JP2001163635A - Lead-free low melting point glass for formation of barrier rib and glass ceramic composition - Google Patents
Lead-free low melting point glass for formation of barrier rib and glass ceramic compositionInfo
- Publication number
- JP2001163635A JP2001163635A JP34675099A JP34675099A JP2001163635A JP 2001163635 A JP2001163635 A JP 2001163635A JP 34675099 A JP34675099 A JP 34675099A JP 34675099 A JP34675099 A JP 34675099A JP 2001163635 A JP2001163635 A JP 2001163635A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- lead
- mol
- free low
- content
- 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.)
- Withdrawn
Links
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
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プラズマディスプ
レイパネル（ＰＤＰ）、蛍光表示管（ＶＦＤ）等におけ
る隔壁形成に好適な無鉛低融点ガラスおよびガラスセラ
ミックス組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lead-free low-melting glass and a glass ceramic composition suitable for forming partition walls in a plasma display panel (PDP), a fluorescent display tube (VFD), and the like.
【０００２】[0002]
【従来の技術】近年、大型の薄型平板型カラー表示装置
としてＰＤＰが注目を集めている。ＰＤＰのパネル構造
の特徴のひとつに画素を区切る隔壁がある。隔壁の幅は
たとえば８０μｍ、高さはたとえば１５０μｍであり、
この隔壁は画面全域に等間隔で形成される。隔壁用材料
としては、隔壁形状保持のための低膨張セラミックスフ
ィラー、色調調整のための耐熱顔料、および固着材とし
ての低融点ガラス粉末からなるガラスセラミックス組成
物を混合したものが用いられている。2. Description of the Related Art In recent years, PDPs have attracted attention as large, thin, flat panel color display devices. One of the features of the PDP panel structure is a partition for partitioning pixels. The width of the partition is, for example, 80 μm, the height is, for example, 150 μm,
The partitions are formed at equal intervals over the entire screen. As a material for the partition, a mixture of a low-expansion ceramic filler for maintaining the shape of the partition, a heat-resistant pigment for adjusting the color tone, and a glass ceramic composition including a low-melting glass powder as a fixing material is used.
【０００３】[0003]
【発明が解決しようとする課題】前記低融点ガラス粉末
は従来、軟化点を下げるために鉛を含有していたが、近
年鉛を含有しないものが求められている。本発明は、以
上の課題を解決する隔壁形成用無鉛低融点ガラスおよび
ガラスセラミックス組成物の提供を目的とする。Conventionally, the above-mentioned low melting point glass powder contains lead in order to lower the softening point, but in recent years, a powder containing no lead has been demanded. An object of the present invention is to provide a lead-free low-melting glass and a glass-ceramic composition for forming a partition wall, which solve the above problems.
【０００４】[0004]
【課題を解決するための手段】本発明は、下記酸化物基
準のモル％表示で、ＳｉＯ2：０〜４５、Ｂ2Ｏ3：０〜
８０、ＺｎＯ：２０〜７０、ＭｇＯ：０〜５０、Ｃａ
Ｏ：０〜５０、ＳｒＯ：０〜５０、ＢａＯ：０〜５０、
Ｌｉ2Ｏ：０〜３０、Ｎａ2Ｏ：０〜３０、Ｋ2Ｏ：０〜
３０、Ａｌ2Ｏ3：０〜１３、ＺｒＯ2：０〜１３、Ｂｉ2
Ｏ3：０〜０．９、から実質的になり、ＳｉＯ2＋Ｂ2Ｏ3
が２５〜８０モル％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ
が０〜５０モル％、Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏが０〜３
０モル％、Ａｌ2Ｏ3＋ＺｒＯ2が０〜１３モル％である
隔壁形成用無鉛低融点ガラス、および、低膨張セラミッ
クスフィラーおよび耐熱顔料の少なくともいずれか一方
と、前記無鉛低融点ガラスの粉末を含有するガラスセラ
ミックス組成物を提供する。According to the present invention, SiO 2 : 0 to 45 and B 2 O 3 : 0 to 0 in terms of mol% based on the following oxides.
