JPS63304592A - Thick film resistance composition and planar heater manufactured by this composition - Google Patents
Thick film resistance composition and planar heater manufactured by this compositionInfo
- Publication number
- JPS63304592A JPS63304592A JP62069082A JP6908287A JPS63304592A JP S63304592 A JPS63304592 A JP S63304592A JP 62069082 A JP62069082 A JP 62069082A JP 6908287 A JP6908287 A JP 6908287A JP S63304592 A JPS63304592 A JP S63304592A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- thick film
- weight
- nickel
- heating element
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 7
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 7
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 7
- 238000010304 firing Methods 0.000 claims abstract description 7
- 239000011812 mixed powder Substances 0.000 claims abstract description 5
- KIRWCRPCYCPJPE-UHFFFAOYSA-N aluminum barium(2+) borate Chemical compound B([O-])([O-])[O-].[Al+3].[Ba+2] KIRWCRPCYCPJPE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 28
- 150000002148 esters Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005385 borate glass Substances 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010665 pine oil Substances 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims 2
- 239000004584 polyacrylic acid Substances 0.000 claims 2
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001120 nichrome Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical compound [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000953 kanthal Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Landscapes
- Surface Heating Bodies (AREA)
- Non-Adjustable Resistors (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、ガラス或いはセラミックスなどの基板上に
抵抗体を印刷・焼成して構成してなる面発熱体に好適な
厚膜抵抗組成物及びこの厚膜抵抗組成物により製造され
る面発熱体に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a thick film resistor composition suitable for a surface heating element formed by printing and firing a resistor on a substrate such as glass or ceramics. The present invention relates to a surface heating element manufactured using this thick film resistor composition.
（従来技術）
従来から暖房器などの発熱体として、ニクロム材料を線
状又は帯状に形成したものか多用されており、また特殊
な高温又は耐久性が要求される場合には、カンタルが熱
源材料として用いられているのは周知のとおりである。(Prior art) Nichrome materials formed into linear or strip shapes have traditionally been widely used as heating elements in space heaters, etc., and when special high temperatures or durability are required, Kanthal is used as a heat source material. As is well known, it is used as
しかしながら、上記従来のニクロム材料を熱源としたも
のにあっては、
（１）抵抗値温度変数が高いため、比較的中温度領域の
５００°Ｃ程度を熱源とするものが得にくいこと、
（２）ニクロム材料を熱源とした場合、この熱源から発
せられる輻射熱の波長は、はとんどか１ミクロン以下で
あり、人間が快く暖かいと感する波長か５〜６ミクロン
程度であることから比較して、ニクロム材料の波長はか
なりの短波長であり、実際には暖かさの中に痛さを感じ
、不快感を与えてしまうこと、（３）シーｌ−抵抗値が
高いため、任意形状の熱源か得られないこと、
なとの問題を有していた。However, for those using the conventional nichrome material as a heat source, (1) the resistance value temperature variable is high, so it is difficult to obtain a heat source that uses a relatively medium temperature range of about 500°C; (2) ) When a nichrome material is used as a heat source, the wavelength of the radiant heat emitted from this heat source is mostly 1 micron or less, which is the wavelength that humans feel pleasantly warm, about 5 to 6 microns. (3) Since the wavelength of nichrome material is quite short, you will actually feel pain in the warmth and feel uncomfortable. (3) Due to the high seal resistance value, it can be used as a heat source of any shape. I had the problem of not being able to get it.
このため、近年では、ガラス或いはセラミックスなどの
基板上に抵抗体を印刷・焼成して構成されてなる面発熱
体か公知である。For this reason, in recent years, surface heating elements have been known that are constructed by printing and firing a resistor on a substrate such as glass or ceramics.
この面発熱体は、中湿度領域の熱源が容易に得られると
共に、人間が快く感じる輻射熱波長が得られ、しかも印
刷技術で任意形状の熱源を構成することかできる、とい
う優れた利点を有している。This surface heating element has the excellent advantages of being able to easily obtain a heat source in the medium humidity range, providing a radiant heat wavelength that is pleasant to humans, and being able to construct a heat source of any shape using printing technology. ing.
