JPH01258303A - Conductive paste - Google Patents
Conductive pasteInfo
- Publication number
- JPH01258303A JPH01258303A JP8478288A JP8478288A JPH01258303A JP H01258303 A JPH01258303 A JP H01258303A JP 8478288 A JP8478288 A JP 8478288A JP 8478288 A JP8478288 A JP 8478288A JP H01258303 A JPH01258303 A JP H01258303A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- paste
- conductive paste
- organic vehicle
- amount
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003086 colorant Substances 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000005751 Copper oxide Substances 0.000 claims abstract 2
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910020617 PbO—B2O3—SiO2 Inorganic materials 0.000 abstract 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000005357 flat glass Substances 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- 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 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
Landscapes
- Glass Compositions (AREA)
- Conductive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、自動車窓ガラスに用いられる曇り止め用熱線
ヒータなどを製造するための導電性のペーストに関する
。さらに詳しくは、車外よりみて濃茶色ないし゛黒色に
近い色調にみえる曇り止め用熱線ヒータなどの製造に用
いる導電性のペーストに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a conductive paste for manufacturing anti-fog hot wire heaters used in automobile window glass. More specifically, the present invention relates to a conductive paste used in the manufacture of anti-fogging hot wire heaters, etc., which appear dark brown or close to black in color when viewed from outside the vehicle.
［従来の技術・発明が解決しようとする課題］従来から
自動車窓ガラスの曇り止め用熱線ヒータには、金属の中
でも最も抵抗率が低い銀を主体とする、いわゆる銀ペー
ストが用いられている。熱線ヒータはこの銀ペーストを
ガラス板上に印刷し、ペーストの焼付け、ガラス板の強
化および曲げ加工を行なうための熱処理を行なうことに
よって製造されている。その際の焼付は温度は６００〜
７００℃であり、この温度範囲で焼付けたものを車外よ
り観察すると、黄色または茶色の色調となる。[Prior Art/Problems to be Solved by the Invention] Conventionally, so-called silver paste, which is mainly composed of silver, which has the lowest resistivity among metals, has been used in hot wire heaters for preventing fogging of automobile window glasses. Hot wire heaters are manufactured by printing this silver paste on a glass plate and performing heat treatment to bake the paste, strengthen the glass plate, and bend it. At that time, the baking temperature is 600~
The temperature is 700°C, and when observed from the outside of the car when baked in this temperature range, the color will be yellow or brown.
しかしながら、近年、自動車の高級化が著しく進んでお
り、熱線ヒータの色調についても黄色または茶色の色調
よりも高級感のある濃茶色や黒色の色調が強く求められ
ている。However, in recent years, automobiles have become significantly more sophisticated, and there is a strong demand for hot wire heaters to have dark brown or black tones that give a more luxurious feel than yellow or brown tones.
［課題を解決するための手段］
本発明者らは上記のごとき実情に鑑み、濃茶色〜黒色の
色調を有する熱線ヒータなどを製造することができる導
電性のペーストをうろことを目的として鋭意研究を重ね
た結果、
（Ａ）銀粉３５〜８５％（重量％、以下同様）、（Ｂ）
ガラス質フリット ０，５〜１５％、（Ｃ）カラーラン
ト成分である酸化マンガン、酸化クロム、酸化コバルト
、酸化鋼、酸化鉄ならびにマンガン、クロム、コバルト
、銅および鉄のなかの少なくとも２種の金属を含む複合
酸化物よりなる群から選ばれた少なくとも１種０．５〜
２０％ならびに
（Ｄ）有機質ビヒクル８〜４０％
を含有してなる導電性のペーストを用いると、濃茶色〜
黒色の色調の熱線ヒータなどを形成しうろことを見出し
、本発明に到達した。[Means for Solving the Problems] In view of the above-mentioned circumstances, the present inventors have conducted extensive research with the aim of developing a conductive paste that can be used to manufacture hot wire heaters and the like having a dark brown to black color tone. As a result of stacking, (A) 35-85% silver powder (weight%, same below), (B)
Glassy frit 0.5-15%, (C) colorant components manganese oxide, chromium oxide, cobalt oxide, steel oxide, iron oxide and at least two metals from manganese, chromium, cobalt, copper and iron At least one selected from the group consisting of complex oxides containing 0.5~
When using a conductive paste containing 20% and (D) organic vehicle 8 to 40%, it becomes dark brown to
The present invention was achieved by discovering scales that form a black-toned hot wire heater.
