JP3498112B2 - Synthetic pearl nuclei for cultured pearls and their production - Google Patents
Synthetic pearl nuclei for cultured pearls and their productionInfo
- Publication number
- JP3498112B2 JP3498112B2 JP06644995A JP6644995A JP3498112B2 JP 3498112 B2 JP3498112 B2 JP 3498112B2 JP 06644995 A JP06644995 A JP 06644995A JP 6644995 A JP6644995 A JP 6644995A JP 3498112 B2 JP3498112 B2 JP 3498112B2
- Authority
- JP
- Japan
- Prior art keywords
- pearl nucleus
- raw material
- synthetic pearl
- synthetic
- firing
- 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 - Fee Related
Links
- 239000011049 pearl Substances 0.000 title claims description 108
- 239000010984 cultured pearl Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 62
- 239000002994 raw material Substances 0.000 claims description 46
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000010521 absorption reaction Methods 0.000 claims description 34
- 239000001569 carbon dioxide Substances 0.000 claims description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 31
- 238000010304 firing Methods 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 26
- -1 carbonate compound Chemical class 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 20
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 13
- 239000001095 magnesium carbonate Substances 0.000 claims description 13
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 13
- 150000002642 lithium compounds Chemical class 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 241000490567 Pinctada Species 0.000 description 8
- 238000009360 aquaculture Methods 0.000 description 7
- 244000144974 aquaculture Species 0.000 description 7
- 235000015170 shellfish Nutrition 0.000 description 7
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 241000237536 Mytilus edulis Species 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 235000020638 mussel Nutrition 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000012258 culturing Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000011050 natural pearl Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000020636 oyster Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
- Y02A40/81—Aquaculture, e.g. of fish
Landscapes
- Farming Of Fish And Shellfish (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、養殖真珠に使用する合
成真珠核及びその製造法に関し、更に詳細には、天然貝
から作製した天然真珠核に代わって、安定供給すること
ができる養殖真珠用合成真珠核及びその製造法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic pearl nucleus used for cultured pearls and a method for producing the same, and more specifically, a cultured pearl that can be stably supplied in place of a natural pearl nucleus prepared from natural shellfish. For synthetic pearl nucleus and its manufacturing method.
【０００２】[0002]
【従来の技術】従来の養殖真珠は、天然の貝殻を研削、
研磨し、約３〜１０ｍｍφの球に形成して真珠核とし、
他の貝から採取した外套の小片（ピース）と共に、例え
ばアコヤ貝、シロチョウ貝、クロチョウ貝、マベ貝、イ
ケチョウ貝、アワビ等の母貝に挿入し、半年から３年間
養殖して真珠核に真珠膜を形成させることによって生産
されている。2. Description of the Related Art Conventional cultured pearls are made by grinding natural shells,
Polished and formed into spheres with a diameter of about 3 to 10 mm to form a pearl nucleus,
It is inserted into mother shells such as pearl oysters, white pearl oysters, black pearl oysters, mabe mussels, mussel pearl oysters, and abalone along with small pieces of cloaks collected from other oysters. It is produced by forming a film.
【０００３】現在養殖真珠核としては、主にアメリカ合
衆国産或いは中国産のどぶ貝を使用して作成されてい
る。しかしこのような天然貝を真珠核とする場合、例え
ば１０ｍｍφ前後の大きい真珠核を作成するには肉厚の
厚いどぶ貝が必要であり、１個のどぶ貝から採取し得る
真珠核には制限がある。またどぶ貝は部分的に着色して
いたり、欠陥がある場合があり、必ずしも良好な品質の
真珠核が得られるとは限らない。従って養殖真珠の品質
にもばらつきが生じ易いのが現状である。更に天然貝の
生産は、天候等の自然環境に左右されるため、安定した
供給が困難である。At present, cultured pearl nuclei are produced mainly from the United States or Chinese dough shells. However, when such a natural shellfish is used as a pearl nucleus, for example, a thick mussel shell is required to create a large pearl nucleus of about 10 mmφ, and the pearl core that can be collected from one pearl shell is limited. There is. In addition, the mussels may be partially colored or have defects, and thus a pearl nucleus of good quality is not always obtained. Therefore, the quality of cultured pearls is likely to vary at present. Furthermore, the production of natural shellfish depends on the natural environment such as the weather, so it is difficult to supply it in a stable manner.
【０００４】このような天然貝からの真珠核の問題点を
解決するために、人工的に合成する合成真珠核の開発が
多数提案されている。例えば特開昭４８−５２５９４号
公報、特開昭６０−２５９１３５号公報、特開昭６３−
２１９３２５号公報等には、炭酸カルシウム、真珠粉、
サンゴ粉、甲殻類の甲殻粉及び無機顔料を合成樹脂と混
合し、球形に成形した真珠核が提案されている。また特
公平２−１２５３７号公報には、快削性結晶化ガラスか
らなる合成真珠核が、特開平４−１１７２２８号公報、
特開平４−３２５０４０号公報等には、セラミック製の
合成真珠核が、実開昭５０−７５９９号公報、特開昭５
９−３１６３６号公報、特開昭５９−２０３４３６号公
報、実開昭６１−１３９６１７号公報、特開平２−１７
４６２１号公報には、真珠核の表面にコーティングを施
して作成された合成真珠核が提案されている。In order to solve the problems of the pearl nucleus from such natural shellfish, many developments of synthetic pearl nucleus artificially synthesized have been proposed. For example, JP-A-48-52594, JP-A-60-259135, and JP-A-63-
No. 219325 discloses calcium carbonate, pearl powder,
A pearl nucleus formed by mixing coral powder, crustacean shell powder and an inorganic pigment with a synthetic resin to form a spherical shape has been proposed. Further, Japanese Patent Publication No. 2-12537 discloses a synthetic pearl nucleus made of free-cutting crystallized glass, which is disclosed in Japanese Patent Laid-Open No. 4-117228.
Japanese Patent Application Laid-Open No. 4-325040 discloses a synthetic pearl nucleus made of ceramics, which is disclosed in Japanese Utility Model Application Laid-Open No. 50-7599 and Japanese Patent Application Laid-Open No.
9-31636, JP-A-59-203436, JP-A-61-139617, JP-A-2-17.
Japanese Patent No. 4621 proposes a synthetic pearl nucleus prepared by coating the surface of the pearl nucleus.
【０００５】前記種々の提案は、前記どぶ貝から作成さ
れる真珠核が、通常炭酸カルシウムの一結晶形態である
カルサイト結晶がコラーゲンによって結合した緻密の組
織から成り、嵩密度２．７ｇ／ｃｍ3、モース硬度３〜
４であることに基づいて、このような物性に近似する合
成品の作成を目的として開発がなされている。The above various proposals suggest that the pearl nucleus formed from the above-mentioned mussel has a dense structure in which calcite crystals, which are usually one crystal form of calcium carbonate, are bound by collagen, and has a bulk density of 2.7 g / cm 3. 3 , Mohs hardness 3 ~
Based on the fact that it is 4, the development has been made for the purpose of producing a synthetic product having such physical properties.
【０００６】しかしながら、従来提案されているいずれ
の合成真珠核も実際には良好な真珠膜を形成することは
もとより、養殖中に合成真珠核を母貝が吐き出してしま
い（脱離）、商業的な実施はなされていないのが現状で
ある。即ち、真珠の養殖においては、母貝が合成真珠核
を異物として認識した場合、脱離が生じ、合成真珠核に
良好な真珠膜が形成されるまで母貝内に保持させること
ができていないのがほとんどである。However, in addition to the fact that any of the synthetic pearl nuclei proposed hitherto actually form a good nacre, the mother pearls spit out (eliminate) the synthetic pearl nuclei during aquaculture, which is a commercial problem. The current situation is that no such implementation has been done. That is, in the cultivation of pearls, when the mother shellfish recognizes the synthetic pearl nucleus as a foreign substance, detachment occurs and it cannot be retained in the mother pearl until a good nacre is formed in the synthetic pearl nucleus. Most of them.
