JPH11314936A - Low melting point glass, composition for sealing, composition for coating and composition for forming partition wall - Google Patents

Low melting point glass, composition for sealing, composition for coating and composition for forming partition wall

Info

Publication number
JPH11314936A
JPH11314936A JP10126271A JP12627198A JPH11314936A JP H11314936 A JPH11314936 A JP H11314936A JP 10126271 A JP10126271 A JP 10126271A JP 12627198 A JP12627198 A JP 12627198A JP H11314936 A JPH11314936 A JP H11314936A
Authority
JP
Japan
Prior art keywords
composition
low
sealing
glass
ceramic filler
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP10126271A
Other languages
Japanese (ja)
Inventor
Ryuichi Tanabe
隆一 田辺
Hiroshi Usui
寛 臼井
Yasuko Douya
康子 堂谷
Tsuneo Manabe
恒夫 真鍋
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.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP10126271A priority Critical patent/JPH11314936A/en
Publication of JPH11314936A publication Critical patent/JPH11314936A/en
Pending 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
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • 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
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Manufacture Of Electron Tubes, Discharge Lamp Vessels, Lead-In Wires, And The Like (AREA)
  • Gas-Filled Discharge Tubes (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a lead-free low m.p. glass suitable for a compsn. for sealing PDP or VFD, a compsn. for coating a substrate and a compsn. for forming the partition walls of PDP or VFD by incorporating specified amts. of tin oxide, ZnO, P2 O5 , Li2 O, Na2 O and K2 O. SOLUTION: The low m.p. glass consists substantially of, by mol, 0.1 to <2% (expressed in terms of SnO) tin oxide, >44 to 74.9% ZnO, 25-50% P2 O5 and 0-4% Li2 O+Na2 O+K2 O. The compsn. for sealing a plasma display panel or a fluorescent display tube consists of 50-100% powder of the low m.p. glass and 0-50% powder of a low expansion ceramic filler and preferably has 60×10<-7> -90×10<-7> / deg.C average coefft. of thermal expansion in the range of 50-250 deg.C after firing. The ceramic filler is selected from the group consisting of zircon, cordierite, aluminum titanate, alumina, etc., and the total amt. of alumina and zircon is adequately <=9 wt.% of the amt. of the compsn.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、低融点ガラスに関
し、またその低融点ガラスを用いた低温度での熱処理が
可能なプラズマディスプレイパネル（ＰＤＰ）および蛍
光表示管（ＶＦＤ）を封着するための組成物、基体被覆
用組成物、ＰＤＰ、ＶＦＤの隔壁形成用組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-melting glass, and more particularly, to a plasma display panel (PDP) and a fluorescent display tube (VFD) which can be heat-treated at a low temperature using the low-melting glass. , A composition for coating a substrate, and a composition for forming partition walls of PDP and VFD.

【０００２】[0002]

【従来の技術】従来、ＰＤＰまたはＶＦＤにおけるガラ
ス基板は、低融点ガラスを用い４４０〜５００℃で封着
していた。ＰＤＰの場合は封着されたパネルは２５０〜
３８０℃に加熱されつつ排気され、１００〜５００Ｔｏ
ｒｒになるようにＮｅ、Ｎｅ−Ｘｅ、Ｈｅ−Ｘｅ等の放
電ガスを封入する。またＶＦＤの場合は真空を得るため
２５０〜３８０℃に加熱されつつ排気される。2. Description of the Related Art Heretofore, a glass substrate in a PDP or VFD has been sealed at 440 to 500.degree. For PDP, the sealed panel is 250 ~
Exhausted while being heated to 380 ° C, 100 to 500 To
A discharge gas such as Ne, Ne—Xe, or He—Xe is sealed so as to be rr. In the case of VFD, the gas is exhausted while being heated to 250 to 380 ° C. in order to obtain a vacuum.

【０００３】従来の封着用粉末ガラスは、鉛成分を含有
するガラスが用いられていたが、最近では鉛成分を含有
しないガラスが求められている。また、従来の封着用粉
末ガラスは、ガラス基板との熱膨張率がマッチングせ
ず、パネルが割れたり、排気のときの加熱によりガラス
が流動したり、発泡したり、シール部分が割れる場合が
あった。[0003] Conventionally, a glass containing a lead component has been used as a powdered glass for sealing, but recently a glass containing no lead component has been demanded. Further, the conventional powdered glass for sealing does not have a matching coefficient of thermal expansion with the glass substrate, so that the panel may be broken, the glass may flow due to heating at the time of exhaustion, foam may occur, or the seal portion may be broken. Was.

【０００４】[0004]

【発明が解決しようとする課題】本発明は、上記課題を
解決し、鉛成分を含有しない低融点ガラスであって、Ｐ
ＤＰ、ＶＦＤを封着するのに適した組成物の提供を目的
とする。また、基体被覆用組成物、ＰＤＰ、ＶＦＤの隔
壁形成用組成物に適した低融点ガラスの提供を目的とす
る。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and is a low-melting glass containing no lead component.
It is intended to provide a composition suitable for sealing DP and VFD. Another object of the present invention is to provide a low-melting glass suitable for a composition for coating a substrate and a composition for forming a partition wall of PDP and VFD.