80, ZnO: 20-70, MgO: 0-50, Ca
O: 0 to 50, SrO: 0 to 50, BaO: 0 to 50,
Li 2 O: 0~30, Na 2 O: 0~30, K 2 O: 0~
30, Al 2 O 3: 0~13 , ZrO 2: 0~13, Bi 2
O 3 : substantially from 0 to 0.9, SiO 2 + B 2 O 3
Is 25 to 80 mol%, MgO + CaO + SrO + BaO
Is 0 to 50 mol%, and Li 2 O + Na 2 O + K 2 O is 0 to 3
0 mol%, Al 2 O 3 + ZrO 2 is 0 to 13 mol%, and is a lead-free low melting glass for forming a partition wall, at least one of a low expansion ceramic filler and a heat-resistant pigment, and a powder of the lead-free low melting glass. A glass ceramic composition is provided.
【０００５】[0005]
【発明の実施の形態】本発明の無鉛低融点ガラス（以下
単に本発明のガラスという。）を、ＰＤＰ、ＶＦＤ等の
隔壁形成に用いるときは、粉末化して使用される。この
粉末化されたガラスは通常、必要に応じて低膨張セラミ
ックスフィラー、耐熱顔料、等と混合され、次にビヒク
ルと混練してペースト化される。このガラスペーストは
下地のガラスの所定部位に塗布され、焼成される。ここ
でいう下地のガラスはガラス基板等であるが、ガラス基
板の上に透明電導膜、不透明電導膜等が被覆されている
ものも含む。また、前記ビヒクルは通常は樹脂を溶剤に
溶解したものである。BEST MODE FOR CARRYING OUT THE INVENTION When the lead-free low-melting glass of the present invention (hereinafter simply referred to as the glass of the present invention) is used for forming partition walls of PDP, VFD, etc., it is used after being powdered. This powdered glass is usually mixed with a low-expansion ceramic filler, a heat-resistant pigment, or the like, if necessary, and then kneaded with a vehicle to form a paste. This glass paste is applied to a predetermined portion of the underlying glass and fired. The base glass referred to here is a glass substrate or the like, but also includes a glass substrate coated with a transparent conductive film, an opaque conductive film, or the like. Further, the vehicle is usually one in which a resin is dissolved in a solvent.
【０００６】前記焼成が行われる温度は５００〜６２０
℃であることが好ましい。５００℃未満では、隔壁に樹
脂成分が一部残留し、ＰＤＰ、ＶＦＤ等においてパネル
を封着した後に該樹脂成分が隔壁から放出されるおそれ
がある。６２０℃超では、ガラス基板が変形するおそれ
がある。The temperature at which the calcination is performed is 500 to 620.
C. is preferred. If the temperature is lower than 500 ° C., some resin components remain on the partition walls, and the resin components may be released from the partition walls after the panel is sealed with PDP, VFD, or the like. If it exceeds 620 ° C., the glass substrate may be deformed.
【０００７】本発明のガラスの軟化点は４５０〜６５０
℃であることが好ましい。４５０℃未満では、焼成時に
ガラスが流動しすぎ、所望の隔壁形状が得られなくなる
おそれがある。より好ましくは５００℃以上である。６
５０℃超では、焼成時のガラスの流動性が低下し、緻密
な隔壁が得られなくなるおそれがある。より好ましくは
６２０℃以下、特に好ましくは６００℃以下である。The softening point of the glass of the present invention is 450-650.
C. is preferred. If the temperature is lower than 450 ° C., the glass may flow too much during firing, and a desired partition shape may not be obtained. It is more preferably at least 500 ° C. 6
If it is higher than 50 ° C., the fluidity of the glass at the time of firing may decrease, and a dense partition wall may not be obtained. It is more preferably at most 620 ° C, particularly preferably at most 600 ° C.
【０００８】次に、本発明のガラスの組成について、モ
ル％を単に％と記して以下に説明する。ＳｉＯ2または
Ｂ2Ｏ3の少なくともいずれか一方は含有しなければなら
ない。ＳｉＯ2のみを含有してもよいし、Ｂ2Ｏ3のみを
含有してもよいし、これら両者を含有してもよい。Ｓｉ
Ｏ2とＢ2Ｏ3の含有量の合計は２５〜８０％であり、好
ましくは２８〜５５％、より好ましくは３０〜４５％で
ある。Next, the composition of the glass of the present invention will be described below by simply writing mol% as%. At least one of SiO 2 and B 2 O 3 must be contained. It may contain only SiO 2, may contain only B 2 O 3, or may contain both. Si
The total content of O 2 and B 2 O 3 is is 25 to 80%, preferably 28 to 55%, more preferably 30% to 45%.
