JP5762677B2 - Method for producing crystallized glass - Google Patents
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- JP5762677B2 JP5762677B2 JP2009228355A JP2009228355A JP5762677B2 JP 5762677 B2 JP5762677 B2 JP 5762677B2 JP 2009228355 A JP2009228355 A JP 2009228355A JP 2009228355 A JP2009228355 A JP 2009228355A JP 5762677 B2 JP5762677 B2 JP 5762677B2
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- 239000011521 glass Substances 0.000 title claims description 131
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 239000013078 crystal Substances 0.000 claims description 29
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 229910000500 β-quartz Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 230000006911 nucleation Effects 0.000 claims description 19
- 238000010899 nucleation Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 description 23
- 238000004031 devitrification Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 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 2
- -1 lanquinite Chemical compound 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910001347 Stellite Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910001597 celsian Inorganic materials 0.000 description 1
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 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
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 1
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910021493 α-cristobalite Inorganic materials 0.000 description 1
- 229910021489 α-quartz Inorganic materials 0.000 description 1
- 229910021491 α-tridymite Inorganic materials 0.000 description 1
Landscapes
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
- Glass Compositions (AREA)
Description
本発明は極低膨張特性を有する結晶化ガラスの製造方法に関する。 The present invention relates to a method for producing crystallized glass having extremely low expansion characteristics.
β−石英及び／又はβ−石英固溶体を含む結晶化ガラスは低い平均線膨張係数を有し、極端紫外線を光源とする極端紫外線露光技術（ＥＵＶＬ）を利用した次世代半導体製造装置などのミラー基板材やフォトマスク基板材としての使用が検討されている。 Crystallized glass containing β-quartz and / or β-quartz solid solution has a low average linear expansion coefficient and is a mirror substrate for next-generation semiconductor manufacturing equipment using extreme ultraviolet exposure technology (EUVL) using extreme ultraviolet light as a light source. Use as a plate material or a photomask substrate material has been studied.
ＥＵＶＬの反射光学系では、ミラー面の投影像が基板材の熱膨張などによって変形すると、最終的な露光品質が劣化してしまうため、ミラーやフォトマスクの基板材料にはｐｐｂ／℃レベルの熱膨張係数が極めて小さな材料を使用する必要がある。
例えばＥＵＶＬのフォトマスク基板の規格であるＳＥＭＩ Ｐ３７−１１０２には、クラスＤで１９℃から２５℃における平均線膨張係数が０±３０ｐｐｂ／℃、クラスＡで１９℃から２５℃における平均線膨張係数が０±５ｐｐｂ／℃と定められている。
In the EUVL reflective optical system, if the projected image on the mirror surface is deformed due to thermal expansion of the substrate material or the like, the final exposure quality deteriorates. Therefore, the substrate material of the mirror or photomask has a heat level of ppb / ° C. It is necessary to use a material with an extremely small expansion coefficient.
For example, SEMI P37-1102, which is the EUVL photomask substrate standard, has an average linear expansion coefficient of 0 ± 30 ppb / ° C. from 19 ° C. to 25 ° C. in class D and an average linear expansion coefficient from 19 ° C. to 25 ° C. in class A. Is defined as 0 ± 5 ppb / ° C.
ここで、Ｔ１℃からＴ２℃における平均線膨張係数αとは次の式によって得られる。
α＝（ＬＴ２−ＬＴ１）／｛Ｌ×（Ｔ２−Ｔ１）｝
Ｌ：室温における試料の長さ（本発明においては室温を２５℃と定義する。）
ＬＴ１：Ｔ１の時の試料の長さ
ＬＴ２：Ｔ２の時の試料の長さ
また、ある温度における膨張傾向を把握する為にＣＴＥ−温度曲線や、ΔＬ／Ｌ曲線を描くことが良く行われる。
ＣＴＥ−温度曲線とは上記の式において、Ｔ１とＴ２の温度範囲を充分に狭くした時の、ある温度Ｔにおける平均線膨張係数をｙ軸に、温度をｘ軸としてプロットした時に得られる曲線を言う。
ΔＬ／Ｌ曲線とは室温における試料の長さをＬとし、温度Ｔの時の試料の長さをＬＴとする時、（ＬＴ−Ｌ）／Ｌの値（ΔＬ／Ｌ）をｙ軸に、温度をｘ軸としてプロットした時に得られる曲線を言う。
また、ｄＣＴＥ／ｄＴ−温度曲線とは、ＣＴＥ−温度曲線を温度で微分した曲線であり、膨張特性の温度依存性を示す。
Here, the average linear expansion coefficient α from T1 ° C. to T2 ° C. is obtained by the following equation.
α = (L T2 −L T1 ) / {L × (T2−T1)}
L: Length of sample at room temperature (in the present invention, room temperature is defined as 25 ° C.)
L T1 : Length of the sample at T1 L T2 : Length of the sample at T2 In order to grasp the expansion tendency at a certain temperature, a CTE-temperature curve and a ΔL / L curve are often drawn. Is called.
The CTE-temperature curve is a curve obtained when the average linear expansion coefficient at a certain temperature T is plotted on the y axis and the temperature is plotted on the x axis when the temperature range of T1 and T2 is sufficiently narrowed in the above formula. say.
The length of the sample at room temperature and [Delta] L / L curve is L, when the length of the sample at the temperature T and L T, y-axis the value of (L T -L) / L ( ΔL / L) And the curve obtained when temperature is plotted on the x-axis.
The dCTE / dT-temperature curve is a curve obtained by differentiating the CTE-temperature curve with temperature, and indicates the temperature dependence of the expansion characteristics.
次世代半導体製造装置などのミラー基板材やフォトマスク基板材として結晶化ガラスを使用するためには、平均線膨張係数がゼロ付近であることに加え、膨張傾向の変化が少ないこと、すなわちΔＬ／Ｌ曲線の傾きの変化が少ないことが好ましい。 In order to use crystallized glass as a mirror substrate material or a photomask substrate material for a next-generation semiconductor manufacturing apparatus or the like, in addition to the average linear expansion coefficient being near zero, there is little change in expansion tendency, that is, ΔL / It is preferable that the change in the slope of the L curve is small.
特許文献１には０℃〜５０℃において、平均線膨張係数が０．０±０．２×１０−７・℃−１以内であり、ΔＬ／Ｌの最大値−最小値が１０×１０−７以内である結晶化ガラスが開示されている。
しかし、特許文献１のΔＬ／Ｌ曲線は２０℃から３０℃の領域では山なりとなっており、ΔＬ／Ｌ曲線の傾きの変化が大きく、使用温度領域での膨張傾向が変化するため、次世代半導体製造装置などのミラー基板材やフォトマスク基板材への適用は必ずしも好ましくない。
However, the ΔL / L curve in Patent Document 1 has a mountain in the region of 20 ° C. to 30 ° C., and the change in the slope of the ΔL / L curve is large, and the expansion tendency in the operating temperature region changes. Application to a mirror substrate material or a photomask substrate material such as a generation semiconductor manufacturing apparatus is not necessarily preferable.
本発明の課題は、０℃から５０℃において平均線膨張係数が極めて小さく、かつΔＬ／Ｌ曲線の傾きの変化が極めて小さい結晶化ガラスの製造方法を提供することである。 An object of the present invention is to provide a method for producing crystallized glass having an extremely low average linear expansion coefficient from 0 ° C. to 50 ° C. and an extremely small change in the slope of the ΔL / L curve.
本発明者は上記の課題に鑑み、鋭意研究を重ねた結果、結晶相にβ−石英及び／又はβ−石英固溶体を含む結晶化ガラスの製造方法において、原ガラスの熱処理の温度、時間を特定の範囲とすることにより、０℃から５０℃において平均線膨張係数が極めて小さく、かつΔＬ／Ｌ曲線の傾きの変化が極めて小さい結晶化ガラスを得ることができる製造方法を見いだしこの発明を完成したものであり、その具体的な構成は以下の通りである。 As a result of intensive studies in view of the above problems, the present inventors have identified the temperature and time of heat treatment of the original glass in the method for producing crystallized glass containing β-quartz and / or β-quartz solid solution in the crystal phase. Thus, the present invention was completed by finding a production method capable of obtaining crystallized glass having an extremely small average linear expansion coefficient from 0 ° C. to 50 ° C. and an extremely small change in the slope of the ΔL / L curve. The specific configuration is as follows.
