JPH02208238A - Glass ceramics and production thereof - Google Patents
Glass ceramics and production thereofInfo
- Publication number
- JPH02208238A JPH02208238A JP2792389A JP2792389A JPH02208238A JP H02208238 A JPH02208238 A JP H02208238A JP 2792389 A JP2792389 A JP 2792389A JP 2792389 A JP2792389 A JP 2792389A JP H02208238 A JPH02208238 A JP H02208238A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- temperature
- heat treatment
- mica
- ceramics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002241 glass-ceramic Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000011521 glass Substances 0.000 claims abstract description 47
- 239000013078 crystal Substances 0.000 claims abstract description 39
- 239000010445 mica Substances 0.000 claims abstract description 35
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 35
- 230000009477 glass transition Effects 0.000 claims abstract description 31
- 229910052634 enstatite Inorganic materials 0.000 claims abstract description 12
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 22
- 229910052788 barium Inorganic materials 0.000 claims description 15
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 15
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 3
- 229910018557 Si O Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052681 coesite Inorganic materials 0.000 abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 9
- 239000000377 silicon dioxide Substances 0.000 abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052593 corundum Inorganic materials 0.000 abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 6
- 239000000919 ceramic Substances 0.000 abstract description 5
- 230000001376 precipitating effect Effects 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 4
- 238000005520 cutting process Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 18
- 238000005452 bending Methods 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000006103 coloring component Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 4
- 239000006060 molten glass Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 210000000214 mouth Anatomy 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- -1 Ba2+ ions Chemical class 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 210000000332 tooth crown Anatomy 0.000 description 1
Classifications
-
- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、機械加工性、機械的強度及び絶縁性に優れた
ガラスセラミックスに関する。また本発明は上記の機械
加工性、機械的強度及び絶縁性とともに透光性にも優れ
、歯冠材料に好ましく用いられるガラスセラミックスの
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to glass ceramics having excellent machinability, mechanical strength and insulation properties. The present invention also relates to a method for producing glass ceramics, which have excellent machinability, mechanical strength, insulation properties, and translucency, and are preferably used as dental crown materials.
［従来の技術］
雲母結晶は、四面体と八面体とから成るダブレットが層
状に重なっており、ダブレットとタブレットの間に眉間
イオンと呼ばれるアルカリ金属あるいはアルカリ土類金
属イオンが四面体相と弱い結合をしているため、雲母は
この眉間域で剥がれやすい性質を持っている。このため
切削加工できる材料としてよく知られている。また、電
気的絶縁性が高いことが知られ、絶縁材料として用いら
れている。特にカリウムイオンを含むカリウム雲母は、
結晶の安定性が高いことで良く使用されている。[Prior art] Mica crystals are made up of doublets consisting of tetrahedrons and octahedrons, and between the doublets, alkali metal or alkaline earth metal ions called glabellar ions form weak bonds with the tetrahedral phase. Because of this, mica tends to peel off in this area between the eyebrows. For this reason, it is well known as a material that can be machined. It is also known to have high electrical insulation properties and is used as an insulating material. In particular, potassium mica containing potassium ions,
It is often used because of its high crystal stability.
天然の雲母結晶は水酸基を含んでいるが、一般的に、人
工的に作製する雲母結晶は弗素を含んでいるものしか得
られない。そこで、雲母を含有したセラミックスの製法
としては、（１）ホットプレス法、（２）ガラスボンド
法、（３）微粉体埋め焼き法、（４）結晶化法等が知ら
れている。Natural mica crystals contain hydroxyl groups, but generally, artificially produced mica crystals can only be obtained containing fluorine. Therefore, known methods for manufacturing mica-containing ceramics include (1) hot pressing method, (2) glass bonding method, (3) fine powder embedding method, and (4) crystallization method.
（１）のホットプレス法は、雲母粒子を高温で加圧して
成形する方法であり、（２）のガラスボンド法は、雲母
粒子を低融点ガラス等の結合剤を用いて結合させる方法
であり、（３）の微粉体埋め焼き法は、雲母の微粉末に
適当な焼結助剤を添加し、弗素含有の耐火粉末中で埋め
焼きする方法である。（４）の結晶化法は、雲母の組成
のガラスから熱処理によって雲母の微結晶を析出させる
方法であり、特公昭５４−：３４７７５号公報にＳｉＯ
２−Ｂ２０３Ｓ１０２−Ｂ２０３− Ｒ２０Ｆ （Ｒ
：Ｎａ＋、 Ｋ＋、 Ｒｂ＋、 Ｃｓ＋、 Ｌｉ” ）
系の組成物を溶融して得られたガラスを熱処理して金雲
母結晶を析出させる方法が開示されている。The hot press method (1) is a method in which mica particles are pressed and molded at high temperatures, and the glass bond method (2) is a method in which mica particles are bonded using a binder such as low-melting glass. The fine powder embedding method (3) is a method in which a suitable sintering aid is added to fine mica powder and the mixture is embedded in a fluorine-containing refractory powder. The crystallization method (4) is a method in which microcrystals of mica are precipitated from glass having a composition of mica through heat treatment, and is described in Japanese Patent Publication No. 54-34775.
2-B203S102-B203- R20F (R
:Na+, K+, Rb+, Cs+, Li")
A method for precipitating phlogopite crystals by heat-treating a glass obtained by melting a composition of the above-mentioned system is disclosed.
又、（４）の結晶化法により作製した雲母については、
特開昭４８−４５０９号公報に５１０２ＭｇＯ−Ａｌ２
Ｏ３−３ｒ○−（ＢａＯ）−Ｆ系ガラスセラミックスが
、特開昭５８−１９９７Ｂ ａ２＋、 Ｔ ｉ ”）系
ガラスセラミックスが記載されている。Regarding mica produced by the crystallization method (4),
5102MgO-Al2 in JP-A-48-4509
O3-3r○-(BaO)-F glass ceramics are described in JP-A-58-1997B a2+, Ti'') glass ceramics.
［発明が解決しようとする課題］
しかしながら、（１）のホットプレス法により得られた
雲母含有セラミックスは絶縁性に優れているが、製造工
程において６００〜８００℃の加熱温度域で加圧を必要
とするため小型形状品には適するが、大型形状品や厚物
品の作製は困難であるという欠点がある。[Problem to be solved by the invention] However, although the mica-containing ceramic obtained by the hot pressing method (1) has excellent insulation properties, it requires pressurization in the heating temperature range of 600 to 800°C during the manufacturing process. Therefore, it is suitable for small-sized products, but it has the disadvantage that it is difficult to produce large-sized products or thick products.