【０００７】[0007]
【発明が解決しようとする課題】従って本発明の目的
は、従来の天然真珠核を使用して養殖した養殖真珠と同
等以上の高品質な真珠を効率良く得ることが可能であっ
て、しかも１０ｍｍ径を超える大きな真珠核であっても
安定供給することができる養殖用合成真珠核を提供する
ことにある。本発明の別の目的は、前記養殖用合成真珠
核を安定的にしかも容易に製造することができる養殖用
合成真珠核の製造法を提供することにある。Therefore, an object of the present invention is to efficiently obtain high-quality pearls having a quality equal to or higher than that of cultured pearls cultivated using a conventional natural pearl nucleus, and further to obtain a pearl having a diameter of 10 mm. It is to provide a synthetic pearl nucleus for aquaculture that can stably supply even a large pearl nucleus that exceeds the diameter. Another object of the present invention is to provide a method for producing a synthetic pearl nucleus for aquaculture, which can stably and easily produce the synthetic pearl nucleus for aquaculture.
【０００８】[0008]
【課題を解決するための手段】本発明によれば、炭酸カ
ルシウム及び／又は炭酸マグネシウムからなる炭酸化合
物９５．０〜９９．５重量％と、該炭酸化合物の焼結助
剤として作用しうるリチウム化合物０．５〜５．０重量
％とからなる主原材料を含む原材料を用いて焼成した焼
結体から構成され、嵩密度が２．５〜２．９ｇ／ｃ
ｍ3、吸水率が３％以下であることを特徴とする養殖真
珠用合成真珠核が提供される。また本発明によれば、前
記養殖真珠用合成真珠核の製造法であって、炭酸カルシ
ウム及び／又は炭酸マグネシウムからなる炭酸化合物９
５．０〜９９．５重量％と、該炭酸化合物の焼結助剤と
して作用しうるリチウム化合物０．５〜５．０重量％と
からなる主原材料を含む原材料を所望形状に成型した
後、炭酸ガス分圧下で５２５℃以上、９００℃未満℃に
おいて焼成する工程と、研磨加工する工程とを行うこと
を特徴とする養殖真珠用合成真珠核の製造法が提供され
る。According to the present invention, 95.0 to 99.5% by weight of a carbonate compound composed of calcium carbonate and / or magnesium carbonate, and lithium capable of acting as a sintering aid of the carbonate compound. It is composed of a sintered body that is fired using a raw material containing a main raw material composed of 0.5 to 5.0% by weight of the compound, and has a bulk density of 2.5 to 2.9 g / c.
There is provided a synthetic pearl nucleus for cultured pearls, which is characterized by having m 3 and a water absorption rate of 3% or less. Further, according to the present invention, there is provided a method for producing the synthetic pearl nucleus for cultured pearls, comprising a carbonic acid compound 9 comprising calcium carbonate and / or magnesium carbonate.
After molding a raw material containing a main raw material composed of 5.0 to 99.5% by weight and a lithium compound 0.5 to 5.0% by weight capable of acting as a sintering aid of the carbonate compound into a desired shape, Provided is a method for producing a synthetic pearl nucleus for cultured pearls, which comprises performing a step of firing at a temperature of 525 ° C. or higher and lower than 900 ° C. under a partial pressure of carbon dioxide and a step of polishing.
【０００９】以下本発明を更に詳細に説明する。本発明
の養殖真珠用合成真珠核は、炭酸カルシウム及び／又は
炭酸マグネシウムからなる炭酸化合物に、該炭酸化合物
の焼結助剤として作用しうるリチウム化合物とを特定割
合で組み合わせて主原材料として採用し、該主原材料を
含む原材料を用いて焼成した焼結体から構成され、嵩密
度２．５〜２．９ｇ／ｃｍ3、吸水率３％以下を示すも
のである。本発明ではこのような構成により、従来提案
されている合成真珠核のような真珠養殖時における脱離
等の可能性が十分に防止され、高品質の真珠の生産が可
能となる。また形状及び大きさも所望に応じて生産する
ことができる。The present invention will be described in more detail below. The synthetic pearl nucleus for cultured pearls of the present invention is used as a main raw material by combining a carbonate compound composed of calcium carbonate and / or magnesium carbonate with a lithium compound that can act as a sintering aid of the carbonate compound in a specific ratio. It is composed of a sintered body obtained by firing a raw material including the main raw material, and has a bulk density of 2.5 to 2.9 g / cm 3 and a water absorption rate of 3% or less. According to the present invention, with such a configuration, it is possible to sufficiently prevent the possibility of detachment at the time of pearl cultivation, such as the conventionally proposed synthetic pearl nucleus, and it is possible to produce high quality pearls. The shape and size can also be produced as desired.
【００１０】本発明の養殖用合成真珠核において、嵩密
度が前記範囲外の場合には、母貝との生体的な馴染みが
低下し、養殖中に真珠核の母貝からの脱離が生じ、真珠
膜形成の歩留りが悪くなる。また吸水率が３％を超える
場合にも、母貝との生体的な馴染みが低下して同様な欠
点が生じる。更に吸水率が３％を超える場合、真珠核に
真珠膜が形成された場合にも、該真珠膜にクラックが生
じ、真珠としての価値が低下する。When the bulk density of the synthetic pearl nucleus for aquaculture of the present invention is out of the above range, the biological familiarity with the pearl oyster is reduced, and the pearl nucleus is detached from the pearl pearl during the culture. , The yield of nacre formation becomes worse. Also, when the water absorption rate exceeds 3%, the biological familiarity with the mother oysters deteriorates and the same drawbacks occur. Further, when the water absorption rate exceeds 3%, even when a nacre is formed in the nacreous nucleus, cracks occur in the nacre and the value as a pearl decreases.
【００１１】前記主原材料として用いる炭酸カルシウム
及び／又は炭酸マグネシウムからなる炭酸化合物の含有
割合が、主原材料中９５．０〜９９．５重量％で、リチ
ウム化合物の含有割合が０．５〜５．０重量％である。
炭酸カルシウム及び炭酸マグネシウムは、焼成時にリチ
ウム化合物が焼成助剤として作用することによって、合
成真珠核として好ましい形態（天然貝に近似したカルサ
イト構造）に焼結成形される。炭酸化合物の含有割合が
主原材料中９９．５重量％を超える場合、即ちリチウム
化合物が０．５重量％未満の場合には、炭酸化合物の焼
結性が十分でなく、得られる吸水率が大きくなり、一方
炭酸化合物が９５．０重量％未満、即ちリチウム化合物
が５．０重量％を超える場合には、焼成時に炭酸化合物
の結晶成長が進行し過ぎて吸水率が大きくなり、母貝と
の生体的な馴染みが低下する恐れがある。また炭酸カル
シウムと炭酸マグネシウムとの両方を使用する場合の各
成分の配合割合は、得られる合成真珠核の嵩密度が前記
範囲内となれば特に限定されず、適宜選択することがで
きる。前記炭酸化合物としては、平均粒径０．３〜３．
０μｍのものを使用するのが好ましい。The content ratio of the carbonate compound composed of calcium carbonate and / or magnesium carbonate used as the main raw material is 95.0 to 99.5% by weight in the main raw material, and the content ratio of the lithium compound is 0.5 to 5. It is 0% by weight.
Calcium carbonate and magnesium carbonate are sinter-molded into a preferable form (calcite structure similar to natural shellfish) as a synthetic pearl nucleus by the lithium compound acting as a firing aid during firing. When the content ratio of the carbonic acid compound exceeds 99.5% by weight in the main raw material, that is, when the lithium compound is less than 0.5% by weight, the sinterability of the carbonic acid compound is insufficient and the obtained water absorption rate is large. On the other hand, when the carbonic acid compound is less than 95.0% by weight, that is, when the lithium compound exceeds 5.0% by weight, the crystal growth of the carbonic acid compound progresses excessively during firing and the water absorption rate becomes large, and The biological familiarity may be reduced. Further, when both calcium carbonate and magnesium carbonate are used, the mixing ratio of each component is not particularly limited as long as the bulk density of the obtained synthetic pearl nucleus is within the above range, and can be appropriately selected. The carbonic acid compound has an average particle size of 0.3 to 3.