（構成１）
Ｌｉ２Ｏ、Ａｌ２Ｏ３及びＳｉＯ２の各成分を含有するガラスを熱処理し、結晶相にβ−石英及び／又はβ−石英固溶体を含む結晶化ガラスとする結晶化ガラスの製造方法であって、前記熱処理における少なくとも一つの保温工程ＮＧは、
温度（℃）をｘ軸、時間（ｈ）をｙ軸として表したグラフにおいて、下記ＡからＤの４点の座標を結んだ領域内であることを特徴とする請求項１に記載の結晶化ガラスの製造方法。
Ａ：（Ｔｇ＋５０，０．１）
Ｂ：（Ｔｇ＋５０，４００）
Ｃ：（Ｔｇ＋８０，４００）
Ｄ：（Ｔｇ＋９５，０．１）
但しＴｇは前記結晶化ガラスの原ガラスのガラス転移点（℃）である。
（構成２）
前記熱処理は核形成工程と核成長工程を有し、前記核形成工程の保温温度がガラス転移点Ｔｇに対して＋１０〜＋５０℃、前記核形成工程の保温時間が２０〜１００時間であることを特徴とする構成１に記載の結晶化ガラスの製造方法。
（構成３）
前記保温工程ＮＧは核成長工程に含まれ、前記核形成工程の保温温度よりも高い保温温度である構成１または２に記載の結晶化ガラスの製造方法。
（構成４）
β−石英及び／又はβ−石英固溶体を含む結晶化ガラスを
２００℃から１５０℃へ降温する工程を少なくとも含み、
前記工程における降温の速度を０．０００５℃／ｍｉｎ〜０．１℃／ｍｉｎの範囲とすることを特徴とする構成１から３のいずれかに記載の結晶化ガラスの製造方法。
（構成５）
前記Ｌｉ２Ｏ、Ａｌ２Ｏ３及びＳｉＯ２の各成分を含有するガラスの組成は酸化物基準の質量％で、
ＳｉＯ２ ４７〜６５％、
Ｐ２Ｏ５ １〜１３％、
Ａｌ２Ｏ３ １７〜２９％、
Ｌｉ２Ｏ １〜８％、
ＭｇＯ ０．５〜５％、
ＺｎＯ ０．５〜５．５％、
ＴｉＯ２ １〜７％、
ＺｒＯ２ １〜７％
の範囲の各成分を含有することを特徴とする構成１から４のいずれかに記載の結晶化ガラスの製造方法。
（構成６）
前記Ｌｉ２Ｏ、Ａｌ２Ｏ３及びＳｉＯ２の各成分を含有するガラスの組成は酸化物基準の質量％で、
Ｎａ２Ｏ ０〜４％、及び／又は
Ｋ２Ｏ ０〜４％、及び／又は
ＣａＯ ０〜７％、及び／又は
ＢａＯ ０〜７％、及び／又は
ＳｒＯ ０〜４％、及び／又は
Ａｓ２Ｏ３ ０〜２％、及び／又は
Ｓｂ２Ｏ３ ０〜２％、
の範囲の各成分を含有することを特徴とする構成１から５のいずれかに記載の結晶化ガラスの製造方法。
（構成７）
前記Ｌｉ２Ｏ、Ａｌ２Ｏ３及びＳｉＯ２の各成分を含有するガラスの組成は、質量百分率で、
ＳｉＯ２＋Ａｌ２Ｏ３＋Ｐ２Ｏ５＝６５．０〜９３．０％であり、
Ｐ２Ｏ５とＳｉＯ２の質量百分率の比、
Ｐ２Ｏ５とＡｌ２Ｏ３の質量百分率の比がそれぞれ、
Ｐ２Ｏ５／ＳｉＯ２＝０．０２〜０．２００、
Ｐ２Ｏ５／Ａｌ２Ｏ３＝０．０５９〜０．４４８、
であることを特徴とする構成５または６に記載の結晶化ガラスの製造方法。
（構成８）
０℃〜５０℃の温度範囲における平均線膨張係数が０．０±０．２×１０−７・℃−１である事を特徴とする、構成１から７のいずれかに記載の結晶化ガラスの製造方法。
（構成９）
０℃〜５０℃の温度範囲におけるΔＬ／Ｌの最大値−最小値の絶対値が１０×１０−７以下である構成１から８のいずれかに記載の結晶化ガラスの製造方法。
（構成１０）
２０℃〜３０℃におけるｄＣＴＥ／ｄＴ−温度曲線の値が−１．０ｐｐｂ・℃−２から＋１．０ｐｐｂ・℃−２の範囲であることを特徴とする構成１から９のいずれかに記載の結晶化ガラスの製造方法。
（構成１１）
前記２００℃から１５０℃へ降温処理する工程によって、当該工程を行う前の結晶化ガラスの０℃〜５０℃の温度範囲における平均線膨張係数を減少させることを特徴とする構成１から１０のいずれかに記載の結晶化ガラスの製造方法。
(Configuration 1)
This is a method for producing crystallized glass by heat-treating glass containing each component of Li 2 O, Al 2 O 3 and SiO 2 to obtain crystallized glass containing β-quartz and / or β-quartz solid solution in the crystal phase. The at least one heat retention step NG in the heat treatment is as follows:
2. The crystallization according to claim 1, wherein the crystallization is in a region where the coordinates of the following four points A to D are connected in a graph in which temperature (° C.) is expressed as x-axis and time (h) is expressed as y-axis. Glass manufacturing method.
A: (Tg + 50, 0.1)
B: (Tg + 50,400)
C: (Tg + 80,400)
D: (Tg + 95, 0.1)
However, Tg is a glass transition point (° C.) of the original glass of the crystallized glass.
(Configuration 2)
The heat treatment includes a nucleation step and a nucleation growth step, and the heat retention temperature of the nucleation step is +10 to + 50 ° C. with respect to the glass transition point Tg, and the heat retention time of the nucleation step is 20 to 100 hours. 2. A method for producing a crystallized glass according to Structure 1, which is characterized.
(Configuration 3)
The method for producing crystallized glass according to Configuration 1 or 2, wherein the heat retention step NG is included in a nucleus growth step and has a heat retention temperature higher than the heat retention temperature of the nucleus formation step.
(Configuration 4)
at least a step of cooling the crystallized glass containing β-quartz and / or β-quartz solid solution from 200 ° C. to 150 ° C.,
4. The method for producing crystallized glass according to any one of Structures 1 to 3, wherein the rate of temperature decrease in the step is in the range of 0.0005 ° C./min to 0.1 ° C./min.
(Configuration 5)
The composition of the glass containing each component of Li 2 O, Al 2 O 3 and SiO 2 is mass% based on oxide,
SiO 2 47~65%,
P 2 O 5 1~13%,
Al 2 O 3 17-29%,
Li 2 O 1-8%,
MgO 0.5-5%,
ZnO 0.5-5.5%,
TiO 2 1-7%,
ZrO 2 1-7%
The method for producing a crystallized glass according to any one of the constitutions 1 to 4, further comprising:
(Configuration 6)
The composition of the glass containing each component of Li 2 O, Al 2 O 3 and SiO 2 is mass% based on oxide,
Na 2 O 0-4% and / or K 2 O 0-4% and / or CaO 0-7% and / or BaO 0-7% and / or SrO 0-4% and / or As 2 O 3 0-2% and / or Sb 2 O 3 0-2%,
6. The method for producing crystallized glass according to any one of constitutions 1 to 5, wherein each component in the range of 1 to 5 is contained.
(Configuration 7)
The composition of the glass containing each component of the Li 2 O, Al 2 O 3 and SiO 2 is a mass percentage,
SiO 2 + Al 2 O 3 + P 2 O 5 = 65.0-93.0%,
Ratio of mass percentage of P 2 O 5 and SiO 2 ,
The ratio of mass percentages of P 2 O 5 and Al 2 O 3 is respectively
P 2 O 5 / SiO 2 = 0.02 to 0.200,
P 2 O 5 / Al 2 O 3 = 0.059 to 0.448,
The manufacturing method of the crystallized glass of the structure 5 or 6 characterized by the above-mentioned.
(Configuration 8)
The crystallized glass according to any one of Structures 1 to 7, wherein an average linear expansion coefficient in a temperature range of 0 ° C. to 50 ° C. is 0.0 ± 0.2 × 10 −7 · ° C. −1. Manufacturing method.
(Configuration 9)
The manufacturing method of the crystallized glass in any one of the structures 1-8 whose absolute value of the maximum value-minimum value of (DELTA) L / L in the temperature range of 0 degreeC-50 degreeC is 10 * 10 < -7 > or less.
