JPH11242913A - Manufacture of platinum paste - Google Patents
Manufacture of platinum pasteInfo
- Publication number
- JPH11242913A JPH11242913A JP5908798A JP5908798A JPH11242913A JP H11242913 A JPH11242913 A JP H11242913A JP 5908798 A JP5908798 A JP 5908798A JP 5908798 A JP5908798 A JP 5908798A JP H11242913 A JPH11242913 A JP H11242913A
- Authority
- JP
- Japan
- Prior art keywords
- platinum
- paste
- platinum paste
- temperature
- powder
- 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
Landscapes
- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
Description
【産業上の利用分野】開示技術は、セラミックス上への
導電回路，発熱体回路、及び、センサーの集電電極等の
形成、詳細には白金ペーストにより塗布後焼成処理して
白金膜を形成する方法であって、特に、発熱体用白金膜
を形成するための焼き付け用の白金ペーストの製造の技
術分野に属する。BACKGROUND OF THE INVENTION The disclosed technology relates to the formation of a conductive circuit, a heating element circuit, and a current collecting electrode of a sensor on ceramics, and more specifically, a platinum film is formed by applying a platinum paste and then firing. The present invention particularly belongs to the technical field of manufacturing a platinum paste for baking to form a platinum film for a heating element.
【０００２】[0002]
【従来の技術】電子装置部品等に用いる焼き付け用白金
ペーストの一般的な成分構成は、白金粉末と基板との結
合剤を担う金属酸化物やガラス系フリット等の無機酸化
物と有機ビヒクルとからなり、そして、セラミックス等
の絶縁基板や素子等へのスクリーン印刷等の手段でコー
ティング処理した後、コーティング層を焼成することに
より導電膜，発熱体回路、及び、電極等の形成が行われ
ている。2. Description of the Related Art The general component composition of a platinum paste for baking used in electronic device parts and the like is composed of an inorganic oxide such as a metal oxide or a glass frit serving as a binder between a platinum powder and a substrate, and an organic vehicle. After coating by means such as screen printing on an insulating substrate such as ceramics or an element by screen printing or the like, the coating layer is fired to form a conductive film, a heating element circuit, an electrode, and the like. .
【０００３】特に、白金ペーストを該絶縁基板等に対し
印刷，コーティング処理して発熱体回路を形成する電子
部品やセンサー部品等の製造の分野においては、極めて
高い精度や高い耐久性を有する白金膜の発熱体の形成の
要求があった。[0003] Particularly, in the field of manufacturing electronic parts and sensor parts which form a heating element circuit by printing and coating a platinum paste on the insulating substrate or the like, a platinum film having extremely high precision and high durability is provided. There was a demand for the formation of a heating element.
【０００４】このような発熱体を形成する白金ペースト
や印刷，コーティングし、コーティング層を焼成した白
金膜には一般的に次のような特性が要求される。The following properties are generally required for a platinum paste for forming such a heating element and for a platinum film obtained by printing, coating and baking a coating layer.
【０００５】即ち、 スクリーン印刷性が良好で均一な印刷膜等のコーテ
ィング層が得られること。 セラミックス基板と焼成した白金膜との相互の高い
密着性を有し、形成した該白金膜の抵抗値のバラツキが
可及的に少いこと。 発熱体として使用した際に、白金の凝集がなく、均
一な発熱をし、耐久性が優れていること。 等の特性が上げられる。That is, a uniform coating layer such as a printed film having good screen printability can be obtained. It has high adhesion between the ceramic substrate and the fired platinum film, and the resistance value of the formed platinum film is as small as possible. When used as a heating element, there should be no aggregation of platinum, uniform heat generation, and excellent durability. And other characteristics.
【０００６】このような要求される特性の条件に対処す
るに、さまざまな白金ペーストの開発，研究がなされて
きた。Various platinum pastes have been developed and studied in order to cope with such required characteristics.
【０００７】そして、特開平２−２９４４１６号公報で
開示されているように球形状白金粉末を使用した金属酸
化物と有機ビヒクルとを混合し、ロールミルで混練して
白金ペーストを得、かくして得られた白金ペーストはセ
ラミックス基板に対して安定した密着性が得られると共
に均一な印刷やコーティング層が得られ、又、発熱体と
して使用した態様では白金の凝集が極めて少く、安定し
て使用出来る優れた特性を得ることが知見出来た。[0007] Then, as disclosed in JP-A-2-294416, a metal oxide using spherical platinum powder and an organic vehicle are mixed and kneaded by a roll mill to obtain a platinum paste. The platinum paste provides stable adhesion to the ceramic substrate and also provides a uniform printing and coating layer.In addition, when used as a heating element, platinum agglomeration is extremely small, and it can be used stably. It was found that characteristics were obtained.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、近年、
特に、白金ペーストを印刷，コーティングして発熱体回
路を形成する電子部品やセンサー部品の製造分野では、
強く要望されているそれらの部品のますますの小型化や
性能向上、並びに、これに伴うより一層の印刷技術の向
上に伴う更なる精度や高い耐久性を有する白金膜の発熱
体の要求が増大してきた。However, in recent years,
In particular, in the field of manufacturing electronic components and sensor components that form a heating element circuit by printing and coating platinum paste,
There is an increasing demand for platinum film heating elements with higher precision and higher durability with the ever-increasing miniaturization and performance improvement of these parts and the further improvement of printing technology. I've been.
