JP2005170762A - Manufacturing method of glass molding for organic el - Google Patents

Manufacturing method of glass molding for organic el Download PDF

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JP2005170762A
JP2005170762A JP2003415931A JP2003415931A JP2005170762A JP 2005170762 A JP2005170762 A JP 2005170762A JP 2003415931 A JP2003415931 A JP 2003415931A JP 2003415931 A JP2003415931 A JP 2003415931A JP 2005170762 A JP2005170762 A JP 2005170762A
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glass
organic
plate
mold
molded body
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Koji Ikegami
耕司 池上
Toshimasa Kanai
敏正 金井
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C03B11/06Construction of plunger or mould
    • C03B11/08Construction of plunger or mould for making solid articles, e.g. lenses
    • C03B11/088Flat discs
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C03B11/06Construction of plunger or mould
    • C03B11/08Construction of plunger or mould for making solid articles, e.g. lenses
    • C03B11/082Construction of plunger or mould for making solid articles, e.g. lenses having profiled, patterned or microstructured surfaces
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00Press-moulding glass
    • C03B2215/40Product characteristics
    • C03B2215/41Profiled surfaces
    • C03B2215/412Profiled surfaces fine structured, e.g. fresnel lenses, prismatic reflectors, other sharp-edged surface profiles
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00Press-moulding glass
    • C03B2215/40Product characteristics
    • C03B2215/44Flat, parallel-faced disc or plate products

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide an efficient method of manufacturing a glass molding for an organic EL, which is environment-friendly because it does not use a lot of solvents and chemicals, of which product has a glass surface whose concave part is smooth and not clouded in white, and is resistant to break, and it does not need many dies nor inactive atmosphere. <P>SOLUTION: This manufacturing method of a glass molding for an organic EL, is a manufacturing method of a glass molding used as a front board or a back board of an organic EL element, and it is manufactured by putting and press molding a softened glass in a die. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、有機EL素子の前面板または背面板に使用される有機EL用ガラス成型体の製造方法に関するものである。   The present invention relates to a method for producing a glass molded body for organic EL used for a front plate or a back plate of an organic EL element.

有機EL素子は、一般的にガラス基板(前面板)上にITO等の透明電極からなる陽極が形成され、その上に有機化合物からなる発光層を含む有機膜が形成され、その上にアルミニウム等の金属電極からなる陰極が形成され、それらを覆うようにガラスまたはステンレス等の金属からなる背面板によって封止された構造を有している。   In general, an organic EL element has an anode formed of a transparent electrode such as ITO formed on a glass substrate (front plate), an organic film including a light emitting layer formed of an organic compound formed thereon, and aluminum or the like formed thereon. A cathode made of a metal electrode is formed and sealed by a back plate made of a metal such as glass or stainless steel so as to cover them.

有機EL素子の有機膜は、水分や酸素と接触すると、発光特性が急激に劣化することが知られており、有機膜と水分や酸素との接触を防止するために種々の提案がなされている。例えば、水分を吸収するために捕水材(乾燥剤)を封入した有機EL素子が提案されている(例えば、特許文献1参照。)。   It is known that when an organic film of an organic EL element comes into contact with moisture or oxygen, the light emission characteristics deteriorate rapidly, and various proposals have been made to prevent contact between the organic film and moisture or oxygen. . For example, an organic EL element in which a water capturing material (desiccant) is enclosed to absorb moisture has been proposed (see, for example, Patent Document 1).

乾燥剤を封入するために有機EL素子は、その封止空間の容積を大きくする必要があり、図3に示すように有機EL素子の前面板または背面板として使用される有機EL用ガラス成型体1は、中央部1aと、中央部1aから垂直に膨出した周辺部1bとからなり、中央に凹部1cが形成されている。   In order to enclose the desiccant, it is necessary to increase the volume of the sealing space of the organic EL element. As shown in FIG. 3, a glass molded body for organic EL used as a front plate or a back plate of the organic EL element. 1 includes a central portion 1a and a peripheral portion 1b bulging perpendicularly from the central portion 1a, and a concave portion 1c is formed at the center.