（２）のガラスボンド法により得られた雲母含有セラミ
ックスは結合剤を使用しているため耐熱温度が７００℃
と低い欠点がある。The mica-containing ceramic obtained by the glass bond method (2) uses a binder, so it has a heat resistance temperature of 700℃.
There is a low drawback.
（３）の微粉体埋め焼き法により得られた雲母含有セラ
ミックスは大型品の製造は可能であるが雲母の微粉末が
得難く、緻密な焼結体を得ることが困難であるという欠
点がある。Mica-containing ceramics obtained by the fine powder embedding method (3) can be manufactured into large products, but have the disadvantage that it is difficult to obtain fine mica powder and it is difficult to obtain dense sintered bodies. .
（４）の結晶化法は前記（１）〜（３）の方法の欠点を
解決した方法であるが、特公昭５４−３４７７５号公報
に記載されているＳｉＯ２−Ｂ２０３−ＭｇＯ−Ａｌ２
Ｏ３−Ｒ２０−Ｆ（Ｒ：Ｎａ 、Ｋ 、Ｒｂ 、
Ｃ８、Ｌｌ ）系ガラスセラミックスは、その曲げ強
度が１４０〜１３００ｋｇ／−程度であり、特開昭５８
−１９９７４２号公報に記載されているＳｉＯ２−Ａｌ
２Ｏ−ＭｇＯＣａＯＭＯ（ＭＯ２） Ｆ （Ｍ：Ｓｒ
２＋、Ｂａ２”、Ｔｉ４＋）系ガラスセラミックスは、
その曲げ強度が、８００〜１３００ ｋｇ／＝程度であ
り、強度的に弱く応力のかかる部分で使用するのにはか
なり制約があった。また特公昭５４３４７７５号公報に
記載されているアルカリ金属雲母ガラスセラミックスは
、高真空中での使用においてはアルカリ金属成分による
電気伝導性が無視できなくなることがあり、絶縁体とし
て用いる場合その解決策が望まれていた。The crystallization method (4) is a method that solves the drawbacks of the methods (1) to (3) above, but it is a method of SiO2-B203-MgO-Al2 described in Japanese Patent Publication No. 54-34775.
O3-R20-F (R: Na, K, Rb,
C8, Ll) type glass ceramics has a bending strength of about 140 to 1300 kg/-, and is
-SiO2-Al described in Publication No. 199742
2O-MgOCaOMO(MO2) F (M:Sr
2+, Ba2”, Ti4+) glass ceramics are
Its bending strength is approximately 800 to 1,300 kg/=, and its use in areas that are weak and subject to stress is severely restricted. Furthermore, when using the alkali metal mica glass ceramics described in Japanese Patent Publication No. 5434775, the electrical conductivity due to the alkali metal component can no longer be ignored when used in a high vacuum. It was wanted.
ところで、従来歯冠材料としてクロム、コバルト、カド
ミウム等の金属を含む金属歯冠材料が使用されてきたが
、この金属歯冠材料は、以下のような欠点があった。Incidentally, metal crown materials containing metals such as chromium, cobalt, and cadmium have been conventionally used as tooth crown materials, but these metal crown materials have the following drawbacks.
（イ） 口腔内の環境は、通常、弱酸性、約３５℃、高
湿度であり、さらに食餌等により、より酸性・高温にな
ることもあり、歯冠材料はかなり苛酷な条件下に置かれ
ことになるが、この様な苛酷の条件下に於て、金属歯冠
の場合、クロム、コバルト、カドミニウム等の有害な金
属イオンの溶出に伴う金属の腐蝕などの問題がある。(b) The environment in the oral cavity is normally weakly acidic, approximately 35°C, and highly humid, and can become even more acidic and hot due to diet, etc., and dental crown materials are placed under quite harsh conditions. However, under such severe conditions, metal crowns have problems such as metal corrosion due to the elution of harmful metal ions such as chromium, cobalt, and cadmium.
（ロ） 金属歯冠は審美性に欠ける。(b) Metal crowns lack aesthetics.
（ハ） 陶材を溶着した金属歯冠は硬すぎる上、対金歯
を摩耗させること、色調が不十分であること、又陶材を
何回も盛り上げなければならないので作製段階が複雑に
なること等の難点がある。(c) Metal crowns with porcelain welded to them are too hard, cause abrasion of the gold tooth, have an insufficient color tone, and require the porcelain to be raised many times, complicating the manufacturing process. There are other difficulties.
そこでガラスセラミックスを歯冠材料として用いること
が試みられているが、前記特開昭４８−４５０９号公報
に記載されているガラスセラミックスはス１へロンチウ
ムイオンを含んでいるので膨潤性があり、歯冠材料とし
て用いるのに好ましくない。さらに、前記公報にはスト
ロンチウムを全部バリウムに置換すると失透を起すと記
載されている。さらに、前記の各特許公報に記載された
ガラスセラミックスは透光性を有していないものであり
、歯冠材料として使用する場合審美性等の点で問題があ
った。Therefore, attempts have been made to use glass ceramics as dental crown materials, but the glass ceramics described in the above-mentioned Japanese Patent Application Laid-Open No. 48-4509 contain rontium ions and are swellable. Not preferred for use as crown material. Furthermore, the above publication states that if all strontium is replaced with barium, devitrification occurs. Furthermore, the glass ceramics described in each of the above-mentioned patent publications do not have translucency, and when used as a dental crown material, there are problems in terms of aesthetics and the like.
従って本発明の第１の目的は、上記従来のガラスセラミ
ックスの欠点を解消し、機械加工性、機械的強度及び絶
縁性に優れたガラスセラミックスを提供することにある
。Therefore, a first object of the present invention is to eliminate the above-mentioned drawbacks of conventional glass-ceramics and to provide a glass-ceramic that has excellent machinability, mechanical strength, and insulation properties.
また本発明の第２の目的は、上記の機械加工性、機械的
強度及び絶縁性とともに透光性にも優れ、歯冠材料に好
ましく用いられるガラスセラミックスの製造方法を提供
することにある。A second object of the present invention is to provide a method for producing glass ceramics, which have excellent machinability, mechanical strength, and insulation properties as well as translucency, and are preferably used as dental crown materials.
［課題を解決するための手段］ 前記の本発明の第１の目的は、ＢａＯ，ＭｇＯ。[Means to solve the problem] The first object of the present invention is to use BaO, MgO.
ＳｉＯ、Ａｌ１ ｏ３及びＦを、重量百分率でＢａＯ３
〜２２％
ＭｇＯ ２０〜３０％
ＳｉＯ２ ３０〜４５％
Ａｌ２Ｏ３５〜３０％
Ｆ １．５〜１４％の範囲で含み
、アルカリ金属成分を実質的に含まないガラスから、Ｂ
ａ−Ｍｇ−Ａ Ｉ −Ｓｉ −０−Ｆよりなるバリウム
雲母結晶と、Ｍｇ−Ｓｉ−Ｏよりなるエンスタタイト結
晶とを析出させてなることを特徴とするガラスセラミッ
クスによって達成された。SiO, Al1 o3 and F in weight percentages BaO3
-22% MgO 20-30% SiO2 30-45% Al2O35-30% F From glass containing substantially no alkali metal component in the range of 1.5-14%, B
This was achieved by a glass ceramic characterized by precipitating barium mica crystals made of a-Mg-A I -Si-0-F and enstatite crystals made of Mg-Si-O.
また本発明の第２の目的は、ＢａＯ，ＭｇＯ。Moreover, the second object of the present invention is BaO, MgO.
Ｓ ｌ ０２ 、 Ａ ｌ ２０３及びＦを、重量百分
率でＢａＯ３〜２２％
ＭｇＯ ２０〜３０％ＳｉＯ２３０
〜４５％
Ａｌ２Ｏ３５〜３０％
Ｆ １，５〜１４％の範囲で含み
、アルカリ金属成分を実質的に含まないガラスを、その
ガラス転移点より５０℃低い温度とガラス転移点より１
００℃高い温度との間で熱処理する第１の熱処理工程と
、第１の熱処理工程後のガラスを、そのガラス転移点よ
り２００〜５００℃高い温度で熱処理する第２の熱処理
工程とを含むことを特徴とする透光性を有するガラスセ
ラミックスの製造方法によって達成された。S l 02 , A l 203 and F in weight percentages BaO3-22% MgO 20-30% SiO230
~45% Al2O35~30% F Glass containing substantially no alkali metal component in the range of 1.5~14% is heated at a temperature 50°C lower than its glass transition point and at a temperature 1.5°C lower than its glass transition point.
a first heat treatment step in which the glass is heat treated at a temperature 00° C. higher; and a second heat treatment step in which the glass after the first heat treatment step is heat treated at a temperature 200 to 500° C. higher than its glass transition point. This was achieved by a method for producing glass ceramics with translucency characterized by the following.
上述の如く本発明は、Ｂａｄ、ＭｇＯ。As mentioned above, the present invention uses Bad, MgO.
Ｓ ｉ ０２ 、 Ａ Ｉ ２０３及びＦを特定範囲で
含有するガラスからバリウム雲母結晶とエンスタタイト
結晶とを析出させてなることを特徴とする機械加工性、
機械的強度及び絶縁性に優れたガラスセラミックス並び
に上記と同一のガラスを２工程で熱処理することを特徴
とする、上記機械的加工性、機械的強度及び絶縁性とと
もに透光性に優れ歯冠材料として好ましく用いられるガ
ラスセラミックスの製造方法からなるものであるので、
以下の記述において、前者のガラスセラミックスの発明
を第１発明、後者のガラスセラミックスの製造方法の発
明を第２発明ということとする。Machinability characterized by precipitating barium mica crystals and enstatite crystals from glass containing S i 02 , A I 203 and F in a specific range,
A dental crown material having excellent mechanical workability, mechanical strength and insulation properties as well as translucency, which is characterized by heat-treating glass-ceramics having excellent mechanical strength and insulation properties and the same glass as above in two steps. It consists of a method for producing glass ceramics that is preferably used as
In the following description, the former invention of glass ceramics will be referred to as the first invention, and the latter invention of the method for manufacturing glass ceramics will be referred to as the second invention.
そこで先ず第１発明のガラスセラミックスについて詳説
する。First, the glass ceramic of the first invention will be explained in detail.
上述の如く第１発明のガラスセラミックスの出発材料で
あるガラスは、Ｂａｄ、ＭｇＯ，ＳｉＯ２ 、Ａｌ２Ｏ
３及びＦを、重量百分率でＢａＯ
３〜２２％ＭｇＯ ２０〜３０％Ｓｉ
Ｏ２ ３０〜４５％
Ａｌ２Ｏ３５〜３０％
Ｆ １，５〜１４％の範囲で含む
ものであるが、各成分の量的限定理由は次の通りである
。重量百分率でＢａＯが３％未満では、バリウム雲母の
析出量が少なく機械的加工性に劣る。また、ＢａＯが２
２％を越えるとガラスの失透が生じやすくなり、気泡が
できやすく所望の形状を得ることが難しいためＢａＯの
含量は３〜２２％に限定される。ＭｇＯが２０％未満で
は、エンスタタイト結晶の析出量が少なくなって高強度
なガラスセラミックスが得られない。As mentioned above, the glasses that are the starting materials for the glass ceramics of the first invention include Bad, MgO, SiO2, Al2O.
3 and F in weight percentage of BaO
3~22%MgO 20~30%Si
O2 30-45% Al2O35-30% F 1.5-14% The reason for quantitative limitation of each component is as follows. If BaO is less than 3% by weight, the amount of barium mica precipitated is small and mechanical workability is poor. Also, BaO is 2
If it exceeds 2%, the glass tends to devitrify, bubbles are easily formed, and it is difficult to obtain a desired shape, so the BaO content is limited to 3 to 22%. If the MgO content is less than 20%, the amount of enstatite crystals precipitated will be small, making it impossible to obtain a high-strength glass ceramic.
また、ＭｇＯが３０％を越えるとバリウム雲母結晶の析
出量が少なくなって好ましくない。従って、ＭｇＯの含
量は２０〜３０％に限定される。ＳｉＯ２が３０％未満
ではガラスが失透しやすく、エンスタタイト結晶の生成
量が低下するので、ガラスセラミックスに高強度を付与
できない。また４５％を越えるとガラス融液の粘性が高
くなり、均質のガラスを得ることが難しい。よって、Ｓ
ｉＣの含量は３０〜４５％に限定される。Ａ Ｉ ２０
３が５％未満では、ガラスが失透しやすく、３０％を越
えるとバリウム雲母の生成量が減少するので好ましくな
い。従って、Ａｌ２Ｏ３の含量は５〜３０％に限定され
る。まなＦが１．５％未満では、バリウム雲母を析出さ
せることが難しく、ガラスセラミックスに切削性を付与
することができず、１−４％を越えるとガラスが失透し
やすくなるため、Ｆの含量は１．５％〜１４％に限定さ
れる。Moreover, if MgO exceeds 30%, the amount of barium mica crystals precipitated will decrease, which is not preferable. Therefore, the MgO content is limited to 20-30%. If SiO2 is less than 30%, the glass tends to devitrify and the amount of enstatite crystals produced decreases, making it impossible to impart high strength to the glass ceramic. Moreover, if it exceeds 45%, the viscosity of the glass melt increases, making it difficult to obtain homogeneous glass. Therefore, S
The content of iC is limited to 30-45%. AI 20
When 3 is less than 5%, the glass tends to devitrify, and when it exceeds 30%, the amount of barium mica produced decreases, which is not preferable. Therefore, the content of Al2O3 is limited to 5-30%. If F is less than 1.5%, it is difficult to precipitate barium mica and machinability cannot be imparted to glass ceramics, and if it exceeds 1-4%, glass tends to devitrify. The content is limited to 1.5% to 14%.
ＢａＯ，ＭｇＯ、ＳｉＯ２、Ａｌ２Ｏ３及びＦを」１記
の範囲で含む本発明のガラスセラミックスは、機械加工
性、機械的強度に優れている。また本発明のガラスセラ
ミックスは、アルカリ金属成分を実質的に含まないので
、絶縁性に優れている。The glass ceramic of the present invention containing BaO, MgO, SiO2, Al2O3, and F in the ranges listed in 1. has excellent machinability and mechanical strength. Further, the glass ceramic of the present invention has excellent insulation properties since it does not substantially contain an alkali metal component.
本発明のガラスセラミックスにおいて、その中に含まれ
る、Ｂａ−Ｍｇ−Ａｌ−Ｓｉ−０−Ｆよりなるバリウム
雲母は、Ｂａ２＋のイオン半径がＫ のイオン半径と近
似しているので、結晶の安定性に優れているカリウム雲
母と同様に結晶の安定性に優れており、さらにこのバリ
ウム雲母は、仮にそのＢａ２＋イオンが口腔内で溶出し
たとしても、カリウム雲母の場合に溶出するＫ イオ／
よりも生体毒性が少ないという利点も有する。In the glass-ceramic of the present invention, the barium mica made of Ba-Mg-Al-Si-0-F contained therein has an ionic radius of Ba2+ that is close to that of K, so that the stability of the crystal can be improved. Similar to potassium mica, which has excellent crystal stability, barium mica has excellent crystal stability, and even if the Ba2+ ions elute in the oral cavity, barium mica has the same K ion/
It also has the advantage of being less toxic to the body.
また本発明のガラスセラミックスは前記のバリラム雲母
とともに、エンスタタイト（ＭｇＳｉＯ３）を必須の結
晶として、またコージェライト（２ＭｇＯ・２Ａｌ２Ｏ
３ ・５ Ｓ １０２ ） 、セルジアン（Ｂａ○’Ａ
ｌ２Ｏ３・２Ｓｉ○２）、フォルステライト（２Ｍ ｇ
Ｏ−Ｓｉ ０２ ＞を任意の結晶として含有することが
できる。In addition to the above-mentioned barylum mica, the glass-ceramic of the present invention also contains enstatite (MgSiO3) as an essential crystal, and cordierite (2MgO.2Al2O).
3 ・5 S 102), Celgian (Ba○'A
l2O3・2Si○2), forsterite (2M g
O—Si 02 > can be contained in the form of any crystal.
なお、本発明のガラスセラミックスは、元の色と異なる
色を出したい場合や歯冠材料として使用する際に天然歯
の色に近すばるために、Ｔ ｉ Ｏ２Ｎｂ２０５ 、Ｔ
ａ２ ｏ５．ＺｒＯ２及びＣｅＯ２から選ばれる１種以
上の着色成分を添加することもできる。これらの着色成
分の添加量は重量百分率で５％以内とするのが好ましい
。その理由は、５％を越えると、失透しやすくなり均質
なガラスが得難くなり、さらに歯冠材料として使用した
場合に色が濃くなりすぎるからである。特に好ましい着
色成分の添加量は３％以下である。Note that the glass ceramics of the present invention can be used in cases where a color different from the original color is desired or when used as a dental crown material, so that the color closely resembles that of natural teeth.
a2 o5. It is also possible to add one or more coloring components selected from ZrO2 and CeO2. The amount of these coloring components added is preferably within 5% by weight. The reason is that if it exceeds 5%, devitrification tends to occur, making it difficult to obtain a homogeneous glass, and furthermore, when used as a dental crown material, the color becomes too dark. A particularly preferable amount of the coloring component added is 3% or less.
優れた機械加工性、機械的強度及び絶縁性を有する、第
１発明のガラスセラミックスは、上記の組成からなるガ
ラスを熱処理し、バリウム雲母結晶及びエンスタタイト
結晶、更に必要によりその他の結晶を析出させることに
より得られる。この熱処理は、ガラスをそのガラス転移
点を越える温度、例えば６００〜千３００℃の温度で所
定時間、例えば０．５〜２００時間加熱することにより
行なわれるが、この熱処理により得られたガラスセラミ
ックスは、機械加工性、機械的強度及び絶縁性を満足す
るものの、透光性を有さず歯冠材料として用いるには不
適当である。The glass-ceramic of the first invention, which has excellent machinability, mechanical strength, and insulation properties, is obtained by heat-treating the glass having the above composition to precipitate barium mica crystals, enstatite crystals, and other crystals as necessary. It can be obtained by This heat treatment is performed by heating the glass at a temperature exceeding its glass transition point, for example, 600 to 1,300 degrees Celsius, for a predetermined period of time, for example, 0.5 to 200 hours. Although it satisfies machinability, mechanical strength, and insulation properties, it does not have translucency and is unsuitable for use as a dental crown material.
そこで、機械加工性、機械的強度及び絶縁性とともに、
同時に透光性をも満足するガラスセラミックスを得るた
めに、前記第２発明のガラスセラミックスの製造方法が
採用される。このガラスセラミックスの製造方法は、上
述の如く、ＢａＯ。Therefore, along with machinability, mechanical strength and insulation,
In order to obtain a glass ceramic that also satisfies translucency at the same time, the method for producing glass ceramics according to the second invention is adopted. As described above, the method for producing this glass ceramic is based on BaO.
ＭｇＯ，ＳｉＯ２，Ａｌ２Ｏ３及びＦを、重量百分率で
ＢａＯ３〜２２％
ＭｇＯ ２０〜３０％
ＳｉＯ２ ３０〜４５％
Ａｌ２Ｏ３５〜３０％
Ｆ １．５〜１４％の範囲で含
み、アルカリ金属成分を実質的に含まないガラスを、そ
のガラス転移点より５０℃低い温度とガラス転移点より
１００℃高い温度との間で熱処理する第１の熱処理工程
と、第１の熱処理工程後のガラスを、そのガラス転移点
より２００〜５００℃高い温度で熱処理する第２の熱処
理工程とを含むことを特徴とする。Contains MgO, SiO2, Al2O3 and F in weight percentages in the range of BaO3 to 22%, MgO 20 to 30%, SiO2 30 to 45%, Al2O35 to 30%, F 1.5 to 14%, and substantially contains an alkali metal component. A first heat treatment step in which the glass is heat treated between a temperature 50°C lower than its glass transition point and a temperature 100°C higher than its glass transition point, and the glass after the first heat treatment step is heated at a temperature below its glass transition point. It is characterized by including a second heat treatment step of heat treatment at a temperature 200 to 500°C higher.
この２工程熱処理において、第１工程でカラスを、ガラ
ス転移点より５０℃低い温度とガラス転移点より１００
℃高い温度との間で熱処理する理由は、ガラス転移点よ
り５０℃低い温度よりさらに低い温度では結晶化するの
に必要な核が生成しないので好ましくなく、ガラス転移
点より１００℃高い温度よりさらに高い温度では核の生
成だけでなく結晶成長が起り、結晶の粒径が大きくなり
透光性に欠けるので好ましくないからである。In this two-step heat treatment, in the first step, the glass is heated at a temperature 50°C lower than the glass transition point and at a temperature 100°C lower than the glass transition point.
The reason why heat treatment is performed at a temperature higher than 50°C is that it is undesirable to use a temperature lower than 50°C below the glass transition point because the nuclei necessary for crystallization will not be generated; This is because, at high temperatures, not only nucleation but also crystal growth occurs, which increases the grain size of the crystals and results in a lack of light transmission, which is undesirable.
また第１−の熱処理工程のための時間は０．５〜２０時
間が好ましい。その理由は、０，５時間未満では、充分
な核の生成が起らず、２００時間を越えても核の生成量
は増えないからである。Moreover, the time for the first heat treatment step is preferably 0.5 to 20 hours. The reason for this is that sufficient nucleation does not occur in less than 0.5 hours, and the amount of nucleation does not increase even after 200 hours.
第１の熱処理工程で核が生成したガラスを次の第２の熱
処理工程でガラス転移点より２００〜５ｏｏ’ｃ高い温
度で熱処理する理由は、前記ガラス転移点より２００℃
高い温度に満たないと結晶成長が充分に行なわれず、ガ
ラス転移点より５００℃高い温度よりさらに高い温度で
は、所望するバリウム雲母結晶やエンスタタイト結晶が
得られないので好ましくないからである。The reason why the glass in which nuclei have been generated in the first heat treatment step is heat-treated at a temperature 200 to 50°C higher than the glass transition point in the second heat treatment step is 200°C higher than the glass transition point.
If the temperature is lower than that, sufficient crystal growth will not occur, and if the temperature is higher than 500° C. above the glass transition point, the desired barium mica crystal or enstatite crystal will not be obtained, which is not preferable.
また、第２の熱処理工程のための時間は０．５〜２００
時間とするのが好ましい。その理由は、０．５時間未満
では、結晶成長が充分に行なわれず、２００時間を越え
ても結晶の成長量は増えないからである。In addition, the time for the second heat treatment step is 0.5 to 200
Preferably, it is an hour. The reason for this is that if the time is less than 0.5 hours, sufficient crystal growth will not occur, and even if the time exceeds 200 hours, the amount of crystal growth will not increase.
なお、第２発明のガラスセラミックスの製造方法を実施
するにあたり、ガラスのガラス転移点（Ｔｇ）は日本光
学硝子工業会規格ＪＯＧＩＳ１９７５に基いて、熱機械
分析装置（ＴＭＡ）で一般に測定されるが、示差熱分析
計（Ｄ ＴＡ＞、示差走査熱量計（ＤＳＣ）で測定して
も良い。さらに、比熱を測定してガラス転移点を求めて
も良い
［実施例］
以下、実施例により本発明を更に説明するが、本発明は
これらの実施例に限定されるものではない
［実施例−１］
重量百分率でＢａＯ３，０％、ＭｇＯ ２８０％、Ｓ
ｉ０２４２ 、０％、Ａｌ２Ｏ３２５．５％、Ｆ １．
５％となるようＢ ａ ＣＯ３、Ｍ ｇ ０ＳｉＯ２、
Ａｌ２Ｏ３、ＭｇＦ２を原料に用いて、２００ｇ調合し
、これを白金ルツボに入れて１５００℃で６０分間溶融
しな。次いで溶融状態のガラスを黒鉛板状にキャストし
、ガラス転移点付近の温度に設定したアニール炉に入れ
徐冷しガラス塊を得た。このガラスのガラス転移点は７
００℃であった。得られたガラスを電気炉に入れ、室温
から１２００℃まで一定の昇温速度３℃／分で加熱し、
１２００℃で２時間保持して熱処理を行なった後、炉内
で室温まで冷却し、ガラスセラミックスを得な。In carrying out the method for producing glass ceramics of the second invention, the glass transition point (Tg) of the glass is generally measured with a thermomechanical analyzer (TMA) based on the Japan Optical Glass Industry Association standard JOGIS 1975. The measurement may be performed using a differential thermal analyzer (D TA) or a differential scanning calorimeter (DSC).Furthermore, the glass transition point may be determined by measuring the specific heat [Examples] The present invention will be explained using Examples below. As will be further explained, the present invention is not limited to these examples [Example-1] BaO 3.0%, MgO 280%, S
i0242, 0%, Al2O3 25.5%, F 1.
B a CO3, M g 0SiO2, so as to be 5%.
Using Al2O3 and MgF2 as raw materials, prepare 200g, put this into a platinum crucible, and melt it at 1500°C for 60 minutes. Next, the molten glass was cast into a graphite plate, which was then placed in an annealing furnace set at a temperature near the glass transition point to be slowly cooled to obtain a glass lump. The glass transition point of this glass is 7
It was 00℃. The obtained glass was placed in an electric furnace and heated from room temperature to 1200°C at a constant temperature increase rate of 3°C/min.
After performing heat treatment by holding at 1200° C. for 2 hours, it is cooled to room temperature in a furnace to obtain glass ceramics.
こうして製造されたガラスセラミックスの一部を粉砕し
、Ｘ線回折により析出結晶を同定した結果、表１に示す
ようにバリウム雲母、エンスタタイト及びコージェライ
トが析出していることが判明しな。 また得られたガラ
スセラミックスの曲げ強度、切削性、伝導率及び透光性
を下記の方法で調べた。（１）曲げ強度・・・ＪＩＳ
Ｒ１６０１に基づく三点曲げ強度
試験法により求めた（単位ｋｇ／ｃｚａ＋ ）。A part of the glass ceramic thus produced was crushed and the precipitated crystals were identified by X-ray diffraction. As a result, as shown in Table 1, it was found that barium mica, enstatite, and cordierite were precipitated. In addition, the bending strength, machinability, conductivity, and translucency of the obtained glass ceramics were examined using the following methods. (1) Bending strength...JIS
It was determined by a three-point bending strength test method based on R1601 (unit: kg/cza+).
（２）切削性・・・１．５ｍ…φの工具鋼製ドリルで穴
をあけ切削加工性を評価し、切削加工可のものを△、切
削加工良のものを○、切削加工優のものを◎で表示した
。(2) Machinability: Drill a hole with a 1.5 m diameter tool steel drill and evaluate the machinability. Those with good machining are △, those with good machining are ○, and those with excellent machining are evaluated. are marked with ◎.
（３）伝導率、、、ＪＩＳ Ｃ２１，！１１に基づく電
気絶縁用セラミックス材料試験法により求めた（単位Ω
−１ｃ＋ｎ−１）。(3) Conductivity, JIS C21,! 11 (unit: Ω)
-1c+n-1).
（４）透光性・・・目視より評価し、透光性があるもの
を○、ないものを×で表示しな。(4) Translucency...Evaluate visually and mark those with translucency as ○, and those without as x.
その結果、曲げ強度は１５００ｋｇ／ｃｍＦ、切削性は
切削加工度（△〉、伝導率は１．２Ｘ１０１３Ω−１ｃ
ｍ−１であり、機械的強度、機械加工性、絶縁性を満足
するものであった。As a result, the bending strength was 1500 kg/cmF, the machinability was 1.2×1013Ω-1c
m-1, and satisfied mechanical strength, machinability, and insulation properties.
しかし熱処理を１工程で行なっているため、透光性の評
価は×であり、透光性を有していなかった。However, since the heat treatment was performed in one step, the light transmittance was evaluated as x, indicating that it did not have light transmittance.
［実施例２〜２７］
ＢａＣＯ２、ＭｇＯ、ＳｉＯ２、Ａ１２ｏ３、ＭｇＦ２
を用いて、表１に示す組成に相当するガラス原料を２０
０ｇ調合し、これを白金ルツボに入れて１４００〜１６
００℃で３０〜６０分間溶融した。次いで溶融状態のガ
ラスを黒鉛板上にキャストし、アニールしてガラス塊を
得た。得られた２６種のガラスのガラス転移点は５８０
〜６８０℃の範囲であった。得られたガラスを電気炉に
入れ、実施例１と同様な熱処理を行なった。すなわち、
室温から６００〜１３００℃の範囲の一定温度まで一定
の昇温速度３℃／分で加熱し、その一定温度で０．５〜
２００時間の範囲で熱処理を行なった後、炉内で室温ま
で冷却し、２６種のガラスセラミックスを得た。[Examples 2 to 27] BaCO2, MgO, SiO2, A12o3, MgF2
Using
Blend 0g, put this into a platinum crucible and make 1400~16
Melt at 00°C for 30-60 minutes. Next, the molten glass was cast onto a graphite plate and annealed to obtain a glass lump. The glass transition point of the 26 types of glasses obtained was 580.
It was in the range of ~680°C. The obtained glass was placed in an electric furnace and subjected to the same heat treatment as in Example 1. That is,
Heating from room temperature to a constant temperature in the range of 600-1300℃ at a constant temperature increase rate of 3℃/min, and at that constant temperature 0.5-1300℃
After heat treatment was performed for 200 hours, the mixture was cooled to room temperature in a furnace to obtain 26 types of glass ceramics.
得られた実施例２〜２７のガラスセラミックスについて
、実施例１と同様にＸ線回折による析出結晶、曲げ強度
、切削性、伝導率及び透光性を測定した結果を表１に示
す。Regarding the obtained glass ceramics of Examples 2 to 27, precipitated crystals, bending strength, machinability, conductivity, and translucency were measured by X-ray diffraction in the same manner as in Example 1. Table 1 shows the results.
表１より明らかなように、実施例２〜２７のガラスセラ
ミックスは、曲げ強度、切削性、絶縁性を満足するもの
であった。なお実施例１４〜２０のガラスセラミックス
は、着色成分を含むものであるが、天然歯に近い色調と
なるので歯冠材料として有用であることが判明した。As is clear from Table 1, the glass ceramics of Examples 2 to 27 satisfied bending strength, machinability, and insulation properties. Although the glass ceramics of Examples 14 to 20 contain coloring components, they were found to be useful as dental crown materials because they had a color tone close to that of natural teeth.
なお上記実施例２〜２７のガラスセラミックスは実施例
１のガラスセラミックスと同様に透光性を有していなか
った。Note that the glass ceramics of Examples 2 to 27 described above did not have light transmittance like the glass ceramic of Example 1.
［実施例２８］
重量百分率でＢａＯ１０，０％、ＭｇＯ２６゜２％、Ｓ
ｉ ０２３８．８％、Ａｌ２Ｏ３１８．１％、Ｆ ６
．９％となるようＢａＣＯ２、ＭｇＯ１ＳｉＯ２、Ａｌ
２Ｏ３、ＭｇＦ２を原料に用いて、２００ｇ調合し、こ
れを白金ルツボに入れて１５００℃で６０分間溶融した
。次いで溶融状態のガラスを黒鉛板上にキャストし、ア
ニールしてガラス塊を得た。得られたガラスのガラス転
移点は６５５℃であった。これを電気炉に入れ、室温か
ら６５０℃まで一定の昇温速度３℃／分で加熱し、その
６５０℃で５０時間保持して第１の熱処理工程を行なっ
た。その後１０００℃まで一定の昇温速度３℃／分で加
熱し、１０００℃で４時間保持して第２の熱処理工程を
行なった。しかる後、炉内で室温まで冷却し、ガラスセ
ラミックスを得た。[Example 28] Weight percentage: BaO 10.0%, MgO 26°2%, S
i0238.8%, Al2O318.1%, F6
．． BaCO2, MgO1SiO2, Al to be 9%
Using 2O3 and MgF2 as raw materials, 200g was prepared, which was placed in a platinum crucible and melted at 1500°C for 60 minutes. Next, the molten glass was cast onto a graphite plate and annealed to obtain a glass lump. The glass transition point of the obtained glass was 655°C. This was placed in an electric furnace, heated from room temperature to 650°C at a constant temperature increase rate of 3°C/min, and held at 650°C for 50 hours to perform a first heat treatment step. Thereafter, it was heated to 1000°C at a constant temperature increase rate of 3°C/min and held at 1000°C for 4 hours to perform a second heat treatment step. Thereafter, it was cooled to room temperature in a furnace to obtain glass ceramics.
こうして製造されたガラスセラミックスを実施例１と同
様の方法で、Ｘ線回折による結晶構造、曲げ強度、切削
性、伝導率及び透光性を測定した結果を表２に示す。表
２より、実施例２８のガラスセラミックスは曲げ強度が
３０００ｋｇ／ｃＡ、切削性が切削加工優（◎）であり
、機械的強度、機械加工性に著るしく優れていた。また
伝導率が０９Ｘ１０−１３Ω−Ｉｃｍ−１であり、絶縁
性に優れていた。さらに透光性にも優れており、歯冠材
料として好ましく用いられることが明らかとなった。Table 2 shows the results of measuring the crystal structure, bending strength, machinability, conductivity, and translucency of the thus produced glass ceramics by X-ray diffraction in the same manner as in Example 1. From Table 2, the glass ceramic of Example 28 had a bending strength of 3000 kg/cA, excellent machinability (◎), and was extremely excellent in mechanical strength and machinability. Further, the conductivity was 09×10-13 Ω-Icm-1, and the insulation was excellent. Furthermore, it has been revealed that it has excellent translucency and is preferably used as a dental crown material.
［実施例２９〜５５］
Ｂ ａ ＣＯ３、Ｍ ｇ○、ＳｉＯ２、Ａ １２０３、
ＭｇＦ２を用いて、表１に示す組成に相当するガラス原
料を２００ｇ調合し、これを白金ルツボに入れて１４０
０〜１６００℃で３０〜６０分間溶融した。次いで溶融
状態のガラスを黒鉛板上にキャストし、アニールしてガ
ラス塊を得た。得られた２７種のガラス転移点は５８０
〜７００℃の範囲であった。得られたガラスを電気炉に
入れ、実施例２８と同様の２工程熱処理を行なった。す
なわち、室温から５５０〜７００の範囲の一定温度まで
一定の昇温速度３℃／分で加熱し、その一定温度で０．
５〜２００時間保持して第１の熱処理工程を行なった。[Examples 29 to 55] B a CO3, M g○, SiO2, A 1203,
Using MgF2, prepare 200g of glass raw material corresponding to the composition shown in Table 1, put this into a platinum crucible, and heat at 140g.
It was melted at 0-1600°C for 30-60 minutes. Next, the molten glass was cast onto a graphite plate and annealed to obtain a glass lump. The glass transition point of the 27 types obtained was 580.
The temperature was in the range of ~700°C. The obtained glass was placed in an electric furnace and subjected to the same two-step heat treatment as in Example 28. That is, heating is performed from room temperature to a constant temperature in the range of 550 to 700℃ at a constant temperature increase rate of 3°C/min, and at that constant temperature 0.
The first heat treatment step was carried out by holding for 5 to 200 hours.
その後８５０〜１１００℃の範囲の一定温度まで一定の
昇温速度３℃／分で加熱し、その一定温度で０．５〜２
００時間保持して第２の熱処理工程を行なった。しかる
後、炉内で室温まで冷却し、ガラスセラミックスを得た
。After that, it is heated at a constant temperature increase rate of 3℃/min to a constant temperature in the range of 850 to 1100℃, and at that constant temperature 0.5 to 2
The second heat treatment step was performed after holding the sample for 00 hours. Thereafter, it was cooled to room temperature in a furnace to obtain glass ceramics.
こうして製造された各ガラスセラミックスについて実施
例１と同様の方法で、Ｘ線回折による結晶構造、曲げ強
度、切削性、伝導率及び透光性を測定しな。The crystal structure, bending strength, machinability, conductivity, and translucency of each of the glass ceramics thus produced were measured by X-ray diffraction in the same manner as in Example 1.
表２から明らかな通り、実施例２９〜５５のガラスセラ
ミックスは１５００〜３０００ ｈｇ／＝という高い値
の曲げ強度を有し、切削加工が可能であり、絶縁性も高
く更に透光性にも優れていた。As is clear from Table 2, the glass ceramics of Examples 29 to 55 have a high bending strength of 1500 to 3000 hg/=, can be cut, have high insulation properties, and have excellent translucency. was.
［比較例１］
実施例４８の２工程熱処理において、第２の熱処理工程
の温度を第２発明において規定された上限（すなわちガ
ラス転移点＋５００℃）よりも高くし、１３００℃（ガ
ラス転移点（６４０℃〉＋６６０℃〉にした以外は実施
例４８と同様に実施してガラスセラミックスを得た。得
られたガラスセラミックスは、表３に示すように、実施
例４８のガラスセラミックスと比べ、曲げ強度が著るし
く低く、切削性も劣り、また透光性を有さず歯冠材料と
して不適当であることが判明した。[Comparative Example 1] In the two-step heat treatment of Example 48, the temperature of the second heat treatment step was set higher than the upper limit specified in the second invention (i.e., glass transition point +500°C), and 1300°C (glass transition point ( Glass ceramics were obtained in the same manner as in Example 48 except that the temperature was 640°C>+660°C>.As shown in Table 3, the obtained glass ceramics had a higher bending strength than the glass ceramics of Example 48. It was found that the material had a significantly low surface area, poor cutting properties, and no translucency, making it unsuitable as a dental crown material.
［比較例２］
実施例４９の２工程熱処理において、第２の熱処理工程
の温度を第２発明において規定された上限（すなわちガ
ラス転移点＋５００℃）よりも高くし、ｉ−３２０℃（
ガラス転移点（６４５℃）＋６７５℃〉にした以外は実
施例４９と同様に実施してガラスセラミックスを得た。[Comparative Example 2] In the two-step heat treatment of Example 49, the temperature of the second heat treatment step was set higher than the upper limit specified in the second invention (i.e., glass transition point +500°C), and i-320°C (
A glass ceramic was obtained in the same manner as in Example 49 except that the glass transition point (645° C.) + 675° C. was adjusted.