【０００９】かかる要求の高まりに対し、上記の優れた
球形状白金粉末を用いた白金ペーストから形成した白金
膜にあっても、近時安定した抵抗値を得るうえでは充分
でないことが判明してきた。In response to the growing demand, it has been found that even a platinum film formed from a platinum paste using the above-mentioned excellent spherical platinum powder is not enough to obtain a stable resistance value in recent years. .
【００１０】そこで、この出願の発明者らは上述従来の
白金ペーストの問題点を解析した結果、球形状白金粉末
を用いた白金ペーストにおいて、白金ペーストを作製し
た後、該白金ペーストの状態が粘度特性等の物性的特性
では測定出来ない程度に僅かに経時的変化を生じ、スク
リーン印刷，コーティング処理後に焼成処理し、形成さ
れる白金膜の抵抗変化に現れる解決されるべき課題の存
在が新たに見出されるに至った。[0010] The inventors of the present application have analyzed the problems of the above-mentioned conventional platinum paste. As a result, after producing a platinum paste using a platinum paste using spherical platinum powder, the state of the platinum paste was changed to a viscosity. There is a new problem to be solved that appears in the resistance change of the platinum film formed by baking after screen printing and coating processing, resulting in a slight temporal change that cannot be measured with physical properties such as properties. It was found.
【００１１】一方、これに対し球形状でない不定形状の
白金粉末を用いた白金ペーストで形成される白金膜で
は、そもそも、精度が高い印刷，コーティングが難しい
こと等により白金ペーストの経時変化以外の要因による
抵抗値が高く、及び、そのバラツキが大きく、白金ペー
ストの経時変化による、白金膜の抵抗値の変化の存在は
実用上、無視し得る程度の問題であることが分った。On the other hand, in the case of a platinum film formed of a platinum paste using an irregularly shaped platinum powder that is not spherical in shape, it is difficult to perform printing and coating with high accuracy in the first place. It was found that the existence of a change in the resistance value of the platinum film due to the aging of the platinum paste was practically negligible.
【００１２】而して、発明者らは前述した白金ペースト
の経時変化に伴う、印刷形成し、焼成処理した白金膜の
抵抗値の変化が発生する問題を解決すべく、その改善に
技術的に鋭意取り組んできたものである。In order to solve the above-mentioned problem that the resistance value of a platinum film formed by printing and firing is changed with the aging of the above-mentioned platinum paste, technical improvements have been made to solve the problem. We have been working hard.
【００１３】[0013]
【発明の目的】この発明の目的は上述従来技術に基いて
白金ペーストの問題点を解決すべき技術的課題とし、白
金ペーストの経時的変化を小さくし、長期間保管した後
にあっても、セラミックス等に印刷，コーティングし、
焼成処理して形成した白金膜の抵抗値が著しく安定する
ようにしてハイテク産業における金属技術利用分野に益
する優れた白金ペーストの製造方法を提供せんとするも
のである。SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the platinum paste based on the prior art described above. Printing and coating on etc.
It is an object of the present invention to provide an excellent method for producing a platinum paste which has an advantage in a metal technology application field in the high-tech industry by making the resistance value of a platinum film formed by firing treatment extremely stable.
【００１４】[0014]
【課題を解決するための手段】上述目的に沿い先述特許
請求の範囲を要旨とするこの発明の構成は、前述課題を
解決するために、発明者らは長期間保管した白金ペース
トで形成した白金膜の抵抗変化が極めて少く、試し刷り
を行い抵抗調整する繁雑さを解消すべく試作を繰返し検
討を行った結果、球形状白金粉末と無機酸化物と有機ビ
ヒクルとを混練した後、５０℃以上温度で熟成する手段
を講ずることにより達成することが出来るようにする技
術的手段を講じたものである。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention aims at solving the above-mentioned problems by providing a platinum paste formed of a platinum paste stored for a long time. The resistance change of the film is extremely small, and trial printing is performed to eliminate the complexity of adjusting the resistance by trial printing. As a result of examination, the spherical platinum powder, the inorganic oxide, and the organic vehicle are kneaded, and the temperature is 50 ° C or more. Technical measures were taken to enable this to be achieved by taking measures to age at temperature.