これまで、凹部1cを有する有機EL用ガラス成型体1は、平板ガラスに凹部を形成するためにレジスト処理を施した後にサンドを用いて切削したり(サンドブラスト法)、フッ酸を用いてエッチングしたり(フッ酸エッチング法)して作製されている(例えば、特許文献2参照。)。または、金型の間に板状のガラスを上下に挟んだままの状態で950℃の炉に投入してガラス板を成型する熱間プレス法を用いた有機EL用ガラス成型体の作製方法も開示されている(例えば、特許文献3参照。)。
特開2000−195662号公報 特開2001−297878号公報 特開2003−7453号公報
Up to now, the organic EL glass molded body 1 having the recesses 1c has been subjected to resist treatment to form recesses in the flat glass and then cut using sand (sand blasting method) or etched using hydrofluoric acid. (For example, refer to Patent Document 2). Alternatively, there is also a method for producing a glass molded body for organic EL using a hot press method in which a glass plate is placed in a furnace at 950 ° C. with a plate-like glass sandwiched between molds. (For example, refer to Patent Document 3).
JP 2000-195562 A JP 2001-297878 A JP 2003-7453 A

しかし、サンドブラスト法は、レジスト処理に多量の水や薬品が使用されるため環境負荷が大きいとともに、切削に時間がかかるため大量生産には不向きであった。また、サンドブラスト法によって形成された凹部のガラス表面が白く曇ったすりガラス状になるため、有機EL素子の前面板には使用できないとともに、切削によって形成された凹部のガラス表面にマイクロクラックが発生しやすいため破損しやすかった。   However, the sand blasting method is not suitable for mass production because a large amount of water and chemicals are used for resist processing, which has a large environmental load and takes time for cutting. Moreover, since the glass surface of the recessed part formed by the sandblasting method becomes a white cloudy ground glass, it cannot be used for the front plate of the organic EL element, and microcracks are easily generated on the glass surface of the recessed part formed by cutting. Therefore, it was easy to break.

また、フッ酸エッチング法は、レジスト処理を行なう上に人体に有害なフッ酸を大量に使用し、また、エッチングによって形成される凹部のガラス表面が平滑な面になりにくいため、有機EL用ガラス成型体の作製に不向きであった。   In addition, the hydrofluoric acid etching method uses a large amount of hydrofluoric acid that is harmful to the human body during resist processing, and the glass surface of the recess formed by etching is difficult to be a smooth surface. It was unsuitable for production of a molding.

また、特許文献3に記載の熱間プレス法は、有機EL用ガラス成型体を作製するために時間がかかるため大量生産に不向きであるとともに、金型とガラス板との熱膨張係数の差によって、冷却時に成型されたガラス板が破損しやすいという問題を有していた。また、長時間にわたって高温に曝されるため金型が酸化されないように窒素雰囲気等の不活性雰囲気で作業を行なければならず、作業効率が悪くなるという問題も有していた。   In addition, the hot pressing method described in Patent Document 3 is not suitable for mass production because it takes time to produce a glass molded body for organic EL, and due to the difference in thermal expansion coefficient between the mold and the glass plate. The glass plate molded at the time of cooling has a problem of being easily damaged. Moreover, since it was exposed to high temperature for a long time, it had to work in inert atmospheres, such as nitrogen atmosphere, so that a metal mold | die might not be oxidized, and there also existed a problem that work efficiency worsened.

本発明の目的は、多量の溶剤や薬品を使用しないため環境に優しく、凹部のガラス表面が白く曇らず、また平滑であり、破損しにくく、多数の金型や不活性雰囲気にする必要がなく、効率のよい有機EL用ガラス成型体の製造方法を提供することである。   The purpose of the present invention is environmentally friendly because a large amount of solvent and chemicals are not used, and the glass surface of the concave portion is not white and cloudy, is smooth and is not easily damaged, and does not require a large number of molds or inert atmospheres. It is to provide an efficient method for producing a glass molded body for organic EL.

