JP6771755B2 - Ornaments and their manufacturing methods - Google Patents
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- JP6771755B2 JP6771755B2 JP2016075233A JP2016075233A JP6771755B2 JP 6771755 B2 JP6771755 B2 JP 6771755B2 JP 2016075233 A JP2016075233 A JP 2016075233A JP 2016075233 A JP2016075233 A JP 2016075233A JP 6771755 B2 JP6771755 B2 JP 6771755B2
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Description
本発明は、装飾品及びその製造方法に関する。 The present invention relates to ornaments and methods for producing the same.
チタンの比重は４．５４ｇ／ｃｍ３であり、金の１９．３２ｇ／ｃｍ３、銀の１０．５０ｇ／ｃｍ３、銅の８．９６ｇ／ｃｍ３、白金の２１．４５ｇ／ｃｍ３、鉄の７．８７ｇ／ｃｍ３等、他の金属に比較して小さく軽量であるので、装飾品の材料として有利である。一方、チタンは、鉄、ステンレス等の金属に比較して柔らかく、装飾品として用いた場合、表面が傷つきやすいという問題がある。 The specific gravity of titanium is 4.54 g / cm 3 , gold is 19.32 g / cm 3 , silver is 10.50 g / cm 3 , copper is 8.96 g / cm 3 , platinum is 21.45 g / cm 3 , and iron. 7.87 g / cm 3 etc., which is smaller and lighter than other metals, is advantageous as a material for ornaments. On the other hand, titanium is softer than metals such as iron and stainless steel, and has a problem that the surface is easily scratched when used as an ornament.
前記問題を解決するために、例えば、チタンの表面にＮｉ−Ｐめっき層と、硬質クロムめっき層とをこの順に備え、表面を硬質化して傷付きにくくしたチタン材料が知られている（例えば、特許文献１）。 In order to solve the above problem, for example, a titanium material in which a Ni-P plating layer and a hard chrome plating layer are provided in this order on the surface of titanium and the surface is hardened to prevent scratches is known (for example, Patent Document 1).
前記チタン材料は、その表面にイオンプレーティングを施して、各種の色調を備える金属光沢を付与することにより、装飾品として使用することが考えられる。 It is conceivable that the titanium material can be used as an ornament by ion-plating its surface to give it a metallic luster having various color tones.
しかしながら、チタンの表面にＮｉ−Ｐめっき層と、硬質クロムめっき層とをこの順に備え表面を硬質化したチタン材料の表面にイオンプレーティングを施した装飾品は、人間の皮膚に触れたときに色調によってはアレルギーを起こすという不都合がある。 However, an ornament in which a Ni-P plating layer and a hard chrome plating layer are provided in this order on the surface of titanium and the surface of the titanium material whose surface is hardened is ion-plated is when it comes into contact with human skin. There is an inconvenience of causing allergies depending on the color tone.
本発明は、かかる不都合を解消して、イオンプレーティングにより付与される色調によらず、人間の皮膚に触れたときにアレルギーを起こすことのない装飾品及びその製造方法を提供することを目的とする。 An object of the present invention is to eliminate such inconvenience and to provide an ornament and a method for producing the same, which does not cause allergies when touching human skin, regardless of the color tone imparted by ion plating. To do.
本発明者らは、チタンの表面にＮｉ−Ｐめっき層と、硬質クロムめっき層とをこの順に備え表面を硬質化したチタン材料の表面にイオンプレーティングを施した装飾品が人間の皮膚に触れたときにアレルギーを起こす原因について鋭意検討を行った。 The present inventors have provided a Ni-P plating layer and a hard chrome plating layer on the surface of titanium in this order, and an ornament in which ion plating is applied to the surface of a hardened titanium material comes into contact with human skin. We enthusiastically investigated the causes of allergies.
この結果、前記硬質クロムめっき層は強く収縮する傾向があり、その表面に目視では確認できない程度の微細な亀裂を備えており、人間の皮膚に触れたときに汗等の塩分を含む体液がこの亀裂から内部に侵入し、下地のＮｉ−Ｐめっき層と反応することを知見した。前記アレルギーは、前記塩分を含む体液と前記Ｎｉ−Ｐめっき層との反応により生成した物質がさらにイオンプレーティングにより形成された層と反応し、イオンプレーティングにより形成された層を変色させたり腐食させたために起こるものと考えられる。 As a result, the hard chrome plating layer tends to shrink strongly, and the surface thereof has fine cracks that cannot be visually confirmed, and the body fluid containing salt such as sweat when it comes into contact with human skin is this. It was found that it penetrates into the inside through cracks and reacts with the underlying Ni-P plating layer. In the allergy, the substance generated by the reaction between the salt-containing body fluid and the Ni-P plating layer further reacts with the layer formed by ion plating, causing discoloration or corrosion of the layer formed by ion plating. It is thought that this is caused by the fact that it was caused.