【０００５】[0005]

【課題を解決するための手段】本発明は、実質的にモル
表示でＳｎＯに換算したスズ酸化物：０．１〜２％未
満、ＺｎＯ：４４超〜７４．９％、Ｐ2 Ｏ5 ：２５〜５
０％、Ｌｉ2 Ｏ＋Ｎａ2Ｏ＋Ｋ2 Ｏ：０〜４％、からな
る組成を有する低融点ガラスを提供する。本ガラスは、
ＰＤＰ、ＶＦＤの封着用、基体の被覆用、ＰＤＰ、ＶＦ
Ｄなどの隔壁形成用の組成物等として用いるのに適す
る。The present invention SUMMARY OF] is tin oxide in terms of SnO substantially molar Display: less than 0.1 to 2%, ZnO: 44 ultra ~74.9%, P 2 O 5: 25-5
0%, Li 2 O + Na 2 O + K 2 O: 0~4%, provides a low-melting glass having a composition consisting of. This glass is
Sealing of PDP, VFD, coating of substrate, PDP, VF
Suitable for use as a composition for forming a partition such as D.

【０００６】[0006]

【発明の実施の形態】本発明において、ガラスが低融点
であるとは、軟化点が６００℃以下のものであることを
いう。また、低膨張セラミックスフィラーとは、５０〜
３００℃における平均熱膨張係数が７０×１０-7／℃以
下であるセラミックスフィラーをいう。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a glass having a low melting point means that the glass has a softening point of 600 ° C. or lower. In addition, the low expansion ceramic filler is 50 to
A ceramic filler having an average coefficient of thermal expansion at 300 ° C. of 70 × 10 −7 / ° C. or less.

【０００７】本発明における低融点ガラスの組成範囲に
ついて説明する。本発明においては、比較的低温の４０
０〜６００℃、かつ短時間（５分〜１時間）で充分に流
動可能なように、低融点ガラスはモル％表示で以下のよ
うな組成範囲を持つ。The composition range of the low-melting glass according to the present invention will be described. In the present invention, a relatively low temperature of 40
The low-melting glass has the following composition range in terms of mol% so that it can flow sufficiently at 0 to 600 ° C and in a short time (5 minutes to 1 hour).

【０００８】 ＳｎＯに換算したスズ酸化物 ０．１〜２％未満、 ＺｎＯ ４４超〜７４．９％、 Ｐ2 Ｏ5 ２５〜５０％、 Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ ０〜４％。[0008] Tin oxide in terms of SnO less than 0.1 to 2%, ZnO 44 super ~74.9%, P 2 O 5 25~50 %, Li 2 O + Na 2 O + K 2 O 0~4%.

【０００９】ＳｎＯに換算したスズ酸化物は、流動性を
向上させる効果があり、含有量が０．１モル％未満の場
合は軟化点が高くなりすぎ、流動性が悪く、封着部の強
度、気密性が損なわれ、４００〜６００℃では充分流動
しない。好ましくは、０．２モル％以上である。その含
有量が２モル％以上では、製造原料コストが高くなる。[0009] Tin oxide in terms of SnO has the effect of improving fluidity. If the content is less than 0.1 mol%, the softening point is too high, the fluidity is poor, and the strength of the sealing portion is low. , Airtightness is impaired, and it does not flow sufficiently at 400 to 600 ° C. Preferably, it is at least 0.2 mol%. When the content is 2 mol% or more, the cost of the raw material for production increases.

【００１０】ＺｎＯは耐水性を向上させ、封着物の熱膨
張係数を低下させる作用があり、含有量が４４モル％以
下では、熱膨張係数が大きくなり、封着対象物や被覆時
の基体の熱膨張係数とマッチングしにくくなる。好まし
くは５４モル％以上である。含有量が７４．９モル％を
超えると、失透しやすくなる。好ましくは７３モル％以
下である。[0010] ZnO has the effect of improving water resistance and lowering the coefficient of thermal expansion of the sealed material. When the content is less than 44 mol%, the coefficient of thermal expansion increases, and the object to be sealed and the base material for coating are reduced. Matching with the coefficient of thermal expansion becomes difficult. It is preferably at least 54 mol%. If the content exceeds 74.9 mol%, devitrification tends to occur. Preferably it is 73 mol% or less.

【００１１】Ｐ2 Ｏ5 の含有量が２５モル％未満の場合
には、ガラス化が困難になるおそれがある。好ましくは
２７モル％以上である。一方、５０モル％超の場合に
は、焼成後のガラスの耐水性が低下するおそれがある。
好ましくは、４０モル％以下である。When the content of P 2 O 5 is less than 25 mol%, vitrification may be difficult. It is preferably at least 27 mol%. On the other hand, if it exceeds 50 mol%, the water resistance of the fired glass may be reduced.
Preferably, it is at most 40 mol%.

