JP2018109144A - Dye, dye of cellulose fiber, and dyeing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel dye mainly composed of genipin used for dyeing a fiber.SOLUTION: A dye according to the present disclosure contains a polymerization product that is obtained by polymerizing a product from the reaction between contains (a) an amino acid, a polypeptide containing the amino acid, a protein containing the amino acid, or a combination of them and (b) iridoid. The amino acid is histidine, lysine, arginine, tryptophan, asparagine, glutamine, leucine, glycine, glutamic acid, aspartic acid, tyrosine, or a combination of them. The dye can be used for dyeing a fiber.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to fiber dyeing, and more particularly to dyes for dyeing.

  There are many kinds of natural pigments, and the color of food pigments is the most. Among these, gardenia pigments include gardenia red pigment, gardenia yellow pigment, and gardenia blue pigment. Gardenia pigment is a safe and non-toxic natural pigment obtained by biotechnology, and gardenia is cultivated on a large scale in Taiwan. Gardenia blue pigment is produced from genipin obtained by hydrolyzing geniposide contained in gardenia fruit.

U.S. Pat. No. 8,993,325 Taiwan Patent No. I326600 Specification

  The polymerization product obtained by polymerizing the reaction product of amino acid and genipin, which is used as a commercially available edible gardenia blue pigment, cannot be used for dyeing cotton cloth. Thus, there is a current need for new dyes, including genipin, that can be used to dye cotton fabrics or other fibers.

  In one embodiment of the present disclosure, it is obtained by polymerizing a reaction product of (a) an amino acid, a polypeptide containing the amino acid, a protein containing the amino acid, or a combination thereof and (b) an iridoid. A dye comprising a polymerization product is provided wherein the amino acids are histidine, lysine, arginine, tryptophan, asparagine, glutamine, leucine ), Glycine, glutamic acid, aspartic acid, tyrosine, or a combination thereof.

  In a further embodiment of the present disclosure, by polymerizing a reaction product of (a) an amino acid, a polypeptide comprising the amino acid, a protein comprising the amino acid, or a combination thereof and (b) an iridoid. Dyes for cellulose fibers containing the resulting polymerization product are provided, where the amino acids are histidine, lysine, arginine, tryptophan, glutamine, leucine ( leucine), tyrosine, or a combination thereof.

  In a further embodiment of the present disclosure, there is provided a dyeing method comprising the step of fixing the dye to a fiber.

  The naturally occurring dye provided by the present disclosure includes a polymerization product obtained by polymerizing a reaction product of an iridoid and a specific amino acid, and is different from a general commercially available gardenia blue pigment. By selecting a specific amino acid, the dye has a dyeing property on cotton cloth. Further, by treating the surface of the cotton fabric with the organic acid of the object to be dyed, the dyeing rate of the dye to the object to be dyed and the dyeing fastness to water of the dyed fiber product are further increased.

FIG. 3 is a diagram illustrating an ultraviolet-visible (UV-VIS) absorption spectrum of a dye solution according to an embodiment of the present disclosure. FIG. 3 is a diagram illustrating an ultraviolet-visible (UV-VIS) absorption spectrum of a dye solution according to an embodiment of the present disclosure. FIG. 3 is a diagram illustrating an ultraviolet-visible (UV-VIS) absorption spectrum of a dye solution according to an embodiment of the present disclosure. FIG. 3 is a diagram illustrating an ultraviolet-visible (UV-VIS) absorption spectrum of a dye solution according to an embodiment of the present disclosure.

