JP5874304B2 - Alkali-free glass - Google Patents

Alkali-free glass Download PDF

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JP5874304B2
JP5874304B2 JP2011230278A JP2011230278A JP5874304B2 JP 5874304 B2 JP5874304 B2 JP 5874304B2 JP 2011230278 A JP2011230278 A JP 2011230278A JP 2011230278 A JP2011230278 A JP 2011230278A JP 5874304 B2 JP5874304 B2 JP 5874304B2
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JP2012111679A (en
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隆 村田
隆 村田
三和　晋吉
晋吉 三和
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Nippon Electric Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Description

本発明は、無アルカリガラスに関し、特に液晶ディスプレイ、有機ＥＬディスプレイ等のフラットディスプレイ用ガラス基板、チップサイズパッケージ（ＣＳＰ）、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ガラス基板に好適な無アルカリガラスに関する。   The present invention relates to alkali-free glass, and in particular, glass substrates for flat displays such as liquid crystal displays and organic EL displays, chip size packages (CSP), charge-coupled devices (CCD), equal-magnification proximity solid-state imaging devices (CIS), and the like. The present invention relates to an alkali-free glass suitable for a glass substrate for an image sensor.

近年、ＣＳＰ等のイメージセンサーは、ますます小型化、薄型化、軽量化が進んでいる。従来、これらのセンサー部は樹脂のパッケージで保護されていたが、近年、更なる小型化等を進めるために、Ｓｉチップ上にガラス基板を貼り付けて保護する方式が採用されつつある。   In recent years, image sensors such as CSP have been increasingly reduced in size, thickness, and weight. Conventionally, these sensor units have been protected by a resin package, but recently, in order to further reduce the size and the like, a method of protecting by attaching a glass substrate on a Si chip is being adopted.

また、このガラス基板も、デバイスの小型化等を図るために、更なる薄肉化が求められており、板厚が小さいガラス基板（例えば、板厚０．５ｍｍ以下のガラス基板）が採用されつつある。   Further, this glass substrate is also required to be thinner in order to reduce the size of the device, and a glass substrate having a small plate thickness (for example, a glass substrate having a plate thickness of 0.5 mm or less) is being adopted. is there.

さらに、熱処理工程でアルカリイオンが成膜された半導体物質中に拡散する事態を防止するため、ガラス基板として、通常、実質的にアルカリ金属酸化物を含有しない無アルカリガラスが用いられている（特許文献１参照）。   Furthermore, in order to prevent a situation in which alkali ions are diffused into the semiconductor material formed into a film in the heat treatment step, an alkali-free glass that does not substantially contain an alkali metal oxide is usually used as a glass substrate (patent) Reference 1).

特開２００６−３４４９２７号公報JP 2006-344927 A

上記の通り、ＣＳＰ等の用途の場合、ガラス基板とＳｉチップが直接貼り付けられる。しかし、無アルカリガラスとＳｉの熱膨張係数が不整合であると、両者の熱膨張係数差によって、ガラス基板に反りが発生してしまう。特に、ガラス基板の板厚が小さい程、ガラス基板に反りが発生し易くなる。   As described above, in the case of use such as CSP, the glass substrate and the Si chip are directly attached. However, if the thermal expansion coefficients of the alkali-free glass and Si are mismatched, the glass substrate is warped due to the difference in thermal expansion coefficient between the two. In particular, the smaller the plate thickness of the glass substrate, the easier it is to warp the glass substrate.

この問題を解決するためには、無アルカリガラスとＳｉの熱膨張係数を厳密に整合させる必要がある。しかし、Ｓｉの熱膨張係数は３２〜３４×１０−７／℃と非常に低く、Ｓｉの熱膨張係数に整合するように、無アルカリガラスの熱膨張係数を低下させると、高品位のガラス基板を作製し難くなる。すなわち、無アルカリガラスにおいて、熱膨張係数を低下させる場合、ガラスの粘性が高くなるため、泡品位を向上させることが困難になり、結果として、高品位のガラス基板を得ることが困難になる。 In order to solve this problem, it is necessary to strictly match the thermal expansion coefficients of the alkali-free glass and Si. However, the thermal expansion coefficient of Si is as low as 32 to 34 × 10 −7 / ° C., and when the thermal expansion coefficient of non-alkali glass is lowered so as to match the thermal expansion coefficient of Si, a high-quality glass substrate It becomes difficult to produce. That is, when reducing the thermal expansion coefficient in non-alkali glass, it becomes difficult to improve the bubble quality because the viscosity of the glass increases, and as a result, it becomes difficult to obtain a high-quality glass substrate.

また、ＣＳＰ等のイメージセンサーは、約２ｍｍ程度のＳｉチップの中に数百万画素分の情報が盛り込まれるため、液晶ディスプレイ、有機ＥＬディスプレイ等の画素とは比較にならない程、極微小な欠点が問題となり得る。さらに、イメージセンサーとガラス基板を貼り合わせる工程は、略最終工程であるため、ガラス基板の欠点によりデバイスの歩留まりが低下すると、デバイスの生産性が著しく低下してしまう。   Also, image sensors such as CSP contain millions of pixels of information in a Si chip of about 2 mm, so there are extremely small defects that cannot be compared with pixels such as liquid crystal displays and organic EL displays. Can be a problem. Furthermore, since the process of bonding the image sensor and the glass substrate is a substantially final process, if the yield of the device is reduced due to a defect of the glass substrate, the productivity of the device is significantly reduced.

したがって、この用途に使用される無アルカリガラスは、特に（１）Ｓｉと整合する熱膨張係数を有すること、（２）泡品位に優れていること、（３）低コストで薄板の成形が可能であること、（４）軽量であること等が要求される。   Therefore, the alkali-free glass used in this application has (1) a thermal expansion coefficient that matches that of Si, (2) excellent foam quality, and (3) enables thin sheet molding at low cost. (4) Light weight is required.

上記事情に鑑み、本発明は、ＣＳＰ等の用途に要求される種々の特性を満足し得る無アルカリガラス、特にＳｉと整合する熱膨張係数を有する無アルカリガラスを提供することを技術的課題とする。   In view of the above circumstances, the present invention is to provide an alkali-free glass that can satisfy various properties required for applications such as CSP, in particular, an alkali-free glass having a thermal expansion coefficient that matches Si. To do.

