JP2007126319A - Bismuth-based lead-free glass composition - Google Patents

Bismuth-based lead-free glass composition Download PDF

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JP2007126319A
JP2007126319A JP2005319574A JP2005319574A JP2007126319A JP 2007126319 A JP2007126319 A JP 2007126319A JP 2005319574 A JP2005319574 A JP 2005319574A JP 2005319574 A JP2005319574 A JP 2005319574A JP 2007126319 A JP2007126319 A JP 2007126319A
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glass
bismuth
glass composition
mass
bao
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Satoshi Kumano
聡 熊野
Hidekazu Sakae
秀和 榮
Ichiro Uchiyama
一郎 内山
Tomoyuki Taguchi
智之 田口
Hideyuki Kuribayashi
秀行 栗林
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Nihon Yamamura Glass Co Ltd
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Nihon Yamamura Glass Co Ltd
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Priority to PCT/JP2006/316306 priority patent/WO2007052400A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J11/38—Dielectric or insulating layers
    • 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
    • C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/16—Compositions for glass with special properties for dielectric 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
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Glass Compositions (AREA)
  • Gas-Filled Discharge Tubes (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lead-free glass composition having ≤600°C softening point and excellent light transmissivity suitable for forming glass for a dielectric layer of PDP or the like. <P>SOLUTION: This bismuth-based lead-free glass composition comprises, in mass% in terms of oxide, 25-45% Bi<SB>2</SB>O<SB>3</SB>and 5-20% BaO, where mass ratio (BaO/Bi<SB>2</SB>O<SB>3</SB>) of the BaO to the Bi<SB>2</SB>O<SB>3</SB>is 0.2-0.7, and further comprises 1-10% SiO<SB>2</SB>, 10-35% B<SB>2</SB>O<SB>3</SB>, 21-35% ZnO, 0-5% Al<SB>2</SB>O<SB>3</SB>, and 0-20% sum total of MgO, CaO and SrO. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、ビスマス系無鉛ガラス組成物に関し、より詳しくは、プラズマディスプレイパネルの誘電体層などの形成に用いられるビスマス系無鉛ガラス組成物に関する。   The present invention relates to a bismuth-based lead-free glass composition, and more particularly to a bismuth-based lead-free glass composition used for forming a dielectric layer of a plasma display panel.

近年、画像表示装置としてプラズマディスプレイパネル（以下「ＰＤＰ」という）が広く用いられている。
このＰＤＰには、前面側と、背面側との２枚のガラス基板が配され、この２枚のガラス基板の間に多数の隔壁が挟持されて、該隔壁間に形成された空間に蛍光体などを配置して表示セルが形成されている。そして、この前面側と、背面側とのそれぞれのガラス基板に形成された電極間に電圧を印加してプラズマ放電を発生させて蛍光体を発光させており、この前面側と背面側との電極は、それぞれ誘電体層と呼ばれるガラスで被覆されている。
このようなＰＤＰの、前面側と背面側の誘電体層ならびに隔壁には粉末状のガラス組成物（粉末ガラス）、あるいは、必要に応じてＡｌ2Ｏ3などのセラミックス粉末を混合して用いたペーストまたはグリーンシートが用いられて形成されている。例えば、ガラス基板上に銀などの電極を形成させた後に、前記ペーストを印刷させたり、あるいは、前記グリーンシートをラミネートしたりして、ガラス基板／電極／ガラスペースト（あるいはグリーンシート）の積層体を形成させて、該積層体を粉末ガラスの軟化点温度以上に加熱して焼成させたりしている。
このとき電極やガラスペーストを積層するガラス基板には、通常、ソーダライムガラスや高歪点ガラスが用いられることから、誘電体層や隔壁に用いられる粉末ガラスにはこれらのガラス基板に熱変形を生じさせないために低い軟化点を有していることが求められ、通常、６００℃以下の軟化点が要望されている。
しかも、前面誘電体層は、表示セルにて発生した蛍光体の発光をより明るく前面側に透過させることが求められており、前記前面誘電体層に用いられるガラス組成物としては、その焼成後の光透過性に優れるものが求められている。 In recent years, plasma display panels (hereinafter referred to as “PDP”) have been widely used as image display devices.
In this PDP, two glass substrates of a front side and a back side are arranged, and a large number of partition walls are sandwiched between the two glass substrates, and a phosphor is formed in a space formed between the partition walls. Etc. are arranged to form a display cell. Then, a voltage is applied between the electrodes formed on the glass substrates on the front side and the back side to generate plasma discharge to emit phosphors. The front and back electrodes Are each covered with glass called a dielectric layer.
In such a PDP, the front and back side dielectric layers and partition walls were mixed with a powdery glass composition (powder glass) or ceramic powder such as Al 2 O 3 as necessary. A paste or a green sheet is used. For example, after an electrode such as silver is formed on a glass substrate, the paste is printed, or the green sheet is laminated, so that a laminate of glass substrate / electrode / glass paste (or green sheet) is obtained. The laminate is heated to a temperature equal to or higher than the softening point temperature of the powder glass and fired.
Since glass substrates on which electrodes and glass paste are laminated are usually soda lime glass and high strain point glass, these glass substrates are thermally deformed in powder glass used for dielectric layers and partition walls. It is required to have a low softening point so that it does not occur. Usually, a softening point of 600 ° C. or lower is desired.
In addition, the front dielectric layer is required to transmit light emitted from the phosphor generated in the display cell to the front side more brightly. As a glass composition used for the front dielectric layer, The thing which is excellent in the light transmittance of is requested | required.