【００１２】Ｌｉ2 Ｏ、Ｎａ2 Ｏ、Ｋ2 Ｏはそれぞれ必
須ではないが、流動性を上げる効果があるので１種以上
含有できる。しかし、その含有量が合量で４モル％を超
えると、熱膨張係数が大きくなりすぎるおそれがある。Each of Li 2 O, Na 2 O and K 2 O is not essential, but can have one or more kinds because it has an effect of increasing fluidity. However, if the total content exceeds 4 mol%, the coefficient of thermal expansion may be too large.

【００１３】本発明のガラス組成物を、ＰＤＰまたはＶ
ＦＤの封着用の組成物に用いる場合は、低融点ガラス粉
末の含有量は封着用組成物の全量に対して、５０〜１０
０重量％の範囲が好ましい。低融点フィラーは含有する
と熱膨張係数を小さくする効果があり、５０重量％未満
では、ガラス分が少なく流動性が悪くなり封着部の気密
性が損なわれる。上記理由により、より好ましくは５５
〜１００重量％、特に好ましくは６０〜１００重量％で
ある。[0013] The glass composition of the present invention is prepared by using PDP or V
When used for a composition for FD sealing, the content of the low melting glass powder is 50 to 10 with respect to the total amount of the sealing composition.
A range of 0% by weight is preferred. When the low melting point filler is contained, it has the effect of reducing the coefficient of thermal expansion, and when it is less than 50% by weight, the glass content is small, the fluidity is deteriorated, and the airtightness of the sealing portion is impaired. For the above reasons, more preferably 55
To 100% by weight, particularly preferably 60 to 100% by weight.

【００１４】一方、この場合の低膨張セラミックスフィ
ラー粉末の含有量は、０〜５０重量％とされるのが好ま
しい。より好ましくは０〜４５重量％、特に好ましくは
０〜４０重量％である。On the other hand, the content of the low expansion ceramic filler powder in this case is preferably 0 to 50% by weight. It is more preferably from 0 to 45% by weight, particularly preferably from 0 to 40% by weight.

【００１５】かかる封着用組成物は、４００〜６００℃
で５分〜１時間程度の加熱で、ＰＤＰもしくはＶＦＤ用
ガラス基板を封着でき、封着後の排気時、２８０〜３８
０℃の加熱により、流動したり、発泡したり、機械的強
度が損なわれたりすることがない。[0015] The sealing composition has a temperature of 400 to 600 ° C.
The glass substrate for PDP or VFD can be sealed by heating for about 5 minutes to 1 hour at a pressure of 280 to 38 hours.
Heating at 0 ° C. does not cause fluidization, foaming, or loss of mechanical strength.

【００１６】低膨張セラミックスフィラーとしては、ジ
ルコン、コージェライト、アルミナ、チタン酸アルミニ
ウム、ムライト、シリカ、β−ユークリプタイト、β−
スポジュメンおよびβ−石英固溶体からなる群より選ば
れた１種以上を使用することが好ましい。かかるセラミ
ックスフィラーのうち、封着強度を向上する観点ではコ
ージェライトが望ましい。Examples of low expansion ceramic fillers include zircon, cordierite, alumina, aluminum titanate, mullite, silica, β-eucryptite, β-
It is preferable to use one or more selected from the group consisting of spodumene and β-quartz solid solution. Among such ceramic fillers, cordierite is desirable from the viewpoint of improving the sealing strength.

【００１７】また、低膨張セラミックスフィラーとして
は、重量表示で、アルミナとジルコンの合量を封着用成
物量に対して９％以下とすることが好ましい。アルミナ
とジルコンは、熱膨張係数が比較的大きく、ガラスと混
合して熱膨張係数を調整する効果が、他の低膨張フィラ
ーより小さいためである。低膨張セラミックスフィラー
の含有量を上記の好ましい範囲にすると、ガラス成分の
量をさほど減らすことなく、所望の熱膨張係数が得られ
るので、耐圧強度の向上に効果がある。Further, as the low expansion ceramics filler, the total amount of alumina and zircon is preferably 9% or less with respect to the amount of the sealing composition in terms of weight. Alumina and zircon have a relatively large coefficient of thermal expansion, and the effect of adjusting the coefficient of thermal expansion by mixing with glass is smaller than that of other low expansion fillers. When the content of the low-expansion ceramic filler is in the above preferable range, a desired coefficient of thermal expansion can be obtained without significantly reducing the amount of the glass component, which is effective in improving the pressure resistance.

【００１８】参考に各種の低膨張セラミックスフィラー
の平均熱膨張係数（５０〜３５０℃、単位：×１０-7／
℃）は、次に示す通りである。 アルミナ ６５〜 ７５、 ジルコン ４２〜 ４８、 コージェライト １０〜 ２０、 チタン酸アルミニウム １０〜 ２０、 ムライト ５０〜 ６０、 シリカ ５〜 ６、 β−ユークリプタイト −６０〜−８０、 β−スポジュメン ８〜 １５、 β−石英固溶体 −１０〜＋１０。For reference, the average thermal expansion coefficient of various low expansion ceramic fillers (50 to 350 ° C., unit: × 10 -7 /
° C) is as follows. Alumina 65-75, zircon 42-48, cordierite 10-20, aluminum titanate 10-20, mullite 50-60, silica 5-6, β-eucryptite -60-80, β-spodumene 8-15 , Β-quartz solid solution -10 to +10.

