JP2007290938A - Jewelry member - Google Patents
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- JP2007290938A JP2007290938A JP2006149694A JP2006149694A JP2007290938A JP 2007290938 A JP2007290938 A JP 2007290938A JP 2006149694 A JP2006149694 A JP 2006149694A JP 2006149694 A JP2006149694 A JP 2006149694A JP 2007290938 A JP2007290938 A JP 2007290938A
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Description
本発明は宝飾部材に関し、オパールのうちで特にピンク色の色調、遊色効果、透明感を呈した宝飾部材に関する。 The present invention relates to a jewelry member, and particularly relates to a jewelry member that exhibits a pink color tone, a play effect, and a transparency among opals.
天然オパールは、多数の非晶質珪酸からなる球状体が規則的に三次元配列した構造を有しており、入射光が多数の非晶質珪酸からなる球状体と該珪酸からなる球状体により形成される空孔により、ブラッグ反射して独特な遊色効果を醸し出すことから、指輪、ペンダント、宝飾板等の宝飾材料として珍重されている。しかしながら、この天然オパールは、産出量が少なく、かつ全体が遊色効果を有していながら透明度が高い良質な物は非常に稀少である。そこで、この天然オパールと同等の発色と遊色効果を有しつつ透明度の高い物として、多数の非晶質珪酸からなる球状体を規則的に三次元配列するとともに該配列によって形成される空孔内にジルコニウムを０．００５〜８．０重量％充填したことを特徴とする宝飾部材の発明が記載されている（特許文献１参照）。 Natural opal has a structure in which a large number of spherical bodies made of amorphous silicic acid are regularly arranged in a three-dimensional structure, and incident light is composed of a spherical body made of many amorphous silicic acids and a spherical body made of the silicic acid. Because of the holes that are formed, it is Bragg-reflected to create a unique color-playing effect, so it is prized as a jewelry material for rings, pendants, jewelry plates, and the like. However, this natural opal has a small amount of production, and a high-quality product with high transparency while having a play-coloring effect as a whole is very rare. Therefore, as a highly transparent product having the same color development and play-free effect as this natural opal, a large number of amorphous silica spheres are regularly arranged in three dimensions and pores formed by the arrangement An invention of a jewelry member characterized in that 0.005 to 8.0% by weight of zirconium is filled therein (see Patent Document 1).
また、黄色やオレンジ色や褐色を呈したファイヤーオパールに酷似した色調、遊色効果、深い透明感を呈した物として、多数の非晶質珪酸からなる球状体を規則的に三次元配列するとともに該配列によって形成される空孔内に鉄を０．００００５〜０．０００６重量％、ジルコニウムを０．００２〜０．５重量％、充填したことを特徴とする宝飾部材の発明が記載されている（特許文献２参照）。 In addition, a large number of amorphous silicic acid spheres are regularly arranged in a three-dimensional array as a product that exhibits a color tone, play-off effect, and deep transparency that resembles a yellow, orange, or brown fire opal. An invention of a jewelery member is described in which 0.00005 to 0.0006% by weight of iron and 0.002 to 0.5% by weight of zirconium are filled in pores formed by the arrangement. (See Patent Document 2).
この従来技術によれば、オパールのうち、特にウォーターオパールやファイヤーオパールに酷似した遊色効果、深い透明感を有するとともに耐候性、耐熱性、耐薬品性にも優れた宝飾部材を得ることができる。
しかしながら、上記従来技術では、非晶質珪酸からなる球状体間にジルコニウムのみを充填することによりウォーターオパールという青みがかったオパールを得ることしかできない。また、非晶質珪酸からなる球状体間に鉄とジルコニウムを同時に充填することによりファイヤーオパールという黄色やオレンジ色や褐色に発色したオパールしか得ることができない。 However, in the above prior art, only a bluish opal called a water opal can be obtained by filling only the zirconium between spherical bodies made of amorphous silicic acid. In addition, by simultaneously filling iron and zirconium between spherical bodies made of amorphous silicic acid, only opal colored yellow, orange or brown, called fire opal, can be obtained.
オパールにはウォーターオパールやファイヤーオパール以外にもピンク色に発色するピンクオパールと呼ばれるものがある。しかしながら天然のピンクオパールは全体が遊色効果を有していながら透明度が高い良質な物は非常に稀少であり、ピンクオパールにおいても全体が遊色効果を有していながら透明度が高い良質な物が望まれる。 In addition to water opal and fire opal, there is an opal called pink opal that develops pink. However, natural pink opal has a playful color effect and high transparency, but it is very rare. Pink opal has a playful color effect and high transparency. desired.