【００１５】[0015]
【作用】上記白金ペーストに使用される球形状白金粉末
は、例えば、次述の手段によって製造することが出来る
が、特に、製造方法については限定する訳ではなく種々
の方法によって得られる球形状白金粉末であれば使用す
ることが出来る。The spherical platinum powder used in the platinum paste can be produced, for example, by the following means. However, the production method is not particularly limited, and the spherical platinum powder obtained by various methods can be used. Any powder can be used.
【００１６】即ち、球形状白金粉末の製造に使用可能な
白金化合物は、塩化白金酸Ｈ2 （ＰｔＣｌ6 ）・６Ｈ2
Ｏ、塩化白金酸アンモニウム（ＮＨ4 ）2 （ＰｔＣ
ｌ6 ）、塩化白金酸カリウムＫ2 （ＰｔＣｌ6 ）等で水
溶液の状態でも、水の懸濁した状態でも良いものであ
る。That is, the platinum compound which can be used for producing spherical platinum powder is chloroplatinic acid H 2 (PtCl 6 ) .6H 2
O, ammonium chloroplatinate (NH 4 ) 2 (PtC
l 6 ), potassium chloroplatinate K 2 (PtCl 6 ) or the like may be in the form of an aqueous solution or a suspended state of water.
【００１７】次に、還元剤についてはヒドラジン水和
物，塩酸ヒドラジン，硫酸ヒドラジン等のヒドラジン化
合物を使用することが可能であり、その使用量は反応時
における理論量より過剰な量であれば良い。Next, as the reducing agent, hydrazine compounds such as hydrazine hydrate, hydrazine hydrochloride, and hydrazine sulfate can be used, and the amount of the hydrazine compound may be an excess of the theoretical amount at the time of the reaction. .
【００１８】又、添加剤として用いるアンモニア化合物
については、水酸化アンモニウム，酢酸アンモニウム，
炭酸アンモニウム，硼酸アンモニウム，塩化アンモニウ
ム等が使用出来、アンモニア化合物の添加量はＰｔ１ｍ
ｏｌに対し、ＮＨ3 ５〜１４ｍｏｌであって、この範囲
での添加量を制御することによって、走査型電子顕微鏡
（ＳＥＭ）の撮影写真から採取した白金粉末の平均粒径
を０．２〜３．０μｍの範囲でコントロールして所定粒
径の白金粉末を得ることが出来る。The ammonia compounds used as additives include ammonium hydroxide, ammonium acetate,
Ammonium carbonate, ammonium borate, ammonium chloride, etc. can be used.
The average particle size of the platinum powder collected from a photograph taken by a scanning electron microscope (SEM) is controlled to 0.2 to 3 by controlling the amount of NH 3 to 5 to 14 mol based on the total amount. A platinum powder having a predetermined particle size can be obtained by controlling the particle size within a range of 0.0 μm.
【００１９】又、上述の如くして得られた球形状白金粉
末を酸化雰囲気中，不活性雰囲気中、及び、活性雰囲気
中のいずれかの雰囲気中で球形形状が失われない温度で
熱処理した粉末も使用することが出来るものである。The spherical platinum powder obtained as described above is heat-treated at a temperature at which the spherical shape is not lost in any of an oxidizing atmosphere, an inert atmosphere, and an active atmosphere. Can also be used.
【００２０】ここで、当該球形形状が失われない温度と
しては球形状粉末の平均粒径や処理時間により異なる
が、通常６００℃以下であり、熱処理の好ましい温度範
囲は２００〜５５０℃である。The temperature at which the spherical shape is not lost depends on the average particle size of the spherical powder and the processing time, but is usually 600 ° C. or less, and the preferable temperature range for the heat treatment is 200 to 550 ° C.
【００２１】無機酸化物はセラミックス基板への白金膜
の密着性の付与や白金膜の抵抗調整剤、及び、発熱体使
用時の白金の凝集等を抑制するために、Ａｌ2 Ｏ3 ，Ｚ
ｒＯ2 ，Ｙ2 Ｏ3 ，Ｖ2 Ｏ5 ，ＳｉＯ2 ，ＭｇＯの１種
以上を使用することが好ましい。The inorganic oxide is made of Al 2 O 3 , Z in order to impart adhesion of the platinum film to the ceramic substrate, to control the resistance of the platinum film, and to suppress the aggregation of platinum when the heating element is used.
It is preferable to use at least one of rO 2 , Y 2 O 3 , V 2 O 5 , SiO 2 and MgO.
【００２２】又、その他Ｂｉ2 Ｏ3 ，ＣｕＯ，ＺｎＯ，
ＣａＯ，ＢａＯ，ＴｉＯ2 ，Ｃｒ2Ｏ3 等も選択出来、
これらの無機酸化物は基板成分や焼成処理温度や使用条
件等によって適宜に成分を選定することが出来る。In addition, Bi 2 O 3 , CuO, ZnO,
CaO, BaO, also TiO 2, Cr 2 O 3 or the like can be selected,
The components of these inorganic oxides can be appropriately selected depending on the components of the substrate, the sintering temperature, the conditions of use, and the like.
