JPH02243560A - Polycrystal alumina ceramics for living body - Google Patents
Polycrystal alumina ceramics for living bodyInfo
- Publication number
- JPH02243560A JPH02243560A JP1064296A JP6429689A JPH02243560A JP H02243560 A JPH02243560 A JP H02243560A JP 1064296 A JP1064296 A JP 1064296A JP 6429689 A JP6429689 A JP 6429689A JP H02243560 A JPH02243560 A JP H02243560A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- polycrystal
- alumina ceramics
- content
- polycrystalline
- 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.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000919 ceramic Substances 0.000 title abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 1
- 230000000254 damaging effect Effects 0.000 abstract 1
- 230000004663 cell proliferation Effects 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000013065 commercial product Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000003462 bioceramic Substances 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000010261 cell growth Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 206010067482 No adverse event Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野コ
本発明は緻密に焼結可能で生体親和性に優れる生体用多
結晶アルミナセラミックスに関する。本発明は、人工骨
、人工関節、人工歯根等として人体に直接、埋火又は接
触させて使用し生体機能の回復及び増強を図るアルミナ
セラミックスを提供することを目的とする。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to polycrystalline alumina ceramics for biological use that can be sintered densely and have excellent biocompatibility. An object of the present invention is to provide alumina ceramics that can be used as artificial bones, artificial joints, artificial tooth roots, etc. by being directly implanted or in contact with the human body to restore and enhance biological functions.
生体用アルミナセラミックスとして高純度のアルミナ原
料を耐熱容器内に入れて真空中で溶融させることにより
約９９．９％程度の高純度アルミナ単結晶よりなる人工
骨用等の生体セラミックスが知られている（特公昭６１
−９０７４号公報等）。また、アルミナ多結晶生体セラ
ミックスとしては、アルミナ含有量が５０〜９５％とＺ
ｒＯ２等からなる骨内インブラント用焼成セラミックス
組成物が知られている（特公昭５１−３９６５４号公報
）。Bioceramics for use in artificial bones, etc., are known as alumina ceramics for biological use, which are made of a single crystal of high-purity alumina of approximately 99.9% by placing a high-purity alumina raw material in a heat-resistant container and melting it in a vacuum. (Tokuko Showa 61
-9074 publication, etc.). In addition, as alumina polycrystalline bioceramics, Z
A fired ceramic composition for intraosseous implants made of rO2 and the like is known (Japanese Patent Publication No. 39654/1983).
更に、電子部品等の分野において高純度アルミナセラミ
ックとして、Ａｊ！＊Ｏｓ ５ｉｎｓ ＭｇＯの３
成分系からなりＡＪ２０コ９９，７〜９９．９重量％含
有する高周波誘電損失の小さなもの（特公昭６３−６６
７９５号公報）、ＡｌｚＯｙ Ｃａ ＯＭ ｇ Ｏの
３成分系からなりＡ ｆ ｘ ０．９９．６〜９９．９
重量％含有する高層２Ｉｌｌ！Ｑ値が高いもの（特開昭
６１−１１８９０５号公報）が知られている。Furthermore, Aj! is a high-purity alumina ceramic used in the field of electronic components. *3 of Os 5ins MgO
A material with low high-frequency dielectric loss containing 99.7 to 99.9% by weight of AJ20 (Japanese Patent Publication No. 63-66
No. 795), it consists of a three-component system of AlzOy Ca OM g O, and A f x 0.99.6 to 99.9.
High rise containing % by weight 2Ill! A material with a high Q value (Japanese Patent Application Laid-Open No. 118905/1983) is known.
上記第１の生体用アルミナセラミックスにおいては、高
アルミナ含を量であるが単結晶に関するものである。一
方、多結晶アルミナについては高純度アルミナとなると
焼結させることが困難となるため、はとんど検討されて
いない。検討されているのは、いずれも上記第２の骨内
インブラント用のもののようにアルミナ純度の低いもの
ばかりである。The first biomedical alumina ceramic has a high alumina content but is a single crystal. On the other hand, polycrystalline alumina has not been studied because it is difficult to sinter high-purity alumina. All of the materials under consideration are those with low alumina purity, such as the second one for intraosseous implants mentioned above.