本発明者等は、種々の実験を繰り返した結果、無アルカリガラスにおいて、各成分の含有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、ｍｏｌ％で、ＳｉＯ２ ５０〜７０％、Ａｌ２Ｏ３ １０．５〜１５％、Ｂ２Ｏ３ １２〜２０％、ＣａＯ ８〜１２％、Ｓｂ ２ Ｏ ３ ０〜０．０５％未満（但し、Ｓｂ ２ Ｏ ３ が０．０５質量％以上の場合を除く）を含有し、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が０．８４〜１．２であって、密度が２．３７ｇ／ｃｍ３以下、１０２．５ｄＰａ・ｓにおける温度が１６００℃以下であることを特徴とする。このようにガラス組成範囲を規制すれば、耐失透性が向上すると共に、Ｓｉの熱膨張係数に整合させ易くなる。ここで、「無アルカリ」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）未満の場合を指す。「ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ」は、ＭｇＯ、ＣａＯ、ＳｒＯ、及びＢａＯの合量である。「密度」は、アルキメデス法により測定可能である。「１０２．５ｄＰａ・ｓにおける温度」は、白金球引き上げ法で測定可能である。 As a result of repeating various experiments, the inventors of the present invention are able to solve the above technical problems by strictly regulating the content range of each component in a non-alkali glass and regulating the glass characteristics to a predetermined range. It is proposed as a heading and the present invention. That is, the alkali-free glass of the present invention has a glass composition of mol%, SiO 2 50 to 70%, Al 2 O 3 10.5 to 15%, B 2 O 3 12 to 20%, CaO 8 to 12%. , Sb 2 O 3 0 to less than 0.05 % (except when Sb 2 O 3 is 0.05% by mass or more) , and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0. It is 84-1.2, Comprising: The temperature in a density of 2.37 g / cm < 3 > or less and 10 < 2.5 > dPa * s is 1600 degrees C or less, It is characterized by the above-mentioned. If the glass composition range is regulated in this way, devitrification resistance is improved and it is easy to match the thermal expansion coefficient of Si. Here, “non-alkali” refers to the case where the content of alkali metal oxides (Li 2 O, Na 2 O, K 2 O) in the glass composition is less than 1000 ppm (mass). “MgO + CaO + SrO + BaO” is the total amount of MgO, CaO, SrO, and BaO. “Density” can be measured by the Archimedes method. “Temperature at 10 2.5 dPa · s” can be measured by the platinum ball pulling method.

本発明の無アルカリガラスは、ガラス組成として、ｍｏｌ％で、ＳｉＯ２ ５０〜７０％、Ａｌ２Ｏ３ １０．５〜１５％、Ｂ２Ｏ３ １２〜２０％、ＣａＯ ９〜１２％、Ｓｂ２Ｏ３ ０〜０．０５％未満（但し、Ｓｂ ２ Ｏ ３ が０．０５質量％以上の場合を除く）を含有し、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が０．８４〜１．０５であって、密度が２．３５ｇ／ｃｍ３以下、歪点が６３０℃以上、１０２．５ｄＰａ・ｓにおける温度が１５４０℃以下、３０〜３８０℃の温度範囲における熱膨張係数が３２〜４０×１０−７／℃であることが好ましい。ここで、「歪点」は、ＡＳＴＭ Ｃ３３６の方法に基づいて測定した値を指す。「３０〜３８０℃の温度範囲における熱膨張係数」は、ディラトメーターで測定した値を指す。 The alkali-free glass of the present invention has a glass composition of mol%, SiO 2 50 to 70%, Al 2 O 3 10.5 to 15%, B 2 O 3 12 to 20%, CaO 9 to 12%, Sb. 2 O 3 0 to less than 0.05% ( excluding the case where Sb 2 O 3 is 0.05% by mass or more) , and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.84 to The thermal expansion coefficient is 1.05, the density is 2.35 g / cm 3 or less, the strain point is 630 ° C. or more, the temperature at 10 2.5 dPa · s is 1540 ° C. or less, and the temperature range is 30 to 380 ° C. It is preferably 32 to 40 × 10 −7 / ° C. Here, the “strain point” refers to a value measured based on the method of ASTM C336. “Thermal expansion coefficient in the temperature range of 30 to 380 ° C.” refers to a value measured with a dilatometer.

本発明の無アルカリガラスは、ガラス組成として、ｍｏｌ％で、ＳｉＯ２ ５５〜７０％、Ａｌ２Ｏ３ １０．５〜１４％、Ｂ２Ｏ３ １４〜２０％、ＣａＯ ９．２〜１１％、Ｓｂ２Ｏ３ ０〜０．０５％未満（但し、Ｓｂ ２ Ｏ ３ が０．０５質量％以上の場合を除く）を含有し、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が０．８４〜１．０であって、密度が２．３５ｇ／ｃｍ３以下、歪点が６３５℃以上、１０２．５ｄＰａ・ｓにおける温度が１５３０℃以下、３０〜３８０℃の温度範囲における熱膨張係数が３２〜３８×１０−７／℃であることが好ましい。 Alkali-free glass of the present invention has a glass composition, in mol%, SiO 2 55~70%, Al 2 O 3 10.5 ~14%, B 2 O 3 14~20%, CaO 9.2~11% , Sb 2 O 3 0 to less than 0.05% (except when Sb 2 O 3 is 0.05% by mass or more) , and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.00. Thermal expansion in a temperature range of 84 to 1.0, a density of 2.35 g / cm 3 or less, a strain point of 635 ° C. or more, a temperature at 10 2.5 dPa · s of 1530 ° C. or less, and a temperature range of 30 to 380 ° C. The coefficient is preferably 32-38 × 10 −7 / ° C.

本発明の無アルカリガラスは、ガラス組成として、ｍｏｌ％で、ＳｉＯ２ ５５〜７０％、Ａｌ２Ｏ３ １０．５〜１４％、Ｂ２Ｏ３ １５〜２０％、ＣａＯ ９．５〜１０．５％、Ｓｂ２Ｏ３ ０〜０．０５％未満（但し、Ｓｂ ２ Ｏ ３ が０．０５質量％以上の場合を除く）を含有し、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が０．８５〜０．９０であって、密度が２．３５ｇ／ｃｍ３以下、歪点が６３５℃以上、１０２．５ｄＰａ・ｓにおける温度が１５２０℃以下、３０〜３８０℃の温度範囲における熱膨張係数が３２〜３６×１０−７／℃であることが好ましい。 Alkali-free glass of the present invention has a glass composition, in mol%, SiO 2 55~70%, Al 2 O 3 10.5~14%, B 2 O 3 15~20%, CaO 9.5~10. 5%, Sb 2 O 3 0 to less than 0.05% (except when Sb 2 O 3 is 0.05% by mass or more) , and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.85 to 0.90, the density is 2.35 g / cm 3 or less, the strain point is 635 ° C. or more, the temperature at 10 2.5 dPa · s is 1520 ° C. or less, and the temperature range is 30 to 380 ° C. The thermal expansion coefficient is preferably 32 to 36 × 10 −7 / ° C.

本発明の無アルカリガラスは、ガラス組成として、ｍｏｌ％で、ＳｉＯ２ ５５〜７０％、Ａｌ２Ｏ３ １０．８〜１４％、Ｂ２Ｏ３ １５．５〜２０％、ＣａＯ ９．５〜１０％、Ｓｂ２Ｏ３ ０〜０．０５％未満（但し、Ｓｂ ２ Ｏ ３ が０．０５質量％以上の場合を除く）を含有し、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が０．８７〜０．９０であって、密度が２．３５ｇ／ｃｍ３以下、歪点が６４０℃以上、１０２．５ｄＰａ・ｓにおける温度が１５２０℃以下、３０〜３８０℃の温度範囲における熱膨張係数が３２〜３６×１０−７／℃であることが好ましい。 Alkali-free glass of the present invention has a glass composition, in mol%, SiO 2 55~70%, Al 2 O 3 10.8~14%, B 2 O 3 15.5~20%, CaO 9.5~ 10%, Sb 2 O 3 0 to less than 0.05% (except when Sb 2 O 3 is 0.05% by mass or more) , and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.87 to 0.90, the density is 2.35 g / cm 3 or less, the strain point is 640 ° C. or more, the temperature at 10 2.5 dPa · s is 1520 ° C. or less, and the temperature range is 30 to 380 ° C. The thermal expansion coefficient is preferably 32 to 36 × 10 −7 / ° C.