そこで、本発明者はかかる欠点に鑑み種々研究の結果、多数の非晶質珪酸からなる球状体を規則的に三次元配列させるとともに、上記球状体間に形成される間隙にエルビウムとジルコニウムを存在させることがピンクオパールを形成させるに肝要であることを見出し、本発明を完成するに至った。 Therefore, the present inventor has conducted various studies in view of such drawbacks, and regularly arranged three-dimensional spheres made of amorphous silicic acid, and erbium and zirconium exist in the gaps formed between the spheres. It has been found that it is essential to form a pink opal, and the present invention has been completed.
本発明は、構造的にみれば多数の非晶質珪酸からなる球状体を規則的に三次元配列させるとともに、上記球状体間に形成される間隙にエルビウムと珪素とを含む非球形物と、平均直径１〜１００ｎｍの球形物を配置させてなり、上記非球形物と球形物が断面視して全体の０．６〜１６．０％の面積を占めることを特徴とする。 According to the present invention, a spherical body composed of a large number of amorphous silicic acids is regularly arranged in a three-dimensional manner, and a non-spherical body containing erbium and silicon in a gap formed between the spherical bodies, A spherical object having an average diameter of 1 to 100 nm is arranged, and the non-spherical object and the spherical object occupy an area of 0.6 to 16.0% of the whole in a sectional view.
また、多数の非晶質珪酸からなる球状体を規則的に三次元配列させるとともに、
上記球状体間に形成される間隙に結晶質組成物及び非晶質組成物を配置させてなり、
上記結晶質組成物が少なくとも珪素とエルビウムを含み、上記非晶質組成物が少なくとも珪素とエルビウムとジルコニウムを含むことを特徴とする。
In addition, regularly and three-dimensionally arrayed spherical bodies made of amorphous silica,
A crystalline composition and an amorphous composition are arranged in the gap formed between the spherical bodies,
The crystalline composition contains at least silicon and erbium, and the amorphous composition contains at least silicon, erbium, and zirconium.
さらに、上記結晶質組成物と非晶質組成物の割合が７５／２５〜２５／７５の範囲であることを特徴とする。 Furthermore, the ratio of the crystalline composition to the amorphous composition is in the range of 75/25 to 25/75.
さらに、エルビウム０．１〜６．０重量％、ジルコニウム０．００５〜５．０重量％を含有する。 Further, it contains 0.1 to 6.0% by weight of erbium and 0.005 to 5.0% by weight of zirconium.
さらに、上記球状体の平均直径が約５ｎｍ〜約４５０ｎｍの範囲内であることを特徴とする。 Furthermore, the average diameter of the spherical body is in the range of about 5 nm to about 450 nm.
本発明によれば、多数の非晶質珪酸からなる球状体を規則的に三次元配列させるとともに該配列によって形成される珪酸からなる球状体間に少なくともエルビウムとジルコニウムを含む結晶質又は非晶質組成物を充填させることにより、ピンク色の発色とオパールに特有の遊色効果、透明感を呈し、かつ天然オパールと比べて耐候性、耐熱性、耐薬品性にも優れた宝飾部材が得られ、極めて市場価値の高い宝飾部材の提供が可能となる。 According to the present invention, a large number of spherical bodies made of amorphous silicic acid are regularly arranged in a three-dimensional manner, and at least erbium and zirconium are included between the spherical bodies made of silicic acid formed by the arrangement. By filling the composition, it is possible to obtain a jewelery member that exhibits pink color development, play-color effect peculiar to opal, and transparency, and also has superior weather resistance, heat resistance, and chemical resistance compared to natural opal. Thus, it is possible to provide a jewelry member having extremely high market value.
図１に示すように、本発明の宝飾部材は多数の非晶質の珪酸からなる球状体（以下、非晶質珪酸球ともいう）１を規則的に三次元配列させるとともに、上記球状体１の間に形成される間隙に結晶質組成物２，３及び非晶質組成物４を配置させてなる宝飾部材である。 As shown in FIG. 1, the jewelry member of the present invention regularly arranges a plurality of spherical bodies (hereinafter also referred to as amorphous silicate spheres) 1 made of amorphous silicic acid three-dimensionally, and the spherical body 1 described above. It is a jewelry member formed by disposing the crystalline compositions 2 and 3 and the amorphous composition 4 in the gap formed between the two.
