JPS6246670B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a dyeing method using organic solvents for natural dyes such as purple root and safflower, and its purpose is to dye purple root and safflower with natural dyes in an extremely short period of time and for a long period of time. It is possible to obtain the same beautiful dyeing condition as traditional dyeing, and it also improves the fastness, making it possible to industrialize dyeing and making it extremely easy to restore cultural properties that have been dyed in this way. The purpose is to make sure that When dyeing with natural dyes such as purple root and safflower, the scouring process to adsorb metal salts to the dyed object such as cloth or thread, and the dyeing process to dye the dyed object take a very long time. Ta. In other words, in scouring, lye from camellia leaves, straw, etc. was used as a mordant to attach metal salts, so it took time to manufacture and prepare the lye, and the lye was applied for more than 10 days in order to adsorb the metal salts in the lye. They were doing it all over the place. In addition, in dyeing, pigments were extracted from purple roots, safflowers, etc. using hot water, which made it difficult and time-consuming to extract the pigments, and the dyeing did not adhere well to the object to be dyed, so it took several months to obtain a beautiful dyed state. It required dyeing. Furthermore, in the above case, since lye from camellia leaves, etc. is used as a mordant, it is difficult to collect the raw materials, resulting in high raw material costs. There was also the problem that the extraction of pigments from plants such as safflower and safflower was poor, resulting in a large amount of purple roots being used for dyeing, resulting in high costs. The inventor completed this invention as a result of intensive research to solve the above-mentioned problems in dyeing using natural dyes such as purple root and safflower. First, the inventor analyzed the lye of camellia leaves, straw, etc. used as a mordant and found out the components of the lye, and found that alumina and silicic acid among the components act effectively as a mordant. If we succeed in producing and using a mordant solution containing the mordant, and if we immerse the object to be dyed in the mordant solution to adsorb the metal salts, we can do so without having to do it for a long period of time as in the past.
They discovered that the metal salt was sufficiently adsorbed to the object to be dyed by carrying out the scouring process continuously over a short period of time, and succeeded in shortening the scouring process. Next, the inventor continued his research and focused on the fact that pigments such as shikonin contained in purple roots are soluble in organic solvents such as benzene and methanol. Using an organic solvent whose main component is a lower alcohol such as ethanol to increase the extraction efficiency of the dye, and using a dye stock solution with a high dye content, immersing the object to be dyed in a gallic acid aqueous solution increases the retention of natural dyes. They discovered that the dyeability of the dye was improved without deteriorating the color, etc., and succeeded in reducing the number of times of dyeing and shortening the dyeing process. This invention will be explained in detail below. First, in the process of producing a dye stock solution, pigments are extracted from natural dyes using an organic solvent whose main component is a lower alcohol such as methanol or ethanol, and this is used as a dye stock solution. As natural dyes, hydrophobic ones such as purple root, safflower, and cochineal, which are difficult to extract with water or hot water, are generally used, but it is also possible to use hydrophilic ones such as Suou. It is. In addition, the organic solvent for extracting pigments from natural dyes may be only lower alcohols such as methanol or ethanol, but considering the properties of the pigments contained in the above natural dyes such as purple root and safflower, the extraction efficiency of the pigments should be determined. It is desirable to add other organic solvents that increase the pH, such as acetone in the case of Shikon. Furthermore, when extracting pigments from natural dyes using organic solvents, it is desirable to subdivide natural dyes such as purple roots to improve the efficiency of pigment extraction. In addition, in the step of scouring the object to be dyed, the object to be dyed is immersed in a mordant solution containing an aluminate and a silicate, and a metal salt such as an aluminum salt is adsorbed onto the object to be dyed. Here, the material to be dyed is cloth and thread made of protein fibers such as silk, hemp, cotton, etc.; It is preferable to use this method, and it is particularly preferable to use silk as the object to be dyed because a beautiful dyed state can be obtained. In addition, as a mordant, it is possible to use lye such as camellia leaves or straw as in the past, but it is also possible to use an aqueous solution containing an aluminate such as sodium aluminate and a phosphate such as sodium phosphate. It is preferable to use it as a liquid because it is extremely easy to manufacture and does not contain unnecessary metal salts that would impair the color during dyeing. In addition, when adjusting the pH of the mordant solution, since phosphoric acid is contained in the lye, it is preferable to use primary salt phosphate and secondary salt phosphate as pH adjusting agents. Depending on the desired color, it is preferable to add other divalent or trivalent metal salts to the mordant. When the object to be dyed is immersed in a mordant liquid to adsorb metal salts such as aluminum salts, the object to be dyed is immersed in the mordant liquid and then tightly squeezed.
Do this several times in a row. Next, in the step of dyeing the object to be dyed, the object to be dyed which has been refined as described above and has had the metal salt adsorbed thereto is immersed in the dyeing stock solution and dried, then immersed in an aqueous gallic acid solution, and then The object to be dyed is alternately immersed in the dyeing stock solution and the mordant solution as necessary. Here, the reason why the object to be dyed is immersed in an aqueous solution of erodible acid after immersion in the dyeing stock solution is to improve the dyeability of the dye attached to the object to be dyed. This also prevents the color of the dye dyed onto the object from deteriorating. Further, as the aqueous erodible acid solution used here, a dilute aqueous solution of about 1% by weight is sufficient.
