WO2021196103A1

WO2021196103A1 - Water-based nano disperse dye useful for softening finishing and use thereof

Info

Publication number: WO2021196103A1
Application number: PCT/CN2020/082858
Authority: WO
Inventors: 胡会娜; 柏俊峰; 朱亚伟
Original assignee: 南通纺织丝绸产业技术研究院; 苏州大学
Priority date: 2020-04-01
Filing date: 2020-04-01
Publication date: 2021-10-07

Abstract

Disclosed are a water-based nano disperse dye useful for softening finishing and the use thereof. The water-based nano disperse dye is obtained by mixing a raw dye, a surfactant mixture and water and then grinding same, or by mixing a raw dye, a surfactant mixture, an organosilicon softener and water and then grinding same. The surfactant mixture is composed of a cationic surfactant and an amphoteric surfactant. By using the compounded cationic surfactant and amphoteric surfactant and in combination with the use of the organosilicon softener, a nanoscale water-based nano disperse dye satisfying printing and dyeing processing requirements can be rapidly prepared. Obtaining a polyester article with an excellent softness during the dyeing of a polyester fabric is achieved; in addition, same has an excellent placement stability. Not only is the process flow shortened, but the production efficiency is also improved and the energy source is saved.

Description

Water-based nano-disperse dyes capable of being used for soft finishing and their applications

Technical field

The invention belongs to the technical field of dye fine chemicals and textile printing and dyeing, and specifically relates to a water-based nano-dispersed dye and a preparation method and application thereof, which are used in a short process, energy-saving and emission-reducing printing and dyeing process of polyester fabrics.

Background technique

The original disperse dyes cannot be directly used in textile printing and dyeing due to their poor water solubility and large particle diameter. It is necessary to grind the original disperse dyes to prepare disperse dyes with fine particle diameter, good dispersibility and stability to meet the quality requirements of textile printing and dyeing. In the grinding process of the original disperse dyes, the choice of surfactants is extremely important; the surfactants can interact with the organic disperse dyes, which can effectively prevent the disperse dyes with finer particles from agglomerating each other, which can stabilize the dispersion. The function of dye can also effectively prevent the sedimentation of dye particles. Therefore, choosing a suitable surfactant for the grinding of disperse dyes is critical to the preparation of high-quality commercial disperse dyes, and is one of the core technologies for dye preparation.

Dispersant MF is the main auxiliary in the grinding process of disperse dyes. It has a strong dispersing effect on disperse dyes and is often used in the preparation of powdered disperse dyes. Dispersant MF is an anionic surfactant. Similar anionic surfactants to dispersant MF include diffusing agent NNO, dispersing agent CNF, and modified dispersing agent MF. From the perspective of structural categories, anionic surfactants suitable for disperse dye grinding are a class of sodium methylene dimethyl naphthalene sulfonate, sodium methylene dinaphthalene sulfonate, sodium methyl naphthalene sulfonate formaldehyde condensate, and lignin Sodium sulfonate.

Due to the poor water solubility of disperse dyes, although anionic surfactants such as dispersant MF can grind coarse disperse dyes into finer particle sizes, disperse dye solutions containing anionic surfactants are extremely unstable. Settlement or even precipitation is easy to occur, which directly affects the use of commercial disperse dyes and greatly reduces the printing and dyeing performance of disperse dyes. Therefore, disperse dyes containing anionic dispersants are generally processed into powdered disperse dyes, and are not suitable for processing into liquid dyes.

In powdered disperse dyes, the existence of a large amount of anionic dispersant is the main cause of high wastewater discharge and high waste residue discharge in the printing and dyeing industry. As the printing and dyeing industry advances the technical demand for energy saving and emission reduction, the disperse dye grinding technology that uses other high-efficiency surfactants to replace or partially replace anionic dispersants can improve the application performance of commercial dyes from the source of dye preparation, which is a great advantage for the downstream printing and dyeing industry. Substantially reduce the discharge of waste water and waste residues to provide technical support.

