JP2003217347A - Conductive paste, glass substrate covered with conductive film and manufacturing method therefor - Google Patents

Conductive paste, glass substrate covered with conductive film and manufacturing method therefor

Info

Publication number
JP2003217347A
JP2003217347A JP2002009037A JP2002009037A JP2003217347A JP 2003217347 A JP2003217347 A JP 2003217347A JP 2002009037 A JP2002009037 A JP 2002009037A JP 2002009037 A JP2002009037 A JP 2002009037A JP 2003217347 A JP2003217347 A JP 2003217347A
Authority
JP
Japan
Prior art keywords
weight
conductive
glass substrate
conductive paste
conductive film
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
Application number
JP2002009037A
Other languages
Japanese (ja)
Other versions
JP3988467B2 (en
Inventor
Toru Nishibe
徹 西部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Narumi China Corp
Original Assignee
Narumi China Corp
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Filing date
Publication date
Application filed by Narumi China Corp filed Critical Narumi China Corp
Priority to JP2002009037A priority Critical patent/JP3988467B2/en
Publication of JP2003217347A publication Critical patent/JP2003217347A/en
Application granted granted Critical
Publication of JP3988467B2 publication Critical patent/JP3988467B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive paste, a glass substrate covered with conductive film using this and a manufacturing method therefor containing no lead and capable of forming a conductive film with excellent abrasion-resistance, acid-resistance and alkali-resistance. <P>SOLUTION: The conductive paste is seized on a surface of a low expansion glass substrate to form the conductive film. The conductive paste contains no lead and comprises 60-80 wt.% of conductive powder material; 20-40 wt.% of glass flux; and 30-100 wt.% of organic binder based on 100 wt.% of a sum weight of the conductive power material and the glass flux. The glass flux comprises 56-69 wt.% of SiO<SB>2</SB>; 0-4 wt.% of Al<SB>2</SB>O<SB>3</SB>; 23-30 wt.% of B<SB>2</SB>O<SB>3</SB>; 0.1-3 wt.% of Li<SB>2</SB>O; 1-5% wt.% of Na<SB>2</SB>O; 0-4 wt.% of K<SB>2</SB>O; 0-5 wt.% of TiO<SB>2</SB>and 1-5 wt.% of ZrO<SB>2</SB>. <P>COPYRIGHT: (C)2003,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【技術分野】本発明は，低膨張ガラス基板の表面に導電
性被膜を施すための導電性ペースト，並びに低膨張ガラ
ス基板の表面に導電性被膜を有する導電性被膜被覆ガラ
ス基板及びその製造方法に関する。TECHNICAL FIELD The present invention relates to a conductive paste for applying a conductive coating to the surface of a low expansion glass substrate, a conductive coating coated glass substrate having a conductive coating on the surface of a low expansion glass substrate, and a method for producing the same. .

【０００２】[0002]

【従来技術】トッププレート下部にハロゲンヒーター等
の発熱体を取り付けた電気調理器，或いは誘電コイルを
用いて電磁誘導作用により発熱させる電磁調理器は，そ
の安全性のため，近年特に需要が高まってきている。こ
れらのトッププレート自体としては，低膨張ガラス基板
の表面に，導電性表示部等の導電性被膜を被覆してなる
導電性被膜被覆ガラス基板がある。2. Description of the Related Art An electric cooker in which a heating element such as a halogen heater is attached to the lower portion of a top plate, or an electromagnetic cooker that uses an inductive coil to generate heat by an electromagnetic induction action, has recently been particularly in demand due to its safety. ing. As these top plates themselves, there is a conductive coating-coated glass substrate obtained by coating the surface of a low expansion glass substrate with a conductive coating such as a conductive display portion.

【０００３】上記導電性被膜は，上記低膨張ガラス基板
の表面に導電性を有する導電性ペーストを，スクリーン
印刷法等により導体路等の所望の形状に印刷し，焼成し
てなる。上記導電性ペーストは，金属等の導電性粉末材
料とガラスフラックス等からなる。従来，このような導
電性ペーストとしては，陶磁器の表面に模様を施すため
に使用されている陶磁器用金属ペースト，又は半導体用
として市販されている半導体用導電性ペーストが使用さ
れていた。The conductive coating is formed by printing a conductive paste having conductivity on the surface of the low-expansion glass substrate in a desired shape such as a conductor path by a screen printing method or the like and firing it. The conductive paste is made of a conductive powder material such as metal and glass flux. Heretofore, as such a conductive paste, a ceramic metal paste used for applying a pattern to the surface of a ceramic or a semiconductor conductive paste commercially available for semiconductors has been used.

【０００４】[0004]

【解決しようとする課題】しかしながら，上記陶磁器用
金属ペースト及び半導体用導電性ペーストを用いた上記
導電性被膜被覆ガラス基板は，摩耗に弱く，低膨張ガラ
ス基板から剥離しやすい。特に，上記導電性被膜被覆ガ
ラス基板を上記電気調理器用のトッププレート等として
用いる場合には，調理や洗浄の際に他の調理器具や洗浄
器具などと導電性被膜とが強く接触することが多い。そ
のため，上記導電性被膜が低膨張ガラス基板から剥離し
たり，また接触が繰り返し起こることにより上記導電性
被膜が摩耗して該導電性被膜の導電性が大幅に低下する
という問題があった。However, the glass substrate coated with a conductive film using the above-mentioned metal paste for ceramics and conductive paste for semiconductors is weak against abrasion and easily peeled off from a low expansion glass substrate. In particular, when the above-mentioned conductive film-coated glass substrate is used as a top plate for the electric cooker or the like, the conductive film often comes into strong contact with other cooking utensils or cleaning equipment during cooking or cleaning. . Therefore, there has been a problem that the conductive coating is peeled from the low expansion glass substrate, and repeated contact causes abrasion of the conductive coating, resulting in a significant decrease in conductivity of the conductive coating.

【０００５】また，上記のように導電性被膜被覆ガラス
基板を上記トッププレート等の調理器具として用いる場
合には，上記導電性被膜被覆ガラス基板は，食料品等に
含まれる酸や洗剤等に含まれるアルカリに優れた耐性を
持つ必要がある。しかし，上記半導体用導電性ペースト
は，耐酸性，耐アルカリ性等の耐化学薬品性があまり考
慮されていない。そのため，上記半導体用導電ペースト
を用いた導電性被膜被覆ガラス基板は，酸やアルカリ等
の化学薬品により導電性被膜が変色，変形または剥離す
ることがあり，電気調理器のトッププレート等の用途に
は使用することができなかった。Further, when the conductive film-coated glass substrate is used as a cookware such as the top plate as described above, the conductive film-coated glass substrate is contained in acids or detergents contained in foods or the like. It must have excellent resistance to alkali. However, resistance to chemicals such as acid resistance and alkali resistance has not been considered so much in the above-mentioned conductive paste for semiconductors. Therefore, the conductive film-coated glass substrate using the above-mentioned conductive paste for semiconductors may be discolored, deformed or peeled off by chemicals such as acid or alkali. Could not be used.

【０００６】また，上記導電性ペーストに用いられるガ
ラスフラックスとしては，例えば熱膨張係数を結晶化ガ
ラスの熱膨張係数と合わせた低膨張セラミックス装飾用
組成物が開示されている（特公平５−４０７０７）。上
記低膨張セラミックス装飾用組成物は，その熱膨張係数
を結晶化ガラスの熱膨張係数に合わせているため，クラ
ックの発生や結晶化ガラスから剥離するという問題を回
避することができる。しかし，調理器として使用される
導電性被膜被覆ガラス基板には，人体への影響が懸念さ
れることから，鉛を含まないことが好ましい。As the glass flux used in the above-mentioned conductive paste, for example, a low-expansion ceramic decorative composition in which the coefficient of thermal expansion is combined with that of crystallized glass is disclosed (Japanese Patent Publication No. 5-40707). ). Since the coefficient of thermal expansion of the low-expansion ceramics decorative composition matches the coefficient of thermal expansion of the crystallized glass, it is possible to avoid problems such as cracking and separation from the crystallized glass. However, it is preferable that the conductive film-coated glass substrate used as a cooking device does not contain lead because it may affect the human body.

【０００７】本発明は，かかる従来の問題点に鑑みてな
されたもので，鉛を含有せず，耐摩耗性，耐酸性及び耐
アルカリ性に優れた導電性被膜を形成することができる
導電性ペースト，及び該導電性ペーストを用いた導電性
被膜被覆ガラス基板及びその製造方法を提供しようとす
るものである。The present invention has been made in view of the above conventional problems, and is a conductive paste containing no lead and capable of forming a conductive coating excellent in abrasion resistance, acid resistance and alkali resistance. , And a conductive film-coated glass substrate using the conductive paste, and a method for manufacturing the same.