【００２３】又、有機ビヒクルは、エチルセルロース，
アルキッド，ポリビニルブチラール，アクリル樹脂等を
ターピネオール，ブチルカルビトール，ブチルカルビト
ールアセテート，セルソルブ等の高沸点溶剤に溶解した
ものが使用可能である。The organic vehicle is ethyl cellulose,
A solution in which alkyd, polyvinyl butyral, an acrylic resin or the like is dissolved in a high boiling point solvent such as terpineol, butyl carbitol, butyl carbitol acetate, cellosolve, or the like can be used.
【００２４】而して、この発明の白金ペーストの製造は
従来周知の製造方法と同様の方法によるものであって、
所謂ロールミルによって得ることが出来る。又、該白金
ペーストの組成は白金粉末の粒径及び量、無機酸化物の
種類及び量、有機ビヒクルの組成及び量並びに焼成条
件、製品の用途等により変化するが、一般に球形状白金
粉末７０〜８５ｗｔ％、無機酸化物５〜１５ｗｔ％、有
機ビヒクル１０〜１５ｗｔ％の範囲の成分組成が適当で
ある。Thus, the production of the platinum paste of the present invention is based on the same method as the conventionally known production method.
It can be obtained by a so-called roll mill. The composition of the platinum paste varies depending on the particle size and amount of the platinum powder, the type and amount of the inorganic oxide, the composition and amount of the organic vehicle, the firing conditions, the use of the product, and the like. A component composition in the range of 85% by weight, 5 to 15% by weight of an inorganic oxide, and 10 to 15% by weight of an organic vehicle is appropriate.
【００２５】[0025]
【発明の背景】上述の如くして作製した白金ペースト
は、大気中５０℃以上の温度で熟成され、ここで、熟成
する温度を５０℃以上と限定した理由は５０℃未満の温
度では熟成に要する時間が長くなって不経済であり、
又、熟成する温度の上限は規定するわけではないが、有
機ビヒクルを構成する樹脂の軟化点以下で行うのが適当
であり、例えば、エチルセルロース（ダウ・ケミカル社
製「エトセル」）を有機ビヒクルの樹脂成分とした場合
は軟化点である１３５℃より低い温度で行うのが適当で
あり、好ましくは、操作性等により６０〜９０℃の温度
範囲である。BACKGROUND OF THE INVENTION The platinum paste prepared as described above is aged at a temperature of 50 ° C. or higher in the atmosphere. The reason for limiting the aging temperature to 50 ° C. or higher is that the temperature is lower than 50 ° C. The time required is long and uneconomical,
Although the upper limit of the aging temperature is not specified, it is appropriate to perform the reaction at a temperature lower than the softening point of the resin constituting the organic vehicle. For example, ethyl cellulose ("Ethocel" manufactured by Dow Chemical Company) may be used as the organic vehicle. In the case of using a resin component, it is appropriate to carry out at a temperature lower than the softening point of 135 ° C, and preferably in a temperature range of 60 to 90 ° C due to operability and the like.
【００２６】そして、熟成する時間は被熟成白金ペース
トの量や熟成温度により異なりはするものの、０．５〜
２４時間行うことが出来、この時、該白金ペースト中の
溶剤が揮発する場合は溶剤を補充後、混練することによ
っても目的とする白金ペーストを得ることが出来、又、
密栓出来る容器を使用することにより、前述操作が不要
となり、更に、加圧下で実施することにより熟成時間の
短縮、及び、溶剤の揮発が抑制されより好ましい態様と
することが可能である。The aging time varies depending on the amount of the aging platinum paste and the aging temperature, but is 0.5 to
It can be performed for 24 hours, at this time, if the solvent in the platinum paste volatilizes, after replenishing the solvent, it is also possible to obtain the target platinum paste by kneading,
By using a container that can be sealed, the above-mentioned operation becomes unnecessary, and furthermore, by carrying out under pressure, the aging time can be shortened, and the volatilization of the solvent can be suppressed.
【００２７】前述によって、作製された白金ペーストは
長期の保管中にあっても、印刷され形成された白金膜は
その抵抗変化が非常に少く発熱体形成用として優れた特
性を有するものである。As described above, even when the produced platinum paste is stored for a long period of time, the printed and formed platinum film has a very small change in resistance and has excellent characteristics for forming a heating element.
【００２８】[0028]
【発明の実施の形態】次に、この発明の実施しようとす
る形態を実施例の態様として比較例と共に図面（写真）
を参照して説明すれば以下の通りである。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, an embodiment of the present invention will be described with reference to a drawing (photograph) together with a comparative example as an embodiment.
This will be described below with reference to FIG.