It is preferable to use one having a thickness of 0 μm.
【００１２】前記リチウム化合物としては、フッ化リチ
ウム、炭酸リチウム、リン酸リチウム等を挙げることが
でき、好ましくは粒径０．３〜２．０μｍのものを使用
するのが望ましい。Examples of the lithium compound include lithium fluoride, lithium carbonate, lithium phosphate and the like, and those having a particle size of 0.3 to 2.0 μm are preferably used.
【００１３】本発明の合成真珠核においては、原材料と
して前記主原材料の他に、副原材料として酸化アルミニ
ウム、酸化珪素、酸化錫、酸化チタン、酸化亜鉛、酸化
セリウム又はこれらの混合物等の金属酸化物を更に含有
させることもできる。これらの金属酸化物の配合割合
は、それぞれの真比重を考慮して、得られる真珠核の嵩
密度が前記範囲内となるように配合すれば特に限定され
るものではないが、好ましくは前記主原材料１００重量
部に対して３０重量部以下が望ましい。In the synthetic pearl nucleus of the present invention, in addition to the main raw material as a raw material, a metal oxide such as aluminum oxide, silicon oxide, tin oxide, titanium oxide, zinc oxide, cerium oxide or a mixture thereof as a sub raw material. Can be further contained. The blending ratio of these metal oxides is not particularly limited as long as it is blended so that the bulk density of the obtained pearl nucleus is within the above range in consideration of the true specific gravity of each, but preferably the above main 30 parts by weight or less is desirable for 100 parts by weight of the raw material.
【００１４】本発明の合成真珠核は、前記原材料を焼成
した焼結体から実質的に構成されるが、この焼結体は必
ずしも吸水率が前記範囲の３％以下である必要はなく、
最終的に得られる合成真珠核の吸水率が３％以下であれ
ば良い。例えば合成真珠核を用いて養殖した真珠を装飾
品に加工する場合には、穴開け加工等を行う必要が有る
が、一般に前記主原材料を含む原材料の焼結では、焼結
が進むに従って硬度が増加するため、前記穴開け加工が
困難となる恐れが有る。そこで合成真珠核のモース硬度
を３〜４に調整するのが好ましいが、このようなモース
硬度に調整する場合、本発明においては、例えば前記焼
結を得られる焼結体の吸水率が１〜１５％程度になる焼
結程度に留め、得られた焼結体に、例えばポリエルテル
樹脂、エポキシ樹脂、コラーゲン等の有機物を含浸さ
せ、該有機物を硬化させて前記嵩密度の範囲内におい
て、吸水率を低下させ、最終的に得られる合成真珠核の
吸水率を３％以下とする方法等により行うことができ
る。前記有機物の含浸及び硬化については、後述する製
造法において詳述する。The synthetic pearl nucleus of the present invention is substantially composed of a sintered body obtained by firing the above raw materials, but the sintered body does not necessarily have a water absorption rate of 3% or less of the above range.
The water absorption of the finally obtained synthetic pearl nucleus may be 3% or less. For example, when processing pearls cultivated using a synthetic pearl nucleus into ornaments, it is necessary to perform drilling, etc.In general, in the sintering of raw materials including the main raw materials, the hardness increases as the sintering progresses. Since the number of holes increases, there is a possibility that the boring process becomes difficult. Therefore, it is preferable to adjust the Mohs hardness of the synthetic pearl nucleus to 3 to 4, but when adjusting to such a Mohs hardness, in the present invention, for example, the water absorption of the sintered body that can obtain the above-mentioned sintering is 1 to 1. The resulting sintered body is impregnated with an organic substance such as polyelter resin, epoxy resin, collagen, etc., and the organic substance is cured to obtain a water absorption rate within the range of the bulk density. And the water absorption of the finally obtained synthetic pearl nucleus is 3% or less. The impregnation and curing of the organic substance will be described in detail in the production method described later.
【００１５】本発明の合成真珠核は、従来の天然真珠核
と同様に養殖するための貝に導入し養殖することによっ
て、真珠を得ることができる。A pearl can be obtained by introducing the synthetic pearl nucleus of the present invention into a shell for aquaculture as in the case of a conventional natural pearl nucleus and culturing.
【００１６】本発明の合成真珠核の製造法では、まず前
記主原材料を含む原材料を球状等の所望形状に成型す
る。この際成型は通常の球状等の所望形状の型枠を用い
た加圧成型等により実施でき、成型にあたっては、通常
の有機バインダーを添加することもできる。In the method for producing a synthetic pearl nucleus of the present invention, first, raw materials including the main raw material are molded into a desired shape such as a sphere. At this time, the molding can be performed by pressure molding using a mold having a desired shape such as a normal spherical shape, and a normal organic binder can be added in the molding.
【００１７】次に本発明の合成真珠核の製造法では、前
記所望形状の成型物を焼成して焼結体を調製する。この
際前記主原材料としての炭酸化合物は、大気雰囲気中に
おいて５２５℃を超える温度で焼成した場合分解が生
じ、得られる焼結体中に酸化カルシウム及び／又は酸化
マグネシウムが多く含有されて、海水等に浸漬するとア
ルカリ成分が溶出し、良好な合成真珠核が得られない恐
れがある。一方５２５℃以下の焼成のみでは、焼結が十
分でなく、所望の嵩密度及び吸水率とするのが困難であ
る。そこで本発明の製造法では、炭酸化合物の分解温度
を高温に移行することができ、且つ十分な焼結を進行さ
せるために、炭酸ガス分圧下において５２５℃以上、９
００℃未満で、好ましくは５２５〜８００℃で焼成する
工程を採用する。５２５℃未満では焼結が十分進行せ
ず、９００℃を超えると焼成時の圧力を１気圧を超える
圧力とする必要が有り、特殊な圧力焼成炉が必要となる
ばかりでなく、エネルギー効率も低下する。Next, in the method for producing a synthetic pearl nucleus of the present invention, the molded product having the desired shape is fired to prepare a sintered body. At this time, the carbonic acid compound as the main raw material is decomposed when fired at a temperature higher than 525 ° C. in the air atmosphere, and the obtained sintered body contains a large amount of calcium oxide and / or magnesium oxide, and seawater etc. If soaked in, the alkaline component may elute and a good synthetic pearl nucleus may not be obtained. On the other hand, sintering only at 525 ° C. or lower is not sufficient for sintering, and it is difficult to achieve desired bulk density and water absorption. Therefore, in the production method of the present invention, the decomposition temperature of the carbonic acid compound can be shifted to a high temperature, and in order to promote sufficient sintering, the carbon dioxide gas partial pressure is 525 ° C. or higher,
A step of firing at less than 00 ° C, preferably 525 to 800 ° C is adopted. If the temperature is lower than 525 ° C, the sintering does not proceed sufficiently, and if the temperature is higher than 900 ° C, the pressure during firing needs to be higher than 1 atm, which requires not only a special pressure firing furnace but also lower energy efficiency. To do.