In this way, the dye is fully dyed on the object to be dyed, but if you want to deepen the color of the object to be dyed, alternately immerse the object in the dye stock solution and the mordant solution as described above. It is repeated. Here, the reason why the object to be dyed is immersed not only in the dyeing stock solution but also in the mordant solution is to make the object to be dyed adsorb metal salts even during the dyeing stage, thereby dyeing more pigments. Although the above-mentioned process for dyeing the object to be dyed can be carried out under heating as in the conventional method, it has been found that in the case of the present invention, the same dyed state can be obtained even at room temperature. In addition, when purple root is used as a natural dye, according to the inventor's experimental knowledge, the scouring of the dyed object and the immersion in the dyeing stock solution are performed under neutral or weakly acidic conditions, and the dyed object is dyed red. After dyeing purple, when immersing in the mordant solution for the final time, check the pH of this mordant solution.
It was found that by adjusting the basicity to 9.8 or less and immersing the dyed object in it to instantly change the color to deep purple, the dyed object could be dyed in a beautiful purple color. In addition,
The reason why the pH of the mordant liquid is set to be 9.8 or less is because if the object to be dyed is immersed in a mordant liquid with a pH value higher than this, the object to be dyed will become bluish-black and the color will deteriorate. The present invention having the above-mentioned configuration, when producing a dye stock solution, extracts pigments from natural dyes such as purple root and safflower using an organic solvent containing lower alcohol as a main component. Compared to extracting pigments with water or hot water, the extraction efficiency of pigments is higher, the time required for extraction is shortened, and the dyeing stock solution has a high pigment content, making it suitable for use in dyeing. The above-mentioned organic solvents have the advantage that they are cheaper than other organic solvents and cause less harm to the human body during dyeing. Next, when scouring the object to be dyed, scouring is performed using a mordant containing aluminate and silicate instead of using lye such as camellia leaves or straw, which is difficult to collect raw materials and takes time to manufacture as in the past. This saves time and preserves resources such as camellia.Also, immersion in mordant solution is done continuously for a short period of time instead of for a long period of time as in the past, so the time required for scouring is reduced. This will be significantly shortened. Furthermore, when dyeing an object to be dyed, it is immersed in a dyeing stock solution with a high pigment content as described above, and in order to improve the dyeability of the dye dyed onto the object by gallic acid. Therefore, it is possible to obtain a product with sufficient dyeing strength after at least the number of dyeing cycles, and the time required for dyeing is significantly shortened compared to the conventional method, and the fastness of the dyeing is also improved. If the refining and dyeing of the objects to be dyed are shortened in this way, this type of dyeing can be used not only for the restoration of cultural properties as in the past, but also for industrial purposes. This will also be much easier than before. Furthermore, since an organic solvent is used in the dyeing stock solution in this invention, its recovery is easy and economical. Next, in order to further clarify the effects of this invention, purple root, which was known as ancient purple dyeing and conventionally required a very long period of several months to dye, was used as a natural dye, and the method based on this invention was used to dye silk and linen fabrics. ,
Examples will be described in which three types of cotton fabrics to be dyed are dyed. In this example, each of these three types of fabrics was dyed in three stages, and the reflectance curves and values according to the CIE standard color system for each stage were measured. First, in order to produce the dye stock solution in this example, purple root was pulverized with a mixer, immersed in an organic solvent containing methanol and acetone mixed at a ratio of 4:1, and the dye was extracted, followed by filtration. death,
A dark red dye stock solution was obtained. In addition, an aqueous solution containing 10 g of sodium aluminate and 2 g of sodium silicate was used as the mordant, and after adding an aqueous monobasic potassium phosphate solution to make it weakly alkaline, phosphoric acid was added to it to reach a pH of 6.0. Adjusted to. In the process of scouring the object to be dyed, the mordant solution prepared in this way is heated to 80°C, and the above-mentioned 3.
After soaking the various cloths for 30 minutes, the cloths were removed, wrung tightly, and air-dried. Next, these cloths were again immersed in the cooled mordant solution for 15 minutes and air-dried in the same manner. Thereafter, these cloths were further immersed in the mordant solution for 15 minutes at room temperature, and then taken out and tightly squeezed to complete the scouring operation. In the process of dyeing the object to be dyed, each cloth refined as described above is immersed in the dark red dyeing stock solution for 30 minutes while being exposed to the wind from time to time, and then taken out and air-dried. % etching acid aqueous solution for 2 minutes, and then taken out and squeezed tightly to complete the first stage of dyeing. Next, in the second stage of dyeing, after the first stage of dyeing, they were again immersed in the dye stock solution for 15 minutes, taken out and air-dried, then immersed in the mordant solution for 5 minutes, taken out and squeezed. I went there. Further, the third stage of staining was carried out in the same manner after the second stage of staining by immersing it in the dye stock solution for 15 minutes. Then, each cloth dyed in the first to third stages was washed with water and dried, and then the cloth in each stage was immersed in a mordant solution adjusted to pH 8.5 with an aqueous monobasic potassium phosphate solution. and stained purple. Then, for each of these fabrics, the reflectance curve and
Values were measured using the CIE standard color system. First, the reflectance curves for each dyeing stage in the case of silk cloth are as shown in Figure 1.
indicates the third stage. Here, in each reflectance curve, the reflectance in the wavelength band showing purple is low, and the reflectance curve is almost the same as that obtained by dyeing 15 times using the conventional method; It was almost the same as the method used 20 times. As a result, it can be seen that when the method according to the present invention is carried out, a sufficient dyeing state with a deep hue can be obtained with a small number of dyeing times, and the number of dyeing times can be reduced. Further, in the case of silk fabric, the measured values according to the CIE standard color system at each dyeing stage were as shown in Table 1 below.