【０００９】ＳｉＯ2はネットワークフォーマであり４
５％まで含有してもよい。４５％超では軟化点が高くな
りすぎる。より好ましくは３５％以下、特に好ましくは
２０％以下である。ＳｉＯ2を含有する場合、その含有
量は１％以上であることが好ましい。より好ましくは３
％以上、特に好ましくは５％以上、最も好ましくは１０
％以上である。[0009] SiO 2 is a network former.
You may contain up to 5%. If it exceeds 45%, the softening point becomes too high. It is more preferably at most 35%, particularly preferably at most 20%. When SiO 2 is contained, its content is preferably at least 1%. More preferably 3
% Or more, particularly preferably 5% or more, and most preferably 10% or more.
% Or more.
【００１０】Ｂ2Ｏ3はガラスを安定化し、また流動性を
増加させる成分であり、８０％まで含有してもよい。８
０％超では化学的耐久性が低下する。より好ましくは６
０％以下、特に好ましくは４０％以下である。Ｂ2Ｏ3を
含有する場合、その含有量は５％以上であることが好ま
しい。より好ましくは１０％以上、特に好ましくは１５
％以上である。B 2 O 3 is a component that stabilizes glass and increases fluidity, and may be contained up to 80%. 8
If it exceeds 0%, the chemical durability decreases. More preferably 6
0% or less, particularly preferably 40% or less. When B 2 O 3 is contained, its content is preferably at least 5%. More preferably 10% or more, particularly preferably 15% or more.
% Or more.
【００１１】ＺｎＯは軟化点を下げ、また失透を抑制す
る成分であり、必須である。２０％未満では軟化点が高
くなりすぎ、また失透しやすくなる。好ましくは３０％
以上、より好ましくは３５％以上である。７０％超では
ガラス化が困難になる。好ましくは６０％以下、より好
ましくは５０％以下である。ZnO is a component that lowers the softening point and suppresses devitrification, and is essential. If it is less than 20%, the softening point becomes too high, and devitrification tends to occur. Preferably 30%
Or more, more preferably 35% or more. If it exceeds 70%, vitrification becomes difficult. It is preferably at most 60%, more preferably at most 50%.
【００１２】ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯはい
ずれも必須ではないが、失透を抑制するために、または
焼成時の結晶化を抑制するために、それぞれ５０％まで
含有してもよい。５０％超ではガラス化が困難になるお
それがある、または軟化点が高くなりすぎるおそれがあ
る。より好ましくはそれぞれ３０％以下、特に好ましく
はそれぞれ１０％以下である。ＭｇＯ、ＣａＯ、ＳｒＯ
またはＢａＯを含有する場合、その含有成分のそれぞれ
について、含有量は１％以上であることが好ましく、２
％以上であることがより好ましい。Although MgO, CaO, SrO and BaO are not essential, they may each be contained up to 50% in order to suppress devitrification or to suppress crystallization during firing. If it exceeds 50%, vitrification may be difficult, or the softening point may be too high. More preferably, each is 30% or less, particularly preferably 10% or less. MgO, CaO, SrO
Alternatively, when BaO is contained, the content of each of the components is preferably 1% or more, preferably 2% or more.
% Is more preferable.
【００１３】ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯのうちの
１種以上を含有する場合、その含有量の合計は５０％以
下でなければならない。５０％超ではガラス化が困難に
なるおそれがある、または軟化点が高くなりすぎるおそ
れがある。好ましくは３０％以下、より好ましくは１３
％以下である。また、前記含有量の合計は２％以上であ
ることが好ましく、４％以上であることがより好まし
い。When one or more of MgO, CaO, SrO and BaO are contained, the total content thereof must be 50% or less. If it exceeds 50%, vitrification may be difficult, or the softening point may be too high. Preferably not more than 30%, more preferably 13%
% Or less. Further, the total of the contents is preferably 2% or more, more preferably 4% or more.