［作用・実施例］
本発明に用いる銀粉の形状、粒径、純度などにはとくに
限定はなく、一般に導電性ペーストの製造に使用されて
いるようなものであればとくに限定なく使用しうる。た
とえば形状は球状、フレーク状など、どのような形状の
ものであっても使用でき、もちろん異なる形状のものを
混合して用いても何ら支障はない。また粒径についても
とくに限定はないが、粒径ｌＯｕｍ以下で平均粒径５扉
以下のものが好ましく、さらにえられるペーストを６０
０〜７００℃の焼付は温度で焼付けるばあいには、平均
粒径３項以下のものが好ましい。[Function/Examples] There are no particular limitations on the shape, particle size, purity, etc. of the silver powder used in the present invention, and any silver powder that is generally used in the production of conductive pastes can be used without particular limitations. For example, it can be used in any shape, such as spherical or flaky, and of course, there is no problem in using a mixture of different shapes. There is also no particular limitation on the particle size, but it is preferable that the particle size is 1 Oum or less and the average particle size is 5 or less.
When baking is performed at a temperature of 0 to 700°C, it is preferable that the average particle size is 3 or less.
銀粉の使用量は本発明のペースト中３５〜８５％、好ま
しくは５０〜８３％である。該使用量が３５％未満では
充分な導電性を有する熱線ヒータなどを製造することが
できなくなり、また８５％をこえるとペースト化が困難
になる。The amount of silver powder used in the paste of the present invention is 35 to 85%, preferably 50 to 83%. If the amount used is less than 35%, it will not be possible to manufacture a hot wire heater or the like having sufficient conductivity, and if it exceeds 85%, it will be difficult to form a paste.
本発明に用いるガラス質フリットは、たとえば本発明の
ペーストが自動車窓ガラスの曇り止め用熱線ヒータの製
造に用いられるばあい、焼付けられた熱線ヒータと基体
であるガラス板とを強固に結合させるための成分である
。The vitreous frit used in the present invention is used to firmly bond the baked hot wire heater to the glass plate as the base when the paste of the present invention is used to manufacture a hot wire heater for defogging automobile window glass. It is a component of
該ガラス質フリットは基体であるガラス板の軟化点付近
の温度で充分流動する性質を有している限り、その組成
などにはとくに限定なく使用しうる。このようなガラス
質フリットの好ましい具体例としては、たとえば軟化点
３５０〜５５０℃のＰｂＯ−Ｂ２Ｏ３−５ｉＯｚ、Ｐｂ
Ｏ−Ｂ２Ｏ３、ＺｎＯ−Ｂ２Ｏ３−３１０２、ＰｂＯ−
ＺｎＯ−Ｂ２Ｏｓなどを主成分（９５％以上含有）とし
、微量のアルカリ金属、アルカリ土類金属などを含有し
たガラス質フリットがあげられる。The vitreous frit can be used without any particular limitations on its composition, as long as it has the property of flowing sufficiently at a temperature near the softening point of the glass plate that is the substrate. Preferred specific examples of such glassy frits include, for example, PbO-B2O3-5iOz, Pb
O-B2O3, ZnO-B2O3-3102, PbO-
Examples include glassy frits containing ZnO-B2Os as a main component (containing 95% or more) and trace amounts of alkali metals, alkaline earth metals, and the like.
前記ガラス質フリットの使用量は本発明のペースト中０
．５〜１５％、好ましくは１．０〜１２％である。該使
用量が０．５％未満ではえられる熱線ヒータなどとガラ
ス板との接着力が充分でなくなり、また１５％をこえる
と熱線ヒータなどの抵抗値が高くなりすぎるため好まし
くない。The amount of the vitreous frit used is 0 in the paste of the present invention.
．． It is 5-15%, preferably 1.0-12%. If the amount used is less than 0.5%, the adhesive strength between the hot wire heater, etc. and the glass plate will not be sufficient, and if it exceeds 15%, the resistance value of the hot wire heater, etc. will become too high, which is not preferable.