本発明者らは、前記知見に基づいてさらに検討を重ね、Ｎｉ−Ｐめっきに代えてパラジウムめっきを用いることにより、前記塩分を含む体液との反応を防止でき、イオンプレーティングにより形成された層の変色や腐食を無くすことができることを見出し、本発明に到達した。 The present inventors further studied based on the above findings, and by using palladium plating instead of Ni-P plating, it was possible to prevent the reaction with the body fluid containing the salt, and the layer formed by ion plating. We have found that the discoloration and corrosion of the plating can be eliminated, and have reached the present invention.
そこで、本発明の装飾品は、チタンからなる基材と、該基材上に形成されたパラジウムめっき層と、該パラジウムめっき層上に形成された硬質クロムめっき層と、該硬質クロムめっき層上に形成された、ＴｉＯ、ＴｉＣ、ＴｉＣＮ、ＴｉＮからなる群から選択される１種の金属光沢を有する被覆層とを備えることを特徴とする。 Therefore, the decorative product of the present invention comprises a base material made of titanium, a palladium plating layer formed on the base material, a hard chrome plating layer formed on the palladium plating layer, and a hard chrome plating layer. It is characterized by comprising a coating layer having a metallic luster of one kind selected from the group consisting of TiO, TiC, TiCN, and TiN formed in.
前記本発明の装飾品は、チタンからなる基材の表面にパラジウムめっきを施してパラジウムめっき層を形成する工程と、該該パラジウムめっき層上に硬質クロムめっきを施して硬質クロムめっき層を形成する工程と、該硬質クロムめっき層上にイオンプレーティングを施してＴｉＯ、ＴｉＣ、ＴｉＣＮ、ＴｉＮからなる群から選択される１種の金属光沢を有する被覆層を形成する工程とを備える製造方法により製造することができる。 The decorative product of the present invention has a step of forming a palladium plating layer by subjecting the surface of a base material made of titanium to a palladium plating layer, and a hard chrome plating on the palladium plating layer to form a hard chrome plating layer. Manufactured by a manufacturing method including a step and a step of applying ion plating on the hard chrome plating layer to form a coating layer having one kind of metallic luster selected from the group consisting of TiO, TiC, TiCN, and TiN. can do.
前記硬質クロムめっき層は、その強く収縮する傾向により表面に目視では確認できない程度の微細な亀裂を備えており、人間の皮膚に触れたときに汗等の塩分を含む体液がこの亀裂から内部に侵入する。しかし、本発明の装飾品によれば、チタンの表面に前記パラジウムめっき層を備え、その上に前記硬質クロムめっき層を備えているので、前記亀裂から内部に侵入した前記塩分を含む体液は該パラジウムめっき層と接触することとなる。 The hard chrome-plated layer has fine cracks on the surface that cannot be visually confirmed due to its strong shrinkage tendency, and when it comes into contact with human skin, body fluid containing salt such as sweat enters from these cracks. invade. However, according to the ornament of the present invention, since the palladium plating layer is provided on the surface of titanium and the hard chrome plating layer is provided on the surface of titanium, the body fluid containing the salt that has penetrated into the inside from the crack is said to be the body fluid. It will come into contact with the palladium plating layer.
このとき、前記パラジウムめっき層は前記塩分を含む体液と反応することがないので、前記イオンプレーティングにより形成されたＴｉＯ、ＴｉＣ、ＴｉＣＮ、ＴｉＮからなる群から選択される１種の金属光沢を有する被覆層の変色や腐食を無くしてアレルギーの発生を防止することができる。 At this time, since the palladium plating layer does not react with the body fluid containing the salt, it has one kind of metallic luster selected from the group consisting of TiO, TiC, TiCN, and TiN formed by the ion plating. It is possible to prevent the occurrence of allergies by eliminating discoloration and corrosion of the coating layer.
また、前記パラジウムめっき層は、前記硬質クロムめっき層に比較して柔軟であり、該硬質クロムめっき層の密着性を向上させることができる。 Further, the palladium plating layer is more flexible than the hard chrome plating layer, and the adhesion of the hard chrome plating layer can be improved.
