JPS5931636A - Production of breeded pearl - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing cultured pearls that can produce high-quality cultured pearls having iridescence and surface characteristics similar to natural pearls in a short period of time and at a high yield.

Conventional cultured pearls mainly use Akoya oysters, and after inserting a pearl nucleus into them, the oysters are cultured in an inland sea suitable for cultivating oysters (hereinafter simply referred to as the sea) for a long period of time, such as several years. It is manufactured by coating the nucleus with pearl substance made from shellfish secretions.

In addition, as an improved method for producing cultured pearls, for example, the surface or inner surface of the original pearl, that is, the core, is coated with celluloid paint containing fish scale foil, etc., and then inserted into the body of the Akoya oyster.
There is also a method of obtaining bitten pearls in a relatively short period of time by sinking them in the sea.

However, with the conventional method, it is rare to obtain pearls with the beautiful iridescence seen in high-quality natural pearls, and even with the improved method described above, the yield was extremely low at around 10%. In addition, in the sea, the temperature changes drastically and it is difficult to control the concentration of alkali metal ions and alkaline earth metal ions contained therein, as well as feed such as algae and plankton. The period required for the formation of a layer of pearl quality using moon secretions is very long, at least one year, even with the top layer improvement method, and furthermore, the quality is not constant.

In view of the current state of the monarchy, the present inventor has conducted extensive research to develop a cultured pearl production method that can produce one II# pearl with high quality natural pearl-like iris and surface characteristics in a short period of time with a high yield. A thin film was formed on artificial pearl frozen soil by Cantos battering method or (and) vacuum evaporation method, and if necessary, a polymer thin film containing or not containing foil pigment was formed, and the material was inserted into live shellfish as a core. sometimes,
They discovered that the 91-M period can be significantly shortened by imparting an iridescent tone to the nucleus in advance, and that it is possible to use live shellfish in an aquarium containing artificial culture liquid, leading to the completion of the present invention. At least II! ! or further, forming at least one polymer thin film containing or not containing a foil pigment as a lower layer, an intermediate layer, or an upper layer of the upper He thin film, and then inserting this into the body of a live shellfish as a core, Artificial raw shellfish? The present invention relates to a method for producing cultured pearls, which is characterized in that cultured pearls are artificially reared in an aquarium containing liquid M, thereby depositing pearl substance from shellfish secretions on the surface of the nucleus.

As the artificial pearl frozen soil in the present invention, any of the conventionally known ones can be used, such as flooring, coral beads, marble beads, synthetic resin balls, ceramic beads, glass beads, synthetic resin with foil pigment, shell powder, lead, barium. Examples include powders of metals or salts thereof, alkaline earth metal salts such as calcium carbonate, glass powder, marble powder, etc., mixed and solidified into a spherical shape. In addition, the diameter of artificial pearls is not particularly limited, but it is usually 2 to 80 mm in diameter so that it can be inserted into a shell.
It is about Jll. Further, the specific gravity is selected from a wide range and is not particularly limited, but the specific gravity is close to that of natural pearls, that is, 2.
It is preferably about 5 to 8.0.

Examples of the cathode sputtering method in the present invention include DC bipolar sputtering method, high frequency sputtering method, asymmetrical AC sputtering method, plasma sputtering method, high speed magnetron sputtering method, etc. Any of these can be adopted. Although there are some differences in the details, the basic method is to immerse the anode (positive electrode) and 4- Glow discharge is performed between the two electrodes of the cathode (cathode), during which the ionized positive ions of the inert gas are accelerated by the electric field and collide with the substance (sputtering material) placed on the cathode surface, that is, the target. , sputtering that knocks out particles of the target material),
It adheres to objects near the cathode (artificial pearl frozen soil) and forms a thin film.

Examples of target materials for the tc-H gel cantos battering method of the present invention include AI, Sb, and Sn.

Co, Zn, Cd, Au, Ag, Cr, C
u, Pb, Ni, V.