(Configuration 10)
The value of the dCTE / dT-temperature curve at 20 ° C. to 30 ° C. is in the range of −1.0 ppb · ° C. −2 to +1.0 ppb · ° C. −2 . A method for producing crystallized glass.
(Configuration 11)
Any one of configurations 1 to 10 characterized in that the average linear expansion coefficient in the temperature range of 0 ° C. to 50 ° C. of the crystallized glass before performing the step is reduced by the step of lowering the temperature from 200 ° C. to 150 ° C. A method for producing the crystallized glass according to claim 1.
本発明によれば結晶化ガラスの熱膨張特性を精密に制御することが可能であり、例えば２０ｐｐｂ・℃−１レベルの平均線膨張係数を調整する結晶化ガラスの製造方法を提供することができる。
より具体的には本発明により、０℃から５０℃において平均線膨張係数が０．０±０．２×１０−７・℃−１、より好ましい態様においては、０．０±０．１×１０−７・℃−１、
ΔＬ／Ｌの最大値−最小値の絶対値が０℃から５０℃において１０×１０−７以下、より好ましい態様においては、８×１０−７以下、最も好ましい態様においては、２×１０−７以下、
かつ２０℃〜３０℃におけるｄＣＴＥ／ｄＴ−温度曲線の値が−１．０ｐｐｂ・℃−２から＋１．０ｐｐｂ・℃−２の範囲内、より好ましい態様においては、−０．７ｐｐｂ・℃−２から＋０．７ｐｐｂ・℃−２の範囲内であり、最も好ましい態様においては−０．５ｐｐｂ・℃−２から＋０．５ｐｐｂ・℃−２の範囲内である結晶化ガラスを得ることができる。
According to the present invention, it is possible to precisely control the thermal expansion characteristics of crystallized glass. For example, it is possible to provide a method for producing crystallized glass that adjusts the average linear expansion coefficient of 20 ppb · ° C. −1 level. .
More specifically, according to the present invention, the average linear expansion coefficient is 0.0 ± 0.2 × 10 −7 · ° C. −1 from 0 ° C. to 50 ° C., and in a more preferred embodiment, 0.0 ± 0.1 × 10 −7 · ° C. −1 ,
The absolute value of the maximum value-minimum value of ΔL / L is 10 × 10 −7 or less at 0 ° C. to 50 ° C., 8 × 10 −7 or less in a more preferable embodiment, and 2 × 10 −7 in the most preferable embodiment. Less than,
And the value of the dCTE / dT-temperature curve at 20 ° C. to 30 ° C. is in the range of −1.0 ppb · ° C. −2 to +1.0 ppb · ° C. −2 , and in a more preferred embodiment, −0.7 ppb · ° C. −2 To +0.7 ppb · ° C.- 2 , and in a most preferred embodiment, a crystallized glass in the range of −0.5 ppb · ° C. −2 to +0.5 ppb · ° C. −2 can be obtained.
１：実施例１
２：実施例２
３：実施例３
４：実施例４
５：実施例５
６：実施例６
７：実施例７
８：実施例８
９：比較例１
１０：比較例２
1: Example 1
2: Example 2
3: Example 3
4: Example 4
5: Example 5
6: Example 6
7: Example 7
8: Example 8
9: Comparative Example 1
10: Comparative Example 2
本発明にかかる製造方法は大きくガラスを製造する工程、ガラスを熱処理する工程の２工程に分けられる。ガラスを製造する工程は結晶を析出させる前の原ガラスを製造する工程である。ガラスの組成については後述する。ガラスの溶融方法、成型方法は公知の方法に従って製造すれば良い。ガラスを成形後にはアニールを施して室温まで冷却しても良いし、室温まで冷却する前にガラスを熱処理する工程を施してもよい。 The production method according to the present invention is roughly divided into two steps, a step of producing glass and a step of heat-treating the glass. The process for producing glass is a process for producing an original glass before crystals are precipitated. The composition of the glass will be described later. What is necessary is just to manufacture the melting method and shaping | molding method of glass in accordance with a well-known method. After the glass is molded, it may be annealed and cooled to room temperature, or may be subjected to a heat treatment step before it is cooled to room temperature.
ガラスを熱処理する工程はガラス相中に結晶を析出させる為に行われ、少なくとも昇温工程と保温工程と降温工程を有する。昇温工程、保温工程、降温工程、はそれぞれ１つの工程であっても良いし、複数の工程であっても良い。
例えばガラスを熱処理する工程は、昇温工程、保温工程、降温工程の３つの工程であって良いし、第１の昇温工程、第１の保温工程、第２の昇温工程、第２の保温工程、第１の降温工程という５段階であって良い。第１の保温工程は核形成の為の核形成工程であり、第２の保温工程は核成長の為の核成長工程であることが好ましい。また、核形成工程の温度より核成長工程の温度の方が高いことが好ましい。
The step of heat-treating the glass is performed in order to precipitate crystals in the glass phase, and includes at least a temperature raising step, a heat retaining step, and a temperature lowering step. Each of the temperature raising step, the heat retaining step, and the temperature lowering step may be one step or a plurality of steps.
For example, the step of heat-treating the glass may be three steps of a temperature raising step, a temperature keeping step, and a temperature lowering step, or a first temperature raising step, a first heat keeping step, a second temperature raising step, and a second step. There may be five stages of a heat retaining process and a first temperature lowering process. The first heat retention step is preferably a nucleation step for nucleation, and the second heat retention step is preferably a nucleus growth step for nucleus growth. Moreover, it is preferable that the temperature of the nucleus growth process is higher than the temperature of the nucleus formation process.
本発明は前記熱処理における少なくとも一つの保温工程ＮＧは、温度（℃）をｘ軸、時間（ｈ）をｙ軸として表したグラフにおいて、下記ＡからＤの４点の座標を結んだ領域内の温度および時間で熱処理するものである。ＡからＤの４点の座標は、Ａ：（Ｔｇ＋５０，０．１）、Ｂ：（Ｔｇ＋５０，４００）、Ｃ：（Ｔｇ＋８０，４００）、Ｄ：（Ｔｇ＋９５，０．１）であり、但しＴｇは前記結晶化ガラスの原ガラスのガラス転移点（℃）である。
保温工程ＮＧをこの範囲で熱処理することにより、所望の平均線膨張係数を有し、且つΔＬ／Ｌ−温度曲線およびｄＣＴＥ／ｄＴ−温度曲線を平坦にすることが出来る。すなわち、０℃から５０℃において平均線膨張係数が０．０±０．２×１０−７・℃−１、ΔＬ／Ｌの最大値−最小値の絶対値が０℃から５０℃において１０×１０−７以下、かつ２０℃〜３０℃におけるｄＣＴＥ／ｄＴ−温度曲線の値が−１．０ｐｐｂ・℃−２から＋１．０ｐｐｂ／・℃−２の範囲内である結晶化ガラスを得ることができる。さらに、析出結晶の粒径分布も均一になりやすく、得られた結晶化ガラスの表面研磨特性が向上しやすくなる。
より平均線膨張係数を零に近づけ、且つΔＬ／Ｌ−温度曲線およびｄＣＴＥ／ｄＴ−温度曲線を平坦にする為にはＡからＤの４点の座標はＡ点が（Ｔｇ＋５５，１０）であることがより好ましく、（Ｔｇ＋６０，３０）であることが最も好ましく、Ｂ点が（Ｔｇ＋５５，２５０）であることがより好ましく、（Ｔｇ＋６０，１５０）であることが最も好ましく、Ｃ点が（Ｔｇ＋７５，２５０）であることがより好ましく、（Ｔｇ＋７５，１５０）であることが最も好ましく、Ｄ点が（Ｔｇ＋８５，１０）であることがより好ましく、（Ｔｇ＋８０，３０）であることが最も好ましい。
さらに所望の平均線膨張係数を有し、且つΔＬ／Ｌ−温度曲線およびｄＣＴＥ／ｄＴ−温度曲線が平坦である結晶化ガラスを得やすくする為に前記保温工程ＮＧは核成長工程であることが好ましい。
In the present invention, at least one heat retaining step NG in the heat treatment is performed in a region where the coordinates of the following four points A to D are connected in a graph in which the temperature (° C.) is represented by the x axis and the time (h) is represented by the y axis. Heat treatment is performed at the temperature and time. The coordinates of the four points A to D are A: (Tg + 50, 0.1), B: (Tg + 50, 400), C: (Tg + 80, 400), D: (Tg + 95, 0.1), where Tg Is the glass transition point (° C.) of the original glass of the crystallized glass.