（従来技術の問題点）
しかしながら、上記従来の面発熱体にあっては、基板上
に抵抗体或は導体を形成するための厚膜抵抗組成物中の
導電成分を、銀、銀−白金混合体、銀−パラジウム混合
体、金、銅、酸化ルテニウムまたは酸化モリブデン等の
金属或は金属酸化物で形成しているため、抵抗体或は導
体としての抵抗温度係数の絶対値が高くて熱的に不安定
であり、しかも、比較的高価な金属を使用するためコス
ト高となるという問題を有していた。(Problems with the prior art) However, in the conventional surface heating element described above, the conductive component in the thick film resistor composition for forming the resistor or conductor on the substrate is silver or a silver-platinum mixture. Because it is made of metals or metal oxides such as silver-palladium mixture, gold, copper, ruthenium oxide, or molybdenum oxide, it has a high absolute value of the temperature coefficient of resistance as a resistor or conductor, and has a high thermal resistance. However, since the metal is unstable and relatively expensive metal is used, the cost is high.
特に、上記従来の面発熱体にあっては、１００ｍΩ／口
程度の非常に低い抵抗値を持つ抵抗体に、上記従来の厚
膜抵抗組成物を使用して面発熱体を形成した場合には、
金属成分の使用割合が高くなり、その抵抗温度係数の絶
対値か高くて熱的に非常に不安定となり易いという問題
を有していた。In particular, in the case of the above-mentioned conventional surface heating element, when the above-mentioned conventional thick film resistor composition is used to form a surface heating element on a resistor having a very low resistance value of about 100 mΩ/hole. ,
The problem is that the proportion of metal components used is high, and the absolute value of the temperature coefficient of resistance is high, making it likely to become very thermally unstable.
この発明は、かかる現状に鑑み創案されたものてあって
、その目的とするところは、第１に、抵抗温度係数の絶
対値か低くて熱的安定性に優れ、かつ、低価格な厚膜抵
抗組成物を提供し、第２に、−上記厚膜抵抗組成物を基
板上に印刷して焼成することて、中湿度領域の熱源か容
易に得られると共に、人間か快く感じる輻射熱波長が得
られ、しかも、印刷技術により任意形状の熱源を構成す
ることかてきる面発熱体を廉価に提供し、第３には、以
上のようにして得られた面発熱体表面に形成される抵抗
体或は導体を、有効に絶縁し、かつ、有効に酸化するの
を防止することができる面発熱体（グレーズヒータ）を
提供しようとするものである。The present invention was devised in view of the current situation, and the first object is to provide a thick film with a low absolute value of the temperature coefficient of resistance, excellent thermal stability, and low cost. Second, by printing the thick film resistor composition on a substrate and firing it, a heat source in a medium humidity range can be easily obtained, and a radiant heat wavelength that is pleasant to humans can be obtained. The present invention provides at low cost a surface heating element which can be formed into a heat source of any shape by printing technology, and thirdly, a resistor formed on the surface of the surface heating element obtained as described above. Another object of the present invention is to provide a surface heating element (glaze heater) that can effectively insulate a conductor and effectively prevent it from oxidizing.
〔問題点を解決するための手段及び作用〕上記目的を達
成するため、この発明に係る厚膜抵抗組成物の組成比率
を、銅とニッケルとの混合粉末からなる導電性成分を３
０〜８５重量％とし、これに対し、ガラスフリットを１
０〜６５重量％とすると共に、有機溶媒を５〜４０重量
％となして構成したことを特徴とするものである。[Means and effects for solving the problem] In order to achieve the above object, the composition ratio of the thick film resistor composition according to the present invention is changed to 3% of the conductive component consisting of a mixed powder of copper and nickel.
0 to 85% by weight, whereas glass frit is 1% by weight.
It is characterized by having an organic solvent content of 0 to 65% by weight and an organic solvent content of 5 to 40% by weight.
また、この発明に係る面発熱体は、上記組成比率からな
る厚膜抵抗組成物を、ガラス或いはセラミックスなどの
基板上に印刷・焼成して抵抗体または導体を構成したこ
とを特徴とするものである。Furthermore, the surface heating element according to the present invention is characterized in that a resistor or conductor is formed by printing and firing a thick film resistor composition having the above-mentioned composition ratio on a substrate such as glass or ceramics. be.