【００１４】Ｌｉ2Ｏ、Ｎａ2ＯおよびＫ2Ｏはいずれも
必須ではないが、軟化点を下げ流動性を増加させため
に、それぞれ３０％まで含有してもよい。３０％超で
は、化学的耐久性が低下したり、電気絶縁性が低下した
り、また膨張係数が大きくなりすぎたりするおそれがあ
る。好ましくはそれぞれ２５％以下、より好ましくはそ
れぞれ１５％以下である。Ｌｉ2Ｏ、Ｎａ2ＯまたはＫ2
Ｏを含有する場合、その含有成分のそれぞれについて、
含有量は０．２％以上であることが好ましく、０．４％
以上であることがより好ましい。Although Li 2 O, Na 2 O and K 2 O are not essential, they may each be contained up to 30% in order to lower the softening point and increase the fluidity. If it exceeds 30%, the chemical durability may be reduced, the electrical insulation may be reduced, and the coefficient of expansion may be too large. Preferably each is 25% or less, more preferably each is 15% or less. Li 2 O, Na 2 O or K 2
When O is contained, for each of the contained components,
The content is preferably 0.2% or more, and 0.4%
More preferably, it is the above.
【００１５】Ｌｉ2Ｏ、Ｎａ2ＯおよびＫ2Ｏのうちの１
種以上を含有する場合、その含有量の合計は３０％以下
でなければならない。３０％超では、化学的耐久性が低
下したり、電気絶縁性が低下したり、また膨張係数が大
きくなりすぎたりするおそれがある。好ましくは２５％
以下、より好ましくは１５％以下である。また、前記含
有量の合計は１％以上であることが好ましく、２％以上
であることがより好ましい。One of Li 2 O, Na 2 O and K 2 O
If it contains more than one species, the total content must be less than 30%. If it exceeds 30%, the chemical durability may be reduced, the electrical insulation may be reduced, and the coefficient of expansion may be too large. Preferably 25%
Or less, more preferably 15% or less. The total content is preferably 1% or more, more preferably 2% or more.
【００１６】Ａｌ2Ｏ3およびＺｒＯ2はいずれも必須で
はないが、化学的耐久性を高くする効果を有し、それぞ
れ１３％まで含有してもよい。１３％超では軟化点が高
くなりすぎるおそれがある。好ましくは５％以下、より
好ましくは３％以下である。Ａｌ2Ｏ3および／またはＺ
ｒＯ2を含有する場合、それぞれの含有量は０．２％以
上であることが好ましく、０．５％以上であることがよ
り好ましい。Al 2 O 3 and ZrO 2 are not essential, but have an effect of increasing chemical durability, and may each contain up to 13%. If it exceeds 13%, the softening point may be too high. It is preferably at most 5%, more preferably at most 3%. Al 2 O 3 and / or Z
When rO 2 is contained, the content of each is preferably 0.2% or more, more preferably 0.5% or more.
【００１７】Ａｌ2Ｏ3およびＺｒＯ2のいずれか少なく
とも一方を含有する場合、その含有量の合計は１３％以
下でなければならない。１３％超では軟化点が高くなり
すぎるおそれがある。好ましくは１０％以下、より好ま
しくは７％以下である。When at least one of Al 2 O 3 and ZrO 2 is contained, the total content thereof must be 13% or less. If it exceeds 13%, the softening point may be too high. It is preferably at most 10%, more preferably at most 7%.
【００１８】Ｂｉ2Ｏ3は必須ではないが、軟化点を下げ
流動性を増加させるために、０．９％まで含有してもよ
い。０．９％超では濃い着色が起るおそれがある。実質
的に含有しないことが好ましい。Bi 2 O 3 is not essential, but may be contained up to 0.9% in order to lower the softening point and increase the fluidity. If it exceeds 0.9%, deep coloring may occur. It is preferred that they are not substantially contained.