Hf, Ha, Bi, Mn, Mg, Be, Rh
, Pd, Rb, Sr.

So, Zr, Nb, Ge, In, Ga,...
Elements or alloys of metals such as Tl, Te, etc., Zn
* Cr m Si e Ce * S 6 eTi
, Pb, Bi, Ba, B etc. oxides, In, Cd
Sulfides such as Cd, Ca, sr, Ba, Mgs
Any of the tetrahalides conventionally used in vacuum evaporation methods, such as Li and Cu', can be used; however, materials that have a high melting point and are difficult to form into thin films by vacuum evaporation methods, such as W, Ta, Mo, Pt, Ir, Os
Metals such as metals or alloys thereof, nonmetallic compounds such as gold-stripe oxides such as alumina, boron nitride, ceramic materials such as fused quartz, alkali glass, lead glass, natural minerals such as mullite, etc. can be used.

When a conductive material such as an elemental metal is used as the target material, it is preferable to use a DC bipolar sputtering method. In this case, the target material is directly used as a cathode and the target material is sputtered by applying a voltage of usually about 500 to 20,000 V to cause glow discharge.

Further, when an insulating material such as a metal salt or oxide, a non-metallic compound, a ceramic material, etc., that is, a galvanic material is used as the target material, it is preferable to use a high frequency sputtering method. In this case, a high frequency potential of usually about 800 to 20,000 V and about 8 to 80 MQ/8 is applied to a metal electrode behind the target material to cause glow discharge and sputter the target material.

The sputtering time is appropriately determined depending on the target material used, the sputtering method, and the desired film thickness.

In the cathode sputtering method of the present invention,
In order to form a thin film as uniform as possible on the spherical surface of the artificial pearl frozen soil that is the adherend, it is preferable to rotate the frozen soil during sputtering and to shape the target to match the curved surface of the frozen soil. In addition, in order to suppress the temperature rise of the artificial pearl frozen soil that is the adherend, the hemispherical surface of the frozen soil sphere on the opposite side of the surface to be sputtered is rotated while passing through a concave mantle that can cool it; Preferably, the target is cooled. Furthermore, as in the above-mentioned high speed magnetron sputtering method, it is also preferable to simultaneously apply a magnetic field to increase the sputtering speed and to suppress the temperature rise of the frozen soil.

The thickness of the thin film formed by the upper rudder cathode sputtering method is not particularly limited, but is usually 0.00
1 to 10 μm radius, preferably 0. The thickness should be approximately 1 to 5 μm. Further, the number of thin films is usually about 1 to 12 layers. According to the cathode sputtering method, the adhesion of the thin film is high, and even materials that cannot be made into a thin film using the vacuum evaporation method can be made into a thin film.

The vacuum evaporation method in the present invention is similar to the method conventionally used in the production of artificial pearls, and uses the thin film material for the vacuum evaporation method described above, and loads an appropriate amount of this into a boat in a evaporation vacuum chamber. It is deposited on artificial pearl frozen soil by evaporation. This deposition can also be carried out sequentially using multiple boats. The conditions at this time vary depending on the type of vapor deposition substance used, but are usually 10-4
The process is carried out under a vacuum of -8- x mHg or less, preferably lOHHg or less, and at a boat temperature of about 200 to aooo'C.

The thickness of the thin film formed by the Queen's vacuum evaporation method is not particularly limited, but is usually about 0.01 to 10 μm, preferably 0.01 to 5 μm. Further, the number of thin films is usually about 1 to 12 layers.

The royal cathode sputtering method (and) the thin film by vacuum evaporation method is used prior to culturing as described below.

Artificial pearl frozen soil can be given beautiful iridescent colors in advance. Furthermore, by making the refractive index of adjacent thin films different, it is possible to make the iridescence more beautiful.

In the present invention, if necessary, the queen cathode sputtering method (and) forms at least one polymer thin film containing or not containing a foil pigment in the lower layer, middle layer, or upper layer of the thin film by vacuum evaporation.