本発明に用いるカラーラント成分は、本発明のペースト
を焼付けたときの色調を調整するための成分であり、そ
の種類および量によって色調が大きく左右される。The colorant component used in the present invention is a component for adjusting the color tone when the paste of the present invention is baked, and the colorant component is greatly influenced by its type and amount.
このようなカラーランド成分の具体例としては、マンガ
ン、クロム、コバルト、銅または鉄の酸化物である酸化
マンガン、酸化クロム、酸化コバルト、酸化鋼、酸化鉄
、さらには前記金属を２種以上含有する複合酸化物があ
げられる。Specific examples of such color land components include manganese oxide, chromium oxide, cobalt oxide, steel oxide, iron oxide, which is an oxide of manganese, chromium, cobalt, copper or iron, and furthermore, a material containing two or more of the above metals. Examples include complex oxides that
これらは単独で用いてもよく、２種以上併用してもよい
。These may be used alone or in combination of two or more.
なお前記金属酸化物は、たとえば酸化マンガンのばあい
、マンガンの価数からＭｎＯとＭｎＯ２が考えられるが
、これら以外の式で示されるものであってもよい。他の
金属酸化物についても同様である。In the case of manganese oxide, for example, the metal oxide may be MnO or MnO2 based on the valence of manganese, but it may be represented by a formula other than these. The same applies to other metal oxides.
また前記複合酸化物は、前記金属のうちの２種以上を含
をする酸化物である限りいずれの方法で製造されたもの
であってもよく、たとえば前記金属酸化物および（また
は）金属の２種以上の粉末を混合し、あらかじめ高温処
理したものを再度粉砕して、酸化物粉にしたものがあげ
られる。これら金属酸化物や金属の複合酸化物の平均粒
径は０．５〜５−であるのが好ましい。Further, the composite oxide may be produced by any method as long as it is an oxide containing two or more of the metals, for example, the metal oxide and/or two or more of the metals. An example is a mixture of powders of seeds or more, which has been previously treated at a high temperature and then ground again to form an oxide powder. The average particle size of these metal oxides and metal composite oxides is preferably 0.5 to 5-.
前記カラーラント成分の使用量は本発明のペースト中０
．５〜２０％、好ましくは１．０〜１５％である。該使
用量が０．５％未満では製造された熱線ヒータなどが濃
茶色ないし黒色の高級感のある色調にならず、また２０
％をこえると熱線ヒータなどの抵抗値が高くなりすぎる
。The amount of the colorant component used in the paste of the present invention is 0.
．． It is 5-20%, preferably 1.0-15%. If the amount used is less than 0.5%, the manufactured hot wire heater etc. will not have a luxurious color tone of dark brown or black, and
If it exceeds %, the resistance value of hot wire heaters etc. will become too high.
本発明に用いる有機質ビヒクルとは、前記銀粉、ガラス
質フリットおよびカラーランド成分をペースト化する成
分である。The organic vehicle used in the present invention is a component that turns the silver powder, glassy frit, and color land component into a paste.
このような有機質ビヒクルにはとくに限定はなく、通常
マイクロエレクトロニクス分野の厚膜ペーストに用いら
れるものであれば使用しうる。There are no particular limitations on such an organic vehicle, and any organic vehicle that is commonly used in thick film pastes in the microelectronics field can be used.
前記有機質ビヒクルの具体例としては、たとえばエチル
セルロース、（メタ）アクリル酸ポリマーなどを樹脂成
分とし、高沸点溶剤であるターピネオール類、ブチルカ
ルピトールアセテート、ジブチルフタレート、セロソル
ブなどに樹脂成分の濃度が３〜１０％になるように溶解
したものなどがあげられる。Specific examples of the organic vehicle include ethyl cellulose, (meth)acrylic acid polymer, etc. as a resin component, and high-boiling point solvents such as terpineols, butylcarpitol acetate, dibutyl phthalate, cellosolve, etc., with a resin component concentration of 3 to 3. Examples include those dissolved to a concentration of 10%.
前記有機質ビヒクルの使用量は本発明のペースト中８〜
４０％、好ましくは１０〜３０％である。The amount of the organic vehicle used in the paste of the present invention is 8 to 8.
40%, preferably 10-30%.
