JP4643352B2 - How to dye pearls - Google Patents

Description

  The present invention relates to a method for dyeing pearls suitable for coloring pearls such as natural pearls or cultured pearls with a dye to a deep and deep hue.

  Pearls can be obtained from natural or aquaculture from pearl oysters, white butterflies, black oysters and other shellfish. The pearl is a spherical or hemispherical solid mainly composed of calcium carbonate, has a gloss and beauty (oriental effect) peculiar to pearls, and has long been prized as a decorative product in the world.

  Here, pearls are generally recognized as white, but “hamaage pearls” that have just been removed from the sea are so different that they do not have the same color. , Silver, cream, gold, green, blue or black.

  In addition, many “hama fried beads” are contaminated with dirt. For this reason, the “hama fried bead” is actually almost bleached and ground before being supplied to the market in order to unify the color and remove dirt.

  Also, some natural pearls are very elegant and prized as they are naturally colored. For example, examples of the South Sea pearl include gold pearls such as white butterfly and black pearls of black butterfly.

  These South Sea pearls have a deep and deep hue, are invaluable, and are expensive ornaments that are generally not available. In addition, the color of pearls as a decorative item changes depending on the difference in preference between races and the fashionability of the times. Therefore, if natural or aquacultured pearls that have been whitened by bleaching or light-colored pearls can later be colored to any color, especially dark and deep shades, according to racial preferences and fashion requirements, the pearl market Value is greatly improved.

  In general, as a coloring method of pearls, there are a coloring method by radiation (cobalt 60) irradiation, a method of immersing the pearl in silver nitrate or a photosensitive silver salt compound solution, and then coloring by applying ultraviolet rays or a reducing agent. However, these are methods for coloring black pearls, and cannot be colored in any color such as gold pearls.

  In addition, as a method for coloring an arbitrary color, a coloring method using a dye has also been put into practical use. However, in general, it takes a long time for dyeing, and a dark color cannot be obtained for that. It has the disadvantage of low fastness.

Therefore, a coloring method related to a colored pearl disclosed in Patent Document 1 below has been proposed. In this coloring method, a colored pearl is characterized in that a main amount composed of a synthetic resin paint containing at least a pigment and an acrylic resin, a thinner, and a curing agent are mixed and applied to the outer surface of the pearl, respectively. Is to provide.
JP 2004-73761 A

  By the way, according to the coloring method relating to the colored pearl as described above, it is possible to provide a beautifully colored pearl without impairing the orientation effect so much, and it is possible to color it in any dark color.

  However, in this method, the original surface layer of the pearl is covered with a layer of an acrylic resin paint containing a pigment. I can't do that.

  In other words, if “high-grade pearls” are colored by this method, even if they can be colored deeply, the quality of the pearls is reduced, and “high-grade pearls” are reduced to “intermediate pearls”. Also, depending on the method, it is not possible to color high-grade white pearls in a deep and deep shade, and to make even more expensive gold pearls.

  Therefore, in order to deal with the above, the present invention does not deteriorate the quality of the pearls even if the pearls of “high-grade pearls” such as natural pearls or cultured pearls are dyed with a dye, and the orientation effect. It is an object of the present invention to provide a method for dyeing pearls having a deep and deep hue.

  In solving the above-mentioned problems, in the method for dyeing pearls according to the present invention, according to claim 1, each of the cationic dye, the cationic surfactant, and the nonionic surfactant contains at least one, and 5 The pearl is exhausted and dyed in a water bath at a pH in the range of ˜9 and a dyeing temperature in the range of 60 ° C. to 95 ° C.

  According to such a dyeing method, even if pearls of “high-grade pearls” such as natural pearls or cultured pearls are dyed with a dye, the pearl quality is not deteriorated, and an orient effect is obtained and a deep and deep hue is obtained. In addition, a colored pearl having good light fastness and friction resistance can be obtained.

  Further, according to the present invention, as described in claim 2, in the pearl dyeing method according to claim 1, the cationic surfactant may be a quaternary ammonium salt type surfactant. Further, according to the present invention, as described in claim 3, in the pearl dyeing method according to claim 1 or 2, the nonionic surfactant may be a polyoxyethylene alkylphenol ether type surfactant. .

  Hereinafter, an embodiment of a pearl dyeing method according to the present invention will be described.

  In the present embodiment, the pearl is not particularly limited as long as it is obtained from pearl oyster, white butterfly, black butterfly, squid butterfly, mabe and other shellfish. The pearls are not limited to natural pearls and may be cultured pearls.

  In particular, the method for dyeing pearls according to the present embodiment does not deteriorate the quality of pearls even when dyeing “high-grade pearls” using a dye, and has an orient effect and is colored in a deep and deep hue. A dyeing method is provided.

