JP2012106919A - Alkali-free glass - Google Patents
Alkali-free glass Download PDFInfo
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- JP2012106919A JP2012106919A JP2011234468A JP2011234468A JP2012106919A JP 2012106919 A JP2012106919 A JP 2012106919A JP 2011234468 A JP2011234468 A JP 2011234468A JP 2011234468 A JP2011234468 A JP 2011234468A JP 2012106919 A JP2012106919 A JP 2012106919A
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- 239000011521 glass Substances 0.000 title claims abstract description 115
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 7
- 238000007500 overflow downdraw method Methods 0.000 claims description 9
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- 238000004031 devitrification Methods 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 7
- 238000005530 etching Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000013078 crystal Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000008602 contraction Effects 0.000 description 4
- 239000006025 fining agent Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000007088 Archimedes method Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000009774 resonance method Methods 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000006066 glass batch Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- -1 F 2 Substances 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 229910052917 strontium silicate Inorganic materials 0.000 description 1
- QSQXISIULMTHLV-UHFFFAOYSA-N strontium;dioxido(oxo)silane Chemical compound [Sr+2].[O-][Si]([O-])=O QSQXISIULMTHLV-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- Electroluminescent Light Sources (AREA)
- Glass Compositions (AREA)
Abstract
Description
本発明は、無アルカリガラスに関し、特に有機ＥＬディスプレイに好適な無アルカリガラスに関する。 The present invention relates to an alkali-free glass, and more particularly to an alkali-free glass suitable for an organic EL display.
有機ＥＬディスプレイ等の電子デバイスは、薄型で動画表示に優れると共に、消費電力も低いため、携帯電話のディスプレイ等の用途に使用されている。 Electronic devices such as organic EL displays are thin and excellent in moving image display and have low power consumption, and are therefore used for applications such as mobile phone displays.
有機ＥＬディスプレイの基板として、ガラス板が広く使用されている。この用途のガラス板には、主に以下の特性が要求される。
（１）熱処理工程で成膜された半導体物質中にアルカリイオンが拡散する事態を防止するため、実質的にアルカリ金属酸化物を含有しないこと、
（２）ガラス板を低廉化するため、生産性に優れること、特に耐失透性や溶融性に優れること、
（３）ｐ−Ｓｉ・ＴＦＴの製造工程において、ガラス板の熱収縮を低減するため、歪点が高いこと。
Glass plates are widely used as substrates for organic EL displays. The glass plate for this application is mainly required to have the following characteristics.
(1) In order to prevent a situation where alkali ions are diffused in the semiconductor material formed in the heat treatment step, substantially no alkali metal oxide is contained;
(2) In order to reduce the cost of the glass plate, it is excellent in productivity, particularly excellent in devitrification resistance and meltability,
(3) In the manufacturing process of p-Si.TFT, the strain point is high in order to reduce the thermal shrinkage of the glass plate.
近年では、上記要求に加えて、ディスプレイの軽量・薄型化、更にはフレキシブル化等の要求が強まっている。 In recent years, in addition to the above requirements, there have been increasing demands for lighter and thinner displays and further flexibility.
ディスプレイの薄型化には、一般的にケミカルエッチングが用いられている。この方法は、２枚のガラス板を張り合わせたディスプレイパネルをフッ酸系薬液に浸漬させることにより、ガラス板を薄くする方法である。 Chemical etching is generally used for thinning the display. This method is a method of thinning a glass plate by immersing a display panel in which two glass plates are bonded together in a hydrofluoric acid chemical solution.
しかし、従来のディスプレイ用ガラス板は、フッ酸系薬液に対する耐性が高いため、エッチングレートが非常に遅いという課題があった。エッチングレートを速めるために、薬液中のフッ酸濃度を高めると、フッ酸系溶液中に不溶な微粒子が多くなり、結果として、この微粒子がガラス表面に付着し易くなり、ガラス板の表面においてエッチングの均一性が損なわれる。 However, the conventional display glass plate has a problem that the etching rate is very slow because it has high resistance to hydrofluoric acid chemicals. Increasing the concentration of hydrofluoric acid in the chemical solution to increase the etching rate increases the number of insoluble fine particles in the hydrofluoric acid solution, and as a result, the fine particles tend to adhere to the glass surface, and etch on the surface of the glass plate. The uniformity of is impaired.
上記課題を解決するために、ガラス組成中のＢ２Ｏ３の含有量を低減して、フッ酸系薬液に対するエッチングレートを速める方法が検討されている。例えば、特許文献１には、Ｂ２Ｏ３を０〜１．５モル％含有する無アルカリガラスが開示されている。しかし、特許文献１に記載の無アルカリガラスは、耐失透性が低いため、成形時に失透が生じ易く、製造が困難である。また、この無アルカリガラスの耐失透性を高めるには、Ａｌ２Ｏ３の含有量を下げる必要があるが、この場合、歪点が低下して、ｐ−Ｓｉ・ＴＦＴの製造工程において、ガラス板の熱収縮が大きくなる。したがって、特許文献１に記載の無アルカリガラスは、高歪点と高耐失透性を両立させることが困難である。 In order to solve the above problems, a method for reducing the content of B 2 O 3 in the glass composition and increasing the etching rate for the hydrofluoric acid chemical solution has been studied. For example, Patent Document 1 discloses an alkali-free glass containing 0 to 1.5 mol% of B 2 O 3 . However, since the alkali-free glass described in Patent Document 1 has low devitrification resistance, devitrification is likely to occur during molding and is difficult to manufacture. Further, in order to increase the devitrification resistance of the alkali-free glass, it is necessary to reduce the content of Al 2 O 3 , but in this case, the strain point is lowered, and in the manufacturing process of the p-Si • TFT, The thermal contraction of the glass plate increases. Therefore, it is difficult for the alkali-free glass described in Patent Document 1 to achieve both a high strain point and high devitrification resistance.