The existing published technology shows that by selecting suitable surfactants and combinations, liquid disperse dyes can be prepared. However, due to the weak water solubility of disperse dyes, a large amount of surfactants and auxiliary auxiliaries are still needed to prevent the liquid disperse dyes from settling and agglomerating. Especially when the solid content of the dye is high and the solid content of the surfactant is low, there are still many difficulties in the preparation of water-based disperse dyes, but the water-based disperse dyes of high solid content dyes and low solid content surfactants , Can greatly reduce the low COD discharge of wastewater at the end of dye application from the source of dye preparation.

Silicone softener finishing of polyester fabrics is a conventional technology. Because silicone softeners have weak cationic properties, it is difficult to dye or print in the same bath or one-step process with disperse dyes containing anionic surfactants. This is silicone soft The weak cation of the agent easily forms an ionic bond with the anionic surfactant in the dye, resulting in aggregation, agglomeration and sedimentation. Therefore, the two are rarely used at the same time in actual production. Therefore, after finishing dyeing or printing with organic silicon softener, the process of padding-drying-baking is used to prepare dyed or printed polyester fabric with softness.

technical problem

The present invention provides a water-based disperse dye, which can not only greatly reduce the amount of surfactant in the dye, but also enable the fabric to obtain an excellent softening effect during use, and solve the shortcomings of the existing disperse dye grinding technology. The realization of energy-saving and emission-reduction technology is extremely advantageous and necessary, specifically a water-based nano-disperse dye and its preparation method and application, which are used in the short process, energy-saving and emission-reduction printing and dyeing process of polyester fabrics.

Technical solutions

The invention provides a disperse dye abrasive containing cationic surfactants and amphoteric surfactants, which solves the problems of high additive content and low grinding processing efficiency in the preparation of water-based nano-disperse dyes, and obtains a water-based water-based with excellent application performance. Nano-disperse dyes solve the problem of high pollution emissions that restrict the printing and dyeing industry from the source of fine chemical dyes, and at the same time obtain printing and dyeing textile products with excellent softness.

The present invention adopts the following technical solutions:

A water-based nano-disperse dye. The preparation method of the water-based nano-disperse dye includes the following steps. The original dye, a surfactant mixture and water are mixed and then ground to obtain a water-based nano-disperse dye; or the original dye and surface active The mixture of agent, organic silicon softener and water are mixed and ground to obtain water-based nano disperse dye; the surfactant mixture is composed of a cationic surfactant and an amphoteric surfactant.

A dyeing finishing solution. The preparation method of the dye finishing solution includes the following steps:

(1) Mix the original dye, surfactant mixture and water and then grind to obtain water-based nano disperse dye; or mix the original dye, surfactant mixture, silicone softener and water and grind to obtain water-based nano disperse dye ; The surfactant mixture is composed of a cationic surfactant and an amphoteric surfactant;

(2) Mix the water-based nano-disperse dye of step (1) with water to obtain a dyeing finishing solution.

A dyed polyester fabric, the preparation method of the dyed polyester fabric includes the following steps:

(2) Mix the water-based nano-disperse dye of step (1) with water to obtain a dyeing finishing solution;

(3) Dyeing the polyester fabric with the dyeing finishing solution in step (2) after padding, and then baking, washing, and drying to obtain a dyed polyester fabric.

In the present invention, the original dye, the surfactant mixture, the organic silicon softener and water are mixed and ground in a vertical continuous zirconia equipment for 30 minutes to 45 minutes to obtain a water-based nano-dispersed dye.

Preferably, the present invention only uses cationic surfactants, amphoteric surfactants and silicone softeners as grinding aids without adding other additives, which can effectively grind and disperse the original dyes; the original dyes are used for disperse dyes. One of the conventional original dyes is an untreated dye and belongs to a conventional dye; in the water-based nano-disperse dye, the particle size of the solid is 100 nm to 600 nm.

In the present invention, the mass ratio of the cationic surfactant and the amphoteric surfactant is 1: (0.5-2); the cationic surfactant is an amine salt type cationic surfactant, a quaternary ammonium salt type cationic surfactant One or more of the amphoteric surfactants; the amphoteric surfactant is one of betaine-type amphoteric surfactants, sulfobetaine-type amphoteric surfactants, amino acid-type amphoteric surfactants, and imidazoline-type amphoteric surfactants Kind or several kinds.