厚膜抵抗組成物の導電性成分である銅
（Ｃｕ）とニッケル（Ｎｉ）の混合比は、重量％て銅３
０〜８０％に対しニッケルが７０〜２０％の範囲て混合
するのが好ましい。この銅とニッケルの組成比を変える
ことにより、抵抗体の抵抗温度係数及び抵抗値を調整す
ることかてきる。The mixing ratio of copper (Cu) and nickel (Ni), which are conductive components of the thick film resistor composition, is 3% by weight of copper.
It is preferable to mix nickel in a range of 70 to 20% with respect to 0 to 80%. By changing the composition ratio of copper and nickel, the temperature coefficient of resistance and resistance value of the resistor can be adjusted.
このようにして混合された導電性成分（微粉末）を、真
空中または不活性ガス中にて１０００〜１４００℃（こ
の温度は、導電性粉末を構成する組成比により多少異る
。）に加熱し合金化する。The conductive component (fine powder) mixed in this way is heated to 1000 to 1400°C (this temperature varies depending on the composition ratio of the conductive powder) in vacuum or inert gas. and alloyed.
このようにして得られた混合物を、粉砕機又は分級機に
より微粉砕し、抵抗体ペースト用の微粉末を作成する。The mixture thus obtained is pulverized using a pulverizer or classifier to create a fine powder for resistor paste.
抵抗体ペーストを基板上に印刷し、焼成した場合、基板
の熱膨張と異るとグレーズ層に剥離か生じるので、グレ
ーズ層と基板の各熱膨張を合わせておく必要がある。こ
の役目をするのか抵抗体ペースト中のガラスフリットで
ある。When a resistor paste is printed on a substrate and fired, the glaze layer may peel if the thermal expansion differs from that of the substrate, so it is necessary to match the thermal expansion of the glaze layer and the substrate. The glass frit in the resistor paste plays this role.
この発明では、このガラスフリットの組成は２つの組成
からなるものが考えられる。In the present invention, the glass frit may have two compositions.
その第１のガラスフリットは、バリウム−アルミニュウ
ム硼酸塩ガラスであり、第２のガラスフリットとしては
、バリウム−カルシウム硼珪酸ガラスである。The first glass frit is a barium-aluminum borate glass and the second glass frit is a barium-calcium borosilicate glass.
これらの各ガラスフリットは、特に、米国特許＠４，２
５６，７９６号公報所載のボースリン被覆金属基板やア
ルミナ製の基板と適合するが、基板の材質や作成される
面発熱体の用途によって、そのどちらかが選択される。Each of these glass frits is specifically described in US Pat.
Although it is compatible with the Bausselin-coated metal substrate and the alumina substrate described in Japanese Patent No. 56,796, one of them is selected depending on the material of the substrate and the purpose of the surface heating element to be produced.
このような組成からなるガラスフリットは、上記組成か
らなるガラスを、粉砕機又は分級機て１〜３ＪＬｍサイ
ズの粉末に粉砕する。Glass frit having such a composition is obtained by pulverizing glass having the above composition into powder having a size of 1 to 3 JLm using a crusher or a classifier.
このようにして得られたガラス粉末を、前記導電性成分
（微粉末）と一定の割合で混合し、これに有機溶媒を加
えて所謂インク状に作成する。The glass powder thus obtained is mixed with the conductive component (fine powder) at a constant ratio, and an organic solvent is added thereto to form a so-called ink.
この有機溶媒としては、例えば、セルローズ誘電体のエ
チルセルロース、ポリアクリル酸エステル、ポリオレフ
ィン、ポリエステルまたはメタクリレートの合成樹脂材
とエステルアルコールとを、
０．５ 〜１．５ ： ９．５〜８．５（重量比）
の比率て混合したもの、その他の類似する結合剤を適用
することができる。As this organic solvent, for example, a synthetic resin material such as cellulose dielectric ethyl cellulose, polyacrylic ester, polyolefin, polyester or methacrylate and ester alcohol are used in a ratio of 0.5 to 1.5: 9.5 to 8.5 ( weight ratio)
Other similar binders can be applied.
また、必要かある場合には、上記有機溶媒に、適宜の粘
度調整剤を添加することもできる。この粘度調整剤とし
ては、パイン油、テルピネオール、ブチルカルビトール
アセテートまたはエステルアルコール系のものを適用す
ることかできる。Furthermore, if necessary, an appropriate viscosity modifier can be added to the organic solvent. As the viscosity modifier, pine oil, terpineol, butyl carbitol acetate or ester alcohol type agents can be used.