本発明者等は、鋭意検討を重ねた結果、軟化したガラスを金型に投入して、プレス成型すると、凹部のガラス表面が平滑な有機EL用ガラス成型体を効率よく作製することができることを見いだし、本発明として提案するものである。   As a result of intensive studies, the present inventors have found that, when softened glass is put into a mold and press-molded, a glass molded body for organic EL with a smooth glass surface of the recess can be efficiently produced. It is found out and proposed as the present invention.

すなわち、本発明の有機EL用ガラス成型体の製造方法は、有機EL素子の前面板または背面板として使用される有機EL用ガラス成型体の製造方法であって、軟化したガラスを金型に投入して、プレス成型することを特徴とする。   That is, the method for producing a glass molded body for organic EL of the present invention is a method for producing a glass molded body for organic EL used as a front plate or a back plate of an organic EL element, and the softened glass is put into a mold. And press molding.

本発明の有機EL用ガラス成型体の製造方法は、有機EL素子の前面板または背面板として使用される有機EL用ガラス成型体の製造方法であって、軟化したガラスを金型に投入して、プレス成型するため、多量の溶剤や薬品を使用せず環境に優しく、凹部のガラス表面が白く曇らず、また平滑であり、多数の金型や不活性雰囲気にする必要がなく、破損しにくく、効率よく凹部を有する有機EL用ガラス成型体を作製することができる。   The method for producing a glass molded body for organic EL of the present invention is a method for producing a glass molded body for organic EL used as a front plate or a back plate of an organic EL element, and the softened glass is put into a mold. Because it is press-molded, it does not use a large amount of solvent or chemicals, is environmentally friendly, the glass surface of the recess is not cloudy white, is smooth, does not need to be in a large number of molds or inert atmosphere, and is not easily damaged The glass molded body for organic EL which has a recessed part efficiently can be produced.

すなわち、レジスト処理を行なう必要がないため、多量の溶剤や薬品を必要とせず環境に対して優しく、また、平滑な金型を使用すると有機EL用ガラス成型体の凹部のガラス表面は白く曇らず、また平滑にすることができる。また、マイクロクラックが凹部のガラス表面に発生しにくいため破損しにくい。また、数個の金型(雌型)と1つの金型(雄型)で作製でき、軟化したガラスとの接触時間が短いため、金型が酸化するほどの高温に曝されず、不活性雰囲気にする必要がない。さらに、1回のプレス成型に長時間かからないため、単位時間あたりの生産量を多くすることができる。   In other words, since it is not necessary to perform resist processing, a large amount of solvent and chemicals are not required, and it is environmentally friendly. If a smooth mold is used, the glass surface of the concave portion of the organic EL glass molding is not white and cloudy. Can also be smooth. In addition, since microcracks are unlikely to occur on the glass surface of the recess, they are not easily damaged. In addition, it can be manufactured with several molds (female molds) and one mold (male molds), and since the contact time with the softened glass is short, it is not exposed to high temperatures that oxidize the molds and is inactive. There is no need to create an atmosphere. Furthermore, since one press molding does not take a long time, the production amount per unit time can be increased.

本発明の有機EL用ガラス成型体の製造方法は、ガラス原料を加熱溶融して、プレス成型に適切な粘度となった塊状ガラス(ゴブ)、または予め球状、塊状もしくは板状に成形されたガラスを加熱炉中で加熱して軟化させたガラスを金型(雌型)に投入し、金型(雄型)でプレスすることによって凹部を有するガラス板を作製する。前者の方法よりも後者の方法の方が精度良く成型出来るため好ましい。   The method for producing a glass molded body for organic EL according to the present invention is a glass block obtained by heating and melting a glass raw material to have a viscosity suitable for press molding, or glass previously molded into a spherical shape, a block shape, or a plate shape. Glass that has been softened by heating in a heating furnace is placed in a mold (female mold) and pressed with a mold (male mold) to produce a glass plate having a recess. The latter method is preferable to the former method because it can be molded with high accuracy.