【０００８】[0008]

【課題の解決手段】第１の発明は，低膨張ガラス基板の
表面に焼き付け，導電性被膜を形成するための導電性ペ
ーストであって，上記導電性ペーストは，鉛を含有せ
ず，導電性粉末材料６０〜８０重量％と，ガラスフラッ
クス２０〜４０重量％と，上記導電性粉末材料及びガラ
スフラックスの合計重量１００重量％に対して有機バイ
ンダー３０〜１００重量％を含有してなり，かつ，上記
ガラスフラックスは，ＳｉＯ2が５６〜６９重量％と，
Ａｌ2Ｏ3が０〜４重量％と，Ｂ2Ｏ3が２３〜３０重量％
と，Ｌｉ2Ｏが０．１〜３重量％と，Ｎａ2Ｏが１〜５重
量％と，Ｋ2Ｏが０〜４重量％と，ＴｉＯ2が０〜５重量
％と，及びＺｒＯ2が１〜５重量％とからなることを特
徴とする導電性ペーストにある（請求項１）。A first invention is a conductive paste for baking on a surface of a low expansion glass substrate to form a conductive coating, wherein the conductive paste does not contain lead and is conductive. It contains 60 to 80% by weight of powder material, 20 to 40% by weight of glass flux, and 30 to 100% by weight of organic binder with respect to 100% by weight of the total weight of the conductive powder material and glass flux, and In the above glass flux, SiO 2 is 56 to 69% by weight,
Al 2 O 3 is 0 to 4 wt% and B 2 O 3 is 23 to 30 wt%.
Li 2 O 0.1 to 3% by weight, Na 2 O 1 to 5% by weight, K 2 O 0 to 4% by weight, TiO 2 0 to 5% by weight, and ZrO 2 1 to 5% by weight of the conductive paste.

【０００９】次に，本発明の作用効果につき説明する。
本発明の導電性ペーストは，鉛を含まないため，人体に
対して安全である。そのため，電磁調理器のトッププレ
ート等の調理器等にも使用することができる。また，上
記導電性ペーストは，導電性粉末材料，ガラスフラック
ス，及び有機バインダーを上記の組成で含有している。
そのため，上記導電性被膜は摩擦により，剥離したり導
電性が低下することがほとんどない。即ち，耐摩耗性に
優れている。Next, the function and effect of the present invention will be described.
Since the conductive paste of the present invention does not contain lead, it is safe for the human body. Therefore, it can also be used for a cooker such as a top plate of an electromagnetic cooker. Further, the conductive paste contains a conductive powder material, a glass flux, and an organic binder in the above composition.
Therefore, the conductive coating is hardly peeled off or its conductivity is deteriorated by friction. That is, it has excellent wear resistance.

【００１０】さらに，上記ガラスフラックスは上記の組
成から成っている。そのため，上記導電性被膜は，耐酸
性及び耐アルカリ性に優れ，熱膨張係数が低膨張ガラス
基板と同程度に低くなる。それ故，上記導電性被膜が低
膨張ガラス基板との熱膨張差により剥離することを防止
することができる。Further, the glass flux has the above composition. Therefore, the conductive coating is excellent in acid resistance and alkali resistance, and has a thermal expansion coefficient as low as that of the low expansion glass substrate. Therefore, it is possible to prevent the conductive coating film from peeling due to the difference in thermal expansion from the low expansion glass substrate.

【００１１】このように，本発明によれば，鉛を含有せ
ず，耐摩耗性，耐酸性及び耐アルカリ性に優れた導電性
被膜を形成することができる導電性ペーストを提供する
ことできる。As described above, according to the present invention, it is possible to provide a conductive paste which does not contain lead and which can form a conductive coating film having excellent wear resistance, acid resistance and alkali resistance.

【００１２】第２の発明は，低膨張ガラス基板の表面に
導電性被膜を形成してなる導電性被膜被覆ガラス基板で
あって，上記導電性被膜は，鉛を含有せず，導電性粉末
材料６０〜８０重量％と，ガラスフラックス２０〜４０
重量％と，上記導電性粉末材料及びガラスフラックス１
００重量％の合計重量に対して有機バインダー３０〜１
００重量％を含有してなる導電性ペーストを，上記低膨
張ガラス基板の表面に，焼き付けてなり，かつ，上記ガ
ラスフラックスは，ＳｉＯ2が５６〜６９重量％と，Ａ
ｌ2Ｏ3が０〜４重量％と，Ｂ2Ｏ3が２３〜３０重量％
と，Ｌｉ2Ｏが０．１〜３重量％と，Ｎａ2Ｏが１〜５重
量％と，Ｋ2Ｏが０〜４重量％と，ＴｉＯ2が０〜５重量
％と，及びＺｒＯ2が１〜５重量％とからなることを特
徴とする導電性被膜被覆ガラス基板にある（請求項
６）。A second aspect of the present invention is a conductive coating-coated glass substrate obtained by forming a conductive coating on the surface of a low expansion glass substrate, wherein the conductive coating does not contain lead and is a conductive powder material. 60-80% by weight and glass flux 20-40
% By weight, and the conductive powder material and glass flux 1
Organic binder 30-1 with respect to total weight of 00% by weight
A conductive paste containing 100% by weight is baked on the surface of the low expansion glass substrate, and the glass flux contains SiO 2 in an amount of 56 to 69% by weight,
0 to 4 wt% of l 2 O 3 and 23 to 30 wt% of B 2 O 3
Li 2 O 0.1 to 3% by weight, Na 2 O 1 to 5% by weight, K 2 O 0 to 4% by weight, TiO 2 0 to 5% by weight, and ZrO 2 Is contained in an amount of 1 to 5% by weight.

【００１３】本発明において最も注目すべきことは，上
記導電性被膜は，第１の発明（請求項１）の導電性ペー
ストを上記低膨張ガラス基板の表面に，焼き付けてなる
ことである。そのため，上記導電性被膜は，耐摩耗性，
耐酸性及び耐アルカリ性に優れている。また，鉛を含有
していない。このような性質を有する導電性被膜被覆を
表面に被覆してなる上記導電性被膜被覆ガラス基板は，
人体に対して安全であり，調理器等の用途として適して
いる。What is most noticeable in the present invention is that the conductive coating film is obtained by baking the conductive paste of the first invention (claim 1) on the surface of the low expansion glass substrate. Therefore, the conductive coating has wear resistance,
Excellent in acid resistance and alkali resistance. Moreover, it does not contain lead. The above-mentioned conductive film-coated glass substrate obtained by coating the surface with a conductive film coating having such properties is
It is safe for the human body and is suitable for applications such as cookers.

【００１４】第３の発明は，低膨張ガラス基板の表面に
導電性ペーストを印刷し，次いでこれを焼き付けするこ
とにより，導電性被膜を有する導電性被膜被覆ガラス基
板を製造する方法であって，上記導電性ペーストは，鉛
を含有せず，導電性粉末材料６０〜８０重量％と，ガラ
スフラックス２０〜４０重量％と，上記導電性粉末材料
及びガラスフラックスの合計重量１００重量％に対して
有機バインダー３０〜１００重量％を含有してなり，か
つ，上記ガラスフラックスは，ＳｉＯ2が５６〜６９重
量％と，Ａｌ2Ｏ3が０〜４重量％と，Ｂ2Ｏ3が２３〜３
０重量％と，Ｌｉ2Ｏが０．１〜３重量％と，Ｎａ2Ｏが
１〜５重量％と，Ｋ2Ｏが０〜４重量％と，ＴｉＯ2が０
〜５重量％と，及びＺｒＯ2が１〜５重量％とからなる
ことを特徴とする導電性被膜被覆ガラス基板の製造方法
にある（請求項１３）。A third invention is a method for producing a conductive film-coated glass substrate having a conductive film by printing a conductive paste on the surface of a low expansion glass substrate and then baking the paste. The conductive paste does not contain lead, and is 60 to 80% by weight of the conductive powder material, 20 to 40% by weight of the glass flux, and 100% by weight of the total weight of the conductive powder material and the glass flux. The binder contains 30 to 100% by weight, and the above glass flux contains 56 to 69% by weight of SiO 2 , 0 to 4% by weight of Al 2 O 3, and 23 to 3 of B 2 O 3 .
0% by weight, Li 2 O 0.1 to 3% by weight, Na 2 O 1 to 5% by weight, K 2 O 0 to 4% by weight, and TiO 2 0.
And 5% by weight, and ZrO 2 is in the method for producing a conductive film coated glass substrate characterized in that consisting of 1 to 5% by weight (claim 13).

【００１５】本発明は，第２の発明にかかる導電性被膜
被覆ガラス基板の製造方法に関する発明である。そのた
め，本発明によれば，鉛を含有せず，耐摩耗性，耐酸性
及び耐アルカリ性に優れた導電性被膜を有する導電性被
膜被覆ガラス基板の製造方法を提供することができる。The present invention is an invention relating to a method for manufacturing a glass substrate coated with a conductive film according to the second invention. Therefore, according to the present invention, it is possible to provide a method for producing a conductive film-coated glass substrate which does not contain lead and has a conductive film having excellent wear resistance, acid resistance and alkali resistance.