このようにして作成されたインク状の抵抗体ペーストは
、スクリーン印刷、刷毛塗り或は吹き付は等の手段て基
板上に印刷等することで、この発明に係る面発熱体は形
成される。The ink-like resistor paste thus prepared is printed on a substrate by means such as screen printing, brush coating, spraying, etc., thereby forming the surface heating element according to the present invention.
このように形成される面発熱体の一製造例を示すと、イ
ンク状の抵抗体ペーストを、テトロンスクリーンを用い
て基板上に印刷し、空気中において１００〜１２５℃の
温度で１０〜１５分間乾燥し、この後、窒素中において
８００〜９５０℃の温度で４〜ｌＯ分間焼成して、基板
の表面に抵抗体層を形成する。電極は、抵抗体層を形成
した後、Ａｇ−Ｐｔ系抵抗体ペーストをスクリーン印刷
し、乾燥後、焼成して得たＡｇ−Ｐｔ電極を用いた。An example of manufacturing a surface heating element formed in this way is to print an ink-like resistor paste on a substrate using a Tetron screen, and then print it in air at a temperature of 100 to 125°C for 10 to 15 minutes. It is dried and then fired in nitrogen at a temperature of 800 to 950° C. for 4 to 10 minutes to form a resistor layer on the surface of the substrate. The electrode used was an Ag-Pt electrode obtained by forming a resistor layer, screen-printing an Ag-Pt-based resistor paste, drying it, and then firing it.
また、この発明にあっては、面発熱体の抵抗体の形成を
、第１図に示す工程によって製造することもできる。Further, in the present invention, the resistor of the surface heating element can also be manufactured by the steps shown in FIG.
即ち、第１図に示す工程は、所謂ｒ無電解メッキ１処理
工程を示しており、先ず、基板の表面をｒ脱脂」した後
、「表面調整」を行い、ｒセンシタイジング」後に「ア
クチベイチング１を行い、次にｒ無電解銅−ニッケルメ
ッキ１を行なった後に、これをＶ活性化」し、「電気銅
−ニッケルメッキ」を行った後に「レジスト塗布Ｊを行
い、「エツチング」処理を行った後に上記「レジストの
剥離」を行い、最後に、これを「乾燥Ｊして形成するこ
とがてきる。That is, the process shown in FIG. 1 shows the so-called electroless plating process, in which the surface of the substrate is first degreased, then surface conditioning is performed, and after sensitizing, activation is performed. Baiting 1 is performed, and then electroless copper-nickel plating 1 is performed, followed by V activation, followed by electrolytic copper-nickel plating, resist application J, and etching. After the processing, the above-mentioned "resist peeling" is performed, and finally, this can be "dried" to form the resist.
以下、実施例について説明する。Examples will be described below.
（実施例） 厚膜抵抗組成物を次の表に示す配合比で構成した。(Example) Thick film resistor compositions were constructed with the blending ratios shown in the following table.
表１
尚、上記配合からなる導電性成分は、銅とニッケルの各
粉末を、重量比率が３０ ： ７０になるように混合し
、１０００・〜１４００℃て加熱処理した後、これを粉
砕機て粉砕し、１０ミクロン以下の粉末となして構成し
た。Table 1 The conductive component having the above composition is prepared by mixing copper and nickel powders at a weight ratio of 30:70, heat-treating the mixture at 1000-1400°C, and then grinding it in a pulverizer. It was ground and constituted as a powder of 10 microns or less.
また、上記表１のガラスフリットは、下記表２の酸化物
を下記表２の重量比率で混合し、白金るつぼに入れて１
５００℃で溶融した後、クエンチンクロールによってフ
リット化し、これを粉砕機および分級機て２〜３ミクロ
ンの粉末となして構成した。The glass frit shown in Table 1 above can be prepared by mixing the oxides shown in Table 2 below at the weight ratio shown in Table 2 below, and placing the mixture in a platinum crucible for 1 hour.
After melting at 500° C., it was fritted using a quenching roll, and this was made into a powder of 2 to 3 microns using a crusher and a classifier.
表２
このようにして作成された前記導電性成分とガラスフリ
ットとを、次に前記各種の有機溶媒の中から選択された
有機溶媒中に入れて混合し、次いで３本のロールミルに
かけて混練し、スクリーン印刷に適するように均一に混
合された抵抗体ペーストを作成した。Table 2 The conductive component and glass frit prepared in this way are then mixed in an organic solvent selected from the various organic solvents, and then kneaded using a three-roll mill. A uniformly mixed resistor paste suitable for screen printing was created.