【００１８】前記炭酸ガス分圧下とは、炭酸ガス雰囲気
中又は炭酸ガスと、空気、水蒸気等との混合ガス雰囲気
中のいずれであっても良い。この際炭酸ガス分圧下の焼
成時の圧力は、１気圧以下が好ましい。実質的には前述
のとおり１気圧を超える圧力とし、温度を９００℃以上
とすることで実施可能であるが、工業的には問題が有
る。具体的には、前記炭酸化合物が分解を開始する炭酸
ガス分圧が、６００℃で０．００５気圧、７００℃で
０．０６気圧、８００℃で０．５気圧、（９００℃で
２．８気圧）であるので、これらの圧力を超える炭酸ガ
ス圧力下で焼成すれば十分である。このような焼成は、
雰囲気調整可能な通常の電気炉、ガス焼成炉、石油焼成
炉等の焼成炉を用いて実施することができ、炭酸ガス分
圧下にする方法としては、炭酸ガスを焼成炉内に流入さ
せる方法、カーボン等の炭酸ガス発生材料を焼成炉内に
設置する方法等のいずれであっても良い。特にガス焼成
炉又は石油焼成炉を採用する場合には、炭酸ガス濃度を
１０％程度に調整するのが好ましい。この炭酸ガス分圧
下における焼成時間は、焼成温度及び焼成炉内の圧力に
応じて適宜選択できるが、好ましくは１〜４８時間で行
うことができる。The term "under the partial pressure of carbon dioxide gas" may be either in a carbon dioxide gas atmosphere or in a mixed gas atmosphere of carbon dioxide gas and air, steam or the like. At this time, the pressure during firing under the partial pressure of carbon dioxide is preferably 1 atm or less. It can be practically carried out by setting the pressure to exceed 1 atm and the temperature to 900 ° C. or higher as described above, but this is industrially problematic. Specifically, the carbon dioxide partial pressure at which the carbonic acid compound starts to decompose is 0.005 atm at 600 ° C., 0.06 atm at 700 ° C., 0.5 atm at 800 ° C. (2.8 at 900 ° C.). Atmospheric pressure), it suffices to perform firing under carbon dioxide gas pressure exceeding these pressures. Such firing is
It can be carried out using a calcining furnace such as a normal electric furnace capable of adjusting the atmosphere, a gas calcining furnace, and a petroleum calcining furnace, and as a method of reducing the carbon dioxide partial pressure, a method of flowing carbon dioxide into the calcining furnace, Any method such as setting a carbon dioxide generating material such as carbon in the firing furnace may be used. Particularly when a gas firing furnace or a petroleum firing furnace is adopted, it is preferable to adjust the carbon dioxide gas concentration to about 10%. The firing time under the partial pressure of carbon dioxide can be appropriately selected depending on the firing temperature and the pressure in the firing furnace, but it is preferably 1 to 48 hours.
【００１９】また前記炭酸ガス分圧かにおける焼成工程
の前に、あらかじめ大気雰囲気下で５２５℃以下におい
て仮焼する工程を行うのが好ましい。この仮焼工程の時
間は１〜６時間が望ましい。Further, it is preferable to carry out a preliminary calcination step at 525 ° C. or lower in an air atmosphere before the calcination step in the partial pressure of carbon dioxide gas. The time for this calcination step is preferably 1 to 6 hours.
【００２０】次に本発明の合成真珠核の製造法では、前
記焼成工程で得られた焼結体を、通常の研磨加工する工
程により、所望の粒度に調整することによって合成真珠
核とすることができる。この研磨加工の前に、前記焼結
体の吸水率が３％を超え、若しくは３％以下であっても
更に吸水率を低下させたい場合には、前述のとおり、焼
結体の細孔内等に有機物を含浸させ、該有機物を硬化さ
せることにより、嵩密度２．５〜２．９ｇ／ｃｍ3の範
囲内において、吸水率を低下させることもできる。Next, in the method for producing a synthetic pearl nucleus of the present invention, the sintered body obtained in the above-mentioned firing step is adjusted to a desired particle size by a usual polishing process to obtain a synthetic pearl nucleus. You can Before the polishing, if it is desired to further reduce the water absorption rate even if the water absorption rate of the sintered body exceeds 3% or is 3% or less, as described above, It is also possible to lower the water absorption within the range of the bulk density of 2.5 to 2.9 g / cm 3 by impregnating the above with an organic substance and curing the organic substance.
【００２１】前記有機物を焼結体に含浸させるには、例
えば焼結体と有機物とを容器に入れ、好ましくは１ｍｍ
Ｈｇ以下となるように真空脱気し、その後、好ましくは
１０００ｋｇ／ｃｍ2以上で加圧する方法等により、所
望量の有機物を焼結体に含浸させることができる。この
際含浸させる有機物の量は、焼結体の細孔及び気孔率等
によって変化し、また含浸率は、加圧時の圧力調整及び
加圧時間を調整することによって変化させることがで
き、所望の嵩密度及び吸水率、更には所望のモース硬度
となるように適宜選択して行うことができる。また含浸
された有機物の硬化は、通常４０〜１８０℃にて、３０
分〜２４時間の条件で実施するのが好ましい。In order to impregnate the sintered body with the organic substance, for example, the sintered body and the organic substance are put in a container, and preferably 1 mm.
The sintered body can be impregnated with a desired amount of organic matter by a method such as vacuum degassing to Hg or less, and then applying pressure preferably at 1000 kg / cm 2 or more. At this time, the amount of the organic substance to be impregnated changes depending on the pores and porosity of the sintered body, and the impregnation ratio can be changed by adjusting the pressure during pressing and the pressing time. The bulk density and the water absorption rate of the above can be appropriately selected so that the desired Mohs hardness can be obtained. Further, the curing of the impregnated organic substance is usually performed at 40 to 180 ° C. for 30
It is preferably carried out under the condition of minutes to 24 hours.
【００２２】[0022]
【発明の効果】本発明の養殖真珠用合成真珠核は、焼結
助剤として作用しうるリチウム化合物を、炭酸カルシウ
ム及び／又は炭酸マグネシウムからなる炭酸化合物と特
定割合で組み合わせ、主原材料として用いて焼成した焼
結体から構成され、しかも嵩密度２．５〜２．９ｇ／ｃ
ｍ3、吸水率３％以下に調整したものであるので、表面
外観、色相、光沢に優れ、しかも養殖時の貝との生体適
合性に優れている。従って従来提案されている合成真珠
核のような真珠養殖時における脱離等の可能性が十分に
防止され、高品質の真珠の生産が可能となり、装飾真珠
としても十分使用できる。INDUSTRIAL APPLICABILITY The synthetic pearl nucleus for cultured pearls of the present invention is used as a main raw material by combining a lithium compound capable of acting as a sintering aid with a carbonate compound composed of calcium carbonate and / or magnesium carbonate in a specific ratio. Composed of a fired sintered body, and has a bulk density of 2.5 to 2.9 g / c
Since m 3, is obtained by adjusting the following water absorption 3%, surface appearance, color, excellent gloss, yet has excellent biocompatibility with shellfish during aquaculture. Therefore, the possibility of detachment at the time of culturing pearls such as the synthetic pearl nucleus which has been proposed so far is sufficiently prevented, high quality pearls can be produced, and the pearls can be sufficiently used as decorative pearls.
【００２３】また本発明の製造法では、前記養殖真珠用
合成真珠核を安定的に且つ容易に製造することができ、
主原材料の配合割合等により容易に焼結形態を制御する
ことができる。しかも１０ｍｍ径を超える大きい真珠核
の生産も容易であるので、真珠核を工業的に安定に供給
することができる。In the production method of the present invention, the synthetic pearl nucleus for cultured pearls can be produced stably and easily,
The sintering form can be easily controlled by the mixing ratio of the main raw materials. Moreover, since it is easy to produce a large pearl nucleus having a diameter of more than 10 mm, it is possible to stably supply the pearl nucleus industrially.
【００２４】[0024]
【実施例】以下実施例及び比較例により更に詳細に説明
するが、本発明はこれらに限定されるものではない。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited thereto.