なお、本発明における非晶質の珪酸からなる球状体１の規則的な三次元配列とは、球状体１を単純立方構造、面心立方構造、六方最密構造、体心立方構造、或いはこれらが部分的に共存している複合構造としたような配列をいう。多数の非晶質珪酸からなる球状体を規則的に三次元配列させるとともに、該配列によって形成される非晶質珪酸からなる球状体間の空孔には、エルビウム０．１〜６．０重量％、ジルコニウム０．００５〜５．０００重量％が充填されている。ただし、微量成分としてナトリウム、カリウム、銅、マグネシウム、アルミニウム、クロム、亜鉛、鉛、鉄、ニッケル、イットリウム、ジスプロシウム、ホルミウム、ツリウム、イッテルビウム等及びこれらの化合物もしくは酸化物などが含まれていても特に問題はない。 In addition, the regular three-dimensional arrangement of the spherical bodies 1 made of amorphous silicic acid in the present invention is a simple cubic structure, a face-centered cubic structure, a hexagonal close-packed structure, a body-centered cubic structure, or these Refers to an arrangement that has a composite structure in which coexists partially. A large number of spheres made of amorphous silicic acid are regularly arranged in a three-dimensional array, and vacancies between the spheres made of amorphous silicate formed by the arrangement are erbium 0.1 to 6.0 weight. %, Zirconium is 0.005 to 5.000% by weight. However, even if trace components include sodium, potassium, copper, magnesium, aluminum, chromium, zinc, lead, iron, nickel, yttrium, dysprosium, holmium, thulium, ytterbium, etc. and their compounds or oxides, etc. No problem.
ここで、球状体１の間に介在する組成物に含まれるエルビウムは、宝飾部材にピンク色を付与するものである。他方、ジルコニウムは宝飾部材にオパール特有の遊色効果を付与するためのものである。なお、遊色効果とは宝飾部材を見る角度によって、色が様々に変化するもののことをいう。 Here, erbium contained in the composition interposed between the spherical bodies 1 imparts a pink color to the jewelry member. On the other hand, zirconium is for imparting an opal-specific play color effect to the jewelry member. The play color effect means that the color changes variously depending on the angle at which the jewelry member is viewed.
さらに上記結晶質の組成物３と非晶質の組成物４の少なくとも一方が、球状をなすことが好ましく、図１では上記球状体間に形成される間隙に配置させる非球形物２及び球形物３，４は、断面視で全体の０．６〜１６．０％の面積を占める。他方、球形物３，４は平均直径１〜１００ｎｍをなしている。球形物３，４の平均直径が１ｎｍ未満の場合には、非晶質珪酸の球状体１の間に介在して接続しても接合強度が弱くなり、１００ｎｍを超える場合には非晶質珪酸の球状体１が規則的な三次元配列を維持できなくなり、遊色効果が得られず、かつ強度が弱くなる。すなわち、球形物の平均直径は強度保持の観点から１ｎｍ以上が重要であり、１００ｎｍを超えると、強度保持性に欠ける。 Furthermore, it is preferable that at least one of the crystalline composition 3 and the amorphous composition 4 has a spherical shape. In FIG. 1, the non-spherical material 2 and the spherical material arranged in the gap formed between the spherical materials. 3 and 4 occupy an area of 0.6 to 16.0% of the whole in a sectional view. On the other hand, the spherical objects 3 and 4 have an average diameter of 1 to 100 nm. When the average diameter of the spheres 3 and 4 is less than 1 nm, the bonding strength is weak even if they are connected between the spherical bodies 1 of amorphous silicic acid, and when the average diameter exceeds 100 nm, amorphous silicic acid is used. The spherical body 1 cannot maintain a regular three-dimensional arrangement, so that no play effect is obtained and the strength is weakened. That is, the average diameter of the spherical object is important to be 1 nm or more from the viewpoint of maintaining the strength.
そして上記球状体間に形成される間隙にエルビウムと珪素を含む非球形物と、平均直径１〜１００ｎｍの球形物とを、断面視して全体の０．６〜１６％の面積を占めるように配置させてなるのが重要であり、０．６〜１６．０％の面積の範囲から外れると、遊色効果、強度が悪化する。 The non-spherical material containing erbium and silicon in the gap formed between the spherical bodies and the spherical material having an average diameter of 1 to 100 nm occupy an area of 0.6 to 16% of the whole in a sectional view. It is important to arrange them, and if they are out of the range of 0.6 to 16.0%, the play effect and strength deteriorate.
また、本発明は多数の非晶質珪酸からなる球状体を規則的に三次元配列させるとともに、上記球状体間に形成される間隙にエルビウムと珪素とを含む非球形物と、平均直径１〜１００ｎｍの球形物を配置させてなり、上記非球形物と球形物が断面視して全体の０．６〜１６．０％の面積を占めるように配置させてなることを特徴とする。 In addition, the present invention regularly arranges a number of spherical bodies made of amorphous silicic acid in a three-dimensional manner, and a non-spherical body containing erbium and silicon in the gap formed between the spherical bodies, and an average diameter of 1 to A spherical object of 100 nm is arranged, and the non-spherical object and the spherical object are arranged so as to occupy an area of 0.6 to 16.0% of the whole in a sectional view.
尚、本発明は上記珪素とエルビウムとジルコニウムが酸化物として存在する場合も含まれるものである。 The present invention includes the case where the silicon, erbium, and zirconium are present as oxides.