【００１６】[0016]

【発明の実施の形態】上記第１の発明（請求項１）にお
いて，上記導電性粉末材料が６０重量％未満の場合，ま
たは上記ガラスフラックスが４０重量％を超える場合に
は，充分な導電性を得ることができないおそれがある。
一方，上記導電性粉末材料が８０重量％を超える場合，
または上記ガラスフラックスが２０重量％未満の場合に
は，上記導電性被膜の表面が粗くなり，汚れ等が付着し
易くなると共に，耐酸性，耐アルカリ性及び耐摩耗性が
低下するおそれがある。なお，上記導電性粉末材料とガ
ラスフラックスとにより１００重量％を構成する。BEST MODE FOR CARRYING OUT THE INVENTION In the first invention (Claim 1), when the conductive powder material is less than 60% by weight or the glass flux exceeds 40% by weight, sufficient conductivity is obtained. May not be obtained.
On the other hand, when the conductive powder material exceeds 80% by weight,
Alternatively, if the glass flux is less than 20% by weight, the surface of the electroconductive coating becomes rough, stains and the like tend to adhere, and the acid resistance, alkali resistance and abrasion resistance may deteriorate. The conductive powder material and glass flux make up 100% by weight.

【００１７】また，上記ガラスフラックスの粒径は，５
μｍ以下であることが好ましい。５μｍを超える場合に
は，上記導電性被膜の表面が粗くなり，汚れ等が付着し
易くなると共に耐摩耗性が低下するおそれがある。な
お，その下限は，０．５μｍである。The particle size of the glass flux is 5
It is preferably μm or less. If it exceeds 5 μm, the surface of the above-mentioned conductive coating becomes rough, stains and the like are likely to adhere, and the abrasion resistance may decrease. The lower limit is 0.5 μm.

【００１８】また，上記有機バインダーは，上記導電性
粉末材料及びガラスフラックスの合計重量１００重量％
に対して，３０〜１００重量％含有する。上記有機バイ
ンダーが３０重量％未満の場合には，上記導電性ペース
トを所望の形状に焼き付けることが困難になるおそれが
ある。一方，１００重量％を超える場合には，充分な導
電性を得ることができないおそれがある。The organic binder is 100 wt% of the total weight of the conductive powder material and the glass flux.
In contrast, 30 to 100% by weight is contained. When the amount of the organic binder is less than 30% by weight, it may be difficult to bake the conductive paste into a desired shape. On the other hand, if it exceeds 100% by weight, sufficient conductivity may not be obtained.

【００１９】次に，上記ガラスフラックスの組成につい
て示す。 （ＳｉＯ2）上記ガラスフラックス中のＳｉＯ2の含有量
は，５６〜６９重量％である。５６重量％未満の場合に
は，熱膨張係数が高くなり，上記低膨張ガラス基板との
熱膨張差が大きくなり，クラックが発生したり，導電性
被膜が剥離するおそれがある。一方，６９重量％を超え
る場合には，上記ガラスフラックスの粘性流動が高くな
り，上記導電性被膜の表面が粗くなるため，汚れ等が付
着し易くなると共に耐摩耗性が低下するおそれがある。Next, the composition of the glass flux will be described. (SiO 2 ) The content of SiO 2 in the above glass flux is 56 to 69% by weight. If it is less than 56% by weight, the coefficient of thermal expansion becomes high, the difference in thermal expansion from the low expansion glass substrate becomes large, and cracks may occur or the conductive coating may peel off. On the other hand, if it exceeds 69% by weight, the viscous flow of the glass flux becomes high and the surface of the conductive coating becomes rough, so that dirt or the like is likely to adhere and abrasion resistance may decrease.

【００２０】（Ａｌ2Ｏ3）また，上記ガラスフラックス
中のＡｌ2Ｏ3の含有量は，０〜４重量％である。４重量
％を超える場合には，上記ガラスフラックスの粘性流動
が高くなり，上記導電性被膜の表面が粗くなるため，汚
れ等が付着し易くなると共に耐摩耗性が低下するおそれ
がある。(Al 2 O 3 ) The content of Al 2 O 3 in the glass flux is 0 to 4% by weight. If it exceeds 4% by weight, the viscous flow of the glass flux becomes high, and the surface of the conductive coating becomes rough, so that dirt or the like is likely to adhere and abrasion resistance may decrease.

【００２１】（Ｂ2Ｏ3）また，上記ガラスフラックス中
のＢ2Ｏ3の含有量は，２３〜３０重量％である。２３重
量％未満の場合には，耐酸性が悪くなるおそれがある。
一方３０重量％を超える場合には，耐アルカリ性が悪く
なるおそれがある。(B 2 O 3 ) The content of B 2 O 3 in the glass flux is 23 to 30% by weight. If it is less than 23% by weight, the acid resistance may deteriorate.
On the other hand, if it exceeds 30% by weight, the alkali resistance may deteriorate.

【００２２】（Ｌｉ2Ｏ）また，上記ガラスフラックス
中のＬｉ2Ｏの含有量は，０．１〜３重量％である。
０．１重量％未満の場合には，上記ガラスフラックスの
熱膨張係数が高くなり，クラック発生や剥離が起こるお
それがある。一方，３重量％を超える場合には，耐アル
カリ性が悪くなるおそれがある。(Li 2 O) The content of Li 2 O in the glass flux is 0.1 to 3% by weight.
If it is less than 0.1% by weight, the coefficient of thermal expansion of the above glass flux becomes high, and cracking or peeling may occur. On the other hand, if it exceeds 3% by weight, the alkali resistance may deteriorate.

【００２３】（Ｎａ2Ｏ）ガラスフラックス中のＮａ2Ｏ
の含有量は，１〜５重量％であり，Ｎａ2Ｏには，ガラ
スフラックスの粘性流動を下げる効果がある。１重量％
未満の場合には，ガラスフラックスの粘性流動が高くな
り，上記導電性被膜の表面が粗くなるため，汚れ等が付
着し易くなると共に耐摩耗性が低下するおそれがある。
一方，５重量％を超える場合には，ガラスフラックスの
熱膨張係数が著しく増加すると共に，耐アルカリ性が悪
くなるおそれがある。[0023] (Na 2 O) Na 2 O in the glass flux
Is 1 to 5% by weight, and Na 2 O has the effect of reducing the viscous flow of the glass flux. 1% by weight
If it is less than the above range, the viscous flow of the glass flux becomes high, and the surface of the above-mentioned conductive coating becomes rough, so that stains and the like are likely to adhere and abrasion resistance may decrease.
On the other hand, if it exceeds 5% by weight, the coefficient of thermal expansion of the glass flux may remarkably increase and the alkali resistance may deteriorate.

【００２４】（Ｋ2Ｏ）ガラスフラックス中のＫ2Ｏの含
有量は，０〜４重量％である。４重量％を超える場合に
は，ガラスの粘性流動が高くなり，上記導電性被膜の表
面が粗くなるため，汚れ等が付着し易くなると共に耐摩
耗性が低下するおそれがある。また，熱膨張係数が著し
く増加するおそれがある。The content of K 2 O in the (K 2 O) glass flux is 0 to 4% by weight. If it exceeds 4% by weight, the viscous flow of the glass becomes high and the surface of the conductive coating becomes rough, so that dirt and the like are likely to adhere and the abrasion resistance may decrease. In addition, the coefficient of thermal expansion may increase significantly.

【００２５】（ＴｉＯ2）ガラスフラックス中のＴｉＯ2
の含有量は，０〜５重量％である。５重量％を超える場
合には，ガラスの粘性流動が高くなり，上記導電性被膜
の表面が粗くなる。そのため，汚れ等が付着し易くなる
と共に耐摩耗性が低下するおそれがある。[0025] (TiO 2) TiO 2 in the glass flux
The content of is 0 to 5% by weight. If it exceeds 5% by weight, the viscous flow of glass becomes high and the surface of the conductive coating becomes rough. As a result, dirt or the like is likely to be attached and wear resistance may be reduced.

【００２６】（ＺｒＯ2）ガラスフラックス中のＺｒＯ2
の含有量は，１〜５重量％であり，ＺｒＯ2には，耐酸
性及び耐アルカリ性を向上させる効果がある。１重量％
未満の場合には，耐酸性が悪くなるおそれがある。一
方，５重量％を超える場合には，ガラスフラックスの粘
性流動が高くなり，上記導電性被膜の表面が粗くなる。
そのため，汚れ等が付着し易くなると共に耐摩耗性が低
下するおそれがある。[0026] (ZrO 2) ZrO 2 in the glass flux
The content of ZrO 2 is 1 to 5% by weight, and ZrO 2 has an effect of improving acid resistance and alkali resistance. 1% by weight
If it is less than 1, the acid resistance may deteriorate. On the other hand, if it exceeds 5% by weight, the viscous flow of the glass flux becomes high and the surface of the conductive coating becomes rough.
As a result, dirt or the like is likely to be attached and wear resistance may be reduced.

【００２７】次に，上記導電性粉末材料は，貴金属又は
／及び貴金属酸化物からなることが好ましい（請求項
２）。この場合には，シート抵抗の値が１ｋΩ／□以下
という低い値を示し，導電性に優れた導電性被膜を形成
することができる。上記貴金属としては，Ａｕ，Ａｇ，
Ｐｔ，Ｐｄ等を用いることができる。また，貴金属酸化
物としては，Ｒｕ，Ｉｒ，Ｒｈ等の貴金属の酸化物を用
いることができる。Next, the conductive powder material is preferably made of a noble metal and / or a noble metal oxide (claim 2). In this case, the sheet resistance value is as low as 1 kΩ / □ or less, and a conductive coating film having excellent conductivity can be formed. The precious metals include Au, Ag,
Pt, Pd, etc. can be used. Further, as the noble metal oxide, an oxide of a noble metal such as Ru, Ir, Rh can be used.