そこで、本発明は、生産性（特に耐失透性）に優れると共に、フッ酸系薬液に対するエッチングレートが速く、しかも歪点が高い無アルカリガラスを創案することにより、ガラス板の製造コストを低廉化しつつ、薄型のディスプレイパネルの製造工程において、スループットを向上させ、更にｐ−Ｓｉ・ＴＦＴの製造工程におけるガラス板の熱収縮を低減することを技術的課題とする。 Therefore, the present invention has a low production cost of a glass plate by creating an alkali-free glass that has excellent productivity (particularly devitrification resistance), a high etching rate with respect to a hydrofluoric acid chemical solution, and a high strain point. The technical problem is to improve the throughput in the manufacturing process of a thin display panel while reducing the thermal shrinkage of the glass plate in the manufacturing process of the p-Si • TFT.
本発明者等は、種々の実験を繰り返した結果、無アルカリガラスのガラス組成範囲を厳密に規制すると共に、ガラス特性を所定範囲に規制することにより、上記技術的課題を解決できることを見出し、本発明として、提案するものである。すなわち、本発明の無アルカリガラスは、ガラス組成として、質量％で、ＳｉＯ２ ５８〜７０％、Ａｌ２Ｏ３ １５．５〜２０％、Ｂ２Ｏ３ ０〜１％、ＭｇＯ ０〜５％、ＣａＯ ３．５〜１６％、ＳｒＯ ０．５〜６．５％、ＢａＯ ５〜１５％を含有し、実質的にアルカリ金属酸化物を含有せず、歪点が７２５℃より高いことを特徴とする。ここで、「実質的にアルカリ金属酸化物を含有せず」とは、ガラス組成中のアルカリ金属酸化物（Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ）の含有量が１０００ｐｐｍ（質量）以下の場合を指す。歪点は、ＡＳＴＭ Ｃ３３６の方法に基づいて測定した値を指す。 As a result of repeating various experiments, the present inventors have found that the technical problem can be solved by strictly regulating the glass composition range of the alkali-free glass and regulating the glass characteristics to a predetermined range. It is proposed as an invention. That is, the alkali-free glass of the present invention has a glass composition of mass%, SiO 2 58 to 70%, Al 2 O 3 15.5 to 20%, B 2 O 3 0 to 1%, MgO 0 to 5%. CaO 3.5 to 16%, SrO 0.5 to 6.5%, BaO 5 to 15%, substantially no alkali metal oxide, and has a strain point higher than 725 ° C. And Here, “substantially no alkali metal oxide” means that the content of alkali metal oxides (Li 2 O, Na 2 O, K 2 O) in the glass composition is 1000 ppm (mass) or less. Refers to the case. The strain point refers to a value measured based on the method of ASTM C336.
第二に、本発明の無アルカリガラスは、実質的にＢ２Ｏ３を含有しないことを特徴とする。ここで、「実質的にＢ２Ｏ３を含有しない」とは、ガラス組成中のＢ２Ｏ３含有量が１０００ｐｐｍ（質量）以下の場合を指す。 Secondly, the alkali-free glass of the present invention is characterized by substantially not containing B 2 O 3 . Here, “substantially does not contain B 2 O 3 ” refers to the case where the B 2 O 3 content in the glass composition is 1000 ppm (mass) or less.
第三に、本発明の無アルカリガラスは、ガラス組成として、更に、ＳｎＯ２を０．００１〜１質量％含むことを特徴とする。 Third, the alkali-free glass of the present invention is characterized by further containing 0.001 to 1% by mass of SnO 2 as a glass composition.
第四に、本発明の無アルカリガラスは、ヤング率が７８ＧＰａより大きいことを特徴とする。なお、ヤング率は、曲げ共振法により測定可能である。 Fourth, the alkali-free glass of the present invention is characterized in that the Young's modulus is greater than 78 GPa. The Young's modulus can be measured by a bending resonance method.
第五に、本発明の無アルカリガラスは、ヤング率／密度（比ヤング率）が２９．５ＧＰａ／ｇ・ｃｍ−３より大きいことを特徴とする。なお、密度は、アルキメデス法により測定可能である。 Fifth, the alkali-free glass of the present invention is characterized in that Young's modulus / density (specific Young's modulus) is larger than 29.5 GPa / g · cm −3 . The density can be measured by the Archimedes method.
第六に、本発明の無アルカリガラスは、液相温度が１２５０℃より低いことを特徴とする。なお、「液相温度」は、標準篩３０メッシュ（５００μｍ）を通過し、５０メッシュ（３００μｍ）に残るガラス粉末を白金ボートに入れた後、温度勾配炉中に２４時間保持して、結晶の析出する温度を測定することにより算出可能である。 Sixth, the alkali-free glass of the present invention is characterized in that the liquidus temperature is lower than 1250 ° C. The “liquid phase temperature” is obtained by passing the standard sieve 30 mesh (500 μm) and putting the glass powder remaining on the 50 mesh (300 μm) in a platinum boat and holding it in a temperature gradient furnace for 24 hours. It can be calculated by measuring the temperature of precipitation.