By heat-treating the heat retaining step NG within this range, it is possible to flatten the ΔL / L-temperature curve and the dCTE / dT-temperature curve while having a desired average linear expansion coefficient. That is, the average linear expansion coefficient is 0.0 ± 0.2 × 10 −7 · ° C. −1 from 0 ° C. to 50 ° C., and the absolute value of the maximum value−minimum value of ΔL / L is 10 × at 0 ° C. to 50 ° C. It is possible to obtain a crystallized glass having a dCTE / dT-temperature curve value of 10 −7 or less and a temperature range of 20 ° C. to 30 ° C. within a range of −1.0 ppb · ° C. −2 to +1.0 ppb / · ° C. −2. it can. Furthermore, the particle size distribution of the precipitated crystals is likely to be uniform, and the surface polishing characteristics of the obtained crystallized glass are easily improved.
In order to make the average linear expansion coefficient closer to zero and to make the ΔL / L-temperature curve and dCTE / dT-temperature curve flat, the coordinates of the four points A to D are (Tg + 55, 10). More preferably, (Tg + 60,30) is most preferable, point B is more preferably (Tg + 55,250), most preferably (Tg + 60,150), and point C is (Tg + 75, 250) is more preferable, (Tg + 75, 150) is most preferable, D point is more preferably (Tg + 85, 10), and (Tg + 80, 30) is most preferable.
Further, in order to make it easy to obtain a crystallized glass having a desired average linear expansion coefficient and having a flat ΔL / L-temperature curve and dCTE / dT-temperature curve, the heat retaining step NG is a nuclear growth step. Is preferred.
保温工程が核形成工程および核成長工程２つの工程である場合、前記核形成工程の保温温度がガラス転移点Ｔｇに対して＋１０℃〜＋５０℃、前記核形成工程の保温時間が２０時間〜１００時間であると結晶核がガラスマトリクス内に均一に生成しやすい為に好ましい。この効果を得やすくする為には前記核形成工程の保温温度の下限がＴｇ＋１５℃であることがより好ましく、Ｔｇ＋２０℃であることが最も好ましく、保温温度の上限がＴｇ＋４５℃であることがより好ましく、Ｔｇ＋４０℃であることが最も好ましい。同様に前記核形成工程の保温時間の下限が２５時間であることがより好ましく、３０時間であることが最も好ましく、保温時間の上限が８０時間であることがより好ましく、７０時間であることが最も好ましい。 In the case where the heat retention step is a nucleation step and a nucleus growth step, the heat retention temperature of the nucleation step is + 10 ° C. to + 50 ° C. with respect to the glass transition point Tg, and the heat retention time of the nucleation step is 20 hours to 100 The time is preferable because crystal nuclei are easily generated uniformly in the glass matrix. In order to easily obtain this effect, the lower limit of the heat retention temperature in the nucleation step is more preferably Tg + 15 ° C., most preferably Tg + 20 ° C., and the upper limit of the heat retention temperature is more preferably Tg + 45 ° C. Tg + 40 ° C. is most preferable. Similarly, the lower limit of the heat retention time in the nucleation step is more preferably 25 hours, most preferably 30 hours, the upper limit of the heat retention time is more preferably 80 hours, and 70 hours. Most preferred.
前記降温工程において、好ましくは最後の降温工程において降温速度を調整することにより、所望の温度範囲における平均線膨張係数をより厳密に調整することが可能となる。 より具体的には前記降温工程は、核形成工程終了後にβ−石英及び／又はβ−石英固溶体を含む結晶化ガラスを２００℃から１５０℃へ降温する工程を少なくとも含み、この時の降温の速度を０．０００５℃／ｍｉｎ〜０．１℃／ｍｉｎの範囲とすることにより、０℃から５０℃の温度範囲におけるＣＴＥ−温度曲線の傾きを維持したまま、平均線膨張係数を微小低下させ、その結果平均線膨張係数を精密に制御することが可能となる。この効果をより得やすくする為には前記降温の速度の下限を０．００１℃／ｍｉｎとすることがより好ましく、０．００３℃／ｍｉｎとすることが最も好ましい。同様にこの効果をより得やすくする為には前記降温の速度の上限を０・０７℃／ｍｉｎとすることがより好ましく、０．０５℃／ｍｉｎとすることが最も好ましい。
前記降温速度での熱処理は、核形成工程終了後の最初の降温工程内であることが好ましいが、核形成終了後に一度室温まで降温し、一定時間保管後に再度昇温工程を施した後の降温工程であって良い。
In the temperature lowering step, preferably, the average linear expansion coefficient in a desired temperature range can be adjusted more strictly by adjusting the temperature lowering rate in the last temperature lowering step. More specifically, the temperature lowering step includes at least a step of lowering the crystallized glass containing β-quartz and / or β-quartz solid solution from 200 ° C. to 150 ° C. after completion of the nucleation step, and the rate of temperature decrease at this time By making the range of 0.0005 ° C./min to 0.1 ° C./min, the average linear expansion coefficient is slightly reduced while maintaining the slope of the CTE-temperature curve in the temperature range of 0 ° C. to 50 ° C., As a result, the average linear expansion coefficient can be precisely controlled. In order to make it easier to obtain this effect, the lower limit of the cooling rate is more preferably 0.001 ° C./min, and most preferably 0.003 ° C./min. Similarly, in order to make it easier to obtain this effect, the upper limit of the temperature lowering rate is more preferably 0.07 ° C./min, and most preferably 0.05 ° C./min.
The heat treatment at the temperature lowering rate is preferably in the first temperature lowering process after the completion of the nucleation process, but after the nucleation is completed, the temperature is decreased to room temperature once, and after the storage for a certain time, the temperature decrease is performed again. It may be a process.
第１の昇温工程および第２の昇温工程における昇温速度は特に制限されないが、原ガラス内の温度分布を均一にするため０．００３℃／ｍｉｎ〜０．５℃／ｍｉｎの範囲が好ましい。 The rate of temperature increase in the first temperature increasing step and the second temperature increasing step is not particularly limited, but a range of 0.003 ° C./min to 0.5 ° C./min is used to make the temperature distribution in the original glass uniform. preferable.
本発明において熱処理の温度は熱処理炉の温度を意味しており、より具体的には炉の扉のある面を正面とするとき、対向する２面の側壁について、各々側壁の中心であって、側壁より５０ｍｍ以上内側の位置で白金、ロジウム−白金熱電対により測定される温度であることが好ましい。 In the present invention, the temperature of the heat treatment means the temperature of the heat treatment furnace, more specifically, when the surface with the door of the furnace is the front, each of the two opposing side walls is the center of the side wall, The temperature is preferably measured by platinum or rhodium-platinum thermocouple at a position 50 mm or more inside from the side wall.
本発明の結晶化ガラスの原ガラスの好ましい組成について説明する。なお、各組成成分について述べるとき、特に記載が無い場合は、各成分の含有量は酸化物基準の質量％で示す。ここで、「酸化物基準」とは、本発明の結晶化ガラスの構成成分の原料として使用される酸化物、硝酸塩等が溶融時にすべて分解され酸化物へ変化すると仮定して、ガラス中に含有される各成分の組成を表記する方法であり、この生成酸化物の質量の総和を１００質量％として、結晶化ガラス中に含有される各成分の量を表記する。
なお、原ガラスを熱処理して結晶を析出させる過程において、原ガラス構成成分の揮発は殆ど無い為、原ガラスの組成は結晶化ガラスの組成と等しい。
The preferable composition of the original glass of the crystallized glass of the present invention will be described. In addition, when describing each composition component, when there is no description in particular, content of each component is shown by the mass% of an oxide basis. Here, the “oxide standard” means that oxides, nitrates, etc. used as raw materials of the constituent components of the crystallized glass of the present invention are all decomposed and converted into oxides when melted. The amount of each component contained in the crystallized glass is expressed with the total mass of the generated oxides being 100% by mass.
In the process of precipitating crystals by heat-treating the raw glass, the composition of the raw glass is almost the same as that of the crystallized glass because the constituent components of the raw glass are hardly volatilized.