【００２５】[0025]
【実施例１】炭酸カルシウム（（株）カルシード製、商
品名「高純度炭酸カルシウムＣＳ」）９８重量部及びフ
ッ化リチウム（片山化学工業（株）製、試薬特級、商品
名「18-1490-56」）２重量部を原材料とし、該原材料
に、バインダー樹脂としてポリエチレングリコール（Ｐ
ＥＧ）（片山化学工業（株）製、商品名「ポリエチレン
グリコール1000 24-3640-51」）１０重量％を含む水溶
液２０ｍｌを加え、乳鉢で十分均一になるまで混合し
た。次いで６００ｋｇ／ｃｍ2の圧力で、直径１０ｍｍ
の球形にプレス成形した。得られた球形の成形体を、雰
囲気調整可能な電気炉で、大気雰囲気において５０℃／
時間の割合で５２５℃まで昇温仮焼した。次に５２５℃
に到達した時点で炭酸ガス（ＣＯ2）を４リットル／
分、空気１リットル／分の流量の混合ガスを電気炉内に
注入し、１時間保持した後、１０℃／時間の割合で７０
０℃まで昇温して６時間保持した。炉内は大気圧とし、
炭酸ガス分圧は０．８気圧であった。その後５０℃／時
間の割合で５００℃まで降温し、５００℃以降は室温ま
で放冷して焼結体を得た。得られた焼結体を研磨加工
し、直径６．０ｍｍ、真球度５／１００、表面粗さ１０
μｍの合成真珠核を作製した。[Example 1] 98 parts by weight of calcium carbonate (manufactured by Calceed Co., Ltd., trade name "high-purity calcium carbonate CS") and lithium fluoride (manufactured by Katayama Chemical Co., Ltd., reagent grade, trade name "18-1490-" 56 ") 2 parts by weight as a raw material, and polyethylene glycol (P
EG) (Katayama Chemical Co., Ltd., trade name "Polyethylene glycol 1000 24-3640-51") 20 ml of an aqueous solution containing 10 wt% was added and mixed in a mortar until sufficiently homogeneous. Then, at a pressure of 600 kg / cm 2 , a diameter of 10 mm
Was pressed into a spherical shape. The obtained spherical molded body was heated at 50 ° C. in an air atmosphere in an electric furnace capable of adjusting the atmosphere.
The temperature was raised to 525 ° C. and calcined at a rate of time. Then 525 ° C
At the time when the temperature reaches to 4 liters of carbon dioxide (CO 2 ) /
Min, air mixed gas with a flow rate of 1 liter / min was injected into the electric furnace and held for 1 hour, and then 70 ° C at a rate of 10 ° C / hour.
The temperature was raised to 0 ° C. and kept for 6 hours. Atmospheric pressure in the furnace,
The carbon dioxide partial pressure was 0.8 atm. Thereafter, the temperature was lowered to 500 ° C. at a rate of 50 ° C./hour, and after 500 ° C., the temperature was allowed to cool to room temperature to obtain a sintered body. The obtained sintered body was polished to a diameter of 6.0 mm, a sphericity of 5/100, and a surface roughness of 10.
A μm synthetic pearl nucleus was prepared.
【００２６】得られた合成真珠核について、嵩密度、吸
水率をＪＩＳ Ｃ２１４１により測定し、外観、色相、
光沢を目視で評価した。結果を表２に示す。尚、外観、
色相及び光沢の評価は以下の規準に従って行った。
外観：○；良好、×；汚れや凹凸が確認できる
色相：○；白色、×；色むらがある
光沢：○；艶が有り良好、×；艶なしThe bulk density and water absorption of the obtained synthetic pearl nucleus were measured according to JIS C2141, and the appearance, hue,
The gloss was visually evaluated. The results are shown in Table 2. The appearance,
The hue and gloss were evaluated according to the following criteria. Appearance: ○; good, ×; stains and unevenness can be confirmed: ○; white, ×; uneven color, gloss: ○; glossy, good, ×; no gloss
【００２７】[0027]
【実施例２及び３】原材料として表１に示す組成を用い
た以外は実施例１と同様に合成真珠核を得、それぞれの
測定及び評価を実施例１と同様に行った。結果を表２に
示す。Examples 2 and 3 Synthetic pearl nuclei were obtained in the same manner as in Example 1 except that the compositions shown in Table 1 were used as raw materials, and the respective measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 2.
【００２８】[0028]
【実施例４〜９】原材料として表１に示す組成を用い、
電気炉内での炭酸ガス注入後の昇温温度７００℃を８０
０℃に（実施例４、５、６、８及び９）又は６００℃に
（実施例７）変えた以外は、実施例１と同様に合成真珠
核を得、それぞれの測定及び評価を実施例１と同様に行
った。結果を表２に示す。Examples 4 to 9 The compositions shown in Table 1 were used as raw materials,
After heating carbon dioxide in the electric furnace, raise the temperature to 700 ℃
A synthetic pearl nucleus was obtained in the same manner as in Example 1 except that the temperature was changed to 0 ° C. (Examples 4, 5, 6, 8 and 9) or 600 ° C. (Example 7), and each measurement and evaluation were carried out in Examples. The same procedure as 1 was performed. The results are shown in Table 2.
【００２９】[0029]
【比較例１〜３】原材料として表１に示す組成を用い、
５２５℃到達後の電気炉内への炭酸ガス注入を行わず、
大気雰囲気のまま５２５℃で４８時間保持して焼成した
以外は、実施例１と同様に合成真珠核を得、それぞれの
測定及び評価を実施例１と同様に行った。結果を表２に
示す。[Comparative Examples 1 to 3] Using the compositions shown in Table 1 as raw materials,
Do not inject carbon dioxide gas into the electric furnace after reaching 525 ° C,
A synthetic pearl nucleus was obtained in the same manner as in Example 1 except that the pearl nucleus was baked in the atmosphere at 525 ° C. for 48 hours, and each measurement and evaluation were performed in the same manner as in Example 1. The results are shown in Table 2.
【００３０】[0030]
【比較例４及び５】原材料として表１に示す組成を用
い、５２５℃到達後の電気炉内への炭酸ガス注入を行わ
ず、大気雰囲気のまま１０℃／時間の割合で６００℃に
昇温し、この温度にて６時間保持して焼成した以外は、
実施例１と同様に合成真珠核を得、それぞれの測定及び
評価を実施例１と同様に行った。結果を表２に示す。[Comparative Examples 4 and 5] Using the compositions shown in Table 1 as raw materials, carbon dioxide gas was not injected into the electric furnace after reaching 525 ° C, and the temperature was raised to 600 ° C at a rate of 10 ° C / hour in the air atmosphere. However, except for holding at this temperature for 6 hours and firing,
A synthetic pearl nucleus was obtained in the same manner as in Example 1, and each measurement and evaluation were performed in the same manner as in Example 1. The results are shown in Table 2.
【００３１】[0031]
【比較例６及び７】原材料として表１に示す組成を用
い、電気炉内での炭酸ガス注入後の昇温温度７００℃を
６００℃に変えた以外は、実施例１と同様に合成真珠核
を得、それぞれの測定及び評価を実施例１と同様に行っ
た。結果を表２に示す。[Comparative Examples 6 and 7] A synthetic pearl nucleus was prepared in the same manner as in Example 1 except that the composition shown in Table 1 was used as a raw material and the temperature rising temperature of 700 ° C after the carbon dioxide gas injection in the electric furnace was changed to 600 ° C. And each measurement and evaluation were performed in the same manner as in Example 1. The results are shown in Table 2.
【００３２】[0032]
【比較例８及び９】原材料として表１に示す組成を用
い、電気炉内での炭酸ガス注入後の昇温温度７００℃を
８００℃に（比較例８）又は９００℃に（比較例９）に
変えた以外は、実施例１と同様に合成真珠核を得、それ
ぞれの測定及び評価を実施例１と同様に行った。結果を
表２に示す。[Comparative Examples 8 and 9] Using the compositions shown in Table 1 as raw materials, the temperature rise temperature after carbon dioxide gas injection in an electric furnace was 700 ° C to 800 ° C (Comparative Example 8) or 900 ° C (Comparative Example 9). A synthetic pearl nucleus was obtained in the same manner as in Example 1 except that the above was changed to, and each measurement and evaluation were performed in the same manner as in Example 1. The results are shown in Table 2.