The method is almost the same as the coating method conventionally used in the production of artificial pearls, and the coating is usually done by applying an organic polymer resin paint containing about 1 to 50% by weight of pigment, or by spraying. Painting, or welding or fusing the organic polymer resin itself, or applying monomers, prepolymers, oligomers, precursors, etc. that are raw materials for organic polymer resins together with polymerization catalysts, curing agents, accelerators, fillers, etc. Alternatively, a single layer of polymer may be formed on the surface of frozen soil.

As the foil pigment, any of the known foil pigments for artificial pearls, such as natural foil pigments such as fish scale foil, and synthetic foil pigments produced from basic lead carbonate, bismuth oxychloride, 9-phenylnylic acid, etc., is used. can. Furthermore, as the organic polymer resin, any known organic polymer resin can be used without particular limitation, such as unsaturated polyester resin, epoxy resin, xylene resin, melamine resin, phenol resin, benzoguanamine resin, furan resin, chroman resin, etc. - indene resin, urea resin, silicone resin, fluororesin, diallyl phthalate resin, polysulfone resin, polyurethane resin, aromatic polyamide resin, polyimide resin, polybenzoic dazole resin, polyamideimide resin, polyamide resin, allyl resin, styrene resin, Acrylic resin, methacrylic resin, acrylonitrile, copolymer resin of two or more of butadiene and styrene, polycarbonate resin, polyallyl carbonate resin, polyacetal resin, polyoxyethylene resin, polyethylene resin, polypropylene resin, polybutene resin, polymethyl Single or copolymer resins such as pentene resin, vinyl chloride, vinylidene chloride, vinyl acetate, general polymers such as polyvinyl butyral resin, polyester resin, polyphenylene oxide resin, polysulfone resin, polybutylene resin, polybutadiene resin, polyisoprene resin, -
11- Examples include metal-binding polymers such as ionomer resins and ion exchange resins, amino acid polymers, hard proteins such as glutin, polysaccharides, and derivatives thereof. Furthermore, organic celluloses such as acetylcellulose, propionylcellulose, benzylcellulose, ethylcellulose, and nitrocellulose may be added to strengthen the polymer thin film.

It is desirable that the above-mentioned thin polymer film has some degree of water resistance, but in the case of ionomer resins, it is rather desirable that the film be hydrophilic to the extent that binding of metal ions occurs.

The thickness of the polymer thin film formed as described above is not particularly limited, but is usually about 5 to 100 μm, preferably about 10 to 50 μm. Father, the number of thin films is usually 1~
There are about 8 layers.

These polymer thin films have good adhesion to artificial pearl frozen soil or to thin films formed by the cuckoo, toss-buttering method, or (and) 12- vacuum evaporation method, thus improving the adhesion of the thin film. Furthermore, prior to the culture described below, the artificial pearl frozen soil can be given a deep, mellow color and luster that is the basis of the beautiful pearl color of the iris. Furthermore, if the thin polymer film formed on the top layer or the layer below it has a negative effect on the growth of shellfish or the adhesion of secretions, the thin film of metal, metal compound, or polymer cape that is the layer below it It is useful as an isolation layer to prevent this. It is also useful for obtaining a smooth surface or a surface active against metal ions, which promotes the secretion of shellfish secretions and on which good pearl quality can be deposited. Treated artificial pearl frozen soil on which approximately 1 to 15 thin films have been formed is inserted into a live shellfish as a core. In this case, any shellfish that has traditionally been used as mother shellfish for cultured pearls can be used; for example,
Mollusks belonging to pseudovalve mosquitoes such as pearl oysters, mabe oysters, pearl oysters, pearl oysters, black lipped oysters, and scallops, orthopodal mosquitoes such as oyster oysters, oyster oysters, and crow oysters, and thread mackerels such as mussels. In addition, the places where the nucleus is inserted are the same as before, for example, in the case of pearl oysters, the so-called ``fukuro'' (midway between the pouch and the ostracod) in the gonad, and the ``skull'' (the pouch between the pouch and the ostracod) and foot)
or "Osae" (a place closer to the feet than "Ukashi"), preferably "Fukuro" or "Ukashi",
Insert along with a piece of mantle epithelial tissue. Tokoro i! is the best way to insert the piece section. l1ll “Additional”, “
It is possible to use either "early" or "simultaneous" methods, but it is easier to obtain high-quality cultured pearls by "post-seating". The size and number of nuclei to be inserted vary depending on the size and type of shellfish to be inserted, but for example, in the case of pearl oyster, 259
8 shells with a diameter of about 4 cm, 60 g of shells with a diameter of 81
It is normal to insert two pieces of about n11. In addition, when inserting the treated frozen soil into the concrete as a core, the core is treated with an alkali metal compound such as sodium chloride, an alkaline earth metal compound such as calcium chloride, or a solution containing both of these to remove shellfish secretions. It is also good to promote the adhesion of

