JPS6112876B2 - - Google Patents
Info
- Publication number
- JPS6112876B2 JPS6112876B2 JP9701480A JP9701480A JPS6112876B2 JP S6112876 B2 JPS6112876 B2 JP S6112876B2 JP 9701480 A JP9701480 A JP 9701480A JP 9701480 A JP9701480 A JP 9701480A JP S6112876 B2 JPS6112876 B2 JP S6112876B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- atmosphere
- sintered body
- milky white
- color
- 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.)
- Expired
Links
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 17
- 239000001506 calcium phosphate Substances 0.000 claims description 16
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 16
- 235000011010 calcium phosphates Nutrition 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229960001714 calcium phosphate Drugs 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229960005069 calcium Drugs 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Dental Prosthetics (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
本発明は人工歯に適した乳白色を呈するリン酸
カルシウム焼結体の製造法に係る。
リン酸カルシウム粉末特に水酸アパタイト粉末
の焼結体は人工歯に用いたとき、生体との親和性
が良いが、大気中で焼結させると淡青色ないし青
紫色を呈するため、人工歯として用いるとき、外
観上違和感を生じる難があつた。一方還元性雰囲
気で焼結すれば色調は天然歯と同じになるが焼結
不十分で強度が低く、使用に耐えない難があつ
た。本発明はこれを改良し天然歯と同様な乳白色
を呈し、且つ強度も高いリン酸カルシウム焼結体
を得ることを目的とするもので、非還元性雰囲気
で焼成したリン酸カルシウム焼結体を、H2及
び／又はCOを0.05〜50重量％好ましくは１〜30
重量％含み残部がN2及び／又はArである雰囲気
中にて再焼成すること特徴とする乳白色リン酸カ
ルシウム焼結体の製造法を提供するものである。
こゝでリン酸カルシウム焼結体がなぜ淡青色な
いし青紫色を呈するかの原因は今の処不明である
が、その発色は焼結開始の約1000℃より始り、更
に焼成温度が高くなると一層濃厚となる。そこ
で、焼結度を落さず色調を乳白色とすることを鋭
意研究したところ、最初大気中又は中性雰囲気中
等の非還元性雰囲気で焼結を進め、次いでH2及
び／又はCOを0.05〜50重量％（以下「重量」を
省く）含む雰囲気、好ましくは１〜30％含む雰囲
気で再焼成すれば、焼結は進み、目的とする高強
度で、且つ乳白色の緻密な焼結体が得られること
を確かめた。こゝで再焼成する雰囲気の還元性ガ
スはH2及び／又はCOが良好であつたが、要は還
元性ガスを含むことが必要で、炭化水素、アルコ
ール等の雰囲気も同様に利用できると考えられ
る。又その含有量を0.05〜50％としたのは0.05％
以下では色調を変える効果が乏しく、50％以上で
はリン酸が還元され、やゝ赤色を帯び、これ又違
和感を生みだすものとなる。次に本発明に用いる
リン酸カルシウムの組成は、主体がリン酸カルシ
ウムであれば何れでも利用可能であるが例えば下
記の組成物がある。特開昭55−42240号公報で公
開したカルシウム／リンの原子比1.40〜1.75のカ
ルシウムのリン酸塩に0.1〜15％のリン酸を加え
た組成物、特開昭55−56062号公報で公開したカ
ルシウム／リンの原子比が1.40〜1.75のカルシウ
ムの燐酸塩に、カルシウム／リンの原子比0.2〜
0.75のフリツトを0.5〜15％加えた組成物、本出
願人により出願された特願昭53−153035（特開昭
55−80771号公報）による、カルシウムのリン酸
塩を主体とする粉末にイツトリアを３〜23％及び
カルシウム−リン酸系フリツトを加えた組成物な
らびに同じく本出願人による特願昭54−46500
（特開昭55−140756号公報）によるカルシウム／
リンの原子比1.40〜1.75のカルシウムのリン酸塩
に0.5〜15％のアルカリ金属、アルカリ土類金属
及び亜鉛の酸化物とリン酸のフリツトならびに３
〜23％のイツトリアを加えた組成物が一例として
あげられるが本発明はこれに拘ることなく、すべ
てのリン酸カルシウム系の焼結体を用いることが
できる。以下実施例により一そう具体的に説明す
る。
実施例 １
水酸アパタイト86％、Y2O39％に第１表の組成
のフリツトA5％を加えた組成物の粉末にカンフ
アー３％を適量のエーテルと共に混合して加え
The present invention relates to a method for producing a calcium phosphate sintered body exhibiting a milky white color suitable for artificial teeth. Sintered bodies of calcium phosphate powder, especially hydroxyapatite powder, have good compatibility with living organisms when used in artificial teeth, but when sintered in the atmosphere, they exhibit a pale blue to bluish-purple color, so when used as artificial teeth, There was a problem with the appearance of the product. On the other hand, if sintered in a reducing atmosphere, the color tone would be the same as natural teeth, but the sintering would be insufficient and the strength would be low, making it unusable. The purpose of the present invention is to improve this and obtain a calcium phosphate sintered body that exhibits a milky white color similar to that of natural teeth and has high strength . / or CO 0.05-50% by weight, preferably 1-30%
