JPH0769761A - Production of ceramic product and composition for sintering - Google Patents
Production of ceramic product and composition for sinteringInfo
- Publication number
- JPH0769761A JPH0769761A JP23725993A JP23725993A JPH0769761A JP H0769761 A JPH0769761 A JP H0769761A JP 23725993 A JP23725993 A JP 23725993A JP 23725993 A JP23725993 A JP 23725993A JP H0769761 A JPH0769761 A JP H0769761A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- sintering
- composition
- noble metal
- ceramic
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5105—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the noble metals or copper
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Devices For Post-Treatments, Processing, Supply, Discharge, And Other Processes (AREA)
- Paints Or Removers (AREA)
- Decoration By Transfer Pictures (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えば陶器、磁器、ガ
ラス器等のセラミック製品等に貴金属の焼結膜を形成さ
せて装飾性に優れた製品を作製することができるセラミ
ック製品の製造方法及び焼結用組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a ceramic product, which is capable of producing a product excellent in decorativeness by forming a sintered film of a noble metal on a ceramic product such as pottery, porcelain and glassware. It relates to a composition for sintering.
【０００２】[0002]
【従来の技術】陶磁器は、陶石、石英、長石、カオリン
（粘土）を主材として、素焼き（８５０℃）または本焼
きして下絵を描き、釉薬をかけて完成するものと、さら
にその上面に上絵を描くものとがある。この陶磁器やガ
ラス製品等に上絵を描くための上絵具としては、古くか
ら金や銀等の貴金属を溶液化した化学品が使用され、廉
価品には０．５μｍ以下の厚みの貴金属薄膜を、高価品
には１μｍ以上の貴金属厚膜を形成させて装飾が施され
てきた。2. Description of the Related Art Ceramics are mainly composed of porcelain stone, quartz, feldspar, and kaolin (clay), which are unglazed (850.degree. C.) or main-baked to draw a sketch and finish with glaze. There is one that draws a picture. As a paint for drawing a painting on this ceramic or glass product, a chemical product in which a precious metal such as gold or silver is solubilized has been used for a long time, and a cheap precious metal thin film with a thickness of 0.5 μm or less is used. However, expensive products have been decorated by forming a noble metal thick film of 1 μm or more.
【０００３】上記貴金属を溶液化した化学品により貴金
属膜を形成させる方法は、例えば金を例にすると、まず
ラベンダー油と硫黄とを１５０〜２００℃で１５時間程
度加熱して、硫化バルサムを作り、これに塩化金（ＨＡ
ｕＣｌ4 ・４Ｈ2 Ｏ）を加えて金バルサムを得る。次
に、これにテレピン油、ニトロベンゾール、クロロホル
ム等を加えて粘稠度及び濃度の調整を行って金液を作製
する。銀やパラジウムについても同様な手法によりそれ
ぞれ銀液、パラジウム液を作製する。そして、上記のよ
うに得られた金液、銀液、パラジウム液を細筆でセラミ
ック成形体の表面に塗りつけたり、転写法等の技術によ
り被着させ、これを乾燥させた後、６５０〜８５０℃程
度で焼成して焼き付け、研磨を施して完成するのであ
る。In the method of forming a noble metal film by a chemical product obtained by dissolving the above noble metal, for example, using gold as an example, first, lavender oil and sulfur are heated at 150 to 200 ° C. for about 15 hours to form balsam sulfide. , To this, gold chloride (HA
uCl 4 .4H 2 O) is added to obtain gold balsam. Next, turpentine oil, nitrobenzol, chloroform, etc. are added to this to adjust the consistency and concentration to prepare a gold solution. A silver solution and a palladium solution are prepared for silver and palladium by the same method. Then, the gold solution, silver solution, and palladium solution obtained as described above are applied to the surface of the ceramic molded body with a fine brush or adhered by a technique such as a transfer method and dried, and then 650 to 850 ° C. It is completed by firing, baking, and polishing.