ガラス板に凹部を形成するための凸部が、金型(雄型)に複数個形成されていると、一度のプレスで複数個の凹部を有するガラス板を作製できるため好ましい。なお、ガラスの材質としてホウケイ酸ガラス、アルミノホウケイ酸ガラス、ソーダライムガラス等が使用可能であり、プレス成型時のガラスの粘度は、104.3〜105.2dPa・sであると好ましい。 It is preferable that a plurality of convex portions for forming concave portions on the glass plate are formed on the mold (male mold) because a glass plate having a plurality of concave portions can be produced by a single press. In addition, borosilicate glass, alumino borosilicate glass, soda lime glass, etc. can be used as the material of the glass, and the viscosity of the glass at the time of press molding is preferably 10 4.3 to 10 5.2 dPa · s.

続いて、金型(雌型)からガラス板を取り出した後、アニールを行なう。アニールは、ガラスの材質によって温度が異なるが、徐冷点付近で1〜5時間行なわれる。1時間よりも短いとガラスの歪を充分に取り除きにくいため、反りが発生したり破損したりしやすく、5時間よりも長くアニールを行なっても歪を除去する効果の向上が見込めないため生産性の点から好ましくない。   Subsequently, after the glass plate is taken out from the mold (female mold), annealing is performed. Annealing is performed for 1 to 5 hours near the annealing point, although the temperature varies depending on the material of the glass. If it is shorter than 1 hour, it is difficult to remove the distortion of the glass sufficiently, so it is prone to warp or break, and even if annealing is performed for longer than 5 hours, the effect of removing the distortion cannot be expected. From the point of view, it is not preferable.

次に、プレス成型されたガラス板の少なくとも片面を研磨すると、有機EL用ガラス成型体の肉厚および凹部の深さを調節しやすい。すなわち、図2の(a)に示すように、ガラス板3の上面3a(凹部3bが形成されている面)を研磨すれば、凹部4bの深さが浅いガラス板4を作製することができる。図3の(b)に示すように、ガラス板3の下面3c(凹部3bが形成されていない面)を研磨すれば、肉厚が薄いガラス板5を作製することができる。また、図3の(c)に示すように、ガラス板3の上面3aおよび下面3cを研磨すれば、肉厚が薄く、凹部6bの深さが浅いガラス板6を作製することができる。   Next, when at least one surface of the press-molded glass plate is polished, it is easy to adjust the thickness of the organic EL glass molded body and the depth of the recess. That is, as shown in FIG. 2A, if the upper surface 3a of the glass plate 3 (the surface on which the recess 3b is formed) is polished, the glass plate 4 having a shallow recess 4b can be produced. . As shown in FIG. 3 (b), if the lower surface 3c of the glass plate 3 (the surface where the recess 3b is not formed) is polished, the glass plate 5 having a small thickness can be produced. Moreover, as shown in FIG. 3C, if the upper surface 3a and the lower surface 3c of the glass plate 3 are polished, the glass plate 6 having a small thickness and a shallow recess 6b can be produced.

最後に、耳部や隣り合う凹部の間の厚肉部を切断することによって凹部を中央に有する有機EL用ガラス成型体を作製する。   Finally, the glass molded body for organic EL which has a recessed part in the center is produced by cut | disconnecting the thick part between an ear | edge part and adjacent recessed parts.

なお、有機EL用ガラス成型体の凹部の深さは、0.35〜0.8mmであると好ましい。0.35mmよりも浅いと充分な量の乾燥剤を有機EL素子に封入しにくく、0.8mmよりも深いと、有機EL素子が厚くなりやすい。   In addition, it is preferable that the depth of the recessed part of the glass molding for organic EL is 0.35-0.8 mm. If it is shallower than 0.35 mm, it is difficult to enclose a sufficient amount of desiccant in the organic EL element, and if it is deeper than 0.8 mm, the organic EL element tends to be thick.

以下、本発明の有機EL用ガラス成型体の製造方法を実施例に基づいて詳細に説明する。   Hereinafter, the manufacturing method of the glass molded object for organic EL of this invention is demonstrated in detail based on an Example.