The molluscs inserted with treated frozen soil as their cores are artificially reared in an aquarium containing an artificial aquaculture solution of artificial seawater or fresh water, and the cores are coated with pearl quality from the mollusc's own secretions.

The desirable composition of artificial seawater is usually 0.5 to 8.0% by weight of alkali metal ions, preferably 0.9 to 1.2% by weight, and preferably 0.1 to 2.0% by weight of alkaline earth metal ions. 0.15-1.0% by weight, halogen ion 1.
It contains 5 to 8.0% by weight, preferably 1.6 to 1.9% by weight, and other ions as necessary, and its specific gravity is 1.01 to 1.08.

In addition, the desirable composition of artificial fresh water is usually 0.1 to 5.0% by weight of alkaline earth metal ions, preferably 0.1% by weight.
It contains 5 to 1.6% by weight of 1 and other ions as necessary, and its specific gravity is 1.00 to 1.
．． It is 10.

In order to obtain a predetermined concentration of each upper rudder ion, the compounds used include, for example, sodium chloride, sodium bicarbonate,
Examples include potassium bromide, boric acid, strontium chloride, barium chloride, magnesium chloride, sodium sulfate, calcium chloride, potassium chloride, and sodium fluoride.

Among the above compositions, especially alkaline earth metal ions are added to 0.1
By containing more than % by weight, the secretion of shellfish secretions is promoted and the rearing period can be further shortened.

However, in some cases alkaline earth metal ions 0.1
It is also possible to use artificial culture liquids containing less than % by weight or without it. It is also possible to replace part or all of the artificial culture liquid with natural seawater or natural fresh water.

When raising shellfish in an artificial culture solution with the above composition, 16
- Oxygen content from 0.8 to 8.0% by volume, preferably from 0.5 to 8.0% by volume
1.0% by volume ◎ If the oxygen content is less than 0.8% by volume, the shellfish may die and are not suitable for breeding.

In addition, the temperature of the artificial culture solution is usually 10 to 800C.
Preferably 15-27°C, particularly preferably 20-25°
C・If the temperature is less than 10@0 or above 80℃, the growth of shellfish will be inhibited and they may die.◎Upper lc! If the temperature is within this range, the shellfish will grow actively, produce a large amount of secretion, and effectively deposit pearl quality.

In addition, the feed used in shellfish breeding includes silica algae such as Physcomitrella spp.
Examples include flagellated algae such as Euglena and Monasmo, green algae such as Rishishira, and other plankton.

Of course, these can be naturally produced, but it is convenient to use artificially cultured diatoms, flagellates, green algae, etc. ◎ Also, during shellfish breeding, bacteria and harmful insects can be used. Antibacterial agents such as tetracycline, terramycin, neoxin, chloromycetin, 1-oxy-
An insect repellent such as 2,2,2-) dimethyl chlorethyl phosphate or the like may be added. Furthermore, a shellfish growth hormone, a shellfish secretion promoter, a pearl layer formation promoter, etc. may be added.