（式中、Ｒ¹、Ｒ²、およびＲ’はそれぞれ独立して、Ｈ、アルキル基、ヒドロキシ基、ヒドロキシアルキル基、または他の任意の官能基である。）本実施形態におけるイリドイドの例としては、例えば、これらに限定される訳ではないが、ゲニポシド（geniposide）、ロガニンアグルコン（loganin aglucon）、オレウロペインアグルコン（oleuropein aglucon）、ペデロシド（Paederoside）、または、これらの加水分解物が挙げられる。ゲニピンを例にとると、加水分解後にゲニピン（genipin，Ｒ’＝ＣＨ₃）またはゲニピン酸（genipin acid，Ｒ’＝Ｈ）になり、ゲニピンやゲニピン酸などのイリドイドとアミノ酸との反応は以下の式１に示すとおりである。

A dye provided by one embodiment of the present disclosure polymerizes a reaction product of (a) an amino acid, a polypeptide comprising an amino acid, a protein comprising an amino acid, or a combination thereof and (b) an iridoid. Wherein the amino acids are histidine, lysine, arginine, tryptophan, asparagine, glutamine, leucine Glycine, glutamic acid, aspartic acid, tyrosine, or combinations thereof. The iridoid has the following structure.

(In the formula, R ¹ , R ² , and R ′ are each independently H, an alkyl group, a hydroxy group, a hydroxyalkyl group, or any other functional group.) Examples of iridoids in this embodiment Includes, but is not limited to, for example, geniposide, loganin aglucon, oleuropein aglucon, pederoside, or hydrolysates thereof. It is done. Taking genipin as an example, it becomes genipin (genipin, R ′ = CH ₃ ) or genipin acid (genipin acid, R ′ = H) after hydrolysis, and the reaction between iridoids such as genipin and genipin acid and amino acids is as follows. As shown in Equation 1.

したがって、式１のＲは、

である。 In Formula 1, when R ′ is CH ₃ , the reaction product exhibits a blue color, that is, a gardenia blue pigment commonly referred to. When R ′ is H, the reaction product exhibits a red color, ie, a gardenia red pigment commonly referred to. The R group in the reaction product depends on the type of amino acid used in the reaction. For example, histidine has the following structure:

Therefore, R in Equation 1 is

It is.

したがって、式１のＲは、

である。 Lysine has the following structure:

Therefore, R in Equation 1 is

It is.

したがって、式１のＲは、

である。 Arginine has the following structure:

Therefore, R in Equation 1 is

It is.

したがって、式１のＲは、

である。 Tryptophan has the following structure:

Therefore, R in Equation 1 is

It is.

したがって、式１のＲは、

である。 Asparagine has the following structure:

Therefore, R in Equation 1 is

It is.

したがって、式１のＲは、

である。 Glutamine has the following structure:

Therefore, R in Equation 1 is

It is.

したがって、式１のＲは、

である。 Leucine has the following structure:

Therefore, R in Equation 1 is

It is.

したがって、式１のＲは、Ｈである。 Glycine has the following structure:

Therefore, R in Formula 1 is H.

したがって、式１のＲは、

である。 Glutamic acid has the following structure:

Therefore, R in Equation 1 is

It is.

したがって、式１のＲは、

である。 Aspartic acid has the following structure:

Therefore, R in Equation 1 is

It is.

When the reaction product of the reaction represented by Formula 1 is polymerized, a dimer, trimer, or tetramer having a structure represented by Formula 2 below is obtained as the polymer. However, the polymer of this embodiment is not limited to these. The reaction product obtained by Formula 1 can be converted into a polymer having a higher molecular weight or a polymer having another structure by a polymerization reaction. That is, it should be noted that the structure of the polymer of the present embodiment is not limited to the structure represented by Formula 2.

  In another embodiment, the starting molar ratio of (a) an amino acid, a polypeptide comprising an amino acid, a protein comprising an amino acid, or a combination thereof and (b) an iridoid is 0.5 : 1 to 30: 1, preferably 1: 1 to 15: 1. When the ratio of (b) iridoid to (a) amino acid, polypeptide containing amino acid, protein containing amino acid, or a combination thereof is too small or too large, the color density of the dye in the object ( Unfavorable effects such as a decrease in color depth.