一方、上記電子部品等に利用されるアルミナセラミック
スは製法からみて多結晶アルミナからなる。しかし、こ
れを長期間生体内で使用する場合には、生体に悪影響を
及ぼさないことが重要であるが、どのような組成のアル
ミナセラミックスが生体に適するかについては言及され
ていない。On the other hand, the alumina ceramics used in the electronic components and the like are made of polycrystalline alumina in terms of manufacturing method. However, if this is to be used in vivo for a long period of time, it is important that the alumina ceramics have no adverse effects on the organism, but there is no mention of what composition of alumina ceramics is suitable for the organism.
本発明は、上記問題点を解消するとともに、種々検討の
結果、ある組成の高純度多結晶アルミナが細胞増殖に極
めて優れることを新たに見出してなされたものであり、
緻密な焼結体が得られかつ生体為害性がなく生体親和性
に極めて優れる生体用多結晶アルミナセラミックスを提
供することを目的とする。The present invention has been made by solving the above-mentioned problems and by newly discovering, as a result of various studies, that high-purity polycrystalline alumina of a certain composition is extremely excellent in cell proliferation.
It is an object of the present invention to provide polycrystalline alumina ceramics for living organisms that can yield a dense sintered body, are not harmful to living organisms, and have extremely excellent biocompatibility.
本発明の生体用多結晶アルミナセラミックスは、酸化ア
ルミニウム（以下、アルミナという）の含有量が９９．
５〜９９．９重量％（以下、単に％という）であり残部
がＭｇ５Ｃａ、５ｒＳＢａＳｃ、Ｙ、Ｌａ及びＣｅから
選択される一種以上の酸化物及び不可避不純物からなり
多結晶焼結体からなることを特徴とする。The polycrystalline alumina ceramic for biological use of the present invention has an aluminum oxide (hereinafter referred to as alumina) content of 99.
5 to 99.9% by weight (hereinafter simply referred to as %), and the remainder is composed of one or more oxides selected from Mg5Ca, 5rSBaSc, Y, La, and Ce and unavoidable impurities, and is made of a polycrystalline sintered body. Features.
本発明者等は、種々検討の結果、アルミナ含有量が９９
．５％以上の多結晶アルミナセラミックスが細胞増殖に
極めて優れること、これを緻密に焼結させるためには、
易焼結性でかつより高純度のアルミナ原料を使用し、適
当な助剤を選択すればよいことという新たな知見を得た
。As a result of various studies, the present inventors found that the alumina content was 99%.
．． Polycrystalline alumina ceramics with a content of 5% or more are extremely good for cell growth, and in order to sinter them densely,
We obtained new knowledge that it is sufficient to use an alumina raw material that is easily sinterable and of higher purity, and to select an appropriate auxiliary agent.
即ち、上記組成にすれば細胞増殖のみならず緻密で高強
度で、更に生体為害性もない焼結体を得ることができる
。That is, by using the above composition, it is possible to obtain a sintered body that not only promotes cell proliferation but also is dense, has high strength, and is not harmful to living organisms.
上記のようにアルミナ含有量を９９．５％以上とするの
は、細胞培養による増殖が優れ、ひいては生体親和性が
極めて優れるからである。特に、アルミナ含有量が９９
．７％以上の場合は、更に良好な細胞増殖を得ることが
できる。更に、Ｍｇ、Ｃａ５Ｓｒ、Ｂａ、５ｃＳＹ、Ｌ
ａ及びＣｅの酸化物の少なくとも一種とするのは、アル
ミナの焼結助剤として優れるとともに生体為害性がほと
んどないからでもある。The reason why the alumina content is set to 99.5% or more as described above is that the growth by cell culture is excellent, and as a result, the biocompatibility is extremely excellent. In particular, the alumina content is 99%
．． If it is 7% or more, even better cell proliferation can be obtained. Furthermore, Mg, Ca5Sr, Ba, 5cSY, L
The reason why at least one of the oxides of a and Ce is used is because it is excellent as a sintering aid for alumina and is hardly harmful to living organisms.