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【表２】 [Table 2]
【００３５】[0035]
【実施例１０】炭酸カルシウム５９．５０重量部、炭酸
マグネシウム４０重量部及び炭酸リチウム（片山化学工
業（株）製、試薬特級、商品名「18-1390-51」）０．５
０重量部を原材料として、該原材料１００重量部にバイ
ンダー樹脂としてポリビニルアルコール（ＰＶＡ）（片
山化学工業（株）製、商品名「ポリビニルアルコール110
0 24-3750-51」）２重量部及び水３０重量部を加え、乳
鉢で十分均一になるまで混合した。次いで６００ｋｇ／
ｃｍ2の圧力で、直径１０ｍｍの球形にプレス成形し
た。得られた球形の成形体を、雰囲気調整可能な電気炉
で、大気雰囲気において５０℃／時間の割合で５２５℃
まで昇温仮焼した。次に５２５℃に到達した時点で炭酸
ガス（ＣＯ2）を５リットル／分の流量で電気炉内に注
入し、１時間保持した。炭酸ガス分圧は約１気圧であっ
た。その後、１０℃／時間の割合で８００℃まで昇温し
て６時間保持した。その後５０℃／時間の割合で５００
℃まで降温し、５００℃以降は室温まで放冷して焼結体
を得た。Example 10 Calcium carbonate 59.50 parts by weight, magnesium carbonate 40 parts by weight and lithium carbonate (Katayama Chemical Co., Ltd., reagent special grade, trade name "18-1390-51") 0.5
With 0 parts by weight as the raw material, polyvinyl alcohol (PVA) as a binder resin in 100 parts by weight of the raw material (Katayama Chemical Industry Co., Ltd., trade name "Polyvinyl alcohol 110"
0 24-3750-51 ") 2 parts by weight and 30 parts by weight of water were added and mixed in a mortar until sufficiently homogeneous. Next 600 kg /
It was pressed into a spherical shape having a diameter of 10 mm with a pressure of cm 2 . The obtained spherical molded body was 525 ° C. at a rate of 50 ° C./hour in an air atmosphere in an electric furnace capable of adjusting the atmosphere.
The temperature was raised to calcination. Next, when the temperature reached 525 ° C., carbon dioxide gas (CO 2 ) was injected into the electric furnace at a flow rate of 5 liters / minute, and held for 1 hour. The carbon dioxide partial pressure was about 1 atm. Then, the temperature was raised to 800 ° C. at a rate of 10 ° C./hour and kept for 6 hours. Then 500 at a rate of 50 ° C / hour
The temperature was lowered to ℃, and after 500 ℃ it was allowed to cool to room temperature to obtain a sintered body.
【００３６】得られた焼結体を実施例１と同様にして合
成真珠核とし、実施例１と同様に各測定及び評価を行っ
た。結果を表４に示す。The obtained sintered body was used as a synthetic pearl nucleus in the same manner as in Example 1, and each measurement and evaluation were performed in the same manner as in Example 1. The results are shown in Table 4.
【００３７】[0037]
【実施例１１〜１３、比較例１０及び１１】原材料とし
て表３に示す組成を用いた以外は実施例１０と同様に合
成真珠核を得（比較例１０）、また原材料として表３に
示す組成を用い、電気炉内での炭酸ガス注入後の昇温温
度８００℃を７００℃に変えた以外は、実施例１０と同
様に合成真珠核を得（実施例１１〜１３及び比較例１
１）、それぞれの測定及び評価を実施例１と同様に行っ
た。結果を表４に示す。[Examples 11 to 13 and Comparative Examples 10 and 11] Synthetic pearl cores were obtained in the same manner as in Example 10 except that the composition shown in Table 3 was used as the raw material (Comparative Example 10), and the composition shown in Table 3 was used as the raw material. Was used, and a synthetic pearl nucleus was obtained in the same manner as in Example 10 except that the temperature rising temperature after carbon dioxide gas injection in the electric furnace was changed to 700 ° C (Examples 11 to 13 and Comparative Example 1).
1) and each measurement and evaluation were performed like Example 1. The results are shown in Table 4.
【００３８】[0038]
【表３】 [Table 3]
【００３９】[0039]
【表４】 [Table 4]
【００４０】[0040]
【実施例１４】炭酸カルシウム９８重量部及びフッ化リ
チウム２重量部を主原材料とし、酸化チタン２０重量部
を副原材料として、該原材料にバインダーとしてシリカ
ゾル（触媒化成工業（株）製、商品名「カタロイド Ｓ
Ｉ−３」）１０重量％を含む水溶液２０ｍｌを加え、乳
鉢で十分均一になるまで混合した。次いで６００ｋｇ／
ｃｍ2の圧力で、直径１０ｍｍの球形にプレス成形し
た。得られた球形の成形体を、ガス窯で、天然ガスを燃
料として、５２５℃までは酸素濃度約１５％の雰囲気で
１００℃／時間で昇温し、５２５℃に到達後、酸素濃度
約５％、炭酸ガス濃度約１０％（分圧０．１気圧）で１
時間保持した後、５０℃／時間の割合で６５０℃まで昇
温し、６時間保持した。その後、５０℃／時間の割合で
５００℃まで、燃焼を継続しながら（炭酸ガス分圧０．
１気圧）、５０℃／時間の割合で降温し、５００℃以降
は室温まで放冷して焼結体を得た。Example 14 98 parts by weight of calcium carbonate and 2 parts by weight of lithium fluoride were used as main raw materials, and 20 parts by weight of titanium oxide was used as a secondary raw material. A silica sol (manufactured by Catalysts & Chemicals Industry Co., Ltd., trade name " Cataloid S
20 ml of an aqueous solution containing 10% by weight of (I-3 ") was added and mixed in a mortar until sufficiently homogenous. Next 600 kg /
It was pressed into a spherical shape having a diameter of 10 mm with a pressure of cm 2 . The obtained spherical molded body was heated in a gas kiln at 100 ° C./hour in an atmosphere with an oxygen concentration of about 15% up to 525 ° C. using natural gas as a fuel, and after reaching 525 ° C., an oxygen concentration of about 5% was reached. %, Carbon dioxide concentration of about 10% (partial pressure 0.1 atm) 1
After holding for a time, the temperature was raised to 650 ° C. at a rate of 50 ° C./hour and held for 6 hours. Then, while continuing combustion at a rate of 50 ° C./hour up to 500 ° C. (carbon dioxide partial pressure of 0.
(1 atm), the temperature was lowered at a rate of 50 ° C./hour, and after 500 ° C., the temperature was allowed to cool to room temperature to obtain a sintered body.
【００４１】得られた焼結体を実施例１と同様に合成真
珠核とし、実施例１と同様な測定及び評価を行った。結
果を表６に示す。Using the obtained sintered body as a synthetic pearl nucleus in the same manner as in Example 1, the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 6.
【００４２】[0042]
【実施例１５〜２０】主原材料及び副原材料として表５
に示す組成を用いた以外は実施例１４と同様に合成真珠
核を得、それぞれの測定及び評価を実施例１と同様に行
った。結果を表６に示す。Examples 15 to 20 Table 5 as main raw materials and auxiliary raw materials
A synthetic pearl nucleus was obtained in the same manner as in Example 14 except that the composition shown in 1 was used, and each measurement and evaluation were performed in the same manner as in Example 1. The results are shown in Table 6.
【００４３】[0043]
【比較例１２〜１６】主原材料及び副原材料として表５
に示す組成を用い、ガス窯内での炭酸ガス注入後の昇温
温度６５０℃を７００℃に変えた以外は実施例１４と同
様に合成真珠核を得、それぞれの測定及び評価を実施例
１と同様に行った。結果を表６に示す。[Comparative Examples 12 to 16] Table 5 as main raw materials and sub raw materials
A synthetic pearl nucleus was obtained in the same manner as in Example 14 except that the temperature rise temperature of 650 ° C. after the carbon dioxide gas injection in the gas kiln was changed to 700 ° C. by using the composition shown in FIG. I went the same way. The results are shown in Table 6.