【０００４】 ．[0004]
【発明が解決しようとする課題】しかしながら、上記従
来の貴金属膜の形成方法では、使用する金液等が極めて
高価であるという問題があった。また、硫化バルサムを
生ずる際に極めて特異な強い臭気が発生するため、換気
を十分に施しても作業者の体に染み付いてしまうので、
作業者の精神的苦痛は甚大なものであった。さらに、焼
成時に４００℃までに亜硫酸ガス等の排出があるため、
この処理が十分でない場合には環境問題を生ずる危険性
もあった。したがって、上記の毒性ガスを排気処理設備
等により厳重に処理する必要があるが、このような付加
設備はコストを上昇させる等の新たな問題を生ずるもの
であった。However, the above-mentioned conventional method for forming a noble metal film has a problem that the gold liquid or the like used is extremely expensive. In addition, since a very peculiar strong odor is generated when producing balsam sulfide, it will permeate the worker's body even with sufficient ventilation,
The worker's emotional distress was enormous. Furthermore, since sulfurous acid gas is emitted up to 400 ° C during firing,
If this treatment is not sufficient, there is a risk of causing environmental problems. Therefore, it is necessary to treat the above-mentioned toxic gas strictly by exhaust treatment equipment or the like, but such additional equipment causes a new problem such as an increase in cost.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記に鑑み提
案されたもので、従来の貴金属の化学品を用いるのでは
なく、貴金属自体を粉体化した貴金属粉末に対して、有
機系結合材溶液１〜４０％と、亜鉛粉末０〜５％と、ア
ンチモン粉末０〜５％と、インジウム粉末０〜５％と、
錫粉末０〜５％と、炭酸鉛粉末０〜５％とを添加して粘
土状若しくは泥漿状にした焼結用組成物を、セラミック
成形体の表面に付着または転写させた後に焼結温度まで
昇温することを特徴とするセラミック製品の製造方法に
関するものである。SUMMARY OF THE INVENTION The present invention has been proposed in view of the above, and does not use a conventional noble metal chemical product, but an organic bond to a noble metal powder obtained by pulverizing the noble metal itself. Material solution 1-40%, zinc powder 0-5%, antimony powder 0-5%, indium powder 0-5%,
Clay-like or slurry-like sintering composition obtained by adding 0 to 5% of tin powder and 0 to 5% of lead carbonate powder is adhered to or transferred to the surface of the ceramic molded body, and then heated to the sintering temperature. The present invention relates to a method for manufacturing a ceramic product, which is characterized by heating.
【０００６】本発明の焼結用組成物に適用する貴金属粉
末は、金、銀等の純貴金属の粉末、或いはこれらの元素
を主成分とする貴金属合金の粉末からなり、一種以上を
組合せて使用してもよい。上記貴金属粉末としては、粒
径０．１〜１０μｍの粉粒体を使用することが望まし
い。The noble metal powder applied to the sintering composition of the present invention is a powder of a pure noble metal such as gold or silver, or a powder of a noble metal alloy containing these elements as a main component, and used in combination of one or more. You may. As the above-mentioned noble metal powder, it is desirable to use a granular material having a particle size of 0.1 to 10 μm.