【００２９】［実施例−１，比較例−１］白金２００ｇ
を含む塩化白金酸水溶液１０００ｍｌを８０℃に加熱
し、予め調製し８０℃に保持した８０％ヒドラジン水和
物１００ｍｌとＮＨ3 として１４０ｇを含む酢酸アンモ
ニウム水溶液１６００ｍｌを徐々に加え反応させ、洗
浄，濾過，乾燥処理を行い、平均粒径１μｍの球形状白
金粉末を得た。[Example-1, Comparative Example-1] 200 g of platinum
Is heated to 80 ° C., and 100 ml of 80% hydrazine hydrate prepared in advance and kept at 80 ° C. and 1600 ml of an ammonium acetate aqueous solution containing 140 g as NH 3 are gradually added to cause a reaction, followed by washing and filtration. And a drying treatment to obtain a spherical platinum powder having an average particle diameter of 1 μm.
【００３０】次に、該球形状白金粉末を８０ｗｔ％とＡ
ｌ2 Ｏ3 粉末８ｗｔ％と有機ビヒクル（６ｗｔ％のエチ
ルセルロースと残部がブチルカルビトールとからなる）
を１２ｗｔ％との成分組成とからなるように計量し、一
次混練後にて仕上混練を行い白金ペースト５０ｇを得
た。Next, 80 wt% of the spherical platinum powder was added to A
8 wt% of l 2 O 3 powder and an organic vehicle (consisting of 6 wt% of ethylcellulose and the balance being butyl carbitol)
Was weighed so as to have a component composition of 12 wt%, and after primary kneading, finish kneading was performed to obtain 50 g of a platinum paste.
【００３１】次に、該白金ペーストを密閉出来る容器に
２５ｇずつ２分割し、一方の容器の白金ペーストを８０
℃の恒温槽中で２時間保持し、熟成処理を行って実施例
−１を試作した。又、他方の容器の白金ペーストを比較
例−１とした。Next, the platinum paste was divided into two pieces each of 25 g each in a sealable container.
The sample was kept in a constant temperature bath at a temperature of 2 ° C. for 2 hours, subjected to an aging treatment, and a prototype of Example 1 was produced. The platinum paste in the other container was used as Comparative Example-1.
【００３２】［実施例−２］上述実施例−１で作製した
平均粒径１μｍの球形状白金粉末を大気中雰囲気で４０
０℃で１６時間熱処理を行い、熱処理球形状白金粉末を
使用して上述実施例−１と同成分組成、及び、製造方法
にて白金ペースト５０ｇを得た。[Embodiment 2] The spherical platinum powder having an average particle diameter of 1 μm produced in the above-mentioned embodiment 1 was subjected to a 40-watt air atmosphere.
Heat treatment was performed at 0 ° C. for 16 hours, and 50 g of a platinum paste was obtained using the heat-treated spherical platinum powder by the same composition and the same production method as in Example 1 described above.
【００３３】次に、該白金ペーストを上述実施例−１と
同様、密閉可能な容器に入れ、９０℃の恒温槽中で１時
間保持し、熟成処理を行って実施例−２を試作した。Next, the platinum paste was placed in a sealable container in the same manner as in Example 1 described above, kept in a thermostat at 90 ° C. for 1 hour, and subjected to aging treatment, thereby producing a prototype of Example-2.
【００３４】［実施例−３，比較例−２］実施例−１で
作製した平均粒径１μｍの球形状白金粉末を水素雰囲気
中で２００℃で４時間熱処理を行い、熱処理球形状白金
粉末を使用して前述実施例−１と同成分組成、及び、製
造方法にて白金ペースト５０ｇを得た。次に、該白金ペ
ーストを前述実施例−１と同様、密閉可能な容器に２５
ｇずつ２分割し、一方の容器の白金ペーストを８０℃の
恒温槽中で２時間保持し熟成を行い、実施例−３を試作
した。又、他方の容器の白金ペーストを比較例−２とし
た。Example 3 and Comparative Example 2 The spherical platinum powder having an average particle diameter of 1 μm prepared in Example 1 was heat-treated at 200 ° C. for 4 hours in a hydrogen atmosphere to obtain a heat-treated spherical platinum powder. Using this, 50 g of a platinum paste was obtained by the same composition and the same manufacturing method as in Example 1 described above. Next, the platinum paste was placed in a sealable container in the same manner as in Example 1 described above.
g was divided into two portions, and the platinum paste in one container was kept in a constant temperature bath at 80 ° C. for 2 hours to ripen, thereby preparing a prototype of Example-3. The platinum paste in the other container was used as Comparative Example-2.
