JPH11180727A - Substrate glass composition for display device - Google Patents

Substrate glass composition for display device

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Publication number
JPH11180727A
JPH11180727A JP35264597A JP35264597A JPH11180727A JP H11180727 A JPH11180727 A JP H11180727A JP 35264597 A JP35264597 A JP 35264597A JP 35264597 A JP35264597 A JP 35264597A JP H11180727 A JPH11180727 A JP H11180727A
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glass
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Japanese (ja)
Inventor
Nobuya Kuriyama
Hiroshi Machishita
延也 栗山
汎史 町下
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Central Glass Co Ltd
セントラル硝子株式会社
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass

Abstract

PROBLEM TO BE SOLVED: To produce the substrate glass for the display device suitable to a melting and floating forming method including a directly energizing melting, having a moderate heat performance, being a low density glass and particularly suitable for PDP. SOLUTION: The glass is incorporated with 61-65 SiO2 , 9-13 Al2 O3 , 0.5-3.5 ZrO2 , 71-78 SiO2 +Al2 O3 +ZrO2 , 1-6 MgO, 3-9 CaO, 1-5 SrO, 0-5 BaO, 10-15 MgO+ CaO+SrO+BaO, 0-3 Li2 O, 7-10 Na2 O, 1-5 K2 O, 9-14 Li2 O+Na2 O+K2 O by wt.%, and the glass has a specific density of <=2.60 and a distortion point of >=570 deg.C, 10<4> poise temp. of <=1200 deg.C, a temp. difference of poise temp.-devitrification temp. of >=10 deg.C and a coefficient of thermal expansion from room temp. to 300 deg.C of >=80×10<-7> / deg.C.

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、各種表示装置用基板ガラス、特にプラズマディスプレイパネル (PDP) The present invention relates to the various display device substrate glass, particularly a plasma display panel (PDP)
用基板ガラスとして好適なガラス組成物であって、電気溶融法を含めた溶融、およびフロート法による成形 (製板) が容易な表示装置用基板ガラス組成物に関する。 A suitable glass composition as use substrate glass, fused, including electric melting method, and forming by a float process (manufacturing plate) regarding easy display substrate glass composition.

【0002】 [0002]

【従来技術および解決すべき課題】従来、表示装置用基板ガラスとしては、ソーダ石灰シリカ系ガラスが用いられるケースが多い。 BACKGROUND OF problem to be solved] Conventionally, as a substrate glass for a display device, in many cases soda-lime-silica based glass. 一例としてPDP用ガラス基板においては、ガラス基板にニッケルやアルミニウム等の電極や絶縁塗膜等をスクリーン印刷などにより施し、 500℃ In the glass substrate for a PDP as an example, the nickel and the electrode and the insulating coating of aluminum or the like applied by screen printing on a glass substrate, 500 ° C.
を越える温度での焼成を繰返してパネルを製作する。 Repeatedly firing at a temperature exceeding by fabricating the panel. 基板ガラスは電極や塗膜との熱膨張率が異なるとそれらの亀裂や剥離を生じ易いので、熱膨張率を整合させる必要があり、前記ソーダ石灰シリカ系ガラスにおいては熱膨張率が90×10 Since the substrate glass thermal expansion coefficient between the electrode and the coating film are different susceptible to their cracking or peeling, it is necessary to match the thermal expansion coefficient, thermal expansion coefficient in the soda-lime-silica glass is 90 × 10 -7 /℃近くと、電極や塗膜との熱膨張率に近い点において有用であるが、歪点が510℃近辺の温度であるため繰返し焼成に際して熱変形を生じ易く、製作歩留りを著しく悪化させるという問題がある。 -7 / ° C. and nearby, it is useful in a point close to the thermal expansion coefficient between the electrode and the coating film, but easily cause thermal deformation during repeated firing because the strain point is at a temperature of around 510 ° C., significantly deteriorated the manufacturing yield there is a problem of.

【0003】特開平3−40933 号公報には、SiO 2成分、 [0003] Japanese Patent Laid-Open No. 3-40933, SiO 2 component,
Al 2 O 3成分、CaO 等の2価金属酸化物、Na 2 O等のアルカリ金属酸化物、ZrO 2成分等よりなる基板用ガラス組成物であって、600 ℃付近の熱処理においても殆ど変形せず、また熱膨張率もソーダ石灰シリカ系ガラスと殆ど変わらないガラスが開示されている。 Al 2 O 3 component, a bivalent metal oxides such as CaO, alkali metal oxides Na 2 O or the like, a glass composition for substrates made of ZrO 2 component and the like, most deformed even in heat treatment in the vicinity of 600 ° C. not, also glass is disclosed a thermal expansion coefficient almost the same as the soda-lime-silica glass. 概してこの成分系では2価金属酸化物が過多で、ガラスの比重を増大させる上に、ガラス融液の高温粘度を上昇し、均質化、清澄性を悪化し、また、成形性も難化するという危惧がある。 Generally divalent metal oxide is too large in this component system, on increasing the specific gravity of the glass, increases the high temperature viscosity of the glass melt, homogenized, worse clarity, also flame of moldability there is a fear that.
均質化、清澄性を改善するためには溶融促進・清澄剤としてのSO 3 、Sb 2 O 3 、またはAs 2 O 3を過剰に添加する必要があるが、例えば直接通電溶融の場合においてはそれらが電極と反応して電極を変質劣化させたり、ガラスに着色を与えたりするという危惧がある。 Homogenization, SO 3 as melting accelerator-refining agent in order to improve clarity, Sb 2 O 3, or As 2 O 3 it is necessary to excessively added, for example in the case of direct current melting them there or denature degrade the electrode reacts with the electrode, there is a fear that or apply colored glass.