ところで、従来、低軟化点を有する低融点ガラスとして酸化鉛を多く含んだガラスが知られている。しかし、近年においては、環境意識の高まりから、廃棄処理、作業環境における問題を抑制することのできる無鉛系の低融点ガラスが望まれている。ＰＤＰにおける前記誘電体層用ガラスにおいても同様に無鉛系の低融点ガラスが望まれており、特許文献１には、酸化ビスマスと酸化ホウ素とを主たる成分とするビスマス系ガラス組成物をＰＤＰに用いることが記載されている。   By the way, conventionally, a glass containing a large amount of lead oxide is known as a low melting point glass having a low softening point. However, in recent years, lead-free low-melting-point glass capable of suppressing problems in disposal processing and work environment has been desired due to an increase in environmental awareness. Similarly, a lead-free low-melting-point glass is also desired for the dielectric layer glass in the PDP. In Patent Document 1, a bismuth-based glass composition containing bismuth oxide and boron oxide as main components is used in the PDP. It is described.

しかし、従来のガラス組成物は、要望される光透過性を十分に満足するものとなっていない。すなわち、従来のビスマス系ガラス組成物においては、ＰＤＰの誘電体層のごとく、無鉛系でありながら、ソーダライムガラスや高歪点ガラスなどが用いられたガラス基板上で焼成し得る低軟化点を有し且つ優れた光透過性が要望される用途において、その要望を満足させることが困難であるという問題を有している。   However, the conventional glass composition does not sufficiently satisfy the required light transmittance. That is, the conventional bismuth-based glass composition has a low softening point that can be fired on a glass substrate using soda-lime glass, high strain point glass, etc. while being lead-free, like the dielectric layer of PDP. It has a problem that it is difficult to satisfy the demand in applications where it has a high light transmittance.

特開２００３−１２８４３０号公報JP 2003-128430 A

本発明の課題は、上記問題点に鑑み６００℃以下の軟化点を有し、優れた光透過性を有するプラズマディスプレイパネルの誘電体層用ガラスの形成などに好適な無鉛ガラス組成物を提供することにある。   In view of the above problems, an object of the present invention is to provide a lead-free glass composition having a softening point of 600 ° C. or lower and suitable for forming a dielectric layer glass of a plasma display panel having excellent light transmittance. There is.

本発明者らは、このようなビスマス系無鉛ガラス組成物について鋭意検討を行ったところ所定の配合組成において、Ｂｉ2Ｏ3とＢａＯとの配合割合を所定の範囲内とすることで、６００℃以下の軟化点を有しつつ優れた光透過性を有する無鉛ガラス組成物が得られることを見出し本発明の完成に到ったのである。
すなわち、本発明は、前記課題を解決すべく、酸化物換算の質量％でＢｉ2Ｏ3：２５〜４５％、ＢａＯ：５〜２０％含有され、且つ前記Ｂｉ2Ｏ3と前記ＢａＯとはＢａＯ／Ｂｉ2Ｏ3の質量比の値が０．２〜０．７となる割合で含有されており、さらにＳｉＯ2：１〜１０％、Ｂ2Ｏ3：１０〜３５％、ＺｎＯ：２１〜３５％、Ａｌ2Ｏ3：０〜５％、ＭｇＯ、ＣａＯ、ＳｒＯの合計：０〜２０％含有されてなることを特徴とするビスマス系無鉛ガラス組成物を提供する。 The present inventors have conducted intensive studies on such a bismuth-based lead-free glass composition and found that the composition ratio of Bi 2 O 3 and BaO is within a predetermined range in a predetermined composition, and thus 600 ° C. The present inventors have found that a lead-free glass composition having the following softening point and excellent light transmittance can be obtained, and the present invention has been completed.
That is, in order to solve the above problems, the present invention contains Bi 2 O 3 : 25 to 45% and BaO: 5 to 20% in terms of oxide%, and the Bi 2 O 3 and BaO are: BaO / Bi 2 O 3 is contained at a ratio of mass ratio of 0.2 to 0.7, and further SiO 2 : 1 to 10%, B 2 O 3 : 10 to 35%, ZnO: 21 Provided is a bismuth-based lead-free glass composition characterized by containing ~ 35%, Al 2 O 3 : 0 to 5%, MgO, CaO and SrO: 0 to 20%.