一方、アルミナ含有量の上限を９９．９％とするのは、
９９．９％を越える場合は細胞増殖の一層の優位性が得
られず安定して焼結することが困難なこと、９９，５〜
９９．９％の範囲内であれば目的とする多結晶体が得ら
れることのｔこめである。On the other hand, the upper limit of alumina content is 99.9%.
If it exceeds 99.9%, it is difficult to obtain a further advantage in cell proliferation and to perform stable sintering; 99.5~
If it is within the range of 99.9%, it is highly likely that the desired polycrystalline material will be obtained.
更に、この焼結体の原料調製から焼成までの製造工程に
おいて、不可避不純物が混入する危険性があるが、細胞
増殖が安定して良好となるためには、この総混入量が０
．１％以下が好ましい。また、使用するアルミナの平均
粒径は０．１〜１μ程度のものが、易焼結性及び製造容
易性の点で好ましい。焼成温度は１２５０〜１６５０℃
の範囲が好ましく、更に粒成長を極力抑えて十分緻密化
させ、かつ強度を保持するためためには１３５０〜１５
００℃の範囲がより好ましい。Furthermore, there is a risk that unavoidable impurities may be mixed in during the manufacturing process of this sintered body, from raw material preparation to firing.
．． It is preferably 1% or less. Further, the average particle size of the alumina used is preferably about 0.1 to 1 μm from the viewpoint of easy sinterability and ease of manufacture. Firing temperature is 1250-1650℃
A range of 1350 to 15 is preferable, and in order to suppress grain growth as much as possible, achieve sufficient densification, and maintain strength.
A range of 00°C is more preferable.
以下、実施例により本発明を具体的に説明する。 Hereinafter, the present invention will be specifically explained with reference to Examples.
アルミナ（純度９９．９９９％、平均粒径０゜５μ）、
炭酸マグネシウム（市販品、試薬特級）、炭酸カルシウ
ム（市販品、試薬特級）、炭酸ストロンチウム（市販品
、試薬特級）、炭酸バリウム（市販品、試薬特級）、酸
化スカンジウム（市販品、試薬特級）、酸化イツトリウ
ム（市販品、試薬特級）、酸化ランタン（市販品、試薬
特級）、酸化セリウム（市販品、試薬特級）及び酸化ニ
ッケル（Ｎ ｉ Ｏ）の１０種を、そのうちの炭酸塩４
種を各々ＭｇＯ１ＣａＯ１ＳｒＯ１３ａ○に換算して、
含量で各々１ｋｇとなるように、表の各割合に秤量し、
混合する。その後その混合物に各々水ＩＩｌ、ポリビニ
ルアルコール５ｇ１ポリエチレングリコール５ｇを配合
し、内容債２１のポリエチレンポットと純度９９．９９
５％のアルミナ原石２ｋｇを用いて４８時間混合した。Alumina (purity 99.999%, average particle size 0°5μ),
Magnesium carbonate (commercial product, special grade reagent), calcium carbonate (commercial product, special grade reagent), strontium carbonate (commercial product, special grade reagent), barium carbonate (commercial product, special grade reagent), scandium oxide (commercial product, special grade reagent), Ten types of yttrium oxide (commercial product, special grade reagent), lanthanum oxide (commercial product, special grade reagent), cerium oxide (commercial product, special grade reagent), and nickel oxide (N i O), 4 of which are carbonates
Convert each species to MgO1CaO1SrO13a○,
Weigh each proportion in the table so that the content is 1 kg each,
Mix. After that, water III, polyvinyl alcohol 5g, and polyethylene glycol 5g were added to the mixture, and a polyethylene pot with a content of 21 and a purity of 99.99 was added.