【００２８】さらに，上記導電性粉末材料の粒径は，１
μｍ以下であることが好ましい。粒径が１μｍを超える
場合には，上記導電性被膜の表面が粗くなり，導電性被
膜に汚れ等が付着し易くなるおそれがある。Further, the particle size of the above conductive powder material is 1
It is preferably μm or less. If the particle size exceeds 1 μm, the surface of the conductive coating may become rough and dirt or the like may easily adhere to the conductive coating.

【００２９】次に，上記有機バインダーは，アクリル樹
脂，アルキッド樹脂，ブチル樹脂から選ばれる一種以上
であることが好ましい（請求項３）。この場合には，上
記導電性ペーストの粘度調整が容易になるため，導電性
ペーストの成膜性を向上させることができる。Next, the organic binder is preferably one or more selected from acrylic resin, alkyd resin and butyl resin (claim 3). In this case, since the viscosity of the conductive paste can be easily adjusted, the film forming property of the conductive paste can be improved.

【００３０】次に，上記導電性ペーストは，着色顔料を
含有することが好ましい（請求項４）。この場合には，
上記導電性被膜に所望の着色を施し，導電性被膜の意匠
性を向上させることができる。Next, the conductive paste preferably contains a coloring pigment (claim 4). In this case,
The conductive coating can be colored as desired to improve the design of the conductive coating.

【００３１】上記着色顔料は，色の種類によって，下記
のようにその材料を変える。例えば，黒（Ｃｒ−Ｆｅ，
Ｃｏ−Ｍｎ−Ｃｒ−Ｆｅ，Ｃｏ−Ｎｉ−Ｃｒ−Ｆｅ，Ｃ
ｏ−Ｎｉ−Ｃｒ−Ｆｅ−Ｍｎ等），グレー（Ｓｎ−Ｓ
ｂ，Ｓｎ−Ｓｂ−Ｖ等），黄（Ｓｎ−Ｖ，Ｚｒ−Ｖ，Ｚ
ｒ−Ｓｉ−Ｐｒ，Ｔｉ−Ｃｒ−Ｓｂ，Ｚｒ−Ｓｉ−Ｃｄ
−Ｓ，ＣｄＳ等），茶（Ｚｎ−Ａｌ−Ｃｒ−Ｆｅ，Ｚｎ
−Ｍｎ−Ａｌ−Ｃｒ−Ｆｅ等），緑（Ｃａ−Ｃｒ−Ｓ
ｉ，Ｃｒ−Ａｌ，Ｃｏ−Ｚｎ−Ａｌ−Ｃｒ，Ｚｒ−Ｓｉ
−Ｐｒ−Ｖ等），青（Ｃｏ−Ａｌ−Ｚｎ，Ｃｏ−Ａｌ，
Ｃｏ−Ｓｉ，Ｚｒ−Ｓｉ−Ｖ等），ピンク（Ｍｎ−Ａ
ｌ，Ｃａ−Ｓｎ−Ｓｉ−Ｃｒ，Ｓｎ−Ｃｒ，Ｚｒ−Ｓｉ
−Ｆｅ等），赤（Ｚｒ−Ｓｉ−Ｃｄ−Ｓｅ−Ｓ，Ｃｄ−
Ｓｅ−Ｓ等）がある。これらは所望の色を得るように任
意の割合で混合することができる。The material of the above color pigment is changed as follows depending on the kind of color. For example, black (Cr-Fe,
Co-Mn-Cr-Fe, Co-Ni-Cr-Fe, C
o-Ni-Cr-Fe-Mn), gray (Sn-S)
b, Sn-Sb-V, etc.), yellow (Sn-V, Zr-V, Z
r-Si-Pr, Ti-Cr-Sb, Zr-Si-Cd
-S, CdS, etc.), brown (Zn-Al-Cr-Fe, Zn
-Mn-Al-Cr-Fe, etc.), green (Ca-Cr-S
i, Cr-Al, Co-Zn-Al-Cr, Zr-Si
-Pr-V, etc.), blue (Co-Al-Zn, Co-Al,
Co-Si, Zr-Si-V, etc.), pink (Mn-A)
1, Ca-Sn-Si-Cr, Sn-Cr, Zr-Si
-Fe, etc.), red (Zr-Si-Cd-Se-S, Cd-
Se-S). These can be mixed in any proportion to obtain the desired color.

【００３２】次に，上記着色顔料の含有量は，上記導電
性粉末材料及びガラスフラックスの合計１００重量％に
対して，１重量％〜２５重量％であることが好ましい
（請求項５）。上記着色顔料の含有量が１重量％未満の
場合には，上記導電性被膜が充分に着色されないおそれ
がある。一方，２５重量％を超える場合には，上記導電
性被膜の導電性が低下するおそれがある。また，上記導
電性被膜の表面が粗くなり汚れが付着し易くなるおそれ
がある。Next, the content of the color pigment is preferably 1% by weight to 25% by weight based on 100% by weight of the total amount of the conductive powder material and the glass flux (claim 5). If the content of the coloring pigment is less than 1% by weight, the conductive coating may not be sufficiently colored. On the other hand, if it exceeds 25% by weight, the electroconductivity of the electroconductive coating may decrease. In addition, the surface of the conductive coating may become rough and dirt may be easily attached.

【００３３】次に，上記第２の発明（請求項６）におい
て，上記導電性ペーストは，第１の発明の導電性ペース
トであり，導電性粉末材料６０〜８０重量％，ガラスフ
ラックス２０〜４０重量％，有機バインダー３０〜１０
０重量％，更にはガラスフラックスを構成する成分の臨
界意義等は，上記の第１の発明と同じである。Next, in the second invention (claim 6), the conductive paste is the conductive paste of the first invention, and the conductive powder material is 60 to 80% by weight and the glass flux is 20 to 40. % By weight, organic binder 30 to 10
0% by weight, and further, the significance of the constituents of the glass flux is the same as that of the first invention.

【００３４】また，上記低膨張ガラス基板としては，例
えば低膨張結晶化ガラス，石英ガラス等がある。上記低
膨張ガラス基板の熱膨張係数は，−７×１０-7／Ｋ〜６
０×１０-7／Ｋであることが好ましい。−７×１０-7／
Ｋ未満の場合には，上記導電性被膜との熱膨張差が大き
くなり，導電性被膜が低膨張ガラス基板から剥離するお
それがある。一方，６０×１０ -7／Ｋを超える場合に
は，熱衝撃により破壊するおそれがある。Examples of the low expansion glass substrate are as follows.
Examples include low expansion crystallized glass and quartz glass. Above low
The coefficient of thermal expansion of the expanded glass substrate is -7 x 10-7/ K ~ 6
0x10-7/ K is preferable. -7 x 10-7/
If it is less than K, the difference in thermal expansion from the conductive coating is large.
And the conductive coating may peel off from the low expansion glass substrate.
It has On the other hand, 60 × 10 -7When / K is exceeded
May be destroyed by thermal shock.

【００３５】また，上記低膨張ガラス基板は，該低膨張
ガラス基板の裏面又は低膨張ガラス基板自体に着色が施
されていてもよい。さらに，上記低膨張ガラス基板に
は，上記導電性被膜とは別に模様等の絵付けが施されて
いてもよい。この場合には，上記導電性被膜被覆ガラス
基板の意匠性が向上する。The low expansion glass substrate may be colored on the back surface of the low expansion glass substrate or on the low expansion glass substrate itself. Further, the low expansion glass substrate may be provided with a pattern or the like in addition to the conductive coating. In this case, the design of the glass substrate coated with the conductive film is improved.

【００３６】また，上記導電性被膜被覆ガラス基板にお
いて，上記導電性被膜は，４探針法（ＪＩＳＫ７１９
４）によるシート抵抗の値が１ｋΩ／□以下であること
が好ましい。１ｋΩ／□を超える場合には，シート抵抗
が高くなるため導電性が低下し，所望の性質を得ること
ができないおそれがある。Further, in the above-mentioned conductive coating-coated glass substrate, the conductive coating is formed by the 4-probe method (JISK719).
The sheet resistance value according to 4) is preferably 1 kΩ / □ or less. If it exceeds 1 kΩ / □, the sheet resistance becomes high and the conductivity is lowered, so that the desired properties may not be obtained.

【００３７】また，上記導電性粉末材料は，貴金属又は
／及び貴金属酸化物からなることが好ましい（請求項
７）。この場合には，上記請求項２の発明と同様な作用
効果を得ることができる。The conductive powder material is preferably made of a noble metal and / or a noble metal oxide (claim 7). In this case, it is possible to obtain the same operational effect as that of the invention of claim 2 above.

【００３８】さらに，上記導電性粉末材料の粒径は，１
μｍ以下であることが好ましい。粒径が１μｍを超える
場合には，上記導電性被膜の表面が粗くなり，汚れ等が
付着し易くなる。Further, the particle size of the conductive powder material is 1
It is preferably μm or less. If the particle size exceeds 1 μm, the surface of the conductive coating becomes rough and stains and the like tend to adhere.