この場合の有機溶媒としては、
■エステルアルコールにエチルセルローズを６％加えた
もの、
■エステルアルコールにキャスターオイル１１％を加え
たもの、
■エステルアルコールにチクサトロールを加えたもの、
のいずれかを用いた。In this case, the organic solvent used was: (6% ethyl cellulose added to ester alcohol), (11% castor oil added to ester alcohol), (2) Thixatrol added to ester alcohol. .
以上のようにして得られた抵抗体ペーストを１８０メツ
シユのスクリーンを用いて基板上に印刷し、空気中１０
０〜１２０°Ｃで１０分間乾燥した後、窒素雰囲気のベ
ルトコンベア炉中において最高温度９００℃で８〜１１
分間焼成した。The resistor paste obtained as described above was printed on a substrate using a 180-mesh screen, and
After drying at 0 to 120°C for 10 minutes, drying at a maximum temperature of 900°C in a belt conveyor oven under nitrogen atmosphere for 8 to 11 minutes.
Bake for a minute.
このようにして得られた面発熱体の抵抗体層は、２０〜
３０ミクロンであり、シート抵抗値（ＳＲ）および抵抗
値温度変数（ＴＣＲ）は、夫々
Ｎｏ Ｉ ＮＯ２
ＳＲ（ｍΩ／口） ５０．１０ ４２．７Ｔ
ＣＲ（ｐｐｍ／’Ｃ） ４２ １００てあった。The resistor layer of the surface heating element thus obtained has a thickness of 20 to
30 microns, and the sheet resistance (SR) and temperature variable resistance (TCR) are No I NO2 SR (mΩ/mouth) 50.10 42.7T, respectively.
CR (ppm/'C) was 42 100.
以上の面発熱体に負荷を加え、表面温度が４００°Ｃに
なるように連続寿命テストを行った結果、抵抗変化率は
、テスト時間７２００時間て３％程度であった。この時
の輻射波の波長は、第１図に示すように、４〜１２ミク
ロンであった。A continuous life test was performed on the surface heating element described above under a load so that the surface temperature reached 400°C. As a result, the rate of change in resistance was about 3% over a test time of 7200 hours. The wavelength of the radiation wave at this time was 4 to 12 microns, as shown in FIG.
第２図と第３図は、上記のようにして形成された基板ｌ
上に形成された抵抗体２の表面に、ガラス製のグレーズ
保護膜３をグレージインクし、抵抗体の絶縁及び酸化を
防止するように構成してなる所謂クレーズヒータの一例
を示している。FIGS. 2 and 3 show the substrate l formed as described above.
An example of a so-called craze heater is shown, in which a glass glaze protective film 3 is coated with glaze ink on the surface of a resistor 2 formed thereon to insulate the resistor and prevent oxidation.
クレーズ保護膜３は、前記適宜の組成からなるガラスフ
リットと適宜の有機溶媒とを選択し、かつ適宜の割合で
混合して形成されておす、印刷等の手段により上記抵抗
体２の表面に塗布され、乾燥後所要の温度で焼成されて
形成される。The craze protective film 3 is formed by selecting a glass frit having an appropriate composition and an appropriate organic solvent and mixing them in an appropriate ratio, and is applied to the surface of the resistor 2 by means such as printing. After drying, it is fired at the required temperature.
この発明に係る厚膜抵抗組成物は以上のように構成され
ているので、抵抗温度係数の絶対値が低くて熱的安定性
に優れ、かつ、低価格に提供することかでき、特に、１
００ｍΩ／口程度の非常に低い抵抗値を持つ抵抗体に好
適であるという効果を奏する。Since the thick film resistor composition according to the present invention is configured as described above, it has a low absolute value of the temperature coefficient of resistance, has excellent thermal stability, and can be provided at a low price.
It has the effect of being suitable for a resistor having a very low resistance value of about 00 mΩ/hole.