さらに上記結晶質の組成物である非球形物２，球形物３と非晶質の組成物４の割合が７５：２５〜２５：７５の範囲であることが好ましい。上記割合の範囲よりも結晶質の組成物である非球形物２，球形物３が多くなる場合には結晶化が局所的に進み、非晶質の珪酸からなる球状体１の間に存在してなる組成物の構造が偏在して強度が低下してしまう。また上記割合の範囲よりも非晶質の球形物４が多い場合には、球状体１が確保されずに強度が低下してしまう。 Furthermore, it is preferable that the ratio of the non-spherical product 2, the spherical product 3 and the amorphous composition 4 which are the crystalline composition is in the range of 75:25 to 25:75. When the amount of the non-spherical material 2 and the spherical material 3 which are crystalline compositions is larger than the above range, crystallization proceeds locally and exists between the spherical bodies 1 made of amorphous silicic acid. The structure of the composition is unevenly distributed and the strength is lowered. In addition, when there are more amorphous spheres 4 than the above range, the spherical body 1 is not secured and the strength is lowered.
さらに上記結晶質の組成物である非球形物２，球形物３におけるエルビウムを０．１〜６．０重量％、ジルコニウムを０．００５〜５．０重量％とするのが好ましい。 Furthermore, it is preferable that erbium in the non-spherical product 2 and the spherical product 3 as the crystalline composition is 0.1 to 6.0% by weight and zirconium is 0.005 to 5.0% by weight.
さらに上記非晶質の組成物におけるエルビウムを０．１〜６．０重量％、ジルコニウムを０．００５〜５．０重量％とするのが好ましい。 Further, the erbium in the amorphous composition is preferably 0.1 to 6.0% by weight and zirconium is preferably 0.005 to 5.0% by weight.
エルビウムが０．１重量％未満の場合には宝飾部材が十分な発色（ピンク色）が得られないという不具合がある。また６．０重量％を超える場合には非晶質の珪酸からなる球状体１の間に介在させることが困難になるという不具合がある。なお、エルビウムの組成は特に１．０重量％以上、３．０重量％以下であることがさらに好ましい。 When erbium is less than 0.1% by weight, there is a problem that the jewelry member cannot obtain a sufficient color (pink). Moreover, when it exceeds 6.0 weight%, there exists a malfunction that it becomes difficult to interpose between the spherical bodies 1 which consist of amorphous silicic acid. The composition of erbium is more preferably 1.0% by weight or more and 3.0% by weight or less.
ジルコニウムが０．００５重量％未満の場合には、宝飾部材が透明体となって遊色効果が現れないという不具合がある。また５．０重量％を超える場合には、透明度が失われ宝飾部材として商品価値が大きく低下する。なお、ジルコニウムの充填量は特に０．０５重量％以上５．０重量％以下であることがさらに好ましい。 When zirconium is less than 0.005% by weight, there is a problem that the jewelry member becomes a transparent body and no play color effect appears. Moreover, when it exceeds 5.0 weight%, transparency will be lost and a commercial value will fall significantly as a jewelry member. In particular, the filling amount of zirconium is more preferably 0.05% by weight or more and 5.0% by weight or less.
ただし微量成分としてナトリウム、カリウム、銅、マグネシウム、アルミニウム、クロム、亜鉛、鉛、鉄、ニッケル、イットリウム、ジスプロシウム、ホルミウム、ツリウム、イッテルビウム等及びこれらの化合物などが含まれていても特に問題はない。 However, there is no particular problem even if a trace component contains sodium, potassium, copper, magnesium, aluminum, chromium, zinc, lead, iron, nickel, yttrium, dysprosium, holmium, thulium, ytterbium, and the like, and their compounds.
さらに上記球状体１の平均直径が約５ｎｍ〜約４５０ｎｍの範囲内であることが好ましい。球状体１の平均直径が５ｎｍよりも小さい場合には白濁した状態となって遊色効果が現れない。これに対して４５０ｎｍよりも大きい場合には透明体となり遊色効果が現れない。特に可視光領域での遊色効果を発現させるためには約１５０ｎｍから約３５０ｎｍの範囲内であることが好ましい。また球状体１を規則的に三次元配列させるためには球状体１の粒径のばらつきを±１５％以内、望ましくは±１０％以内に調整すればよい。 Furthermore, the average diameter of the spherical body 1 is preferably in the range of about 5 nm to about 450 nm. When the average diameter of the spherical body 1 is smaller than 5 nm, it becomes clouded and no play color effect appears. On the other hand, when it is larger than 450 nm, it becomes a transparent body and no play color effect appears. In particular, in order to exhibit the play-color effect in the visible light region, it is preferably in the range of about 150 nm to about 350 nm. In order to regularly arrange the spherical bodies 1 in a three-dimensional arrangement, the variation in the particle diameter of the spherical bodies 1 may be adjusted to within ± 15%, preferably within ± 10%.