【０００７】上記貴金属粉末に有機系結合材溶液を加え
て粘土状若しくは泥漿状の焼結用組成物を作製する。こ
の有機系結合材（溶液）としては、「粉体理論と応用」
（丸善株式会社，昭和４８年８月１０日発行）の８１９
頁に記載されているように、メチルセルロースやエチル
セルロース等のセルロース誘導体を使用することもでき
るし、また、オリーブ油（オレイン酸ＣＨ3 （ＣＨ2 ）
7 ＣＨ及びリノール酸のグリセリドよりなる）溶液など
の油脂類やスキージオイル（アクリル系溶剤＋ブチラー
ル系樹脂）などを使用することもできる。尚、セルロー
ス誘導体としては特にその水溶液濃度５〜６％で、粘度
７０００〜１００００センチポイズを示す高分子量のも
のを使用することが好ましい。そして、前記貴金属合金
に上記有機系結合材溶液を１〜４０％の範囲で添加して
粘土状或いは泥漿状の焼結用組成物にするのであるが、
添加量が１％より低いと混練ができないほど硬くなり、
４０％より多いとセラミック成形体に付着させた場合に
垂れ落ちてしまうので好ましくない。また、特にセルロ
ース誘導体を用いる場合には焼結した際の収縮を考慮し
て１０％より少ない範囲で添加することが望ましい。
尚、上記有機系結合材溶液は食用、薬用、化学用等の種
々の用途に使用されているものであり、公害的な要素は
極めて低いものである。An organic binder solution is added to the precious metal powder to prepare a clay-like or slurry-like sintering composition. For this organic binder (solution), "powder theory and application"
819 (published by Maruzen Co., Ltd. on August 10, 1973)
As described on the page, cellulose derivatives such as methyl cellulose and ethyl cellulose may be used, or olive oil (oleic acid CH 3 (CH 2 )) may be used.
It is also possible to use oils and fats such as a solution of 7 CH and glyceride of linoleic acid) and squeegee oil (acrylic solvent + butyral resin). As the cellulose derivative, it is preferable to use a high molecular weight cellulose derivative having an aqueous solution concentration of 5 to 6% and a viscosity of 7,000 to 10,000 centipoise. Then, the organic binder solution is added to the noble metal alloy in the range of 1 to 40% to form a clay-like or slurry-like composition for sintering.
If the amount added is less than 1%, it becomes too hard to knead,
If it is more than 40%, it will drop when attached to the ceramic molded body, which is not preferable. Further, particularly when a cellulose derivative is used, it is desirable to add it in a range of less than 10% in consideration of shrinkage at the time of sintering.
The organic binder solution is used for various purposes such as edible, medicinal, and chemical purposes, and the pollution factor is extremely low.
【０００８】また、上記焼結用組成物には、必要に応じ
て亜鉛（Ｚｎ）粉末０〜５％、アンチモン（Ｓｂ）粉末
０〜５％、インジウム（Ｉｎ）粉末０〜５％、錫（Ｓ
ｎ）粉末０〜５％、炭酸鉛（ＰｂＣＯ3 ）粉末０〜５％
を添加し、密着性を向上させるようにしてもよい。この
密着性を向上する効果については後述するが、それぞれ
５％以上添加すると、焼結した後の焼結膜が黒ずんだり
変色して装飾的価値が低下する。In addition, in the above-mentioned sintering composition, 0 to 5% zinc (Zn) powder, 0 to 5% antimony (Sb) powder, 0 to 5% indium (In) powder, and tin ( S
n) powder 0 to 5%, lead carbonate (PbCO 3 ) powder 0 to 5%
May be added to improve the adhesion. Although the effect of improving the adhesiveness will be described later, if 5% or more of each is added, the sintered film after sintering is darkened or discolored, and the decorative value is reduced.
【０００９】このように構成される焼結用組成物は、原
材料自体並びに調製（混合）中などに全く臭気を発生さ
せることがなく、６５０〜８５０℃で焼成する工程にお
いても特異なガスを発生させることがないので、従来の
ように換気等の作業条件を特に重視する必要がない。The sintering composition thus constituted does not generate an odor at all in the raw materials themselves and during preparation (mixing), and generates a unique gas even in the step of firing at 650 to 850 ° C. Since it is not performed, it is not necessary to attach special importance to work conditions such as ventilation as in the conventional case.