該使用量が８％未満のばあいには良好な流動性を有する
ペーストかえられず、ダンゴ状になり、また、４０％を
こえるとペーストを焼き付けたとき、焼き付は膜厚が薄
くなり抵抗値が高くなる。If the amount used is less than 8%, the paste will not have good fluidity and will become lump-like, and if it exceeds 40%, the film thickness will become thinner and the resistance value will decrease. becomes higher.
さらに、本発明のペーストには抵抗値の調整のためニ５
１０２、ｚ「０２、＃２０ｘなトラ、ペースト中の含有
量が２％をこえない範囲で配合してもよい。Furthermore, the paste of the present invention has a Ni-5 for adjusting the resistance value.
102, z "02, #20x" may be blended within the range where the content in the paste does not exceed 2%.
本発明のペーストは、前記銀粉、ガラス質フリット、カ
ラーラント成分、有機質ビヒクルおよび要すれば使用さ
れるその他の成分をあらかじめ混合し、三本ロールミル
を通過せしめてペースト化することにより容品に調製す
ることができる。The paste of the present invention is prepared into a container by pre-mixing the silver powder, vitreous frit, colorant component, organic vehicle, and other components used if necessary, and passing the mixture through a three-roll mill to form a paste. can do.
このようにして調製された本発明の導電性のペーストは
スクリーン印刷に適した粘度（１００〜５００Ｐ）を有
し、印刷幅が１２０ρ以上であれば問題なく印刷できる
ものである。また、本発明の導電性のペーストをガラス
基体に印刷、焼成してガラス面より導体の色を観察する
と、従来の色調よりも濃くなっていることがわかる。さ
らに、采発明のペーストから製造される導体回路の抵抗
（幅０．５ｍｍ、長さ１２００ｍｍのパターンで回路抵
抗を測定し、１０ｕｍの膜厚に換算して算出した値）は
、３〜１８ｍΩ／口／１０ρ程度である。The conductive paste of the present invention thus prepared has a viscosity (100 to 500 P) suitable for screen printing, and can be printed without problems if the printing width is 120 P or more. Furthermore, when the conductive paste of the present invention is printed on a glass substrate and fired, and the color of the conductor is observed from the glass surface, it is found that the color tone is darker than the conventional color tone. Furthermore, the resistance of the conductor circuit manufactured from the paste of the Kame invention (value calculated by measuring the circuit resistance with a pattern of width 0.5 mm and length 1200 mm and converting it to a film thickness of 10 um) is 3 to 18 mΩ/ It is about mouth/10ρ.
なお、通常この抵抗の値は、２０ｍΩ／口／１０−以下
であれば導体回路として使用しうる。In addition, if the value of this resistance is usually 20 mΩ/hole/10 − or less, it can be used as a conductor circuit.
本発明の導電性のペーストは、前記のごとき自動車窓ガ
ラスの曇り止め用熱線ヒータの製造、自動車用のアンテ
ナの製造などの用途に好適に使用しうる。The conductive paste of the present invention can be suitably used in applications such as manufacturing hot wire heaters for preventing fogging of automobile window glass as described above and manufacturing antennas for automobiles.
たとえば本発明のペーストを用いて自動車窓ガラスの曇
り止め用熱線ヒータを製造するばあい、従来のペースト
を用いる方法と同様の方法で用いればよく、たとえば前
記のようにしてえられたペーストをガラス板上にスクリ
ーン印刷し、１５０〜２００℃で５〜ｌＯ分間乾燥した
のち、６００〜７００℃で１〜５分間焼付けを行なえば
よい。For example, if the paste of the present invention is used to manufacture a hot wire heater for preventing fogging of automobile window glass, it may be used in the same manner as the conventional paste. After screen printing on the plate, drying at 150 to 200°C for 5 to 10 minutes, baking may be performed at 600 to 700°C for 1 to 5 minutes.
このようにして製造された熱線ヒータは車外からみたば
あい、濃茶色ないし黒色の高級感のある色調を呈する。When viewed from outside the vehicle, the hot wire heater manufactured in this manner exhibits a luxurious color tone of dark brown to black.
つぎに本発明を実施例に基づき、さらに具体的に説明す
るが、本発明はかかる実施例のみに限定されるものでは
ない。Next, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.