【００３９】次に，上記有機バインダーは，アクリル樹
脂，アルキッド樹脂，ブチル樹脂から選ばれる一種以上
であることが好ましい（請求項８）。この場合には，上
記請求項３の発明と同様の作用効果を得ることができ
る。Next, the organic binder is preferably one or more selected from acrylic resins, alkyd resins and butyl resins (claim 8). In this case, it is possible to obtain the same operational effect as the invention of claim 3 above.

【００４０】次に，上記導電性ペーストは，着色顔料を
含有することが好ましい（請求項９）。この場合には，
上記請求項４の発明と同様の作用効果を得ることができ
る。また，上記着色顔料は，上記請求項４の発明と同様
である。Next, it is preferable that the conductive paste contains a coloring pigment (claim 9). In this case,
It is possible to obtain the same effect as that of the invention of claim 4. The color pigment is the same as that of the invention of claim 4.

【００４１】次に，上記着色顔料の含有量は，上記導電
性粉末材料及びガラスフラックスの合計１００重量％に
対して，１重量％〜２５重量％であることが好ましい
（請求項１０）。上記含有量の臨界意義については，請
求項５の発明と同様である。Next, the content of the color pigment is preferably 1% by weight to 25% by weight based on 100% by weight of the total amount of the conductive powder material and the glass flux (claim 10). The significance of the content is the same as that of the invention of claim 5.

【００４２】次に，上記導電性被膜の厚みは，５μｍ〜
１０μｍであることが好ましい（請求項１１）。上記厚
みが５μｍ未満の場合には，充分な導電性が得られない
おそれがあると共に，摩耗による剥離が起こりやすくな
るおそれがある。一方，１０μｍを超える場合には，上
記導電性被膜が上記低膨張ガラス基板から剥離し易くな
るおそれがある。Next, the thickness of the conductive coating is 5 μm to
It is preferably 10 μm (claim 11). If the thickness is less than 5 μm, sufficient conductivity may not be obtained, and peeling due to abrasion may be likely to occur. On the other hand, when it exceeds 10 μm, the conductive coating may be easily peeled from the low expansion glass substrate.

【００４３】次に，上記導電性被膜は導電性表示部であ
り，上記導電性被膜被覆ガラス基板は，調理器用トップ
プレートであることが好ましい（請求項１２）。この場
合には，上記導電性被膜被覆ガラス基板を，導電性表示
部を有する調理器用トッププレートとして利用すること
ができる。上記導電性表示部とは，例えばタッチパネル
のように指で触れることにより機器を動作させるスイッ
チ等をいう。Next, it is preferable that the conductive coating is a conductive display portion, and the conductive coating-coated glass substrate is a top plate for a cooker (claim 12). In this case, the conductive film-covered glass substrate can be used as a cooker top plate having a conductive display portion. The conductive display unit refers to, for example, a switch that operates a device by touching it with a finger like a touch panel.

【００４４】次に，上記第３の発明（請求項１３）にお
いて，上記導電性ペーストの印刷方法としては，例えば
スクリーン印刷法，ロールコート印刷等がある。また，
上記低膨張ガラス基板への上記導電性ペーストの焼き付
けは，成形し，焼成した低膨張ガラス基板，又は焼成前
の低膨張ガラス基板即ちグリーンシートに対して行うこ
とができる。Next, in the third invention (claim 13), the method for printing the conductive paste includes, for example, a screen printing method and a roll coat printing method. Also,
The baking of the conductive paste on the low-expansion glass substrate can be performed on the low-expansion glass substrate that has been molded and fired, or the low-expansion glass substrate before firing, that is, the green sheet.

【００４５】上記グリーンシートに対して焼き付けを行
う場合には，該グリーンシートの表面に上記導電性ペー
ストを所望の形状に印刷し，加熱することによってグリ
ーンシートの焼成と導電性ペーストの焼き付けを同時に
行うことができる。When the green sheet is baked, the conductive paste is printed on the surface of the green sheet in a desired shape and heated to simultaneously bake the green sheet and bake the conductive paste. It can be carried out.

【００４６】次に，上記焼き付けの加熱温度は，７６０
〜９００℃であることが好ましい（請求項１４）。上記
焼き付け温度が７６０℃未満の場合には，上記焼き付け
が充分に行われず，上記導電性被膜が上記低膨張ガラス
基板から剥離し易くなるおそれがある。一方，９００℃
を超える場合には，焼き付け時に上記導電性ペーストが
溶融し，所望の形状の導電性被膜が得られないおそれが
ある。尚，上記焼き付けを行う時間は３０分以内である
ことが好ましい。Next, the heating temperature for the above baking is 760
The temperature is preferably 900 ° C (claim 14). When the baking temperature is lower than 760 ° C., the baking is not sufficiently performed, and the conductive coating may be easily peeled from the low expansion glass substrate. On the other hand, 900 ° C
If it exceeds, the conductive paste may be melted during baking, and a conductive coating having a desired shape may not be obtained. The baking time is preferably 30 minutes or less.

【００４７】[0047]

【実施例】以下に，本発明の実施例について説明する。
本例においては，低膨張ガラス基板の表面に焼き付け，
導電性被膜を形成するための導電性ペースト，及び導電
性被膜被覆ガラス基板を作製する。EXAMPLES Examples of the present invention will be described below.
In this example, baking on the surface of the low expansion glass substrate,
A conductive paste for forming a conductive coating and a glass substrate coated with a conductive coating are prepared.

【００４８】本例の導電性ペーストは，鉛を含有せず，
導電性粉末材料６０〜８０重量％と，ガラスフラックス
２０〜４０重量％と，上記導電性粉末材料及びガラスフ
ラックスの合計重量１００重量％に対して有機バインダ
ー３０〜１００重量％を含有してなる。さらに，上記ガ
ラスフラックスは，ＳｉＯ2が５６〜６９重量％と，Ａ
ｌ2Ｏ3が０〜４重量％と，Ｂ2Ｏ3が２３〜３０重量％
と，Ｌｉ2Ｏが０．１〜３重量％と，Ｎａ2Ｏが１〜５重
量％と，Ｋ2Ｏが０〜４重量％と，ＴｉＯ2が０〜５重量
％と，及びＺｒＯ2が１〜５重量％とからなる。The conductive paste of this example does not contain lead,
It contains 60 to 80% by weight of conductive powder material, 20 to 40% by weight of glass flux, and 30 to 100% by weight of organic binder with respect to 100% by weight of the total weight of the conductive powder material and glass flux. Further, the above glass flux contains 56 to 69% by weight of SiO 2 , and A
0 to 4 wt% of l 2 O 3 and 23 to 30 wt% of B 2 O 3
Li 2 O 0.1 to 3% by weight, Na 2 O 1 to 5% by weight, K 2 O 0 to 4% by weight, TiO 2 0 to 5% by weight, and ZrO 2 Is 1 to 5% by weight.

【００４９】また，本例の導電性被膜被覆ガラス基板
は，低膨張ガラス基板の表面に導電性被膜を有する。上
記導電性被膜は，上記導電性ペーストを低膨張ガラス基
板の表面に焼き付けてなる。以下，導電性ペースト，導
電性被膜被覆ガラス基板及びその製造方法につき説明す
る。The electrically conductive film-coated glass substrate of this example has an electrically conductive film on the surface of the low expansion glass substrate. The conductive coating is formed by baking the conductive paste on the surface of the low expansion glass substrate. Hereinafter, the conductive paste, the conductive coating-coated glass substrate, and the manufacturing method thereof will be described.

【００５０】（実施例１）まず，導電性粉末材料として
銀を含有した，表１に示す組成の導電性ペーストを調整
した。この導電性ペーストを低膨張ガラス基板の表面
に，３５０メッシュのスクリーンを用いて，膜厚が５〜
１０μｍとなるようにスクリーン印刷法により印刷し
た。次いで，これらを加熱炉に入れて，８００℃に２０
分間加熱して，導電性ペーストを焼き付けた。これによ
り導電性被膜被覆ガラス基板を得た。これを試料Ｅ１と
した。なお，上記低膨張ガラス基板は，常温における熱
膨張係数が−５×１０-7／Ｋのものを用いた。Example 1 First, a conductive paste containing silver as a conductive powder material and having a composition shown in Table 1 was prepared. This conductive paste is applied to the surface of the low expansion glass substrate with a screen of 350 mesh to obtain a film thickness of 5 to 5.
It was printed by a screen printing method so as to have a thickness of 10 μm. Then, put them in a heating furnace and bring them to 800 ° C for 20
The conductive paste was baked by heating for a minute. Thus, a glass substrate coated with a conductive film was obtained. This was designated as sample E1. The low-expansion glass substrate used had a coefficient of thermal expansion of −5 × 10 −7 / K at room temperature.