ＳｉＯ２成分は、原ガラスの熱処理により、結晶相として析出するβ−石英及び／又はβ−石英固溶体を生成する成分であり、その量が４７％以上であると、原ガラスの熱膨張係数が小さくなり、所望の熱膨張係数を有する結晶化ガラスが得やすくなる。また、６５％以下であると原ガラスの溶融・成形性が容易であり、均質性が向上する。前記効果をより容易に得るには、成分量の下限は５１％が好ましく、５３％がより好ましい。また、成分量の上限は６０％が好ましく、５８％がより好ましい。 The SiO 2 component is a component that generates β-quartz and / or β-quartz solid solution that precipitates as a crystal phase by heat treatment of the raw glass. If the amount is 47% or more, the thermal expansion coefficient of the raw glass is high. It becomes small and it becomes easy to obtain the crystallized glass which has a desired thermal expansion coefficient. On the other hand, if it is 65% or less, the melting and moldability of the original glass is easy and the homogeneity is improved. In order to obtain the effect more easily, the lower limit of the component amount is preferably 51%, more preferably 53%. Further, the upper limit of the component amount is preferably 60%, more preferably 58%.
Ａｌ２Ｏ３成分は、その量が１７％以上２９％以下であると原ガラスの溶融が容易となり、そのため、得られる結晶化ガラスの均質性が向上し、更に結晶化ガラスの化学的耐久性も良好なものとなる。また、２９％以下であると原ガラスの耐失透性が向上し、耐失透性の低下が原因となって結晶化段階で結晶化ガラスの組織が粗大化することがなくなり、機械的強度が向上する。
前記効果をより容易に得るには、成分量の下限は２０％が好ましく、２２％がより好ましい。また、成分量の上限は２７％が好ましく、２６％がより好ましい。
When the amount of the Al 2 O 3 component is 17% or more and 29% or less, melting of the original glass is facilitated. Therefore, the homogeneity of the obtained crystallized glass is improved, and the chemical durability of the crystallized glass is further improved. Will also be good. Further, if it is 29% or less, the devitrification resistance of the original glass is improved, and the structure of the crystallized glass is not coarsened in the crystallization stage due to the decrease in the devitrification resistance. Will improve.
In order to obtain the effect more easily, the lower limit of the component amount is preferably 20%, more preferably 22%. Further, the upper limit of the component amount is preferably 27%, more preferably 26%.
Ｌｉ２Ｏ成分はβ−石英固溶体の構成要素となる成分であり、結晶化ガラスの低膨張特性向上や高温時のたわみ量を低減させ、更に原ガラスの溶融性、清澄性を著しく向上させる成分である。Ｌｉ２Ｏ成分の量が１％以上であると前記効果が飛躍的に向上し、また、原ガラスの溶融性が向上することにより均質性が向上し、さらに目的とする結晶相の析出が飛躍的に向上する。また８％以下であると低膨張特性が飛躍的に向上し、極低膨張特性を容易に得ることができ、原ガラスの耐失透性がより向上し、耐失透性の低下に起因する結晶化段階後の結晶化ガラス中の析出結晶の粗大化を抑制し、機械的強度が向上する。前記効果をより容易に得るには、成分量の下限は２％がより好ましく、３％が最も好ましい。また、成分量の上限は６％がより好ましく、５％が最も好ましい。 The Li 2 O component is a component that is a constituent element of β-quartz solid solution, which improves the low expansion characteristics of crystallized glass and reduces the amount of deflection at high temperatures, and further significantly improves the meltability and fining of the original glass. It is. When the amount of the Li 2 O component is 1% or more, the above-described effect is drastically improved, the homogeneity is improved by improving the meltability of the original glass, and the precipitation of the target crystal phase is further leap. Improve. Further, if it is 8% or less, the low expansion characteristic is remarkably improved, and the extremely low expansion characteristic can be easily obtained, the devitrification resistance of the original glass is further improved, and the devitrification resistance is lowered. The coarsening of the precipitated crystal in the crystallized glass after the crystallization stage is suppressed, and the mechanical strength is improved. In order to obtain the effect more easily, the lower limit of the component amount is more preferably 2%, and most preferably 3%. Further, the upper limit of the component amount is more preferably 6%, and most preferably 5%.
Ｐ２Ｏ５成分は、原ガラスの溶融・清澄性を向上させる効果と、熱処理結晶化後の熱膨張を所望の値に安定化させる効果を有する。本願の結晶化ガラスにおいてはＰ２Ｏ５成分の量が１％以上であると前記の効果が飛躍的に向上し、また１３％以下であると、原ガラスの耐失透性が良く、耐失透性の低下が原因となって結晶化段階で結晶化ガラスの組織が粗大化することがなくなり、機械的強度が向上する。前記効果をより容易に得るには、成分量の下限は４％がより好ましく、６％が最も好ましい。また、成分量の上限は１０％がより好ましく、９％が最も好ましい。 The P 2 O 5 component has the effect of improving the melting and clarifying properties of the original glass and the effect of stabilizing the thermal expansion after heat treatment crystallization to a desired value. In the crystallized glass of the present application, when the amount of the P 2 O 5 component is 1% or more, the above effect is remarkably improved, and when it is 13% or less, the devitrification resistance of the original glass is good, The structure of crystallized glass is not coarsened in the crystallization stage due to the decrease in devitrification, and the mechanical strength is improved. In order to obtain the effect more easily, the lower limit of the component amount is more preferably 4%, and most preferably 6%. Further, the upper limit of the component amount is more preferably 10%, and most preferably 9%.
本発明の結晶化ガラスはＳｉＯ２成分、Ａｌ２Ｏ３成分、Ｐ２Ｏ５成分の合計量（ＳｉＯ２＋Ａｌ２Ｏ３＋Ｐ２Ｏ５）を６５．０〜９３．０％とすることにより、低膨張特性を著しく向上させ、極低膨張特性を得ることができる。より容易に前記効果を得るには、ＳｉＯ２＋Ａｌ２Ｏ３＋Ｐ２Ｏ５の含有量の下限は７５％がより好ましく、８０％が最も好ましい。また、ＳｉＯ２＋Ａｌ２Ｏ３＋Ｐ２Ｏ５の含有量の上限は９１％がより好ましく、８９％が最も好ましい。 In the crystallized glass of the present invention, the total amount of SiO 2 component, Al 2 O 3 component and P 2 O 5 component (SiO 2 + Al 2 O 3 + P 2 O 5 ) is 65.0 to 93.0%. It is possible to remarkably improve the low expansion characteristic and obtain an extremely low expansion characteristic. In order to obtain the effect more easily, the lower limit of the content of SiO 2 + Al 2 O 3 + P 2 O 5 is more preferably 75%, and most preferably 80%. Further, the upper limit of the content of SiO 2 + Al 2 O 3 + P 2 O 5 is more preferably 91%, and most preferably 89%.
本発明の結晶化ガラスはＳｉＯ２成分に対するＰ２Ｏ５成分の比の値（Ｐ２Ｏ５／ＳｉＯ２）を０．０２〜０．２０とすることにより、低膨張特性を著しく向上させ、極低膨張特性を得ることができる。より容易に前記効果を得るには、Ｐ２Ｏ５／ＳｉＯ２の下限は０．０８がより好ましく、０．１２が最も好ましい。Ｐ２Ｏ５／ＳｉＯ２の上限は０．１６がより好ましく、０．１４が最も好ましい。 In the crystallized glass of the present invention, the value of the ratio of the P 2 O 5 component to the SiO 2 component (P 2 O 5 / SiO 2 ) is 0.02 to 0.20, thereby significantly improving the low expansion property, Extremely low expansion characteristics can be obtained. In order to obtain the effect more easily, the lower limit of P 2 O 5 / SiO 2 is more preferably 0.08, and most preferably 0.12. The upper limit of P 2 O 5 / SiO 2 is more preferably 0.16, and most preferably 0.14.
本発明の結晶化ガラスはＡｌ２Ｏ３成分に対するＰ２Ｏ５成分の比の値（Ｐ２Ｏ５／Ａｌ２Ｏ３）を０．０５９〜０．４４８とすることにより、低膨張特性を著しく向上させ、極低膨張特性を得ることができる。より容易に前記効果を得るには、Ｐ２Ｏ５／Ａｌ２Ｏ３の下限は０．１５０がより好ましく、０．２５０が最も好ましい。Ｐ２Ｏ５／Ａｌ２Ｏ３の上限は０．４００がより好ましく０．３５０が最も好ましい。 The crystallized glass of the present invention has a low expansion property by setting the value of the ratio of P 2 O 5 component to Al 2 O 3 component (P 2 O 5 / Al 2 O 3 ) to 0.059 to 0.448. It can be remarkably improved and extremely low expansion characteristics can be obtained. In order to obtain the effect more easily, the lower limit of P 2 O 5 / Al 2 O 3 is more preferably 0.150, and most preferably 0.250. The upper limit of P 2 O 5 / Al 2 O 3 is more preferably 0.400, and most preferably 0.350.