【００１９】ＰＤＰ、ＶＦＤの封着用組成物としては、
焼成後の５０〜２５０℃における封着用組成物の平均熱
膨張係数が６０×１０-7〜９０×１０-7／℃の範囲にあ
るのが好ましい。上記平均熱膨張係数がこの範囲外で
は、基板ガラスまたは封着物に引張応力が強く働き、耐
圧強度が低下する。As the sealing composition for PDP and VFD,
The average thermal expansion coefficient of the sealing composition at 50 to 250 ° C after firing is preferably in the range of 60 × 10 -7 to 90 × 10 -7 / ° C. If the average coefficient of thermal expansion is out of this range, tensile stress acts strongly on the substrate glass or the sealing material, and the pressure resistance decreases.

【００２０】この組成物に着色のために顔料を添加し使
用することもできる。A pigment may be added to the composition for coloring.

【００２１】基体の被覆用に用いる場合は、重量表示で
低融点ガラスの粉末５０〜１００％と、低膨張セラミッ
クスフィラー０〜５０％とからなる組成物とすることが
好ましい。かかる被覆用組成物は４００〜７００℃で５
分〜１時間程度の加熱で基体の被覆ができる。ここで、
基体の材料としては、ガラスやセラミックスなどの耐熱
材料を用いることができる。When used for coating a substrate, it is preferable to use a composition comprising 50 to 100% of a low melting glass powder by weight and 0 to 50% of a low expansion ceramic filler. Such a coating composition is 5 to 400 ° C. to 700 ° C.
The substrate can be coated by heating for about 1 minute to 1 hour. here,
As a material for the base, a heat-resistant material such as glass or ceramics can be used.

【００２２】ＰＤＰ、ＶＦＤ用の隔壁形成に用いる場合
は、重量表示で低融点ガラスの粉末４０〜１００％とセ
ラミックスフィラー粉末０〜６０％とからなる組成物と
することが好ましい。場合に応じて白色顔料（例えばＴ
ｉＯ2 ）、黒色顔料（例えばＦｅ−Ｍｎ系、Ｆｅ−Ｃｏ
−Ｃｒ系、Ｆｅ−Ｍｎ−Ａｌ系の顔料）を添加すること
ができる。When used for forming a partition wall for PDP and VFD, it is preferable to use a composition comprising 40 to 100% of low melting glass powder and 0 to 60% of ceramic filler powder by weight. Optionally, a white pigment (for example, T
iO 2 ), black pigment (eg, Fe—Mn, Fe—Co
-Cr-based, Fe-Mn-Al-based pigments) can be added.

【００２３】本発明の低融点ガラスの粉末やこれを用い
た各種用途の組成物粉末は、エチルセルロース、ニトロ
セルロース、ブチラール樹脂などの樹脂成分やα−テル
ピネオール、酢酸イソアミル、フェキシエタノール、エ
チルセロソルブ、ジブチルセロソルブ、ブチルカルビト
ールアセテート、エチレングリコールモノフェニルエー
テル等の適当な溶剤を含むビヒクルと混練してぺースト
化して使用することができる。The low-melting glass powder of the present invention and the composition powder for various uses using the same include resin components such as ethyl cellulose, nitrocellulose, and butyral resin, α-terpineol, isoamyl acetate, fexethanol, ethyl cellosolve, and the like. It can be kneaded with a vehicle containing a suitable solvent such as dibutyl cellosolve, butyl carbitol acetate, ethylene glycol monophenyl ether and the like, and used as a paste.

【００２４】また、本発明の低融点ガラスは導電性ペー
スト、抵抗ペースト、誘電ペーストなどのバインダーと
して用いることができる。たとえば、導電性ペーストの
バインダーとして用いる場合は、重量表示で低融点ガラ
スの粉末１〜５０％と導電性粉末５０〜９０％からなる
導電性組成物に適宜有機質のビヒクルを加えて、ペ−ス
ト状にすることが好ましい。ここで、導電性粉末として
はＡｇ、Ｐｄ、Ａｌ、Ｎｉ、Ｃｕ、Ａｕ、またはこれら
の混合物等の導電性を持つ粉末である。かかる導電性ペ
ーストは４００〜９００℃、５分〜１時間程度の加熱焼
成をすることにより、導電体を形成できる。Further, the low melting point glass of the present invention can be used as a binder such as a conductive paste, a resistance paste and a dielectric paste. For example, when used as a binder for a conductive paste, an organic vehicle is appropriately added to a conductive composition composed of 1 to 50% by weight of a low-melting glass powder and 50 to 90% of a conductive powder to give a paste. It is preferable to make the shape. Here, the conductive powder is a conductive powder such as Ag, Pd, Al, Ni, Cu, Au, or a mixture thereof. The conductive paste can be formed by baking the conductive paste at 400 to 900 ° C. for about 5 minutes to 1 hour.