  In still another embodiment of the present disclosure, a dyeing method including the step of fixing a dye to a fiber is provided. In this embodiment, the fibers subjected to dyeing can be, for example, plant fibers such as cellulose fibers (for example cotton or hemp) or animal fibers (for example wool or silk) that are protein polymers. In certain embodiments, the fiber can be a cellulose fiber (eg, cotton) and the amino acids are histidine, lysine, arginine, tryptophan, glutamine, leucine ), Tyrosine, or a combination thereof. In another embodiment, the fiber can be a protein macromolecule (eg, wool) and the amino acids are histidine, lysine, arginine, tryptophan, asparagine, glutamine ( It can be selected from glutamine, leucine, glycine, glutamic acid, aspartic acid, tyrosine, or combinations thereof.

  In one embodiment, the reaction to produce the dye is performed in a buffer. In order to fix the dye to the fiber, the fiber is directly immersed in a buffer solution in which the dye is dispersed, and for a predetermined time (for example, for 30 minutes to 2 hours), for a predetermined temperature (for example, 70 ° C to 90 ° C). So that the temperature is between). If the heating temperature is too low and / or the heating time is too short, the dye may not be effectively fixed to the fiber. On the other hand, when the heating temperature is too high and / or the heating time is too long, the production cost increases and the dyeing effect may not be further improved. The pH value of the buffer solution containing the dye is preferably between 3 and 12, more preferably between 4 and 9. If the pH value of the buffer is too high, the dyeing depth will be insufficient. On the other hand, if the pH value of the buffer solution is too low, the tissue may be easily damaged depending on the fiber.

  In one embodiment, the fibers are cellulose fibers such as cotton cloth. In the present embodiment, prior to dyeing the cotton cloth, the cotton cloth may be oxidized using an organic acid. For example, the temperature of the oxidation treatment may be between 100 ° C. and 200 ° C., and the treatment time may be between 1 minute and 15 minutes. If the temperature of the oxidation treatment is too low and / or the time is too short, the effect of the oxidation treatment may not be sufficiently obtained. On the other hand, if the temperature of the oxidation treatment is too high and / or the oxidation time is too long, the manufacturing cost increases, and further improvement in the effect of the oxidation treatment may not be obtained. In one embodiment, the organic acid is a polybasic acid, such as a dibasic acid (such as maleic acid), a tribasic acid (such as citric acid), a tetrabasic acid (such as butanetetracarboxylic acid), or a combination thereof. It is. By using a polybasic acid, a part of the carboxylic acid contained in the polybasic acid can react with a large amount of hydroxy groups present on the cotton cloth, and another carboxylic acid can react with the hydroxy group contained in the dye. This increases the fastness between the dye and the cotton fabric. In one embodiment, the concentration of the organic acid contained in the oxidation treatment solution used for the oxidation treatment is, for example, between 0.1 wt% and 30 wt%. If the concentration of the organic acid is too low, the effect of oxidizing the cotton fabric cannot be obtained sufficiently. If the concentration of the organic acid is too high, the fibers of the cotton fabric may be destroyed.

  In one embodiment, the catalyst can be used in combination with an organic acid with additional catalyst in the oxidation process. For example, examples of the catalyst include sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hypophosphite, sodium pyrophosphate, or a combination thereof. By using the catalyst, the treatment time of the oxidation treatment can be shortened.

  The naturally-derived dye provided by the present disclosure includes a polymerization product obtained by polymerizing a reaction product obtained by reacting an iridoid and a specific amino acid. What is a general commercially available gardenia blue pigment? Different. By selecting specific amino acids of the present disclosure, the dye becomes dyeable to cotton fabric. Furthermore, by treating the surface of the cotton fabric of the object to be dyed with an organic acid, the dyeing rate of the dye and the dyeing fastness to water of the dyed cotton fabric can be further enhanced.

  After polymerization of the reaction product of some amino acids (eg glycine, glutamic acid, asparagine, aspartic acid) and iridoid, the polymerization product is a cellulose polymer. The plant fiber (for example, cotton cloth) made of can not be effectively dyed, but has an excellent dyeing effect for animal fiber (for example, wool) made of protein polymer.

  In order that the above and other objects, features and advantages of the present disclosure will be more clearly and easily understood, some examples are given below and described in detail in conjunction with the drawings.

Example 1
Weigh 0.12 g (0.5 mmol) of genipin and 0.077 g (0.5 mmol) of glutamine into 120 mL of acetate buffer (pH = 5.5), and stir at room temperature for 1 hour. The mixture was heated to 80 ° C., reacted for 4 hours, and polymerized to obtain a dye solution in which the dye was dispersed in an acetate buffer.

Example 2
Weigh out 0.12 g (0.5 mmol) of genipin and 0.077 g (0.5 mmol) of lysine, place it in 120 mL of acetate buffer (pH = 5.5), and stir at room temperature for 1 hour. , Heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution. The UV-VIS absorption spectrum of the obtained dye solution is shown in FIG.

Example 3
Weigh out 0.12 g (0.5 mmol) of genipin and 0.092 g (0.5 mmol) of arginine, put it in 120 mL of acetate buffer (pH = 5.5), and stir at room temperature for 1 hour. , Heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution. The UV-VIS absorption spectrum of the obtained dye solution is shown in FIG.

  In addition, 0.12 g (0.5 mmol) of genipin is added to 120 mL of phosphate buffer (pH = 6.5), arginine is added at various molar ratios to genipin shown in Table 1 below, The mixture was stirred for 1 hour, heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution in which the dye was dispersed in the phosphate buffer. Cotton fabric (100% cotton / 20 counts / weight per yard 320g, purchased from Jiaxing Industrial Co., Ltd.) was put into the obtained dye, then heated to 80 ° C and dyed for 1 hour did. Next, the dyed cotton cloth was washed (soaped) with neutral soap, and the color depth of the dyed cotton cloth after washing was observed. The results are shown in Table 1.

Example 4
Weigh out 0.12 g (0.5 mmol) of genipin and 0.069 g (0.5 mmol) of leucine, put them in 120 mL of acetate buffer (pH = 5.5), and stir at room temperature for 1 hour. , Heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution.

Example 5
Weigh out 0.12 g (0.5 mmol) of genipin and 0.108 g (0.5 mmol) of tryptophan, put it in 120 mL of acetate buffer (pH = 5.5), and stir at room temperature for 1 hour. , Heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution.

Example 6
Weigh out 0.12 g (0.5 mmol) of genipin and 0.082 g (0.5 mmol) of histidine, put it in 120 mL of acetate buffer (pH = 5.5), and stir at room temperature for 1 hour. , Heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution.

Example 7
Weigh out 0.12 g (0.5 mmol) of genipin and 0.29 g (1.6 mmol) of tyrosine, put it in 120 mL of acetate buffer (pH = 5.5), and stir at room temperature for 1 hour. , Heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution. The UV-VIS absorption spectrum of the obtained dye solution is shown in FIG.

Example 8
Weigh out 0.12 g (0.5 mmol) of genipin and 0.078 g (0.5 mmol) of glutamic acid, put it in 120 mL of acetate buffer (pH = 5.5), and stir at room temperature for 1 hour. , Heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution. The UV-VIS absorption spectrum of the obtained dye solution is shown in FIG.

Example 9
Weigh out 0.12 g (0.5 mmol) of genipin and 0.21 g (1.5 mmol) of aspartic acid, put it in 120 mL of phosphate buffer (pH = 6.5), and stir at room temperature for 1 hour. Then, the mixture was heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution.

  After putting cotton fabric (100% cotton / 20 count / 320 g weight per yard, purchased from Jiaoxi Co., Ltd.) into the dye solution obtained in Examples 1-9 above, 80% Heated to 0 ° C. and dyed for 1 hour. The staining results are shown in Table 2 below.

  As shown in Table 2, the dye obtained by polymerizing the reaction product obtained by reacting a specific amino acid with genipin was sufficient in the color depth of the cotton fabric after dyeing. . As is apparent from FIGS. 1 to 4, it can be seen that just because the color of the dye solution is relatively dark (the absorbance is higher), the color of the cotton fabric after dyeing does not necessarily become darker. The color depth of the dyed cotton fabric is believed to depend primarily on the strength of the dye to the cotton fabric fibers.

Example 10
Cotton fabric (100% cotton / 20 count / weight per yard 320g, purchased from Jiaoxi Industrial Co., Ltd.), organic acid (optionally added with catalyst) It was put in an aqueous solution containing the composition shown in Table 3, and then taken out and dried under pressure. Next, the treated cotton fabric was dipped again in the above-described aqueous solution containing an organic acid, and then taken out and dried under pressure. The cotton cloth was preheated and dried at 90 ° C. for 3 minutes, and then dried at 150 ° C. for 5 minutes. The cotton cloth obtained by finally washing the cotton cloth with water and then drying by heating was used as the acid-treated cotton cloth.

  Weigh out 0.12 g (0.5 mmol) of genipin and 0.26 g (1.5 mmol) of arginine and place in 120 mL of phosphate buffer (pH = 6.5) for 1 hour at room temperature. After stirring, the mixture was heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution. After the acid-treated cotton cloth was put into the obtained dye solution, it was heated to 80 ° C. and dyed for 1 hour. Next, the dyed cotton cloth was washed (soaped) with neutral soap, and the color depth of the dyed cotton cloth after washing was observed. The results are shown in Table 3.

  As shown in Table 3, the color depth in the cotton fabric dyed by the dye by treating the cotton fabric with a suitable amount of organic polybasic acid (in combination with or in the absence of catalyst). It can be seen that can be further increased.

Example 11
The cotton cloth was placed in an aqueous solution containing an infectious agent such as citric acid, chitosan, and soy protein as shown in Table 4 below, and then taken out and dried under pressure (first treatment). Optionally, the treated cotton fabric may be dipped again in an aqueous solution containing another infectious agent and then taken out and dried under pressure (second treatment). Next, the cotton cloth was preheated and dried at 90 ° C. for 3 minutes, and then dried at 150 ° C. for 5 minutes. Finally, after washing the cotton cloth with water, the cotton cloth obtained by heating and drying was used as the cotton cloth after the dyeing agent treatment. The composition of the aqueous solution containing the infectious agent is shown in Table 4 below.

  Weigh out 0.12 g (0.5 mmol) of genipin and 0.26 g (1.5 mmol) of arginine and place in 120 mL of phosphate buffer (pH = 6.5) for 1 hour at room temperature. After stirring, the mixture was heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution. The cotton fabric after the above-described sensitizing agent treatment was put into this dye solution, heated to 80 ° C., and dyed for 1 hour. Next, the dyed cotton cloth was washed (soaped) with neutral soap, and the color depth of the dyed cotton cloth after washing was observed. The results are shown in Table 4.

  As shown in Table 4, the treatment using an organic acid such as citric acid as an infectious agent is performed by using only soybean protein or chitosan as the infectious agent in dyeing the treated cotton cloth with the dye of this embodiment. The effect is superior to the treatment using.

Comparative Example 1
Weigh out 0.12 g (0.5 mmol) of genipin and 0.198 g (1.5 mmol) of asparagine and place in 120 mL of phosphate buffer (pH = 6.5) for 1 hour at room temperature. After stirring, the mixture was heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution. The cotton cloth was put into this dye solution, heated to 80 ° C., and dyed for 1 hour. The color depth of the cotton fabric after dyeing was low (0.1 k / s).

  Weigh out 0.12 g (0.5 mmol) of genipin and 0.112 g (1.5 mmol) of glycine and place in 120 mL of phosphate buffer (pH = 6.5) for 1 hour at room temperature. After stirring, the mixture was heated to 80 ° C., reacted for 4 hours, and then polymerized to obtain a dye solution. The cotton cloth was put into this dye solution, heated to 80 ° C., and dyed for 1 hour. The color depth of the cotton fabric after dyeing was low (0.23 k / s).

  From the results of Comparative Example 1, not all dyes after reacting and polymerizing all amino acids with genipin are suitable for dyeing cotton fabric.

Comparative Example 2
The cotton cloth was put in a commercially available gardenia blue dye (purchased from Kashin Seikagaku Co., Ltd.) solution, heated to 80 ° C., and dyed for 1 hour. The color depth of the cotton fabric after dyeing was low (0.25 k / s).