図1は、本発明に係る実施例の有機EL用ガラス成型体の製造方法を示し、(a)は、板状ガラスであり、(b)は、加熱工程、(c)は、金型にガラスを投入する工程、(d)は、プレス成型工程、(e)は、脱型工程、(f)は、研磨工程、(g)は、切断工程を示す説明図である。   FIG. 1 shows a method for producing a glass molded body for organic EL according to an embodiment of the present invention, in which (a) is a sheet glass, (b) is a heating step, and (c) is a mold. (D) is a press molding process, (e) is a demolding process, (f) is a polishing process, and (g) is an explanatory view showing a cutting process.

有機EL用ガラス成型体は、以下のようにして作製した。   The glass molded body for organic EL was produced as follows.

まず、質量%でSiO2 70.2%、Al23 5.4%、B23 13.5%、CaO 0.5%、Na2O 6.7%、K2O 2.2%の組成を有するホウケイ酸ガラスからなる略矩形の板状ガラス10(100×150×5mm)177gを準備する(図1(a))。 First, by mass%, SiO 2 70.2%, Al 2 O 3 5.4%, B 2 O 3 13.5%, CaO 0.5%, Na 2 O 6.7%, K 2 O 2.2 A substantially rectangular plate-like glass 10 (100 × 150 × 5 mm) made of borosilicate glass having a composition of% is prepared (FIG. 1A).

次に、この板状ガラス10は加熱炉11中で1000℃(ガラス粘度:104.8dPa・s)に加熱されて軟化ガラス体12とする(図1(b))。 Next, the plate glass 10 is heated to 1000 ° C. (glass viscosity: 10 4.8 dPa · s) in a heating furnace 11 to obtain a softened glass body 12 (FIG. 1B).

続いて、この軟化ガラス体12を100×100mmの凹部13aを有し、内表面13aaを平滑面にしてある金型(雌型)13に投入し(図3(c))、45×45×0.7mmの4つの凸部14aを有し、凸部14aの表面14aaを平滑面にしてある金型(雄型)でプレスする(図1(d))。   Subsequently, the softened glass body 12 was put into a mold (female mold) 13 having a recess 13a of 100 × 100 mm and the inner surface 13aa being a smooth surface (FIG. 3 (c)), and 45 × 45 ×. It presses with the metal mold | die (male type | mold) which has four convex parts 14a of 0.7 mm, and made the surface 14aa of the convex part 14a into the smooth surface (FIG.1 (d)).

その後、プレス成型された4個の凹部15aを有するガラス板15(100×100×8mm)を金型(雌型)13から取り出した後(図1(e))、560℃で4時間保持してアニールを行なう。   Then, after taking out the press-molded glass plate 15 (100 × 100 × 8 mm) having four concave portions 15a from the mold (female mold) 13 (FIG. 1 (e)), it is held at 560 ° C. for 4 hours. And anneal.

ガラス板15の下面15bの研磨を行ない、ガラス板15の肉厚と凹部15aの深さを所定のサイズに調整した後、光学研磨する。   The lower surface 15b of the glass plate 15 is polished, the thickness of the glass plate 15 and the depth of the recess 15a are adjusted to a predetermined size, and then optically polished.

最後に、耳部15cや凹部15aの間にある厚肉部15dを切断することによって49×49×1.1mmで45×45×0.5mmの凹部16aを中央に有する有機EL用ガラス成型体16を4枚作製する(図1(g))。   Finally, a glass molded body for organic EL having a recess 16a of 49 × 49 × 1.1 mm and 45 × 45 × 0.5 mm in the center by cutting the thick portion 15d between the ear portion 15c and the recess 15a Four 16 pieces are produced (FIG. 1 (g)).

以上のように、本発明の有機EL用ガラス成型体は、多量の溶剤や薬品を使用しないため環境に優しく、破損しにくく、凹部の表面が曇らず、また平滑であり、短時間で効率よく有機EL用ガラス成型体を作製することができるため、有機EL素子の前面板または背面板に使用することができる。   As described above, the glass molded body for organic EL of the present invention is environmentally friendly because it does not use a large amount of solvent or chemical, is not easily damaged, the surface of the concave portion is not cloudy, is smooth, and is efficient in a short time. Since the glass molding for organic EL can be produced, it can be used for the front plate or the back plate of the organic EL element.