第七に、本発明の無アルカリガラスは、１０２．５ポアズにおける温度が１６６０℃以下であることを特徴とする。 Seventh, the alkali-free glass of the present invention is characterized in that the temperature at 10 2.5 poise is 1660 ° C. or lower.
第八に、本発明の無アルカリガラスは、液相温度における粘度（液相粘度）が１０４．８ポアズ以上であることを特徴とする。なお、「液相温度における粘度」は、白金球引き上げ法で測定可能である。 Eighth, the alkali-free glass of the present invention is characterized in that the viscosity at the liquidus temperature (liquidus viscosity) is 10 4.8 poise or more. The “viscosity at the liquidus temperature” can be measured by a platinum ball pulling method.
第九に、本発明の無アルカリガラスは、オーバーフローダウンドロー法で成形されてなることを特徴とする。 Ninth, the alkali-free glass of the present invention is characterized by being formed by an overflow downdraw method.
第十に、本発明の無アルカリガラスは、有機ＥＬデバイス、特に有機ＥＬディスプレイに用いることを特徴とする。 Tenth, the alkali-free glass of the present invention is characterized by being used for an organic EL device, particularly an organic EL display.
本発明の無アルカリガラスにおいて、上記のように各成分の含有量を限定した理由を以下に示す。なお、各成分の含有量の説明において、％表示は質量％を表す。 The reason for limiting the content of each component as described above in the alkali-free glass of the present invention will be described below. In addition, in description of content of each component,% display represents the mass%.
ＳｉＯ２は、ガラスの骨格を形成する成分である。ＳｉＯ２の含有量は５８〜７０％、好ましくは５８〜６８％、より好ましくは５８〜６５％である。ＳｉＯ２の含有量が５８％より少ないと、歪点を高めることが困難になり、また密度が高くなり過ぎる。一方、ＳｉＯ２の含有量が７０％より多いと、高温粘度が高くなり、溶融性が低下することに加えて、クリストバライト等の失透結晶が析出し易くなり、液相温度が高くなる。 SiO 2 is a component that forms a glass skeleton. The content of SiO 2 is 58 to 70%, preferably 58 to 68%, more preferably 58 to 65%. When the content of SiO 2 is less than 58%, it becomes difficult to increase the strain point, and the density becomes too high. On the other hand, when the content of SiO 2 is more than 70%, the high-temperature viscosity is increased and the meltability is lowered, and devitrification crystals such as cristobalite are liable to precipitate, and the liquidus temperature is increased.
Ａｌ２Ｏ３は、ガラスの骨格を形成する成分であり、また歪点を高める成分であり、更に分相を抑制する成分である。Ａｌ２Ｏ３の含有量は１５．５〜２０％、好ましくは１５．５〜１９％、より好ましくは１５．５〜１８．５％である。Ａｌ２Ｏ３の含有量が１５．５％より少ないと、歪点が低下し、またガラスが分相し易くなる。一方、Ａｌ２Ｏ３の含有量が２０％より多いと、ムライトやアノーサイト等の失透結晶が析出し易くなり、液相温度が高くなる。 Al 2 O 3 is a component that forms a glass skeleton, a component that increases the strain point, and a component that further suppresses phase separation. The content of Al 2 O 3 is 15.5 to 20%, preferably 15.5 to 19%, more preferably 15.5 to 18.5%. When the content of Al 2 O 3 is less than 15.5%, the strain point is lowered and the glass is easily phase-separated. On the other hand, when the content of Al 2 O 3 is more than 20%, devitrification crystals such as mullite and anorthite are liable to precipitate, and the liquidus temperature becomes high.
Ｂ２Ｏ３は、溶融性を高めると共に、耐失透性を高める成分である。Ｂ２Ｏ３の含有量は０〜１％、好ましくは０〜０．８％、より好ましくは０〜０．６％、更に好ましくは０〜０．４％、特に好ましくは０〜０．２％であり、実質的に含有しないことが最も好ましい。Ｂ２Ｏ３の含有量が１％より多いと、歪点が大幅に低下することに加えて、フッ酸系薬液に対するエッチングレートが遅くなる。 B 2 O 3 is a component that enhances meltability and increases devitrification resistance. The content of B 2 O 3 is 0 to 1%, preferably 0 to 0.8%, more preferably 0 to 0.6%, still more preferably 0 to 0.4%, and particularly preferably 0 to 0.2%. % And most preferably not contained. When the content of B 2 O 3 is more than 1%, the strain point is significantly lowered, and the etching rate with respect to the hydrofluoric acid chemical is slowed.
ＭｇＯは、高温粘性を下げて、溶融性を高める成分である。ＭｇＯの含有量は０〜５％、好ましくは０〜４％、より好ましくは０〜３％、更に好ましくは０〜２％、特に好ましくは０．５〜２％である。ＭｇＯの含有量が５％より多いと、歪点が大幅に低下する。 MgO is a component that lowers the high temperature viscosity and increases the meltability. The content of MgO is 0 to 5%, preferably 0 to 4%, more preferably 0 to 3%, still more preferably 0 to 2%, and particularly preferably 0.5 to 2%. When the content of MgO is more than 5%, the strain point is significantly lowered.