[Table] The values shown in Table 1 are similar to the values obtained as a result of many conventional stainings, and this table also shows that as the number of staining increases, the Y value decreases and the color density increases. It can be seen that as the value increases, the Pe value increases and the vividness of the color increases. Next, the reflectance curves for each dyeing stage in the case of linen cloth are shown in FIG. 2 in the same manner as in the case of silk cloth, and the measured values according to the CIE standard color system are shown in Table 2 below.

[Table] Here, although the reflectance curve shown in FIG. 2 shows a slightly higher reflectance than that of silk fabric, sufficient dyeing with a deep hue was obtained with a small number of dyeing cycles. Also, the second
The values shown in the table were also slightly inferior to those of silk, but the color density was sufficient and the color was bright. Next, the reflectance curves at each dyeing stage in the case of cotton cloth are shown in FIG. 3, and the measured values according to the CIE standard color system are shown in Table 3 below.

[Table] Here, the state of the reflectance curve shown in Figure 3 and each value shown in Table 3 are inferior to those of silk and linen cloth, but the dyeing state is better than the conventional one. Similarly, the number of times of staining can be reduced. Moreover, from these results, it can be understood that the dyeing method according to the present invention is effective for dyeing protein fibers such as silk cloth.

[Brief explanation of the drawing]

Figures 1 to 3 are diagrams showing reflectance curves at each stage when the dyed material is dyed in three stages using purple root as a natural dye in the present invention. 2 is a diagram when the object to be dyed is linen cloth, and FIG. 3 is a diagram when the object to be dyed is cotton cloth.

Claims (1)

[Claims] 1. A process of extracting pigments from natural dyes such as purple root and safflower using an organic solvent containing a lower alcohol as a main component to produce a dye stock solution, and adding aluminates and silicates to the object to be dyed. A process of immersing the object in a mordant solution containing mordant, squeezing it tightly, and doing this several times in succession to refine the object to be dyed. Dyeing of natural dyes with an organic solvent, comprising the steps of: immersing the object in an aqueous solution, and then repeating, if necessary, alternately immersing the object in the dyeing stock solution and the mordant solution to dye the object. Law. 2 In the process of producing the dye stock solution, purple root is used as a natural dye, the dye is extracted with an organic solvent in which methanol, which is the main component, and acetone are mixed, to produce a dye stock solution, and the object to be dyed is refined. In the process, the mordant solution is adjusted to be neutral or weakly acidic, and the object to be dyed is immersed in it.In the step of dyeing the object, it is immersed in an aqueous gallic acid solution, and if necessary, the object to be dyed is mixed with the dye stock solution and mordant. The natural dye according to claim 1, characterized in that when the object to be dyed is immersed in the mordant solution alternately, the mordant solution is adjusted to have a basic pH of 9.8 or less. Dyeing method using organic solvents.