【００２５】[0025]

【実施例】ガラス成分のうちＰ2 Ｏ5 成分を除く固体原
料中に、８５％正リン酸を滴下することによって得られ
た原料スラリーをよく混合した後に、１２０℃で乾燥す
ることによって粉末バッチを作成した。この原料を石英
ルツボ中に入れ、ふたをして９００〜１２００℃で溶融
した後、水砕またはローラーを通すことによりフレーク
状のガラスにした。次いでこれをボールミルにて所定時
間粉砕し、表１に示す組成の低融点ガラスの粉末を製造
した。EXAMPLE A raw material slurry obtained by dropping 85% orthophosphoric acid into a solid raw material excluding a P 2 O 5 component of a glass component was thoroughly mixed, and then dried at 120 ° C. to obtain a powder batch. It was created. This raw material was put in a quartz crucible, covered and melted at 900 to 1200 ° C., and then flaked into glass by granulation or through a roller. Next, this was pulverized for a predetermined time by a ball mill to produce a low melting glass powder having the composition shown in Table 1.

【００２６】これらの低融点ガラスの粉末と低膨張セラ
ミックスフィラー粉末とを表１に示す重量割合で混合
し、封着用組成物を調製した。ここで例１〜例３は実施
例である。例４、例５は比較例である。この封着用組成
物について、以下のように、フローボタン径、接着残留
歪、平均熱膨張係数を測定した結果を表１に示す。These low-melting glass powders and low-expansion ceramic filler powders were mixed at the weight ratio shown in Table 1 to prepare a sealing composition. Here, Examples 1 to 3 are examples. Examples 4 and 5 are comparative examples. Table 1 shows the results of measuring the flow button diameter, the adhesive residual strain, and the average thermal expansion coefficient of the sealing composition as described below.

【００２７】フローボタン径：封着時の組成物の流動性
を示すもので、封着組成物の試料粉末、３．５ｇを、直
径１２．７ｍｍの円柱状に加圧成形後、表１に記載した
焼成温度（単位：℃）に、３０分間保持したとき、封着
組成物が流動した直径（単位：ｍｍ）である。このフロ
ーボタン径は２０．０ｍｍ以上が望ましい。Flow button diameter: This indicates the fluidity of the composition at the time of sealing, and 3.5 g of a sample powder of the sealing composition is pressed into a columnar shape having a diameter of 12.7 mm. It is the diameter (unit: mm) at which the sealing composition has flowed when held at the described firing temperature (unit: ° C) for 30 minutes. The diameter of the flow button is desirably 20.0 mm or more.

【００２８】接着残留歪：封着組成物とビヒクル（酢酸
イソアミルにニトロセルロース１．２％を溶解した溶
液）とを重量比６．５：１の割合で混合してペーストと
した。このペーストを基板ガラス片の上に塗布し、フロ
ーボタン径の場合と同条件で焼成後、ガラス片と封着用
組成物との間に発生した残留歪（単位：ｎｍ／ｃｍ）を
ポーラリメーターを用いて測定した。「＋」は封着用組
成物が圧縮歪を受ける場合、「−」は封着用組成物が引
張歪を受ける場合をそれぞれ示す。この残留歪は−１０
０〜＋５００ｎｍ／ｃｍの範囲が望ましい。Adhesive residual strain: A paste was prepared by mixing the sealing composition and a vehicle (a solution of 1.2% nitrocellulose in isoamyl acetate) at a weight ratio of 6.5: 1. The paste was applied on a glass piece of a substrate, baked under the same conditions as in the case of the flow button diameter, and the residual strain (unit: nm / cm) generated between the glass piece and the sealing composition was measured by a polarimeter. It measured using. “+” Indicates that the sealing composition is subjected to compressive strain, and “−” indicates that the sealing composition is subjected to tensile strain. This residual strain is -10.
A range of 0 to +500 nm / cm is desirable.

【００２９】平均熱膨張係数：封着用組成物をフローボ
タン径の場合と同条件で焼成後、所定寸法に研磨して、
熱膨張測定装置により昇温速度１０℃／分の条件で伸び
の量を測定し、５０〜２５０℃の平均熱膨張係数（単
位：×１０-7／℃）を算出した。基板ガラスとの熱膨張
係数のマッチングを考慮すると、この平均熱膨張係数は
６０×１０-7〜９０×１０-7／℃の範囲が望ましい。Average thermal expansion coefficient: After baking the sealing composition under the same conditions as in the case of the flow button diameter, it is polished to a predetermined size,
The amount of elongation was measured by a thermal expansion measuring device at a temperature rising rate of 10 ° C./min, and an average thermal expansion coefficient (unit: × 10 −7 / ° C.) at 50 to 250 ° C. was calculated. Considering the matching of the coefficient of thermal expansion with the substrate glass, the average coefficient of thermal expansion is desirably in the range of 60 × 10 −7 to 90 × 10 −7 / ° C.