ＣａＯは、歪点を低下させずに、高温粘性を下げて、溶融性を顕著に高める成分である。また、ＣａＯは、アルカリ土類金属酸化物の中では、導入原料が比較的安価であるため、原料コストを低廉化する成分である。ＣａＯの含有量は３．５〜１６％、好ましくは４．５〜１６％、より好ましくは５．５〜１５％、特に好ましくは６．５〜１０％である。ＣａＯの含有量が３．５％より少ないと、上記効果を享受し難くなる。一方、ＣａＯの含有量が１６％より多いと、ガラスが失透し易くなると共に、熱膨張係数が高くなり過ぎる。 CaO is a component that lowers the high-temperature viscosity without significantly reducing the strain point and significantly increases the meltability. In addition, CaO is a component that lowers the raw material cost because the introduced raw material is relatively inexpensive among alkaline earth metal oxides. The content of CaO is 3.5 to 16%, preferably 4.5 to 16%, more preferably 5.5 to 15%, and particularly preferably 6.5 to 10%. When the content of CaO is less than 3.5%, it is difficult to enjoy the above effect. On the other hand, if the content of CaO is more than 16%, the glass tends to devitrify and the thermal expansion coefficient becomes too high.
ＳｒＯは、分相を抑制し、また耐失透性を高める成分である。更に、歪点を低下させずに、高温粘性を下げて、溶融性を高める成分であると共に、液相温度の上昇を抑制する成分である。ＳｒＯの含有量は０．５〜６．５％、好ましくは０．５〜６％、より好ましくは０．５〜５．５％、特に好ましくは１〜４．５％である。ＳｒＯの含有量が０．５％より少ないと、分相を抑制する効果や耐失透性を高める効果を享受し難くなる。一方、ＳｒＯの含有量が６．５％より多いと、ストロンチウムシリケート系の失透結晶が析出し易くなり、耐失透性が低下し易くなる。 SrO is a component that suppresses phase separation and increases devitrification resistance. Furthermore, it is a component that lowers the high-temperature viscosity without increasing the strain point and increases the meltability, and also suppresses the rise in the liquidus temperature. The content of SrO is 0.5 to 6.5%, preferably 0.5 to 6%, more preferably 0.5 to 5.5%, and particularly preferably 1 to 4.5%. When the content of SrO is less than 0.5%, it is difficult to enjoy the effect of suppressing phase separation and the effect of improving devitrification resistance. On the other hand, if the SrO content is more than 6.5%, strontium silicate devitrified crystals are likely to precipitate, and devitrification resistance tends to be lowered.
ＢａＯは、アルカリ土類金属酸化物の中では、耐失透性を顕著に高める成分である。ＢａＯの含有量は５〜１５％、好ましくは５〜１４％、より好ましくは５〜１２％、特に好ましくは５．５〜１０．５％である。ＢａＯの含有量が５％より少ないと、液相温度が高くなり、耐失透性が低下する。一方、ＢａＯの含有量が１５％より多いと、高温粘度が高くなり過ぎて、溶融性が低下することに加えて、ＢａＯを含む失透結晶が析出し易くなり、液相温度が高くなる。 BaO is a component that significantly increases devitrification resistance among alkaline earth metal oxides. The content of BaO is 5 to 15%, preferably 5 to 14%, more preferably 5 to 12%, and particularly preferably 5.5 to 10.5%. When the content of BaO is less than 5%, the liquidus temperature increases and the devitrification resistance decreases. On the other hand, when the content of BaO is more than 15%, the high-temperature viscosity becomes too high, and the meltability is lowered. In addition, devitrified crystals containing BaO are liable to precipitate and the liquidus temperature is increased.
上記成分以外にも、例えば、以下の成分をガラス組成中に添加してもよい。なお、上記成分以外の他成分の含有量は、本発明の効果を的確に享受する観点から、合量で１０％以下、特に５％以下が好ましい。 In addition to the above components, for example, the following components may be added to the glass composition. In addition, the content of other components other than the above components is preferably 10% or less, particularly preferably 5% or less in total, from the viewpoint of accurately enjoying the effects of the present invention.
ＳｎＯ２は、高温域で良好な清澄作用を有する成分であると共に、歪点を高める成分であり、また高温粘性を低下させる成分である。ＳｎＯ２の含有量は０〜１％、０．００１〜１％、０．０１〜０．５％、特に０．０５〜０．３％が好ましい。ＳｎＯ２の含有量が１％より多いと、ＳｎＯ２の失透結晶が析出し易くなる。なお、ＳｎＯ２の含有量が０．００１％より少ないと、上記効果を享受し難くなる。 SnO 2 is a component that has a good clarification action in a high temperature range, a component that increases the strain point, and a component that decreases high temperature viscosity. The SnO 2 content is preferably 0 to 1%, 0.001 to 1%, 0.01 to 0.5%, particularly preferably 0.05 to 0.3%. If the content of SnO 2 is more than 1%, SnO 2 devitrified crystals are likely to precipitate. Incidentally, when the content of SnO 2 is less than 0.001%, it becomes difficult to enjoy the above-mentioned effects.
上記の通り、ＳｎＯ２は、清澄剤として好適であるが、ガラス特性が損なわれない限り、清澄剤として、更にＦ２、Ｃｌ２、ＳＯ３、Ｃ、或いはＡｌ、Ｓｉ等の金属粉末を５％まで添加することができる。また、清澄剤として、ＣｅＯ２等も５％まで添加することができる。 As described above, SnO 2 is suitable as a fining agent. However, as long as the glass properties are not impaired, a metal powder such as F 2 , Cl 2 , SO 3 , C, Al, Si or the like is further added as the fining agent. % Can be added. Further, as a fining agent, also CeO 2 or the like may be added up to 5%.