本発明によれば、ガラス組成物としてビスマス系ガラス組成物を用いるため、ガラス組成物を無鉛にすることができ、６００℃以下の軟化点を有することからソーダライムガラスや高歪点ガラスなどのガラス基板上で焼成することができる。また、従来よりも焼成後の光透過性に優れたガラス組成物とさせ得る。したがって、プラズマディスプレイパネルの誘電体層用ガラスの形成などに好適なガラス組成物を提供し得る。   According to the present invention, since a bismuth-based glass composition is used as the glass composition, the glass composition can be made lead-free and has a softening point of 600 ° C. or lower, soda lime glass, high strain point glass, etc. It can be fired on a glass substrate. Moreover, it can be set as the glass composition excellent in the light transmittance after baking compared with the past. Therefore, it is possible to provide a glass composition suitable for forming a dielectric layer glass of a plasma display panel.

以下に、本発明の好ましい実施の形態について説明する。   The preferred embodiments of the present invention will be described below.

本実施形態におけるビスマス系無鉛ガラス組成物は、Ｂｉ2Ｏ3、ＢａＯ、ＳｉＯ2、Ｂ2Ｏ3、ＺｎＯが含有されている。
また、本実施形態のビスマス系無鉛ガラス組成物は、任意成分としてＡｌ2Ｏ3、ＭｇＯ、ＣａＯ、ＳｒＯ、ＣｕＯが含有されている。 The bismuth-based lead-free glass composition in the present embodiment contains Bi 2 O 3 , BaO, SiO 2 , B 2 O 3 and ZnO.
Further, the bismuth-based lead-free glass composition of the present embodiment contains Al 2 O 3 , MgO, CaO, SrO, and CuO as optional components.

前記Ｂｉ2Ｏ3は、ビスマス系無鉛ガラス組成物に必須な成分で含有量は、酸化物換算で２５〜４５質量％である。含有量が２５質量％未満の場合は、得られるビスマス系無鉛ガラス組成物の軟化点が高くなり６００℃を上回り焼成が困難になるためである。また、４５質量％を超えて含有されると得られるビスマス系無鉛ガラス組成物の光透過性が低下したり、熱膨張係数（線膨張係数）が大きくなって焼成時に割れ、ひびを生じさせたりしてしまうためである。
このような点において、前記Ｂｉ2Ｏ3の含有量は、２８〜４２質量％であることが好ましく、３０〜４０質量％であることがさらに好ましい。 The Bi 2 O 3 is an essential component for the bismuth-based lead-free glass composition, and its content is 25 to 45% by mass in terms of oxide. This is because when the content is less than 25% by mass, the softening point of the resulting bismuth-based lead-free glass composition is high, and the temperature exceeds 600 ° C., making firing difficult. In addition, if the content exceeds 45% by mass, the light transmittance of the resulting bismuth-based lead-free glass composition decreases, or the thermal expansion coefficient (linear expansion coefficient) increases, causing cracks and cracks during firing. It is because it will do.
In such a point, the content of Bi 2 O 3 is preferably 28 to 42% by mass, and more preferably 30 to 40% by mass.

前記ＢａＯは、ビスマス系無鉛ガラス組成物に必須な成分で含有量は、酸化物換算で５〜２０質量％である。含有量が５質量％未満の場合は、得られるガラスの比誘電率が低くなりすぎ、しかも、ガラス組成物の軟化点が高くなって６００℃を上回り焼成が困難になるためである。また、２０質量％を超えて含有されると得られるビスマス系無鉛ガラス組成物の光透過性が低下したり、熱膨張係数が大きくなって焼成時に割れ、ひびを生じさせたりしてしまうためである。
このような点において、前記ＢａＯの含有量は、８〜２０質量％であることが好ましく、１０〜２０質量％であることがさらに好ましい。 BaO is an essential component for the bismuth-based lead-free glass composition, and its content is 5 to 20% by mass in terms of oxide. When the content is less than 5% by mass, the relative dielectric constant of the glass obtained becomes too low, and the softening point of the glass composition becomes high, and the temperature exceeds 600 ° C., making baking difficult. In addition, when the content exceeds 20% by mass, the light transmittance of the resulting bismuth-based lead-free glass composition is reduced, or the thermal expansion coefficient is increased, causing cracks and cracks during firing. is there.
In such a point, the content of the BaO is preferably 8 to 20% by mass, and more preferably 10 to 20% by mass.

なお、前記ビスマス系無鉛ガラス組成物には、前記Ｂｉ2Ｏ3と前記ＢａＯとがＢａＯ／Ｂｉ2Ｏ3の質量比の値が０．２〜０．７となる割合で含有される。このＢａＯ／Ｂｉ2Ｏ3の値が０．２〜０．７とされるのは、ＢａＯ／Ｂｉ2Ｏ3の値が０．２未満の場合には、Ｂｉ2Ｏ3の還元による着色が発生して、得られるガラスの光透過性が低下するためである。
一方、ＢａＯ／Ｂｉ2Ｏ3の値が０．７を超える場合には、ガラスが不安定なものとなり結晶化を起こして光透過性を低下させてしまうためである。
このような点において、ＢａＯ／Ｂｉ2Ｏ3の値は、０．２２〜０．６８であることが好ましく、０．２５〜０．６５であることがさらに好ましい。 The bismuth-based lead-free glass composition contains Bi 2 O 3 and BaO at a ratio such that the mass ratio of BaO / Bi 2 O 3 is 0.2 to 0.7. The value of the BaO / Bi 2 O 3 is a 0.2 to 0.7, when the value of the BaO / Bi 2 O 3 is less than 0.2, coloring due to the reduction of Bi 2 O 3 This is because the light transmission of the resulting glass is reduced.
On the other hand, when the value of BaO / Bi 2 O 3 exceeds 0.7, the glass becomes unstable and crystallizes to lower the light transmittance.
In such a point, the value of BaO / Bi 2 O 3 is preferably 0.22 to 0.68, and more preferably 0.25 to 0.65.