【００１０】そして、粘土状或いは泥漿状にした焼結用
組成物をセラミック成形体に付着または転写させるに
は、どのような公知の手段を採るようにしてもよい。焼
結用組成物を粘土状にした場合には、主に手で成形した
ものをセラミック成形体に圧着する方法が採られるが、
焼結用組成物を泥漿状にした場合には、刷毛等を用いて
直接塗りつけるようにしてもよいし、透水性を有する紙
基材上に水溶性接着剤が塗布されてなる陶磁器用転写紙
を用いて転写するようにしてもよい。Any known means may be used to attach or transfer the clay-like or slurry-like sintering composition to the ceramic compact. When the composition for sintering is made into a clay shape, a method of pressing a molded product mainly by hand onto a ceramic molded body is adopted,
When the composition for sintering is made into a slurry, it may be directly applied with a brush or the like, or a transfer paper for ceramics obtained by applying a water-soluble adhesive on a paper base material having water permeability. You may make it transfer using.
【００１１】上記転写方法の一例を示す。上記構成の
陶磁器用転写紙の上にスクリーン製版を用いて前記組成
の焼結用組成物を所望の図柄に印刷し、これを乾燥させ
て転写マークを作製する。次に、この転写マークの印刷
面が下になるようにセラミック成形体に臨ませた状態で
水を湿潤させると、転写マークの水溶性接着剤が溶解し
て紙基材が剥れ、焼結用組成物の印刷膜だけがセラミッ
ク成形体の表面に付着するのである。前記の方法と
同様に陶磁器用転写紙の上に焼結用組成物を印刷し、乾
燥させる。さらに、その表面に造膜性を有する樹脂組成
物を印刷し、これを乾燥させて転写マークを作製する。
この場合、転写マークを予め水に湿潤させた状態で転写
マークの印刷面が上になるようにセラミック成形体に臨
ませ、紙基材を剥がして造膜した樹脂組成物及び焼結用
組成物の印刷膜だけがセラミック成形体の表面に付着す
るのである。An example of the above transfer method will be described. On the transfer paper for ceramics having the above structure, a sintering composition having the above composition is printed in a desired pattern using a screen printing plate, and this is dried to produce a transfer mark. Next, when water is moistened while facing the ceramic molded body so that the printed surface of the transfer mark faces down, the water-soluble adhesive of the transfer mark is dissolved and the paper substrate is peeled off and sintered. Only the printed film of the composition for use adheres to the surface of the ceramic molded body. The composition for sintering is printed on the transfer paper for ceramics and dried as in the above-mentioned method. Further, a resin composition having a film-forming property is printed on the surface and dried to prepare a transfer mark.
In this case, a resin composition and a sintering composition in which the transfer mark is pre-wetted with water so that the printed surface of the transfer mark faces the ceramic molded body and the paper substrate is peeled off to form a film. Only the printed film of (3) adheres to the surface of the ceramic molded body.
【００１２】上記焼結用組成物が焼結する状況を以下に
説明する。加熱されて温度が上がると、貴金属粉末の粒
子の表面に吸着されていたセルロース誘導体、スキージ
オイル、オリーブ油などの有機系結合材が２２０〜２５
０℃程度で逸散し、貴金属粉末の粒子を自由に接触させ
る。さらに温度が上がると、貴金属粉末を構成する原子
の熱的振動が盛んになり、イオンの運動を促進する。そ
して、表面張力が十分に大きくなると、表面拡散或いは
流動が行われ、貴金属粉末の粒子間の接触面積が増加す
る。即ち焼結が起る。尚、前記転写マークにおける樹脂
組成物も焼結温度に達する前に燃焼して消失する。The situation in which the above-mentioned composition for sintering is sintered will be described below. When heated and the temperature rises, 220 to 25 organic binders such as cellulose derivative, squeegee oil and olive oil adsorbed on the surface of the noble metal powder particles are adsorbed.
Disperses at about 0 ° C., allowing particles of noble metal powder to come into contact freely. When the temperature further rises, the thermal vibration of the atoms forming the precious metal powder becomes active, which promotes the movement of ions. When the surface tension becomes sufficiently large, surface diffusion or flow occurs and the contact area between the noble metal powder particles increases. That is, sintering occurs. The resin composition in the transfer mark also burns and disappears before reaching the sintering temperature.