次に、添付の図面を参照しながら本発明の実施の形態についてさらに詳しく説明する。 Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings.
図１に示すように、本実施形態の装飾品１は、チタンからなる基材２（以下、チタン基材２と略記する）の上に形成されたパラジウムめっき層３と、パラジウムめっき層３上に形成された硬質クロムめっき層４と、硬質クロムめっき層４上にイオンプレーティングにより形成されたＴｉＯ、ＴｉＣ、ＴｉＣＮ、ＴｉＮからなる群から選択される１種の金属光沢を有する被覆層５を備えている。装飾品１は被覆層５により種々の色調の金属光沢を備えるものとすることができ、しかも軽量で、表面が硬く傷つきにくいので、バングル、ブレスレットやアンクレットのビーズ（飾り玉）、バックル等に好適に用いることができる。 As shown in FIG. 1, the ornament 1 of the present embodiment has a palladium plating layer 3 formed on a base material 2 made of titanium (hereinafter, abbreviated as titanium base material 2) and a palladium plating layer 3 on the palladium plating layer 3. A hard chrome plating layer 4 formed on the above, and a coating layer 5 having one kind of metallic luster selected from the group consisting of TiO, TiC, TiCN, and TiN formed on the hard chrome plating layer 4 by ion plating. I have. The ornament 1 can have various tones of metallic luster due to the coating layer 5, is lightweight, has a hard surface and is not easily scratched, and is therefore suitable for bangles, bracelets, anklet beads (decorative balls), buckles, etc. Can be used for.
本実施形態の装飾品１は、次のようにして製造することができる。 The ornament 1 of the present embodiment can be manufactured as follows.
まず、図２のＳＴＥＰ１で、チタン基材２からなる素材を加工し、バングル、ブレスレットやアンクレットのビーズ（飾り玉）、バックル等の所定の形状にする。 First, in STEP 1 of FIG. 2, a material made of a titanium base material 2 is processed into a predetermined shape such as a bangle, a bracelet, anklet beads (decorative ball), or a buckle.
次に、図２のＳＴＥＰ２で、所定の形状に加工されたチタン基材２上にパラジウムめっきを施す。前記パラジウムめっきは、市販のめっき浴を用い、それ自体公知の方法により行うことができる。この結果、チタン基材２上にパラジウムめっき層３が形成される。 Next, in STEP 2 of FIG. 2, palladium plating is applied on the titanium base material 2 processed into a predetermined shape. The palladium plating can be carried out by a method known per se using a commercially available plating bath. As a result, the palladium plating layer 3 is formed on the titanium base material 2.
次に、図２のＳＴＥＰ３で、パラジウムめっき層３上に硬質クロムめっきを施す。前記硬質クロムめっきは、例えば、無水クロム酸１００〜４００ｇ／リットル、硫酸１〜４ｇ／リットルを含むめっき浴にパラジウムめっき層３が形成されたチタン基材２を浸漬し、３Ｖの電圧を４分間印加することにより施すことができる。この結果、パラジウムめっき層３上に、膜厚１μｍ程度の硬質クロムめっき層４を形成することができる。 Next, in STEP 3 of FIG. 2, hard chrome plating is applied on the palladium plating layer 3. In the hard chrome plating, for example, the titanium base material 2 on which the palladium plating layer 3 is formed is immersed in a plating bath containing 100 to 400 g / liter of chromic anhydride and 1 to 4 g / liter of sulfuric acid, and a voltage of 3 V is applied for 4 minutes. It can be applied by applying. As a result, a hard chrome plating layer 4 having a film thickness of about 1 μm can be formed on the palladium plating layer 3.
次に、図２のＳＴＥＰ４で、硬質クロムめっき層４が形成されたチタン基材２に対し、イオンプレーティングを施す。前記イオンプレーティングは、ＴｉＯ、ＴｉＣ、ＴｉＣＮ、ＴｉＮからなる群から選択される１種の金属化合物をターゲットとしてそれ自体公知の方法により行うことができる。この結果、装飾品１として、硬質クロムめっき層４上に種々の色調の金属光沢を有する被覆層５を形成することができる。 Next, in STEP 4 of FIG. 2, ion plating is applied to the titanium base material 2 on which the hard chrome plating layer 4 is formed. The ion plating is, T iO, TiC, TiCN, the one metal compound selected from the group consisting of TiN can be carried out by known methods as a target. As a result, as the ornament 1, a coating layer 5 having metallic luster of various colors can be formed on the hard chrome plating layer 4.