本発明の無アルカリガラスは、液相粘度が１０５．０ｄＰａ・ｓ以上であることが好ましい。ここで、「液相粘度」は、液相温度におけるガラスの粘度を白金球引き上げ法で測定した値である。「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。なお、液相粘度が高く、液相温度が低い程、耐失透性や成形性に優れている。 The alkali-free glass of the present invention preferably has a liquidus viscosity of 10 5.0 dPa · s or more. Here, the “liquid phase viscosity” is a value obtained by measuring the viscosity of the glass at the liquid phase temperature by a platinum ball pulling method. “Liquid phase temperature” is obtained by passing the standard sieve 30 mesh (500 μm) and putting the glass powder remaining in 50 mesh (300 μm) into a platinum boat, and then holding it in a temperature gradient furnace for 24 hours to precipitate crystals. It can be calculated by measuring the temperature. In addition, the higher the liquidus viscosity and the lower the liquidus temperature, the better the devitrification resistance and 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。ここで、「オーバーフローダウンドロー法」は、フュージョン法とも称されており、溶融ガラスを耐熱性の樋状構造物の両側から溢れさせて、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板状に成形する方法である。 The alkali-free glass of the present invention is preferably formed by an overflow down draw method. Here, the “overflow down draw method” is also referred to as a fusion method, in which molten glass overflows from both sides of a heat-resistant bowl-like structure, and the overflowing molten glass is joined at the lower end of the bowl-like structure. However, this is a method of forming a plate by stretching downward.

本発明の無アルカリガラスは、ＣＳＰの基板に用いることが好ましい。 The alkali-free glass of the present invention is preferably used for a CSP substrate.

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、％表示はモル％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 mol%.

ＳｉＯ２の含有量は５０〜７０％、好ましくは５５〜７０％、より好ましくは６０〜７０％、更に好ましくは６２〜６９％、最も好ましくは６２〜６７％である。ＳｉＯ２の含有量が５０％より少ないと、密度が上昇し易くなる。一方、ＳｉＯ２の含有量が７０％より多いと、高温粘度が高くなり、溶融性が低下し易くなることに加えて、ガラス中に失透結晶（クリストバライト）等の欠陥が生じ易くなる。 The content of SiO 2 is 50 to 70%, preferably 55 to 70%, more preferably 60 to 70%, still more preferably 62 to 69%, and most preferably 62 to 67%. When the content of SiO 2 is less than 50%, the density tends to increase. On the other hand, when the content of SiO 2 is more than 70%, the high-temperature viscosity becomes high and the meltability tends to be lowered, and defects such as devitrified crystals (cristobalite) are likely to occur in the glass.

Ａｌ２Ｏ３の含有量は１０．５〜１５％である。Ａｌ２Ｏ３の含有量が９％より少ないと、耐熱性を高め難くなったり、高温粘性が高くなって、溶融性が低下し易くなる。また、Ａｌ２Ｏ３には、ヤング率、比ヤング率を高める働きがあるが、Ａｌ２Ｏ３の含有量が９％より少ないと、ヤング率が低下し易くなる。Ａｌ２Ｏ３の好適な下限範囲は１０．８％以上である。一方、Ａｌ２Ｏ３の含有量が１５％より多いと、液相温度が高くなるため、耐失透性が低下し易くなる。Ａｌ２Ｏ３の好適な上限範囲は１４％以下、１３％以下、１２％以下、特に１１．５％以下である。 The content of Al 2 O 3 is 10.5 to 15%. When the content of Al 2 O 3 is less than 9%, it becomes difficult to increase the heat resistance, or the high temperature viscosity becomes high, so that the meltability tends to be lowered. In addition, Al 2 O 3 has a function of increasing the Young's modulus and specific Young's modulus, but if the content of Al 2 O 3 is less than 9%, the Young's modulus tends to decrease. A suitable lower limit range of Al 2 O 3 is 10.8% or more. On the other hand, when the content of Al 2 O 3 is more than 15%, the liquidus temperature becomes high, and thus the devitrification resistance tends to be lowered. A preferable upper limit range of Al 2 O 3 is 14% or less, 13% or less, 12% or less, and particularly 11.5% or less.

Ｂ２Ｏ３は、融剤として働き、高温粘性を下げて、溶融性を高める成分であり、その含有量は１１〜２０％である。Ｂ２Ｏ３の含有量が１１％より少ないと、融剤として作用し難くなるため、高温粘性が高くなり、ガラスの泡品位が低下し易くなる。また、密度が上昇し易くなる。Ｂ２Ｏ３の好適な下限範囲は１２％以上、１３％以上、１４％以上、１５％以上、特に１５．５％以上である。一方、Ｂ２Ｏ３の含有量が２０％より多いと、歪点、ヤング率が低下し易くなる。Ｂ２Ｏ３の好適な上限範囲は１９％以下、１８％以下、特に１７％以下である。 B 2 O 3 is a component that works as a flux, lowers the high-temperature viscosity, and increases the meltability, and its content is 11 to 20%. When the content of B 2 O 3 is less than 11%, it becomes difficult to act as a flux, so that the high temperature viscosity becomes high and the bubble quality of the glass tends to be lowered. Further, the density is likely to increase. A preferable lower limit range of B 2 O 3 is 12% or more, 13% or more, 14% or more, 15% or more, particularly 15.5% or more. On the other hand, when the content of B 2 O 3 is more than 20%, the strain point and Young's modulus are likely to be lowered. A preferable upper limit range of B 2 O 3 is 19% or less, 18% or less, and particularly 17% or less.

ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯは、液相温度を下げて、ガラス中に結晶異物を発生させ難くする成分であり、また溶融性や成形性を高める成分であり、その含有量は５〜１２％、７〜１１％、８〜１０．５％、８．５〜１０％、特に９〜１０％が好ましい。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの含有量が少ないと、融剤としての働きを十分に発揮できず、溶融性が低下することに加えて、熱膨張係数が低くなり過ぎて、Ｓｉの熱膨張係数に整合し難くなる。一方、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの含有量が多いと、密度が上昇して、ガラスを軽量化し難くなり、また比ヤング率が低下し、更に熱膨張係数が高くなり過ぎる。   MgO + CaO + SrO + BaO is a component that lowers the liquidus temperature and makes it difficult to generate crystalline foreign matter in the glass, and is a component that improves meltability and formability, and its content is 5 to 12%, 7 to 11%, 8 to 10.5%, 8.5 to 10%, particularly 9 to 10% are preferable. If the content of MgO + CaO + SrO + BaO is small, the function as a flux cannot be sufficiently exhibited, and in addition to the decrease in meltability, the thermal expansion coefficient becomes too low, making it difficult to match the thermal expansion coefficient of Si. On the other hand, when there is much content of MgO + CaO + SrO + BaO, a density will rise, it will become difficult to reduce the weight of glass, a specific Young's modulus will fall, and a thermal expansion coefficient will become high too much.

モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値は０．８４〜１．２である。モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が小さくなると、耐失透性が低下し易くなって、オーバーフローダウンドロー法による成形を行い難くなる。一方、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が大きくなると、密度や熱膨張係数が高くなり過ぎる。モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の好適な数値範囲は０．８４〜１．０５、０．８４〜１．０、０．８４〜１．０、０．８５〜０．９５、０．８５〜０．９０、特に０．８７〜０．９０である。 The value of molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.84 to 1.2. If the value of the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is small, the devitrification resistance is likely to be lowered, and it is difficult to perform molding by the overflow down draw method. On the other hand, when the value of the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 increases, the density and thermal expansion coefficient become too high. Suitable numerical ranges of the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 are 0.84 to 1.05, 0.84 to 1.0, 0.84 to 1.0, 0.85 to 0.95,. 85 to 0.90, especially 0.87 to 0.90.

ＭｇＯは、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り、またアルカリ土類金属酸化物の中では最も密度を下げる効果がある成分であり、その含有量は０〜８％、０〜６％、０〜２％、０〜１％、０〜０．５％、特に０〜０．１％が好ましい。しかし、ＭｇＯの含有量が多過ぎると、液相温度が上昇して、耐失透性が低下し易くなる。またガラスが分相し易くなって、透明性が低下し易くなる。   MgO is a component that increases the meltability by lowering the high-temperature viscosity without lowering the strain point, and is the component that has the effect of reducing the density most among the alkaline earth metal oxides. 0 to 8%, 0 to 6%, 0 to 2%, 0 to 1%, 0 to 0.5%, particularly 0 to 0.1% are preferable. However, when there is too much content of MgO, liquidus temperature will rise and devitrification resistance will fall easily. Moreover, it becomes easy to phase-divide glass and transparency will fall easily.

質量比ＭｇＯ／Ｂ２Ｏ３の値が０．６以上になると、ガラスが分相し易くなる。よって、質量比ＭｇＯ／Ｂ２Ｏ３の値は０．５以下、０．３以下、０．１以下、０．０８未満、特に０．０５未満が好ましい。 When the value of the mass ratio MgO / B 2 O 3 is 0.6 or more, the glass is easily phase-separated. Therefore, the value of the mass ratio MgO / B 2 O 3 is preferably 0.5 or less, 0.3 or less, 0.1 or less, less than 0.08, particularly preferably less than 0.05.

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と共に、本発明のガラス組成系において、失透を抑制する効果が高い成分である。また、アルカリ土類金属酸化物の中でＣａＯの含有比率を相対的に増加させると、密度が低下し易くなる。ＣａＯの好適な下限範囲は８％以上、８．５％以上、９％以上、９．２％以上、９．４％以上、特に９．５％以上である。一方、ＣａＯの含有量が多過ぎると、熱膨張係数や密度が高くなり過ぎたり、ガラス組成の成分バランスを損なわれて、耐失透性が低下し易くなる。ＣａＯの好適な上限範囲は１２％以下、１１％以下、１０．５％以下、特に１０％以下である。   CaO is a component that lowers the high-temperature viscosity without significantly reducing the strain point and significantly increases the meltability, and is a component that has a high effect of suppressing devitrification in the glass composition system of the present invention. Moreover, when the content ratio of CaO is relatively increased in the alkaline earth metal oxide, the density tends to decrease. The preferable lower limit range of CaO is 8% or more, 8.5% or more, 9% or more, 9.2% or more, 9.4% or more, particularly 9.5% or more. On the other hand, when there is too much content of CaO, a thermal expansion coefficient and a density will become high too much, the component balance of a glass composition will be impaired, and devitrification resistance will fall easily. A preferable upper limit range of CaO is 12% or less, 11% or less, 10.5% or less, and particularly 10% or less.

ＳｒＯは、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が、ＳｒＯの含有量が多くなると、密度や熱膨張係数が上昇し易くなる。また、ＳｒＯの含有量が多くなると、Ｓｉの熱膨張係数に整合させるために、相対的にＣａＯやＭｇＯの含有量を低下せざるを得ず、結果として、耐失透性が低下したり、高温粘性が高くなり易い。ＳｒＯの含有量は０〜２％、０〜１．５％、０〜１％、０〜０．５％、特に０〜０．１％が好ましい。   SrO is a component that increases the meltability by lowering the high-temperature viscosity without lowering the strain point. However, as the SrO content increases, the density and thermal expansion coefficient tend to increase. Further, when the content of SrO increases, in order to match the thermal expansion coefficient of Si, the content of CaO and MgO has to be relatively decreased, and as a result, the devitrification resistance decreases, High temperature viscosity tends to increase. The SrO content is preferably 0 to 2%, 0 to 1.5%, 0 to 1%, 0 to 0.5%, particularly preferably 0 to 0.1%.

ＢａＯは、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が、ＢａＯの含有量が多くなると、密度や熱膨張係数が上昇し易くなる。また、ＢａＯの含有量が多くなると、Ｓｉの熱膨張係数に整合させるために、相対的にＣａＯやＭｇＯの含有量を低下せざるを得ず、結果として、耐失透性が低下したり、高温粘性が高くなり易い。ＢａＯの含有量は０〜２％、０〜１．５％、０〜１％、０〜０．５％、特に０〜０．１％未満が好ましい。   BaO is a component that increases the meltability by lowering the high-temperature viscosity without lowering the strain point. However, when the content of BaO increases, the density and thermal expansion coefficient tend to increase. In addition, when the content of BaO increases, in order to match the thermal expansion coefficient of Si, the content of CaO and MgO has to be relatively reduced, and as a result, the devitrification resistance decreases, High temperature viscosity tends to increase. The BaO content is preferably 0 to 2%, 0 to 1.5%, 0 to 1%, 0 to 0.5%, particularly preferably 0 to less than 0.1%.

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２５％以下、特に１５％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. The content of other components other than the above components is preferably 25% or less, particularly preferably 15% or less in terms of the total amount, 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示す成分であり、また高温粘性を低下させる成分であり、その含有量は０〜１％、０．００１〜１％、０．０１〜０．５％、０．０５〜０．３％、特に０．１〜０．３％が好ましい。ＳｎＯ２の含有量が１％より多いと、ＳｎＯ２の失透結晶がガラス中に析出し易くなる。なお、ＳｎＯ２の含有量が０．００１％より少ないと、上記の効果を享受し難くなる。 SnO 2 is a component that exhibits a good clarification action in a high temperature range, and is a component that lowers the high temperature viscosity, and its content is 0 to 1%, 0.001 to 1%, 0.01 to 0.5. %, 0.05 to 0.3%, particularly 0.1 to 0.3% is preferable. When the content of SnO 2 is more than 1%, a devitrified crystal of SnO 2 is likely to be precipitated in the glass. Incidentally, when the content of SnO 2 is less than 0.001%, it becomes difficult to enjoy the effect of the above.

ＺｎＯは、溶融性を高める成分であるが、ガラス組成中に多量に含有させると、ガラスが失透し易くなり、また歪点が低下する上、密度も上昇し易くなる。よって、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０．１％以下の場合を指す。   ZnO is a component that enhances the meltability, but if it is contained in a large amount in the glass composition, the glass tends to be devitrified, the strain point is lowered, and the density is easily increased. Therefore, the content of ZnO is preferably 0 to 5%, 0 to 3%, 0 to 0.5%, particularly preferably 0 to 0.3%, and is desirably not substantially contained. Here, “substantially does not contain ZnO” refers to a case where the content of ZnO in the glass composition is 0.1% or less.