また、前記ビスマス系無鉛ガラス組成物に含有されるＢｉ2Ｏ3とＢａＯとの合計量は、酸化物換算で４０〜６０質量％とされることが好ましい。このＢｉ2Ｏ3とＢａＯとの合計量が、酸化物換算で４０〜６０質量％とされることが好ましいのは、Ｂｉ2Ｏ3とＢａＯとの合計量が４０質量％未満の場合には、得られるガラスの比誘電率が低く、しかも、ビスマス系無鉛ガラス組成物の軟化点が高くなって、ガラス基板に熱変形を生じさせないビスマス系無鉛ガラス組成物の焼成が困難となるおそれがあるためである。
一方、Ｂｉ2Ｏ3とＢａＯとの合計量が６０質量％を超える量とした場合には、熱膨張係数が大きくなり、焼成時の加熱、冷却の作業の際にガラスに割れ、ひびが発生するおそれがあるためである。
このような点において、Ｂｉ2Ｏ3とＢａＯとの合計量は、４２〜５８質量％であることが好ましく、４５〜５５質量％であることがさらに好ましい。 The total amount of Bi 2 O 3 and BaO contained in the bismuth-based lead-free glass composition is preferably 40 to 60% by mass in terms of oxide. The total amount of Bi 2 O 3 and BaO is preferably 40 to 60% by mass in terms of oxide when the total amount of Bi 2 O 3 and BaO is less than 40% by mass. The resulting glass has a low dielectric constant, and the softening point of the bismuth-based lead-free glass composition is high, which may make it difficult to fire the bismuth-based lead-free glass composition that does not cause thermal deformation of the glass substrate. Because.
On the other hand, when the total amount of Bi 2 O 3 and BaO exceeds 60% by mass, the coefficient of thermal expansion increases, and the glass is cracked and cracked during heating and cooling during firing. It is because there is a possibility of doing.
In this respect, the total amount of Bi 2 O 3 and BaO is preferably 42 to 58% by mass, and more preferably 45 to 55% by mass.

前記Ｂ2Ｏ3も、ビスマス系無鉛ガラス組成物に必須な成分で含有量は、酸化物換算で、１０〜３５質量％である。含有量が１０質量％未満の場合は、得られるビスマス系無鉛ガラス組成物が不安定なものとなり結晶化を起こして光透過性を低下させてしまうためである。また、３５質量％を超えて含有されると得られるビスマス系無鉛ガラス組成物の軟化点が高くなり、６００℃を上回り焼成が困難となるためである。
このような点において、前記Ｂ2Ｏ3の含有量は、１３〜３２質量％であることが好ましく、１５〜３０質量％であることがさらに好ましい。 B 2 O 3 is also an essential component for the bismuth-based lead-free glass composition, and its content is 10 to 35% by mass in terms of oxide. When the content is less than 10% by mass, the resulting bismuth-based lead-free glass composition becomes unstable, causing crystallization and reducing light transmittance. Moreover, it is because the softening point of the bismuth-type lead-free glass composition obtained will become high when it contains exceeding 35 mass%, 600 degreeC is exceeded, and baking becomes difficult.
In such a point, the content of B 2 O 3 is preferably 13 to 32% by mass, and more preferably 15 to 30% by mass.

前記ＺｎＯも、ビスマス系無鉛ガラス組成物に必須な成分で含有量は、酸化物換算で、２１〜３５質量％である。含有量が２１質量％未満の場合は、得られるビスマス系無鉛ガラス組成物が着色し光透過性が低いものとなり、３５質量％を超えて含有されると得られるビスマス系無鉛ガラス組成物が結晶化を起こしてやはり光透過性が低いものとなる。
このような点において、前記ＺｎＯの含有量は、２１〜３３質量％であることが好ましく、２１〜３０質量％であることがさらに好ましい。 ZnO is also an essential component for the bismuth-based lead-free glass composition, and its content is 21 to 35% by mass in terms of oxide. When the content is less than 21% by mass, the resulting bismuth-based lead-free glass composition is colored and has low light transmittance. When the content exceeds 35% by mass, the resulting bismuth-based lead-free glass composition is crystallized. As a result, the light transmittance is low.
In such a point, the content of the ZnO is preferably 21 to 33% by mass, and more preferably 21 to 30% by mass.

