TWI806322B - Dye for material with amide functional groups and dyeing method of using the same - Google Patents

Abstract

A dye for a material with amide functional groups and a dyeing method of using the same are provided. The dye includes a compound represented by Formula (I) and a solvent. Based on the total weight of the dye of 100 wt%, a content of the compound represented by Formula (I) is 40 wt% to 95 wt%.

(I) In Chemical Formula (I), R ₁, R ₂and R ₃are each independently H, -OH or -COOH, wherein at least one of R ₁, R ₂and R ₃is -OH or -COOH.

Description

Dyes for materials having amide functional groups and dyeing methods using the same

The present disclosure relates to a dye and a dyeing method using the same, and in particular to a dye for an amide functional material and a dyeing method using the same.

Polyamide-containing materials (such as nylon materials) are mostly dyed with acid dyes. Acid dyes and polyamide-containing materials form a strong combination of ionic bonds, hydrogen bonds, and van der Waals forces for dyeing. However, currently common acid dyes are mostly azo dyes (-N=N-) containing sulfonic acid groups (-SO ₃ H), and the raw materials for producing such azo dyes (such as aniline or its derivatives substances) are suspected of being carcinogenic and toxic, and will be banned in the future.

Therefore, finding a dye that does not use aniline as a raw material, can be used for dyeing polyamide-containing materials, and can reduce the risk of harm to the environment and human health is a problem that researchers are eager to solve.

The disclosure provides a dye that does not use aniline as a raw material and has excellent dyeing strength for materials with amide functional groups, which is not only beneficial to low-carbon manufacturing processes, but also has commercial value.

The disclosure provides a dyeing method, which can be applied to materials with amide functional groups, and can make the dyed materials have excellent dyeing strength.

(I) 在式(I)中，R ₁、R ₂及R ₃各自獨立地為H、-OH或-COOH， 其中R ₁、R ₂及R ₃中的至少一者為-OH或-COOH，且 按所述染料的總重量為100 wt%計，所述式(I)表示的化合物的含量為40 wt%至95 wt%。 The present disclosure proposes a dye for dyeing materials with amide functional groups, the dye comprising: a compound represented by formula (I); and a solvent,

(I) In formula (I), R ₁ , R ₂ and R ₃ are each independently H, -OH or -COOH, wherein at least one of R ₁ , R ₂ and R ₃ is -OH or -COOH , and based on the total weight of the dye being 100 wt%, the content of the compound represented by the formula (I) is 40 wt% to 95 wt%.

(I) 在式(I)中，R ₁、R ₂及R ₃各自獨立地為H、-OH或-COOH， 其中R ₁、R ₂及R ₃中的至少一者為-OH或-COOH，且 按所述染料的總重量為100 wt%計，所述式(I)表示的化合物的含量為40 wt%至95 wt%。 The disclosure proposes a dyeing method, which includes using a dye solution to contact a material with an amide functional group to perform a dyeing step, wherein the dye solution includes a dye comprising a compound represented by formula (I),

(I) In formula (I), R ₁ , R ₂ and R ₃ are each independently H, -OH or -COOH, wherein at least one of R ₁ , R ₂ and R ₃ is -OH or -COOH , and based on the total weight of the dye being 100 wt%, the content of the compound represented by the formula (I) is 40 wt% to 95 wt%.

Based on the above, the dyes provided in this disclosure can be used for dyeing polyamide materials, and do not use aniline, which is suspected of being toxic, as a raw material, which is not only beneficial to low-carbon manufacturing processes, but also can effectively reduce the risk of harm to the environment and human health. .

Herein, a range indicated by "one value to another value" is a general representation which avoids enumerating all values in the range in the specification. Therefore, the description of a specific numerical range covers any numerical value in the numerical range and the smaller numerical range bounded by any numerical value in the numerical range, as if the arbitrary numerical value and the smaller numerical value are expressly written in the specification. same range.

As used herein, "about," "approximately," "essentially," or "essentially" includes the stated value and averages within acceptable deviations from the particular value as determined by one of ordinary skill in the art, taking into account the The measurement in question and the specific amount of error associated with the measurement (ie, the limitations of the measurement system). For example, "about" can mean within one or more standard deviations of the stated value, or for example within ±30%, ±20%, ±15%, ±10%, ±5%. Furthermore, the terms "about", "approximately", "essentially" or "substantially" used herein can choose a more acceptable range of deviation or standard deviation according to the nature of measurement or other properties, instead of using a standard Deviations apply to all properties.

In order to provide a dye that does not use aniline as a raw material, can be used for polyamide materials, and is beneficial to low-carbon manufacturing processes, the present disclosure proposes a dye containing an indole structure and a dyeing method using the same, which can achieve the above advantages. Hereinafter, the implementation manners are specifically cited as an example in which the present disclosure can be actually implemented.

In this embodiment, the dyes of the present disclosure are dyes for dyeing amide-functional materials. In one embodiment, the material with amide functional groups is, for example, nylon or artificial leather with amide functional groups, or a combination thereof. In one embodiment, the artificial leather with amide functional groups is, for example, polyurethane (Polyurethane, PU) including amide functional groups.

(I) 在式(I)中，R ₁、R ₂及R ₃各自獨立地為H、-OH或-COOH， 其中R ₁、R ₂及R ₃中的至少一者為-OH或-COOH。 In this embodiment, the dye containing an indole structure includes a compound represented by the following formula (I) and a solvent,

(I) In formula (I), R ₁ , R ₂ and R ₃ are each independently H, -OH or -COOH, wherein at least one of R ₁ , R ₂ and R ₃ is -OH or -COOH .

In one embodiment, at least one of R ₁ and R ₂ is —OH, and R ₃ is H or —COOH.

In one embodiment, the compound represented by the formula (I) may include 5,6-dihydroxyindole (5,6-dihydroxyindole; DHI), 5,6-dihydroxyindole-2-carboxylic acid (5 ,6-dihydroxyindole-2-carboxylic acid; DHICA) or a combination of the foregoing.

(DHI)                   (DHICA) The structural formulas of the above-mentioned 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA) are shown below, respectively.

(DHI) (DHICA)

In this embodiment, the compound represented by formula (I) can be obtained by chemical synthesis or biological synthesis. In one embodiment, biosynthesis is, for example, a fermentation product of microorganisms. It should be noted that the compound represented by formula (I) of the present disclosure does not need to use aniline or aniline derivatives as synthetic raw materials, thus reducing the risk of harm to the environment and human health.

In one embodiment, based on the total weight of the dye as 100 wt%, the content of the compound represented by formula (I) can be about 40 wt% to 95 wt%, such as about 55 wt% to 90 wt%, 60 wt% % to 85 wt%, 52 wt%, 58 wt%, 66 wt%, 73 wt%, 76 wt%, 87 wt%, 92 wt%, etc., but the disclosure is not limited thereto.

In one embodiment, the dye of the present disclosure includes a compound represented by formula (I), but the present disclosure is not limited thereto. In another embodiment, the dye of the present disclosure includes more than one, such as two or more compounds represented by formula (I).

In one embodiment, the compound represented by formula (I) includes 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA), and 5,6-dihydroxyindole The weight ratio of indole to 5,6-dihydroxyindole-2-carboxylic acid can be about 1:15 to 15:1, for example can be about 1:12 to 12:1, 1:10 to 10:1, 1:8 to 8:1, 1:5 to 5:1, 1:3 to 3:1, 1:2 to 2:1, 1:9, 5:5, 7:3, 9:1, etc., but The present disclosure is not limited thereto. In one embodiment, users can choose different weight ratios of DHI and DHICA to prepare dyes according to their desired hue (such as brownish or blackish), and use materials with amide functional groups for the dyestuffs. on the dyeing. In one embodiment, the material having the amide functional group is nylon, artificial leather or a combination thereof, but the disclosure is not limited thereto.

In this embodiment, the dye solvent may include water, such as distilled water, deionized water, ultrapure water, or a combination thereof, but the disclosure is not limited thereto. Under the premise that there is no risk of harm to the environment and human beings, users can choose suitable solvents for the preparation of dyes according to actual needs.

In one embodiment, the hue dyed by the dye of the present disclosure is black, brown or a mixture thereof. In one embodiment, the dye of the present disclosure includes 5,6-dihydroxyindole (DHI), and the hue dyed by the dye is black. In another embodiment, the dye of the present disclosure includes 5,6-dihydroxyindole-2-carboxylic acid (DHICA), and the hue dyed by this dye is brown. In one embodiment, the dye disclosed herein includes 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA), and the hue dyed by the dye is Black, brown or a mixture of both. Specifically, the hue can be controlled by adjusting the ratio of 5,6-dihydroxyindole (DHI) to 5,6-dihydroxyindole-2-carboxylic acid (DHICA). In more detail, the higher the content of 5,6-dihydroxyindole-2-carboxylic acid (DHICA), the more brown the hue, and the higher the content of 5,6-dihydroxyindole (DHI), the more brown the hue. leaning toward black.

In one embodiment, the dye is dyed in an acidic environment. In one embodiment, the pH value of the dye of the present disclosure may be 3.5 to 6.5, such as 3.8 to 6.3, 4.0 to 6.0, 4.2 to 5.8, 4.5 to 5.5, etc., but the present disclosure is not limited thereto. In one embodiment, the dye of the present disclosure may have a pH of 4-6. When the dye is in the above pH range, it can ensure that the dyed material has excellent dyeing strength, washing fastness, washing fastness and dry and wet rubbing fastness. In one embodiment, the dye of the present disclosure may further include a pH adjusting agent, and the pH of the dye of the present disclosure may be adjusted through the pH adjusting agent. In one embodiment, the acid-base regulator is, for example, an organic acid, an organic base, an inorganic acid, an inorganic base, or a combination thereof.

In addition, the present disclosure also proposes a dyeing method using the above-mentioned dyes. In this embodiment, a dyeing solution is used to contact the material with amide functional groups to perform the dyeing step. In this embodiment, the dye solution includes the above-mentioned dye containing the compound represented by formula (I), but the present disclosure is not limited thereto. In this embodiment, the material with amide functional group will form -NH ₃ ⁺ in an acidic environment with positive charge, and the functional group ₍ such as hydroxyl or carboxyl) on the dye of the present disclosure has Negatively charged, it will ionic bond with the material with amide functional group, and then dye the material. In one embodiment, the dye solution may further include at least one other dye, such as a commercial dye.

In this embodiment, the concentration of the dyestuff in the dye solution of the present disclosure may be 1% to 25% on weight of the fabric (on weight of the fabric, o.w.f.), such as 2% to 20% to the weight of the fabric, 5% to 18% by weight of fabric, 8% to 15% by weight of fabric, 10% by weight of fabric, 12.5% by weight of fabric, etc., but the disclosure is not limited thereto. The dyestuff disclosed in the present disclosure can ensure that the dyed material has excellent dyeing strength, washing fastness, washing fastness and dry and wet rubbing fastness within the above concentration range.

Generally speaking, in the dyeing and finishing process, the dyeing color depth (K/S, Color strength value) > 3 is the basic condition for dyeing and finishing, and the depth of color strength is related to the amount of dye used and its coloring efficiency. When the concentration of the dye in the dyeing solution used is lower than 1% o.w.f., because the colored component of the dye is too low, the dyeing result will be too light (that is, the K/S value is less than 3), and the dyeing effect will be poor. Conversely, if an excessive amount of dye is used (that is, greater than 25% by weight of the fabric), the discharge residue after dyeing will contain too much dye, which may increase the cost of wastewater treatment and the risk of environmental pollution.

In this embodiment, the reaction temperature of the dyeing step can be 80°C to 130°C, for example, it can be 85°C to 125°C, 90°C to 120°C, 95°C to 115°C, 82°C, 87°C, 93°C, 98°C °C, 105 °C, 112 °C, 122 °C, etc., but the present disclosure is not limited thereto. In this embodiment, the reaction time of the dyeing step can be 30 minutes to 60 minutes, such as 35 minutes to 55 minutes, 40 minutes to 50 minutes, 32 minutes, 38 minutes, 40 minutes, 45 minutes, 50 minutes, 58 minutes Minutes, etc., but not limited to this. In this embodiment, the reaction pH value of the dyeing step may be 3.5 to 6.5, such as 3.8 to 6.3, 4.0 to 6.0, 4.2 to 5.8, 4.5 to 5.5, etc., but not limited thereto. Dyeing the dyestuff disclosed in the present disclosure under the above reaction conditions can ensure that the dyed material has excellent dyeing strength, washing fastness, washing fastness and dry and wet rubbing fastness.

In this embodiment, after the dyeing step is performed to dye the material with amide functional group, the dyed material with amide functional group can be further cleaned to remove excess dye. For the cleaning treatment, water, a lotion, or the like can be used.

In addition, in this embodiment, no matter whether the washing process is performed or not, the dyed material with amide functional group will be dried for subsequent application. The drying treatment is, for example, natural air drying, hot air drying, spin drying, suction drying, and the like.

In this embodiment, the dry and wet rubbing fastness test (AATCC 8) of the dyed material having amide functional groups is grade 4 to 5. The water fastness test (AATCC 107) of the dyed material with amide functional group is grade 4 to 5. The washing fastness test (AATCC 61) of the dyed material having an amide functional group is grade 4 to 5. The dyed material with amide functional groups has an L* value of 8 to 60, an a* value of -5 to 15, a b* value of -10 to 25, and a K/S value of 3 to 35. "L*" represents the perceived brightness (Lightness), L* = 0 indicates black, and L* = 100 indicates white. "a*" and "b*" represent the four unique colors of human vision: red, green, blue and yellow, where "a*" is the Red/Green Value and "a*" is negative A value indicates green, while a positive value of "a*" indicates red. "b*" is blue/yellow value (Blue/Yellow Value), negative value of "b*" indicates blue, and positive value of "b*" indicates yellow.

In addition, as mentioned above, the hue of the dyed material having amide functional groups is black, brown or a mixture of the two. In addition, by adjusting the ratio of the compounds represented by different formulas (I) in the dye, the hue can be controlled as required.

By performing the above steps, the dyeing method proposed in an embodiment of the present disclosure can be completed. It is worth noting that the dyes disclosed herein use non-aniline or non-aniline derivatives as synthetic raw materials, which can not only reduce environmental damage and human health risks, but also meet the requirements of sustainable and low-carbon manufacturing processes in the nylon industry. In addition, the dye disclosed in the present disclosure can effectively dye materials with amide functional groups, and can have dyeing formulas of different shades, which is beneficial for the nylon functional market.

Hereinafter, the present disclosure will be described more specifically with reference to Examples. Although the following examples are described, materials used, their amounts and ratios, processing details, processing flow, and the like can be appropriately changed without departing from the scope of the present disclosure. Accordingly, the present disclosure should not be construed restrictively based on the experiments described below.

Experimental example 1: Use contains DHICA dyes for dyeing nylon cloth

< Example 1>

First, prepare a dye containing 90wt% 5,6-dihydroxyindole-2-carboxylic acid (DHICA), then add the dye to water to prepare a 2% o.w.f. dye solution, and adjust its pH for 5. Next, soak the nylon cloth in the dye solution, and dye it at a reaction temperature of 105°C and a pH value of 5 for 50 minutes, then soap it at 65°C for 15 minutes, then wash it with water and carry out Dried to obtain the dyed nylon cloth of Example 1.

< Example 2>

Dyeing was carried out in a manner similar to that of Example 1, the only difference being that the dye concentration of Example 2 was 5% o.w.f.

< Example 3＞

Dyeing was carried out in a manner similar to Example 1 except that the dye concentration of Example 3 was 10% o.w.f.

< Example 4＞

Dyeing was carried out in a manner similar to that of Example 1 except that the dye concentration of Example 4 was 15% o.w.f.

< Example 5＞

Dyeing was carried out in a manner similar to Example 1 except that the dye concentration of Example 5 was 20% o.w.f.

< Example 6＞

Dyeing was carried out in a manner similar to Example 1 except that the dye concentration of Example 6 was 25% o.w.f.

After obtaining the dyed nylon fabrics of Examples 1-6, the measurement of dyeing strength and physical property tests were performed on the dyed nylon fabrics of Examples 1-6, and the results are shown in Table 1 below. <Measurement of dyeing strength>

， 其中K為吸收係數，S為散射係數，R為最大吸收波長之反射率。 The dyeing strengths of the dyed nylon cloths of Examples 1-6 were measured with a color spectrophotometer (i1Basic Pro 2), and the unit is K/S. The light-absorbing substance is mainly a dye, and the higher the dye concentration, the greater the absorption intensity and the smaller the scattering intensity. The dyeing strength is calculated by the following formula proposed by Kubelka-Munk theory (Kubelka-Munk theory):

, where K is the absorption coefficient, S is the scattering coefficient, and R is the reflectance of the maximum absorption wavelength.

The evaluation methods used in the physical property test of dyed nylon cloth are washing fastness test (AATCC 61), water fastness test (AATCC 107), and dry and wet rubbing fastness test (AATCC 8).

The washing fastness test (AATCC 61) and the water fastness test (AATCC 107) are used to evaluate the degree of fading after washing. It is divided into five grades, and the higher the grade, the less it will fade.

The dry and wet rubbing fastness test (AATCC 8) is an evaluation of the degree of fading after dry rubbing or wet rubbing. It is divided into five grades, and the higher the grade, the less fading.

It is worth noting that the washing fastness test (AATCC 61), water fastness test (AATCC 107), and dry and wet rubbing fastness test have commercial value above level 4.

[Table 1] % owf L* a* b* K/S The color of dyed nylon cloth Washing Fastness Test (AATCC 61) Water Fastness Test (AATCC 107) Dry and Wet Rubbing Fastness Test (AATCC 8) Example 1 2 52.6 5.5 14.1 4.0 brown 4-5 4-5 4-5 Example 2 5 49.2 6.9 14.8 4.7 brown 4-5 4-5 4-5 Example 3 10 45.1 6.9 15.8 7.1 brown 4-5 4-5 4-5 Example 4 15 38.9 6.0 13.5 9.2 brown 4-5 4-5 4-5 Example 5 20 41.2 8.3 16.9 9.6 brown 4-5 4-5 4-5 Example 6 25 34.2 6.9 13.8 13.8 brown 4 4 4

From the above evaluation results, the washing fastness test, water fastness test, and dry and wet rubbing fastness test of the nylon cloth of Examples 1-5 dyed using the disclosed dye (DHICA) are all 4 -5 grade, while the washing fastness test, water fastness test and dry and wet rubbing fastness test of the nylon cloth of embodiment 6 are grade 4, showing that the nylon cloth obtained by dyeing with the dyestuff disclosed has good water washing Comprehensive properties such as fastness, water fastness, dry and wet rubbing fastness, etc., are in line with industrial applicability. In addition, as the dye concentration (% o.w.f.) is higher, its color depth (ie K/S value) is higher. Furthermore, under the dyeing conditions disclosed in the present disclosure, the color of the nylon fabrics of Examples 1-6 has a brown hue.

Experimental example 2: Use contains DHI dyes for dyeing nylon cloth

< Example 7＞

Firstly, 90wt% of 5,6-dihydroxyindole (DHI) was prepared as a dye, and then the dye was added to water to prepare a 5% o.w.f. dye solution, and its pH value was adjusted to 5. Next, immerse the nylon cloth in the dye solution, and dye it at a reaction temperature of 105°C and a pH value of 5 for 50 minutes, then soap it at 65°C for 15 minutes, then wash it with water and dry it. , to obtain the dyed nylon cloth of embodiment 7.

After obtaining the dyed nylon cloth of Example 7, the measurement of dyeing strength and the physical property test were carried out on the dyed nylon cloth of Example 7, and the results are shown in Table 2 below.

[Table 2] % owf L* a* b* K/S The color of dyed nylon cloth Washing Fastness Test (AATCC 61) Water Fastness Test (AATCC 107) Dry and Wet Rubbing Fastness Test (AATCC 8) Example 7 5 12.3 3.7 1.4 21.3 black 4-5 4-5 4-5

From the above evaluation results, the washing fastness test, water fastness test, and dry and wet rubbing fastness test of the nylon cloth of Example 7 dyed with the disclosed dye (DHI) are all 4-5 Grade, showing that the nylon cloth obtained by dyeing with the dye disclosed in this disclosure has good comprehensive properties such as washing fastness, water fastness, dry and wet rubbing fastness, and is in line with industrial applicability. In addition, under the dyeing conditions of the present disclosure, the color of the nylon cloth of Example 7 has a black hue.

Experimental example 3: Use contains DHICA dyes for artificial leather

< Example 8＞

First, prepare a dye containing 90wt% 5,6-dihydroxyindole-2-carboxylic acid (DHICA), then add the dye to water to prepare a 2% o.w.f. dye solution, and adjust its pH for 5. Next, the artificial leather (polyurethane with amide functional groups) is immersed in the dyeing solution, and after dyeing at a reaction temperature of 90°C and a pH value of 5 for 50 minutes, soaping is carried out at 65°C for 15 minutes. Minutes, then washed with clear water and dried to obtain the dyed artificial leather of Example 8.

< Example 9＞

Dyeing was carried out in a similar manner to that of Example 8, the only difference being the polyurethane composition of the artificial leathers of Example 9 and Example 8. In detail, the artificial leather of Example 9 and Example 8 are synthesized by different processes, wherein Example 8 is an artificial leather composed of polyester fiber and polyurethane, while Example 9 is made of polyester microfiber Artificial leather composed of polyurethane.

After obtaining the dyed artificial leathers of Examples 8 and 9, the dyeing intensity and physical properties of the dyed artificial leathers of Examples 8 and 9 were measured respectively, and the results are shown in Table 3 below.

[table 3] % owf L* a* b* K/S Color of artificial leather after dyeing Water Fastness Test (AATCC 107) Example 8 5 59.11 2.78 12.29 8.2 brown 4 Example 9 5 59.31 2.83 11.81 6.9 brown 4

From the above evaluation results, the water fastness tests of the artificial leathers of Examples 8 and 9 after dyeing with the dye (DHICA) disclosed in the present disclosure are all grade 4, which shows that the artificial leather dyed with the dye disclosed in the present disclosure It has good water fastness and meets industrial applicability. In addition, under the dyeing conditions of the present disclosure, the artificial leathers of Examples 8 and 9 have a brown hue.

Experimental example 4: Use contains DHICA as well as DHI dyes for dyeing nylon cloth

< Example 10＞

First, the preparation contains 90wt% of 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA) as dyes, wherein the weight ratio of DHI to DHICA is 1:9 , then add the dye to water to prepare a 2% o.w.f. dye solution, and adjust its pH to 5. Next, immerse the nylon cloth in the dye solution, and dye it at a reaction temperature of 105°C and a pH value of 5 for 50 minutes, then soap it at 65°C for 15 minutes, then wash it with water and dry it. , to obtain the dyed nylon cloth of Example 10.

< Example 11＞

Use the method similar to embodiment 10 to carry out dyeing, and its difference is that the weight ratio of DHI and DHICA in embodiment 11 is 5:5.

< Example 12＞

Use the method similar to embodiment 10 to carry out dyeing, and its difference is that the weight ratio of DHI and DHICA is 7:3 in embodiment 12.

< Example 13＞

Use the method similar to embodiment 10 to carry out dyeing, and its only difference is that the weight ratio of DHI and DHICA in embodiment 13 is 9:1.

After obtaining the dyed nylon fabrics of Examples 10-13, the dyeing intensity and physical property tests were respectively carried out on the dyed nylon fabrics of Examples 10-13, and the results are shown in Table 4 below.

[Table 4] % owf DHI:DHICA L* a* b* K/S The color of dyed nylon cloth Water Fastness Test (AATCC 107) Example 10 2 1:9 52.11 8.32 20.84 4.3 brown black 4-5 Example 11 2 5:5 45.84 7.16 16.09 7.2 brown black 4-5 Example 12 2 7:3 27.81 3.21 6.73 13.8 brown black 4-5 Example 13 2 9:1 18.64 2.82 1.51 19.5 brown black 4

From the above evaluation results, the water fastness test of the nylon fabrics of Examples 10-12 after dyeing using the dyes disclosed in the present disclosure (including DHI and DHICA) are all grades 4-5, while the nylon fabrics of Example 13 The water fastness test is grade 4, which shows that the nylon cloth obtained by dyeing with the dye disclosed in this disclosure has good water fastness, which is in line with industrial applicability. In addition, as the ratio of DHI is higher, the K/S value is higher. In addition, under the dyeing conditions disclosed in the present disclosure, the color of the nylon cloth of Examples 10-13 has a brown-black hue. More specifically, the higher the ratio of DHI, the more black the hue (that is, dark brown-black), and the higher the ratio of DHICA, the more brown the hue (that is, light brown-black). In other words, the dye of the present disclosure can control the hue by adjusting the ratio between DHI and DHICA.

Experimental example 5: in difference pH Dyeing nylon cloth

< Example 14＞

First, the preparation contains 90wt% of 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA) as dyes, wherein the weight ratio of DHI to DHICA is 5:5 , then add the dye to water to prepare a 1% o.w.f. dye solution and adjust its pH to 4.5. Next, soak the nylon cloth in the dyeing solution, and dye it at a reaction temperature of 105°C and a pH value of 4.5 for 50 minutes, then soap it at 65°C for 15 minutes, then wash it with water and dry it. , to obtain the dyed nylon cloth of Example 14.

< Example 15＞

Dyeing was carried out using a method similar to Example 14, the only difference being that the pH value of the dye in Example 15 was 5.

< Example 16＞

Dyeing was carried out using a method similar to Example 14, the only difference being that the pH value of the dye in Example 16 was 6.

< comparative example 1>

Dyeing was performed using a method similar to that of Example 14, the only difference being that the pH value of the dye in Comparative Example 1 was 7.

< comparative example 2>

Dyeing was performed using a method similar to that of Example 14, the only difference being that the pH value of the dye in Comparative Example 2 was 8.

< comparative example 3＞

Dyeing was performed using a method similar to that of Example 14, the only difference being that the pH value of the dye in Comparative Example 3 was 10.

< comparative example 4＞

Dyeing was performed using a method similar to that of Example 14, the only difference being that the pH value of the dye in Comparative Example 4 was 11.

< comparative example 5＞

Dyeing was carried out using a method similar to that of Example 14, the only difference being that the pH value of the dye in Comparative Example 4 was 12.

After obtaining the dyed nylon fabrics of Examples 14-16 and Comparative Examples 1-5, the dyed nylon fabrics of Examples 14-16 and Comparative Examples 1-5 were respectively measured for dyeing strength and physical property tests, The results are shown in Table 5 below.

[table 5] pH value L* a* b* K/S Water Fastness Test (AATCC 107) Example 14 4.5 46.49 7.81 17.34 7.11 4-5 Example 15 5 49.71 7.41 16.70 5.53 4-5 Example 16 6 55.82 7.54 16.61 3.69 4-5 Comparative example 1 7 60.23 7.31 16.71 2.79 4-5 Comparative example 2 8 68.93 3.95 12.32 1.31 4-5 Comparative example 3 10 78.45 2.10 12.45 0.78 4-5 Comparative example 4 11 80.31 1.08 10.42 0.67 4-5 Comparative Example 5 12 87.55 -0.46 2.79 0.31 4-5

From the above evaluation results, dyeing was performed under acidic conditions (pH 4.5-6) compared to Comparative Examples 1-5, which were dyed under neutral or alkaline conditions (pH 7-12). The nylon cloth of Examples 14-16 not only has a water fastness test of 4-5 grades, but also exhibits a better color depth (K/S value).

Experimental example 6: Dyeing nylon cloth at different temperatures

< Example 17＞

Dyeing was carried out using a method similar to that of Example 15, the only difference being that the reaction temperature of Example 17 was 85°C.

< Example 18＞

Dyeing was carried out using a method similar to that of Example 15, the only difference being that the reaction temperature of Example 18 was 95°C.

< Example 19＞

Dyeing was carried out using a method similar to that of Example 15, the only difference being that the reaction temperature of Example 19 was 115°C.

< Example 20＞

Dyeing was carried out using a method similar to that of Example 15, the only difference being that the reaction temperature of Example 20 was 125°C.

< comparative example 6＞

Dyeing was performed using a method similar to that of Example 15, the only difference being that the reaction temperature of Comparative Example 6 was 75°C.

After obtaining the dyed nylon fabrics of Examples 17-20 and Comparative Example 6, the dyed nylon fabrics of Examples 17-20 and Comparative Example 6 were respectively measured for dyeing strength and physical property tests, and the results are shown in the following table 6.

[Table 6] Reaction temperature (°C) L* a* b* K/S Water Fastness Test (AATCC 107) Example 15 105 49.71 7.41 16.70 5.5 4-5 Example 17 85 53.2 6.6 14.9 3.9 4-5 Example 18 95 52.2 7.6 14.4 4.2 4-5 Example 19 115 48.9 7.0 14.1 5.1 4-5 Example 20 125 50.0 7.0 14.0 4.6 4-5 Comparative Example 6 75 60.9 4.9 14.9 2.6 4-5

From the above evaluation results, compared to Comparative Example 6 dyed at a reaction temperature of 75°C, the nylon fabrics of Examples 15, 17-20 dyed at a reaction temperature of 85°C to 125°C , not only the water fastness test can reach 4-5 grades, but also shows a better color depth (K/S value).

Experimental example 7: Use contains DHI Dyes and commercial black dyes for dyeing nylon cloth

< Example 21＞

First, mix 5,6-dihydroxyindole (DHI) and a commercial black dye (Oriental Giant Dyes & Chemical, dye name: Bestalan Black D-R3) to prepare a dye containing 50 wt% DHI, The weight ratio of DHI to commercial black dye is 1:1, and then the mixed dye is added to water to prepare a dye solution (the content of DHI and commercial acid black dye in the dye solution is 5% o.w.f.), and the The pH value was adjusted to 5. Next, immerse the nylon cloth in the dye solution, and dye it at a reaction temperature of 105°C and a pH value of 5 for 50 minutes, then soap it at 65°C for 15 minutes, then wash it with water and dry it. , to obtain the dyed nylon cloth of Example 21.

After obtaining the dyed nylon cloth of Example 21, the measurement of dyeing strength and the physical property test were carried out on the dyed nylon cloth of Example 21, and the results are shown in Table 7 below.

[Table 7] L* a* b* K/S The color of dyed nylon cloth Washing Fastness Test (AATCC 61) Water Fastness Test (AATCC 107) Dry and Wet Rubbing Fastness Test (AATCC 8) Example 21 12.3 -0.7 -2.1 31.5 black 4-5 4-5 4-5

Judging from the above evaluation results, the washing fastness test, water fastness test, and dry and wet dyeing of the nylon cloth of Example 21 after dyeing with the dye mixed with the disclosed dye (DHI) and the commercial black dye were carried out. The rubbing fastness tests are all 4-5 grades, showing that the dyes disclosed in this disclosure can be matched with other commercial dyes, and the nylon cloth obtained by dyeing has good washing fastness, water fastness, dry and wet rubbing fastness, etc. performance, in line with industrial availability. In addition, under the dyeing conditions of the present disclosure, the color of the nylon cloth of Example 21 has a black hue.

In summary, since the dye disclosed herein does not use aniline as a raw material, and can be used for dyeing polyamide materials and is beneficial to low-carbon manufacturing processes, it can effectively reduce environmental hazards and human health risks.

Although the present disclosure has been disclosed above with embodiments, it is not intended to limit the present disclosure. Anyone with ordinary knowledge in the technical field may make some changes and modifications without departing from the spirit and scope of the present disclosure. The scope of protection of this disclosure should be defined by the scope of the appended patent application.

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Claims (19)

A kind of dye, is used for dyeing the material with amide functional group, and described dye is made up of the compound represented by formula (I) and solvent, and wherein said solvent is distilled water, deionized water, ultrapure water or its combination

In the formula (I), R ₁ , R ₂ and R ₃ are each independently H, -OH or -COOH, wherein at least one of R ₁ , R ₂ and R ₃ is -OH or -COOH, And based on the total weight of the dye being 100wt%, the content of the compound represented by the formula (I) is 40wt% to 95wt%. The dye as claimed in item 1, wherein the compound represented by the formula (I) is obtained by chemical synthesis or biological synthesis. The dye as claimed in item 1, wherein the compound represented by the formula (I) includes 5,6-dihydroxyindole (5,6-dihydroxyindole; DHI), 5,6-dihydroxyindole-2-carboxy Acid (5,6-dihydroxyindole-2-carboxylic acid; DHICA) or a combination of the foregoing. The dye according to claim 1, wherein the material having amide functional groups includes nylon, artificial leather or a combination thereof. The dye as claimed in item 1, wherein the dye includes 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid, and 5,6-dihydroxyindole and 5,6 - Dihydroxyindole-2-carboxylic acid in a weight ratio of 1:15 to 15:1. The dye as claimed in item 1, wherein the hue dyed by the dye is black, brown or a mixed color of the two. The dye as claimed in item 1, wherein the pH of the dye is 3.5-6.5. A dyeing method, comprising using a dye solution to contact a material with an amide functional group to carry out a dyeing step, wherein the dye solution includes a dye comprising a compound represented by formula (I), and the dye in the dye solution The concentration is 1% to the weight of the fabric (on weight of the fabric, owf) to 25% to the weight of the fabric,

In the formula (I), R ₁ , R ₂ and R ₃ are each independently H, -OH or -COOH, wherein at least one of R ₁ , R ₂ and R ₃ is -OH or -COOH, And based on the total weight of the dye being 100wt%, the content of the compound represented by the formula (I) is 40wt% to 95wt%. The dyeing method as described in Claim 8, wherein the compound represented by the formula (I) includes 5,6-dihydroxyindole (5,6-dihydroxyindole; DHI), 5,6-dihydroxyindole-2- Carboxylic acid (5,6-dihydroxyindole-2-carbexylic acid; DHICA) or a combination of the foregoing. The dyeing method as claimed in claim 8, wherein the material having amide functional groups includes nylon, artificial leather or a combination thereof. The dyeing method as claimed in item 8, wherein the dye includes 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid, and 5,6-dihydroxyindole and 5, The weight ratio of 6-dihydroxyindole-2-carboxylic acid is 1:15 to 15:1. The dyeing method as claimed in item 8, wherein the hue of the dyed material having an amide functional group is black, brown or a mixed color of the two. The dyeing method as claimed in item 8, wherein the reaction temperature of the dyeing step is carried out at 80°C to 130°C. The dyeing method as claimed in item 8, the reaction pH value of the dyeing step is 3.5 to 6.5. The dyeing method as claimed in item 8, the reaction time of the dyeing step is 30 minutes to 60 minutes. According to the dyeing method described in claim item 8, the wet and dry rubbing fastness test (AATCC 8) of the dyed material having amide functional groups is grade 4 to 5. According to the dyeing method described in claim item 8, the water fastness test (AATCC 107) of the dyed material having amide functional groups is grade 4 to grade 5. According to the dyeing method described in Claim 8, the washing fastness test (AATCC 61) of the dyed material having amide functional groups is grade 4 to 5. According to the dyeing method described in Claim 8, the K/S value of the dyed material having amide functional groups is 3 to 35.