本発明のように三次元配列された非晶質の珪酸からなる球状体１の間に、少なくとも珪素とエルビウムからなる結晶質の組成物である非球形物２，球形物３、及び少なくとも珪素とエルビウムとジルコニウムからなる非晶質の組成物である球形物４とを、上記適正範囲内で混在した状態で充填させた場合、得られる宝飾部材はピンク色の発色が得られ、かつ機械的強度が大で、黄ばみ等の経時変化や熱、溶剤等の印加、付着による変形・破壊が一切なく、かつオパール特有の遊色効果を備えた物として、市場価値の極めて高い宝飾部材となる。 Between the spherical body 1 made of amorphous silicic acid arranged three-dimensionally as in the present invention, a non-spherical material 2, a spherical material 3, and at least silicon, which are crystalline compositions of at least silicon and erbium When the spherical product 4, which is an amorphous composition composed of erbium and zirconium, is filled in a mixed state within the above appropriate range, the resulting jewelery member is colored pink and has a mechanical strength. It is a jewelery member with extremely high market value as a product that has no change over time due to yellowing or the like, application of heat, solvent, etc., deformation or destruction due to adhesion, and an opal-specific play effect.
上述した本発明の顕著な利点は以下に示す実施例により容易に認識される。 The significant advantages of the present invention described above are readily appreciated by the examples that follow.
平均直径が種々の大きさの非晶質の珪酸からなる球状体１を２０体積％と、水を８０体積％とを攪拌混合し、その後これを放置して球状体１を自然沈降させ、球状体１が規則正しく配列したゼリー状物を生成させる。 20% by volume of the spherical body 1 made of amorphous silicic acid having various average diameters and 80% by volume of water are mixed with stirring, and then left to stand to allow the spherical body 1 to naturally settle. A jelly-like body in which the body 1 is regularly arranged is generated.
次にこのゼリー状物を空気中にて自然乾燥させるとともに、該乾燥物を約８００℃の温度で仮焼し、球状体１の三次元配列構造体を得る。 Next, the jelly-like product is naturally dried in the air, and the dried product is calcined at a temperature of about 800 ° C. to obtain a three-dimensional array structure of spherical bodies 1.
そして次に上記三次元配列構造体を種々濃度のエルビウム塩水溶液に浸漬し、一度約８００℃の温度で仮焼する。 Next, the three-dimensional array structure is immersed in erbium salt aqueous solutions having various concentrations and once calcined at a temperature of about 800 ° C.
その後ジルコニウム−ｎ−プロポキシドをｎ−プロピルアルコールで希釈した種々濃度のジルコニウム溶液に浸漬し、構造体内部の空孔にジルコニウム−ｎ−プロポキシドを含浸させるとともに、該ジルコニウム−ｎ−プロポキシドの加水分解を行い、乾燥させる。 Thereafter, zirconium-n-propoxide is immersed in various concentrations of zirconium solutions diluted with n-propyl alcohol to impregnate the pores inside the structure with zirconium-n-propoxide, and the zirconium-n-propoxide. Hydrolyze and dry.
乾燥の後、全体を約１１５０℃の温度で約３０時間焼成して宝飾部材を得た。 After drying, the whole was baked at a temperature of about 1150 ° C. for about 30 hours to obtain a jewelry member.
非晶質の珪酸からなる球状体１，１間でのエルビウム、ジルコニウム、珪素の様子を模式図にて図１に示す。 The state of erbium, zirconium, and silicon between the spherical bodies 1 and 1 made of amorphous silicic acid is schematically shown in FIG.
図１に示すように非晶質の珪酸からなる球状体１，１の間でのエルビウム、ジルコニウム、珪素の状態は、少なくとも珪素とエルビウムからなる結晶質の組成物と、少なくとも珪素とエルビウムとジルコニウムからなる非晶質の組成物及び結晶質の組成物である。なお、図１では球状体１，１間に空隙が存在するように見受けられるが、実際には該珪酸からなる球状体は粒成長により真球状を保っておらず、粒間に空隙は残っていない。 As shown in FIG. 1, the state of erbium, zirconium and silicon between the spherical bodies 1 and 1 made of amorphous silicic acid is a crystalline composition comprising at least silicon and erbium, and at least silicon, erbium and zirconium. An amorphous composition and a crystalline composition. In FIG. 1, it seems that there are voids between the spherical bodies 1 and 1, but in reality, the spherical body made of silicic acid does not maintain a true spherical shape due to grain growth, and voids remain between the grains. Absent.