【0004】特開平7−257937号公報には、SiO 2成分、 [0004] Japanese Patent Laid-Open No. 7-257937, SiO 2 component,
Al 2 O 3成分、CaO 等2価金属酸化物、K 2 O 等アルカリ金属酸化物、ZrO 2成分等よりなり、PDP用基板に適用するガラス組成物が開示されている。 Al 2 O 3 component, CaO and a divalent metal oxide, K 2 O or the like alkali metal oxides, consists ZrO 2 component and the like, glass compositions are disclosed to be applied to the substrate for PDP. しかし、ネットワークフォーマーとしてのSiO 2成分が低く、その分ガラス形成が不安定で、失透が生じ易い。 However, low SiO 2 component as a network former, correspondingly glass forming is unstable, easily occurs devitrification. またガラス比重を増大し易く、特に大サイズの表示装置においては装置の重量が増大し、その取扱を困難とするという危惧がある。 The easy to increase the glass density, increases the weight of the device, particularly in a display device of a large size, there is a fear that a difficult its handling.

【0005】特表平9−507207号公報には、ネットワークフォーマーであるSiO 2成分や、Al [0005] JP Hei 9-507207 is, SiO 2 component and a network former, Al 2 O 3成分、B 2 O 3成分、ZrO 2成分と、2価金属酸化物、およびアルカリ金属酸化物を含み、歪点がソーダ石灰系ガラスより高く、熱膨張率がソーダ石灰系ガラス並に高い、基板ガラスや耐火ガラスとして好適なガラス組成物が開示されている。 2 O 3 component, B 2 O 3 component, a ZrO 2 component, the divalent metal oxide, and comprises an alkali metal oxide, a strain point higher than a soda-lime glass, coefficient of thermal expansion to the parallel soda-lime glass high, suitable glass composition is disclosed as the substrate glass and refractory glass.
しかし、SiO 2成分等の割合が低く、相対的に2価金属酸化物、アルカリ金属酸化物等が高く、前記同様ガラス形成が不安定で、失透が生じ易く、またガラス比重を増大する。 However, low proportion of such SiO 2 component, relatively divalent metal oxide, high alkali metal oxide or the like, the same glass forming is unstable, easily occurs devitrification and increases the glass density.

【0006】本発明はそれら従来技術における問題点に鑑みて種々検討の末、完成に達したものであり、直接通電溶融を含めた溶融、フロート法成形に適し、適度な熱特性を有し、比較的低比重のガラスであって、特にPD The present invention end of various studies in view of the problems in those prior art, which has reached completion, the melt including the direct current melt, suitable for float process molding, has an appropriate thermal characteristics, a relatively low density glass, especially PD
P用として好適な表示装置用基板ガラス組成物を提供するものである。 It is to provide a suitable display device substrate glass compositions for the P.

【0007】 [0007]

【課題を解決するための手段】本発明は、wt%で、SiO 2 SUMMARY OF THE INVENTION The present invention is, in wt%, SiO 2
61〜65、Al 2 O 3 9〜13、ZrO 2 0.5〜3.5 、SiO 2 +Al 61~65, Al 2 O 3 9~13, ZrO 2 0.5~3.5, SiO 2 + Al 2 O 2 O
3 +ZrO 2 71〜78、MgO 1〜6、CaO 3〜9、SrO 1〜 3 + ZrO 2 71~78, MgO 1~6 , CaO 3~9, SrO 1~
5、BaO 0〜5、MgO+CaO +Sr0 +BaO 10〜15、Li 2 O 5, BaO 0~5, MgO + CaO + Sr0 + BaO 10~15, Li 2 O
0〜3、Na 2 O 7〜10、K 2 O 1〜5、Li 2 O+Na 2 O+K 2 O 0~3, Na 2 O 7~10, K 2 O 1~5, Li 2 O + Na 2 O + K 2 O
9〜14の範囲で含有し、ガラス比重が2.60以下、ガラスの歪点が 570℃以上、ガラスの10 4ポイズ温度(ガラス粘度が10 4ポイズになる温度で、成形作業をするうえで基準となる)が1200℃以下であり、10 4ポイズ温度− Contained in the range of 9 to 14, the glass specific gravity of 2.60 or less, the strain point of the glass is 570 ° C. or higher, at a temperature of glass 10 4 poise temperature (glass viscosity becomes 10 4 poises, and a reference in terms of the molding operation made) is at 1200 ° C. or less, 10 4 poise temperature -
失透温度の温度差が10℃以上、かつガラスの室温から 3 Temperature difference between liquidus temperature 10 ° C. or higher, and room temperature of the glass 3
00℃における熱膨張率が80×10 -7 /℃以上である表示装置用基板ガラス組成物である。 00 is a display device substrate glass composition is thermal expansion coefficient of 80 × 10 -7 / ℃ or higher at ° C.. である表示装置用基板ガラス組成物である。 A display device substrate glass composition is.