【００１３】また、焼結用組成物中の貴金属粉末がセラ
ミック成形体の表面に焼結膜として固定化される状況は
次のように考えられる。The situation where the noble metal powder in the sintering composition is fixed as a sintered film on the surface of the ceramic compact is considered as follows.
【００１４】第一に、セラミック成形体と貴金属粉末
（焼結膜）との物理的からみ合いによる結合である。セ
ラミック成形体（陶材）の表面はポーラス（多孔質）で
あり、また自然に或いは人為的に凹凸が加えられてい
る。したがって、泥漿状の焼結用組成物を塗布すると、
その微細な表面内部に焼結用組成物が十分に追従、浸透
（からみ合い）するので、焼結膜とセラミック成形体の
接触面積は極めて大きいものとなり、焼結膜はセラミッ
ク成形体の表面に物理的に強固に固定される。さらに、
収縮は、セラミック成形体（陶材）では約１０〜１５
％、有機系結合材溶液としてセルロース誘導体溶液を用
いた焼結用組成物では約１５〜２０％であるため、収縮
率の大きい焼結用組成物（焼結膜）がセラミック成形体
に圧縮応力を与え、セラミック成形体を締め付けるよう
に圧縮して強固に固定される。尚、上記収縮係数の隔り
が大きいと亀裂等を生ずることになるが、本発明では近
似しているためにそのような亀裂等を生じない。また、
セラミック成形体の表面に低融点の釉薬層が設けられて
いる場合には、高温時には貴金属粉末がポーラスとなっ
ているために吸引浸透して密着する。したがって、積極
的に低釉フリットを貴金属粉末に微量（０．５〜１％）
添加することも十分に考えられる。First, there is a physical interlocking of the ceramic compact and the noble metal powder (sintered film). The surface of the ceramic molded body (porcelain) is porous, and irregularities are added to it naturally or artificially. Therefore, when a slurry-like sintering composition is applied,
Since the sintering composition sufficiently follows and permeates (entangles) inside the fine surface, the contact area between the sintered film and the ceramic molded body becomes extremely large, and the sintered film physically adheres to the surface of the ceramic molded body. It is firmly fixed to. further,
Shrinkage is about 10-15 in a ceramic molded body (porcelain)
%, The composition for sintering using a cellulose derivative solution as the organic binder solution has a content of about 15 to 20%, so that the composition for sintering (sintered film) having a large shrinkage rate exerts compressive stress on the ceramic molded body. Then, the ceramic molded body is compressed and clamped so as to be firmly fixed. It should be noted that if the difference between the above-mentioned shrinkage coefficients is large, cracks or the like will occur, but since they are similar in the present invention, such cracks or the like do not occur. Also,
When the glaze layer having a low melting point is provided on the surface of the ceramic molded body, since the precious metal powder is porous at the time of high temperature, the precious metal powder is sucked and permeated to adhere. Therefore, a small amount (0.5 to 1%) of low glaze frit is added to the precious metal powder.
It is fully conceivable to add it.