2 kg of 5% alumina raw stone was mixed for 48 hours.
これにより得られた１９種類のスラリーを凍結乾燥し、
その後６０メツシユの篩によって造粒した。The resulting 19 types of slurry were freeze-dried,
Thereafter, it was granulated using a 60 mesh sieve.
この造粒粉末を１５００ｋｇ／ｃｍ”の金型ブレスによ
って所定の寸法に成形し、空気炉１２５０〜１６００℃
、１時間の焼成を行って焼結体を得た。この焼結体の化
学成分の分析値、密度、曲げ強度及び３日後の細胞数の
結果を表に示した。This granulated powder was molded into a specified size using a 1500 kg/cm" mold press, and heated in an air oven at 1250 to 1600°C.
A sintered body was obtained by firing for 1 hour. The analytical values of chemical components, density, bending strength, and cell count after 3 days of this sintered body are shown in the table.
Ｎα１〜Ｎα１４は本発明品、Ｎα１５〜ｋ ｌ ９は
比較例である。Nα1 to Nα14 are products of the present invention, and Nα15 to kl9 are comparative examples.
曲げ強度は３Ｘ４Ｘ４０ｍｍの焼結体を用い、ＪＩＳＲ
１６０１に準じて測定した。細胞増殖は３７℃、３，１
ｍｊ！培地中に２．８Ｘ１０’ Ｃｅ１ｌ／ｍｌの細胞
濃度で播種し、１日毎に試料上の細胞数を計測した。尚
、細胞としてＬ−９２９を用いた。The bending strength is JISR using a 3X4X40mm sintered body.
Measured according to 1601. Cell growth at 37℃, 3,1
mj! The cells were seeded in the culture medium at a cell concentration of 2.8 x 10' Ce1l/ml, and the number of cells on the sample was counted every day. Note that L-929 was used as the cell.
表に示すように、アルミナ含有量が９９．５％以上でか
つＭｇＯ１ＣａＯ，５ｒＯ１ＢａＯ，ＳＣ２０ｓ 、Ｙ
２０３、Ｌａ２０ｚ及びＣｅ Ｏ２の少なくとも一種を
添加した場合（Ｎα１〜１４）はいずれも、通常の焼成
条件にて３． ９２ ｇ／ｃｍ’上の良好に緻密な焼結
体を得ることができ、曲げ強度が５２ Ｋｇ／…ｍ２以
上であり９８．４％を含有する場合（Ｎα１７）と比べ
て同等またはそれ以上であり、更に、細胞増殖が９９．
３％以下の場合（Ｎα１５〜＋８）と比べると良好な生
体親和性を示した。As shown in the table, the alumina content is 99.5% or more and MgO1CaO, 5rO1BaO, SC20s, Y
203, La20z, and CeO2 (Nα1 to 14) were all 3.2% under normal firing conditions. A highly dense sintered body with a bending strength of 92 g/cm' or higher can be obtained, and the bending strength is equal to or higher than that of the case containing 98.4% (Nα17). Yes, and cell proliferation was 99.
It showed good biocompatibility compared to the case where it was 3% or less (Nα15 to +8).
尚、ＮｉＯを添加しアルミナ含有量が９９，６％の場合
（Ｎα１９）はアルミナ含有量が本発明範囲に含まれる
に係わらず曲げ強度及び細胞増殖率は良くなかった。こ
の生型の添加においても細胞増殖の低下を来たす点にお
いて、上記本発明組成範囲のものとの差が大きいことを
示している。更に、このＮｉは生体為害性の点でも問題
があり、一方上記ＣａＯ等はその心配がない。In addition, when NiO was added and the alumina content was 99.6% (Nα19), the bending strength and cell proliferation rate were not good even though the alumina content was within the range of the present invention. This shows that there is a large difference from the above-mentioned composition range of the present invention in that the addition of this live form also causes a decrease in cell proliferation. Furthermore, this Ni has a problem in terms of being harmful to living organisms, whereas the above-mentioned CaO and the like do not have this concern.