【0008】 [0008]

【発明の実施の形態】以下の各成分において'%'表示はwt%のことをあらわす。 '%' Display DETAILED DESCRIPTION OF THE INVENTION In each of the following components represents that of wt%. 本発明の成分系において、Si In the component system of the present invention, Si
O 2はガラスのネットワークフォーマーとして作用する主成分であり、ガラス中61%未満ではガラスを安定して形成し難く、失透を生じさせ易く、またガラスの歪点が低下し、耐水性、耐薬品性を悪化させ、ガラス比重を増大する傾向にある。 O 2 is the main component acting as a network former of the glass, difficult to form a stable glass is less than 61% in the glass, easily cause devitrification, also reduces the strain point of the glass, water resistance, chemical resistance worsen, there is a tendency to increase the glass specific gravity. 他方65%を越えるとガラス融液の高温粘度が高くなり、フロート法成形が困難になる。 High temperature viscosity of the glass melt increases exceeds the other 65%, float forming becomes difficult. 従って Therefore
61〜65%の範囲で導入する。 To introduce in the range of 61-65%.

【0009】Al 2 O 3はガラスネットワークの一翼を担うもので、ガラスを安定して形成でき、ガラスの歪点、粘度を上昇して耐熱性を向上し、またガラスの耐薬品性、 [0009 Al 2 O 3 is plays a role in the glass network, glass can be stably formed by a strain point of the glass, and increase the viscosity to improve the heat resistance and chemical resistance of the glass,
耐水性を向上する。 To improve the water resistance. Al 2 O 3がガラス中9%未満であるとガラスの歪点が低下し、他方13%を超えるとガラス融液の高温粘度が高くなり、失透傾向が増大し、フロート法成形が困難になる。 Al 2 O 3 decreases the strain point of the glass is less than 9% in the glass, high temperature viscosity of the glass melt increases exceeds the other 13%, devitrification tendency is increased, difficult float forming Become. 従って9〜13%の範囲で導入する。 Thus the introduction in the range 9 to 13%.

【0010】ZrO 2はガラスの耐水性、耐薬品性を向上する。 [0010] ZrO 2 is to improve the water resistance, chemical resistance of the glass. またガラスの歪点を上昇させ、失透の発生を抑える作用を有するので 0.5%以上含有させるのがよく、他方 Further raising the strain point of the glass, good be contained 0.5% or more because it has an effect of suppressing the occurrence of devitrification, while
3.5%を超えると逆に失透傾向が増大し、ガラスの溶融およびフロート法成形を困難とするとともにガラス比重を増大させる。 More than 3.5% devitrification tendency is increased on the contrary, increasing the glass density as well as difficult to melt and float forming of a glass. 従って 0.5〜 3.5%の範囲で導入する。 Accordingly introduced in the range of 0.5 to 3.5%.

【0011】なお、ガラス中SiO 2 +Al 2 O 3 +ZrO 2を71% [0011] The glass in SiO 2 + Al 2 O 3 + ZrO 2 71%
未満とし、相対的に2価成分酸化物やアルカリ金属酸化物を過量に含ませると、ガラス比重が増大するので好ましくない。 Less than a, and is not preferred the inclusion of relatively divalent component oxides or alkali metal oxides in excess, the glass density is increased. またSiO 2 +Al 2 O 3 +ZrO 2を78%を越えて含有すると、熱膨張率が低下する上に、ガラス融液の高温粘度が高くなり、フロート法成形が困難になる。 Further, when containing SiO 2 + Al 2 O 3 + ZrO 2 exceeds 78%, on the coefficient of thermal expansion is reduced, high temperature viscosity of the glass melt increases, float forming becomes difficult. 従って71 Therefore 71
〜78wt%の範囲とし、好適には74〜77%の範囲とする。 In the range of ~78wt%, preferably in the range of 74-77%.

【0012】本成分系において、SiO 2同様のネットワークフォーマーであり、ガラスを安定して形成するB 2 O 3を適宜導入することができる。 In the present component system, a SiO 2 same network former can be introduced into B 2 O 3 to form a glass stably appropriately. B 2 O 3は高温粘度を下げてガラス溶融を容易にする。 B 2 O 3 is to facilitate the glass melt to lower the high temperature viscosity. ただし歪点と熱膨張率を低下する傾向にあり、導入量は2%以下とすべきである。 However tends to lower the strain point and thermal expansion coefficient, the introduced amount should be 2% or less.

【0013】MgO は失透温度を低下させ、また他の二価成分酸化物に比べガラスの歪点を上昇させ、適度に調整するうえで有用であるが、ガラス中1%未満であると上記作用に乏しく、6%を越えて含有すると、ガラスの熱膨張率を低下させ、失透傾向が大きくなる。 [0013] MgO lowers the devitrification temperature and increase the strain point of the glass as compared to other divalent component oxides are useful in order to properly adjust, the is less than 1% in the glass poor effect, when the content exceeds 6%, reduces the thermal expansion coefficient of the glass, the devitrification tendency increases. 従って1〜 Therefore 1
6%の範囲で導入する。 Introduced in the 6% range.

【0014】CaO は主要な2価成分酸化物として、SiO 2 [0014] CaO is as a major divalent component oxide, SiO 2
やAl 2 O 3を主体とするガラスにおける融液の高温粘度を下げ、またその適度な導入により失透の発生を抑制する作用を有するが、ガラス中3%未満ではその作用が不充分であり、他方9%を超えると失透傾向が大きくなり、 , Al 2 O 3, or the lower the high temperature viscosity of the melt in the glass mainly comprising, also has the effect of suppressing the occurrence of devitrification due to its moderate introduced, is insufficient its effect in the glass less than 3% , devitrification tendency is increased when more than the other 9%,
またガラス比重を増大する。 In addition to increase the glass specific gravity. 従って3〜9%の範囲で導入する。 Thus the introduction in the range 3 to 9%.