次に、イオンプレーティングのターゲット及び雰囲気を変えて、種々の色調の金属光沢を有する被覆層５を備える装飾品１（サンプル１〜１１）を製造し、得られた装飾品１に対して塩水噴霧試験を行った。前記塩水噴霧試験は、装飾品１が人間の皮膚から分泌される汗等の塩分を含む体液に接触した状況を想定した加速劣化試験である。前記塩水噴霧試験は、ＪＩＳ Ｚ ２３７１に基づき、装飾品１に、５０±５ｇ／リットルの濃度の食塩水（ｐＨ６．５〜７．２）を３５±２℃の温度下、１．５±０．５ミリリットル／ｃｍ２／時間の噴霧量で４８時間噴霧することにより行った。 Next, ornaments 1 (samples 1 to 11) having a coating layer 5 having metallic luster of various colors were produced by changing the target and atmosphere of ion plating, and salt water was added to the obtained ornament 1. A spray test was performed. The salt spray test is an accelerated deterioration test assuming a situation in which the ornament 1 comes into contact with a body fluid containing salt such as sweat secreted from human skin. In the salt spray test, based on JIS Z 2371, a saline solution (pH 6.5 to 7.2) having a concentration of 50 ± 5 g / liter was added to the ornament 1 at a temperature of 35 ± 2 ° C. and 1.5 ± 0. This was done by spraying for 48 hours at a spray rate of 5.5 ml / cm 2 / hour.
次に、比較のために、パラジウムめっき層３に代えて硬質ニッケルめっき層を備えることを除いて、本実施形態の装飾品１と全く同一の構成を備える装飾品（サンプル１２〜１４）を製造し、得られた装飾品に対して装飾品１と全く同一にして塩水噴霧試験を行った。結果を表１に示す。 Next, for comparison, ornaments (samples 12 to 14) having exactly the same configuration as the ornament 1 of the present embodiment are manufactured except that a hard nickel plating layer is provided instead of the palladium plating layer 3. Then, the obtained ornament was subjected to a salt spray test in exactly the same manner as the ornament 1. The results are shown in Table 1.
表１から、チタン基材２上にパラジウムめっき層３、硬質クロムめっき層４、イオンプレーティングにより形成されたＴｉＯ、ＴｉＣ、ＴｉＣＮ、ＴｉＮからなる群から選択される１種の金属光沢を有する被覆層５を備える本実施形態の装飾品１（サンプル１〜１１）によれば、前記塩水噴霧試験によっても変色が無いことが明らかである。一方、比較例として、本実施形態の装飾品１におけるパラジウムめっき層３に代えて硬質ニッケルめっき層を備える装飾品（サンプル１２〜１４）では、前記塩水噴霧試験によって変色することが明らかである。 From Table 1, a coating having one kind of metallic luster selected from the group consisting of a palladium plating layer 3, a hard chrome plating layer 4, and TiO, TiC, TiCN, and TiN formed by ion plating on a titanium base material 2. According to the ornaments 1 (samples 1 to 11) of the present embodiment including the layer 5, it is clear that there is no discoloration even by the salt spray test. On the other hand, as a comparative example, it is clear that the ornaments (samples 12 to 14) provided with the hard nickel plating layer instead of the palladium plating layer 3 in the ornament 1 of the present embodiment are discolored by the salt spray test.
従って、本実施形態の装飾品１によれば、人間の皮膚から分泌される汗等の塩分を含む体液に接触したときにも変色等がなく、アレルギーを起こさないことが期待される。 Therefore, according to the ornament 1 of the present embodiment, it is expected that there will be no discoloration or the like even when it comes into contact with a body fluid containing salt such as sweat secreted from human skin, and that allergies will not occur.
１…装飾品、 ２…チタン基材、 ３…パラジウムめっき層、 ４…硬質クロムめっき層、 ５…被覆層。 1 ... Ornament, 2 ... Titanium base material, 3 ... Palladium plating layer, 4 ... Hard chrome plating layer, 5 ... Coating layer.
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| JPS61596A (en) * | 1985-05-23 | 1986-01-06 | Canon Inc | Formation of chromium plated film having metallic luster |
| JP2001234392A (en) * | 2000-02-28 | 2001-08-31 | Seiko Corp | Decorative member |
| JP3969296B2 (en) * | 2001-12-13 | 2007-09-05 | セイコーエプソン株式会社 | Surface treatment method for ornaments, ornaments and watches |
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