When a shellfish is reared in which a raw ball that has been coated as described above is inserted as a nucleus, a pearl-like film mainly composed of calcium carbonate is formed on the surface of the nucleus, and its thickness is When reared properly, the length reaches approximately 20 μm in the first month, approximately 40 μm in the second month, and approximately 60 μm in the B month.

Next, cultured pearls of excellent quality are obtained by removing the pearls from the shellfish at an appropriate time. According to the method of the present invention, artificial pearl frozen soil is treated in the manner described above to obtain an iridescent tone similar to that of natural pearls. Because it is a supplement, when breeding shellfish with this inserted in an aquarium containing artificial Vfi solution, the breeding environment is easy to control, and the breeding time is extremely short, only about 1 to 8 months. It has an extremely high yield of over 80% over a long period of time, and has a beautiful, deep, mellow iridescent luster similar to that of high-quality natural pearls. Pearls can be obtained easily.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 A polymer thin film of bisphenol A type Evokin resin (film thickness, approximately 100 μm) was placed in advance on a bed with a diameter of 8 Hk and a specific gravity of 2.8.
The formed product was placed in a vacuum evaporation tank with an internal volume of 1 yd, and magnesium fluoride (MgF2), zinc sulfide (ZnS), and cerium oxide (
Ce0) and silicon dioxide (Sin2) were sequentially heated, vaporized, and evaporated to deposit four different thin films (film thickness, total 19 - about 2 μm), and then 2% by weight of fish scale foil and An acetate ester (equal mixture of ethyl acetate and butyl acetate) solution containing 4% by weight of polymethyl methacrylate was applied and dried to form a thin polymer film with a thickness of 10 μm.

Two pieces are approximately 60f, with the original ball processed as in the first generation as the core.
A fresh piece section taken from the shell's mantle was inserted into a ``bag'' inside the body of a pearl oyster (raw oyster) using the ``post-attaching method''. The shellfish with the nucleus inserted was treated with 28k sodium chloride.
g, magnesium chloride 5kQ, sodium sulfate 4~, calcium chloride 1kg, potassium chloride 6001. Sodium bicarbonate 200f1 Potassium bromide 1001. Boric acid 809
, strontium chloride 26f and sodium fluoride 8f
was dissolved in water and placed in 1 ton of artificial seawater, and the oxygen content in the water was adjusted to around 0.6% by volume by blowing in oxygen appropriately, and the water temperature was kept in the range of 23 to 25°C. The animals were reared while being adjusted accordingly.

20- As feed, Monasmo obtained in advance by tank culture was used, and the culture was continued for about 1 month to coat the surface of the nucleus inserted into the Akoya concrete to a thickness of 20 μm of pearl quality due to secretion of the shellfish.
A cultured pearl having the same iridescent luster and surface characteristics as a high-quality natural pearl was obtained by extracting it from the shellfish.

Example 2 Pale white glass beads with a diameter of 10 fi and a specific gravity of 2.7 were placed in a vacuum tank for high frequency sputtering, and
nHg (D Under reduced pressure, zinc sulfide (ZnS), silicon dioxide (Sing), titanium dioxide (TiOs+) and glass X (A140g 16% by weight, Ca07% by weight, 5
10277% by weight) was successively sputtered to adhere to the surface of the rotating glass bead to form a multilayer thin film (film thickness, approximately 2 μm) consisting of four layers, and this was then used as a core to be deposited on the "Ukashi" inside Akoya Gutai. , and a piece section taken from the mantle was inserted. The pearl oysters containing the kernels were mixed with 40 kQ of sodium chloride, 15 kQ of magnesium chloride, thorium 8 calcium chloride in filL acid and 2 parts calcium chloride. The mixture was placed in 2 tons of artificial seawater obtained by dissolving 1 1 potassium chloride, 5 oy of sodium bicarbonate, 100 g of strontium chloride, 50 y of notrium chloride, and 60 F of boric acid in water, and the oxygen content was maintained at about 0.6 volume at all times. The water temperature is maintained at 20-2%.
The animals were kept at a temperature within the range of 5°C. Feed terramycin to approx. IF was added in portions. After being reared for about two months, the surface of the nucleus inserted into the Akoya oyster was coated with 40 μm thick pearl material, which is secreted by the oyster.
Relatively large cultured pearls with iridescent luster, surface characteristics, and specific gravity similar to those of high-quality natural pearls could be obtained in a short period of time.

Example 8 It was made of polyester resin with a diameter of 121 g and contained 70% by weight of lead glass powder, and the specific gravity was adjusted to about 2.7.
) and zinc oxide (ZnO) are sequentially heated and evaporated to form a multilayer thin film (film thickness, total thickness of approximately 1 μm) consisting of two layers by vapor deposition, and on top of this, approximately 1 Kt% of polyvinyl butylene resin is applied. A butanol solution containing the above was applied and dried to form a thin polymer film (thickness: approximately 5 μm). This material was placed in the vacuum evaporation tank again and copper iodide (Ct
ll) and magnesium fluoride (MgFs) were sequentially evaporated to form a multilayer film consisting of two layers [film thickness, approximately 1 μm].
) was applied and dried to form a polymeric Wt film with a film thickness of 10 μm. Two pieces were inserted.The live TNi gland near the scallop was selected as the insertion site, and the pieces were inserted so as to be in close contact with the external epithelium of the mantle piece section that had been inserted in advance. Add this to 70% sodium chloride, 25 g of 9% magnesium chloride, 8 and 9 g of calcium chloride, 1 kg of potassium chloride, 600 g of sodium bicarbonate, ao o y of potassium bromide, 1 g of boric acid.
00jF, strontium chloride 100f! and sodium fluoride log dissolved in water and placed in 3 tons of artificial seawater, the oxygen content was always maintained in the range of 0.5 to 0.7% by volume, and the water temperature was kept at 25 to 27 °C. They were reared under controlled conditions. As feed, euglena and Euglena were given as appropriate, and chloromycetin and tetracycline were added in an amount of about 100 η each to prevent bacteria. After being reared for about 2 months, the nucleus inserted into the concrete (thickness of the pearl quality thin film about 40 μm) is taken out and has iridescence and surface characteristics almost similar to rare large natural pearls. Obtained cultured pearls.

Example 4 Translucent ceramic beads with a diameter of 8 to 5 sots and a specific gravity of 2.7 were used as frozen soil, placed in a vacuum tank for high frequency sputtering, and gold sputtered under a vacuum of 5 x 10 = 24-mIIg in argon gas. (Au), mullite, and glass (same as those used in Example 2) were sequentially sputtered to form a multilayer film (film thickness, approximately 8 μm) consisting of 8 layers on the surface of rotating frozen soil. Five of these cores were inserted into the ovary part of Ikecho Gutai with a grain height of about 12 cII together with the mantle piece section, and these shells were made using chloride magnesium fs&
9. [Acid 80f1 Strontium chloride 80F and sodium bicarbonate 1) Place 200f of ram in 1 ton of artificial fresh water obtained by dissolving it in water, and keep the oxygen content in the water at around 0.6% by volume at all times. The animals were reared for 8 months at a water temperature of 20 to 28°C.

Claims (1)

[Claims] ■ The cathode sputtering method on the artificial pearl raw material (and) forms at least one thin film by vacuum evaporation, or further includes a foil pigment as a lower layer, an intermediate layer, or an upper layer of the thin film. Alternatively, at least one layer of polymer thin film containing no molluscs is formed, and then this is inserted into the body of a live shellfish as a core, and the live shellfish is artificially reared in an aquarium containing an artificial culture solution. A patented method for manufacturing cultured pearls that coats them with pearl quality. (2) The production method according to claim 1, wherein the artificial culture liquid contains 0.1% by weight or more of alkaline earth metal ions.