【0015】SrO はCaO とともにガラス融液の高温粘度を下げ、また失透の発生を抑制する作用を有し、ガラスの熱膨張率、歪点を調整するうえで有用であるが、ガラス中1%未満ではその作用が不充分であり、5%を越えて導入すると比重が増大するので好ましくなく、従って1〜5%の範囲で導入する。 [0015] SrO lowers the high-temperature viscosity of the glass melt along with CaO, also has an action to suppress the occurrence of devitrification, the thermal expansion coefficient of the glass, but is useful for adjusting the strain point, the glass 1 is less than% is insufficient its action, it is not preferable because the specific gravity increases when introduced than 5%, thus introducing in the range of 1-5%.

【0016】BaO はCaO 等とともにでガラス融液の高温粘度を下げ失透の発生を抑制する作用を有するので適宜導入することができるが、ガラス中5%を超えるとガラスの歪点が低下し過ぎ、ガラスの比重を増大する。 [0016] BaO is may be appropriately introduced since it has an action to suppress the occurrence of devitrification lowering the high temperature viscosity of the glass melt in with CaO or the like, the strain point of the glass is lowered when more than 5% in the glass only, to increase the specific gravity of the glass. 従って5%以下の範囲で随時導入する。 Therefore from time to time it introduced in the range of 5% or less.

【0017】さらに、上記組成範囲内において、2価金属酸化物 (CaO 、MgO 、BaO 、SrO)の合計を10〜15%の範囲とすることによって、ガラスの溶融性を良好な範囲に維持しつつ、粘度−温度勾配を適度として成形性を良好とし、耐熱性、化学的耐久性等に優れ、適切な範囲の熱膨張率を有するガラスを得ることができる。 Furthermore, within the above composition range, divalent metal oxides (CaO, MgO, BaO, SrO) by a range total of 10-15%, maintaining the meltability of the glass in good range while, the viscosity - temperature gradient formability was good as appropriate, heat resistance, excellent chemical durability, etc., it is possible to obtain a glass having a thermal expansion coefficient of an appropriate range. 2価金属酸化物の合計が15%を越えると、ガラスの熱膨張率が上昇するとともに失透傾向が増大し、化学的耐久性が低下し、またガラス比重が増大する。 If the total divalent metal oxide exceeds 15%, devitrification tendency with thermal expansion of the glass is increased is increased, and decrease chemical durability, also the glass density is increased. 10%未満では、高温粘度が上昇して溶融および成形を困難とし、熱膨張率が低下する。 In less than 10%, and difficult to melt and mold the high temperature viscosity rises, the thermal expansion coefficient is lowered.

【0018】Li 2 Oは強力なガラス溶融剤として作用するが、ガラスの熱膨張率を低下させ、また歪点も低下させる傾向があるので、ガラス中3%以下の範囲で適宜導入するものである。 [0018] Li 2 O is acts as a potent glass melting agent, lowers the thermal expansion coefficient of the glass, and since also the strain point tends to decrease, but by appropriately introduced within a range of 3% or less in the glass is there.

【0019】Na 2 OはK 2 O とともに主要なガラス溶融剤として作用し、またガラスの熱膨張率を適度な高さに維持するうえで不可欠である。 [0019] Na 2 O acts as the primary glass melting agents with K 2 O, also is essential in maintaining the thermal expansion coefficient of the glass to a proper height. Na 2 Oがガラス中7%未満であると、ガラス溶融が不充分となり、均質性、清澄性も損なう。 When Na 2 O is less than 7% in the glass, it becomes insufficient glass melting impairs homogeneity, also clarity. 他方10%を超えるとガラスの歪点が低下し過ぎ、 More than the other 10% when too low is the strain point of the glass,
耐水性、耐薬品性も劣化する。 Water resistance, also deteriorated chemical resistance. 従って7〜10%の範囲で導入する。 Thus the introduction in the range 7-10%.

【0020】K 2 O は上記理由、およびNa 2 Oとの混合アルカリ効果によりアルカリイオンのガラス中での移動を抑制し、ガラスの体積抵抗率を高める。 The K 2 O is to suppress the movement of the above reasons, and mixed alkali effect by glass of the alkali ions with Na 2 O, increase the volume resistivity of the glass. 2%未満であるとそれら作用が不充分であり、5%を超えると熱膨張率が過大となり、また歪点も低下し過ぎるため、2〜5%の範囲とする。 It is less than 2% is insufficient their action, more than 5%, the become excessive thermal expansion coefficient, and since the strain point excessively lowers, the range of 2-5%. また、ガラス比重をより低くするうえでは、2〜4%の範囲とするのがよい。 Further, in order to lower the glass density is preferably set to the range of 2-4%.

【0021】前記アルカリ金属酸化物 (Li 2 O、Na 2 O、K 2 [0021] The alkali metal oxides (Li 2 O, Na 2 O , K 2
O ) の量に関し、そのガラス中の合計量を9〜14%とすることにより、ガラスの歪点、熱膨張率、高温粘度および失透温度を適切な範囲に維することができる。 It relates the amount of O), the total amount of the glass by a 9-14%, the strain point of the glass, the thermal expansion coefficient, it is possible to Wei high temperature viscosity and devitrification temperature in the appropriate range. アルカリ金属酸化物の合計量が9%未満では熱膨張率が低下し、失透傾向が増大する。 The total amount is less than 9% of alkali metal oxide decreases the thermal expansion coefficient, devitrification tendency is increased. 14%を越えるとガラスの歪点が低下し過ぎるうえに、比重を増大し、体積抵抗率が低下する。 Exceeds 14% in terms of too low the strain point of the glass, to increase the specific gravity, the volume resistivity is lowered. 従って9〜14%の範囲とするものであるが、特にガラスの易溶融性を考慮すれば、12〜14%の範囲がよい。 Thus it is intended that the range 9 to 14% if particularly considering easy meltability, good range 12 to 14%.