ＭｇＯ成分は、β−石英固溶体の構成要素となる成分であり、結晶化ガラスの低膨張特性向上や高温時のたわみ量を低減させ、更に原ガラスの溶融性、清澄性を著しく向上させる成分である。ＭｇＯ成分の量が０．１％以上であると前記効果が飛躍的に向上し、また５％以下であると低膨張特性が飛躍的に向上し、極低膨張特性を得ることができる。前記効果をより容易に得るには、成分量の下限は０．４％がより好ましく、０．６％が最も好ましい。また、成分量の上限は３％がより好ましく、２％が最も好ましい。 The MgO component is a component that is a constituent element of β-quartz solid solution, and is a component that improves the low expansion characteristics of crystallized glass and reduces the amount of deflection at high temperatures, and further significantly improves the meltability and fining of the original glass. is there. When the amount of the MgO component is 0.1% or more, the effect is drastically improved, and when it is 5% or less, the low expansion characteristic is drastically improved and an extremely low expansion characteristic can be obtained. In order to obtain the effect more easily, the lower limit of the component amount is more preferably 0.4%, and most preferably 0.6%. Further, the upper limit of the component amount is more preferably 3%, and most preferably 2%.
ＺｎＯ成分は、β−石英固溶体の構成要素となる成分であり、結晶化ガラスの低膨張特性向上や高温時のたわみ量を低減させ、更に原ガラスの溶融性、清澄性を著しく向上させる成分である。ＺｎＯ成分の量が０．１％以上であると前記効果が飛躍的に向上し、また５．５％以下であると低膨張特性が飛躍的に向上し、極低膨張特性を容易に得ることができ、原ガラスの耐失透性がより向上し、耐失透性の低下に起因する結晶化段階後の結晶化ガラス中の析出結晶の粗大化を抑制し、機械的強度が向上する。前記効果をより容易に得るには、成分量の下限は０．２％がより好ましく、０．３％が最も好ましい、また、成分量の上限は４％がより好ましく、３％が最も好ましい。 The ZnO component is a component that is a constituent element of β-quartz solid solution, and is a component that improves the low expansion characteristics of crystallized glass and reduces the amount of deflection at high temperatures, and further significantly improves the meltability and fining of the original glass. is there. When the amount of ZnO component is 0.1% or more, the above-mentioned effect is drastically improved, and when it is 5.5% or less, the low expansion characteristic is drastically improved, and extremely low expansion characteristic can be easily obtained. Thus, the devitrification resistance of the original glass is further improved, the coarsening of the precipitated crystals in the crystallized glass after the crystallization step due to the decrease in the devitrification resistance is suppressed, and the mechanical strength is improved. In order to obtain the effect more easily, the lower limit of the component amount is more preferably 0.2%, most preferably 0.3%, and the upper limit of the component amount is more preferably 4%, and most preferably 3%.
ＣａＯ、ＢａＯの２成分は、基本的にガラス中に析出した結晶以外のガラスマトリックスとして残存するものであり、極低膨張特性および溶融性改善の効果に対して、結晶相とガラスマトリックス相の微調整成分として任意に添加しうる。 The two components CaO and BaO basically remain as a glass matrix other than the crystals precipitated in the glass, and the crystal phase and the glass matrix phase have a fine effect on the effect of improving the extremely low expansion characteristics and the meltability. It can be optionally added as a regulating component.
ＣａＯ成分は熔融性の改善とともに、原ガラスの耐失透性の向上、耐失透性の低下に起因する結晶化段階後の結晶化ガラス中における析出結晶の粗大化抑制および機械的強度の向上が期待できる。しかしながら、７％を超えると原ガラスの膨張係数が大きくなり、所望の結晶化ガラスが得難くなるため、成分量の上限は５％がより好ましく、３％が最も好ましい。 The CaO component improves meltability, improves devitrification resistance of the original glass, suppresses coarsening of precipitated crystals in the crystallized glass after the crystallization stage due to reduced devitrification resistance, and improves mechanical strength Can be expected. However, if it exceeds 7%, the expansion coefficient of the original glass increases, making it difficult to obtain the desired crystallized glass. Therefore, the upper limit of the component amount is more preferably 5%, and most preferably 3%.
ＢａＯ成分は熔融性の改善とともに、原ガラスの耐失透性の向上、耐失透性の低下に起因する結晶化段階後の結晶化ガラス中における析出結晶の粗大化抑制および機械的強度の向上が期待できる。しかしながら、７％を超えると原ガラスの膨張係数が大きくなり、所望の結晶化ガラスが得難くなるため、成分量の上限は５％がより好ましく、３％が最も好ましい。 The BaO component improves the meltability, improves the devitrification resistance of the original glass, suppresses the coarsening of the precipitated crystals in the crystallized glass after the crystallization stage due to the decrease in the devitrification resistance, and improves the mechanical strength. Can be expected. However, if it exceeds 7%, the expansion coefficient of the original glass increases, making it difficult to obtain the desired crystallized glass. Therefore, the upper limit of the component amount is more preferably 5%, and most preferably 3%.
ＴｉＯ２およびＺｒＯ２成分は、いずれも結晶核形成剤として用いられる。これらの量がそれぞれＴｉＯ２１％、ＺｒＯ２１％以上であると目的とする結晶相の析出が可能となる。またそれぞれ７％以下であると不熔物の発生が無くなって原ガラスの溶融性が良好となり均質性が向上する。前記効果をより容易に得るには、ＴｉＯ２の成分量の下限は１．３％がより好ましく、１．５％が最も好ましい。ＺｒＯ２の成分量の下限は１．３％がより好ましく、１．３％が最も好ましい。また、ＴｉＯ２の成分量の上限は、５％がより好ましく、３％が最も好ましい。ＺｒＯ２の成分量の上限は５％がより好ましく、３％が最も好ましい。 Both TiO 2 and ZrO 2 components are used as crystal nucleating agents. When these amounts are 1% or more of TiO 2 and 1% or more of ZrO 2 , the target crystal phase can be precipitated. Further, when the content is 7% or less, insoluble matters are not generated, the meltability of the original glass is improved, and the homogeneity is improved. In order to obtain the effect more easily, the lower limit of the component amount of TiO 2 is more preferably 1.3%, and most preferably 1.5%. The lower limit of the amount of the ZrO 2 component is more preferably 1.3%, and most preferably 1.3%. Further, the upper limit of the component amount of TiO 2 is more preferably 5%, and most preferably 3%. The upper limit of the component amount of ZrO 2 is more preferably 5%, and most preferably 3%.
Ａｓ２Ｏ３成分やＳｂ２Ｏ３成分は、均質な製品を得るためガラス溶融の際の清澄剤として添加し得る。その効果を得るには各々の成分量が２％以下の範囲が良い。 As 2 O 3 component and Sb 2 O 3 component can be added as a fining agent during glass melting in order to obtain a homogeneous product. In order to obtain the effect, the amount of each component is preferably 2% or less.
上記Ａｓ２Ｏ３成分やＳｂ２Ｏ３成分は、環境や人体への影響を考慮してその使用が控えられる傾向にあり、Ａｓ２Ｏ３成分やＳｂ２Ｏ３成分に代えて、Ｃｅ２Ｏ３成分やＳｎ２Ｏ３成分を用いることも可能である。この場合、清澄剤としての効果を得る為には各々の成分量が２％以下の範囲が良い。 The As 2 O 3 component and the Sb 2 O 3 component tend to be refrained from use in consideration of the influence on the environment and the human body. Instead of the As 2 O 3 component and the Sb 2 O 3 component, Ce 2 It is also possible to use O 3 component or Sn 2 O 3 component. In this case, in order to obtain the effect as a clarifier, the amount of each component is preferably in the range of 2% or less.