本発明に係る実施例の成型体の製造方法を示し、(a)は、板状ガラスであり、(b)は、加熱工程、(c)は、金型にガラスを投入する工程、(d)は、プレス成型工程、(e)は、脱型工程、(f)は、研磨工程、(g)は、切断工程を示す説明図である。The manufacturing method of the molded object of the Example which concerns on this invention is shown, (a) is plate glass, (b) is a heating process, (c) is the process of throwing glass into a metal mold, (d ) Is a press molding process, (e) is a demolding process, (f) is a polishing process, and (g) is an explanatory view showing a cutting process. ガラス板の研磨方法を示す説明図であり、(a)は、凹部の深さが浅いガラス板、(b)は、肉厚が薄いガラス板、(c)は、凹部の深さが浅く、肉厚が薄いガラス板を示す説明図である。It is explanatory drawing which shows the grinding | polishing method of a glass plate, (a) is a glass plate with a shallow depth of a recessed part, (b) is a thin glass plate, (c) is a depth of a recessed part, It is explanatory drawing which shows a glass plate with thin thickness. 有機EL用ガラス成型体を示す断面図である。It is sectional drawing which shows the glass molding for organic EL.

符号の説明Explanation of symbols

1、16 有機EL用ガラス成型体
1a 中央部
1b、3d 周辺部
1c、3b、4b、6b、13a、15a、16a 凹部
3、15 ガラス板
3a 上面
3c 下面
10 板状ガラス
11 加熱炉
12 軟化ガラス
13 金型(雌型)
13aa 内表面
14 金型(雄型)
14a 凸部
14aa 表面
15b 下面
15c 耳部
15d 厚肉部
DESCRIPTION OF SYMBOLS 1,16 Glass molded object for organic EL 1a Central part 1b, 3d Peripheral part 1c, 3b, 4b, 6b, 13a, 15a, 16a Recessed part 3, 15 Glass plate 3a Upper surface 3c Lower surface 10 Plate glass 11 Heating furnace 12 Softened glass 13 Mold (Female)
13aa Inner surface 14 Mold (male)
14a convex part 14aa surface 15b lower surface 15c ear | edge part 15d thick part

Claims (3)

有機EL素子の前面板または背面板として使用される有機EL用ガラス成型体の製造方法であって、軟化したガラスを金型に投入して、プレス成型することを特徴とする有機EL用ガラス成型体の製造方法。   A method for producing a glass molded body for organic EL used as a front plate or a back plate of an organic EL element, wherein softened glass is put into a mold and press-molded. Body manufacturing method. 球状、塊状または板状に成形したガラスを加熱炉中で加熱して軟化したガラスを用いることを特徴とする請求項1に記載の有機EL用ガラス成型体の製造方法。   2. The method for producing a glass molded body for organic EL according to claim 1, wherein the glass formed into a spherical shape, a block shape, or a plate shape is heated in a heating furnace and softened. プレス成型して作製したガラス板の少なくとも片面を研磨することを特徴とする請求項1または2に記載の有機EL用ガラス成型体の製造方法。   The method for producing a glass molded body for organic EL according to claim 1 or 2, wherein at least one surface of a glass plate produced by press molding is polished.
JP2003415931A 2003-12-15 2003-12-15 Manufacturing method of glass molding for organic el Pending JP2005170762A (en)

Priority Applications (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010132348A (en) * 2008-10-01 2010-06-17 Nippon Electric Glass Co Ltd Glass roll
EP3450408A1 (en) * 2017-09-01 2019-03-06 LIBBEY GLASS Inc. Glass tile and method of making the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010132348A (en) * 2008-10-01 2010-06-17 Nippon Electric Glass Co Ltd Glass roll
EP3450408A1 (en) * 2017-09-01 2019-03-06 LIBBEY GLASS Inc. Glass tile and method of making the same

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