【００５１】（実施例２）実施例１と同様に，導電性粉
末材料として銀を含有した，表１に示す組成の導電性ペ
ーストを調整した。この導電性ペーストを実施例１の上
記低膨張ガラス基板の表面に，２５０メッシュのスクリ
ーンを用いて，膜厚が５〜１０μｍとなるようにスクリ
ーン印刷法により印刷した。次いで，これらを加熱炉に
入れて，８００℃に３０分間加熱して，導電性ペースト
を焼き付けた。これにより導電性被膜被覆ガラス基板を
得た。これを試料Ｅ２とした。(Example 2) As in Example 1, a conductive paste containing silver as a conductive powder material and having a composition shown in Table 1 was prepared. This conductive paste was printed on the surface of the low expansion glass substrate of Example 1 by a screen printing method using a 250 mesh screen so that the film thickness was 5 to 10 μm. Then, these were put in a heating furnace and heated at 800 ° C. for 30 minutes to burn the conductive paste. Thus, a glass substrate coated with a conductive film was obtained. This was designated as sample E2.

【００５２】（実施例３）実施例１と同様に，導電性粉
末材料として銀を含有した，表１に示す組成の導電性ペ
ーストを調整した。この導電性ペーストを実施例１の上
記低膨張ガラス基板の表面に，３５０メッシュのスクリ
ーンを用いて，膜厚が５〜１０μｍとなるようにスクリ
ーン印刷法により印刷した。次いで，これらを加熱炉に
入れて，８００℃に１５分間加熱して，導電性ペースト
を焼き付けた。これにより導電性被膜被覆ガラス基板を
得た。これを試料Ｅ３とした。(Example 3) In the same manner as in Example 1, a conductive paste containing silver as a conductive powder material and having a composition shown in Table 1 was prepared. This conductive paste was printed on the surface of the low expansion glass substrate of Example 1 by a screen printing method using a 350 mesh screen so that the film thickness was 5 to 10 μm. Then, these were put in a heating furnace and heated at 800 ° C. for 15 minutes to burn the conductive paste. Thus, a glass substrate coated with a conductive film was obtained. This was designated as sample E3.

【００５３】（実施例４）実施例１と同様に，導電性粉
末材料として銀を含有した，表１に示す組成の導電性ペ
ーストを調整した。この導電性ペーストを実施例１の上
記低膨張ガラス基板の表面に３００メッシュのスクリー
ンを用いて，膜厚が５〜１０μｍとなるようにスクリー
ン印刷法により印刷した。次いで，これらを加熱炉に入
れて８２０℃に２５分間加熱して，導電性ペーストを焼
き付けた。これにより導電性被膜被覆ガラス基板を得
た。これを試料Ｅ４とした。(Example 4) As in Example 1, a conductive paste containing silver as a conductive powder material and having a composition shown in Table 1 was prepared. This conductive paste was printed on the surface of the low expansion glass substrate of Example 1 by a screen printing method using a 300 mesh screen so that the film thickness was 5 to 10 μm. Then, these were placed in a heating furnace and heated to 820 ° C. for 25 minutes to burn the conductive paste. Thus, a glass substrate coated with a conductive film was obtained. This was designated as sample E4.

【００５４】（実施例５）実施例１と同様に，導電性粉
末材料として銀を含有した，表１に示す組成の導電性ペ
ーストを調整した。この導電性ペーストを実施例１の上
記低膨張ガラス基板の表面に２５０メッシュのスクリー
ンを用いて，膜厚が５〜１０μｍとなるようにスクリー
ン印刷法により印刷した。次いで，これらを加熱炉に入
れて７９０℃に３０分間加熱して，導電性ペーストを焼
き付けた。これにより導電性被膜被覆ガラス基板を得
た。これを試料Ｅ５とした。Example 5 As in Example 1, a conductive paste containing silver as a conductive powder material and having a composition shown in Table 1 was prepared. This conductive paste was printed on the surface of the low expansion glass substrate of Example 1 by a screen printing method using a 250 mesh screen so that the film thickness was 5 to 10 μm. Then, these were placed in a heating furnace and heated to 790 ° C. for 30 minutes to burn the conductive paste. Thus, a glass substrate coated with a conductive film was obtained. This was designated as sample E5.

【００５５】[0055]

【表１】 [Table 1]

【００５６】（比較例１）次に，市販の陶磁器用無鉛金
ぺーストを実施例１〜実施例５と同様の低膨張結晶化ガ
ラスの表面に，３５０メッシュのスクリーンを用いて，
膜厚が５〜１０μｍとなるようにスクリーン印刷法によ
り印刷した。次いで，これらを加熱炉に入れて，７８０
℃に２０分間加熱して，導電性ペーストを焼き付けた。
これにより導電性被膜被覆ガラス基板を得た。これを試
料Ｃ１とした。Comparative Example 1 Next, a commercially available lead-free gold paste for ceramics was placed on the surface of the low expansion crystallized glass similar to that in Examples 1 to 5 using a 350 mesh screen,
Printing was performed by a screen printing method so that the film thickness was 5 to 10 μm. Then, put them in a heating furnace and
The conductive paste was baked by heating at 0 ° C. for 20 minutes.
Thus, a glass substrate coated with a conductive film was obtained. This was designated as sample C1.

【００５７】（比較例２）次に，市販の半導体用無鉛銀
ペーストを実施例１〜実施例５と同様の低膨張結晶化ガ
ラスの表面に，３５０メッシュのスクリーンを用いて，
膜厚が５〜１０μｍとなるようにスクリーン印刷法によ
り印刷した。次いで，これらを加熱炉に入れて，８１０
℃に３０分間加熱して，導電性ペーストを焼き付けた。
これにより導電性被膜被覆ガラス基板を得た。これを試
料Ｃ２とした。(Comparative Example 2) Next, a commercially available lead-free silver paste for semiconductors was applied on the surface of the low expansion crystallized glass as in Examples 1 to 5 using a 350 mesh screen,
Printing was performed by a screen printing method so that the film thickness was 5 to 10 μm. Then, put them in a heating furnace and
The conductive paste was baked by heating at 30 ° C. for 30 minutes.
Thus, a glass substrate coated with a conductive film was obtained. This was designated as sample C2.

【００５８】（比較例３）次に，市販の半導体用有鉛銀
ペーストを実施例１〜実施例５と同様の低膨張結晶化ガ
ラスの表面に，３５０メッシュのスクリーンを用いて，
膜厚が５〜１０μｍとなるようにスクリーン印刷法によ
り印刷した。次いで，これらを加熱炉に入れて，８００
℃に１０分間加熱して，導電性ペーストを焼き付けた。
これにより導電性被膜被覆ガラス基板を得た。これを試
料Ｃ３とした。(Comparative Example 3) Next, a commercially available lead-containing silver paste for semiconductors was applied to the surface of the low expansion crystallized glass similar to that in Examples 1 to 5 using a 350 mesh screen,
Printing was performed by a screen printing method so that the film thickness was 5 to 10 μm. Then, put these in a heating furnace and
The conductive paste was baked by heating at 0 ° C. for 10 minutes.
Thus, a glass substrate coated with a conductive film was obtained. This was designated as Sample C3.

【００５９】（実験例）上記試料Ｅ１〜Ｅ５，及び試料
Ｃ１〜Ｃ３について，以下の物性を測定した。その結果
を表２に示す。(Experimental Example) The following physical properties of the above samples E1 to E5 and samples C1 to C3 were measured. The results are shown in Table 2.

【００６０】[0060]

【表２】 [Table 2]

【００６１】（テープ剥離試験）市販のセロハン粘着テ
ープを導電性被膜の表面に貼り付け，爪等で強くこすり
つけた後，勢いよく剥がした。このとき，導電性被膜が
剥離しなかった場合を○，剥離した場合を×と判定し
た。(Tape Peeling Test) A commercially available cellophane adhesive tape was attached to the surface of the conductive film, strongly rubbed with a nail or the like, and then vigorously peeled off. At this time, when the conductive coating was not peeled off, it was judged as ◯, and when peeled off, it was judged as x.

【００６２】（耐酸試験）市販の酸性飲料水（レモン水
ｐＨ２〜３）に２４時間常温で浸し，表面の変化を目
視にて観察した。表面の変化がなかった場合を○，表面
が変化した場合を×と判定した。(Acid resistance test) A commercially available acidic drinking water (lemon water pH 2 to 3) was soaked at room temperature for 24 hours, and the surface change was visually observed. When there was no change in the surface, it was judged as ◯, and when the surface changed, it was judged as x.

【００６３】（耐アルカリ試験）市販のアルカリ性洗剤
（キッチン用油汚れ洗浄剤原液 ｐＨ９〜１２）に２４
時間常温で浸し，表面の変化を目視にて観察した。表面
の変化がなかった場合を○，表面が変化した場合を×と
判定した。(Alkali resistance test) A commercially available alkaline detergent (kitchen oil stain cleaner stock solution pH 9 to 12)
After immersing at room temperature for a period of time, the surface change was visually observed. When there was no change in the surface, it was judged as ◯, and when the surface changed, it was judged as x.

【００６４】（鉛溶出試験）食品衛生法の試験方法で行
い，鉛の溶出が検出されなかったものを○，少量でも鉛
の溶出が検出されたものを×と判定した。(Lead Elution Test) The test method of the Food Sanitation Law was carried out. When the lead elution was not detected, it was judged as ○, and when the lead elution was detected even in a small amount, it was judged as ×.