尚、上記成分の他に特性の微調整等を目的として、本発明の結晶化ガラスの特性を損なわない範囲で、ＳｒＯ、Ｂ２Ｏ３、Ｆ２、Ｌａ２Ｏ３、Ｂｉ２Ｏ３、ＷＯ３、Ｙ２Ｏ３、Ｇｄ２Ｏ３、ＳｎＯ２成分を１種または２種以上の合計量で２％以下、他にもＣｏＯ、ＮｉＯ、ＭｎＯ２、Ｆｅ２Ｏ３、Ｃｒ２Ｏ３等の着色成分を１種または２種以上の合計量で２％以下まで、それぞれ添加し得る。しかし、本発明の結晶化ガラスを高い光線透過率が求められる用途に用いる場合には、前記着色成分は含まない事が好ましい。 In addition to the above components, SrO, B 2 O 3 , F 2 , La 2 O 3 , Bi 2 O 3 , S2O 3 , F 2 , La 2 O 3 , Bi 2 O 3 , as long as the characteristics of the crystallized glass of the present invention are not impaired. WO 3 , Y 2 O 3 , Gd 2 O 3 , SnO 2 component may be one or two or more in total amount of 2% or less, besides CoO, NiO, MnO 2 , Fe 2 O 3 , Cr 2 O 3 Such coloring components as 1 type or 2 types or more can be added up to 2% or less, respectively. However, when the crystallized glass of the present invention is used for applications requiring high light transmittance, it is preferable that the colored component is not included.
本発明の結晶化ガラスにおいては、負の平均線膨張係数を有する主結晶相を析出させ、正の平均線膨張係数を有するガラスマトリックス相と相まって、全体として極低膨張特性を実現している。このためには正の平均線膨張係数を有する結晶相、すなわち、二珪酸リチウム、珪酸リチウム、α−石英、α−クリストバライト、α−トリジマイト、Ｚｎ−ペタライトをはじめとするペタライト、ウォラストナイト、フォルステライト、ディオプサイト、ネフェリン、クリノエンスタタイト、アノーサイト、セルシアン、ゲーレナイト、フェルスパー、ウィレマイト、ムライト、コランダム、ランキナイト、ラルナイトおよびこれらの固溶体等を含まないことが好ましく、これらに加えて、良好な機械的強度を維持するためには、Ｈｆ−タングステン酸塩やＺｒ−タングステン酸塩をはじめとするタングステン酸塩、チタン酸マグネシウムやチタン酸バリウムやチタン酸マンガンをはじめとするチタン酸塩、ムライト、３ケイ酸２バリウム、Ａｌ２Ｏ３・５ＳｉＯ２およびこれらの固溶体等も含まないことが好ましい。 In the crystallized glass of the present invention, a main crystal phase having a negative average linear expansion coefficient is precipitated, and combined with a glass matrix phase having a positive average linear expansion coefficient, an extremely low expansion characteristic is realized as a whole. For this purpose, a crystalline phase having a positive average linear expansion coefficient, namely, lithium disilicate, lithium silicate, α-quartz, α-cristobalite, α-tridymite, Zn-petalite and other petalites, wollastonite, forma It is preferable not to contain stellite, diopsite, nepheline, clinoenstatite, anorthite, celsian, gelenite, felsper, willemite, mullite, corundum, lanquinite, larnite and solid solutions thereof, in addition to these, good In order to maintain high mechanical strength, tungstates such as Hf-tungstate and Zr-tungstate, titanates such as magnesium titanate, barium titanate and manganese titanate, mullite 3 barium silicates, is preferably free l 2 O 3 · 5SiO 2 and also those solid solutions.
以下、本発明の実施例を説明する。 Examples of the present invention will be described below.
酸化物基準の質量％で表１及び表２に記載の組成となるように原料として酸化物、炭酸塩あるいは硝酸塩等の原料を混合し、これを通常の溶解装置を用いて約１４５０〜１５５０℃ の温度で溶解し攪拌均質化した後、成形、冷却しガラス成形体（原ガラス）を得た。 A raw material such as oxide, carbonate or nitrate is mixed as a raw material so as to have the composition described in Table 1 and Table 2 by mass% based on the oxide, and this is mixed at about 1450 to 1550 ° C. using a normal melting apparatus. Then, the mixture was stirred and homogenized, and then molded and cooled to obtain a glass molded body (original glass).
得られたガラス成形体を、表１及び表２に記載の条件で熱処理し、結晶化ガラスを作製した。具体的には室温から第１の昇温速度（０．３℃／ｍｉｎ）で核形成保温温度まで昇温後に保温、第２の昇温速度（０．００４℃／ｍｉｎ）で核成長保温温度まで昇温後に保温、その後第１の降温速度で室温まで降温した。第１の降温工程では核成長保温温度から２００℃までは０．１℃／ｍｉｎで降温し、２００℃から１５０℃までは表１に記載の降温速度で降温し、１５０℃から室温までは熱処理炉の電源を切り、熱処理炉の扉を閉めたまま、約２００時間放冷した。得られた結晶化ガラスはβ−石英およびβ−石英固溶体が析出しており、この時の平均結晶粒径、結晶粒径分布、結晶化度、原ガラスのＴｇ、０℃から５０℃における平均線膨張係数α、０℃から５０℃の温度範囲内でのΔＬ／Ｌ−温度曲線の最大値−最小値を表１及び表２に示す。
なお、平均結晶粒径、結晶粒径分布はＴＥＭにより得られた画像から無作為に選んだ３０個の結晶の最大幅を測定して算出した。平均結晶粒径はこれらの個数基準の平均値であり、結晶粒径分布は標準偏差である。また、結晶化度は以下の通り算出した。予め原ガラス粉末と目的とする析出結晶粉末（例えばβ−ユークリプタイト）を任意比で混合し、さらに標準試料となるＳｉＯ２を加えた混合粉末数種のＸＲＤ測定によって、析出結晶粉末量（ｗｔ％）をｘ軸に、結晶積分強度／標準試料積分強度をｙ軸にプロットした検量線を作成した。次に本発明の結晶化ガラスおよび標準試料の混合粉末のＸＲＤ測定を行い、求められた結晶積分強度／標準試料積分強度から検量線を用いて結晶化度を算出した。
The obtained glass molded body was heat-treated under the conditions described in Tables 1 and 2 to produce crystallized glass. Specifically, the temperature is increased from room temperature to the nucleation temperature at the first temperature increase rate (0.3 ° C./min), and then the temperature is maintained at the second temperature increase rate (0.004 ° C./min). After the temperature was raised, the temperature was kept, and then the temperature was lowered to room temperature at the first rate of temperature drop. In the first temperature lowering step, the temperature is decreased at a rate of 0.1 ° C./min from the nuclear growth heat retention temperature to 200 ° C., the temperature is decreased from 200 ° C. to 150 ° C. at the temperature decreasing rate shown in Table 1, and the heat treatment is performed from 150 ° C. to room temperature. The furnace was turned off and allowed to cool for about 200 hours with the heat treatment furnace door closed. In the obtained crystallized glass, β-quartz and β-quartz solid solution are precipitated. At this time, the average crystal grain size, crystal grain size distribution, crystallinity, Tg of the original glass, average at 0 ° C. to 50 ° C. Tables 1 and 2 show the linear expansion coefficient α and the maximum value-minimum value of the ΔL / L-temperature curve in the temperature range of 0 ° C to 50 ° C.
The average crystal grain size and crystal grain size distribution were calculated by measuring the maximum width of 30 crystals randomly selected from images obtained by TEM. The average crystal grain size is an average value based on these numbers, and the crystal grain size distribution is a standard deviation. The crystallinity was calculated as follows. The amount of precipitated crystal powder (by the XRD measurement of several kinds of mixed powders obtained by previously mixing the original glass powder and the target precipitated crystal powder (for example, β-eucryptite) at an arbitrary ratio and further adding SiO 2 as a standard sample ( wt%) was plotted on the x-axis, and a calibration curve was plotted with the crystal integrated intensity / standard sample integrated intensity plotted on the y-axis. Next, XRD measurement was performed on the mixed powder of the crystallized glass of the present invention and the standard sample, and the degree of crystallinity was calculated using a calibration curve from the obtained crystal integral intensity / standard sample integral intensity.