【0022】本発明において、原料バッチ中に塩化物、 [0022] In the present invention, the chloride in the raw material batch,
フッ化物を導入するのが望ましく、例えばCaF 2 、MgF 2 It is desirable to introduce the fluoride, for example CaF 2, MgF 2,
NaCl、CaCl 2等の金属フッ化物、塩化物を導入することにより、ガラス融液の粘度、表面張力を降下させ溶融、 NaCl, metal fluoride CaCl 2, etc., by introducing a chloride, lowers viscosity of the glass melt, the surface tension melt,
清澄性を向上し、かつ電気溶融法を採用した場合においては電極を変質劣化させないうえで有効であるが、フッ素、または塩素分として原料バッチのガラス換算量 (酸化物)100重量%に対して0.5 重量%以下外挿添加するのが肝要であり、0.5 重量%を超えると炉材の侵食等が激しくなる傾向があるうえに、ガラスの歪点を低下させる。 Improved clarity, and although in the case of adopting the electric melting method is effective in not altered degrade the electrodes, fluorine or glass in terms of the raw batch as chlorine (oxide) with respect to 100% by weight, 0.5 percent by weight essential to add the following extrapolation, on top there is a tendency for erosion, etc. becomes violently exceeds 0.5 wt% furnace material lowers the strain point of the glass.

【0023】さらにガラスの溶融、清澄性を向上させる原料としては硝酸塩の導入が好ましい。 Furthermore melting of glass, as a raw material for improving the clarity introduction of nitrates are preferred. すなわち例えば硝酸バリウム、硝酸ナトリウム、硝酸カリウム等の原料形態で原料バッチ中に導入するが、硝酸塩の殆どはガラスの初期溶融の過程で酸素を発生し、S 、FeおよびTiのようなガラス中の微量還元成分を酸化状態に維持するため、これら還元成分がモリブデン等の電極と反応して電極が損耗するような弊害を抑制する。 Thus, for example barium nitrate, sodium nitrate, but introduced into the raw batch in raw material form of the potassium nitrate and the like, most of the nitrate to generate oxygen in the course of the initial melting of the glass, traces of glass, such as S, Fe and Ti to maintain a reducing component oxidation state, it suppresses the adverse effects such as these reducing components to wear the electrode reacts with the electrode, such as molybdenum.

【0024】硝酸塩はNO 3として原料バッチのガラス換算量 (酸化物)100重量%に対して4重量%以下、さらに望ましくは 1〜 4重量%の範囲で外挿添加するのが好ましい。 [0024] Nitrates glass in terms of the raw batch as NO 3 (oxide) 4% by weight relative to 100 wt% or less, more preferably preferably added extrapolation in the range of 1-4 wt%. 4重量%を超えると原料バッチの溶解速度が過大となり、安定した溶融状態を得るのが困難となる。 If more than 4 wt% the dissolution rate of the raw batch becomes excessive, it becomes difficult to obtain a stable molten state. 前記塩化物、フッ化物または硝酸塩は必要に応じ適宜導入するもので、両者を併存させてもよい。 The chloride, fluoride or nitrate intended to appropriately introduced as needed, may be coexist both.

【0025】本発明において、直接通電による電気溶融法を採用する場合は、汎用されるモリブデン等の電極と反応して合金を形成したりするようなことは避けねばならず、従って原料バッチ中に清澄剤としてのAs 2 O 3 、Sb [0025] In the present invention, in the case of employing the electric melting method with direct current reacts with the electrode such as molybdenum used frequently must be avoided is that, as or to form an alloy, thus in the raw material batch as 2 O 3 as a refining agent, Sb
2 O 3およびS分、硫酸塩(ガラス中に一部SO 3として残留する) は少量(0.3%以下)に留めるべきである。 2 O 3 and S min, (remaining as part SO 3 in glass) sulfates should be kept in a small amount (0.3%). また、反応性を有するZnO 原料の混入は避けた方がよい。 Further, it is preferable to avoid contamination of ZnO material having reactive.

【0026】さらにフロート法成形による量産を容易とし、成形時の窒素および水素等の還元雰囲気下で揮発したり、ガラスに着色を与えないようにするために、PbO Furthermore to facilitate the production by the float process molding, or volatilized in a reducing atmosphere of nitrogen and hydrogen, such as at the time of molding, in order not to give a colored glass, PbO
、ZnO 等の揮発成分の混入も避けるべきである。 , It should be avoided contamination of volatile components such as ZnO.