前記ＳｉＯ2も、ビスマス系無鉛ガラス組成物に必須な成分で含有量は、酸化物換算で、１〜１０質量％である。含有量が１質量％未満の場合は、得られるビスマス系無鉛ガラス組成物が不安定なものとなり結晶化を起こして光透過性が低いものとなる。
一方、１０質量％を超えて含有されると得られるビスマス系無鉛ガラス組成物の軟化点が高くなり、６００℃を上回り焼成が困難となるためである。
このような点において、前記ＳｉＯ2の含有量は、１〜９質量％であることが好ましく、１〜８質量％であることがさらに好ましい。 The SiO 2 is also an essential component for the bismuth-based lead-free glass composition, and its content is 1 to 10% by mass in terms of oxide. When the content is less than 1% by mass, the resulting bismuth-based lead-free glass composition becomes unstable and crystallizes, resulting in low light transmittance.
On the other hand, when the content exceeds 10% by mass, the resulting bismuth-based lead-free glass composition has a high softening point, and the temperature exceeds 600 ° C., which makes firing difficult.
In such a point, the content of SiO 2 is preferably 1 to 9% by mass, and more preferably 1 to 8% by mass.

前記Ａｌ2Ｏ3は、任意成分でガラスの安定化に効果があり、酸化物換算で、５質量％以下の含有量であることが好ましい。Ａｌ2Ｏ3の含有量がこのような範囲であることが好ましいのは、含有量を増大させると得られるビスマス系無鉛ガラス組成物が安定化するものの軟化点が高くなるためである。 The Al 2 O 3 is an optional component that is effective for stabilizing the glass, and is preferably 5% by mass or less in terms of oxide. The reason why the content of Al 2 O 3 is in such a range is that, if the content is increased, the resulting bismuth-based lead-free glass composition is stabilized, but the softening point is increased.

前記ＭｇＯ、ＣａＯ、およびＳｒＯは、任意成分でガラスの安定化に効果がある。これらが含有される場合には、それらの合計量が酸化物換算で、２０質量％以下の含有量であることが好ましい。含有量が２０質量％を超えると、かえってガラスの安定化を低下させたり、得られるビスマス系無鉛ガラス組成物の線膨張係数を上昇させたりするためである。   MgO, CaO, and SrO are optional components and are effective for stabilizing the glass. When these are contained, the total amount thereof is preferably 20% by mass or less in terms of oxide. This is because if the content exceeds 20% by mass, the stabilization of the glass is reduced, or the linear expansion coefficient of the resulting bismuth-based lead-free glass composition is increased.

前記ＣｕＯは、任意成分でビスマス系無鉛ガラス組成物の焼成時に銀などの電極との反応によるガラスの着色を抑制する効果を有し、このＣｕＯを酸化物換算で、０．１〜１．０質量％含有することによって、ＰＤＰの誘電体層のごとく銀などの電極上において焼成される用途などに、より適したものとなる。   The CuO is an optional component and has an effect of suppressing coloration of the glass due to a reaction with an electrode such as silver at the time of firing the bismuth-based lead-free glass composition. By containing the content by mass%, it becomes more suitable for applications such as firing on an electrode such as silver like a dielectric layer of PDP.

なお、このＣｕＯをビスマス系無鉛ガラス組成物に含有させる場合には、併せてＶ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｅ、Ｉｎ、Ｓｎ、Ｓｂの何れかの酸化物を含有させることがより好ましい。これらは、例えば、酸化物換算で、０．１〜０．５質量％含有させることによって、ビスマス系無鉛ガラス組成物の焼成時に銀などの電極との反応によるガラスの着色をさらに抑制する効果を奏し、これらが含有されるビスマス系無鉛ガラス組成物をＰＤＰの誘電体層のごとく銀などの電極上において焼成される用途などに、より適したものとさせ得る。   In addition, when making this CuO contain in a bismuth-type lead-free glass composition, it is more preferable to contain any oxide of V, Mn, Fe, Co, Ce, In, Sn, and Sb together. These include, for example, an effect of further suppressing coloring of glass due to reaction with an electrode such as silver at the time of firing a bismuth-based lead-free glass composition by containing 0.1 to 0.5% by mass in terms of oxide. Thus, the bismuth-based lead-free glass composition containing them can be made more suitable for use such as firing on an electrode such as silver like a PDP dielectric layer.

また、ビスマス系無鉛ガラス組成物には、上記のようなものの他に本発明の効果を損ねない範囲において微量の成分が含有されていてもよい。   The bismuth-based lead-free glass composition may contain a trace amount of components in addition to the above-described components within a range not impairing the effects of the present invention.