Specifically, the cationic surfactant has one or more of the following structures:

(A-1)

(A-2)

(A-3)

In the formula: R ₁ is monostearic acid substituent, coconut oleic acid substituent, lauric acid substituent, oleic acid substituent; R ₂ is -C ₁₂ H ₂₅ , -C ₁₆ H ₃₃ , and R ₃ is methyl, Ethyl hydroxyethyl; R ₄ is -C ₁₇ H ₃₃ , -C ₁₇ H ₃₅ ; R ₅ is ethyl, benzyl, hydroxyethyl; X is chlorine, bromine;

The amphoteric surfactant has one or more of the following structures:

(B-1)

(B-2)

(B-3)

(B-4)

In the formula: R ₆ is -C _14-18 alkyl.

In the present invention, in the water-based nano-disperse dye, the mass percentage of the original dye is 30-60%, the amount of the surfactant mixture is 8-15% of the original dye, and the amount of silicone softener is 0 of the original dye. ～15%, the balance is water.

In the present invention, during padding, the rolling rate is 85%; the drying temperature is 110°C, and the drying time is 150 seconds; the baking temperature is 190°C, and the baking time is 1 minute; and the washing temperature is The temperature is 75°C, and the time is 5 minutes; drying is a conventional technique.

In the present invention, only cationic surfactants and non-ionic surfactants are used as grinding aids without adding other additives, which can effectively disperse the original dye; in particular, in the present invention, without other additives, the disperse dye can be It exists stably with the organic silicon softener, and solves the defect that the prior art requires a large amount of auxiliary agents to stabilize the disperse dyes.

The present invention further discloses the application of the water-based nano-disperse dyes in polyester fabric dyeing, polyester printing or preparing water-based watercolor marker pens.

Beneficial effect

The effective effects of the present invention are: 1) Obtain a water-based nano-dispersed dye with high solid content, the particle size of the dye particles is relatively fine, nano-scale, and has excellent placement stability. 2) Obtain a low surfactant content to prepare water-based nano-disperse dye cationic surfactant and amphoteric surfactant grinding dye formula. 3) Obtain a high-efficiency dye grinding technology with high dye content and low auxiliary agent content. The grinding time is only 30 minutes to 90 minutes, which not only improves production efficiency, but also saves energy. 4) The present invention discloses a grinding technology using cationic surfactants and amphoteric surfactants, which can quickly prepare nano-scale water-based nano-dispersed dyes. 5) Obtain a stable, water-based disperse dye that does not undergo sedimentation and aggregation in which a weak cationic silicone softener and dye coexist, which can realize one-step processing of soft finishing and dyeing. 6) Water-based disperse dyes in which silicone softeners and dyes coexist can improve the color fastness of dyed products, greatly reduce the burden on post-dyeing treatment, significantly reduce wastewater discharge, and reduce the COD value in wastewater .

Description of the drawings

Figure 1 is a particle size distribution diagram of the water-based dye of Example 1.

FIG. 2 is a particle size distribution diagram of the water-based dye of Example 2. FIG.

FIG. 3 is a particle size distribution diagram of the water-based dye of Example 3. FIG.

FIG. 4 is a particle size distribution diagram of the water-based dye in Example 4. FIG.

FIG. 5 is a particle size distribution diagram of the water-based dye of Example 5. FIG.

FIG. 6 is a particle size distribution diagram of the water-based dye of Example 6. FIG.

FIG. 7 is a particle size distribution diagram of the water-based dye of Example 7. FIG.

Fig. 8 is a particle size distribution diagram of the water-based dye of Example 9.

Fig. 9 is a particle size distribution diagram of the water-based dye of Example 11.

10 is a particle size distribution diagram of the water-based dye of Example 13.

11 is a particle size distribution diagram of the water-based dye of Example 15.

FIG. 12 is a particle size distribution diagram of the water-based dye of Example 16. FIG.

FIG. 13 is a particle size distribution diagram of the water-based dye of Example 19.

14 is a particle size distribution diagram of the water-based dye of Example 20.

Figure 15 is a water-based dye particle size distribution diagram of Comparative Example 1.

Figure 16 is a particle size distribution diagram of water-based dyes in Comparative Example 2.

FIG. 17 is a particle size distribution diagram of water-based dyes in Comparative Example 4. FIG.