【0027】本発明においては、ガラス比重を2.60以下としたことにより、特に大サイズ化しつつあるPDP等の表示装置の軽量化、取扱容易性を高めることができる。 [0027] In the present invention, by which the glass specific gravity 2.60 or less, especially lightweight display device such as a PDP which is becoming larger sized, it is possible to enhance the ease of handling. また、ガラスの歪点 (ガラスが粘度10 14.5ポイズを示す温度) を 570℃以上としたことにより、500 ℃を越える各種繰返し熱処理に対しても基板ガラスが歪んだりすることがなく、更に熱膨張率 (室温〜300 ℃) を80× Further, since the strain point of the glass was (glass viscosity of 10 14.5 Temperature indicating a poise) of 570 ° C. or more, without having to distort the substrate glass against various repeating heat treatment exceeding 500 ° C., further thermal expansion rate (at room temperature to 300 ° C.) 80 ×
10 -7 /℃以上に、かつ90×10 -7 /℃付近まで調整することができるので、厚膜等(熱膨張率は、その組成にもよるが略80〜90×10 -7 /℃である) との熱膨張率差を僅少とし、又は無くし、それらとの密着性を良好としたガラスが得られる。 10 -7 / ° C. or higher, and can be adjusted to around 90 × 10 -7 / ° C., the thick film or the like (the thermal expansion coefficient is approximately 80-90 × 10 -7 / ° C. depending on the composition the thermal expansion coefficient difference is insignificant and is it), or eliminate, the glass was considered good adhesion with them are obtained. 加えて成形作業をするうえで基準となるガラス粘度である10 4ポイズになる温度を、1200℃以下とすることができ、失透温度を10 4ポイズ温度より10℃ In addition the temperature becomes 10 4 poises is a glass viscosity as a reference in terms of the molding work can be a 1200 ° C. or less, 10 ° C. than 10 4 poise temperature devitrification temperature
以上低くしたことにより、成形作業を容易とするものである。 By the low above, it is to facilitate the molding operation.

【0028】 [0028]

【実施例】珪砂、水酸化アルミニウム、無水硼酸、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、炭酸ストロンチウム、ジルコン砂、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、フッ化カルシウムおよび硝酸バリウムよりなる調合原料を白金製耐火坩堝に充填し電気炉内で1500℃、約 4時間加熱溶融した。 EXAMPLES silica sand, aluminum hydroxide, boric acid anhydride, magnesium carbonate, calcium carbonate, barium carbonate, strontium carbonate, zircon sand, lithium carbonate, sodium carbonate, potassium carbonate, platinum a formulation material consisting of calcium fluoride and barium nitrate 1500 ° C. in an electric furnace was charged into a refractory crucible and about 4 hours heating and melting. 次に溶融ガラスを鋳型に流し込み、約 200mm□×35mm厚の大きさのガラスブロックとし、 630℃に保持した電気炉に移入して該炉内で徐冷した。 Then pouring the molten glass into a mold, a glass block of about 200 mm □ × 35 mm thickness of the size, slow cooling in the furnace to transfer the electric furnace maintained at 630 ° C..

【0029】原料調合に基づくガラス (酸化物) 組成を表1、表2に示す。 The glass-based raw material preparation (oxide) Table 1 The composition shown in Table 2. なおいずれのケースにおいても、Ca Note In either case, Ca
F 2のかたちで導入されるF 分、Ba(NO 3 ) 2のかたちで導入されるNO 3分についてはガラス酸化物成分計100 wt%に対する外挿添加・導入量 (wt%) としてF 0.2 %、NO 3 F content to be introduced in the form of F 2, F 0.2 as Ba (NO 3) extrapolation added and introduction amount to the glass oxide components total 100 wt% for NO 3 minutes to be introduced in the second form (wt%) %, NO 3
0.3 %と共通とした。 It was 0.3% and the common.

【0030】これらのガラス試料について、室温〜 300 [0030] For these glass samples, room temperature to 300
℃における平均熱膨張率( X10 -7 /℃) 、歪点 (ガラスが粘度10 14.5ポイズを示す温度) 、転移点(熱膨張率測定に際する温度−膨張量勾配の変化 <転移> 点)、溶融温度(ガラスが粘度10 2ポイズを示す温度)、成形温度 Average thermal expansion coefficient at ° C. (X10 -7 / ° C.), (temperature showing a glass viscosity of 10 14.5 poise) strain point, transition point (temperature to time to measure the coefficient of thermal expansion - the change in the expansion amounts gradient <Transition> point) , (the temperature at which the glass exhibits a viscosity of 10 2 poises) melt temperature, mold temperature
(ガラスが粘度10 4ポイズを示す温度=10 4ポイズ温度)、失透温度(ガラスを一定温度に2時間維持して失透が生ずる上限温度)、作業温度範囲(上記成形温度− (Temperature glass exhibits a viscosity of 10 4 poise = 10 4 poise temperature), (upper limit temperature devitrification occurs maintained 2 hours glass at a constant temperature) the devitrification temperature, the working temperature range (the molding temperature -
失透温度)、およびガラス比重を測定した。 Devitrification temperature), and it was measured glass gravity. それらの結果を表1(実施例)、表2(実施例、比較例)に示す。 Table The results 1 (Example) shown in Table 2 (Example, Comparative Example).