実施例１〜ＩＯ
粒径５燗以下、平均粒径１．２Ｊ！ｍの球状銀粉、ガラ
ス質フリットとして軟化点４９０℃のＰｂＯ−Ｂ２Ｏ３
−８ｉＯ２系ガラス、ビヒクルとしてエチルセルロース
をβ −ターピネオールに濃度が６％になるように溶解
した溶液およびカラーランドとして第１表に示す平均粒
径０．５〜４ＡＩｍの無機物を用い、ペースト中の含有
量が第１表に示す比率になるように配合し、あらかじめ
混合後、三本ロールミルを通してペースト化した。Example 1 - IO Particle size 5 or less, average particle size 1.2J! m spherical silver powder, PbO-B2O3 with a softening point of 490°C as a glassy frit
-8iO2 glass, a solution of ethyl cellulose dissolved in β-terpineol at a concentration of 6% as a vehicle, and an inorganic substance with an average particle size of 0.5 to 4 AIm shown in Table 1 as a color land, and the content in the paste. The amounts were blended in the proportions shown in Table 1, mixed in advance, and passed through a three-roll mill to form a paste.
えられたペーストを厚さ ３．５ｍ１１のガラス板上に
スクリーン印刷し、２００℃で１０分間乾燥したのち、
８６０℃で３分間焼付け、熱線ヒーターを製造した。え
られた熱線ヒーターの厚さはいずれも約８Ｉであつた。The resulting paste was screen printed on a glass plate with a thickness of 3.5 m11, and after drying at 200°C for 10 minutes,
A hot wire heater was manufactured by baking at 860°C for 3 minutes. The thickness of the obtained hot wire heaters was approximately 8I.
ガラス上に設けられた熱線ヒーターの色調を熱線ヒータ
ーが設けられていない面から肉眼で観察した。結果を第
１表に示す。なお、色調は、１を白色、２を黄色、３を
茶色、４を濃いあずき色、５を黒色として数字をもって
評価した。The color tone of the hot wire heater provided on the glass was observed with the naked eye from the side where the hot wire heater was not provided. The results are shown in Table 1. The color tone was evaluated numerically, with 1 being white, 2 being yellow, 3 being brown, 4 being deep maroon, and 5 being black.
また、前記ペーストを用いて幅０．５ｍｍ、長さ１２０
０ｍｍのパターンを製造し、導体抵抗を測定した。結果
をＩＯ論の膜厚に換算して算出し、第１表に示す。Also, using the paste, a width of 0.5 mm and a length of 120
A 0 mm pattern was manufactured and the conductor resistance was measured. The results were calculated by converting them into film thicknesses according to IO theory, and are shown in Table 1.
比較例１および２
実施例１〜１０で用いたものと同一の銀粉、ガラス質フ
リットおよび有機質ビヒクルを、ペースト中の含有量が
第１表に示す比率になるように用い、カラーラント成分
を加えずに実施例１と同様にしてペースト化した。つぎ
に実施例１〜ｌＯと同様にして熱線ヒーターを製造し、
色調を評価し、導体抵抗を測定した。結果を第１表に示
す。Comparative Examples 1 and 2 The same silver powder, glass frit, and organic vehicle as those used in Examples 1 to 10 were used so that the content in the paste was in the ratio shown in Table 1, and a colorant component was added. Instead, it was made into a paste in the same manner as in Example 1. Next, a hot wire heater was manufactured in the same manner as in Examples 1 to 1O,
The color tone was evaluated and the conductor resistance was measured. The results are shown in Table 1.
第１表かられかるように、色調はカラーラント成分を配
合することで著しく濃くなっており、その量を増すこと
により、顕著に黒色に近づくことがわかる。As can be seen from Table 1, the color tone becomes significantly darker by adding the colorant component, and as the amount of the colorant component is increased, it becomes significantly closer to black.
［発明の効果］
本発明の導電性のペーストを用いると、濃茶色ないし黒
色の高級感のある自動車窓ガラスの曇り止め用熱線ヒー
ターなどが形成できる。[Effects of the Invention] When the conductive paste of the present invention is used, it is possible to form a hot wire heater for preventing fogging of automobile window glass, which has a dark brown to black color and has a luxurious appearance.