The object of the present invention is to provide a method for producing a milky white calcium phosphate sintered body, which is characterized in that re-firing is carried out in an atmosphere in which the balance by weight is N 2 and/or Ar. The reason why the calcium phosphate sintered body exhibits a pale blue to bluish-purple color is currently unknown, but the color begins to develop at about 1000℃ at the start of sintering, and becomes even more intense as the firing temperature increases. becomes. Therefore, we conducted intensive research on making the color milky white without reducing the degree of sintering, and found that sintering was first carried out in a non-reducing atmosphere such as air or a neutral atmosphere, and then H 2 and/or CO was added at 0.05 to If re-fired in an atmosphere containing 50% by weight (hereinafter "weight" will be omitted), preferably in an atmosphere containing 1 to 30%, sintering will proceed and the desired high strength, milky white, dense sintered body will be obtained. I made sure that it was possible. In this case, H 2 and/or CO were suitable as the reducing gas for the re-firing atmosphere, but it is necessary to contain a reducing gas, and an atmosphere containing hydrocarbons, alcohol, etc. can be used as well. Conceivable. Also, the content is 0.05% to 50%.
If it is less than 50%, the effect of changing the color tone will be poor, and if it is more than 50%, the phosphoric acid will be reduced, giving it a reddish tinge, which will also create a strange feeling. Next, regarding the composition of calcium phosphate used in the present invention, any composition can be used as long as the main component is calcium phosphate, and examples include the following compositions. A composition prepared by adding 0.1 to 15% phosphoric acid to a calcium phosphate with a calcium/phosphorus atomic ratio of 1.40 to 1.75, published in JP-A-55-42240, published in JP-A-55-56062 Calcium phosphate with a calcium/phosphorus atomic ratio of 1.40 to 1.75, and a calcium/phosphorus atomic ratio of 0.2 to 1.75.
A composition containing 0.5 to 15% of frit of
55-80771), a composition prepared by adding 3 to 23% ittria and a calcium-phosphate frit to powder mainly composed of calcium phosphate, and Japanese Patent Application No. 54-46500 also filed by the present applicant.
(Japanese Unexamined Patent Publication No. 55-140756)
Calcium phosphate with phosphorus atomic ratio 1.40-1.75, 0.5-15% alkali metal, alkaline earth metal and zinc oxides and phosphoric acid frit and 3
Although a composition containing up to 23% of ittria is given as an example, the present invention is not limited thereto, and any calcium phosphate-based sintered body can be used. A more specific explanation will be given below with reference to Examples. Example 1 3% camphor was mixed with an appropriate amount of ether and added to a powder of a composition of 86% hydroxyapatite, 9% Y 2 O 3 and 5% frit A having the composition shown in Table 1.