  Therefore, colored pearls with even higher added value can be obtained by applying to high-grade pearl oyster cultured pearls, and also to high-grade southern pearls such as white pearl oysters.

  Further, the pearl before dyeing may be white or faintly colored. By adjusting the blend of the dye in consideration of the color before dyeing, it is possible to obtain the target color and density by color mixing. However, from the dyeing method according to the present embodiment, it is particularly preferable that the pearl before dyeing is bleached white. For example, white white pearls of white butterfly can be colored into expensive gold pearls.

  The pearl is formed by overlapping about 1000 layers with a pearl layer of about 0.5 micron mainly composed of calcium carbonate. As a result, it has an oriental effect peculiar to pearls. On the other hand, if the thin pearl layer is scratched or peeled off, the value of the pearls is drastically reduced.

  Accordingly, mild conditions that do not damage the nacreous layer are required for processing such as bleaching and dyeing. Therefore, in the present embodiment, a dyeing solution that can be dyed in a deep and deep color under mild conditions at the dyeing pH and dyeing temperature is prepared, and dyeing is performed by exhaust dyeing.

  For actual staining, first, a staining solution is prepared. The dyeing solution is an aqueous solution containing one or two or more cationic dyes, one or two or more cationic surfactants, and one or two or more nonionic surfactants. Below, each component of a dyeing | staining liquid is demonstrated.

  In the present embodiment, the dyeing is performed using one kind or two or more kinds of cationic dyes. As described above, the main component of the pearl is calcium carbonate, but a hard protein called conchiolin forms a network and sandwiches calcium carbonate crystals. Therefore, any color can be imparted to the pearl by dyeing this conchiolin.

  In this regard, the present inventors have intensively researched and found that cationic dyes are preferable. The cationic dye refers to a group of water-soluble dyes that are soluble in water and exhibit basicity, and are generally used for dyeing acrylic fibers, wool, cationic dyeable polyester fibers, and the like.

  The cationic dye used for pearl dyeing can be appropriately selected from these fiber dyes. Examples of the cationic dye include diacrylmethane and triacrylmethane, quinoneimine (azine, oxazine, thiazine), xanthene, methine (polymethine, azamethine), and heterocyclic azo (thiazoleazo, triazoleazo, benzoate). Thiazoleazo), anthraquinone and the like. These cationic dyes are appropriately blended to prepare a dyeing liquid having a desired hue.

  In the present embodiment, the dyeing is performed using one or more kinds of cationic surfactants and one or more kinds of nonionic surfactants as described above. In dyeing pearls with a cationic dye, it is preferable to use a surfactant in combination in order to ensure the dissolved state of the dye and to obtain good leveling.

  The surfactant used for this purpose is selected from cationic surfactants and nonionic surfactants from the viewpoint of compatibility with the cationic dye. In particular, in this embodiment, it is preferable to use a cationic surfactant and a nonionic surfactant in combination.

  Here, examples of the cationic surfactant include a fatty amine salt type, a quaternary ammonium salt type, and an alkylpyridinium salt type, and any of these or a mixture thereof may be used. The use of a quaternary ammonium salt type surfactant is preferred.

  On the other hand, examples of the nonionic surfactant include polyoxyethylene alkyl ether type, polyoxyethylene alkyl phenol ether type, polyoxyethylene alkyl ester type, sorbitan alkyl ester type, and polyoxyethylene sorbitan alkyl ester type. Alternatively, these may be used in combination, but the use of a polyoxyethylene alkylphenol ether type surfactant is particularly preferred.

  The amount of these cationic surfactants or nonionic surfactants used is not particularly limited, but the range of 0.1% to 10% is preferable for each active agent with respect to the weight of the dyeing solution. In particular, a range of 0.5% to 5% is preferable respectively.

  Next, the pH of an aqueous solution in which the one or more cationic dyes, one or two or more cationic surfactants and one or two or more nonionic surfactants are dissolved is adjusted.

  In the present embodiment, staining is performed with the pH of the staining solution in a neutral range of 5-9. More preferably, the staining is performed at a pH of 6 to 8 of the staining solution.

  When the pH of the staining solution is less than 5, the surface of the pearl layer of the pearl is dissolved, and the orientation effect may be lost. On the other hand, when the pH of the dyeing liquid exceeds 9, the orientation effect on the surface of the pearl layer of the pearl may be lost. In particular, when the temperature is applied to the nacreous layer during dyeing due to acidity or alkalinity, damage to the nacreous layer of the nacre increases.

  In the present embodiment, the relationship between the pH of the staining solution and the staining temperature is important. Therefore, in this embodiment, dyeing is performed at a dyeing temperature in the range of 60 ° C to 95 ° C. More preferably, the dyeing is performed at a dyeing temperature of 70 ° C to 90 ° C.

  If the dyeing temperature is less than 60 ° C., it takes a long time for dyeing and there is a possibility that the desired dyeing concentration cannot be obtained. On the other hand, as the dyeing temperature is higher, a dark dyed color can be obtained in a shorter time. However, if the dyeing temperature exceeds 95 ° C., the surface of the pearl layer of the pearl may be damaged and the orientation effect may be lost. Good dyeing can be performed by these neutral pH and mild dyeing temperature.

  Next, the dyeing process will be described. Dyeing is performed by exhaust dyeing in which pearls are immersed in a dyeing solution. Here, the pearls may be dyed while standing still, but if dyeing is performed for a long time while the contact part between the pearls and the container is fixed, there is a risk of uneven dyeing. Better. For example, uniform staining can be achieved by moving the staining container.

  However, when the movement is intense, the pearl collides with the container wall and damages the surface of the pearl layer. Therefore, a mild movement is necessary.

  The bath ratio, which is the weight ratio between the pearl and the dyeing solution, may be arbitrarily determined, but is generally 1: 1 to 1: 5. This is because when the bath ratio is small and the dyeing solution is small, the dye concentration in the dyeing solution is increased, the dissolved state of the dye is deteriorated, and uneven dyeing may occur. On the other hand, when the bath ratio is large and the dyeing solution is large, it is necessary to use a large amount of dye to obtain the desired dyeing density, which may result in poor utilization of the dye and increase in cost. .

  Dyeing requires a dyeing temperature of 60 ° C. to 95 ° C. as described above. Dyeing may be performed at the same temperature from the beginning of dyeing. Preferably, the pearl is familiarized with the dyeing liquid at a low temperature, for example, near room temperature, and then the temperature of the dyeing liquid is increased to a predetermined temperature, and the dyeing is performed while maintaining the same temperature for a predetermined time.

  After dyeing, the pearls are removed from the dyeing solution and washed with water and hot water. Furthermore, the undyed dye on the surface of the nacre is removed by performing soaping using a surfactant and sodium tripolyphosphate. Subsequently, by washing with water and drying at room temperature or low temperature, a colored pearl having a desired color can be obtained.

  As described above, in this embodiment, a hard protein called reticulated conchiolin sandwiching a crystal of calcium carbonate in the nacre is dyed. That is, pearls are in a water bath containing one or more cationic dyes, one or more cationic surfactants, and one or more nonionic surfactants, and the pH is adjusted. The pearl is exhausted and dyed in a water bath having a neutral range of 5 to 9 and a dyeing temperature of 60 ° C to 95 ° C.

  Thereby, the pearl dye | stained as mentioned above does not reduce the quality of the pearl of "high-grade pearls", such as a natural pearl or a cultured pearl, and has an orient effect, and can be colored deeply and deeply.

  Hereinafter, in the present embodiment, the following examples and comparative examples were prepared and evaluated.

Example 1:
As a staining solution, it contains 1% CIBasic Yellow 45, 5% CIBasic Yellow 91 and 0.5% CIBasic Blue 3, and further 3% Sanmor D267 (manufactured by Nikka Chemical Co., Ltd., quaternary ammonium salt) Type surfactant), 4% Sunmol NS3 (manufactured by Nikka Chemical Co., Ltd., quaternary ammonium salt type surfactant), and 2% Newsolv ES (manufactured by Nikka Chemical Co., Ltd., polyoxyethylene alkylphenol) An aqueous solution containing an ether type surfactant) was prepared, and the pH was adjusted to 7. 100 g of white southern pearls of white butterfly were placed in an Erlenmeyer flask, and the above dyeing solution was applied at a bath ratio of 1: 1.

  Thereafter, the Erlenmeyer flask was set on a shaking constant temperature dyeing machine at 40 ° C., and the amplitude was set to 40 mm and a stroke of 10 times / minute. After treatment for 7 hours at the same dyeing temperature, the dyeing temperature was raised to 80 ° C., and dyeing was continued for 8 hours.

  After dyeing, using the same apparatus, soaped with an aqueous solution containing 1 g / L sodium tripolyphosphate and 0.5 g / L nonionic surfactant at a bath ratio of 1: 1 and 80 ° C. for 30 minutes, and Washed with water and dried naturally. The obtained dyed pearl was a gold pearl with a deep and deep hue without impairing the orientation effect.