  The cotton cloth was treated with a dyeing agent in the same manner as in Example 11 to obtain a cotton cloth after the dyeing agent treatment. The composition of the aqueous solution containing the infectious agent is shown in Table 5 below. The cotton fabric after treatment with the infectious agent was put into a commercially available gardenia blue dye (purchased from Kashin Seikagaku Co., Ltd.) solution, heated to 80 ° C., and dyed for 1 hour. Next, the dyed cotton cloth was washed (soaped) with neutral soap, and the color depth of the dyed cotton cloth after washing was observed. The results are shown in Table 5.

  As shown in Table 5, even when the cotton fabric was first treated with the dyeing agent and dyed, the dyeing effect was still not good when the commercially available gardenia blue pigment was used.

  While the invention has been disclosed in terms of preferred embodiments, they are not intended to limit the invention and those skilled in the art will recognize several variations and modifications without departing from the spirit and scope of the invention. It will be understood that can be added. Therefore, the protection scope of the present invention should be based on what is defined in the following claims.

Claims (15)

(A) an amino acid, a polypeptide containing the amino acid, a protein containing the amino acid, or a combination thereof;
(B) a dye comprising a polymer of a reaction product with an iridoid,
The amino acid is histidine, lysine, arginine, tryptophan, asparagine, glutamine, leucine, glycine, glutamic acid, A dye that is aspartic acid, tyrosine, or a combination thereof.   The dye according to claim 1, wherein the iridoid is genipin or genipin acid.   The molar ratio as a starting material of (a) an amino acid, a polypeptide containing the amino acid, a protein containing the amino acid, or a combination thereof and (b) an iridoid is 0.5: 1 to 30: 3. A dye according to claim 1 or 2 which is between 1.   The molar ratio as a starting material of (a) an amino acid, a polypeptide containing the amino acid, a protein containing the amino acid, or a combination thereof and (b) an iridoid is 1: 1 to 15: 1. 4. A dye according to claim 3, which is open. (A) an amino acid, a polypeptide containing the amino acid, a protein containing the amino acid, or a combination thereof;
(B) a dye for cellulose fibers comprising a polymer of the reaction product with an iridoid,
For cellulose fibers, wherein the amino acid is histidine, lysine, arginine, tryptophan, glutamine, leucine, tyrosine, or combinations thereof Dyes.   A method for dyeing fibers, comprising a step of fixing the dye according to any one of claims 1 to 5 to the fibers.   The method for dyeing fibers according to claim 6, wherein the fibers are fibers made of cellulose fibers or protein polymers.   The fiber is a cellulose fiber, and the amino acids are histidine, lysine, arginine, tryptophan, glutamine, leucine, tyrosine, Alternatively, the fiber dyeing method according to claim 6, which is a combination thereof.   The fiber is a fiber made of a protein polymer, and the amino acids are histidine, lysine, arginine, tryptophan, asparagine, glutamine, leucine ), Glycine, glutamic acid, aspartic acid, tyrosine, or a combination thereof.   The method for dyeing fibers according to claim 6, further comprising a step of oxidizing the fibers with an organic acid before fixing the dye to the fibers, wherein the fibers are cellulose fibers.   The method for dyeing fibers according to claim 10, wherein the temperature of the oxidation treatment is between 100 ° C and 200 ° C, and the treatment time is between 1 minute and 15 minutes.   The method for dyeing fibers according to claim 10 or 11, wherein the organic acid comprises a dibasic acid, a tribasic acid, a tetrabasic acid, or a combination thereof.   In the step of oxidizing the fiber with the organic acid, a catalyst is added, and the catalyst is sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hypophosphite, sodium pyrophosphate, or these The method for dyeing fibers according to claim 10, comprising a combination.   The method for dyeing fibers according to claim 6, wherein the dye is dispersed in a buffer solution.   The method for dyeing fibers according to claim 14, wherein the pH of the buffer solution is between 3 and 12.

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