清澄剤として、Ａｓ２Ｏ３、Ｓｂ２Ｏ３も有効である。本発明の無アルカリガラスは、これらの成分の含有を完全に排除するものではないが、環境的観点から、これらの成分を極力使用しないことが好ましい。さらに、Ａｓ２Ｏ３は、ガラス中に多量に含有させると、耐ソラリゼーション性が低下する傾向にあるため、その含有量は１％以下、０．５％以下、特に０．１％以下が好ましく、実質的に含有させないことが望ましい。ここで、「実質的にＡｓ２Ｏ３を含有しない」とは、ガラス組成中のＡｓ２Ｏ３の含有量が０．０５％未満の場合を指す。また、Ｓｂ２Ｏ３の含有量は２％以下、１％以下、特に０．５％以下が好ましく、実質的に含有させないことが望ましい。ここで、「実質的にＳｂ２Ｏ３を含有しない」とは、ガラス組成中のＳｂ２Ｏ３の含有量が０．０５％未満の場合を指す。 As 2 O 3 and Sb 2 O 3 are also effective as fining agents. The alkali-free glass of the present invention does not completely exclude the inclusion of these components, but it is preferable not to use these components as much as possible from an environmental viewpoint. Furthermore, when As 2 O 3 is contained in a large amount in the glass, the resistance to solarization tends to decrease. Therefore, its content is preferably 1% or less, 0.5% or less, particularly preferably 0.1% or less. , It is desirable not to contain substantially. Here, “substantially does not contain As 2 O 3 ” refers to the case where the content of As 2 O 3 in the glass composition is less than 0.05%. Further, the content of Sb 2 O 3 is preferably 2% or less, 1% or less, and particularly preferably 0.5% or less, and it is desirable not to contain it substantially. Here, “substantially does not contain Sb 2 O 3 ” refers to a case where the content of Sb 2 O 3 in the glass composition is less than 0.05%.
Ｃｌは、無アルカリガラスの溶融を促進する効果があり、Ｃｌを添加すれば、溶融温度を低温化できると共に、清澄剤の作用を促進し、結果として、溶融コストを低廉化しつつ、ガラス製造窯の長寿命化を図ることができる。しかし、Ｃｌの含有量が多過ぎると、歪点が低下するため、Ｃｌの含有量は３％以下、１％以下、特に０．５％以下が好ましい。なお、Ｃｌの導入原料として、塩化ストロンチウム等のアルカリ土類金属酸化物の塩化物、或いは塩化アルミニウム等の原料を使用することができる。 Cl has an effect of promoting the melting of alkali-free glass, and if Cl is added, the melting temperature can be lowered and the action of a clarifying agent is promoted. As a result, the melting cost is reduced and the glass manufacturing kiln is reduced. It is possible to extend the service life. However, if the content of Cl is too large, the strain point decreases, so the Cl content is preferably 3% or less, 1% or less, and particularly preferably 0.5% or less. In addition, as a raw material for introducing Cl, a raw material such as an alkaline earth metal oxide chloride such as strontium chloride or aluminum chloride can be used.
ＺｎＯは、溶融性を高める成分であるが、多量にＺｎＯを含有させると、ガラスが失透し易くなり、また歪点が低下し易くなる。ＺｎＯの含有量は０〜５％、０〜３％、０〜０．５％、特に０〜０．３％が好ましく、実質的に含有しないことが望ましい。ここで、「実質的にＺｎＯを含有しない」とは、ガラス組成中のＺｎＯの含有量が０．２％以下の場合を指す。 ZnO is a component that enhances the meltability. However, if ZnO is contained in a large amount, the glass tends to be devitrified and the strain point tends to be lowered. The content of ZnO is preferably from 0 to 5%, from 0 to 3%, from 0 to 0.5%, particularly preferably from 0 to 0.3%, and desirably not substantially contained. Here, “substantially does not contain ZnO” refers to a case where the content of ZnO in the glass composition is 0.2% or less.
Ｐ２Ｏ５は、歪点を高める成分であるが、多量にＰ２Ｏ５を含有させると、ガラスが分相し易くなる。Ｐ２Ｏ５の含有量は０〜１．５％、０〜１．２％、特に０〜１％が好ましい。 P 2 O 5 is a component that increases the strain point. However, if P 2 O 5 is contained in a large amount, the glass is likely to undergo phase separation. The content of P 2 O 5 is preferably 0 to 1.5%, 0 to 1.2%, particularly preferably 0 to 1%.
ＴｉＯ２は、高温粘性を下げて、溶融性を高める成分であると共に、ソラリゼーションを抑制する成分であるが、多量にＴｉＯ２を含有させると、ガラスが着色して、透過率が低下し易くなる。ＴｉＯ２の含有量は０〜５％、０〜３％、０〜１％、特に０〜０．０２％が好ましい。 TiO 2 is a component that lowers the viscosity at high temperature and increases the meltability, and is a component that suppresses solarization. However, if a large amount of TiO 2 is contained, the glass is colored and the transmittance tends to decrease. . The content of TiO 2 is preferably 0 to 5%, 0 to 3%, 0 to 1%, particularly preferably 0 to 0.02%.
Ｙ２Ｏ３、Ｎｂ２Ｏ５、Ｌａ２Ｏ３には、歪点、ヤング率等を高める働きがある。しかし、これらの成分の含有量が各々５％より多いと、密度が増加し易くなる。 Y 2 O 3 , Nb 2 O 5 , and La 2 O 3 have a function of increasing the strain point, Young's modulus, and the like. However, if the content of these components is more than 5%, the density tends to increase.