本発明は、高アルミナ含有量でＭｇ等の所定の添加剤を
所定量配合することにより、多結晶焼結体でも緻密で高
強度で生体為害がない焼結体を製造でき、かつこの焼結
体の細胞増殖率が極めて優れる。従って、本焼結体は生
体に大変好ましいものである。The present invention makes it possible to produce a dense, high-strength, and non-hazardous sintered body even in a polycrystalline sintered body by blending a predetermined amount of a predetermined additive such as Mg with a high alumina content. The cell proliferation rate of the body is extremely high. Therefore, this sintered body is very preferable to living organisms.
Claims (1)
重量％であり残部がＭｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ
、Ｌａ及びＣｅから選択される一種以上の酸化物及び不
可避不純物からなり多結晶焼結体からなることを特徴と
する生体用多結晶アルミナセラミックス。(1) Aluminum oxide content is 99.5 to 99.9
% by weight and the balance is Mg, Ca, Sr, Ba, Sc, Y
A polycrystalline alumina ceramic for biological use, characterized in that it is a polycrystalline sintered body comprising one or more oxides selected from , La, and Ce, and inevitable impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1064296A JP2579212B2 (en) | 1989-03-16 | 1989-03-16 | Polycrystalline alumina ceramic for living body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1064296A JP2579212B2 (en) | 1989-03-16 | 1989-03-16 | Polycrystalline alumina ceramic for living body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02243560A true JPH02243560A (en) | 1990-09-27 |
| JP2579212B2 JP2579212B2 (en) | 1997-02-05 |
Family
ID=13254139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1064296A Expired - Fee Related JP2579212B2 (en) | 1989-03-16 | 1989-03-16 | Polycrystalline alumina ceramic for living body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2579212B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265816B1 (en) * | 1998-04-30 | 2001-07-24 | Ngk Spark Plug Co., Ltd. | Spark plug, insulator for spark plug and process for fabricating the insulator |
| JP2006076857A (en) * | 2004-09-13 | 2006-03-23 | National Institute Of Advanced Industrial & Technology | Alumina-boron nitride composite and method for producing the same |
| US7295318B2 (en) | 2001-07-09 | 2007-11-13 | Mitsui Mining & Smelting Co., Ltd. | Apparatus and method for evaluating the interior quality of fruits and vegetables |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62260766A (en) * | 1986-05-08 | 1987-11-13 | 東レ株式会社 | Alumina sintered body |
| JPS63174646A (en) * | 1987-01-12 | 1988-07-19 | 住友化学工業株式会社 | Orthodontic material |
| JPH0211135A (en) * | 1988-06-29 | 1990-01-16 | Kobe Steel Ltd | Production of artificial bone |
-
1989
- 1989-03-16 JP JP1064296A patent/JP2579212B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62260766A (en) * | 1986-05-08 | 1987-11-13 | 東レ株式会社 | Alumina sintered body |
| JPS63174646A (en) * | 1987-01-12 | 1988-07-19 | 住友化学工業株式会社 | Orthodontic material |
| JPH0211135A (en) * | 1988-06-29 | 1990-01-16 | Kobe Steel Ltd | Production of artificial bone |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265816B1 (en) * | 1998-04-30 | 2001-07-24 | Ngk Spark Plug Co., Ltd. | Spark plug, insulator for spark plug and process for fabricating the insulator |
| US7295318B2 (en) | 2001-07-09 | 2007-11-13 | Mitsui Mining & Smelting Co., Ltd. | Apparatus and method for evaluating the interior quality of fruits and vegetables |
| JP2006076857A (en) * | 2004-09-13 | 2006-03-23 | National Institute Of Advanced Industrial & Technology | Alumina-boron nitride composite and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2579212B2 (en) | 1997-02-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |