JPS6256336A - Production of crystallized cao-al2o3-p2o5 glass - Google Patents

Abstract

PURPOSE:To produce titled glass adequate as a dental material without having defects such as cracks by subjecting a glassy casting formed by adding F atoms to the compsn of a ternary component system of CaO-Al2O3-P2O5 to multiple stages of crystallization treatments while heating up the casting. CONSTITUTION:F atoms are added to a raw material mixtue of the compsn. composed of 10-60wt% CaO, 5-35wt% Al2O3 and 25-85wt% P2O5 at <=3pts. wt. by 100pts.wt. in total of the above-mentioned compsn. The mixture is melted and cast to produce the glassy casting. The glassy casting is subjected to >=2 stages of the crystallization treatment while the temp. is gradually increased between the softening point thereof and the crystallization temp. of calcium phosphate. The melting of Al2O3 at the lower temp. is made possible by the incorporation of the F atoms into the compsn.; in addition, the cleaning up of the raw material is made easy and the time when the glass is kept melted is shorter; further the formation of crystal nuclei is accelerated in the crystallization stage of the glass. The titled glass having no voids and cracks is obtd. by multiple stages of the crystallization treatments.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は歯科材料や人工骨材料等として最適であるリン
酸カルシウム結晶を含有するＣａＯ−Ａｌ２Ｏ３Ｐ２０
Ｂ結晶化ガラス医用材料の製造方法に関するものである
。Detailed Description of the Invention [Industrial Field of Application] The present invention provides a CaO-Al2O3P20 material containing calcium phosphate crystals, which is most suitable for dental materials, artificial bone materials, etc.
This invention relates to a method for producing B-crystallized glass medical material.

〔従来の技術〕[Conventional technology]

近年セラミックの応用範囲の拡大は目ざましく医用分野
にまで適用が及んでおり、従来は金属、プラスチックが
主に使用されて来た医用材料、例えば人工歯根等へもセ
ラミックの応用が試みられている。In recent years, the range of applications for ceramics has expanded rapidly, reaching the medical field, and attempts are being made to apply ceramics to medical materials, such as artificial tooth roots, for which metals and plastics have traditionally been used. .

本発明者らは生体に対する親和性を有するセラミック材
料を探し出し、それを任意の形状に自由にかつ高精度に
成形して高強度セラミックを製造する方法に関して研究
を重ねた結果、リン酸カルシウム系材料を素材として選
択することにより、それが可能であることを見出し、そ
れについて鋭意研究を重ねている。The present inventors searched for a ceramic material that has an affinity for living organisms, and as a result of repeated research into a method for manufacturing high-strength ceramic by freely and highly precisely molding it into any shape, they found that a calcium phosphate-based material was used as a raw material. We have discovered that this is possible by selecting the appropriate method, and have been conducting extensive research on it.

この優れた特徴を有するリン酸カルシウム系材料も、一
旦ガラス化し結晶化させた際に、ガラスと結晶との比重
差に基づく内部欠陥が発生し、そのため機械的強度が低
下したり、細面などが侵入しやすくなる。Even with calcium phosphate materials that have these excellent characteristics, once they are vitrified and crystallized, internal defects occur due to the difference in specific gravity between the glass and the crystal, resulting in a decrease in mechanical strength and the intrusion of fine surfaces. It becomes easier.

例えば、カルシウムとリンとの原子比Ｃａ　／　Ｐが０
．４８のリン酸カルシウムガラスの比重は２．６３であ
り、これを熱処理して結晶化するとＣａＯ・Ｐ２Ｏ６が
生成する。このＣａＯ−ＰｚＯｓ結晶の真比重は２．８
５であり、ガラスの比重よりかなり大きい。ところが結
晶化は表面失透機構で進行するため、結晶化に伴なう体
積減少はほとんどない。For example, the atomic ratio of calcium and phosphorus, Ca/P, is 0.
．． The specific gravity of calcium phosphate glass No. 48 is 2.63, and when it is heat-treated and crystallized, CaO.P2O6 is produced. The true specific gravity of this CaO-PzOs crystal is 2.8
5, which is considerably larger than the specific gravity of glass. However, since crystallization proceeds by a surface devitrification mechanism, there is almost no volume reduction accompanying crystallization.

ところが結晶化によって比重が増加するということは体
積が減少することを意味し、全体の体積が変化しなけれ
ば、結晶内部には比重の増加に相当する体積減少分の空
隙が発生し、これがクラックやボアのような内部欠陥と
なる。この内部欠陥のため結晶体の強度は欠陥のないも
のに比べて低下してしまうのである。また、ボアなどの
発生の様子はガラスのカルシウムとリンの原子比、結晶
化温度、結晶化時間などの種々の要因に左右されるため
、機械的強度のバラツキも大きくなることも避けられな
い。However, an increase in specific gravity due to crystallization means a decrease in volume, and if the overall volume does not change, voids corresponding to the decrease in volume corresponding to the increase in specific gravity will occur inside the crystal, which will cause cracks. or internal defects such as bores. Because of these internal defects, the strength of the crystal is lower than that of a crystal without defects. Furthermore, since the appearance of bores and the like depends on various factors such as the atomic ratio of calcium and phosphorus in the glass, crystallization temperature, and crystallization time, it is inevitable that the mechanical strength will vary widely.

この内部欠陥は、添加物を加えたり、結晶化の方法に工
夫を加えたバルク・クリスタリゼーシコン機構による結
晶化でも結晶化の体積収縮が表面失透機構による場合よ
りや＼大きいので内部欠陥の発生する程度は小さいけれ
ども、やはり同様に起こるのである。These internal defects are caused by the fact that even when crystallization is carried out by the bulk crystallization mechanism by adding additives or devising the crystallization method, the volume contraction during crystallization is larger than that by the surface devitrification mechanism. Although the degree of occurrence is small, it still occurs in the same way.

上述の欠点を解消するためには、結晶化前後の比重差を
なくすればよいわけで、本発明者らはリン酸カルシウム
の生体親和性と結晶化の際の体積収縮の無いという特徴
を損なわずに内部欠陥を生じないような方法について種
々検討した結果、ＣａＯ−Ａｌ２Ｏ３−Ｐ２０５３成分
系結晶化ガラスを採用することによって、上記問題を解
決することに成功した。In order to eliminate the above-mentioned drawbacks, it is sufficient to eliminate the difference in specific gravity before and after crystallization, and the present inventors have developed a method that does not impair the biocompatibility of calcium phosphate and the characteristics of no volume contraction during crystallization. As a result of various studies on methods that do not cause internal defects, we succeeded in solving the above problem by employing CaO-Al2O3-P205 ternary crystallized glass.

〔発明が解決しようとする問題〕[Problem that the invention seeks to solve]

しかし、結晶化前後の比重差を小さくするためにはある
程度以上のＡｌ２Ｏ３量が必要であるが、Ａｌ２Ｏ３の
量を増すに従って次第に融点が上昇してしまい、添加し
たＡｌ２Ｏ３を完全に溶融するためには、かなり高温に
しなければならなくなる。However, in order to reduce the difference in specific gravity before and after crystallization, a certain amount of Al2O3 is required, but as the amount of Al2O3 increases, the melting point gradually increases, and in order to completely melt the added Al2O3, , it would have to be heated to a fairly high temperature.

しかし、溶融のために温度を上げるとリン酸成分の窯発
が顕著になるという不都合が生ずる。However, when the temperature is increased for melting, a disadvantage arises in that the phosphoric acid component is significantly released in the kiln.

またＡｌ２Ｏ３の量が多くなるとガラスの軟化点もリン
酸カルシウムの結晶化温度も上昇し、比重差を補正する
はずのＡｌ２Ｏ３・Ｐ２Ｏ５の結晶が十分に生成せず、
そのため結晶化前後の比重差による空隙やクラックの発
生が防げないという問題が発生するのである。Furthermore, when the amount of Al2O3 increases, the softening point of the glass and the crystallization temperature of calcium phosphate also rise, and the Al2O3/P2O5 crystals that should compensate for the difference in specific gravity are not sufficiently formed.
Therefore, a problem arises in that the generation of voids and cracks due to the difference in specific gravity before and after crystallization cannot be prevented.

〔問題点を解決するための手段〕[Means for solving problems]

本発明者らはＣａＯ−Ａｌ２Ｏ３Ｐ２Ｏ１５３成分系の
組成にフッ素原子を含有させることによりＡｌ２Ｏ３の
溶解度を増し、さらに結晶化の際にガラス質鋳造体の軟
化点とリン酸カルシウムの結晶化温度との間の温度で次
第に温度を上げながら２段階以上の結晶化処理を行なう
ことにより上記の問題点を解消し本発明を完成させたの
である。The present inventors increased the solubility of Al2O3 by including fluorine atoms in the composition of the CaO-Al2O3P2O15 3-component system, and furthermore, during crystallization, the temperature between the softening point of the glassy casting and the crystallization temperature of calcium phosphate was increased. By performing two or more stages of crystallization treatment while gradually increasing the temperature, the above problems were solved and the present invention was completed.

〔作用〕[Effect]

本発明による製造方法の特徴はＣａＯ１０〜６０重量％
、Ａｌ２０３５〜３５重量％、Ｐ　２０　ｓ　２５〜８
５重量％なる組成範囲（７）ＣａＯ−Ａｌ２Ｏ３−Ｐ２
０Ｓ系素材においてＣａＯＳＡｌ２Ｏ３およびＰ２Ｏ５
の合量１００重量部に対しＦ原子として３重量部以下を
含有せしめ、溶融、鋳造後、ガラス質鋳造体の軟化点と
リン酸カルシウムの結晶化温度との間の温度で次第に温
度を上げながら２段階以上の結晶化処理を行なうことに
ある。The feature of the production method according to the present invention is that CaO is 10 to 60% by weight.
, Al2035-35% by weight, P20s 25-8
Composition range of 5% by weight (7) CaO-Al2O3-P2
CaOSAl2O3 and P2O5 in OS-based materials
3 parts by weight or less of F atoms are contained per 100 parts by weight of the total amount of F atoms, and after melting and casting, it is heated in two stages while gradually increasing the temperature between the softening point of the glassy casting and the crystallization temperature of calcium phosphate. The purpose is to perform the above crystallization treatment.

上記組成のガラスを結晶化した場合に生成する結晶は主
にＣａＯ−Ｐ２０ａと２ＣａＣＩＰｚ○６とそれにＡｌ
２Ｏ３・Ｐ２Ｏ５である。その真比重はそれぞれ順に２
．８５．３．０９、および２．５９となっており、Ａｌ
２Ｏ３・Ｐ２０Ｅ＋の比重が他の２種のリン酸カルシウ
ム結晶よりかなり低い。When glass with the above composition is crystallized, the crystals produced are mainly CaO-P20a, 2CaCIPz○6, and Al.
2O3・P2O5. Their true specific gravity is 2 in order
．． 85.3.09, and 2.59, and Al
The specific gravity of 2O3.P20E+ is considerably lower than the other two types of calcium phosphate crystals.

例えば、Ｃａ　０２１．８重量％、Ａｌ２Ｏ３９，３重
量％、Ｐ２０ｒ、　６８．９重量％の組成のガラスの比
重は２．６４であり、このガラスを結晶化させる際に、
生成する結晶が上記２種のリン酸カルシウムのみであれ
ば、その結晶の比重がガラスの比重より大きいため体積
収縮を起こして外形に歪が生ずるか、あるいは体積収縮
がなければ、結晶内部にボアなどの欠陥が生ずる。しか
しガラス中にＡｌ２Ｏ３を含むため比重の小さいＡｌ２
Ｏ３・Ｐ２Ｏ６が同時に生成する。Ａｌ２Ｏ３・Ｐ２Ｏ
６の結晶を十分に生成させると、その体積膨張により、
リン酸カルシウムによる体積収縮を補なうことになり、
結晶化後の比重は２．６５となり、比重差はほとんどな
くなり、内部欠陥は全（見られなくなる。For example, a glass with a composition of 21.8% by weight of Ca, 9.3% by weight of Al2O3, and 68.9% by weight of P20r has a specific gravity of 2.64, and when this glass is crystallized,
If the crystals formed are only the above two types of calcium phosphate, the specific gravity of the crystals is greater than the specific gravity of the glass, causing volumetric contraction and distortion of the external shape, or, if there is no volumetric contraction, there may be holes such as holes inside the crystals. Defects occur. However, since Al2O3 is included in the glass, Al2 has a low specific gravity.
O3 and P2O6 are generated simultaneously. Al2O3・P2O
When enough crystals of 6 are formed, due to their volumetric expansion,
This will compensate for the volumetric contraction caused by calcium phosphate,
The specific gravity after crystallization is 2.65, the difference in specific gravity almost disappears, and all internal defects disappear.

しかしＣａＯ／Ｐ２Ｏ５のモル比の範囲によってはガラ
スの結晶化前後の比重差を無くすためにはＡｌ２Ｏ３の
量を多くしなければならない場合がある。しかし、Ａｌ
２Ｏ３の量を増すに従って次第に融点が上昇してしまい
、添加したＡｌ２Ｏ３を完全に溶融するためには、かな
り高温にしなければならなくなる。しかし、溶融のため
に温度を上げるとリン酸成分の蒸発が顕著になるという
不都合が生ずるのである。そこで　ＣａＯ−Ａｌ２Ｏ３
−Ｐ２０ｓ　３成分系素材中にＦ原子を含有させるとよ
り低温でのＡｌ２Ｏ３の溶解が可能となるのである。な
お含有するＦ原子は結晶化に際してはガラス中に残り結
晶化前後の比重差には影響しない。However, depending on the range of the CaO/P2O5 molar ratio, it may be necessary to increase the amount of Al2O3 in order to eliminate the difference in specific gravity before and after crystallization of the glass. However, Al
As the amount of 2O3 increases, the melting point gradually increases, and in order to completely melt the added Al2O3, a considerably high temperature is required. However, when the temperature is raised for melting, the evaporation of the phosphoric acid component becomes significant, which is a disadvantage. So CaO-Al2O3
-P20s When F atoms are included in the three-component material, Al2O3 can be dissolved at lower temperatures. The F atoms contained remain in the glass during crystallization and do not affect the difference in specific gravity before and after crystallization.

もちろんＡｌ２Ｏ３量がそれほど多（ない領域であって
もＦ原子の含有は試料の溶融の助けになるので含有して
いることが望ましい。Of course, even in a region where the amount of Al2O3 is not so large, it is desirable to contain F atoms since it helps in melting the sample.

またＦ原子の含有は溶融した原料の清澄化が容易となり
、溶融している時間が短くなり、さらにガラスの結晶化
の際に結晶核の核形成を促進する作用もあり、製品の強
度向上に貢献するという利点も合わせ持つ。In addition, the inclusion of F atoms makes it easier to clarify the molten raw material, shortens the melting time, and also has the effect of promoting the formation of crystal nuclei during glass crystallization, which improves the strength of the product. It also has the advantage of contributing.

一方Ａｌ２Ｏ３が存在することはＣａＯＨＰ２Ｏ５と２
ＣａＯ−Ｐ２Ｏ５の結晶化温度を上昇させ、もともとあ
ったＡｌ２Ｏ３・Ｐ２Ｏ５の結晶化温度との開きをさら
に大きくする。従って２種のリン酸カルシウムの結晶化
温度付近で結晶化させた場合は２種のリン酸カルシウム
の結晶が主として生成してしまい、Ａｌ２Ｏ３・Ｐ２Ｏ
５の結晶はあまり生成せず、その体積膨張による比重差
の補填効果が発揮されないのである。On the other hand, the presence of Al2O3 means that CaOHP2O5 and 2
The crystallization temperature of CaO-P2O5 is increased to further increase the difference from the crystallization temperature of Al2O3.P2O5, which was originally present. Therefore, if crystallization is performed near the crystallization temperature of two types of calcium phosphate, two types of calcium phosphate crystals will be mainly formed, and Al2O3・P2O
The crystals of No. 5 do not form much, and the effect of compensating for the difference in specific gravity due to their volumetric expansion is not exhibited.

この難点を解決するために、ガラスの軟化点よりや＼高
い温度であって、リン酸カルシウムの結晶化温度より低
い温度で処理して、まずリン酸アルミニウムの結晶を生
成させ、次いで、リン酸カルシウムの結晶化温度に上げ
てリン酸カルシウムの結晶化を完成させる方法を採用す
ることによって、結晶内でのリン酸アルミニウムによる
体積補填効果を十分に発揮させることができる。この結
晶化の操作を上記の２段階でなく、ガラスの軟化点とリ
ン酸カルシウムの結晶化温度との間の温度で次第に温度
を上げながら３段階以上行なうことも可能である。さら
にガラスの軟化点とリン酸カルシウムの結晶化温度との
間で連続的に温度を上げて行ってもよい。In order to solve this problem, we first produced crystals of aluminum phosphate by processing at a temperature slightly higher than the softening point of glass and lower than the crystallization temperature of calcium phosphate, and then crystallized calcium phosphate. By employing a method of raising the temperature to complete the crystallization of calcium phosphate, it is possible to fully exhibit the volume compensation effect of aluminum phosphate within the crystal. It is also possible to carry out this crystallization operation in three or more stages while gradually increasing the temperature between the softening point of the glass and the crystallization temperature of calcium phosphate, instead of the above two stages. Furthermore, the temperature may be raised continuously between the softening point of the glass and the crystallization temperature of calcium phosphate.

この多段階処理による結晶化によって、ガラスと結晶と
の間の比重差を無くして、結晶内の欠陥の発生を防ぐと
同時に、低温での結晶化によって結晶内部にも結晶核が
生成し、表面から結晶が発達する表面失透性を弱め、ク
ラックの発生を防止し、さらに高温での結晶化処理時間
が短くなることで、製品の軟化変形を少なくできる効果
も生ずる。This multi-step crystallization process eliminates the difference in specific gravity between the glass and the crystal, preventing the formation of defects within the crystal. At the same time, crystallization at low temperatures also generates crystal nuclei inside the crystal, and the surface By weakening the surface devitrification that causes crystals to develop, preventing the occurrence of cracks, and shortening the crystallization time at high temperatures, it also has the effect of reducing softening and deformation of the product.

〔発明の構成〕[Structure of the invention]

本発明の出発原料は酸化カルシウムあるいは水酸化カル
シウム、炭酸カルシウム、蓚酸カルシウムなど焼成によ
つてＣａＯを生成するカルシウム含有化合物と、リン酸
、ポリリン酸など同じ（焼成によってリンの酸化物を生
成するリン含有化合物およびアルミナ、水酸化アルミニ
ウムなど焼成してＡｌ２Ｏ３となるようなアルミニウム
含有化合物が用いられる。またリン酸カルシウム、アパ
タイト類、リン酸アルミニウム、アルミン酸カルシウム
なども使用出来る。またフッ素源としてはフッ化カルシ
ウム、フッ化アルミニウム、フッ素含有アパタイトなど
が利用できるが、昇華のないフッ化カルシウムが最も適
している。The starting materials of the present invention are calcium-containing compounds that produce CaO upon calcination, such as calcium oxide, calcium hydroxide, calcium carbonate, and calcium oxalate, and phosphoric acid, polyphosphoric acid, etc., which produce phosphorus oxides upon calcination. Aluminum-containing compounds and aluminum-containing compounds that become Al2O3 when fired, such as alumina and aluminum hydroxide, are used.Also, calcium phosphate, apatites, aluminum phosphate, calcium aluminate, etc. can be used.Also, as a fluorine source, calcium fluoride is used. , aluminum fluoride, fluorine-containing apatite, etc. can be used, but calcium fluoride, which does not sublimate, is the most suitable.

カルシウム、ワン、アルミニウムおよびフッ素を含有す
る化合物のそれぞれ１種あるいは２這以上を選び、ガラ
スの組成をＣａＯ１０〜６０重量％、Ａｌ２Ｏ３５〜３
５重量％、Ｐ　２０　ｓ　２５〜８５重量％の範囲に、
またＦ原子としてはＣａ　Ｏ，Ａｌ２Ｏ３、Ｐ２Ｏ６の
合量１圓重量部に対し、３重量部以下とする。One or more compounds containing calcium, aluminum, aluminum, and fluorine are selected, and the composition of the glass is set to 10 to 60% by weight of CaO and 35 to 3% of Al2O.
5% by weight, P20s in the range of 25-85% by weight,
Further, the F atom should be 3 parts by weight or less per 1 part by weight of the total amount of CaO, Al2O3, and P2O6.

ＣａＯ６０重量％以上あるいはＰ　２０６２５重量％未
満では溶融温度が高くなり、かつガラス化しない。逆に
ＣａＯ１０重量％未満またはＰ　２０　ｓ　８５重量％
以上では溶融温度が低下すると同時にガラス化も容易に
なるが、結晶化処理が難しくなり、かつ過剰のリン酸が
遊離して化学的に不安定となり好マしくない。一方アル
ミナの含有量が３５重量％を越えると溶融温度が高くな
り、また５重量％未満とするとＡｌ２Ｏ３・Ｐ２Ｏ５の
結晶が生成しないか生成量が少な（、ボアなどの内部欠
陥の発生が防げないので好ましくない。一方Ｆ原子の含
有量が３重量部以上ではＣａＦ２の結晶が析出し、この
比重が大きいためＡｌ２Ｏ３の効果がなくなり好ましく
ない。If CaO is 60% by weight or more or P is less than 20625% by weight, the melting temperature becomes high and vitrification does not occur. Conversely, less than 10% by weight of CaO or 85% by weight of P 20 s
In this case, the melting temperature is lowered and vitrification becomes easier, but the crystallization process becomes difficult and excess phosphoric acid is liberated, resulting in chemical instability, which is not preferable. On the other hand, if the alumina content exceeds 35% by weight, the melting temperature will become high, and if it is less than 5% by weight, Al2O3/P2O5 crystals will not form or will be formed in small amounts (and the generation of internal defects such as bores cannot be prevented). On the other hand, if the F atom content is 3 parts by weight or more, CaF2 crystals will precipitate, and the specific gravity of these crystals will be large, so that the effect of Al2O3 will be lost, which is not preferable.

本発明のリン酸カルシウム系ガラスは基本的にはＣａ　
ｓ　Ａ　ｌ及びＰの３成分から構成されるが、本発明の
方法により製造された結晶化ガラスを歯冠材料として使
用する場合は、天然の歯牙と全（同じ色沢とするために
着色剤成分を加えることも出来る。着色剤成分を加える
場合にはＺｎ、Ｆｅ。The calcium phosphate glass of the present invention basically consists of Ca
It is composed of three components: Al and P. However, when using the crystallized glass produced by the method of the present invention as a dental crown material, it is necessary to use the same coloring agent as natural teeth. It is also possible to add other components.If a colorant component is added, Zn, Fe.

Ｍｎ、　Ｗ、　Ｃｅ、　Ｔｉ、　Ｎｉ、　Ｇｏ、　Ｃｒ
、　Ｖの酸化物の中から選ばれた１種あるいは２種以上
を使用し、特に２種以上を組合せて使用することが好ま
しい。その添加量は　Ｃａｂ−Ａｌｔｏｓ−Ｐ２０Ｓ３
成分系酸化物の１００重量部に対して０．０１〜１５重
量部とする。Mn, W, Ce, Ti, Ni, Go, Cr
, V oxides are used, and it is particularly preferable to use two or more of them in combination. The amount added is Cab-Altos-P20S3
The amount is 0.01 to 15 parts by weight per 100 parts by weight of the component oxide.

原料配合は秤量後よく混合し、容器に入れ９０口°Ｃ以
上、好ましくは１０００〜１７００″Ｃに加熱して溶融
する。溶融は１８００＠Ｃ以上となるとリン成分の蒸発
が始まるので注意が必要である。本発明の場合にはＦ原
子の存在により、上記温度範囲でＡｌ２Ｏ３が十分融解
するはずである。After weighing the raw materials, mix well, place in a container, and heat to 90°C or higher, preferably 1000 to 1700"C to melt. Care must be taken when melting at 1800°C or higher, as the phosphorus component will begin to evaporate. In the case of the present invention, Al2O3 should be sufficiently melted in the above temperature range due to the presence of F atoms.

溶融終了後冷却ガラス化する。続いて再度溶融して鋳造
するのであるが、最初の溶融物を一旦冷却ガラス化せず
、直接鋳造してもよい。本発明のＣａＯ−Ａｌ２Ｏ３−
Ｐ２Ｏ５３成分系材料の場合には、鋳造成形は金属の歯
科材料において行なわれるロストワックス法が適してい
る。鋳造型の予熱温度は８００９Ｃ以下、好ましくは２
００〜８００°Ｃの範囲で鋳造型の材質、ガラス質の組
成により適宜選択される。After the melting is completed, it is cooled and vitrified. Subsequently, it is melted and cast again, but the first melt may be directly cast without being cooled and vitrified. CaO-Al2O3- of the present invention
In the case of P2O5 tricomponent based materials, the lost wax method, which is carried out on metal dental materials, is suitable for casting. The preheating temperature of the casting mold is 8009C or less, preferably 2
The temperature is appropriately selected within the range of 00 to 800°C depending on the material of the casting mold and the composition of the glass.

このようにして鋳造された鋳造物はガラス質である。こ
のガラス質の材料に適切な熱処理を加えて結晶化ガラス
とする際の結晶化処理方法に本発明の製造方法の一つの
特徴がある。本発明による３成分系結晶化ガラスの結晶
化方法は次の通りである。ロストワックス法などにより
成形された成形体は通常埋没型のま＼電気炉などの適当
な加熱装置中で加熱される。この際の加熱温度はまず示
差熱分析などを利用して、ガラスの軟化点とリン酸カル
シウムの結晶化温度を求める。まずガラスの軟化点より
や−高い温度で結晶化し、次いで温度を少し上げ再び結
晶化処理を行なう。こうして温度を上げなから結晶化処
理し、最後はリン酸カルシウムの結晶化温度で処理する
。この処理段階は２段階以上何段階でもよいが、操作性
の点から２〜４段階が好ましい。処理時間は全体で５〜
５０ｈｒとする。The casting thus cast is glassy. One of the features of the manufacturing method of the present invention is the crystallization treatment method in which this glassy material is subjected to appropriate heat treatment to produce crystallized glass. The method for crystallizing the three-component crystallized glass according to the present invention is as follows. A molded body formed by a lost wax method or the like is usually heated in a suitable heating device such as an immersion mold or an electric furnace. As for the heating temperature at this time, first, the softening point of the glass and the crystallization temperature of calcium phosphate are determined using differential thermal analysis. First, the glass is crystallized at a temperature slightly higher than the softening point of the glass, and then the temperature is slightly raised and the crystallization process is performed again. In this way, the crystallization process is performed without raising the temperature, and the final process is performed at the crystallization temperature of calcium phosphate. The number of stages of this treatment may be two or more, but from the viewpoint of operability, two to four stages are preferred. Total processing time is 5~
It will be 50 hours.

〔実施例〕〔Example〕

実施例　１ 炭酸カルシウム粉末、アルミナ粉末、正リン酸およびフ
ッ化カルシウム粉末を最終組成がＣａＯ１３，６重量％
、Ａｌ２０３２８．０重量％、Ｐ　２０　ｒ、　５８．
４重量％、ＣａＯ＋ＡｌｚＯ３＋Ｐ２Ｏ６１００重量部
に対しＦ原子が１．５重量部となるように秤量し、よく
混練した後白金ルツボ中１６００＠Ｃでｌｈｒ熔融して
、連結歯冠を埋没した型に圧迫鋳造し、冷却ガラス化し
た。得られたガラスを埋没型のま＼電気炉中で６８８℃
で２ｈｒ、６９０℃で２ｈｒ、次いで７００℃で１０ｈ
ｒ処理し結晶化した。Example 1 Calcium carbonate powder, alumina powder, orthophosphoric acid, and calcium fluoride powder with a final composition of 13.6% by weight CaO
, Al20328.0% by weight, P 20 r, 58.
4% by weight, CaO + AlzO3 + P2O6 100 parts by weight, F atoms were weighed so that 1.5 parts by weight were mixed, thoroughly kneaded, melted in a platinum crucible at 1600@C for lhr, and pressure cast into a mold in which the connecting crown was embedded. It was then cooled and vitrified. The obtained glass was kept buried in an electric furnace at 688°C.
2 hours at 690℃, then 10 hours at 700℃
It was treated with r and crystallized.

得られた結晶体は白色半透明で、結晶体の微細組織を顕
微鏡により観察したところボアやクラッタなどの欠陥は
全（見られなかった。結晶体のＸ線回折の結果は結晶体
中にはＣａＯ・Ｐ２Ｏ６とＡｌ２Ｏ３・Ｐ２Ｏ６が存在
した。またガラスの比重は２．６４で、結晶体の比重は
２゜６５であった。The obtained crystal was white and translucent, and when the microstructure of the crystal was observed under a microscope, no defects such as bores or clutter were observed. CaO.P2O6 and Al2O3.P2O6 were present.The specific gravity of the glass was 2.64, and the specific gravity of the crystal was 2.65.

比較例　１ フッ化カルシウムを含有しない以外は実施例１と同様の
材料を溶融しようとしたが、１６００℃では原料が完全
には溶融しないので、温度を１８５０℃まで上げるとや
っと溶融したが、融液が清澄となるまで加熱を続ける間
にリン酸成分が蒸発し、次第に結晶が析出しはじめた。Comparative Example 1 An attempt was made to melt the same material as in Example 1 except that it did not contain calcium fluoride, but the raw material did not melt completely at 1600°C, so it finally melted when the temperature was raised to 1850°C, but the melting failed. While heating was continued until the liquid became clear, the phosphoric acid component evaporated and crystals gradually began to precipitate.

比較例　２ 実施例１と全く同じ組成の原料を溶融、鋳造後７００℃
、１０ｈｒで一段階で結晶化した。Comparative Example 2 Raw materials with exactly the same composition as Example 1 were melted and cast at 700°C.
, crystallized in one step for 10 hr.

得られた結晶化ガラスも白色半透明ではあったが、結晶
体にはＡｌ２Ｏ３・Ｐ２Ｏ５の結晶は少なく、ガラスの
比重は２．６４で、結晶体の比重は２．７０で、結晶内
部にはボアがわずか見られた。The obtained crystallized glass was also white and translucent, but there were few Al2O3/P2O5 crystals in the crystal, the specific gravity of the glass was 2.64, and the specific gravity of the crystal was 2.70, and there was no crystal inside the crystal. A few boas were visible.

〔発明の効果〕〔Effect of the invention〕

比較例１に見られるように、フッ素を含有しないＣａＯ
−Ａｌ２Ｏ３−Ｐ２Ｏ６のみの原料混合物では、ＡｈＯ
３ｆｆｉが多いと溶融が不可能であり、比較例２のよう
にフッ素を含有させると溶融は可能であるが、Ａｌ２Ｏ
３量が多いため一段階で結晶化させるとＡｌ２Ｏ３・Ｐ
２Ｏ５の結晶が十分に生成しないため内部欠陥が生じて
しまう。As seen in Comparative Example 1, fluorine-free CaO
-In the raw material mixture of only -Al2O3-P2O6, AhO
If 3ffi is too large, melting is impossible, and if fluorine is contained as in Comparative Example 2, melting is possible, but Al2O
Since the amount of 3 is large, if it is crystallized in one step, Al2O3・P
Internal defects occur because 2O5 crystals are not sufficiently produced.

ところが、実施例１にみられるように、本発明のＦ原子
を含むＣａＯ−Ａｌ２Ｏ３−ＰｚＯｓ系結晶化ガラスは
内部欠陥もなく、医用材料として最適であることを示し
ている。However, as seen in Example 1, the CaO-Al2O3-PzOs-based crystallized glass containing F atoms of the present invention has no internal defects, indicating that it is optimal as a medical material.

Claims (1)

【特許請求の範囲】[Claims] ＣａＯ１０〜６０重量％、Ａｌ＿２Ｏ＿３５〜３５重量
％、Ｐ＿２Ｏ＿５２５〜８５重量％よりなる組成の原料
混合物にＣａＯ、Ａｌ＿２Ｏ＿３およびＰ＿２Ｏ＿５の
合量１００重量部に対しＦ原子として３重量部以下を添
加し、溶融、鋳造後、ガラス質鋳造体の軟化点とリン酸
カルシウムの結晶化温度との間の温度で次第に温度を上
げながら２段階以上の結晶化処理を行なうことを特徴と
するＣａＯ−Ａｌ＿２Ｏ＿３−Ｐ＿２Ｏ＿５結晶化ガラ
スの製造方法。To a raw material mixture having a composition of 10 to 60% by weight of CaO, 35 to 35% by weight of Al_2O_, and 525 to 85% by weight of P_2O, 3 parts by weight or less of F atoms are added to 100 parts by weight of the total amount of CaO, Al_2O_3 and P_2O_5, and melted. After casting, a crystallization treatment of CaO-Al_2O_3-P_2O_5 is performed in two or more stages while gradually increasing the temperature between the softening point of the glassy cast body and the crystallization temperature of calcium phosphate. Production method.