【００４４】尚、表５中の成分は以下のものを使用し
た。
酸化チタン：片山化学工業（株）製、試薬１級、商品名
「30-2740-51」
酸化アルミニウム：昭和電工（株）製、商品名「細粒ア
ルミナＡ−４３−Ｍ」
酸化セリウム：片山化学工業（株）製、試薬１級、商品
名「05-2330-51」
酸化亜鉛：片山化学工業（株）製、試薬特級、商品名
「37-0470-51」
酸化錫：片山化学工業（株）製、化学用、商品名「30-2
610-51」The following components were used in Table 5. Titanium oxide: Katayama Chemical Co., Ltd., reagent first grade, trade name "30-2740-51" Aluminum oxide: Showa Denko KK, trade name "fine-grained alumina A-43-M" Cerium oxide: Katayama Chemical Industry Co., Ltd., reagent grade 1, product name “05-2330-51” Zinc oxide: Katayama Chemical Industry Co., Ltd., reagent grade, product name “37-0470-51” Tin oxide: Katayama Chemical industry ( Ltd., for chemicals, trade name "30-2
610-51 "
【００４５】[0045]
【表５】 [Table 5]
【００４６】[0046]
【表６】 [Table 6]
【００４７】以上の結果より、炭酸カルシウムを比較的
に真比重の大きい炭酸マグネシウムに置換すると、嵩比
重は増加し、リチウム化合物の割合によって焼結性が異
なり、リチウム化合物の割合が０．５〜５．０重量％の
範囲で、吸水率が３％以下となるが、０．５重量％より
少ないと焼結不足により吸水率が大きくなり、また５．
０重量％を超えると炭酸化合物の結晶成長が進行して吸
水率が大きくなることが判る。焼成温度が高くなると吸
水率が小さくなる傾向にあり、焼結が進行していること
が判るが、空気雰囲気で焼結温度を５２５〜６００℃に
した場合には吸水率が大きくなり、炭酸カルシウムある
いは炭酸マグネシウムの分解が生じていると推定され
る。焼結温度が８００℃である実施例９の吸水率が０．
２％であるのに対して、同一配合組成で焼結温度が９０
０℃である比較例９の吸水率が４．８％であることか
ら、焼結温度が９００℃になると吸水率が大きくなる傾
向が見られ、炭酸ガス雰囲気が１気圧以下では、炭酸カ
ルシウムあるいは炭酸マグネシウムの分解が生じる領域
になったと考えられる。From the above results, when calcium carbonate is replaced with magnesium carbonate having a relatively large true specific gravity, the bulk specific gravity increases, the sinterability varies depending on the proportion of the lithium compound, and the proportion of the lithium compound is 0.5 to. In the range of 5.0% by weight, the water absorption rate becomes 3% or less, but if it is less than 0.5% by weight, the water absorption rate becomes large due to insufficient sintering.
It can be seen that when the content exceeds 0% by weight, the crystal growth of the carbonate compound proceeds to increase the water absorption. The water absorption tends to decrease as the firing temperature increases, and it can be seen that the sintering is progressing. However, when the sintering temperature is set to 525 to 600 ° C. in the air atmosphere, the water absorption increases and the calcium carbonate increases. Alternatively, it is presumed that magnesium carbonate is decomposed. The water absorption rate of Example 9 in which the sintering temperature is 800 ° C. is 0.
2%, the sintering temperature is 90 with the same composition.
Since the water absorption rate of Comparative Example 9 at 0 ° C. is 4.8%, the water absorption rate tends to increase at a sintering temperature of 900 ° C. When the carbon dioxide gas atmosphere is 1 atm or less, calcium carbonate or It is considered that this is the region where the decomposition of magnesium carbonate occurs.
【００４８】[0048]
【実施例２１及び比較例１７】表７に示す前記実施例及
び比較例で作製した合成真珠核を、アコヤ貝に挿入し、
海中で約半年間養殖した。その後真珠を取り出し、表面
外観、色相及び光沢を目視で観察し、真珠膜の接着性並
びに１１０℃加熱後、真珠膜の形態を観察した。また真
珠膜の接着性を観察するために、真珠断面の微構造を電
子顕微鏡により測定した。結果を表７に示す。尚、外
観、色相及び光沢、更には真珠断面の微構造の評価は以
下の規準に従って行った。
外観：○；良好、×；汚れ又は凹凸が確認できる。[Example 21 and Comparative Example 17] The synthetic pearl cores prepared in the above Examples and Comparative Examples shown in Table 7 were inserted into pearl oysters,
It was cultivated in the sea for about half a year. Thereafter, the pearls were taken out, and the surface appearance, hue and gloss were visually observed, and the pearl morphology was observed after the adhesion of the pearl membranes and heating at 110 ° C. Moreover, in order to observe the adhesiveness of the nacre, the microstructure of the pearl cross section was measured by an electron microscope. The results are shown in Table 7. The appearance, hue and gloss, and the microstructure of the pearl cross section were evaluated according to the following criteria. Appearance: Good; good; stains or irregularities can be confirmed.
【００４９】色相：○；白色、×；色むらがある
光沢：○；艶が有り良好、×；艶なし
真珠断面の微構造：○；クラックなし、△；一部クラッ
ク有り、×；クラック有りHue: ○; white, ×; uneven color, gloss: ○: glossy and good, ×: matte pearl cross-section microstructure: ○: no crack, Δ: partially cracked, ×: cracked
【００５０】[0050]
【表７】 [Table 7]
【００５１】[0051]
【比較例１８】比較例３、４、１０、１１及び１４で作
製した合成真珠核を実施例２１と同様に、アコヤ貝に挿
入し、海中で養殖したところ、いずれも養殖中に合成真
珠核の脱離が生じ、真珠膜の形成ができなかった。Comparative Example 18 The synthetic pearl nuclei produced in Comparative Examples 3, 4, 10, 11 and 14 were inserted into pearl oysters and cultured in the sea as in Example 21, and all of them were synthetic pearl nuclei during culture. Desorption occurred, and the nacre could not be formed.
【００５２】[0052]
【実施例２２及び比較例１９】表８に示す前記実施例及
び比較例で作製した焼結体に、表８に示す有機物を含浸
させ硬化させた。得られた硬化物を研磨加工し、実施例
１と同様に合成真珠核を作製し、また実施例２１と同様
に真珠の養殖を行って各測定及び評価をした。結果を表
８に示す。Example 22 and Comparative Example 19 The organic materials shown in Table 8 were impregnated and cured in the sintered bodies prepared in the above-mentioned Examples and Comparative Examples shown in Table 8. The obtained cured product was subjected to polishing, a synthetic pearl nucleus was prepared in the same manner as in Example 1, and pearls were cultured in the same manner as in Example 21 for each measurement and evaluation. The results are shown in Table 8.
【００５３】尚、有機物の含浸は、まず焼結体と有機物
とを容器に入れ、１ｍｍＨｇ以下になるように真空脱気
し、次に１５００ｋｇ／ｃｍ2で加圧して、１０分間保
持し有機物を焼結体に含浸させ、その後焼結体を取り出
して焼結体同士又は焼結体と容器が有機物により接合し
ないように配置し、容器を表８に示す硬化温度で２４時
間加熱して硬化させた。In the impregnation of the organic substance, first, the sintered body and the organic substance are put into a container, vacuum degassing is performed so that the pressure becomes 1 mmHg or less, and then the pressure is applied at 1500 kg / cm 2 to hold the organic substance for 10 minutes. The sintered body is impregnated, and then the sintered body is taken out and arranged so that the sintered bodies or the sintered body and the container are not joined by an organic substance, and the container is heated at the curing temperature shown in Table 8 for 24 hours to cure. It was
【００５４】[0054]
【表８】 [Table 8]
【００５５】表８より有機物を含浸させると、空隙が樹
脂で充填された分だけ嵩密度が増加し、吸水率が低下さ
せることができることが判る。これらを真珠養殖した結
果、吸水率が３．０％以下に減少し、嵩密度が２．５〜
２．９ｇ／ｃｍ3であるものは良好な外観で、良好な真
珠膜を形成するが、有機物を含浸しても吸水率が３％を
超えるものあるいは嵩密度が２．５ｇ／ｃｍ3未満の場
合は、真珠養殖中に脱離が生じ、真珠膜を形成すること
ができないことが判る。It can be seen from Table 8 that when the organic substance is impregnated, the bulk density is increased by the amount of the voids filled with the resin, and the water absorption can be reduced. As a result of culturing these pearls, the water absorption rate is reduced to 3.0% or less, and the bulk density is 2.5-
Those having 2.9 g / cm 3 have a good appearance and form a good nacre, but have water absorption of more than 3% or a bulk density of less than 2.5 g / cm 3 even when impregnated with an organic substance. In this case, it can be seen that desorption occurs during pearl cultivation and the nacre cannot be formed.