【００６５】（表面粗さ（Ｒａ）測定試験）表面粗さ計
（株式会社小坂研究所製，商品名 ＳＥ−３Ｃ）にて，
ＪＩＳ Ｂ０６０１に基づき，表面粗さのＲａ（μｍ）
を測定した。(Surface Roughness (Ra) Measurement Test) With a surface roughness meter (manufactured by Kosaka Laboratory Ltd., trade name SE-3C),
Ra (μm) of surface roughness based on JIS B0601
Was measured.

【００６６】（シート抵抗測定試験）四探針法による抵
抗測定器（三菱化学株式会社製，商品名 ロレスタＧ
Ｐ）にて，ＪＩＳ Ｋ７１９４に基づき，シート抵抗
（Ω／□）を測定した。(Sheet resistance measurement test) Resistance measuring device by four-point probe method (trade name: Loresta G, manufactured by Mitsubishi Chemical Corporation)
In P), sheet resistance (Ω / □) was measured based on JIS K7194.

【００６７】（耐摩耗試験）上記シート抵抗測定試験を
行った後の各試料の表面をＰＥＩ試験器（ＫＥＹＳＴＯ
ＮＥ ＥＬＥＣＴＲＩＣ ＣＯ，ＩＮＣ．製 商品名 Ｐ
ＥＩ ＡＢＲＡＳＩＯＮ）を用いてＡＳＴＭ Ｃ４４８に
基づき摩耗させ，摩耗後，各試料の表面のシート抵抗を
上記シート抵抗測定試験と同様にして測定した。(Abrasion resistance test) The surface of each sample after the above sheet resistance measurement test was carried out by a PEI tester (KEYSTO).
NE ELECTRIC CO, INC. Product name P
EI ABRASION) was used for abrasion based on ASTM C448, and after abrasion, the sheet resistance of the surface of each sample was measured in the same manner as the sheet resistance measurement test.

【００６８】（外観判定試験）各試料の導電性被膜の色
を目視により観察した。(Appearance judgment test) The color of the conductive coating film of each sample was visually observed.

【００６９】表２より知られるごとく，本例の試料Ｅ１
〜Ｅ５は，テープ剥離試験，耐酸性試験及び耐アルカリ
試験において，導電性被膜の変化は観察されず，これら
の性質に優れていた。また，鉛溶出試験においても鉛は
検出されず，安全性が確認された。As known from Table 2, sample E1 of this example
In the tape peeling test, the acid resistance test, and the alkali resistance test, no changes in the conductive coating were observed, and E5 to E5 were excellent in these properties. In addition, lead was not detected in the lead elution test, and safety was confirmed.

【００７０】また，表面粗さ（Ｒａ）は，いずれも１．
３μｍ以下という低い値を示した。さらに，シート抵抗
は，いずれも１Ω／□以下という低い値を示し，本例の
試料Ｅ１〜Ｅ５は充分な導電性を有していた。The surface roughness (Ra) is 1.
The value was as low as 3 μm or less. Further, the sheet resistances were all low values of 1 Ω / □ or less, and the samples E1 to E5 of this example had sufficient conductivity.

【００７１】また，上記耐摩耗試験においては，３００
０回後の摩耗後においても各試料Ｅ１〜Ｅ５のシート抵
抗にほとんど変化はなかった。さらに，外観上において
も剥離等の変化は生じておらず，優れた耐摩耗性を有し
ていた。また，本例の試料Ｅ２，Ｅ３の導電性被膜は，
それぞれ黒銀色，白銀色に呈色しており，意匠性に優れ
ていた。In the above abrasion resistance test, 300
The sheet resistances of the respective samples E1 to E5 were hardly changed even after wear after 0 times. In addition, there was no change in appearance such as peeling, and it had excellent wear resistance. In addition, the conductive coatings of Samples E2 and E3 of this example are
They were colored in black silver and white silver, respectively, and were excellent in design.

【００７２】一方，試料Ｃ１は，上記テープ剥離試験に
おいて，導電性被膜に剥離が観察され，試料Ｃ２は，耐
酸性試験及び耐アルカリ性試験において，導電性被膜に
変形，変色，剥離等が観察された。試料Ｃ３は耐酸性の
特性が弱く，鉛溶出試験においても鉛が検出され，人体
への安全性において問題があった。On the other hand, sample C1 was observed to have peeling on the conductive coating in the tape peeling test, and sample C2 was observed to be deformed, discolored, and peeling on the conductive coating in the acid resistance test and alkali resistance test. It was Sample C3 had a weak acid resistance property, and lead was detected in the lead elution test, and there was a problem in safety to the human body.

【００７３】さらに，上記試料Ｃ１〜Ｃ３のシート抵抗
は，実施例Ｅ１〜Ｅ５と同様に１Ω／□以下という低い
値を示したが，摩耗試験３０００回後のシート抵抗は，
いずれも１００００Ω／□以上という非常に高い値を示
した。即ち，上記試料Ｃ１〜Ｃ３導電性被膜は，摩耗に
より導電性が著しく低下し，耐摩耗性に欠陥があること
がわかる。Further, the sheet resistance of the samples C1 to C3 showed a low value of 1 Ω / □ or less as in the case of Examples E1 to E5, but the sheet resistance after 3000 abrasion tests was
All showed extremely high values of 10,000 Ω / □ or more. That is, it can be seen that the conductive coatings of the above-mentioned samples C1 to C3 have a marked decrease in conductivity due to wear and have a defect in wear resistance.

───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G062 AA08 AA09 BB05 DA06 DB01 DB02 DB03 DC04 DD01 DE01 DF01 EA03 EB03 EC01 EC02 EC03 ED01 EE01 EF01 EG01 FA01 FB01 FB02 FB03 FC03 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM07 MM12 MM27 NN32 PP01 PP12 PP14 PP15 5G301 DA02 DA23 DA34 DA36 DA38 DA39 5G307 GA08 GC02    ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4G062 AA08 AA09 BB05 DA06 DB01                       DB02 DB03 DC04 DD01 DE01                       DF01 EA03 EB03 EC01 EC02                       EC03 ED01 EE01 EF01 EG01                       FA01 FB01 FB02 FB03 FC03                       FD01 FE01 FF01 FG01 FH01                       FJ01 FK01 FL01 GA01 GA10                       GB01 GC01 GD01 GE01 HH01                       HH03 HH05 HH07 HH09 HH11                       HH13 HH15 HH17 HH20 JJ01                       JJ03 JJ05 JJ07 JJ10 KK01                       KK03 KK05 KK07 KK10 MM07                       MM12 MM27 NN32 PP01 PP12                       PP14 PP15                 5G301 DA02 DA23 DA34 DA36 DA38                       DA39                 5G307 GA08 GC02

Claims (14)