FIG. 18 is a particle size distribution diagram of water-based dyes in Comparative Example 5. FIG.

Fig. 19 is an experimental diagram of the dye of Comparative Example 6 being ground into agglomerates.

Fig. 20 is an experimental diagram of the dye of Comparative Example 7 being ground into agglomerates.

Fig. 21 is a diagram showing the residual liquid after the dyed fabric of Example 21 is washed with water.

Fig. 22 is a diagram showing the residual liquid after the dyed fabric of Example 22 is washed with water.

Fig. 23 is a diagram showing the residual liquid after the dyed fabric of Example 23 is washed with water.

Fig. 24 is a diagram of the residual liquid after the dyed fabric of Example 24 is washed with water.

Figure 25 is a diagram of the residual liquid after washing the dyed fabric of Example 25.

Fig. 26 is a diagram of the residual liquid after the dyed fabric of Comparative Example 8 is washed with water.

Fig. 27 is a diagram of the residual liquid after the dyed fabric of Comparative Example 9 is washed with water.

Fig. 28 is a diagram of the residual liquid after the dyed fabric of Comparative Example 10 is washed with water.

Figure 29 is a diagram of the residual liquid after the dyed fabric of Comparative Example 11 is washed with water.

Figure 30 is a diagram of the residual liquid after the dyed fabric of Comparative Example 12 is washed with water.

Embodiments of the present invention

The present invention will be further described below in conjunction with embodiments:

All raw materials in the examples are commercially available products, and the weakly cationic silicone softener is softener HS06.

Table 1 is a comparison table of original dyes, Table 2 is a comparison table of cationic surfactants, and Table 3 is a comparison table of amphoteric surfactants, wherein the structure of the cationic surfactant is as follows:

(A-1)

(A-2)

(A-3)

The structure of the amphoteric surfactant is as follows:

(B-1)

(B-2)

(B-3)

(B-4)

The preparation method of the water-based nano disperse dye of the present invention is as follows: the original dye, the surfactant mixture and water are mixed and then ground in a vertical continuous zirconia equipment for 30 minutes to 45 minutes to obtain the water-based nano disperse dye; or the original dye , Surfactant mixture, organic silicon softener and water are mixed and ground in a vertical continuous zirconia equipment for 30 minutes to 45 minutes to obtain water-based nano-dispersed dyes.

... (1) Preparation of water-based disperse dyes

Example 1: Mix 30.00 g of red 92, 1.68 g of A001, 0.84 g of B001 and the remaining amount of water, and grind in a vertical continuous zirconia equipment for 35 minutes to obtain 100 g of water-based nano-disperse dye red 92.

Example 2: Mix 30.00g red 92, 1.68g A001, 0.84g B001, 1.50g softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 40 minutes to obtain 100g water-based nano-disperse dye red 92.

Example 3: Mix 30.00g of red 152, 1.50g of A003, 1.50g of B003, 3.00g of softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 45 minutes to obtain 100g of water-based nano-disperse dye red 152.

Example 4: Mix 35.00 g of red 343, 1.96 g of A004, 0.98 g of B004 and the remaining amount of water, and grind in a vertical continuous zirconia equipment for 45 minutes to obtain 100 g of water-based nano-disperse dye red 343.

Example 5: Mix 35.00g of red 343, 1.67g of A005, 3.35g of B005, 1.75g of softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 35 minutes to obtain 100g of water-based nano-dispersed dye red 343.

Example 6: Mix 35.00g of yellow 114, 1.75g of A006, 1.75g of B006, 5.20g of softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 40 minutes to obtain 100g of water-based nano-dispersed dye yellow 114.

Example 7: Mix 40.00g of yellow 211, 2.00g of A007, 2.00g of B007, 4.00g of softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 30 minutes to obtain 100g of water-based nano-dispersed dye yellow 211.

Example 8: Mix 40.00g orange 30, 2.24g A008, 1.12g B008, 5.80g softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 35 minutes to prepare 100g water-based nano-dispersed dye orange 30.

Example 9: Mix 40.00 g orange 30, 1.91 g A009, 3.00 g B002, 0.83 g B007, 2.50g softener HS and the remaining amount of water are mixed, and ground in a vertical continuous zirconia equipment for 45 minutes to obtain 100g of water-based nano-disperse dye Orange 30.