本発明の無アルカリガラスにおいて、歪点は７２５℃超であり、好ましくは７３０℃以上、より好ましくは７３５℃以上、更に好ましくは７４０℃以上である。このようにすれば、ｐ−Ｓｉ・ＴＦＴの製造工程において、ガラス板の熱収縮を抑制することができる。 In the alkali-free glass of the present invention, the strain point is higher than 725 ° C., preferably 730 ° C. or higher, more preferably 735 ° C. or higher, and further preferably 740 ° C. or higher. If it does in this way, the thermal contraction of a glass plate can be suppressed in the manufacturing process of p-Si * TFT.
本発明の無アルカリガラスにおいて、ヤング率は７８ＧＰａ超、７９ＧＰａ以上、８０ＧＰａ以上、８１ＧＰａ以上、特に８２ＧＰａ以上が好ましい。このようにすれば、ガラス板の撓みを抑制できるため、製造プロセス等においてガラス板の取扱いが容易になる。 In the alkali-free glass of the present invention, the Young's modulus is preferably more than 78 GPa, 79 GPa or more, 80 GPa or more, 81 GPa or more, particularly 82 GPa or more. If it does in this way, since the bending of a glass plate can be suppressed, handling of a glass plate becomes easy in a manufacturing process etc.
本発明の無アルカリガラスにおいて、ヤング率／密度が２９．５ＧＰａ／ｇ・ｃｍ−３超、３０．０ＧＰａ／ｇ・ｃｍ−３以上、３０．５ＧＰａ／ｇ・ｃｍ−３以上、３１．０ＧＰａ／ｇ・ｃｍ−３以上、特に３１．５ＧＰａ／ｇ・ｃｍ−３以上が好ましい。ガラス板の撓み量は、密度の影響も受ける。ヤング率／密度の値を大きくすると、ガラス板の撓み量を大幅に抑制することができる。 In the alkali free glass of the present invention, the Young's modulus / density 29.5GPa / g · cm -3 greater, 30.0GPa / g · cm -3 or more, 30.5GPa / g · cm -3 or more, 31.0GPa / g · cm −3 or more, particularly 31.5 GPa / g · cm −3 or more is preferable. The amount of bending of the glass plate is also affected by the density. When the value of Young's modulus / density is increased, the amount of bending of the glass plate can be significantly suppressed.
本発明の無アルカリガラスにおいて、液相温度は１２５０℃未満、１２４０℃以下、特に１２３０℃以下が好ましい。このようにすれば、ガラス製造時に失透結晶が発生して、生産性が低下する事態を防止し易くなる。更に、オーバーフローダウンドロー法でガラス板を成形し易くなるため、ガラス板の表面品位を高めることが可能になると共に、ガラス板の製造コストを低廉化することができる。なお、液相温度は、耐失透性の指標であり、液相温度が低い程、耐失透性に優れる。 In the alkali-free glass of the present invention, the liquidus temperature is preferably less than 1250 ° C, 1240 ° C or less, particularly preferably 1230 ° C or less. If it does in this way, it will become easy to prevent the situation where devitrification crystal occurs at the time of glass manufacture, and productivity falls. Furthermore, since it becomes easy to shape | mold a glass plate by the overflow down draw method, while being able to improve the surface quality of a glass plate, the manufacturing cost of a glass plate can be reduced. The liquidus temperature is an index of devitrification resistance. The lower the liquidus temperature, the better the devitrification resistance.
本発明の無アルカリガラスにおいて、１０２．５ポアズにおける温度は１６６０℃以下、１６５０℃以下、特に１６４０℃以下が好ましい。１０２．５ポアズにおける温度が高くなると、ガラス溶解が困難になり、ガラス板の製造コストが高騰する。なお、１０２．５ポアズにおける温度は、溶融温度に相当し、この温度が低い程、溶融性に優れる。 In the alkali-free glass of the present invention, the temperature at 10 2.5 poise is preferably 1660 ° C. or lower, 1650 ° C. or lower, particularly 1640 ° C. or lower. When the temperature at 10 2.5 poise increases, glass melting becomes difficult and the production cost of the glass plate increases. The temperature at 10 2.5 poise corresponds to the melting temperature, and the lower this temperature, the better the meltability.
本発明の無アルカリガラスにおいて、液相温度における粘度は１０４．８ポアズ以上、１０５．０ポアズ以上、１０５．２ポアズ以上、特に１０５．３ポアズ以上が好ましい。このようにすれば、成形時に失透が生じ難くなるため、オーバーフローダウンドロー法でガラス板を成形し易くなり、結果として、ガラス板の表面品位を高めることが可能になり、またガラス板の製造コストを低廉化することができる。なお、液相粘度は、成形性の指標であり、液相粘度が高い程、成形性に優れる。 In the alkali free glass of the present invention, the viscosity is 10 4.8 poise or more at the liquidus temperature, 10 5.0 poise or more, 10 5.2 poise or higher, particularly preferably at least 10 5.3 poise. In this way, devitrification is less likely to occur at the time of molding, so it becomes easier to mold the glass plate by the overflow downdraw method, and as a result, the surface quality of the glass plate can be improved, and the production of the glass plate Cost can be reduced. The liquid phase viscosity is an index of moldability. The higher the liquid phase viscosity, the better the moldability.