【００５６】[0056]
【実施例２３】実施例８と同様な組成を、直径１２ｍｍ
の金型で、６００ｋｇ／ｃｍ2の圧力で成形して球と
し、実施例８と同様な条件で焼成した。焼成収縮率は約
１５％で、直径１０．２ｍｍの焼結球が得られた。吸水
率は０．７％、嵩密度２．７ｇ／ｃｍ3で、白色で良好
な表面状態であった。次いで得られた焼結球を研磨加工
し、直径８．０ｍｍ、真球度５／１００、表面粗さ１０
μｍの球とし、アコヤ貝に挿入し、海中で約１年間養殖
した。その後、真珠を取り出し、表面外観、色相、光沢
を目視により観察した。その結果、白色で良好な外観の
真珠膜が形成されていた。また真珠断面の微構造を電子
顕微鏡で観察した結果も合成真珠核と真珠膜の境界には
クラック等の欠陥は認められず、良好な真珠膜が観察さ
れた。Example 23 The same composition as in Example 8 was used, with a diameter of 12 mm.
The mold was molded into a sphere with a pressure of 600 kg / cm 2 and fired under the same conditions as in Example 8. The firing shrinkage was about 15%, and sintered spheres with a diameter of 10.2 mm were obtained. The water absorption was 0.7%, the bulk density was 2.7 g / cm 3 , and the surface was white and had a good surface condition. Then, the obtained sintered spheres were polished to a diameter of 8.0 mm, a sphericity of 5/100, and a surface roughness of 10.
It was made into a μm ball, inserted into an pearl oyster, and cultured in the sea for about 1 year. Then, the pearls were taken out, and the surface appearance, hue and gloss were visually observed. As a result, a white and good-looking nacre was formed. As a result of observing the microstructure of the pearl cross section with an electron microscope, defects such as cracks were not observed at the boundary between the synthetic pearl nucleus and the nacre, and a good nacre was observed.
Claims (7)
ウムからなる炭酸化合物９５．０〜９９．５重量％と、
該炭酸化合物の焼結助剤として作用しうるリチウム化合
物０．５〜５．０重量％とからなる主原材料を含む原材
料を用いて焼成した焼結体から構成され、嵩密度が２．
５〜２．９ｇ／ｃｍ3、吸水率が３％以下であることを
特徴とする養殖真珠用合成真珠核。1. A carbonate compound consisting of calcium carbonate and / or magnesium carbonate 95.0 to 99.5% by weight,
It is composed of a sintered body obtained by firing a raw material containing a main raw material composed of 0.5 to 5.0% by weight of a lithium compound capable of acting as a sintering aid of the carbonate compound, and having a bulk density of 2.
A synthetic pearl nucleus for cultured pearls, which has a water absorption rate of 5 to 2.9 g / cm 3 and a water absorption rate of 3% or less.
ミニウム、酸化珪素、酸化錫、酸化チタン、酸化亜鉛、
酸化セリウム又はこれらの混合物を更に含有することを
特徴とする請求項１記載の養殖真珠用合成真珠核。2. The raw material is aluminum oxide, silicon oxide, tin oxide, titanium oxide, zinc oxide, as a sub raw material,
The synthetic pearl nucleus for cultured pearls according to claim 1, further comprising cerium oxide or a mixture thereof.
物を硬化させて、嵩密度２．５〜２．９ｇ／ｃｍ3の範
囲内において、吸水率を低下させたことを特徴とする請
求項１又は２記載の養殖真珠用合成真珠核。3. The sintered body is impregnated with an organic substance, and the organic substance is cured to reduce the water absorption within a bulk density range of 2.5 to 2.9 g / cm 3. The synthetic pearl nucleus for cultured pearls according to claim 1.
製造法であって、炭酸カルシウム及び／又は炭酸マグネ
シウムからなる炭酸化合物９５．０〜９９．５重量％
と、該炭酸化合物の焼結助剤として作用しうるリチウム
化合物０．５〜５．０重量％とからなる主原材料を含む
原材料を所望形状に成型した後、炭酸ガス分圧下で５２
５℃以上、９００℃未満において焼成する工程と、研磨
加工する工程とを行うことを特徴とする養殖真珠用合成
真珠核の製造法。4. The method for producing a synthetic pearl nucleus for cultured pearls according to claim 1, which comprises 95.0 to 99.5% by weight of a carbonate compound composed of calcium carbonate and / or magnesium carbonate.
And a raw material containing a main raw material of 0.5 to 5.0% by weight of a lithium compound capable of acting as a sintering aid of the carbonic acid compound, and molding the raw material into a desired shape.
A method for producing a synthetic pearl nucleus for cultured pearls, which comprises performing a step of firing at 5 ° C or higher and lower than 900 ° C and a step of polishing.
００℃未満において焼成する工程の前に、大気雰囲気下
で５２５℃以下において仮焼する工程を行うことを特徴
とする請求項４記載の養殖真珠用合成真珠核の製造法。5. The carbon dioxide gas partial pressure is 525.degree.
The method for producing a synthetic pearl nucleus for cultured pearls according to claim 4, wherein a step of calcination at 525 ° C or lower in an air atmosphere is performed before the step of firing at less than 00 ° C.
００℃未満において焼成する工程における圧力が１気圧
以下であることを特徴とする請求項４又は５記載の養殖
真珠用合成真珠核の製造法。6. The carbon dioxide gas under partial pressure of 525 ° C. or higher, 9
The method for producing a synthetic pearl nucleus for cultured pearls according to claim 4 or 5, wherein the pressure in the step of firing at less than 00 ° C is 1 atm or less.
００℃未満において焼成する工程により得られた焼結体
に、有機物を含浸させ、該有機物を硬化させて、嵩密度
２．５〜２．９ｇ／ｃｍ3の範囲内において、吸水率を
低下させることを特徴とする請求項４〜６のいずれか１
項記載の養殖真珠用合成真珠核の製造法。7. The carbon dioxide gas partial pressure is 525 ° C. or higher, 9
The sintered body obtained by the step of firing at less than 00 ° C. is impregnated with an organic substance, and the organic substance is cured to reduce the water absorption rate in the range of a bulk density of 2.5 to 2.9 g / cm 3 . Any one of claims 4 to 6 characterized in that
A method for producing a synthetic pearl nucleus for cultured pearls according to the item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06644995A JP3498112B2 (en) | 1995-03-24 | 1995-03-24 | Synthetic pearl nuclei for cultured pearls and their production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06644995A JP3498112B2 (en) | 1995-03-24 | 1995-03-24 | Synthetic pearl nuclei for cultured pearls and their production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08266183A JPH08266183A (en) | 1996-10-15 |
| JP3498112B2 true JP3498112B2 (en) | 2004-02-16 |
Family
ID=13316101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06644995A Expired - Fee Related JP3498112B2 (en) | 1995-03-24 | 1995-03-24 | Synthetic pearl nuclei for cultured pearls and their production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3498112B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7330484B2 (en) * | 2019-03-19 | 2023-08-22 | 株式会社白石中央研究所 | Calcium carbonate sintered body and bone filling material |
-
1995
- 1995-03-24 JP JP06644995A patent/JP3498112B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08266183A (en) | 1996-10-15 |
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