【００１９】本発明のガラスは実質的に上記成分からな
るが、これ以外の成分を合計で５モル％まで含有しても
よい。このような成分として、Ｌａ2Ｏ3等の希土類酸化
物、Ｐ2Ｏ5、ＴｉＯ2、ＭｎＯ、Ｆｅ2Ｏ3、ＣｏＯ、Ｎ
ｉＯ、ＣｕＯ、ＧｅＯ2、Ｙ2Ｏ3、ＭｏＯ3、Ｒｈ2Ｏ3、
Ａｇ2Ｏ、Ｉｎ2Ｏ3、ＴｅＯ2、ＷＯ3、ＲｅＯ2、Ｖ
2Ｏ5、ＰｄＯ、が例示される。なお、ＰｂＯ、ＣｄＯに
ついてはいずれも実質的に含有せず、不純物レベル以下
である。The glass of the present invention consists essentially of the above components, but may contain other components up to a total of 5 mol%. Such components include rare earth oxides such as La 2 O 3 , P 2 O 5 , TiO 2 , MnO, Fe 2 O 3 , CoO, N
iO, CuO, GeO 2 , Y 2 O 3 , MoO 3 , Rh 2 O 3 ,
Ag 2 O, In 2 O 3 , TeO 2 , WO 3 , ReO 2 , V
2 O 5 and PdO are exemplified. In addition, PbO and CdO are not substantially contained, and are lower than the impurity level.
【００２０】本発明のガラスセラミックス組成物は本発
明のガラスの粉末を含有し、この他に、低膨張セラミッ
クスフィラー、耐熱顔料のうちの少なくとも一方を含有
する。低膨張セラミックスフィラーは所望の隔壁形状を
得るための成分であり、隔壁の強度を高める効果も有す
る成分であり、膨張係数が７０×１０-7／℃以下である
セラミックスフィラーである。アルミナ、ムライト、ジ
ルコン、コーディエライト、チタン酸アルミニウム、β
−スポデュメン、α−石英、β−石英固溶体およびβ−
ユークリプタイトから選ばれる１種以上の粉末であるこ
とが、取り扱いやすさまたは入手しやすさの点から好ま
しい。The glass ceramic composition of the present invention contains the powder of the glass of the present invention, and further contains at least one of a low expansion ceramic filler and a heat resistant pigment. The low expansion ceramic filler is a component for obtaining a desired partition shape and also has an effect of increasing the strength of the partition, and is a ceramic filler having an expansion coefficient of 70 × 10 −7 / ° C. or less. Alumina, mullite, zircon, cordierite, aluminum titanate, β
-Spodumene, α-quartz, β-quartz solid solution and β-quartz
One or more powders selected from eucryptite are preferred from the viewpoint of ease of handling or availability.
【００２１】また、耐熱顔料は色調調整成分であり、た
とえばチタニア等の白色顔料、Ｆｅ−Ｍｎ複酸化物系、
Ｆｅ−Ｃｏ−Ｃｒ複酸化物系、Ｆｅ−Ｍｎ−Ａｌ複酸化
物系等の黒色顔料が挙げられる。The heat-resistant pigment is a color tone adjusting component, for example, a white pigment such as titania, an Fe—Mn double oxide,
Black pigments such as Fe-Co-Cr double oxides and Fe-Mn-Al double oxides are exemplified.
【００２２】本発明のガラスセラミックス組成物におい
て、体積百分率表示で、無鉛低融点ガラスの粉末の含有
量は７０〜９９．９％、低膨張セラミックスフィラーの
含有量は０．１〜３０％、かつ耐熱顔料の含有量は０〜
３０％であることが好ましい。In the glass-ceramic composition of the present invention, the content of the lead-free low-melting glass powder is 70 to 99.9%, the content of the low expansion ceramic filler is 0.1 to 30%, and the content is expressed by volume percentage. The content of the heat-resistant pigment is 0 to
It is preferably 30%.
【００２３】以下、本発明のガラスセラミックス組成物
の体積百分率表示の組成について説明する。本発明のガ
ラスの粉末の含有量が７０％未満では焼成時の流動性が
低下しすぎ、隔壁断面に連続的な空隙が生じ緻密な隔壁
が得られなくなるおそれがある。９９．９％超では低膨
張セラミックスフィラーまたは耐熱顔料の含有量が小さ
くなりすぎる。好ましくは８５％以下である。Hereinafter, the composition of the glass ceramic composition of the present invention in terms of volume percentage will be described. If the content of the glass powder of the present invention is less than 70%, the fluidity at the time of firing is excessively reduced, and continuous voids may be generated in the cross section of the partition wall, so that a dense partition wall may not be obtained. If it exceeds 99.9%, the content of the low expansion ceramic filler or the heat-resistant pigment becomes too small. Preferably it is 85% or less.