これらの含有される成分を原料としてビスマス系無鉛ガラス組成物を作製する場合は、すべての原料を、例えば１２００〜１３５０℃の温度で、混合溶融して均一なガラスを作製し、該ガラスをボールミルなどの粉砕手段により粉末とすることで均一な性状のビスマス系無鉛ガラス組成物を得ることができる。
また、上記のように作製された粉末を、一般的なバインダー樹脂ならびに溶剤などを用いてペースト化し、スクリーン印刷法などにより塗布、乾燥して焼成させることで均一な厚みのガラスとすることができる。
このようにして得られるビスマス系無鉛ガラス組成物は、ＰＤＰの誘電体層、中でも、優れた光透過性が要望される前面誘電体層のガラスの形成に好適である。
なお、ＰＤＰの誘電体層に用いる場合には、ガラスの比誘電率が９．５〜１２．５となるように上記の材料を調整することが好ましい。この比誘電率とは、本明細書中においては、２５℃の温度下で１ＭＨｚの周波数で測定される値を意図しており、例えば、厚さ５ｍｍ、直径３０ｍｍの円板状ガラス試料を、横河ヒューレットパッカード社製インピーダンスアナライザー（型名「ＨＰ４１４９Ａ」）などを用いて測定することができる。 In the case of producing a bismuth-based lead-free glass composition using these contained components as raw materials, all the raw materials are mixed and melted at, for example, a temperature of 1200 to 1350 ° C. to produce a uniform glass, and the glass is ball milled. A bismuth-based lead-free glass composition having a uniform property can be obtained by using a pulverizing means such as a powder.
Moreover, the powder produced as described above can be made into a paste using a general binder resin and a solvent, and applied to the glass by a screen printing method, dried, and fired to obtain a glass having a uniform thickness. .
The bismuth-based lead-free glass composition thus obtained is suitable for the formation of a PDP dielectric layer, particularly a front dielectric layer glass that requires excellent light transmission.
In addition, when using for the dielectric layer of PDP, it is preferable to adjust said material so that the dielectric constant of glass may be 9.5-12.5. In this specification, the relative dielectric constant is intended to be a value measured at a frequency of 1 MHz at a temperature of 25 ° C. For example, a disk-shaped glass sample having a thickness of 5 mm and a diameter of 30 mm is used. It can be measured using an impedance analyzer (model name “HP4149A”) manufactured by Yokogawa Hewlett-Packard Company.

次に実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。
ビスマス系無鉛ガラス組成物の作製：（実施例１〜１６、比較例１〜１０）
表１、２に示す配合組成となるよう原料を調合し、混合の後、約１２００〜１３５０℃の温度で１〜２時間溶融した。該溶融したガラスをステンレス製の冷却ロールにて急冷し、ガラスフレークを作製した。 EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.
Preparation of bismuth-based lead-free glass composition: (Examples 1 to 16, Comparative Examples 1 to 10)
The raw materials were prepared so as to have the blending compositions shown in Tables 1 and 2, and after mixing, they were melted at a temperature of about 1200 to 1350 ° C. for 1-2 hours. The molten glass was quenched with a stainless steel cooling roll to produce glass flakes.

Figure 2007126319
※表中の数値の単位は、各配合剤については質量％、（ＢａＯ／Ｂｉ2Ｏ3）については無次元、（Ｂｉ2Ｏ3＋ＢａＯ）については質量％である。
Figure 2007126319
 * Units of numerical values in the table are mass% for each compounding agent, dimensionless for (BaO / Bi 2 O 3 ), and mass% for (Bi 2 O 3 + BaO).

Figure 2007126319
※表中の数値の単位は、各配合剤については質量％、（ＢａＯ／Ｂｉ2Ｏ3）については無次元、（Ｂｉ2Ｏ3＋ＢａＯ）については質量％である。
Figure 2007126319
 * Units of numerical values in the table are mass% for each compounding agent, dimensionless for (BaO / Bi 2 O 3 ), and mass% for (Bi 2 O 3 + BaO).

次いで、ガラスフレークを粉砕して平均粒径１〜３μｍの粉末ガラスを作製し示差熱分析（ＤＴＡ）用の試料とした。   Next, the glass flakes were pulverized to produce a powder glass having an average particle diameter of 1 to 3 μm, which was used as a sample for differential thermal analysis (DTA).

また、このガラス粉末をプレス成形して焼成した後に所定形状に加工し、線膨張係数測定用試料、比誘電率測定用試料を作製した。   Further, this glass powder was press-molded and fired, and then processed into a predetermined shape to prepare a linear expansion coefficient measurement sample and a relative dielectric constant measurement sample.

また、各実施例、比較例の粉末ガラスとエチルセルロース、ターピネオールを主成分とするビヒクルとによりガラスペーストを作製した。得られた、ガラスペーストをガラス基板（旭硝子社製「ＰＤ２００」）上に、焼成後に３０μｍの厚さとなるようスクリーン印刷して、ガラス基板が熱変形を生じるおそれのない５８０℃の温度で３０分間焼成し、ガラス基板上に、厚さ３０μｍのガラス膜を形成し光透過性測定用試料を作製した。   Moreover, the glass paste was produced with the powder glass of each Example and a comparative example, and the vehicle which has ethylcellulose and a terpineol as a main component. The obtained glass paste was screen-printed on a glass substrate ("PD200" manufactured by Asahi Glass Co., Ltd.) so as to have a thickness of 30 [mu] m after firing, and the glass substrate was heated at a temperature of 580 [deg.] C. for 30 minutes so as not to cause thermal deformation. Firing was performed to form a glass film with a thickness of 30 μm on the glass substrate, and a sample for light transmittance measurement was produced.