また、この厚膜抵抗組成物によって製造される面発熱体
は、以上のように構成されているのて、シート抵抗値が
低いため印刷技術により任意形状のものを容易に作成す
ることがてき、また、熱源からの輻射波の波長は、第４
図に示すように、４〜１２ミクロンの長波長のものか得
られるのて、痛さを感じない快い暖かさか得られると共
に、抵抗値温度変数が低いので、比較的中温度領域の温
度を安定化させることがてき、用途か拡大する他、抵抗
体の表面にグレーズ層を形成することて、抵抗体或は導
体を、有効に絶縁し、かつ、有効に酸化するのを防止す
ることがてきるので耐久性か向上する等、幾多の優れた
効果を奏する。In addition, since the sheet heating element manufactured using this thick film resistive composition is constructed as described above, it has a low sheet resistance value, so it can be easily manufactured into any shape by printing technology. In addition, the wavelength of the radiation wave from the heat source is the fourth
As shown in the figure, since the long wavelength of 4 to 12 microns can be obtained, it provides a comfortable warmth that does not cause pain, and the resistance value temperature variable is low, so the temperature is relatively stable in the medium temperature range. In addition to expanding its applications, forming a glaze layer on the surface of a resistor can effectively insulate the resistor or conductor and prevent it from oxidizing. It has many excellent effects, such as improved durability.
第１図は、この発明の一実施例に係る面発熱体の製造工
程の−・例を示すフローチャート図、第２図はグレーズ
層が形成されたこの発明の一実施例に係る面発熱体の斜
視図、第３図は同面発熱体の断面図、第４図はこの発明
の一実施例に係る面発熱体の放射特性を示すグラフ図で
ある。
〔符号の説明〕
ｌ・・・基板 ２・・・抵抗体３・・・グレー
ズ保護膜
特許出願人 サンウェーブ工業株式会社第１図FIG. 1 is a flowchart showing an example of the manufacturing process of a surface heating element according to an embodiment of the present invention, and FIG. FIG. 3 is a perspective view, FIG. 3 is a cross-sectional view of the surface heating element, and FIG. 4 is a graph diagram showing the radiation characteristics of the surface heating element according to an embodiment of the present invention. [Explanation of symbols] l...Substrate 2...Resistor 3...Glaze protective film Patent applicant Sunwave Industries Co., Ltd. Figure 1
Claims (13)
３０〜８５重量％であり、ガラスフリットが１０〜６５
重量％であり、有機溶媒が５〜４０重量％の混合比率で
ある厚膜抵抗組成物。(1) The conductive component consisting of a mixed powder of copper and nickel is 30 to 85% by weight, and the glass frit is 10 to 65% by weight.
% by weight, and the organic solvent is mixed at a mixing ratio of 5 to 40% by weight.
重量％に対し、ニッケルが７０〜２０重量％であること
を特徴とする特許請求の範囲第１項記載の厚膜抵抗組成
物。(2) The mixing ratio of copper and nickel is 30 to 80
The thick film resistor composition according to claim 1, characterized in that nickel is present in an amount of 70 to 20% by weight.
ム硼酸塩ガラスで構成されていることを特徴とする特許
請求の範囲第１項記載の厚膜抵抗組成物。(3) The thick film resistive composition according to claim 1, wherein the glass frit is made of barium-aluminum borate glass.
硼珪酸で構成されていることを特徴とする特許請求の範
囲第１項記載の厚膜抵抗組成物。(4) The thick film resistor composition according to claim 1, wherein the glass frit is made of barium-calcium borosilicate.
ル酸エステル、メタクリレート、ポリエステルまたはポ
リオレフィン等のセルローズ誘導体で構成されているこ
とを特徴とする特許請求の範囲第１項記載の厚膜抵抗組
成物。(5) The thick film resistor composition according to claim 1, wherein the organic solvent is composed of a cellulose derivative such as ethyl cellulose, polyacrylate, methacrylate, polyester, or polyolefin.
ル酸エステル、メタクリレート、ポリエステルまたはポ
リオレフィン等のセルローズ誘導体と、パイン油、テル
ピネオール、ブチルカルビトールアセテートまたはエス
テルアルコール系の粘度調整剤と、で構成されているこ
とを特徴とする特許請求の範囲第１項記載の厚膜抵抗組
成物。(6) The organic solvent is composed of a cellulose derivative such as ethyl cellulose, polyacrylic ester, methacrylate, polyester or polyolefin, and a viscosity modifier such as pine oil, terpineol, butyl carbitol acetate or ester alcohol. The thick film resistor composition according to claim 1, characterized in that:
３０〜８５重量％であり、ガラスフリットが１０〜６５
重量％であり、有機溶媒が５〜４０重量％の混合比率で
ある厚膜抵抗組成物を、基板上に印刷し焼成して構成さ
れてなる面発熱体。(7) The conductive component consisting of a mixed powder of copper and nickel is 30 to 85% by weight, and the glass frit is 10 to 65% by weight.