かくして得られた宝飾部材について、ＳＥＭ（走査型電子顕微鏡）により非晶質の珪酸からなる球状体１の平均粒径を分析した。サンプルは５ｍｍ角の立方体とし、そのうちの1面の６μｍ×４μｍの範囲を１ｎｍの分解能で分析した。 About the jewelry member obtained in this way, the average particle diameter of the spherical body 1 which consists of amorphous silicic acid was analyzed by SEM (scanning electron microscope). The sample was a 5 mm square cube, and an area of 6 μm × 4 μm on one side was analyzed with a resolution of 1 nm.
またＴＥＭ（透過型電子顕微鏡）により非晶質の珪酸からなる球状体１の間での状態を分析した。サンプルは３ｍｍφの円柱状とし、その中心をうすくしていって穴をあけ、その穴の周辺で厚さが１００ｎｍ以下となる部分のうち、６μｍ×６μｍの範囲を０．１ｎｍの分解能で分析した。 Moreover, the state between the spherical bodies 1 made of amorphous silicic acid was analyzed by TEM (transmission electron microscope). The sample had a cylindrical shape of 3 mmφ, a hole was formed in the center, and a 6 μm × 6 μm range was analyzed with a resolution of 0.1 nm in a portion having a thickness of 100 nm or less around the hole. .
また、ＥＤＳ分析はスポット径１ｎｍの分解能で分析し、各組成物の成分を分析した。 In addition, EDS analysis was performed with a resolution of a spot diameter of 1 nm, and the components of each composition were analyzed.
各組成物が結晶質であるか非晶質であるかを調べるために制限視野電子回折像によりスポット径１０ｎｍの範囲で観測した。 In order to examine whether each composition is crystalline or amorphous, it was observed in a spot diameter range of 10 nm by a limited-field electron diffraction image.
ここで、これら非球形物２，球形物３，４の各々を個別に測定するためには、宝飾部材各組成物を湿式ミルで粉砕し、粉砕が不十分であればさらに超音波にて非球形物２，球形物３，４個別になるまで分解することで破壊検査することになる。湿式ミルも超音波も非球形物２，球形物３，４の各々が分離すれが粉砕条件は任意である。 Here, in order to measure each of these non-spherical objects 2, spherical objects 3, and 4 individually, each composition of the jewelry member is pulverized with a wet mill. Destructive inspection is performed by disassembling the spherical object 2, the spherical object 3 and 4 individually. Both the wet mill and the ultrasonic wave are separated from each of the non-spherical object 2, the spherical object 3 and 4, and the pulverization conditions are arbitrary.
次に、粉砕物である非球形物２，球形物３，４の各々を有機物が溶解した有機溶媒に分散させ、適度な粘性としたスラリーにする。有機溶媒にはアセトン、ベンゼン、ＩＰＡを適時用いるとともに、有機物にはアクリル樹脂、グリセリン、多糖類などを適時用いる。 Next, each of the non-spherical material 2 and the spherical materials 3 and 4 which are pulverized products is dispersed in an organic solvent in which the organic material is dissolved to form a slurry having an appropriate viscosity. Acetone, benzene, and IPA are used as appropriate for the organic solvent, and acrylic resin, glycerin, polysaccharides, and the like are used as appropriate for the organic substance.
次に、上記スラリーを沈殿させて各沈殿層から選択的に抽出するか、あるいは遠心分離させて抽出することも可能である。抽出は上記スラリーからスポットピンなどの微細なストローを用いた抽出手段により、非球形物２，球形物３，４の各々を個別に抽出する。 Next, the slurry may be precipitated and selectively extracted from each precipitation layer, or may be extracted by centrifugation. In the extraction, each of the non-spherical object 2, the spherical object 3 and 4 is individually extracted from the slurry by an extraction means using a fine straw such as a spot pin.
そして個別に抽出した非球形物２，球形物３，４の各々を、使用した上記有機溶媒による超音波洗浄で十分に洗浄した後、制限視野電子回折像によりスポット径１０ｎｍの範囲で観測を行うことになる。これにより非球形物２，球形物３，４の各々が同一スポット内で互いに干渉することなく分析することができる。 Each of the non-spherical object 2, spherical object 3 and 4 extracted individually is sufficiently cleaned by ultrasonic cleaning with the organic solvent used, and then observed with a limited field electron diffraction image in a spot diameter range of 10 nm. It will be. Thus, each of the non-spherical object 2, the spherical objects 3 and 4 can be analyzed without interfering with each other in the same spot.