【0031】 〔表1・実施例〕 実 施 例 (wt%) 1 2 3 4 5 6 7 SiO 2 * 62.1 62.5 62.6 62.8 61.3 60.8 60.6 Al 2 O 3 * 9.6 9.6 9.7 9.7 11.9 11.9 11.8 ZrO 2 * 2.5 2.5 2.5 2.5 2.5 2.3 2.5 B 2 O 3 0 0 0 0 0 0 0 *小計 74.2 74.6 74.8 75.0 75.7 75.0 74.9 Li 2 O 0 0 0 0 0.5 0.5 0 Na 2 O 8.1 8.2 8.2 8.2 8.2 8.2 8.1 K 2 O 4.5 4.5 4.5 4.6 3.0 2.9 4.5 小計 12.6 12.7 12.7 12.8 11.7 11.6 12.6 MgO 2.0 2.0 2.5 3.1 2.0 2.5 3.0 CaO 7.6 7.7 7.0 6.1 7.7 7.7 6.6 SrO 1.6 3.1 3.1 3.1 3.1 3.2 3.0 BaO 2.1 0 0 0 0 0 0 小計 13.3 12.7 12.5 12.3 12.7 13.4 12.6熱膨張率(X10 ー7 /・c) 83 85 82 82 82 83 83 歪点 581 580 573 575 573 574 593 転移点 620 620 610 612 605 610 632 溶融温度 1554 1576 1576 1594 1596 1599 1594 成形温度 1138 1142 1146 1156 1160 1173 1152 失透温度 1120 1129 1108 1100 1110 1109 1120 作業温度範囲 18 13 38 56 50 64 32 比重 2.59 2.58 2.59 2.59 2.59 2.59 2.59 (注:各成分、小計のwt%表示において下位数値は四捨五入した [0031] Table 1 - Example] implementation examples (wt%) 1 2 3 4 5 6 7 SiO 2 * 62.1 62.5 62.6 62.8 61.3 60.8 60.6 Al 2 O 3 * 9.6 9.6 9.7 9.7 11.9 11.9 11.8 ZrO 2 * 2.5 2.5 2.5 2.5 2.5 2.3 2.5 B 2 O 3 0 0 0 0 0 0 0 * subtotal 74.2 74.6 74.8 75.0 75.7 75.0 74.9 Li 2 O 0 0 0 0 0.5 0.5 0 Na 2 O 8.1 8.2 8.2 8.2 8.2 8.2 8.1 K 2 O 4.5 4.5 4.5 4.6 3.0 2.9 4.5 subtotal 12.6 12.7 12.7 12.8 11.7 11.6 12.6 MgO 2.0 2.0 2.5 3.1 2.0 2.5 3.0 CaO 7.6 7.7 7.0 6.1 7.7 7.7 6.6 SrO 1.6 3.1 3.1 3.1 3.1 3.2 3.0 BaO 2.1 0 0 0 0 0 0 subtotal 13.3 12.7 12.5 12.3 12.7 13.4 12.6 thermal expansion coefficient (X10 over 7 / · c) 83 85 82 82 82 83 83 strain point 581 580 573 575 573 574 593 transition 620 620 610 612 605 610 632 melt temperature 1554 1576 1576 1594 1596 1599 1594 molding temperature 1138 1142 1146 1156 1160 1173 1152 liquidus temperature 1120 1129 1108 1100 1110 1109 1120 working temperature range 18 13 38 56 50 64 32 density 2.59 2.58 2.59 2.59 2.59 2.59 2.59 (Note: lower numerical in wt% representation of each component, subtotal I was rounding

【0032】 〔表2・実施例、比較例〕 実 施 例 比 較 例 (wt%) 8 9 1 2 3 4 5 SiO 2 * 61.3 63.4 67.1 65.0 61.5 54.0 57.7 Al 2 O 3 * 10.0 9.8 6.1 12.0 9.5 9.0 6.5 ZrO 2 * 2.5 2.5 1.3 2.0 2.5 3.7 3.0 [0032] Table 2 - Examples and Comparative Examples] implementation example comparisons Example (wt%) 8 9 1 2 3 4 5 SiO 2 * 61.3 63.4 67.1 65.0 61.5 54.0 57.7 Al 2 O 3 * 10.0 9.8 6.1 12.0 9.5 9.0 6.5 ZrO 2 * 2.5 2.5 1.3 2.0 2.5 3.7 3.0 B 2 O 3 1.3 0 0 0 0 0 0 *小計 73.8 75.7 74.5 79.0 73.5 66.7 67.2 Li 2 O 0 0 0 0 0 0 0 Na 2 O 7.6 8.3 7.3 7.0 8.0 4.0 4.5 B 2 O 3 1.3 0 0 0 0 0 0 * Subtotal 73.8 75.7 74.5 79.0 73.5 66.7 67.2 Li 2 O 0 0 0 0 0 0 0 Na 2 O 7.6 8.3 7.3 7.0 8.0 4.0 4.5 K 2 O 4.7 4.6 2.7 2.0 4.5 9.0 6.6 小計 12.3 12.9 10.0 9.0 12.5 13.0 11.1 MgO 2.0 5.4 3.6 4.0 2.0 3.0 1.8 CaO 7.5 3.0 9.8 8.0 7.5 7.7 5.1 SrO 3.1 3.1 0 0 0 0 7.0 K 2 O 4.7 4.6 2.7 2.0 4.5 9.0 6.6 Subtotal 12.3 12.9 10.0 9.0 12.5 13.0 11.1 MgO 2.0 5.4 3.6 4.0 2.0 3.0 1.8 CaO 7.5 3.0 9.8 8.0 7.5 7.7 5.1 SrO 3.1 3.1 0 0 0 0 7.0 BaO 0 0 2.1 0 4.5 9.6 8.0 小計 12.6 11.5 15.5 12.0 14.0 20.3 21.9熱膨張率(X10 ー7 /・c) 82 82 77 72 83 85 81 歪点 575 589 592 631 598 603 581 転移点 622 630 634 670 623 637 627 溶融温度 1575 1600 1590 1650 1557 1506 1538 成形温度 1130 1194 1170 1225 1130 1129 1135 失透温度 1115 1106 1175 1202 1129 1115 1065 作業温度範囲 15 88 ー5 23 1 14 70 比重 2.59 2.58 2.62 2.52 2.59 2.74 2.77 (注:各成分、小計のwt%表示において下位数値は四捨五入した) BaO 0 0 2.1 0 4.5 9.6 8.0 Subtotal 12.6 11.5 15.5 12.0 14.0 20.3 21.9 thermal expansion coefficient (X10 over 7 / · c) 82 82 77 72 83 85 81 strain point 575 589 592 631 598 603 581 transition 622 630 634 670 623 637 627 melt temperature 1575 1600 1590 1650 1557 1506 1538 forming temperature 1130 1194 1170 1225 1130 1129 1135 liquidus temperature 1115 1106 1175 1202 1129 1115 1065 working temperature range 15 88 -5 23 1 14 70 density 2.59 2.58 2.62 2.52 2.59 2.74 2.77 ( Note: lower numerical in wt% representation of each component, subtotal rounded off)

【0033】表1、表2中実施例NO.1〜 NO.9は本発明におけるガラスであり、10 2ポイズ温度が1600℃以下であって、電気溶融等により、容易に溶融、清澄化できる。 [0033] Table 1, in Table 2 Example NO.1~ NO.9 is glass in the present invention, there is 10 2 poise temperature 1600 ° C. or less, the electric melting or the like, easily melted, it clarified . 10 Ten 4ポイズ温度を1200℃以下とし、失透温度を10 4 4 poise temperature of 1200 ° C. or less, the devitrification temperature 10 4
ポイズ温度より10℃以上低くしたことにより、成形性も容易としフロート法成形に適する。 By the low 10 ° C. or higher than poise temperature, moldability and easily adapted to float molding. ガラスの歪点は570 Strain point of the glass is 570
℃以上で耐熱性が良好である。 ℃ is good heat resistance more. 熱膨張率は80×10 -7 /℃ Thermal expansion coefficient 80 × 10 -7 / ℃
以上で電極や厚膜との熱膨張率に近似している。 It approximates the thermal expansion coefficient between the electrode and a thick film above. またガラス比重を2.60以下としたことにより、大サイズ化しつつある表示装置の軽量化、取扱容易性を高めることができる。 Also by that the glass specific gravity 2.60 or less, weight saving of the display device is becoming larger sized, it is possible to enhance the ease of handling. 更に、表示しないが体積抵抗率も10 9 Ω.cm 以上で電気絶縁性に優れ、表示装置用基板ガラス、殊にPD Furthermore, although not displayed excellent electrical insulation volume resistivity 10 9 Ω.cm or more, the display device substrate of glass, in particular PD
P用の基板ガラスとして好適である。 It is suitable as a substrate glass for P.

【0034】 [0034]

【発明の効果】本発明のガラスは、ガラスの熱膨張率、 The glass of the present invention exhibits a thermal expansion coefficient of the glass,
歪点、ガラス比重等の点で表示装置用基板ガラス、特にPDP用の基板ガラスとして好適であり、またガラスの溶融性も良好で、直接通電法による溶融およびフロート法による成形に適し、均質なガラスを連続的に低いコストで製造することができ、量産に適するという効果を奏する。 Strain point, the display device substrate glass in terms of glass gravity such, is particularly suitable as a substrate glass for PDP, also meltability was good, suitable for forming by melting and float by the direct current method, a homogeneous It can produce glass continuously low cost, an effect that is suitable for mass production.

Claims (1)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】wt%で、SiO 2 61〜65、Al 2 O 3 9〜13、Zr 1. A in wt%, SiO 2 61~65, Al 2 O 3 9~13, Zr
    O 2 0.5〜3.5 、SiO 2 +Al 2 O 3 +ZrO 2 71〜78、MgO 1〜 O 2 0.5~3.5, SiO 2 + Al 2 O 3 + ZrO 2 71~78, MgO 1~
    6、CaO 3〜9、SrO 1〜5、BaO 0〜5、MgO +CaO 6, CaO 3~9, SrO 1~5, BaO 0~5, MgO + CaO
    +Sr0 +BaO 10〜15、Li 2 O 0〜3、Na 2 O 7〜10、K 2 + Sr0 + BaO 10~15, Li 2 O 0~3, Na 2 O 7~10, K 2
    O 1〜5、Li 2 O+Na 2 O+K 2 O9〜14の範囲で含有し、ガラス比重が2.60以下、ガラスの歪点が 570℃以上、ガラスの10 4ポイズ温度が1200℃以下であり、10 4ポイズ温度−失透温度の温度差が10℃以上、かつガラスの室温から 300℃における熱膨張率が80×10 -7 /℃以上であることを特徴とする表示装置用基板ガラス組成物。 O 1 to 5, incorporated within a range of Li 2 O + Na 2 O + K 2 O9~14, glass specific gravity of 2.60 or less, the strain point of the glass is 570 ° C. or higher, 10 4 poise temperature of the glass is at 1200 ° C. or less, 10 4 poise temperature - devitrification temperature difference in temperature 10 ° C. or higher, and the display device substrate glass composition characterized in that the thermal expansion coefficient at 300 ° C. from room temperature of the glass is 80 × 10 -7 / ℃ above.
JP35264597A 1997-12-22 1997-12-22 Substrate glass composition for display device Pending JPH11180727A (en)

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