さらに、この光透過性測定用試料の作製と同様に、銀導体を所定パターンで印刷、焼成させたガラス基板を用いて、各実施例、比較例の粉末ガラスのペーストを焼成して銀導体部の変色状況を観察した。   Further, similarly to the preparation of the light transmission measurement sample, using the glass substrate on which the silver conductor was printed and baked in a predetermined pattern, the powdered glass paste of each example and comparative example was baked to obtain a silver conductor portion. The discoloration situation of was observed.

（評価）
１）軟化点
各実施例、比較例のガラス試料を、理学電機社製ＤＴＡ（型名「ＴＧ８１２０」）を用いて、大気雰囲気下において２０℃／分の昇温速度で示差熱分析測定を行い、軟化時の吸熱ピークが終了した点を接線法により求め軟化点とした。評価結果を表３に示す。 (Evaluation)
1) Softening point Differential thermal analysis measurement was performed on the glass samples of each Example and Comparative Example using a DTA (model name “TG8120”) manufactured by Rigaku Corporation at a heating rate of 20 ° C./min in an air atmosphere. The point at which the endothermic peak during softening was completed was determined by the tangent method and used as the softening point. The evaluation results are shown in Table 3.

２）線膨張係数
各実施例、比較例のガラス粉末をプレス成形し、焼成した後、直径５ｍｍ、長さ１５ｍｍの円柱状試料を作製し、該円柱状試料を理学電機社製ＴＭＡ（型名「ＴＭＡ８３１０」）を用いて、昇温速度１０℃／ｍｉｎの条件で５０〜３５０℃の範囲の平均線膨張係数を求めた。評価結果を表３、表４に示す。
なお、同様にして求められる一般に用いられるガラス基板の線膨張係数から、ガラス基板上において焼成されるガラス組成物として、通常、６０〜８５×１０-7／℃の範囲内の線膨張係数であれば、焼成時に割れ、ひびなどが発生するおそれを十分低減できる。 2) Linear expansion coefficient After press-molding and firing the glass powders of the examples and comparative examples, a cylindrical sample having a diameter of 5 mm and a length of 15 mm was prepared, and the cylindrical sample was made into a TMA (model name) manufactured by Rigaku Corporation. Using “TMA8310”), an average linear expansion coefficient in the range of 50 to 350 ° C. was obtained under the condition of a temperature increase rate of 10 ° C./min. The evaluation results are shown in Tables 3 and 4.
In addition, from the linear expansion coefficient of a commonly used glass substrate obtained in the same manner, the glass composition to be baked on the glass substrate is usually a linear expansion coefficient within the range of 60 to 85 × 10 −7 / ° C. If it is, the possibility that cracks, cracks and the like are generated during firing can be sufficiently reduced.

３）光透過性
各実施例、比較例の厚さ３０μｍのガラス膜を形成した試験片を日立ハイテクノロジーズ社製分光光度計（型名「Ｕ−３０１０（積分球なし）」）を用いて、５５０ｎｍの光の透過率を求めた。評価結果を表３、表４に示す。 3) Light transmittance Using a spectrophotometer (model name “U-3010 (without integrating sphere)”) manufactured by Hitachi High-Technologies Corporation, a test piece on which a glass film having a thickness of 30 μm of each example and comparative example was formed. The transmittance of light at 550 nm was determined. The evaluation results are shown in Tables 3 and 4.

４）比誘電率
各実施例、比較例のガラス粉末をプレス成形し、焼成し、直径３０ｍｍ、厚さ５ｍｍの円板状試料を作製し、横河ヒューレットパッカード社製インピーダンスアナライザー（型名「ＨＰ４１４９Ａ」）を用いて、２５℃雰囲気下において、１ＭＨｚでの比誘電率の測定を行った。評価結果を表３、表４に示す。 4) Relative permittivity The glass powder of each example and comparative example was press-molded and fired to prepare a disk-shaped sample having a diameter of 30 mm and a thickness of 5 mm. )) Was used to measure the relative dielectric constant at 1 MHz in an atmosphere of 25 ° C. The evaluation results are shown in Tables 3 and 4.

５）銀との反応性
銀との反応性の評価は、各実施例、比較例の粉末ガラスのペーストの焼成後の銀導体部の変色状況を目視で観察して実施した。変色の見られなかったものを「○」、変色の見られたものを「×」として判定した。評価結果を表３、表４に示す。 5) Reactivity with silver Evaluation of the reactivity with silver was carried out by visually observing the discoloration of the silver conductor part after firing the powder glass pastes of the examples and comparative examples. The case where no discoloration was observed was determined as “◯”, and the case where discoloration was observed was determined as “x”. The evaluation results are shown in Tables 3 and 4.

Figure 2007126319
Figure 2007126319

Figure 2007126319
Figure 2007126319

以上のように、酸化物換算の質量％でＢｉ2Ｏ3：２５〜４５％、ＢａＯ：５〜２０％含有され、且つ前記Ｂｉ2Ｏ3と前記ＢａＯとがＢａＯ／Ｂｉ2Ｏ3の質量比の値が０．２〜０．７となる割合で含有されており、さらにＳｉＯ2：１〜１０％、Ｂ2Ｏ3：１０〜３５％、ＺｎＯ：２１〜３５％、Ａｌ2Ｏ3：０〜５％、ＭｇＯ、ＣａＯ、ＳｒＯの合計：０〜２０％含有されてなるビスマス系無鉛ガラス組成物を用いることで、無鉛系のガラス組成物でありながらソーダライムガラスや高歪点ガラスなどが用いられたガラス基板が変形するおそれのない低い軟化点を有するものとすることができ、優れた光透過性のガラスとし得ることがわかる。 As described above, Bi 2 O 3 : 25 to 45% and BaO: 5 to 20% in mass% in terms of oxide, and the Bi 2 O 3 and BaO are the mass of BaO / Bi 2 O 3 . The ratio value is 0.2 to 0.7. Further, SiO 2 : 1 to 10%, B 2 O 3 : 10 to 35%, ZnO: 21 to 35%, Al 2 O 3 : Total of 0 to 5%, MgO, CaO and SrO: By using a bismuth lead-free glass composition containing 0 to 20%, soda lime glass or high strain point glass while being lead-free glass composition It can be seen that the glass substrate using the above can have a low softening point with no fear of deformation, and can be an excellent light-transmitting glass.

また、各実施例のガラス組成物は、線膨張係数もガラス基板上での焼成時に割れ、ひびの発生するおそれがない範囲内で、ＰＤＰの誘電体層用ガラスに好適に用い得るものであることもわかる。
また、ＣｕＯが０．１〜１．０質量％含有されることで、銀電極との反応によるガラスの着色を抑制することができ、ＰＤＰ誘電体層用ガラスとしてより好適なものとし得ることがわかる。 In addition, the glass composition of each example can be suitably used for the dielectric layer glass of PDP within a range where the coefficient of linear expansion is not likely to crack or crack when fired on a glass substrate. I understand that.
Moreover, by containing 0.1 to 1.0% by mass of CuO, it is possible to suppress the coloring of the glass due to the reaction with the silver electrode, and it can be more suitable as a glass for a PDP dielectric layer. Recognize.

Claims (7)

酸化物換算の質量％でＢｉ2Ｏ3：２５〜４５％、ＢａＯ：５〜２０％含有され、且つ前記Ｂｉ2Ｏ3と前記ＢａＯとはＢａＯ／Ｂｉ2Ｏ3の質量比の値が０．２〜０．７となる割合で含有されており、さらにＳｉＯ2：１〜１０％、Ｂ2Ｏ3：１０〜３５％、ＺｎＯ：２１〜３５％、Ａｌ2Ｏ3：０〜５％、ＭｇＯ、ＣａＯ、ＳｒＯの合計：０〜２０％含有されてなることを特徴とするビスマス系無鉛ガラス組成物。 Bi 2 O 3 : 25 to 45% and BaO: 5 to 20% by mass in terms of oxide, and the Bi 2 O 3 and BaO have a BaO / Bi 2 O 3 mass ratio of 0. 2 to 0.7, and SiO 2 : 1 to 10%, B 2 O 3 : 10 to 35%, ZnO: 21 to 35%, Al 2 O 3 : 0 to 5% , MgO, CaO, SrO: bismuth-based lead-free glass composition containing 0 to 20%. 酸化物換算の質量％で前記Ｂｉ2Ｏ3と前記ＢａＯとの合計量が４０〜６０％である請求項１に記載のビスマス系無鉛ガラス組成物。 2. The bismuth-based lead-free glass composition according to claim 1, wherein the total amount of the Bi 2 O 3 and the BaO is 40 to 60% in terms of mass% in terms of oxide. 酸化物換算の質量％でＣｕＯ：０．１〜１．０％がさらに含有されてなる請求項１または２に記載のビスマス系無鉛ガラス組成物。 The bismuth-based lead-free glass composition according to claim 1 or 2, further comprising CuO: 0.1 to 1.0% by mass% in terms of oxide. Ｖ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｅ、Ｉｎ、Ｓｎ、Ｓｂの何れかの酸化物が少なくとも１種類以上がさらに含有され、該含有される酸化物の合計量が酸化物換算の質量％で０．１〜０．５％である請求項３記載のビスマス系無鉛ガラス組成物。 At least one oxide of any one of V, Mn, Fe, Co, Ce, In, Sn, and Sb is further contained, and the total amount of the oxides contained is 0. 0% by mass in terms of oxide. The bismuth-based lead-free glass composition according to claim 3, which is 1 to 0.5%. プラズマディスプレイパネルの誘電体層用ガラスであって、請求項１乃至４の何れかに記載のビスマス系無鉛ガラス組成物が用いられていることを特徴とする誘電体層用ガラス。 A dielectric layer glass for a plasma display panel, wherein the bismuth-based lead-free glass composition according to any one of claims 1 to 4 is used. プラズマディスプレイパネルの前面側に配される請求項５に記載の誘電体層用ガラス。 The glass for a dielectric layer according to claim 5, which is disposed on the front side of the plasma display panel. 比誘電率が９．５〜１２．５の範囲内となるように形成されている請求項５または６に記載の誘電体層用ガラス。 The dielectric layer glass according to claim 5 or 6, wherein the dielectric layer glass is formed so as to have a relative dielectric constant in a range of 9.5 to 12.5.
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