ＺｒＯ２は、ヤング率を高める成分であり、その含有量は０〜５％、０〜３％、０〜０．５％、特に０〜０．２％が好ましく、実質的に含有しないことが望ましい。ＺｒＯ２の含有量が多過ぎると、液相温度が上昇し、ジルコンの失透結晶が析出し易くなる。また、ＺｒＯ２の含有量が多過ぎると、α線のカウント値が上昇し易くなるため、ＣＳＰ等のデバイスに適用し難くなる。ここで、「実質的にＺｒＯ２を含有しない」とは、ガラス組成中のＺｒＯ２の含有量が０．０１％以下の場合を指す。なお、ヤング率を高める必要性が高い場合は、ＺｒＯ２の含有量を０．０１％以上とすればよい。 ZrO 2 is a component that increases the Young's modulus, and its content is preferably 0 to 5%, 0 to 3%, 0 to 0.5%, particularly preferably 0 to 0.2%, and is not substantially contained. desirable. When the content of ZrO 2 is too large, the liquidus temperature increases, devitrification zircon crystals are easily precipitated. Further, if the content of ZrO 2 is too large, the α-ray count value is likely to increase, making it difficult to apply to devices such as CSP. Here, “substantially does not contain ZrO 2 ” refers to a case where the content of ZrO 2 in the glass composition is 0.01% or less. If there is a high need for increasing the Young's modulus, the ZrO 2 content may be set to 0.01% or more.

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、ガラス組成中に多く含有させると、ガラスが着色し、透過率が低下し易くなる。よって、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 improves the meltability, and is a component that suppresses solarization. However, when it is contained in the glass composition in a large amount, the glass is colored and the transmittance tends to decrease. Therefore, the content of TiO 2 is preferably 0 to 5%, 0 to 3%, 0 to 1%, particularly preferably 0 to 0.02%.

Ｐ２Ｏ５は、耐失透性を高める成分であるが、ガラス組成中に多く含有させると、ガラス中に分相、乳白が生じることに加えて、耐水性が顕著に低下する。よって、Ｐ２Ｏ５の含有量は０〜５％、０〜１％、０〜０．５％、特に０〜０．１％が好ましい。 P 2 O 5 is a component that enhances devitrification resistance. However, when a large amount of P 2 O 5 is contained in the glass composition, in addition to the occurrence of phase separation and milk white in the glass, the water resistance is significantly reduced. Therefore, the content of P 2 O 5 is preferably 0 to 5%, 0 to 1%, 0 to 0.5%, particularly preferably 0 to 0.1%.

Ｙ２Ｏ３は、歪点、ヤング率等を高める働きを有する。しかし、Ｙ２Ｏ３の含有量が多過ぎると、密度が上昇し易くなる。よって、Ｙ２Ｏ３の含有量は５％以下が好ましい。Ｎｂ２Ｏ５は、歪点、ヤング率等を高める働きを有する。しかし、Ｎｂ２Ｏ５の成分の含有量が多過ぎると、密度が上昇し易くなる。よって、Ｎｂ２Ｏ５の含有量は５％以下が好ましい。Ｌａ２Ｏ３は、歪点、ヤング率等を高める働きを有する。しかし、Ｌａ２Ｏ３の含有量が多過ぎると、密度が上昇し易くなる。よって、Ｌａ２Ｏ３の含有量は５％以下が好ましい。 Y 2 O 3 has a function of increasing the strain point, Young's modulus, and the like. However, if the content of Y 2 O 3 is too large, the density tends to increase. Therefore, the content of Y 2 O 3 is preferably 5% or less. Nb 2 O 5 has a function of increasing the strain point, Young's modulus, and the like. However, when the content of the components of Nb 2 O 5 is too large, the density tends to increase. Therefore, the content of Nb 2 O 5 is preferably 5% or less. La 2 O 3 has a function of increasing the strain point, Young's modulus, and the like. However, when the content of La 2 O 3 is too large, the density tends to increase. Therefore, the content of La 2 O 3 is preferably 5% or less.

上記の通り、清澄剤として、ＳｎＯ２が好適であるが、ガラス特性を損なわない限り、清澄剤として、ＣｅＯ２、ＳＯ３、Ｃ、金属粉末（例えばＡｌ、Ｓｉ等）を５％まで添加することができる。 As described above, SnO 2 is suitable as the fining agent, but unless the glass properties are impaired, CeO 2 , SO 3 , C, and metal powder (eg, Al, Si, etc.) are added up to 5% as the fining agent. be able to.

Ａｓ２Ｏ ３ も清澄剤として有効に作用し、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、これらの成分の含有量は０．１％未満、特に０．０５％未満が好ましい。また、Ｓｂ ２ Ｏ ３ も清澄剤として有効に作用し、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、これらの成分の含有量は０．０５％未満である。また、Ｆ、Ｃｌ等のハロゲンは、溶融温度を低温化すると共に、清澄剤の作用を促進させる効果があり、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、Ｆ、Ｃｌの含有量が多過ぎると、ＣＳＰ等の用途において、ガラス基板上に形成される金属の配線パターンが腐食する場合がある。よって、Ｆ、Ｃｌの含有量は、それぞれ１％以下、０．５％以下、０．１％未満、０．０５％以下、０．０３％以下、特に０．０１％以下が好ましい。 As 2 O 3 also acts effectively as a fining agent, and the alkali-free glass of the present invention does not completely exclude the inclusion of these components, but from an environmental point of view, the content of these components is 0 . Less than 1%, especially less than 0.05% is preferred. Further, Sb 2 O 3 also acts effectively as a fining agent, and the alkali-free glass of the present invention does not completely exclude the inclusion of these components, but from an environmental point of view, the content of these components is It is less than 0.05%. In addition, halogens such as F and Cl have the effect of lowering the melting temperature and promoting the action of the clarifying agent. As a result, it is possible to extend the life of the glass manufacturing kiln while reducing the melting cost. it can. However, if the contents of F and Cl are too large, the metal wiring pattern formed on the glass substrate may corrode in applications such as CSP. Therefore, the contents of F and Cl are preferably 1% or less, 0.5% or less, less than 0.1%, 0.05% or less, 0.03% or less, particularly preferably 0.01% or less, respectively.

本発明の無アルカリガラスにおいて、密度は２．３７ｇ／ｃｍ３以下、好ましくは２．３５ｇ／ｃｍ３以下である。密度が大きくなると、ガラスを軽量化し難くなり、また平板形状の場合、自重によりガラスが撓み易くなる。 In the alkali-free glass of the present invention, the density is 2.37 g / cm 3 or less, preferably 2.35 g / cm 3 or less. When the density increases, it becomes difficult to reduce the weight of the glass, and in the case of a flat plate shape, the glass is easily bent by its own weight.