【００１５】第二に、セラミック成形体と貴金属粉末
（焼結膜）との化学的（或いは電気的）な結合である。
セラミック成形体はそれ自体に多くの酸化物、例えばＦ
ｅ2 Ｏ3 、ＴｉＯ2 、ＭｎＯ、ＭｇＯ等を含有してお
り、また、その表面に図柄等を装飾する絵具顔料は全て
金属酸化物で構成されている。そして、その表面は全体
として電気的に陰性を帯びており、貴金属粉体は陽性で
あるから「ぬれ」が悪い。この改善のために亜鉛（Ｚ
ｎ）粉末、アンチモン（Ｓｂ）粉末、錫（Ｓｎ）粉末、
インジウム（Ｉｎ）粉末、或いは炭酸鉛（ＰｂＣＯ3 ）
粉末を微量添加すると、加熱時にこれらが選択酸化され
て表層部に金属酸化物層を形成する。しかもこれらの金
属は、低融点であるために、焼成温度内で容易に酸化物
を生成する。このようにして焼結膜中に選択酸化物を形
成すると、この選択酸化物とセラミック成形体中の酸化
物が接触して加熱され熱力学的に平衡になって分子間引
力によって「ぬれ」易くなって結合する。この熱塑性流
動を持つセラミック成形体（釉薬）が室温まで冷却して
剛体となった時はさらに分子間引力が働くことになる。
このようにして選択酸化物層を形成することが密着性を
向上する一方法であり、特に貴金属のような不活性金属
には有用であるが、色沢その他から添加量はおのずと制
限を受ける。Second, there is a chemical (or electrical) bonding between the ceramic compact and the noble metal powder (sintered film).
The ceramic compact itself has many oxides, such as F.
e 2 O 3, TiO 2, MnO, and contains MgO and the like, also, paint pigments to decorate images, etc. on its surface is composed of all metal oxides. And the surface thereof is electrically negative as a whole, and the precious metal powder is positive, so that "wetting" is bad. Zinc (Z
n) powder, antimony (Sb) powder, tin (Sn) powder,
Indium (In) powder or lead carbonate (PbCO 3 )
When a small amount of powder is added, these are selectively oxidized during heating to form a metal oxide layer on the surface layer portion. Moreover, since these metals have low melting points, they easily form oxides within the firing temperature. When the selective oxide is formed in the sintered film in this way, the selective oxide and the oxide in the ceramic molded body come into contact with each other and are heated to be in thermodynamic equilibrium, so that “wetting” easily occurs due to intermolecular attractive force. Join together. When the ceramic molded body (glaze) having this thermoplastic flow is cooled to room temperature and becomes a rigid body, an intermolecular attractive force is further exerted.
Forming the selective oxide layer in this manner is one method for improving the adhesion, and is particularly useful for an inert metal such as a noble metal, but the amount to be added is naturally limited by color and other factors.
【００１６】このように本発明のセラミック製品の製造
方法は、素焼き等のセラミック成形体の表面に焼結用組
成物を付着して焼成することにより、装飾性に優れた工
芸品等の製品を得ることもできるし、釉薬等をかけたセ
ラミック成形体の表面に前述した各種粉末を添加した焼
結用組成物を付着して焼成することにより、実用性のあ
る容器等の製品を得ることもできる。また、その際に従
来の方法のような臭気を生ずることもないので、作業者
の精神的苦痛を伴うことなく加工作業を行うことができ
るものである。As described above, according to the method for producing a ceramic product of the present invention, a product such as a craft product having an excellent decorative property is obtained by adhering the composition for sintering to the surface of a ceramic compact such as unglazed and firing it. It is also possible to obtain a product such as a container having practicality by adhering the composition for sintering to which the above-mentioned various powders are added to the surface of the ceramic molded body to which a glaze or the like is applied and firing the product. it can. Further, at that time, no odor is generated as in the conventional method, so that the working operation can be performed without causing mental distress of the operator.
【００１７】[0017]
【実施例】以下に本発明の実施例を示す。EXAMPLES Examples of the present invention will be shown below.
【００１８】実施例１〜１０；表１及び表２に示す組成
の焼結用組成物を用いて、それぞれの目的の製造品を加
工、作製した。Examples 1 to 10: Using the sintering compositions having the compositions shown in Tables 1 and 2, the respective manufactured products were processed and produced.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【表２】 [Table 2]
【００２１】以上本発明を実施例に基づいて説明した
が、本発明は前記した実施例に限定されるものではな
く、特許請求の範囲に記載した構成を変更しない限りど
のようにでも実施することができる。The present invention has been described above based on the embodiments, but the present invention is not limited to the above-mentioned embodiments, and can be carried out in any manner as long as the configuration described in the claims is not changed. You can
【００２２】[0022]
【発明の効果】以上説明したように、本発明のセラミッ
ク製品の製造方法は、特定の焼結用組成物を付着または
転写させて焼成するだけで、セラミック成形体の表面に
貴金属の焼結膜を形成させて装飾性に優れた製品を作製
することができる。As described above, according to the method for producing a ceramic product of the present invention, the sintered film of the noble metal is formed on the surface of the ceramic molded body only by adhering or transferring the specific sintering composition and firing it. By forming it, a product with excellent decorativeness can be manufactured.
【００２３】また、形成される焼結膜は、第一に物理的
からみ合いによる結合、即ちセラミック成形体の表面の
凹凸に焼結用組成物が十分に追従、浸透して接触面積が
大きくするため、さらに、焼結膜とセラミック成形体と
の圧縮係数の相違により焼結膜がセラミック成形体を圧
縮するため、セラミック成形体に強固に固定される。第
二に化学的（或いは電気的）な結合、即ち焼結用組成物
に添加した亜鉛粉末、アンチモン粉末、インジウム粉
末、錫粉末、炭酸鉛粉末が焼成過程で選択酸化物を生成
することにより酸化物を多量含有するセラミック成形体
と「ぬれ」易くなって密着性を向上する。また、銀の硫
化は避けられないことであるが、亜鉛、錫、アンチモン
等は銀の硫化を防止する傾向があることが判っている。
したがって、本発明により得られるセラミック製品は、
工芸品として作製した場合は勿論であるが、実用性を有
する容器とした場合にも洗浄等では全く剥離されない強
固な焼結膜を有するものとなり、硫化は極めてしにくく
なる傾向がある。In the formed sintered film, firstly, the bonding by physical entanglement, that is, the sintering composition sufficiently follows and permeates the irregularities on the surface of the ceramic molded body to increase the contact area. Further, since the sintered film compresses the ceramic molded body due to the difference in compression coefficient between the sintered film and the ceramic molded body, it is firmly fixed to the ceramic molded body. Secondly, chemical (or electrical) bonding, that is, zinc powder, antimony powder, indium powder, tin powder, lead carbonate powder added to the sintering composition is oxidized by forming a selective oxide in the firing process. Improves adhesion by facilitating "wetting" with a ceramic compact containing a large amount of material. Further, it is known that sulfuration of silver is unavoidable, but zinc, tin, antimony and the like tend to prevent sulfuration of silver.
Therefore, the ceramic product obtained by the present invention is
Not only when it is produced as a craft, but also when it is used as a container having practicality, it has a strong sintered film that is not peeled at all by washing and the like, and it tends to be extremely difficult to sulfurize.
【００２４】さらに、本発明に使用される焼結用組成物
の調製中や加工中において、従来の方法のように強い臭
気を生ずることもないので、作業者は精神的苦痛を伴う
ことなく快適に作業を行うことができる。また、亜硫酸
ガス等の汚染物質も全く生じないので、排気処理設備等
を設けなくても周囲の環境を汚染する危険性は全くな
い。Further, during the preparation and processing of the sintering composition used in the present invention, no strong odor is generated unlike the conventional method, so that the worker is comfortable without any mental distress. Can work on it. Moreover, since pollutants such as sulfurous acid gas are not generated at all, there is no risk of polluting the surrounding environment without providing exhaust treatment equipment.
【００２５】また、本発明の焼結用組成物は、安定に供
給される貴金属粉末及びセルロース誘導体、油脂類、オ
リーブ等の有機系結合材、さらに必要に応じて添加され
る亜鉛粉末、アンチモン粉末、インジウム粉末、錫粉
末、炭酸鉛粉末などを原材料とするものであり、しかも
これらを汎用の攪拌機等で混合（または混練）して簡単
に調製することができる。したがって、少なくとも従来
のものに比べてコストを低廉に抑えることができ、また
従来のもののように強い臭気を伴うこともないので調製
（混合）作業を簡便に行うことができる。The composition for sintering of the present invention comprises a stable supply of noble metal powder and cellulose derivative, organic binders such as fats and oils, olive powder, and zinc powder and antimony powder which are optionally added. , Indium powder, tin powder, lead carbonate powder and the like are used as raw materials, and can be easily prepared by mixing (or kneading) these with a general-purpose stirrer or the like. Therefore, the cost can be reduced at least as compared with the conventional one, and the strong odor unlike the conventional one can be avoided, so that the preparation (mixing) operation can be easily performed.
【表３】 [Table 3]
【表４】 [Table 4]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 41/90 Ｄ Ｃ０９Ｄ 5/38 ＰＲＦ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI Technical display location C04B 41/90 D C09D 5/38 PRF
Claims (2)
１〜４０％と、亜鉛粉末０〜５％と、アンチモン粉末０
〜５％と、インジウム粉末０〜５％と、錫粉末０〜５％
と、炭酸鉛粉末０〜５％とを添加して粘土状若しくは泥
漿状にした焼結用組成物を、セラミック成形体の表面に
付着または転写させた後に焼結温度まで昇温することを
特徴とするセラミック製品の製造方法。1. An organic binder solution of 1 to 40%, a zinc powder of 0 to 5%, and an antimony powder of 0 based on the noble metal powder.
~ 5%, indium powder 0-5%, tin powder 0-5%
And 0 to 5% of lead carbonate powder are added to form a clay-like or slurry-like composition for sintering, which is adhered or transferred to the surface of the ceramic molded body and then heated to the sintering temperature. And a method of manufacturing a ceramic product.
１〜４０％と、亜鉛粉末０〜５％と、アンチモン粉末０
〜５％と、インジウム粉末０〜５％と、錫粉末０〜５％
と、炭酸鉛粉末０〜５％とを添加して粘土状若しくは泥
漿状にしたことを特徴とする焼結用組成物。2. An organic binder solution of 1 to 40%, a zinc powder of 0 to 5%, and an antimony powder of 0 with respect to the precious metal powder.
~ 5%, indium powder 0-5%, tin powder 0-5%
And a lead carbonate powder of 0 to 5% to form a clay-like or sludge-like composition for sintering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23725993A JPH0769761A (en) | 1993-06-30 | 1993-08-31 | Production of ceramic product and composition for sintering |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-183515 | 1993-06-30 | ||
| JP18351593 | 1993-06-30 | ||
| JP23725993A JPH0769761A (en) | 1993-06-30 | 1993-08-31 | Production of ceramic product and composition for sintering |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0769761A true JPH0769761A (en) | 1995-03-14 |
Family
ID=26501924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23725993A Pending JPH0769761A (en) | 1993-06-30 | 1993-08-31 | Production of ceramic product and composition for sintering |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0769761A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000327462A (en) * | 1999-05-24 | 2000-11-28 | Aida Kagaku Kogyo Kk | Noble metal sintering composition and production of noble metallic decorative product |
| KR100436748B1 (en) * | 2001-10-29 | 2004-06-22 | 신홍대 | Method of precious metals dissolution plating on the vessel |
| JP2005272151A (en) * | 2004-02-16 | 2005-10-06 | Hiromasa Yoshikawa | Minus ion generation ceramic |
-
1993
- 1993-08-31 JP JP23725993A patent/JPH0769761A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000327462A (en) * | 1999-05-24 | 2000-11-28 | Aida Kagaku Kogyo Kk | Noble metal sintering composition and production of noble metallic decorative product |
| KR100436748B1 (en) * | 2001-10-29 | 2004-06-22 | 신홍대 | Method of precious metals dissolution plating on the vessel |
| JP2005272151A (en) * | 2004-02-16 | 2005-10-06 | Hiromasa Yoshikawa | Minus ion generation ceramic |
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