Exterior decorative parts for pocket watch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56152939A JPS56152939A (en) | 1981-11-26 |
| JPH0149783B2 true JPH0149783B2 (en) | 1989-10-26 |
Family
ID=13050085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5724380A Granted JPS56152939A (en) | 1980-04-30 | 1980-04-30 | Exterior decorative parts for pocket watch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56152939A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4876721A (en) * | 1972-01-19 | 1973-10-16 | ||
| JPS49126511A (en) * | 1973-04-11 | 1974-12-04 | ||
| JPS52120220A (en) * | 1976-04-03 | 1977-10-08 | Nippon Musical Instruments Mfg | Corrosion resistant nickel based alloy |
-
1980
- 1980-04-30 JP JP5724380A patent/JPS56152939A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4876721A (en) * | 1972-01-19 | 1973-10-16 | ||
| JPS49126511A (en) * | 1973-04-11 | 1974-12-04 | ||
| JPS52120220A (en) * | 1976-04-03 | 1977-10-08 | Nippon Musical Instruments Mfg | Corrosion resistant nickel based alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56152939A (en) | 1981-11-26 |
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