【００２４】また、低膨張セラミックスフィラーおよび
耐熱顔料の含有量の合計が０．１％未満では低膨張セラ
ミックスフィラーまたは耐熱顔料を含有する効果が小さ
すぎるおそれがある。より好ましくは１５％以上であ
る。３０％超では焼成時の流動性が低下するおそれがあ
る。If the total content of the low-expansion ceramic filler and the heat-resistant pigment is less than 0.1%, the effect of containing the low-expansion ceramic filler or the heat-resistant pigment may be too small. It is more preferably at least 15%. If it exceeds 30%, the fluidity during firing may decrease.
【００２５】低膨張セラミックスフィラーの含有量は１
０〜２５％であることが好ましい。１０％未満では強度
が低くなりすぎるおそれがある。より好ましくは１５％
以上である。２５％超では隔壁の空隙が大きくなり、か
えって強度が低下するおそれがある。耐熱顔料の含有量
は２０％以下であることが好ましい。より好ましくは１
５％以下、特に好ましくは１０％以下、最も好ましくは
５％以下である。The content of the low expansion ceramic filler is 1
Preferably it is 0 to 25%. If it is less than 10%, the strength may be too low. More preferably 15%
That is all. If it exceeds 25%, the voids in the partition walls become large, and the strength may be reduced. The content of the heat-resistant pigment is preferably 20% or less. More preferably 1
It is at most 5%, particularly preferably at most 10%, most preferably at most 5%.
【００２６】本発明のガラスフリットは、通常はビヒク
ルと混合してガラスペーストとされる。ビヒクルとの混
合は、乳鉢、三本ロール、等を用いて行われる。このガ
ラスペーストをスクリーン印刷等の方法により下地のガ
ラス、たとえばガラス基板またはガラス基板上に形成さ
れた薄膜の所定部位に塗布後焼成する。前記ビヒクルと
しては、エチルセルロース、ニトロセルロース、等の樹
脂を、α−テルピネオール、ブチルカルビトールアセテ
ート、酢酸イソペンチル、等の溶剤に溶解したものが通
常用いられる。The glass frit of the present invention is usually mixed with a vehicle to form a glass paste. Mixing with the vehicle is performed using a mortar, a three-roll mill, or the like. This glass paste is applied to a base glass, for example, a glass substrate or a predetermined portion of a thin film formed on the glass substrate, by a method such as screen printing, and then fired. As the vehicle, those obtained by dissolving a resin such as ethyl cellulose or nitrocellulose in a solvent such as α-terpineol, butyl carbitol acetate, or isopentyl acetate are generally used.
【００２７】[0027]
【実施例】表のＳｉＯ2〜ＺｒＯ2の欄にモル％表示で示
した組成となるように原料を調合、混合して白金るつぼ
に入れ、１２００℃に加熱し３０分間溶融した。次いで
溶融ガラスをステンレス鋼製ローラに流し込んでフレー
ク化した。得られたフレーク状のガラスをアルミナ製ボ
ールミルで１８時間湿式粉砕してガラス粉末とした。得
られたガラス粉末の軟化点Ｔs（単位：℃）を、平均粒
径が１０〜２０μｍのガラス粉末を試料として昇温速度
１０℃／分の示差熱分析により測定した。結果を表に示
す。例１〜４のガラスは実施例である。例５〜８のガラ
スは比較例であり、その軟化点は組成から計算で求めた
ものである。EXAMPLES Raw materials were prepared, mixed and placed in a platinum crucible so as to have a composition indicated by mol% in the column of SiO 2 to ZrO 2 in the table, and heated at 1200 ° C. and melted for 30 minutes. Next, the molten glass was poured into a stainless steel roller to form flakes. The obtained flaky glass was wet-pulverized with an alumina ball mill for 18 hours to obtain glass powder. The softening point T s (unit: ° C.) of the obtained glass powder was measured by differential thermal analysis at a heating rate of 10 ° C./min using a glass powder having an average particle size of 10 to 20 μm as a sample. The results are shown in the table. The glasses of Examples 1 to 4 are examples. The glasses of Examples 5 to 8 are comparative examples, and the softening points thereof were calculated from the compositions.
【００２８】次に、平均粒径が３．５μｍの例１〜４の
ガラス粉末、平均粒径が３．０μｍのアルミナ粉末、平
均粒径が０．３μｍのチタニア粉末を体積比で７４：２
１：５で混合したガラスセラミックス組成物１００ｇ
を、α−テルピネオール２０〜２４ｇとエチルセルロー
ス１〜５ｇからなるビヒクルと混練してガラスペースト
とした。Next, the glass powder of Examples 1 to 4 having an average particle size of 3.5 μm, the alumina powder having an average particle size of 3.0 μm, and the titania powder having an average particle size of 0.3 μm were mixed in a volume ratio of 74: 2.