平均線膨張係数はフィゾー干渉式精密膨張率測定装置を用いて測定した。測定試料の形状は直径６ｍｍ、長さ約８０ｍｍの円柱状である。測定方法として、この試料の両端に光学平面板を接触させ、Ｈｅ−Ｎｅレーザーによる干渉縞が観察できるようにし、温度コントロール可能な炉に入れる。次に測定試料の温度を変化させ、干渉縞の変化を観察することによって、温度による測定試料長さの変化量を測定する。本発明においては、０℃から５０℃の温度範囲において０．５℃・ｍｉｎ−１で昇温あるいは降温させ、５秒毎に測定試料長さの変化量をプロットし、さらに５次の近似曲線を描いたうえで、０℃から５０℃における平均線膨張係数および０℃から５０℃の温度範囲内でのΔＬ／Ｌの最大値−最小値を算出した。なお、平均線膨張係数およびΔＬ／Ｌ−温度曲線の最大値−最小値はいずれも昇温時と降温時の平均値である。 The average linear expansion coefficient was measured using a Fizeau interferometric precise expansion coefficient measuring device. The shape of the measurement sample is a cylindrical shape having a diameter of 6 mm and a length of about 80 mm. As a measuring method, an optical flat plate is brought into contact with both ends of the sample so that interference fringes by a He—Ne laser can be observed, and the sample is placed in a temperature-controllable furnace. Next, by changing the temperature of the measurement sample and observing the change in interference fringes, the amount of change in the measurement sample length due to temperature is measured. In the present invention, the temperature is raised or lowered at 0.5 ° C./min −1 in the temperature range from 0 ° C. to 50 ° C., the amount of change in the measured sample length is plotted every 5 seconds, and a fifth order approximate curve Then, the average linear expansion coefficient from 0 ° C. to 50 ° C. and the maximum value-minimum value of ΔL / L within the temperature range of 0 ° C. to 50 ° C. were calculated. Note that the average linear expansion coefficient and the maximum value-minimum value of the ΔL / L-temperature curve are both average values during temperature rise and temperature drop.
また、図１および図２は本発明の実施例のΔＬ／Ｌ−温度グラフであり、図３および図４は本発明の実施例のｄＣＴＥ／ｄＴ−温度グラフである。
これによればいずれの実施例も所望の平均線膨張係数α、ΔＬ／Ｌ−温度曲線およびｄＣＴＥ／ｄＴ−温度曲線が得られており、特に実施例１及び３においては極めて平均線膨張係数が零に近いことが分かる。また実施例１及び３においては２００℃から１５０℃までの降温速度を調整することにより、平均線膨張係数の微調整が可能であることも示している。
また、いずれの実施例も２０℃〜３０℃におけるｄＣＴＥ／ｄＴ−温度曲線の値が０±１．０ｐｐｂ・℃−２の範囲内であり、特に実施例１から４は２０℃〜３０℃におけるｄＣＴＥ／ｄＴ−温度曲線の値が０±０．２ｐｐｂ・℃−２の範囲内となっており、室温領域におけるＣＴＥの温度依存性が非常に小さいことが分かる。
なお、実施例５から８は、本発明の参考例である。
1 and FIG. 2 are ΔL / L-temperature graphs of the examples of the present invention, and FIGS. 3 and 4 are dCTE / dT-temperature graphs of the examples of the present invention.
According to this, the desired average linear expansion coefficient α, ΔL / L-temperature curve and dCTE / dT-temperature curve are obtained in any of the examples, and in Examples 1 and 3, the average linear expansion coefficient is extremely high. You can see that it is close to zero. In Examples 1 and 3, it is also shown that the average linear expansion coefficient can be finely adjusted by adjusting the temperature decrease rate from 200 ° C. to 150 ° C.
Also, in all examples, the value of the dCTE / dT-temperature curve at 20 ° C. to 30 ° C. is in the range of 0 ± 1.0 ppb · ° C. −2 , especially Examples 1 to 4 are at 20 ° C. to 30 ° C. The value of the dCTE / dT-temperature curve is in the range of 0 ± 0.2 ppb · ° C.- 2 , indicating that the temperature dependence of CTE in the room temperature region is very small.
Examples 5 to 8 are reference examples of the present invention.
Claims (10)
前記熱処理は核形成工程と核成長工程を有し、
前記保温工程ＮＧは核成長工程に含まれ、
核成長工程に含まれる保温工程ＮＧは、（Ｔｇ＋６０）℃以上かつ７４０℃以下（但しＴｇは前記結晶化ガラスの原ガラスのガラス転移点（℃）である）、５０時間以上かつ７０時間以内で行われ、
前記Ｌｉ ２ Ｏ、Ａｌ ２ Ｏ ３ 及びＳｉＯ ２ の各成分を含有するガラスの組成は酸化物基準の質量％で、
ＳｉＯ ２ ４７〜６５％、
Ｐ ２ Ｏ ５ １〜１３％、
Ａｌ２Ｏ３ １７〜２９％、
Ｌｉ ２ Ｏ １〜８％、
ＭｇＯ ０．５〜５％、
ＺｎＯ ０．５〜５．５％、
ＴｉＯ ２ １〜７％、
ＺｒＯ ２ １〜７％の範囲の各成分を含有する、
ことを特徴とする結晶化ガラスの製造方法。 This is a method for producing crystallized glass by heat-treating glass containing each component of Li 2 O, Al 2 O 3 and SiO 2 to obtain crystallized glass containing β-quartz and / or β-quartz solid solution in the crystal phase. And
The heat treatment includes a nucleation step and a nucleation growth step,
The thermal insulation process NG is included in the nuclear growth process,
The temperature maintaining step NG included in the nucleus growth step is (Tg + 60) ° C. or higher and 740 ° C. or lower (where Tg is the glass transition point (° C.) of the original glass of the crystallized glass), 50 hours or longer and 70 hours or shorter. done in,
The composition of the glass containing each component of Li 2 O, Al 2 O 3 and SiO 2 is mass% based on oxide,
SiO 2 47~65%,
P 2 O 5 1~13%,
Al2O3 17-29%,
Li 2 O 1-8%,
MgO 0.5-5%,
ZnO 0.5-5.5%,
TiO 2 1-7%,
Containing each component in the range of ZrO 2 1-7%,
A method for producing crystallized glass, characterized in that:
前記工程における降温の速度を０．０００５℃／ｍｉｎ〜０．１℃／ｍｉｎの範囲とすることを特徴とする請求項１から３のいずれかに記載の結晶化ガラスの製造方法。 at least a step of cooling the crystallized glass containing β-quartz and / or β-quartz solid solution from 200 ° C. to 150 ° C.,
The method for producing crystallized glass according to any one of claims 1 to 3, wherein a rate of temperature drop in the step is set in a range of 0.0005 ° C / min to 0.1 ° C / min.
Ｎａ２Ｏ ０〜４％、及び／又は
Ｋ２Ｏ ０〜４％、及び／又は
ＣａＯ ０〜７％、及び／又は
ＢａＯ ０〜７％、及び／又は
ＳｒＯ ０〜４％、及び／又は
Ａｓ２Ｏ３ ０〜２％、及び／又は
Ｓｂ２Ｏ３ ０〜２％、
の範囲の各成分を含有することを特徴とする請求項１から４のいずれかに記載の結晶化ガラスの製造方法。 The composition of the glass containing each component of Li 2 O, Al 2 O 3 and SiO 2 is mass% based on oxide,
Na 2 O 0-4% and / or K 2 O 0-4% and / or CaO 0-7% and / or BaO 0-7% and / or SrO 0-4% and / or As 2 O 3 0-2% and / or Sb 2 O 3 0-2%,
5. The method for producing crystallized glass according to claim 1, wherein each component in the range of 1 to 4 is contained.
ＳｉＯ２＋Ａｌ２Ｏ３＋Ｐ２Ｏ５＝６５．０〜９３．０％であり、
Ｐ２Ｏ５とＳｉＯ２の質量百分率の比、
Ｐ２Ｏ５とＡｌ２Ｏ３の質量百分率の比がそれぞれ、
Ｐ２Ｏ５／ＳｉＯ２＝０．０２〜０．２００、
Ｐ２Ｏ５／Ａｌ２Ｏ３＝０．０５９〜０．４４８、
であることを特徴とする請求項１から５に記載の結晶化ガラスの製造方法。 The composition of the glass containing each component of the Li 2 O, Al 2 O 3 and SiO 2 is a mass percentage,
SiO 2 + Al 2 O 3 + P 2 O 5 = 65.0-93.0%,
Ratio of mass percentage of P 2 O 5 and SiO 2 ,
The ratio of mass percentages of P 2 O 5 and Al 2 O 3 is respectively
P 2 O 5 / SiO 2 = 0.02 to 0.200,
P 2 O 5 / Al 2 O 3 = 0.059 to 0.448,
The method for producing crystallized glass according to claim 1, wherein:
項１から９のいずれかに記載の結晶化ガラスの製造方法。 The step of temperature lowering process from the 200 ° C. to 0.99 ° C., to reduce the average linear expansion coefficient in a temperature range of 0 ° C. to 50 ° C. before the crystallization glass for performing the process from請項1, wherein 9 The manufacturing method of the crystallized glass in any one.
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