【表】
巾12×長さ40×厚み４mmの成型体をプレス圧800
Kg／cm2にて加圧成型し、成型体を第二表に示す焼
成条件で焼成したものの特性を同じく第二表に併
記する。[Table] A molded body of width 12 x length 40 x thickness 4 mm was pressed at a pressure of 800.
The properties of the molded products, which were molded under pressure at Kg/cm 2 and fired under the firing conditions shown in Table 2, are also listed in Table 2.
【表】
第二表に示した如く大気中焼成によるNo.1Rは
抗折強度2050Kg／cm2と高いが青色を呈し外観的に
違和感を起し又H230％とN270％中での焼成によ
るNo.2Rは乳白色であるが抗折力600Kg／cm2で強度
が低く使用に耐えるいのに対し、本発明によるNo.
３〜11は色調、抗折強度共に良好で、二次焼成雰
囲気がH2雰囲気で25％含有する所の試料である
No.10は色調が特に天然歯に酷似していた。又強度
においても二次焼成の雰囲気がH2又はCOか50％
であるNo.７とNo.11は1550Kg／cm2、1500Kg／cm2であ
るのに対し、H2及び／又はCOが３〜25％のNo.
３，４，５，６，８，９，10は強度が1960Kg／cm2
以上で強度的にも特に優れていた。[Table] As shown in Table 2, No. 1R fired in the atmosphere has a high bending strength of 2050 kg / cm2 , but exhibits a blue color and an unnatural appearance. No. 2R produced by firing is milky white but has a transverse rupture strength of 600 Kg/cm 2 and is not strong enough to withstand use.
Samples 3 to 11 have good color tone and bending strength, and the secondary firing atmosphere is an H2 atmosphere containing 25%.
The color tone of No. 10 was particularly similar to natural teeth. Also, in terms of strength, the atmosphere for secondary firing is H 2 or CO or 50%.
No. 7 and No. 11 have 1550Kg/cm 2 and 1500Kg/cm 2 , while No. 1 has 3 to 25% H 2 and/or CO.
3, 4, 5, 6, 8, 9, 10 have a strength of 1960Kg/cm 2
In view of the above, it was particularly excellent in terms of strength.
Claims (1)
焼結体を、H2及び／又はCOを0.05〜50重量％含
み残部がN2及び／又はArである雰囲気中にて再
焼成することを特徴とする乳白色リン酸カルシウ
ム焼結体の製造法。 ２ 特許請求の範囲第１項においてH2及び／又
はCOの含有量が１〜30重量％である乳白色リン
酸カルシウム焼結体の製造法。[Claims] 1. A calcium phosphate sintered body fired in a non-reducing atmosphere is re-fired in an atmosphere containing 0.05 to 50% by weight of H 2 and/or CO and the balance being N 2 and/or Ar. A method for producing a milky white calcium phosphate sintered body. 2. A method for producing a milky white calcium phosphate sintered body as set forth in claim 1, wherein the content of H 2 and/or CO is 1 to 30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9701480A JPS5722168A (en) | 1980-07-16 | 1980-07-16 | Manufacture of milkwhite calcium phosphate sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9701480A JPS5722168A (en) | 1980-07-16 | 1980-07-16 | Manufacture of milkwhite calcium phosphate sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5722168A JPS5722168A (en) | 1982-02-05 |
| JPS6112876B2 true JPS6112876B2 (en) | 1986-04-10 |
Family
ID=14180476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9701480A Granted JPS5722168A (en) | 1980-07-16 | 1980-07-16 | Manufacture of milkwhite calcium phosphate sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5722168A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0158373U (en) * | 1987-10-09 | 1989-04-12 |
-
1980
- 1980-07-16 JP JP9701480A patent/JPS5722168A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0158373U (en) * | 1987-10-09 | 1989-04-12 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5722168A (en) | 1982-02-05 |
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