ガラスの泡品位は、ガラスの良品率のみならず、デバイスの良品率にも影響を及ぼす。このため、高温粘性を低下させてガラスの泡品位を高めることは重要である。本発明の無アルカリガラスにおいて、１０２．５ｄＰａ・ｓにおける温度は１６００℃以下であり、１５４０℃以下、１５３０℃以下、特に１５２０℃以下が好ましい。１０２．５ｄＰａ・ｓにおける温度が１６００℃より高いと、低温溶融が困難になり、またガラスの泡品位が低下し易くなるため、ガラスの製造コストのみならず、デバイスの製造コストも高騰し易くなる。 The bubble quality of glass affects not only the yield rate of glass but also the yield rate of devices. For this reason, it is important to increase the bubble quality of the glass by reducing the high temperature viscosity. In the alkali-free glass of the present invention, the temperature at 10 2.5 dPa · s is 1600 ° C. or lower, preferably 1540 ° C. or lower, 1530 ° C. or lower, particularly preferably 1520 ° C. or lower. When the temperature at 10 2.5 dPa · s is higher than 1600 ° C., it becomes difficult to melt at a low temperature and the bubble quality of the glass tends to be lowered, so that not only the glass manufacturing cost but also the device manufacturing cost increases. It becomes easy.

本発明の無アルカリガラスにおいて、歪点は６３０℃以上、６３５℃以上、特に６４０℃以上が好ましい。ＣＳＰ等の用途の場合、ガラス同士を樹脂等で接着させることがある。その場合、歪点が６３０℃より低いと、ガラス同士を接着させる際に、ガラス品位が低下するおそれがある。また、歪点が６３０℃より低いと、有機ＥＬ用ガラス基板として使用する場合、ｐ−Ｓｉ・ＴＦＴの製造工程でガラスが熱収縮し易くなる。   In the alkali-free glass of the present invention, the strain point is preferably 630 ° C. or higher, 635 ° C. or higher, particularly 640 ° C. or higher. In the case of applications such as CSP, the glass may be bonded with a resin or the like. In that case, when the strain point is lower than 630 ° C., the glass quality may be lowered when the glasses are bonded to each other. When the strain point is lower than 630 ° C., when used as a glass substrate for organic EL, the glass is likely to be thermally contracted in the manufacturing process of the p-Si • TFT.

本発明の無アルカリガラスにおいて、３０〜３８０℃の温度範囲における熱膨張係数は３２〜４０×１０−７／℃、３２〜３８×１０−７／℃、３２〜３６×１０−７／℃、特に３３〜３５×１０−７／℃である。熱膨張係数が上記範囲外となると、ガラス基板とＳｉチップと貼り合わせる際に、ガラス基板の反り量が大きくなり易い。また、ガラス基板の板厚が小さい程、熱膨張係数の差に起因するガラス基板の反り量が大きくなる。よって、ガラス基板の板厚が小さい場合（例えば、ガラス基板の板厚が０．２ｍｍ以下の場合）、熱膨張係数を上記範囲内に規制する意義が大きくなる。 In the alkali-free glass of the present invention, the thermal expansion coefficient in the temperature range of 30 to 380 ° C. is 32 to 40 × 10 −7 / ° C., 32 to 38 × 10 −7 / ° C., 32 to 36 × 10 −7 / ° C., In particular, it is 33 to 35 × 10 −7 / ° C. If the thermal expansion coefficient is out of the above range, the amount of warpage of the glass substrate tends to increase when the glass substrate and the Si chip are bonded together. Further, the smaller the plate thickness of the glass substrate, the larger the amount of warpage of the glass substrate due to the difference in thermal expansion coefficient. Therefore, when the thickness of the glass substrate is small (for example, when the thickness of the glass substrate is 0.2 mm or less), the significance of regulating the thermal expansion coefficient within the above range is increased.

本発明の無アルカリガラスにおいて、液相温度は１１８０℃以下、１１５０℃以下、１１３０℃以下、１１１０℃以下、１０９０℃以下、特に１０７０℃以下が好ましい。このようにすれば、ガラスに失透結晶が発生し難くなるため、オーバーフローダウンドロー法等で成形し易くなる。結果として、ガラスの製造コストを低廉化できると共に、ガラスの表面品位を高めることができる。   In the alkali-free glass of the present invention, the liquidus temperature is preferably 1180 ° C. or lower, 1150 ° C. or lower, 1130 ° C. or lower, 1110 ° C. or lower, 1090 ° C. or lower, particularly 1070 ° C. or lower. In this way, devitrification crystals are less likely to occur in the glass, which makes it easier to form by the overflow downdraw method or the like. As a result, the manufacturing cost of the glass can be reduced and the surface quality of the glass can be improved.

本発明の無アルカリガラスにおいて、液相粘度は１０５．０ｄＰａ・ｓ以上、１０５．２ｄＰａ・ｓ以上、１０５．３ｄＰａ・ｓ以上、１０５．５ｄＰａ・ｓ以上、特に１０５．７ｄＰａ・ｓ以上が好ましい。このようにすれば、成形時に失透結晶が発生し難くなるため、オーバーフローダウンドロー法等で成形し易くなる。結果として、ガラスの製造コストを低廉化できると共に、ガラスの表面品位を高めることができる。 In the alkali-free glass of the present invention, the liquid phase viscosity is 10 5.0 dPa · s or more, 10 5.2 dPa · s or more, 10 5.3 dPa · s or more, 10 5.5 dPa · s or more, particularly 10 5.7 dPa · s or more is preferable. In this way, devitrification crystals are less likely to occur during molding, and it becomes easier to mold by the overflow down draw method or the like. As a result, the manufacturing cost of the glass can be reduced and the surface quality of the glass can be improved.

本発明の無アルカリガラスは、所定のガラス組成となるように調合したガラス原料を連続式ガラス溶融窯に投入した後、このガラス原料を加熱溶融し、得られた溶融ガラスを清澄した上で、成形装置に供給して平板形状等に成形することで作製可能である。   The alkali-free glass of the present invention, after putting the glass raw material prepared so as to have a predetermined glass composition into a continuous glass melting furnace, this glass raw material is heated and melted, and the obtained molten glass is clarified, It can be manufactured by supplying it to a molding apparatus and molding it into a flat plate shape or the like.

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では、ガラス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平板形状のガラス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, the surface to be the surface of the glass is formed in the state of a free surface without contacting the bowl-like refractory. For this reason, it is possible to produce a flat plate glass that is unpolished and has a good surface quality at a 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.

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以外にも、種々の成形方法を採用することができる。例えば、ダウンドロー法（スロットダウン法等）、フロート法、ロールアウト法等を採用することができる。   The alkali-free glass of the present invention can employ various molding methods other than the overflow downdraw method. For example, a downdraw method (such as a slot down method), a float method, a rollout method, or the like can be employed.

本発明の無アルカリガラスは、平板形状を有することが好ましい。このようにすれば、液晶ディスプレイ、有機ＥＬディスプレイ等のフラットディスプレイ用ガラス基板、ＣＳＰ、ＣＣＤ、ＣＩＳ等のイメージセンサー用ガラス基板に適用することができる。また、本発明の無アルカリガラスは、平板形状の場合、その板厚は０．６ｍｍ以下、０．５ｍｍ以下、０．３ｍｍ以下、０．２ｍｍ以下、特に０．１ｍｍ以下が好ましい。板厚が小さい程、ガラスを軽量化することができ、結果として、デバイスも軽量化し易くなる。なお、本発明の無アルカリガラスは、液相粘度が高いため、オーバーフローダウンドロー法で成形し易い性質を有する。オーバーフローダウンドロー法で成形すれば、未研磨で表面品位が良好な平板形状のガラスを安価に製造することができる。   The alkali-free glass of the present invention preferably has a flat plate shape. If it does in this way, it can apply to glass substrates for flat displays, such as a liquid crystal display and an organic EL display, and glass substrates for image sensors, such as CSP, CCD, and CIS. Further, when the alkali-free glass of the present invention has a flat plate shape, the thickness is preferably 0.6 mm or less, 0.5 mm or less, 0.3 mm or less, 0.2 mm or less, particularly preferably 0.1 mm or less. The smaller the plate thickness, the lighter the glass, and as a result, the device is also lighter. In addition, since the alkali-free glass of the present invention has a high liquidus viscosity, it has the property of being easily molded by the overflow down draw method. If it is formed by the overflow downdraw method, flat glass having good surface quality that is unpolished can be produced at a low cost.

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１〜３は、試料Ｎｏ．１〜１３を示している。
Table 1-3, specimen No. 1 to 13 are shown.

次のようにして、試料Ｎｏ．１〜１３を作製した。まず表中のガラス組成になるように調合したガラス原料を白金坩堝に入れ、１６００℃で２４時間溶融した後、カーボン板上に流し出して平形板状に成形した。次に、得られた各試料について、密度、熱膨張係数α、歪点Ｐｓ、徐冷点Ｔａ、軟化点Ｔｓ、１０４ｄＰａ・ｓにおける温度、１０３ｄＰａ・ｓにおける温度、１０２．５ｄＰａ・ｓにおける温度、液相温度ＴＬ、液相粘度ｌｏｇ１０ηＴＬ、ヤング率を評価した。 Sample no. 1-13 were produced. First, glass raw materials prepared so as to have the glass composition shown in the table were put in a platinum crucible and melted at 1600 ° C. for 24 hours, and then poured onto a carbon plate to form a flat plate. Next, for each of the obtained samples, density, thermal expansion coefficient α, strain point Ps, annealing point Ta, softening point Ts, temperature at 10 4 dPa · s, temperature at 10 3 dPa · s, 10 2.5 The temperature in dPa · s, the liquidus temperature TL, the liquidus viscosity log 10 ηTL, and Young's modulus 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.

熱膨張係数αは、ディラトメーターで測定した値であり、３０〜３８０℃の温度範囲における平均値である。   The thermal expansion coefficient α is a value measured with a dilatometer, and is an average value in a temperature range of 30 to 380 ° C.

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.

１０４．０ｄＰａ・ｓにおける温度、１０３．０ｄＰａ・ｓにおける温度、１０２．５ｄＰａ・ｓ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 10 4.0 dPa · s, the temperature at 10 3.0 dPa · s, and the temperature at 10 2.5 dPa · s are values measured by the 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、温度勾配炉中に２４時間保持した後、結晶の析出する温度を測定した値である。   The liquid phase temperature TL passes through a standard sieve 30 mesh (500 μm), puts the glass powder remaining in 50 mesh (300 μm) into a platinum boat, holds it in a temperature gradient furnace for 24 hours, and then measures the temperature at which crystals precipitate. It is the value.

液相粘度ｌｏｇ１０ηＴＬは、液相温度ＴＬにおけるガラスの粘度を白金球引き上げ法で測定した値である。 The liquidus viscosity log 10 ηTL is a value obtained by measuring the viscosity of the glass at the liquidus temperature TL by a platinum ball pulling method.

ヤング率は、共振法で測定した値である。なお、本発明の無アルカリガラスにおいて、ヤング率は６４ＧＰａ以上が好ましい。ヤング率が大きい程、比ヤング率（ヤング率／密度）が大きくなるため、平板形状の場合、自重によりガラスが撓み難くなる。   The Young's modulus is a value measured by a resonance method. In the alkali-free glass of the present invention, the Young's modulus is preferably 64 GPa or more. Since the specific Young's modulus (Young's modulus / density) increases as the Young's modulus increases, the glass is less likely to be bent due to its own weight in the case of a flat plate shape.

表１〜３から明らかなように、試料Ｎｏ．１〜１３は、ガラス組成が所定範囲に規制されているため、密度が２．３７ｇ／ｃｍ３以下、歪点が６３０℃以上、１０２．５ｄＰａ・ｓにおける温度が１６００℃以下であった。なお、試料Ｎｏ．１〜１３は、ガラス組成中にＡｓ２Ｏ３、Ｓｂ２Ｏ３を含有していないが、泡品位が良好であった。 As is apparent from Tables 1 to 3, sample No. In Nos. 1 to 13, since the glass composition was regulated within a predetermined range, the density was 2.37 g / cm 3 or less, the strain point was 630 ° C. or more, and the temperature at 10 2.5 dPa · s was 1600 ° C. or less. . Sample No. 1-13, but it does not contain As 2 O 3, Sb 2 O 3 in the glass composition, the foam quality was good.

試験溶融炉で表１に記載の試料Ｎｏ．１〜４を溶融した後、オーバーフローダウンドロー法で厚み０．１ｍｍの平板形状に成形した。成形に際し、引っ張りローラーの速度、冷却ローラーの速度、加熱装置の温度分布、溶融ガラスの温度、溶融ガラスの流量、板引き速度、攪拌スターラーの回転数等を適宜調整することにより、ガラス板の表面品位を調節した。得られたガラス板の表面品位を測定したところ、反りは０．０７５％以下、うねり（ＷＣＡ）は０．１５μｍ以下（カットオフｆｈ：０．８ｍｍ、ｆｌ：８ｍｍ）、表面粗さ（Ｒｙ）は２０Å以下（カットオフλｃ：９μｍ）であった。なお、「反り」は、ガラス板を光学定盤上に置き、ＪＩＳ Ｂ−７５２４に記載のすきまゲージを用いて測定した値である。「うねり」は、触針式の表面形状測定装置を用いて、ＪＩＳ Ｂ−０６１０に記載のＷＣＡ（ろ波中心線うねり）を測定した値であると共に、ＳＥＭＩ ＳＴＤ Ｄ１５−１２９６「ＦＰＤガラス基板の表面うねりの測定方法」に準拠した方法により測定した値である。「平均表面粗さ（Ｒｙ）」は、ＳＥＭＩ Ｄ７−９４「ＦＰＤガラス基板の表面粗さの測定方法」に準拠した方法により測定した値である。
In the test melting furnace, sample No. After melting 1-4, it was formed into a flat plate shape with a thickness of 0.1 mm by the overflow down draw method. During molding, the surface of the glass plate is adjusted by appropriately adjusting the speed of the pulling roller, the speed of the cooling roller, the temperature distribution of the heating device, the temperature of the molten glass, the flow rate of the molten glass, the drawing speed, the rotational speed of the stirring stirrer, etc. The quality was adjusted. When the surface quality of the obtained glass plate was measured, warpage was 0.075% or less, waviness (WCA) was 0.15 μm or less (cut-off fh: 0.8 mm, fl: 8 mm), surface roughness (Ry). Was 20 mm or less (cut-off λc: 9 μm). “Warpage” is a value measured by placing a glass plate on an optical surface plate and using a clearance gauge described in JIS B-7524. “Waviness” is a value obtained by measuring WCA (filtered centerline waviness) described in JIS B-0610 using a stylus type surface shape measuring device, and SEMI STD D15-1296 “FPD glass substrate It is a value measured by a method based on “Measurement method of surface waviness”. “Average surface roughness (Ry)” is a value measured by a method based on SEMI D7-94 “Measurement method of surface roughness of FPD glass substrate”.