本発明の無アルカリガラスは、オーバーフローダウンドロー法で成形されてなることが好ましい。オーバーフローダウンドロー法は、耐熱性の樋状構造物の両側から溶融ガラスを溢れさせて、溢れた溶融ガラスを樋状構造物の下端で合流させながら、下方に延伸成形してガラス板を製造する方法である。オーバーフローダウンドロー法では、ガラス板の表面になるべき面は樋状耐火物に接触せず、自由表面の状態で成形される。このため、未研磨で表面品位が良好なガラス板を安価に製造することができる。なお、オーバーフローダウンドロー法で用いる樋状構造物の構造や材質は、所望の寸法や表面精度を実現できるものであれば、特に限定されない。また、下方への延伸成形を行う際に、力を印加する方法も特に限定されない。例えば、充分に大きい幅を有する耐熱性ロールをガラスに接触させた状態で回転させて延伸する方法を採用してもよいし、複数の対になった耐熱性ロールをガラスの端面近傍のみに接触させて延伸する方法を採用してもよい。 The alkali-free glass of the present invention is preferably formed by an overflow down draw method. In the overflow down draw method, molten glass overflows from both sides of a heat-resistant bowl-shaped structure, and the molten glass overflows and joins at the lower end of the bowl-shaped structure to produce a glass plate by drawing downward. Is the method. In the overflow downdraw method, the surface to be the surface of the glass plate is not in contact with the bowl-shaped refractory, and is formed in a free surface state. For this reason, the glass plate which is unpolished and has a good surface quality can be manufactured at low cost. The structure and material of the bowl-shaped structure used in the overflow downdraw method are not particularly limited as long as desired dimensions and surface accuracy can be realized. In addition, the method of applying a force when performing downward stretch molding is not particularly limited. For example, a method may be adopted in which a heat-resistant roll having a sufficiently large width is rotated and stretched in contact with glass, or a plurality of pairs of heat-resistant rolls are contacted only near the end face of the glass. It is also possible to adopt a method of stretching by stretching.
オーバーフローダウンドロー法以外にも、例えば、ダウンドロー法（スロットダウン法等）、フロート法等でガラス板を成形することも可能である。 In addition to the overflow downdraw method, the glass plate can be formed by, for example, a downdraw method (slot down method or the like), a float method, or the like.
本発明の無アルカリガラスは、有機ＥＬデバイス、特に有機ＥＬディスプレイに用いることが好ましい。有機ＥＬディスプレイのパネルメーカーでは、ガラスメーカーで成形された大型のガラス板の上に複数個分のデバイスを作製した後、デバイス毎に分割切断して、コストダウンを図っている（所謂、多面取り）。特にＴＶ用途では、デバイス自体が大型化しており、これらのデバイスを多面取りするために、大型のガラス板が要求されている。本発明の無アルカリガラスは、液相温度が低く、また液相粘度が高いため、大型のガラス板を成形し易く、このような要求を満たすことができる。 The alkali-free glass of the present invention is preferably used for an organic EL device, particularly an organic EL display. A panel manufacturer of an organic EL display manufactures a plurality of devices on a large glass plate formed by a glass manufacturer, and then cuts and cuts each device in order to reduce costs (so-called multi-surface processing). ). Particularly in TV applications, the devices themselves are becoming larger, and a large glass plate is required in order to obtain a large number of these devices. Since the alkali-free glass of the present invention has a low liquidus temperature and a high liquidus viscosity, it can easily form a large glass plate and can satisfy such a requirement.
本発明の無アルカリガラスにおいて、厚み（板厚）は０．７ｍｍ以下、０．５ｍｍ以下、０．４ｍｍ以下、０．３ｍｍ以下、特に０．１ｍｍ以下が好ましい。厚みが小さい程、ディスプレイの軽量・薄型化、更にはフレキシブル化を図り易くなる。 In the alkali-free glass of the present invention, the thickness (plate thickness) is preferably 0.7 mm or less, 0.5 mm or less, 0.4 mm or less, 0.3 mm or less, particularly preferably 0.1 mm or less. The smaller the thickness, the easier it is to make the display lighter, thinner, and more flexible.
以下、実施例に基づいて、本発明を説明する。但し、以下の実施例は、単なる例示である。本発明は、以下の実施例に何ら限定されない。 Hereinafter, the present invention will be described based on examples. However, the following examples are merely illustrative. The present invention is not limited to the following examples.
表１、２は、本発明の実施例（試料Ｎｏ．１〜７）と比較例（試料Ｎｏ．８〜１０）を示している。 Tables 1 and 2 show examples (samples Nos. 1 to 7) and comparative examples (samples Nos. 8 to 10) of the present invention.
まず表中のガラス組成になるように、ガラス原料を調合したガラスバッチを白金坩堝に入れた後、１６００〜１６５０℃で２４時間溶融した。ガラスバッチの溶解にあたっては、白金スターラーを用いて攪拌し、均質化を行った。次いで、溶融ガラスをカーボン板上に流し出して、板状に成形した後、徐冷点付近の温度で３０分間徐冷した。得られた各試料について、密度、３０〜３８０℃の温度範囲における平均熱膨張係数ＣＴＥ、ヤング率、ヤング率／密度（比ヤング率）、歪点Ｐｓ、徐冷点Ｔａ、軟化点Ｔｓ、高温粘度１０４ポアズにおける温度、高温粘度１０３ポアズにおける温度、高温粘度１０２．５ポアズにおける温度、液相温度ＴＬ、及び液相温度における粘度（液相粘度ｌｏｇ１０ηＴＬ）を評価した。 First, after putting the glass batch which prepared the glass raw material into a platinum crucible so that it might become the glass composition in a table | surface, it melted at 1600-1650 degreeC for 24 hours. In melting the glass batch, the mixture was stirred and homogenized using a platinum stirrer. Next, the molten glass was poured onto a carbon plate and formed into a plate shape, and then slowly cooled at a temperature near the annealing point for 30 minutes. About each obtained sample, density, average thermal expansion coefficient CTE in a temperature range of 30 to 380 ° C., Young's modulus, Young's modulus / density (specific Young's modulus), strain point Ps, annealing point Ta, softening point Ts, high temperature The temperature at a viscosity of 10 4 poise, the temperature at a high temperature viscosity of 10 3 poise, the temperature at a high temperature viscosity of 10 2.5 poise, the liquidus temperature TL, and the viscosity at the liquidus temperature (liquidus viscosity log 10 ηTL) were evaluated.