【００３０】また、この封着用組成物をあらかじめ電極
や隔壁リブを形成したＰＤＰの基板の端部に介在させ、
４００〜６００℃で３０分保持して封着しＰＤＰを製造
した。また、電極等を形成したガラス基板の端部の間に
グリッドを設置して介在させ４００〜６００℃で３０分
間保持してガラス基板どうしを封着し、ＶＦＤパネルを
製造した。これらのパネルについて、耐水圧強度、耐熱
強度を測定した結果を表１に示した。それぞれの測定法
は次のとおりである。Further, this sealing composition is interposed at the edge of the PDP substrate on which electrodes and partition ribs have been formed in advance,
The resultant was held at 400 to 600 ° C. for 30 minutes for sealing to produce PDP. In addition, a grid was placed between the ends of the glass substrate on which the electrodes and the like were formed, interposed and held at 400 to 600 ° C. for 30 minutes to seal the glass substrates together to produce a VFD panel. Table 1 shows the results of measuring the water pressure resistance and the heat resistance of these panels. Each measuring method is as follows.

【００３１】耐水圧強度：パネルの内外に水による圧力
差を与えて破壊するときの圧力差を測定した（単位：ｋ
ｇ／ｃｍ2 、５個の平均値）。パネルとしての強度を保
証するために、通常この耐水圧強度は３ｋｇ／ｃｍ2 以
上が望ましい。Water pressure strength: The pressure difference when breaking by applying a pressure difference due to water inside and outside the panel was measured (unit: k).
g / cm 2 , average of 5). In order to guarantee the strength of the panel, usually, the water pressure resistance is desirably 3 kg / cm 2 or more.

【００３２】耐熱強度：パネルの内外に水と湯による温
度差を与えて破壊するときの温度差を測定した（単位：
℃、５個の平均値）。ＰＤＰ、ＶＦＤを製造する際の熱
処理工程で発熱する熱応力を考慮すると、通常この耐熱
強度は４０℃以上が望ましい。Heat resistance: The temperature difference when the panel was broken by giving a temperature difference between water and hot water inside and outside the panel was measured (unit:
° C, average of 5 samples). In consideration of the thermal stress generated in the heat treatment step when manufacturing PDPs and VFDs, the heat resistance is usually preferably 40 ° C. or higher.

【００３３】表から、本発明に係る封着用組成物は従来
品以上の特性を有することがわかる。例１は熱膨張係数
の比較的大であるジルコンおよびアルミナの合量が少な
いため、耐水圧強度が例２より高めである。From the table, it can be seen that the sealing composition according to the present invention has more properties than conventional products. In Example 1, since the combined amount of zircon and alumina having relatively large thermal expansion coefficients is small, the water pressure resistance is higher than that of Example 2.

【００３４】また、本発明の低融点ガラスを基体被覆
用、導電性ペーストのバインダー用、隔壁形成用として
用いた場合の例を表２に示す。それぞれ、表中の焼成温
度で焼成した場合の焼結性と平均熱膨張係数とを記載し
た。例６〜８は実施例、例９は比較例である。なお、焼
結性の評価は、焼成後の焼結体の断面を電子顕微鏡によ
り１０００倍で観察し、ボイド割合（空孔割合）が２０
％未満のものを焼結性良とし、２０％以上のものを焼結
性不良とした。Table 2 shows examples in which the low-melting glass of the present invention is used for coating a substrate, as a binder for a conductive paste, and for forming partition walls. In each case, the sinterability and average coefficient of thermal expansion when fired at the firing temperatures in the table are described. Examples 6 to 8 are working examples, and example 9 is a comparative example. The sinterability was evaluated by observing the cross section of the sintered body after firing at a magnification of 1000 with an electron microscope and finding that the void ratio (void ratio) was 20%.
% Or less was evaluated as good sinterability, and 20% or more was evaluated as poor sinterability.

【００３５】被覆用に用いる場合としては表２に示す割
合で低融点ガラス粉末とセラミックスフィラー粉末を混
合し、エチルセルロースを溶解させたα−テルピネオー
ルまたはニトロセルロースを溶解させたブチルカルビト
ールアセテートからなるビヒクルと混練し、ペースト化
した。When used for coating, a low melting glass powder and a ceramic filler powder are mixed in the proportions shown in Table 2 and a vehicle comprising α-terpineol in which ethyl cellulose is dissolved or butyl carbitol acetate in which nitrocellulose is dissolved. And kneaded into a paste.

【００３６】そのペーストをスクリーン印刷し、乾燥後
４００〜７００℃で焼成した。焼結性、平均熱膨張係数
を表２に示す。The paste was screen-printed, dried and fired at 400 to 700 ° C. Table 2 shows the sinterability and the average coefficient of thermal expansion.