またＩＣＰ発光分光分析法によりエルビウム、ジルコニウムの含有量を分析した。サンプルは試料０．１ｇにフッ酸、硝酸、硫酸を加えて蒸発乾固したものに塩酸を加えて溶液としたものを用いて分析した。
非球形物及び球状物の面積比率、球状物の平均直径、Ｅｒ、Ｚｒの有無を満足するものは発色や遊色効果だけでなく強度も良好だが、満足しない場合は特に強度が顕著に悪化する。たとえば、球形物３，４の平均直径が１ｎｍ未満の場合には、非晶質珪酸の球状体１の間に介在して接続しても接合強度が弱くなり、１００ｎｍを超える場合には非晶質珪酸の球状体１が規則的な三次元配列を維持できなくなり、遊色効果が得られず、かつ強度が弱くなることがわかる。すなわち、球形物の平均直径は強度保持の観点から１ｎｍ以上が好ましく、１００ｎｍを超えると、強度保持性に欠ける。 Those satisfying the area ratio of non-spherical and spherical objects, the average diameter of spherical objects, and the presence or absence of Er and Zr are good not only in coloring and play-coloring effects but also in strength. . For example, when the average diameter of the spheres 3 and 4 is less than 1 nm, the bonding strength is weak even if they are connected between the spherical bodies 1 of amorphous silicic acid, and when the average diameter exceeds 100 nm, it is amorphous. It turns out that the spherical body 1 of the siliceous silicic acid cannot maintain a regular three-dimensional arrangement, the play-color effect is not obtained, and the strength is weakened. That is, the average diameter of the sphere is preferably 1 nm or more from the viewpoint of maintaining the strength, and if it exceeds 100 nm, the strength retention is insufficient.
そして上記球状体間に形成される間隙にエルビウムおよび珪素を含む非球形物と平均直径１〜１００ｎｍの球形物とを、断面視して全体の０．６〜１６．０％の面積を占めるように配置させてなるのが好ましく、０．６〜１６．％の面積の範囲から外れると、遊色効果、強度が悪化することがわかる。
結晶質の存在、非晶質の存在、Ｓｉ、Ｅｒ、Ｚｒの有無を満足するものは発色や遊色効果だけでなく強度も良好だが、満足しない場合は特に発色や遊色効果が顕著に悪化する。 Those that satisfy the presence of crystalline, amorphous, Si, Er, or Zr have good strength as well as coloring and play-off effects, but if they are not satisfied, the color formation and play-off effects are significantly worsened. To do.
たとえば、上記結晶質の組成物である非球形物２，球形物３と非晶質の組成物４の割合が７５：２５〜２５：７５の範囲であることが好ましいことがわかる。すなわち、上記割合の範囲よりも結晶質の組成物である非球形物２，球形物３が多くなる場合には結晶化が局所的に進み、非晶質の珪酸からなる球状体１の間に存在してなる組成物の構造が偏在して強度が低下してしまう。また上記割合の範囲よりも非晶質の組成物４が多い場合には、球状体１が確保されずに強度が低下してしまう。 For example, it can be seen that the ratio of the non-spherical product 2, the spherical product 3 and the amorphous composition 4 which are the crystalline compositions is preferably in the range of 75:25 to 25:75. That is, when the amount of the non-spherical material 2 and the spherical material 3 that are crystalline compositions is larger than the above range, crystallization proceeds locally, and between the spherical bodies 1 made of amorphous silicic acid. The structure of the existing composition is unevenly distributed and the strength is lowered. In addition, when the amorphous composition 4 is more than the above range, the spherical body 1 is not secured and the strength is lowered.
また、上記結晶質の組成物である非球形物２，球形物３におけるエルビウムを０．１〜６．０重量％、ジルコニウムを０．００５〜５．０重量％とするのが好ましいことがわかる。すなわち、エルビウムが０．１重量％未満の場合には宝飾部材が十分な発色（ピンク色）が得られないという不具合がある。また６．０重量％を超える場合には非晶質の珪酸からなる球状体１の間に介在させることが困難になるという不具合がある。ジルコニウムが０．００５重量％未満の場合には、宝飾部材が透明体となって遊色効果が現れないという不具合がある。また５．０重量％を超える場合には、透明度が失われ宝飾部材として商品価値が大きく低下する。 Moreover, it turns out that it is preferable to make 0.1 to 6.0 weight% of erbium, and 0.005 to 5.0 weight% of zirconium in the non-spherical material 2 and the spherical material 3 which are the said crystalline composition. . That is, when erbium is less than 0.1% by weight, there is a problem that the jewelry member cannot obtain a sufficient color (pink). Moreover, when it exceeds 6.0 weight%, there exists a malfunction that it becomes difficult to interpose between the spherical bodies 1 which consist of amorphous silicic acid. When zirconium is less than 0.005% by weight, there is a problem that the jewelry member becomes a transparent body and no play color effect appears. Moreover, when it exceeds 5.0 weight%, transparency will be lost and a commercial value will fall significantly as a jewelry member.
尚、上記珪素とエルビウムとジルコニウムは酸化物として存在する場合は、酸化物換算して計算されるものである。 When silicon, erbium, and zirconium are present as oxides, they are calculated in terms of oxides.
なお原料の組成は、当然に宝飾部材としての組成と同様である。 The composition of the raw material is naturally the same as the composition as a jewelry member.