Example 2:
As a staining solution, it contains 5% CIBasic Blue 47, 3% Sanmor D267 (manufactured by Nikka Chemical Co., Ltd., quaternary ammonium salt type surfactant), 4% Sanmor NS3 (Nikka Chemical) An aqueous solution containing 2% Newsolv ES (manufactured by Nikka Chemical Co., Ltd., polyoxyethylene alkylphenol ether type surfactant) is prepared, and the pH is 7 Adjusted. 100 g of cultured pearls of pearl oysters were placed in an Erlenmeyer flask, and the dyeing solution was applied at a bath ratio of 1: 1.

  Thereafter, the Erlenmeyer flask was set on a shaking constant temperature dyeing machine at 40 ° C., and the amplitude was set to 40 mm and a stroke of 10 times / minute. After treatment at the same dyeing temperature for 4 hours, the dyeing temperature was raised to 80 ° C., and dyeing was further continued for 4 hours.

  After dyeing, using the same apparatus, soaped with an aqueous solution containing 1 g / L sodium tripolyphosphate and 0.5 g / L nonionic surfactant at a bath ratio of 1: 1 and 80 ° C. for 30 minutes, and Washed with water and dried naturally. The obtained dyed pearl was a blue pearl having a deep and deep hue without impairing the orientation effect.

Comparative Example 1:
This Comparative Example 1 was prepared by staining the same sample as in Example 1 above, except that only the pH was adjusted to 4 in the staining solution of Example 1 above.

Comparative Example 2:
This Comparative Example 2 was prepared by staining the same sample as in Example 2 above, except that only the pH was adjusted to 10 in the staining solution of Example 2 above.

Comparative Example 3:
In this Comparative Example 3, the same sample as in Example 1 is dyed in the same manner as in Example 1 except that only the dyeing temperature is dyed in a boil state of 100 ° C. in the dyeing process of Example 1. Prepared for that. However, when dyeing in a boiled state, the Erlenmeyer flask was used in a sealed state in order to prevent evaporation of the staining solution.

Comparative Example 4:
This Comparative Example 4 is the same as the above Example 2 except that the staining solution containing only the cationic surfactant and the nonionic surfactant in the staining solution of Example 2 was adjusted. Prepared by staining as in Example 2.

  The characteristics of each Example and each Comparative Example produced as described above were evaluated. In this evaluation, hue, orientation effect, leveling property, light fastness and friction resistance were adopted as evaluation items.

  In addition, these evaluation was performed with the following method. Hue, orientation effect, and leveling were evaluated visually. The fastness to light was evaluated by the color fading after the fourth grade irradiation according to the method of JIS L 0842. The abrasion resistance was evaluated by a method of rubbing strongly 10 times with a dry and wet brushed cotton cloth.

  According to these evaluations, the evaluation results as shown in Table 1 below were obtained.

  According to this Table 1, each of the above Examples 1 and 2 is the above Comparative Examples 1, 2, 3, 4 for any of the evaluation items of hue, orientation effect, leveling, light fastness and friction resistance. It can be seen that it is superior to

In carrying out the present invention, not only the above-described embodiment but also the following various modifications can be mentioned.
(1) The pearl to be dyed may not be a white pearl white pearl or a cultured pearl pearl oyster. Any pearls obtained from black mussel, mussel mussel, mussel or other shellfish can be dyed.
Therefore, it is effective not only to make “high-grade pearls” more expensive colored pearls but also to make “lower pearls” “intermediate pearls” or “intermediate pearls” to “high-grade pearls”.
(2) The pearl before dyeing may be colored. The dye composition can be determined in consideration of the hue and density before dyeing. For example, it can be dyed on a pale cream color to make it dark gold.
(3) The dyeing device may not be a shaking constant temperature dyeing machine, but may be a rotary dyeing machine. It is preferable that the pearl and the dyeing liquid do not remain stationary during dyeing.
Therefore, it may be a beam type dyeing machine in which the pearl is allowed to stand and the dyeing liquid is distributed. These devices can use a dyeing tester for fibers based on the size of pearls and the amount dyed at one time.
(4) Each of the first and second embodiments is an exemplification, and the present invention is not limited to each of the embodiments.

Claims (3)

In the method of dyeing pearls,
A cation dye, a cationic surfactant, and a nonionic surfactant, each containing at least one of the pearls in a water bath at a pH in the range of 5-9 and a dyeing temperature in the range of 60 ° C-95 ° C. A method for dyeing pearls, characterized by exhausting dyeing. The method for dyeing pearls according to claim 1, wherein the cationic surfactant is a quaternary ammonium salt type surfactant. The method for dyeing pearls according to claim 1 or 2, wherein the nonionic surfactant is a polyoxyethylene alkylphenol ether type surfactant.