【００３５】［実施例−４，比較例−３］白金１００ｇ
を含む塩化白金酸水溶液５００ｍｌを８０℃に加熱し、
予め調製し８０℃に保持した８０％ヒドラジン水和物５
０ｍｌとＮＨ3 として１１０ｇを含む酢酸アンモニウム
水溶液８００ｍｌを除除に加え反応させ、洗浄，濾過，
乾燥を行い、平均粒径０．５μｍの球形状白金粉末を
得、該球形状白金粉末を使用して前述実施例−１と同成
分組成、及び、製造方法にて白金ペースト５０ｇ得、次
に、該白金ペーストを前述実施例−１と同様、密閉出来
る容器に２５ｇずつ分割し、一方の容器の白金ペースト
を７０℃の恒温槽中で５時間保持し、熟成処理を行った
実施例−４を試作した。又、他方の容器の白金ペースト
を４０℃の恒温槽中で２８時間保持し、熟成処理を行
い、比較例−３を試作した。Example-4, Comparative Example-3 100 g of platinum
500 ml of chloroplatinic acid aqueous solution containing
80% hydrazine hydrate 5 previously prepared and maintained at 80 ° C.
0 ml and 800 ml of an aqueous ammonium acetate solution containing 110 g of NH 3 were added and removed, followed by reaction, washing, filtration,
Drying was performed to obtain a spherical platinum powder having an average particle diameter of 0.5 μm. Using the spherical platinum powder, 50 g of a platinum paste was obtained by the same component composition as in Example 1 described above, and the production method. In the same manner as in Example 1 above, 25 g of the platinum paste was divided into hermetically sealable containers, and the platinum paste in one container was kept in a constant temperature bath at 70 ° C. for 5 hours to perform aging treatment. Was prototyped. Further, the platinum paste in the other container was kept in a constant temperature bath at 40 ° C. for 28 hours, subjected to aging treatment, and a prototype of Comparative Example-3 was produced.
【００３６】［比較例−４］白金１００ｇを含む塩化白
金酸アンモニウムに純水４００ｍｌに懸濁させ７０℃に
加熱し、予め調製しておいた水酸化ナトリウム５０ｇと
８０％ヒドラジン水和物１００ｍｌと純水４００ｍｌと
から溶液を徐々に加え反応させ、洗浄，濾過，乾燥を行
って不定形の白金粉末を得た。[Comparative Example 4] Suspended in 400 ml of pure water in ammonium chloroplatinate containing 100 g of platinum and heated to 70 ° C., 50 g of sodium hydroxide prepared in advance and 100 ml of 80% hydrazine hydrate were added. A solution was gradually added from 400 ml of pure water to cause a reaction, followed by washing, filtration and drying to obtain an amorphous platinum powder.
【００３７】該不定形形状白金粉末を使用して前述実施
例−１と同成分組成、及び、製造方法にて白金ペースト
５０ｇを得、次に、該白金ペーストを前述実施例−１と
同様、密閉出来る容器に２５ｇずつ２分割し、一方の容
器の白金ペーストを８０℃の恒温槽中で２時間保持し、
熟成処理を行って比較例４−１を試作した。又、他方の
容器の白金ペーストを比較例４−２とした。Using the irregular-shaped platinum powder, 50 g of a platinum paste was obtained by the same composition and the same manufacturing method as in Example 1 described above, and then the platinum paste was used in the same manner as in Example 1 described above. Divide 25g into two into a sealable container, hold the platinum paste in one container in a constant temperature bath at 80 ° C for 2 hours,
An aging treatment was performed to produce a prototype of Comparative Example 4-1. The platinum paste in the other container was used as Comparative Example 4-2.
【００３８】以上各実施例及び比較例について、白金ペ
ーストの製造直後と２０日間保管した後の白金ペースト
をアルミナ基板にスクリーン印刷し、コーティング処理
した後、１００℃で２０分間乾燥後、１５００℃で１０
分間保持するプロファイルにて焼成処理して白金膜を形
成した。In each of the above Examples and Comparative Examples, the platinum paste immediately after the production of the platinum paste and after storage for 20 days were screen-printed on an alumina substrate, coated, dried at 100 ° C. for 20 minutes, and then dried at 1500 ° C. 10
A platinum film was formed by performing a baking treatment with a profile held for a minute.
【００３９】得られた該白金膜について、デジタルマル
チメータ（アドバンテスト社製）を用いて抵抗値を求
め、経時的な抵抗変化率を求め、その結果、次の表１の
通りであり、又、表面粗さ計により焼成処理した白金膜
表面の平滑性を評価した。その結果は同じく該表１に示
す。With respect to the obtained platinum film, a resistance value was obtained by using a digital multimeter (manufactured by Advantest), and a rate of change in resistance with time was obtained. As a result, the results are as shown in Table 1 below. The smoothness of the surface of the baked platinum film was evaluated by a surface roughness meter. The results are also shown in Table 1.
【００４０】尚、該表１の抵抗変化率は次の数１により
算出した変化率の絶対値とした。The resistance change rate in Table 1 was the absolute value of the change rate calculated by the following equation (1).
【００４１】[0041]
【表１】 [Table 1]
【００４２】[0042]
【数１】 Ａ：製造直後の白金ペーストにて印刷後焼成処理した白
金膜の平均抵抗値 Ｂ：２０日間の保管した後の白金ペーストにて印刷後焼
成処理した白金膜の平均抵抗値(Equation 1) A: Average resistance value of platinum film printed and fired with platinum paste immediately after production B: Average resistance value of platinum film printed and fired with platinum paste after storage for 20 days
【００４３】而して、表１から明らかな如く、製造した
白金ペーストを５０℃以上の温度で熟成処理することに
より長期間保管後の白金ペーストを使用し、焼成処理し
て形成した白金膜の抵抗の変化が少く、優れた性能を有
していることが判る。As apparent from Table 1, the produced platinum paste is aged at a temperature of 50 ° C. or more, so that the platinum paste that has been stored for a long period of time is used, and the platinum paste formed by firing is used. It can be seen that there is little change in resistance, and that it has excellent performance.
【００４４】特に、球形状白金粉末を大気雰囲気中で４
００℃、１６時間処理し、更に、ペースト製造後、熟成
処理した実施例−２は特に性能的に優れていることが判
る。In particular, a spherical platinum powder was prepared in an air atmosphere.
It can be seen that Example-2, which was treated at 00 ° C. for 16 hours and further aged after the paste was produced, was particularly excellent in performance.
【００４５】又、比較例４の不定形形状白金粉末を使用
した白金ペーストでは抵抗値が高く、又、バラツキが大
きく、抵抗変化率の検討が出来ず、そして、白金ペース
トの熟成効果については解析も出来なかった。Further, the platinum paste using the irregularly shaped platinum powder of Comparative Example 4 has a high resistance value, a large variation, the resistance change rate cannot be examined, and the aging effect of the platinum paste is analyzed. I couldn't do it either.
【００４６】そこで、実施例−１と比較例４−１の白金
膜の走査型電子顕微鏡（ＳＥＭ）により焼成した白金膜
を図１，図２（写真）として示す。The platinum films of Example 1 and Comparative Example 4-1 which were fired by a scanning electron microscope (SEM) are shown in FIGS. 1 and 2 (photographs).
【００４７】該図１，図２のＳＥＭ写真により、球形状
白金粉末を使用した実施例−１の白金膜は均一であるの
に対し、不定形状白金粉末を使用した比較例４−１の白
金膜では白金粉末が一部凝集し、又、空孔が見られポー
ラスな膜を形成しており、不定形状白金粉末を使用した
白金ペーストは発熱体用としては不適であることが判
る。According to the SEM photographs of FIGS. 1 and 2, the platinum film of Example-1 using the spherical platinum powder was uniform, while the platinum film of Comparative Example 4-1 using the irregularly shaped platinum powder was uniform. In the film, the platinum powder partially aggregates, and pores are formed to form a porous film. It is understood that the platinum paste using the irregularly shaped platinum powder is not suitable for a heating element.
【００４８】[0048]
【発明の効果】以上、この発明によれば、発熱体を形成
する白金ペーストの製造方法において、球形状白金粉末
と無機酸化物と有機ビヒクルとを混練した後、５０℃以
上の温度で熟成処理することにより、熟成に要する時間
が長くかからず、経済的であるメリットがあり、そのう
え、熟成する時間は被熟成白金ペーストの量や熟成温度
により異なりはするものの、０．５〜２４時間行うこと
が出来、この時、該白金ペースト中の溶剤が揮発する場
合は溶剤を補充後、混練することによっても目的とする
白金ペーストを得ることが出来、又、密栓出来る容器を
使用することにより、前述操作が不要となり、更に、加
圧下で実施することにより熟成時間の短縮、及び、溶剤
の揮発が抑制されより好ましい態様とすることが可能で
あるという効果もある。As described above, according to the present invention, in a method for producing a platinum paste for forming a heating element, a spherical platinum powder, an inorganic oxide and an organic vehicle are kneaded and then aged at a temperature of 50 ° C. or more. By doing so, there is an economical advantage that the time required for ripening is not long, and the aging time is 0.5 to 24 hours, although it depends on the amount of ripened platinum paste and the aging temperature. At this time, if the solvent in the platinum paste volatilizes, after replenishing the solvent, the target platinum paste can be obtained by kneading, and by using a container that can be sealed, The above-mentioned operation becomes unnecessary, and furthermore, the effect of shortening the ripening time by carrying out under pressure, and suppressing the volatilization of the solvent can be a more preferable embodiment. That.
【００４９】そして、得られた白金ペーストの経時的変
化に伴う抵抗値の経時変化を小さくさせ、これによって
長期間保管した後においても、セラミックス等に印刷等
の手段でコーティングし、焼成処理して形成した白金膜
の抵抗値が著しく安定する優れた効果が奏される。The change in resistance of the obtained platinum paste with the passage of time is reduced so that even after storage for a long period of time, ceramics or the like can be coated by printing or the like and fired. An excellent effect of remarkably stabilizing the resistance value of the formed platinum film is exhibited.
【図１】実施例１の白金膜の走査型電子顕微鏡（ＳＥ
Ｍ）の組成拡大写真である。FIG. 1 shows a scanning electron microscope (SE) of a platinum film of Example 1.
It is a composition enlarged photograph of M).
【図２】比較例４−１の白金膜の走査型電子顕微鏡（Ｓ
ＥＭ）の組成拡大写真である。FIG. 2 shows a scanning electron microscope (S) of a platinum film of Comparative Example 4-1.
2 is an enlarged photograph of the composition of (EM).
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐々木 幸記 埼玉県草加市青柳２丁目12番30号 石福金 属興業株式会社草加第一工場内 (72)発明者 朝木 知美 埼玉県草加市青柳２丁目12番30号 石福金 属興業株式会社草加第一工場内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koki Sasaki 2-12-30 Aoyagi, Soka City, Saitama Prefecture Ishifuku Kinzoku Kogyo Co., Ltd. Soka 1st Plant (72) Inventor Tomomi Asagi 2-chome Aoyagi, Soka City, Saitama Prefecture 12-30 Ishifuku Kinzoku Kogyo Co., Ltd.
Claims (1)
ルとを混練した後、５０℃以上の温度で熟成処理するよ
うにすることを特徴とする白金ペーストの製造方法。 【０００１】1. A method for producing a platinum paste, comprising kneading a spherical platinum powder, an inorganic oxide, and an organic vehicle, followed by aging at a temperature of 50 ° C. or higher. [0001]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05908798A JP4097237B2 (en) | 1998-02-25 | 1998-02-25 | Method for producing platinum paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05908798A JP4097237B2 (en) | 1998-02-25 | 1998-02-25 | Method for producing platinum paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11242913A true JPH11242913A (en) | 1999-09-07 |
| JP4097237B2 JP4097237B2 (en) | 2008-06-11 |
Family
ID=13103220
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05908798A Expired - Fee Related JP4097237B2 (en) | 1998-02-25 | 1998-02-25 | Method for producing platinum paste |
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| Country | Link |
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| JP (1) | JP4097237B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7615939B2 (en) | 2003-03-17 | 2009-11-10 | C&D Zodiac, Inc. | Spectrally calibratable multi-element RGB LED light source |
| JP2011228308A (en) * | 2005-07-06 | 2011-11-10 | Suntech Co Ltd | Method of manufacturing planar heating element, and planar heating element manufactured by the same |
| US20150004359A1 (en) * | 2013-06-27 | 2015-01-01 | Heraeus Precious Metals North America Conshohocken LLP | Platinum containing conductive paste |
| JP2016012697A (en) * | 2014-06-30 | 2016-01-21 | 日本特殊陶業株式会社 | Thermistor element and temperature sensor |
| KR20210073555A (en) * | 2018-11-21 | 2021-06-18 | 헤라우스 넥센소스 게엠베하 | Improved precious metal paste for screen-printed electrode structures |
| CN114038607A (en) * | 2021-09-29 | 2022-02-11 | 航天特种材料及工艺技术研究所 | Platinum slurry for ceramic substrate FSS structure and preparation method thereof |
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1998
- 1998-02-25 JP JP05908798A patent/JP4097237B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7615939B2 (en) | 2003-03-17 | 2009-11-10 | C&D Zodiac, Inc. | Spectrally calibratable multi-element RGB LED light source |
| JP2011228308A (en) * | 2005-07-06 | 2011-11-10 | Suntech Co Ltd | Method of manufacturing planar heating element, and planar heating element manufactured by the same |
| US20150004359A1 (en) * | 2013-06-27 | 2015-01-01 | Heraeus Precious Metals North America Conshohocken LLP | Platinum containing conductive paste |
| US9892816B2 (en) * | 2013-06-27 | 2018-02-13 | Heraeus Precious Metals North America Conshohocken Llc | Platinum containing conductive paste |
| JP2016012697A (en) * | 2014-06-30 | 2016-01-21 | 日本特殊陶業株式会社 | Thermistor element and temperature sensor |
| KR20210073555A (en) * | 2018-11-21 | 2021-06-18 | 헤라우스 넥센소스 게엠베하 | Improved precious metal paste for screen-printed electrode structures |
| JP2022509142A (en) * | 2018-11-21 | 2022-01-20 | ヘレウス ネクセンソス ゲゼルシャフト ミット ベシュレンクテル ハフツング | Improved precious metal paste for screen-printed electrode structures |
| US11621100B2 (en) | 2018-11-21 | 2023-04-04 | Heraeus Nexensos Gmbh | Noble-metal pastes for screen-printed electrode structures |
| CN114038607A (en) * | 2021-09-29 | 2022-02-11 | 航天特种材料及工艺技术研究所 | Platinum slurry for ceramic substrate FSS structure and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP4097237B2 (en) | 2008-06-11 |
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