なお、本発明の宝飾部材は上述の実施例にのみ限定されるものではなく、特許請求の範囲において種々の変更、代替、付加が可能となる。 The jewelry member of the present invention is not limited to the above-described embodiments, and various modifications, substitutions, and additions are possible within the scope of the claims.
１ 非晶質の珪酸からなる球状体
２ 少なくともＳｉ、Ｅｒ（の単体もしくは酸化物）を含む結晶質の非球形物
３ 少なくともＳｉ、Ｅｒ、Ｚｒ（の単体もしくは酸化物）を含む結晶質の球形物
４ 少なくともＳｉ、Ｅｒ、Ｚｒ（の単体もしくは酸化物）を含む非晶質の球形物
DESCRIPTION OF SYMBOLS 1 Spherical body consisting of amorphous silicic acid 2 Crystalline non-spherical material containing at least Si and Er (single or oxide) 3 Crystalline spherical containing at least Si, Er and Zr (single or oxide) 4 Amorphous sphere containing at least Si, Er, Zr (single or oxide thereof)
Claims (5)
上記球状体間に形成される間隙にエルビウムと珪素とを含む非球形物と、
平均直径１〜１００ｎｍの球形物を配置させてなり、
上記非球形物と球形物が断面視して全体の０．６〜１６．０％の面積を占めることを特徴とする宝飾部材。 While regularly arranging three-dimensional spherical bodies made of amorphous silicic acid,
A non-spherical material containing erbium and silicon in the gap formed between the spherical bodies;
A spherical object having an average diameter of 1 to 100 nm is arranged,
A jewelery member characterized in that the non-spherical object and the spherical object occupy an area of 0.6 to 16.0% of the whole in a sectional view.
上記球状体間に形成される間隙に結晶質組成物及び非晶質組成物を配置させてなり、
上記結晶質組成物が少なくとも珪素とエルビウムを含み、上記非晶質組成物が少なくとも珪素とエルビウムとジルコニウムを含むことを特徴とする宝飾部材。 While regularly arranging three-dimensional spherical bodies made of amorphous silicic acid,
A crystalline composition and an amorphous composition are arranged in a gap formed between the spherical bodies,
A jewelry member, wherein the crystalline composition contains at least silicon and erbium, and the amorphous composition contains at least silicon, erbium and zirconium.
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| JP2011063481A (en) * | 2009-09-17 | 2011-03-31 | Nippon Chem Ind Co Ltd | Flake like silica presenting opal like color play effect, and method for manufacturing the same |
| WO2012039494A1 (en) * | 2010-09-24 | 2012-03-29 | 京セラ株式会社 | Opal and method of production therefor |
| JP2012126872A (en) * | 2010-12-17 | 2012-07-05 | Sumika Styron Polycarbonate Ltd | Polycarbonate resin composition |
| CN112384100A (en) * | 2018-07-17 | 2021-02-19 | 京瓷株式会社 | Jewel ornament component |
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| JPH04193760A (en) * | 1990-11-26 | 1992-07-13 | Nkk Corp | Colored light-transmissive alumina sintered body and its production |
| JP2002255673A (en) * | 2001-02-28 | 2002-09-11 | Gifu Prefecture | Ceramic product having color rendering property and colorant |
| JP2003073170A (en) * | 2001-08-30 | 2003-03-12 | Kyocera Corp | Jewelry |
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| JPS6096589A (en) * | 1983-10-26 | 1985-05-30 | 京セラ株式会社 | Jewel dressing member |
| JPS61270274A (en) * | 1985-05-24 | 1986-11-29 | 河合 正 | Pressure reduced sealing pre-treatment on artificial coloring process for natural gems such as agate |
| JPH04193760A (en) * | 1990-11-26 | 1992-07-13 | Nkk Corp | Colored light-transmissive alumina sintered body and its production |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011063481A (en) * | 2009-09-17 | 2011-03-31 | Nippon Chem Ind Co Ltd | Flake like silica presenting opal like color play effect, and method for manufacturing the same |
| WO2012039494A1 (en) * | 2010-09-24 | 2012-03-29 | 京セラ株式会社 | Opal and method of production therefor |
| JP5047402B2 (en) * | 2010-09-24 | 2012-10-10 | 京セラ株式会社 | Opal and its manufacturing method |
| JP2012126872A (en) * | 2010-12-17 | 2012-07-05 | Sumika Styron Polycarbonate Ltd | Polycarbonate resin composition |
| CN112384100A (en) * | 2018-07-17 | 2021-02-19 | 京瓷株式会社 | Jewel ornament component |
| CN112384100B (en) * | 2018-07-17 | 2022-11-01 | 京瓷株式会社 | Jewelry component |
| US11925243B2 (en) | 2018-07-17 | 2024-03-12 | Kyocera Corporation | Jewelry member |
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