100 g of glass ceramic composition mixed at 1: 5
Was mixed with a vehicle composed of 20 to 24 g of α-terpineol and 1 to 5 g of ethyl cellulose to obtain a glass paste.
【００２９】このガラスペーストを、厚さ２．８ｍｍ、
大きさ１００ｍｍ×１００ｍｍのソーダライムシリカガ
ラス基板にブレードコートし、これを１２０℃で３０分
間乾燥し、膜厚２００μｍの未焼成隔壁層を得た。この
未焼成隔壁層の上にドライフィルムレジストをラミネー
トした後、隔壁パターンの露光マスクをセットして露光
した。その後、濃度３ｇ／ｌの炭酸ナトリウム水溶液で
現像して、ライン幅１００μｍ、スペース幅１５０μｍ
の隔壁パターンを前記未焼成隔壁層の上に形成した。This glass paste was 2.8 mm thick,
A soda lime silica glass substrate having a size of 100 mm × 100 mm was coated with a blade and dried at 120 ° C. for 30 minutes to obtain an unfired partition wall layer having a thickness of 200 μm. After laminating a dry film resist on this unfired partition wall layer, an exposure mask for the partition wall pattern was set and exposed. Thereafter, the film is developed with an aqueous solution of sodium carbonate having a concentration of 3 g / l.
Was formed on the unfired partition wall layer.
【００３０】次にサンドブラストを行い不要部分を切削
して未焼成隔壁を得た。なお、未焼成隔壁の上に残って
いるドライフィルムは濃度１０ｇ／ｌの水酸化ナトリウ
ム水溶液により除去した。この未焼成隔壁を焼成して隔
壁を得た。焼成温度ＴB（単位：℃）を表に示す。Next, sandblasting was performed to cut off unnecessary portions to obtain unfired partition walls. The dry film remaining on the unfired partition was removed with a 10 g / l aqueous sodium hydroxide solution. This unfired partition was fired to obtain a partition. Sintering temperature T B (unit: ° C.) are shown in Table.
【００３１】得られた隔壁を、隔壁パターンのラインに
直交する向きに切断し、隔壁断面を電子顕微鏡により観
察した。隔壁断面における大きさが３μｍ以上の空隙の
有無と、隔壁幅を隔壁高さで除した値Ｗ／Ｈとを表に示
す。ここで、隔壁幅は隔壁高さの１／２の高さでの幅で
あり、Ｗ／Ｈは０．７未満であることが好ましい。Ｗ／
Ｈが０．７以上では隔壁形状が保持されず、好ましくな
い。また、前記空隙の有無は隔壁の緻密性の指標であ
り、無であることが好ましい。The obtained partition was cut in a direction orthogonal to the line of the partition pattern, and the cross section of the partition was observed with an electron microscope. The table shows the presence / absence of a void having a size of 3 μm or more in the partition wall cross section and the value W / H obtained by dividing the partition wall width by the partition wall height. Here, the partition wall width is a width at half the height of the partition wall, and W / H is preferably less than 0.7. W /
When H is 0.7 or more, the shape of the partition wall is not maintained, which is not preferable. The presence or absence of the void is an index of the denseness of the partition, and is preferably zero.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【発明の効果】本発明のガラスまたは本発明のガラスセ
ラミックス組成物を用いることにより、ＰＤＰ、ＶＦ
Ｄ、等における隔壁を緻密にすることができ、また、こ
の隔壁は鉛を含まない特長を有する。By using the glass of the present invention or the glass ceramic composition of the present invention, PDP, VF
D and the like can be made dense, and this partition has a feature not containing lead.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大滝 史郎 福島県郡山市待池台１−８ 郡山西部第二 工業団地 旭硝子郡山電材株式会社内 (72)発明者 真鍋 恒夫 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社内 Ｆターム(参考） 4G062 AA09 BB01 BB05 BB08 DA01 DA02 DA03 DA04 DA05 DB01 DB02 DB03 DB04 DC01 DC02 DC03 DC04 DC05 DC06 DC07 DD01 DE04 DE05 DE06 DF01 EA01 EA02 EA03 EA04 EA10 EB01 EB02 EB03 EB04 EC01 EC02 EC03 EC04 ED01 ED02 ED03 ED04 ED05 EE01 EE02 EE03 EE04 EE05 EF01 EF02 EF03 EF04 EF05 EG01 EG02 EG03 EG04 EG05 FA01 FA10 FB01 FC01 FC02 