【００３７】導電性ペーストに用いる場合としては、表
２に示す割合で、Ａｇ、Ａｌ等の導電粉末と低融点ガラ
ス粉末とを混合し、エチルセルロースを溶解させたα−
テルピネオールまたはニトロセルロースを溶解させたブ
チルカルビトールアセテートからなるビヒクルと混練
し、ペースト化した。そのペーストを所定のパターンに
スクリーン印刷し、乾燥後４００〜９００℃で焼成し、
導電体を形成した。焼結性、平均熱膨張係数を表２に示
す。When used as a conductive paste, a conductive powder such as Ag or Al and a low-melting glass powder are mixed at the ratios shown in Table 2 and α-
The mixture was kneaded with a vehicle made of butyl carbitol acetate in which terpineol or nitrocellulose was dissolved, to give a paste. The paste is screen-printed in a predetermined pattern, fired at 400 to 900 ° C. after drying,
A conductor was formed. Table 2 shows the sinterability and the average coefficient of thermal expansion.

【００３８】ＰＤＰ、ＶＦＤの隔壁に用いる場合として
は、表２に示す割合で、低融点ガラス粉末とセラミック
スフィラー粉末とを混合し、エチルセルロースを溶解さ
せたα−テルピネオールまたはニトロセルロースを溶解
させたブチルカルビトールアセテートからなるビヒクル
と混練し、ペースト化した。When used for the partition walls of PDPs and VFDs, low-melting glass powder and ceramic filler powder are mixed at the ratio shown in Table 2, and α-terpineol in which ethyl cellulose is dissolved or butyl in which nitrocellulose is dissolved. The mixture was kneaded with a vehicle made of carbitol acetate to form a paste.

【００３９】そのペーストをスクリーン印刷し、乾燥後
サンドブラストによりパターンニングを行った。あるい
はペースト中に感光性樹脂を混合し、スクリーン印刷し
乾燥後露光し、エッチングによりパターン形成してもよ
い。パターン形成後４００〜６００℃で焼成し、所定の
リブ（隔壁）を形成した。The paste was screen-printed, dried and patterned by sandblasting. Alternatively, a photosensitive resin may be mixed into the paste, screen printed, dried, exposed, and then patterned by etching. After pattern formation, baking was performed at 400 to 600 ° C. to form predetermined ribs (partitions).

【００４０】表から本発明に係わる組成物は従来品以上
の特性を有することがわかる。From the table, it can be seen that the composition according to the present invention has more properties than conventional products.

【００４１】[0041]

【表１】 [Table 1]

【００４２】[0042]

【表２】 [Table 2]

【００４３】[0043]

【発明の効果】本発明による低融点ガラスは、鉛成分を
含有しない低融点ガラスであって、ＰＤＰ、ＶＦＤを封
着するための組成物、基体被覆用組成物、導電性組成
物、ＰＤＰ、ＶＦＤの隔壁形成用組成物に適する。この
低融点ガラスを用いて封着したＰＤＰ、ＶＦＤは耐水圧
強度、耐熱強度に優れる。The low-melting glass according to the present invention is a low-melting glass containing no lead component. The low-melting glass contains a composition for sealing PDP, VFD, a composition for coating a substrate, a conductive composition, PDP, Suitable for a composition for forming a partition of VFD. PDPs and VFDs sealed using this low-melting glass are excellent in water pressure resistance and heat resistance.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｊ 11/02 Ｈ０１Ｊ 11/02 Ｂ (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────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification code FI H01J 11/02 H01J 11/02 B (72) Inventor Tsuneo Manabe 1150 Hazawacho, Kanagawa-ku, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Asahi Glass Co., Ltd.