特許出願人 第一工業製薬株式会社 同和鉱業株式会社Patent applicant: Daiichi Kogyo Seiyaku Co., Ltd. Dowa Mining Co., Ltd.
Claims (1)
ラーラント成分である酸化マンガン、酸化クロム、酸化
コバルト、酸化銅、酸化鉄ならびにマンガン、クロム、
コバルト、銅および鉄のなかの少なくとも２種の金属を
含む複合酸化物よりなる群から選ばれた少なくとも１種
０．５〜２０重量％ならびに （Ｄ）有機質ビヒクル８〜４０重量％ を含有してなる導電性のペースト。[Claims] 1 (A) 35 to 85% by weight of silver powder, (B) 0.5 to 15% by weight of vitreous frit, (C) colorant components of manganese oxide, chromium oxide, cobalt oxide, and copper oxide , iron oxide as well as manganese, chromium,
Contains 0.5 to 20% by weight of at least one selected from the group consisting of complex oxides containing at least two metals among cobalt, copper, and iron, and (D) 8 to 40% by weight of an organic vehicle. A conductive paste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8478288A JPH01258303A (en) | 1988-04-06 | 1988-04-06 | Conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8478288A JPH01258303A (en) | 1988-04-06 | 1988-04-06 | Conductive paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01258303A true JPH01258303A (en) | 1989-10-16 |
Family
ID=13840266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8478288A Pending JPH01258303A (en) | 1988-04-06 | 1988-04-06 | Conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01258303A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5296413A (en) * | 1991-12-03 | 1994-03-22 | E. I. Du Pont De Nemours And Company | Automotive glass thick film conductor paste |
| US5795501A (en) * | 1995-09-22 | 1998-08-18 | Murata Manufacturing Co., Ltd. | Electrically-conductive composition |
| WO2003025954A1 (en) * | 2001-09-20 | 2003-03-27 | E. I. Du Pont De Nemours And Company | Silver conductor composition |
| JP2008277247A (en) * | 2007-04-25 | 2008-11-13 | Samsung Sdi Co Ltd | Composition for electrode formation, and plasma display panel |
| US8004192B2 (en) | 2001-11-08 | 2011-08-23 | Panasonic Corporation | Black paste and plasma display panel and method for preparation thereof |
| US10056508B2 (en) | 2015-03-27 | 2018-08-21 | Heraeus Deutschland GmbH & Co. KG | Electro-conductive pastes comprising a metal compound |
| US10636540B2 (en) | 2015-03-27 | 2020-04-28 | Heraeus Deutschland GmbH & Co. KG | Electro-conductive pastes comprising an oxide additive |
-
1988
- 1988-04-06 JP JP8478288A patent/JPH01258303A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5296413A (en) * | 1991-12-03 | 1994-03-22 | E. I. Du Pont De Nemours And Company | Automotive glass thick film conductor paste |
| CN1036739C (en) * | 1991-12-03 | 1997-12-17 | E·I·内穆尔杜邦公司 | Automotive class thick film comductor paste |
| US5795501A (en) * | 1995-09-22 | 1998-08-18 | Murata Manufacturing Co., Ltd. | Electrically-conductive composition |
| WO2003025954A1 (en) * | 2001-09-20 | 2003-03-27 | E. I. Du Pont De Nemours And Company | Silver conductor composition |
| US8004192B2 (en) | 2001-11-08 | 2011-08-23 | Panasonic Corporation | Black paste and plasma display panel and method for preparation thereof |
| JP2008277247A (en) * | 2007-04-25 | 2008-11-13 | Samsung Sdi Co Ltd | Composition for electrode formation, and plasma display panel |
| US8188659B2 (en) | 2007-04-25 | 2012-05-29 | Samsung Sdi Co., Ltd. | Composition for forming a multi-layered electrode and plasma display panel manufactured with the same |
| US10056508B2 (en) | 2015-03-27 | 2018-08-21 | Heraeus Deutschland GmbH & Co. KG | Electro-conductive pastes comprising a metal compound |
| US10636540B2 (en) | 2015-03-27 | 2020-04-28 | Heraeus Deutschland GmbH & Co. KG | Electro-conductive pastes comprising an oxide additive |
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