【特許請求の範囲】[Claims] 【請求項１】 低膨張ガラス基板の表面に焼き付け，導
電性被膜を形成するための導電性ペーストであって，上
記導電性ペーストは，鉛を含有せず，導電性粉末材料６
０〜８０重量％と，ガラスフラックス２０〜４０重量％
と，上記導電性粉末材料及びガラスフラックスの合計重
量１００重量％に対して有機バインダー３０〜１００重
量％を含有してなり，かつ，上記ガラスフラックスは，
ＳｉＯ2が５６〜６９重量％と，Ａｌ2Ｏ3が０〜４重量
％と，Ｂ2Ｏ3が２３〜３０重量％と，Ｌｉ2Ｏが０．１
〜３重量％と，Ｎａ2Ｏが１〜５重量％と，Ｋ2Ｏが０〜
４重量％と，ＴｉＯ2が０〜５重量％と，及びＺｒＯ2が
１〜５重量％とからなることを特徴とする導電性ペース
ト。1. A conductive paste for baking on the surface of a low expansion glass substrate to form a conductive coating, wherein the conductive paste does not contain lead and the conductive powder material 6
0-80% by weight and glass flux 20-40% by weight
And 30 to 100% by weight of an organic binder with respect to a total weight of 100% by weight of the conductive powder material and the glass flux, and the glass flux is
SiO 2 is 56 to 69% by weight, Al 2 O 3 is 0 to 4% by weight, B 2 O 3 is 23 to 30% by weight, and Li 2 O is 0.1% by weight.
~ 3 wt%, Na 2 O 1-5 wt%, K 2 O 0-
A conductive paste comprising 4% by weight, TiO 2 of 0 to 5% by weight, and ZrO 2 of 1 to 5% by weight. 【請求項２】 請求項１において，上記導電性粉末材料
は，貴金属又は／及び貴金属酸化物からなることを特徴
とする導電性ペースト。2. The conductive paste according to claim 1, wherein the conductive powder material is made of a noble metal and / or a noble metal oxide. 【請求項３】 請求項１または２において，上記有機バ
インダーは，アクリル樹脂，アルキッド樹脂，ブチル樹
脂から選ばれる一種以上であることを特徴とする導電性
ペースト。3. The conductive paste according to claim 1, wherein the organic binder is at least one selected from acrylic resin, alkyd resin, and butyl resin. 【請求項４】 請求項１〜３のいずれか１項において，
上記導電性ペーストは，着色顔料を含有することを特徴
とする導電性ペースト。4. The method according to claim 1, wherein
The conductive paste contains a coloring pigment. 【請求項５】 請求項４において，上記着色顔料の含有
量は，上記導電性粉末材料及びガラスフラックスの合計
１００重量％に対して，１重量％〜２５重量％であるこ
とを特徴とする導電性ペースト。5. The conductive material according to claim 4, wherein the content of the color pigment is 1% by weight to 25% by weight based on 100% by weight of the total of the conductive powder material and the glass flux. Sex paste. 【請求項６】 低膨張ガラス基板の表面に導電性被膜を
形成してなる導電性被膜被覆ガラス基板であって，上記
導電性被膜は，鉛を含有せず，導電性粉末材料６０〜８
０重量％と，ガラスフラックス２０〜４０重量％と，上
記導電性粉末材料及びガラスフラックス１００重量％の
合計重量に対して有機バインダー３０〜１００重量％を
含有してなる導電性ペーストを，上記低膨張ガラス基板
の表面に，焼き付けてなり，かつ，上記ガラスフラック
スは，ＳｉＯ2が５６〜６９重量％と，Ａｌ2Ｏ3が０〜
４重量％と，Ｂ2Ｏ3が２３〜３０重量％と，Ｌｉ2Ｏが
０．１〜３重量％と，Ｎａ2Ｏが１〜５重量％と，Ｋ2Ｏ
が０〜４重量％と，ＴｉＯ2が０〜５重量％と，及びＺ
ｒＯ2が１〜５重量％とからなることを特徴とする導電
性被膜被覆ガラス基板。6. A conductive film-coated glass substrate obtained by forming a conductive film on the surface of a low expansion glass substrate, wherein the conductive film does not contain lead, and the conductive powder materials 60 to 8 are used.
0% by weight, 20 to 40% by weight of glass flux, and 30 to 100% by weight of an organic binder with respect to the total weight of the above-mentioned electrically conductive powder material and 100% by weight of glass flux. The glass flux is formed by baking on the surface of an expanded glass substrate, and the glass flux contains SiO 2 in an amount of 56 to 69% by weight and Al 2 O 3 in an amount of 0 to 0.
4% by weight, B 2 O 3 23 to 30% by weight, Li 2 O 0.1 to 3% by weight, Na 2 O 1 to 5% by weight, K 2 O
Is 0 to 4% by weight, TiO 2 is 0 to 5% by weight, and Z
A glass substrate coated with a conductive film, characterized in that rO 2 is 1 to 5% by weight. 【請求項７】 請求項６において，上記導電性粉末材料
は，貴金属又は／及び貴金属酸化物からなることを特徴
とする導電性被膜被覆ガラス基板。7. The conductive film-coated glass substrate according to claim 6, wherein the conductive powder material is made of a noble metal and / or a noble metal oxide. 【請求項８】 請求項６または７において，上記有機バ
インダーは，アクリル樹脂，アルキッド樹脂，ブチル樹
脂から選ばれる一種以上であることを特徴とする導電性
被膜被覆ガラス基板。8. The conductive film-coated glass substrate according to claim 6, wherein the organic binder is one or more selected from acrylic resin, alkyd resin, and butyl resin. 【請求項９】 請求項６〜８のいずれか１項において，
上記導電性ペーストは，着色顔料を含有することを特徴
とする導電性被膜被覆ガラス基板。9. The method according to any one of claims 6 to 8,
The conductive paste-coated glass substrate, wherein the conductive paste contains a coloring pigment. 【請求項１０】 請求項９において，上記着色顔料の含
有量は，上記導電性粉末材料及びガラスフラックスの合
計１００重量％に対して，１重量％〜２５重量％である
ことを特徴とする導電性被膜被覆ガラス基板。10. The conductive material according to claim 9, wherein the content of the color pigment is 1% by weight to 25% by weight based on 100% by weight of the total of the conductive powder material and the glass flux. Coating coated glass substrate. 【請求項１１】 請求項６〜１０のいずれか１項におい
て，上記導電性被膜の厚みは，５μｍ〜１０μｍである
ことを特徴とする導電性被膜被覆ガラス基板。11. The conductive coated glass substrate according to claim 6, wherein the conductive coated film has a thickness of 5 μm to 10 μm. 【請求項１２】 請求項６〜１１のいずれか１項におい
て，上記導電性被膜は導電性表示部であり，上記導電性
被膜被覆ガラス基板は，調理器用トッププレートである
ことを特徴とする導電性被膜被覆ガラス基板。12. The conductive film according to claim 6, wherein the conductive film is a conductive display portion, and the conductive film-coated glass substrate is a top plate for a cooker. Coating coated glass substrate. 【請求項１３】 低膨張ガラス基板の表面に導電性ペー
ストを印刷し，次いでこれを焼き付けすることにより，
導電性被膜を有する導電性被膜被覆ガラス基板を製造す
る方法であって，上記導電性ペーストは，鉛を含有せ
ず，導電性粉末材料６０〜８０重量％と，ガラスフラッ
クス２０〜４０重量％と，上記導電性粉末材料及びガラ
スフラックスの合計重量１００重量％に対して有機バイ
ンダー３０〜１００重量％を含有してなり，かつ，上記
ガラスフラックスは，ＳｉＯ2が５６〜６９重量％と，
Ａｌ2Ｏ3が０〜４重量％と，Ｂ2Ｏ3が２３〜３０重量％
と，Ｌｉ2Ｏが０．１〜３重量％と，Ｎａ2Ｏが１〜５重
量％と，Ｋ2Ｏが０〜４重量％と，ＴｉＯ2が０〜５重量
％と，及びＺｒＯ2が１〜５重量％とからなることを特
徴とする導電性被膜被覆ガラス基板の製造方法。13. A method of printing a conductive paste on the surface of a low expansion glass substrate and then baking the conductive paste,
A method for producing a conductive film-coated glass substrate having a conductive film, wherein the conductive paste does not contain lead, and the conductive powder material is 60 to 80% by weight and the glass flux is 20 to 40% by weight. An organic binder of 30 to 100% by weight based on the total weight of the conductive powder material and glass flux of 100% by weight, and the glass flux contains SiO 2 of 56 to 69% by weight,
Al 2 O 3 is 0 to 4 wt% and B 2 O 3 is 23 to 30 wt%.
Li 2 O 0.1 to 3% by weight, Na 2 O 1 to 5% by weight, K 2 O 0 to 4% by weight, TiO 2 0 to 5% by weight, and ZrO 2 Of 1 to 5% by weight, the method for producing a conductive-coating-coated glass substrate. 【請求項１４】 請求項１３において，上記焼き付けの
加熱温度は，７６０〜９００℃であることを特徴とする
導電性被膜被覆ガラス基板の製造方法。14. The method for manufacturing a glass substrate coated with a conductive film according to claim 13, wherein the heating temperature for the baking is 760 to 900 ° C.
JP2002009037A 2002-01-17 2002-01-17 Conductive paste, conductive coating-coated glass substrate and method for producing the same Expired - Fee Related JP3988467B2 (en)

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Publication number Priority date Publication date Assignee Title
WO2009067151A3 (en) * 2007-11-20 2009-11-26 Corning Incorporated Frit-containing pastes for producing sintered frit patterns on glass sheets
US8867220B2 (en) 2010-12-14 2014-10-21 Sumitomo Wiring Systems, Ltd. Packaging board with visual recognition windows
US9039940B2 (en) 2011-03-25 2015-05-26 Samsung Electronics Co., Ltd. Conductive paste and electronic device, and solar cell including an electrode formed using the conductive paste
US9218898B2 (en) 2011-12-09 2015-12-22 Samsung Electronics Co., Ltd. Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste
WO2016084627A1 (en) * 2014-11-25 2016-06-02 日本電気硝子株式会社 Glass powder, composite powder, and low expansion substrate with decorative layer
JP2016104684A (en) * 2014-11-25 2016-06-09 日本電気硝子株式会社 Glass powder, composite powder and low expansion substrate with picture layer
US9947809B2 (en) 2009-11-11 2018-04-17 Samsung Electronics Co., Ltd. Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009067151A3 (en) * 2007-11-20 2009-11-26 Corning Incorporated Frit-containing pastes for producing sintered frit patterns on glass sheets
US8025975B2 (en) 2007-11-20 2011-09-27 Corning Incorporated Frit-containing pastes for producing sintered frit patterns on glass sheets
US9947809B2 (en) 2009-11-11 2018-04-17 Samsung Electronics Co., Ltd. Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste
US8867220B2 (en) 2010-12-14 2014-10-21 Sumitomo Wiring Systems, Ltd. Packaging board with visual recognition windows
US9039940B2 (en) 2011-03-25 2015-05-26 Samsung Electronics Co., Ltd. Conductive paste and electronic device, and solar cell including an electrode formed using the conductive paste
US9218898B2 (en) 2011-12-09 2015-12-22 Samsung Electronics Co., Ltd. Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste
WO2016084627A1 (en) * 2014-11-25 2016-06-02 日本電気硝子株式会社 Glass powder, composite powder, and low expansion substrate with decorative layer
JP2016104684A (en) * 2014-11-25 2016-06-09 日本電気硝子株式会社 Glass powder, composite powder and low expansion substrate with picture layer

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