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】実質的にモル表示で、 ＳｎＯに換算したスズ酸化物 ０．１〜２％未満、 ＺｎＯ ４４超〜７４．９％、 Ｐ2 Ｏ5 ２５〜５０％、 Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ ０〜４％、 からなる組成を有する低融点ガラス。1. Substantially in terms of mol, tin oxide calculated as SnO 0.1 to less than 2 %, ZnO 44 to 74.9%, P 2 O 5 25 to 50%, Li 2 O + Na 2 O + K A low-melting glass having a composition of 0 to 4% 2 O. 【請求項２】重量表示で請求項１記載の低融点ガラスの
粉末５０〜１００％と低膨張セラミックスフィラー粉末
０〜５０％とからなり、焼成後の５０〜２５０℃の平均
熱膨張係数が６０×１０-7〜９０×１０-7／℃であるこ
とを特徴とするプラズマディスプレイパネルまたは蛍光
表示管の封着用組成物。2. A low melting point glass powder according to claim 1, comprising 50 to 100% and a low expansion ceramic filler powder of 0 to 50%, and having an average coefficient of thermal expansion at 50 to 250 ° C. after firing of 60. A composition for sealing a plasma display panel or a fluorescent display tube, wherein the composition has a temperature of × 10 -7 to 90 × 10 -7 / ° C. 【請求項３】低膨張セラミックスフィラーが、ジルコ
ン、コージェライト、チタン酸アルミニウム、アルミ
ナ、ムライト、シリカ、β−ユークリプタイト、β−ス
ポジュメンおよびβ−石英固溶体からなる群より選ばれ
た１種以上であることを特徴とする請求項２記載の封着
用組成物。3. The low-expansion ceramic filler is at least one selected from the group consisting of zircon, cordierite, aluminum titanate, alumina, mullite, silica, β-eucryptite, β-spodumene and β-quartz solid solution. 3. The sealing composition according to claim 2, wherein: 【請求項４】低膨張セラミックスフィラーとしての、ア
ルミナとジルコンとの合量が封着用組成物量に対して重
量表示で９％以下であることを特徴とする請求項２また
は３記載の封着用組成物。4. The sealing composition according to claim 2, wherein the total amount of alumina and zircon as the low expansion ceramic filler is 9% or less by weight based on the amount of the sealing composition. Stuff. 【請求項５】請求項１記載の低融点ガラスの粉末５０〜
１００％と低膨張セラミックスフィラー粉末０〜５０％
とからなる基体の被覆用組成物。5. The low melting point glass powder according to claim 1,
100% and low expansion ceramic filler powder 0-50%
A composition for coating a substrate comprising: 【請求項６】請求項１記載の低融点ガラスの粉末４０〜
１００％とセラミックスフィラー粉末０〜６０％からな
るプラズマディスプレイパネルまたは蛍光表示管の隔壁
形成用組成物。6. The low melting glass powder according to claim 1, wherein
A composition for forming a partition wall of a plasma display panel or a fluorescent display tube, comprising 100% and 0 to 60% of a ceramic filler powder.
JP10126271A 1998-05-08 1998-05-08 Low melting point glass, composition for sealing, composition for coating and composition for forming partition wall Pending JPH11314936A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10126271A JPH11314936A (en) 1998-05-08 1998-05-08 Low melting point glass, composition for sealing, composition for coating and composition for forming partition wall

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP10126271A JPH11314936A (en) 1998-05-08 1998-05-08 Low melting point glass, composition for sealing, composition for coating and composition for forming partition wall

Publications (1)

Publication Number Publication Date
JPH11314936A true JPH11314936A (en) 1999-11-16

Family

ID=14931073

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Link
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001158803A (en) * 1999-12-02 2001-06-12 Toray Ind Inc Photosensitive glass paste, back face plate for plasma display and plasma display using the same
WO2001079361A1 (en) * 2000-04-17 2001-10-25 Matsushita Electric Industrial Co., Ltd. Ink for display panel and method for producing plasma display panel using the same
WO2005052071A1 (en) * 2003-11-25 2005-06-09 Johnson Matthey Public Limited Company Digital printing ink composition
WO2007099890A1 (en) * 2006-02-28 2007-09-07 Matsushita Electric Industrial Co., Ltd. Plasma display panel
CN113905994A (en) * 2019-06-05 2022-01-07 费罗公司 Dark low expansion fillers
CN114341070A (en) * 2019-08-30 2022-04-12 昭和电工材料株式会社 Lead-free low-melting-point glass composition, low-melting-point glass composite material and low-melting-point glass paste each comprising same, and sealing structure, electric/electronic component, and coated component each using same

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001158803A (en) * 1999-12-02 2001-06-12 Toray Ind Inc Photosensitive glass paste, back face plate for plasma display and plasma display using the same
WO2001079361A1 (en) * 2000-04-17 2001-10-25 Matsushita Electric Industrial Co., Ltd. Ink for display panel and method for producing plasma display panel using the same
US6855196B2 (en) 2000-04-17 2005-02-15 Matsushita Electric Industrial Co., Ltd. Ink for a display panel and method for producing plasma display panel using the ink
US6893490B2 (en) 2000-04-17 2005-05-17 Matsushita Electric Industrial Co., Ltd. Ink for display panel and method for producing plasma display panel using the same
WO2005052071A1 (en) * 2003-11-25 2005-06-09 Johnson Matthey Public Limited Company Digital printing ink composition
WO2007099890A1 (en) * 2006-02-28 2007-09-07 Matsushita Electric Industrial Co., Ltd. Plasma display panel
JP2007234283A (en) * 2006-02-28 2007-09-13 Matsushita Electric Ind Co Ltd Plasma display panel
JP4513769B2 (en) * 2006-02-28 2010-07-28 パナソニック株式会社 Plasma display panel
US7999476B2 (en) 2006-02-28 2011-08-16 Panasonic Corporation Plasma display sealing structure
CN113905994A (en) * 2019-06-05 2022-01-07 费罗公司 Dark low expansion fillers
CN114341070A (en) * 2019-08-30 2022-04-12 昭和电工材料株式会社 Lead-free low-melting-point glass composition, low-melting-point glass composite material and low-melting-point glass paste each comprising same, and sealing structure, electric/electronic component, and coated component each using same
CN114341070B (en) * 2019-08-30 2023-11-24 株式会社力森诺科 Lead-free low-melting glass composition, low-melting glass composite material and low-melting glass paste each comprising the same, and sealing structure, electrical/electronic component, and coated component each comprising the same

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