密度は、周知のアルキメデス法で測定した値である。 The density is a value measured by a well-known Archimedes method.
３０〜３８０℃の温度範囲における平均熱膨張係数ＣＴＥは、ディラトメーターで測定した値である。 The average coefficient of thermal expansion CTE in the temperature range of 30 to 380 ° C. is a value measured with a dilatometer.
ヤング率は、曲げ共振法により測定した値である。 The Young's modulus is a value measured by a bending resonance method.
ヤング率／密度（比ヤング率）は、曲げ共振法により測定したヤング率をアルキメデス法で測定した密度で除した値である。 The Young's modulus / density (specific Young's modulus) is a value obtained by dividing the Young's modulus measured by the bending resonance method by the density measured by the Archimedes method.
歪点Ｐｓ、徐冷点Ｔａ、軟化点Ｔｓは、ＡＳＴＭ Ｃ３３６の方法に基づいて測定した値である。 The strain point Ps, the annealing point Ta, and the softening point Ts are values measured based on the method of ASTM C336.
高温粘度１０４ポアズ、１０３ポアズ、１０２．５ポアズにおける温度は、白金球引き上げ法で測定した値である。 The temperature at a high temperature viscosity of 10 4 poise, 10 3 poise, and 10 2.5 poise is a value measured by a platinum ball pulling method.
液相温度ＴＬは、標準篩３０メッシュ（５００μｍ）を通過し、５０メッシュ（３００μｍ）に残るガラス粉末を白金ボートに入れた後、温度勾配炉中に２４時間保持して、結晶の析出する温度を測定した値である。 The liquidus temperature TL is a temperature at which crystals pass through a standard sieve 30 mesh (500 μm) and the glass powder remaining on 50 mesh (300 μm) is placed in a platinum boat and then kept in a temperature gradient furnace for 24 hours to precipitate crystals. Is a measured value.
液相温度における粘度（液相粘度ｌｏｇ１０ηＴＬ）は、白金球引き上げ法で測定した値である。 The viscosity at the liquidus temperature (liquidus viscosity log 10 ηTL) is a value measured by a platinum ball pulling method.
表から明らかなように、試料Ｎｏ．１〜７は、アルカリ金属酸化物を含有せず、歪点が７２５℃より高く、液相温度が１２５０℃以下であった。このため、試料Ｎｏ．１〜７は、ｐ−Ｓｉ・ＴＦＴの熱処理工程において、ガラス板の熱収縮が発生し難いと共に、生産性が良好である。また、試料Ｎｏ．１〜７は、Ｂ２Ｏ３の含有量が０〜１質量％であるため、薄型のディスプレイパネルの製造工程において、スループットを向上させることが可能になる。したがって、試料Ｎｏ．１〜７は、有機ＥＬディスプレイ用ガラス板として好適に使用可能であると考えられる。 As is apparent from the table, sample No. Nos. 1 to 7 did not contain an alkali metal oxide, had a strain point higher than 725 ° C. and a liquidus temperature of 1250 ° C. or lower. For this reason, sample no. In Nos. 1 to 7, in the heat treatment process of the p-Si • TFT, thermal contraction of the glass plate hardly occurs and productivity is good. Sample No. In Nos. 1 to 7, since the content of B 2 O 3 is 0 to 1% by mass, the throughput can be improved in the manufacturing process of a thin display panel. Therefore, sample no. 1-7 can be used suitably as a glass plate for organic EL displays.
一方、試料Ｎｏ．８、１０は、液相温度が高く、耐失透性が低いため、成形性に劣っている。また、試料Ｎｏ．９は、歪点が低いため、ｐ−Ｓｉ・ＴＦＴの熱処理工程において、ガラス板の熱収縮が大きくなって、ＴＦＴの画素ピッチズレによる表示不良を惹起させるおそれがある。 On the other hand, Sample No. Nos. 8 and 10 are inferior in moldability because the liquidus temperature is high and the devitrification resistance is low. Sample No. In No. 9, since the strain point is low, the thermal contraction of the glass plate is increased in the heat treatment process of the p-Si • TFT, which may cause a display defect due to the pixel pitch shift of the TFT.
本発明の無アルカリガラスは、液晶ディスプレイ、ＥＬディスプレイ等のフラットパネルディスプレイ基板、電荷結合素子（ＣＣＤ）、等倍近接型固体撮像素子（ＣＩＳ）等のイメージセンサー用のカバーガラス、太陽電池用の基板及びカバーガラス、有機ＥＬ照明用基板等に好適に使用可能であり、特に有機ＥＬディスプレイ用ガラス板として好適に使用可能である。
The alkali-free glass of the present invention is a flat panel display substrate such as a liquid crystal display or an EL display, a cover glass for an image sensor such as a charge coupled device (CCD) or a 1 × proximity solid-state imaging device (CIS), or a solar cell. It can be suitably used for a substrate, a cover glass, a substrate for organic EL lighting, and the like, and can be particularly suitably used as a glass plate for an organic EL display.
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