% by weight, and a thick film resistor composition having a mixing ratio of 5 to 40% by weight of an organic solvent is printed on a substrate and fired.
重量％に対し、ニッケルが７０〜２０重量％であること
を特徴とする特許請求の範囲第７項記載の面発熱体。(8) The mixing ratio of copper and nickel is 30 to 80
8. The surface heating element according to claim 7, wherein the content of nickel is 70 to 20% by weight.
ム硼酸塩ガラスで構成されていることを特徴とする特許
請求の範囲第７項記載の面発熱体。(9) The surface heating element according to claim 7, wherein the glass frit is made of barium-aluminum borate glass.
ム硼珪酸で構成されていることを特徴とする特許請求の
範囲第７項記載の面発熱体。(10) The surface heating element according to claim 7, wherein the glass frit is made of barium-calcium borosilicate.
リル酸エステル、メタクリレート、ポリエステルまたは
ポリオレフィン等のセルローズ誘導体で構成されている
ことを特徴とする特許請求の範囲第７項記載の面発熱体
。(11) The surface heating element according to claim 7, wherein the organic solvent is composed of a cellulose derivative such as ethyl cellulose, polyacrylic acid ester, methacrylate, polyester, or polyolefin.
リル酸エステル、メタクリレート、ポリエステルまたは
ポリオレフィン等のセルローズ誘導体と、パイン油、テ
ルピネオール、ブチルカルビトールアセテートまたはエ
ステルアルコール系の粘度調整剤と、で構成されている
ことを特徴とする特許請求の範囲第７項記載の面発熱体
。(12) The organic solvent is composed of a cellulose derivative such as ethyl cellulose, polyacrylic acid ester, methacrylate, polyester or polyolefin, and a viscosity modifier such as pine oil, terpineol, butyl carbitol acetate or ester alcohol. 8. A surface heating element according to claim 7, characterized in that:
の表面には、ガラスを主成分とする保護膜層が形成され
ていることを特徴とする特許請求の範囲第７項、第８項
、第９項、第１０項、第１１項または第１２項いずれか
記載の面発熱体。(13) Claim 7, characterized in that a protective film layer containing glass as a main component is formed on the surface of the resistor obtained by firing the thick film resistor composition. The surface heating element according to any one of Item 8, Item 9, Item 10, Item 11, or Item 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62069082A JPS63304592A (en) | 1987-01-07 | 1987-03-25 | Thick film resistance composition and planar heater manufactured by this composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-510 | 1987-01-07 | ||
| JP51087 | 1987-01-07 | ||
| JP62069082A JPS63304592A (en) | 1987-01-07 | 1987-03-25 | Thick film resistance composition and planar heater manufactured by this composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63304592A true JPS63304592A (en) | 1988-12-12 |
Family
ID=26333506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62069082A Pending JPS63304592A (en) | 1987-01-07 | 1987-03-25 | Thick film resistance composition and planar heater manufactured by this composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63304592A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02242581A (en) * | 1989-02-23 | 1990-09-26 | Ego Elektro Geraete Blanc & Fischer | Cooker |
| JP2012503859A (en) * | 2008-09-27 | 2012-02-09 | ホツトセツト・ハイツパトローネン・ウント・ツーベヘール・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Electric heating element for technical purposes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57201739A (en) * | 1981-05-14 | 1982-12-10 | Ford Motor Co | Electric heating plate |
-
1987
- 1987-03-25 JP JP62069082A patent/JPS63304592A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57201739A (en) * | 1981-05-14 | 1982-12-10 | Ford Motor Co | Electric heating plate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02242581A (en) * | 1989-02-23 | 1990-09-26 | Ego Elektro Geraete Blanc & Fischer | Cooker |
| JP2012503859A (en) * | 2008-09-27 | 2012-02-09 | ホツトセツト・ハイツパトローネン・ウント・ツーベヘール・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Electric heating element for technical purposes |
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