得られたガラスセラミックスは、表３に示すように、実
施例４９のガラスセラミックスと比べ、曲げ強度が著る
しく低く、切削性も劣り、また透光性を有さず歯冠材料
として不適当であることが判明した。As shown in Table 3, the obtained glass-ceramics had significantly lower bending strength and poorer machinability than the glass-ceramics of Example 49, and also had no translucency, making them unsuitable as dental crown materials. It turned out to be.
［比較例３］
実施例５５の２工程熱処理において、第２の熱処理工程
の温度を第２発明において規定された下限（すなわちガ
ラス転移点＋２００℃）よりも低くし、７５０℃（ガラ
ス転移点（６００℃）＋１５０℃）にした以外は実施例
５５と同様に実施してガラスセラミックスを得た。得ら
れたガラスセラミックスは、表３に示すように、実施例
５５のガラスセラミックスと比べ、曲げ強度が著るしく
低く、切削性及び絶縁性も劣り、また透光性を有さず歯
冠材料として不適当であることが判明しな。[Comparative Example 3] In the two-step heat treatment of Example 55, the temperature of the second heat treatment step was lower than the lower limit specified in the second invention (i.e., glass transition point + 200 ° C.), and 750 ° C. (glass transition point ( A glass ceramic was obtained in the same manner as in Example 55 except that the temperature was changed to 600°C) + 150°C. As shown in Table 3, the obtained glass-ceramics had significantly lower bending strength, poorer machinability and insulation properties, and lacked translucency, making them suitable for dental crown materials than the glass-ceramics of Example 55. It was found to be inappropriate as such.
（以下余白）
［発明の効果］
以上述べたように、ＢａＯ，ＭｇＯ，ＳｉＯ２Ａｌ２Ｏ
３及びＦを所定比率で含み、アルカリ金属成分を実質的
に含まないガラスから、バリウム雲母結晶とエンスタタ
イト結晶とを析出してなる、本発明のガラスセラミック
スは機械加工性、機械的強度及び絶縁性に優れていると
いう利点を有する。さらに上記ガラスに必要に応じて着
色成分を加えることにより天然歯に近い色となるので歯
冠材料として有用となる。(Left below) [Effects of the invention] As stated above, BaO, MgO, SiO2Al2O
The glass ceramic of the present invention, which is made by precipitating barium mica crystals and enstatite crystals from glass containing 3 and F in a predetermined ratio and substantially free of alkali metal components, has excellent machinability, mechanical strength, and insulation properties. It has the advantage of excellent properties. Furthermore, by adding a coloring component to the above-mentioned glass as necessary, it becomes a color close to that of natural teeth, making it useful as a dental crown material.
また上記ガラスを２工程で熱処理する、本発明のガラス
セラミックスの製造方法は、上記の機械加工性、機械的
強度及び絶縁性とともに透光性に優れ、歯冠材料として
好適なガラスセラミックスが得られるという利点を有す
る。Furthermore, the method for manufacturing glass ceramics of the present invention, which heat-treats the glass in two steps, can yield glass ceramics that have excellent machinability, mechanical strength, and insulation properties as well as translucency, and are suitable as dental crown materials. It has the advantage of
Claims (2)
びＦを、重量百分率で ＢａＯ３〜２２％ ＭｇＯ２０〜３０％ ＳｉＯ＿２３０〜４５％ Ａｌ＿２Ｏ＿３５〜３０％ Ｆ１．５〜１４％ の範囲で含み、アルカリ金属成分を実質的に含まないガ
ラスから、Ｂａ−Ｍｇ−Ａｌ−Ｓｉ−Ｏ−Ｆよりなるバ
リウム雲母結晶と、Ｍｇ−Ｓｉ−Ｏよりなるエンスタタ
イト結晶とを析出させてなることを特徴とするガラスセ
ラミックス。(1) Contains BaO, MgO, SiO_2, Al_2O_3 and F in weight percentages of BaO3 to 22%, MgO20 to 30%, SiO_230 to 45%, Al_2O_35 to 30%, F1.5 to 14%, and substantially contains alkali metal components. A glass ceramic characterized in that barium mica crystals made of Ba-Mg-Al-Si-O-F and enstatite crystals made of Mg-Si-O are precipitated from a glass that does not contain Ba-Mg-Al-Si-O-F.
びＦを、重量百分率で ＢａＯ３〜２２％ ＭｇＯ２０〜３０％ ＳｉＯ＿２３０〜４５％ Ａｌ＿２Ｏ＿３５〜３０％ Ｆ１．５〜１４％ の範囲で含み、アルカリ金属成分を実質的に含まないガ
ラスを、そのガラス転移点より５０℃低い温度とガラス
転移点より１００℃高い温度との間で熱処理する第１の
熱処理工程と、第１の熱処理工程後のガラスを、そのガ
ラス転移点より２００〜５００℃高い温度で熱処理する
第２の熱処理工程とを含むことを特徴とする透光性を有
するガラスセラミックスの製造方法。(2) Contains BaO, MgO, SiO_2, Al_2O_3 and F in weight percentages in the range of BaO3 to 22%, MgO20 to 30%, SiO_230 to 45%, Al_2O_35 to 30%, F1.5 to 14%, and substantially contains alkali metal components. A first heat treatment step of heat-treating the glass that does not contain the glass at a temperature between 50°C lower than its glass transition point and 100°C higher than its glass transition point; A method for producing glass ceramics having translucency, the method comprising: a second heat treatment step of heat treatment at a temperature 200 to 500° C. higher than the point.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2792389A JPH02208238A (en) | 1989-02-07 | 1989-02-07 | Glass ceramics and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2792389A JPH02208238A (en) | 1989-02-07 | 1989-02-07 | Glass ceramics and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02208238A true JPH02208238A (en) | 1990-08-17 |
Family
ID=12234406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2792389A Pending JPH02208238A (en) | 1989-02-07 | 1989-02-07 | Glass ceramics and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02208238A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004071979A3 (en) * | 2003-02-12 | 2005-01-20 | Univ Leeds | Glass ceramics |
| JP2007253284A (en) * | 2006-03-23 | 2007-10-04 | Kyocera Corp | Vacuum chuck and vacuum suction device using it |
-
1989
- 1989-02-07 JP JP2792389A patent/JPH02208238A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004071979A3 (en) * | 2003-02-12 | 2005-01-20 | Univ Leeds | Glass ceramics |
| JP2007253284A (en) * | 2006-03-23 | 2007-10-04 | Kyocera Corp | Vacuum chuck and vacuum suction device using it |
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