Claims (7)

ガラス組成として、ｍｏｌ％で、ＳｉＯ２ ５０〜７０％、Ａｌ２Ｏ３ １０．５〜１５％、Ｂ２Ｏ３ １２〜２０％、ＣａＯ ８〜１２％、Ｓｂ２Ｏ３ ０〜０．０５％未満（但し、Ｓｂ２Ｏ３が０．０５質量％以上の場合を除く）を含有し、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が０．８４〜１．２であって、
密度が２．３７ｇ／ｃｍ３以下、１０２．５ｄＰａ・ｓにおける温度が１６００℃以下であることを特徴とする無アルカリガラス。 As a glass composition, in mol%, SiO 2 50~70%, Al 2 O 3 10.5~15%, B 2 O 3 12~20%, CaO 8~12%, Sb 2 O 3 0~0.05 % (Provided that Sb 2 O 3 is 0.05% by mass or more), and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.84 to 1.2,
A non-alkali glass having a density of 2.37 g / cm 3 or less and a temperature at 10 2.5 dPa · s of 1600 ° C. or less. ガラス組成として、ｍｏｌ％で、ＳｉＯ２ ５０〜７０％、Ａｌ２Ｏ３ １０．５〜１５％、Ｂ２Ｏ３ １２〜２０％、ＣａＯ ９〜１２％、Ｓｂ２Ｏ３ ０〜０．０５％未満（但し、Ｓｂ２Ｏ３が０．０５質量％以上の場合を除く）を含有し、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が０．８４〜１．０５であって、
密度が２．３５ｇ／ｃｍ３以下、歪点が６３０℃以上、１０２．５ｄＰａ・ｓにおける温度が１５４０℃以下、３０〜３８０℃の温度範囲における熱膨張係数が３２〜４０×１０−７／℃であることを特徴とする請求項１に記載の無アルカリガラス。 As a glass composition, in mol%, SiO 2 50~70%, Al 2 O 3 10.5~15%, B 2 O 3 12~20%, CaO 9~12%, Sb 2 O 3 0~0.05 % (Provided that Sb 2 O 3 is 0.05% by mass or more), and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.84 to 1.05,
The density is 2.35 g / cm 3 or less, the strain point is 630 ° C. or more, the temperature at 10 2.5 dPa · s is 1540 ° C. or less, and the thermal expansion coefficient is 32 to 40 × 10 −7 in the temperature range of 30 to 380 ° C. The alkali-free glass according to claim 1, which is / ° C. ガラス組成として、ｍｏｌ％で、ＳｉＯ２ ５５〜７０％、Ａｌ２Ｏ３ １０．５〜１４％、Ｂ２Ｏ３ １４〜２０％、ＣａＯ ９．２〜１１％、Ｓｂ２Ｏ３ ０〜０．０５％未満（但し、Ｓｂ２Ｏ３が０．０５質量％以上の場合を除く）を含有し、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が０．８４〜１．０であって、
密度が２．３５ｇ／ｃｍ３以下、歪点が６３５℃以上、１０２．５ｄＰａ・ｓにおける温度が１５３０℃以下、３０〜３８０℃の温度範囲における熱膨張係数が３２〜３８×１０−７／℃であることを特徴とする請求項１又は２に記載の無アルカリガラス。 As a glass composition, in mol%, SiO 2 55~70%, Al 2 O 3 10.5~14%, B 2 O 3 14~20%, CaO 9.2~11%, Sb 2 O 3 0~0 Less than 0.05% (except when Sb 2 O 3 is 0.05% by mass or more), and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.84 to 1.0. ,
The density is 2.35 g / cm 3 or less, the strain point is 635 ° C. or more, the temperature at 10 2.5 dPa · s is 1530 ° C. or less, and the thermal expansion coefficient is 32 to 38 × 10 −7 in the temperature range of 30 to 380 ° C. The alkali-free glass according to claim 1 or 2, which is / ° C. ガラス組成として、ｍｏｌ％で、ＳｉＯ２ ５５〜７０％、Ａｌ２Ｏ３ １０．５〜１４％、Ｂ２Ｏ３ １５〜２０％、ＣａＯ ９．５〜１０．５％、Ｓｂ２Ｏ３ ０〜０．０５％未満（但し、Ｓｂ２Ｏ３が０．０５質量％以上の場合を除く）を含有し、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が０．８５〜０．９０であって、
密度が２．３５ｇ／ｃｍ３以下、歪点が６３５℃以上、１０２．５ｄＰａ・ｓにおける温度が１５２０℃以下、３０〜３８０℃の温度範囲における熱膨張係数が３２〜３６×１０−７／℃であることを特徴とする請求項１〜３のいずれかに記載の無アルカリガラス。 As a glass composition, in mol%, SiO 2 55~70%, Al 2 O 3 10.5~14%, B 2 O 3 15~20%, CaO 9.5~10.5%, Sb 2 O 3 0 Less than 0.05% (excluding the case where Sb 2 O 3 is 0.05% by mass or more), and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.85 to 0.90. There,
The density is 2.35 g / cm 3 or less, the strain point is 635 ° C. or more, the temperature at 10 2.5 dPa · s is 1520 ° C. or less, and the thermal expansion coefficient is 32 to 36 × 10 −7 in the temperature range of 30 to 380 ° C. The alkali-free glass according to any one of claims 1 to 3, which is / ° C. ガラス組成として、ｍｏｌ％で、ＳｉＯ２ ５５〜７０％、Ａｌ２Ｏ３ １０．８〜１４％、Ｂ２Ｏ３ １５．５〜２０％、ＣａＯ ９．５〜１０％、Ｓｂ２Ｏ３ ０〜０．０５％未満（但し、Ｓｂ２Ｏ３が０．０５質量％以上の場合を除く）を含有し、モル比（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／Ａｌ２Ｏ３の値が０．８７〜０．９０であって、
密度が２．３５ｇ／ｃｍ３以下、歪点が６４０℃以上、１０２．５ｄＰａ・ｓにおける温度が１５２０℃以下、３０〜３８０℃の温度範囲における熱膨張係数が３２〜３６×１０−７／℃であることを特徴とする請求項１〜４のいずれかに記載の無アルカリガラス。 As a glass composition, in mol%, SiO 2 55~70%, Al 2 O 3 10.8~14%, B 2 O 3 15.5~20%, CaO 9.5~10%, Sb 2 O 3 0 Less than 0.05% (except when Sb 2 O 3 is 0.05% by mass or more), and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.87 to 0.90. There,
The density is 2.35 g / cm 3 or less, the strain point is 640 ° C. or more, the temperature at 10 2.5 dPa · s is 1520 ° C. or less, and the thermal expansion coefficient is 32 to 36 × 10 −7 in the temperature range of 30 to 380 ° C. The alkali-free glass according to any one of claims 1 to 4, which is / ° C. 液相粘度が１０５．０ｄＰａ・ｓ以上であることを特徴とする請求項１〜５のいずれかに記載の無アルカリガラス。 Liquid phase viscosity is 10 < 5.0 > dPa * s or more, The alkali free glass in any one of Claims 1-5 characterized by the above-mentioned. チップサイズパッケージの基板に用いることを特徴とする請求項１〜６のいずれかに記載の無アルカリガラス。 It uses for the board | substrate of a chip size package, The alkali free glass in any one of Claims 1-6 characterized by the above-mentioned.
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