FC03 FC04 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GA02 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 MM12 MM31 NN32 PP03 PP04 5C040 GF18 KA08 KA11 KB01 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shiro Otaki 1-8 Machiikedai, Koriyama-shi, Fukushima Prefecture The second industrial park in Koriyama Asahi Glass Koriyama Electric Materials Co., Ltd. 1150-cho Asahi Glass Co., Ltd. F-term (reference) 4G062 AA09 BB01 BB05 BB08 DA01 DA02 DA03 DA04 DA05 DB01 DB02 DB03 DB04 DC01 DC02 DC03 DC04 DC05 DC06 DC07 DD01 DE04 DE05 DE06 DF01 EA01 EA02 EA03 EA04 EC03 EB03 EB03 EC04 ED01 ED02 ED03 ED04 ED05 EE01 EE02 EE03 EE04 EE05 EF01 EF02 EF03 EF04 EF05 EG01 EG02 EG03 EG04 EG05 FA01 FA10 FB01 FC01 FC02 FC03 FC04 FD01 FE01 FF01 FG01 H01 FL01H01 F01G01 H01 FL01H01 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM12 MM31 NN32 PP03 PP04 5C040 GF18 KA0 8 KA11 KB01
Claims (4)
％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯが０〜５０モル
％、Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏが０〜３０モル％、Ａｌ2
Ｏ3＋ＺｒＯ2が０〜１３モル％である隔壁形成用無鉛低
融点ガラス。1. The following oxide percentages are expressed in terms of mol%: SiO 2 0-45, B 2 O 3 0-80, ZnO 20-70, MgO 0-50, CaO 0-50, SrO 0-50, BaO 0-50, Li 2 O 0-30, Na 2 O 0-30, K 2 O 0-30, Al 2 O 3 0-13, ZrO 2 0-13, Bi 2 O 3 0-0.9 It becomes substantially, SiO 2 + B 2 O 3 is 25 to 80 mol%, MgO + CaO + SrO + BaO is 0 to 50 mol%, Li 2 O + Na 2 O + K 2 O is 0 to 30 mol%, Al 2
A lead-free low-melting glass for forming partition walls, wherein O 3 + ZrO 2 is 0 to 13 mol%.
に記載の隔壁形成用無鉛低融点ガラス。2. The method according to claim 1, wherein the softening point is 450 to 650 ° C.
4. The lead-free low-melting glass for forming a partition wall according to item 1.
料の少なくともいずれか一方と、請求項１または２に記
載の無鉛低融点ガラスの粉末を含有するガラスセラミッ
クス組成物。3. A glass-ceramic composition comprising at least one of a low-expansion ceramic filler and a heat-resistant pigment, and the powder of the lead-free low-melting glass according to claim 1 or 2.
末の含有量が７０〜９９．９％、低膨張セラミックスフ
ィラーの含有量が０．１〜３０％、かつ耐熱顔料の含有
量が０〜３０％である請求項３に記載のガラスセラミッ
クス組成物。4. In terms of volume percentage, the content of the lead-free low melting glass powder is 70 to 99.9%, the content of the low expansion ceramic filler is 0.1 to 30%, and the content of the heat-resistant pigment is 0. The glass-ceramic composition according to claim 3, wherein the content is from 30% to 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34675099A JP2001163635A (en) | 1999-12-06 | 1999-12-06 | Lead-free low melting point glass for formation of barrier rib and glass ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34675099A JP2001163635A (en) | 1999-12-06 | 1999-12-06 | Lead-free low melting point glass for formation of barrier rib and glass ceramic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001163635A true JP2001163635A (en) | 2001-06-19 |
Family
ID=18385567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34675099A Withdrawn JP2001163635A (en) | 1999-12-06 | 1999-12-06 | Lead-free low melting point glass for formation of barrier rib and glass ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001163635A (en) |
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