Example 10: Mix 45.00g orange 44, 2.00g A010, 0.52g A002, 1.26 g B005, 2.25g softener HS and the remaining amount of water are mixed, and grind in a vertical continuous zirconia equipment for 45 minutes to obtain 100g of water-based nano-disperse dye Orange 44.

Example 11: Mix 45.00g orange 44, 2.00g A011, 0.15g A005, 2.00 g B006, 2.31g B003, 6.00g softener HS and the remaining amount of water are mixed, and milled in a vertical continuous zirconia equipment for 40 minutes to obtain 100g of water-based nano-disperse dye orange 44.

Example 12: Mix 50.00g Violet 63, 2.81g A002, 1.40g B006, 2.50g softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 35 minutes to obtain 100g of water-based nano-disperse dye violet 63.

Example 13: Mix 50.00g of Violet 63, 2.39g of A011, 4.79g of B003, 5.00g of softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 40 minutes to obtain 100g of water-based nano-disperse dye violet 63.

Example 14: Combine 50.00g purple 93, 2.00g A011, 0.50g A002, 2.50g Mix B008, 7.40g softener HS and the remaining amount of water, and grind in a vertical continuous zirconia equipment for 40 minutes to obtain 100g of water-based nano disperse dye Violet 93.

Example 15: Mix 55.00g blue 60, 1.00g A009, 1.75g A004, 2.75g B004, 5.50g softener HS and the remaining amount of water were mixed and ground in a vertical continuous zirconia equipment for 35 minutes to obtain 100g of water-based nano-disperse dye blue 60.

Example 16: 55.00g blue 79, 1.00g A007, 2.09g A001, 1.00 g B005, 0.54g B008, 8.00g softener HS and the remaining amount of water are mixed, and milled in a vertical continuous zirconia equipment for 40 minutes to obtain 100g of water-based nano-disperse blue 79.

Example 17: Mix 55.00g blue 79, 2.63g A003, 3.00g B005, 5.26g B001, 2.00g softener HS and the remaining amount of water are mixed, and ground in a vertical continuous zirconia equipment for 40 minutes to obtain 100g of water-based nano-disperse blue 79.

Example 18: Mix 60.00g blue 183, 3.37g A009, 1.68g B007, 8.50g softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 35 minutes to prepare 100g water-based nano-disperse dye blue 183.

Example 19: Mix 60.00g of blue 183, 2.87g of A006, 5.74g of B007, 6.00g of softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 40 minutes to prepare 100g of water-based nano-disperse dye blue 183.

Example 20: Mix 60.00g blue 29:1, 3.00g A008, 1.50g B004, 1.50g B008, 3.50g softener HS and the remaining amount of water were mixed and ground in a vertical continuous zirconia equipment for 30 minutes to obtain 100g of water-based nano-disperse dye blue 291:1.

Comparative Example 1: Mix 40.00 g of Yellow 211, 2.00 g of A007, 4.00 g of softener HS and the remaining amount of water, and grind in a vertical continuous zirconia equipment for 30 minutes to obtain 100 g of disperse dye yellow 211-A.

Comparative Example 2: Mix 45.00g of Orange 44, 2.00g of B006, 2.31g of B003, 6.00g of softener HS and the balance of water, and grind in a vertical continuous zirconia equipment for 40 minutes to obtain 100g of disperse dye orange 44-A .

Comparative Example 3: Take 98.5 g of the water-based disperse dye in Example 1, add 1.5 g of softener HS, and mechanically stir for 5 minutes to obtain 100 g of disperse dye red 92-B.

Comparative example 4: 35.00g yellow 54, 2.10g Tween 80 (polyoxyethylene sorbitan monooleate), 1.05 g glycidyl trimethylammonium chloride (2,3-epoxypropyl trimethyl Ammonium chloride) and the remaining amount of water are mixed, grind in a vertical continuous zirconia equipment for 85 minutes to obtain 100g of water-based disperse dye yellow 54-B.

Comparative example 5: 35.00g yellow 54, 2.10g Tween 80 (polyoxyethylene sorbitan monooleate), 1.05 g glycidyl trimethylammonium chloride (2,3-epoxypropyl trimethyl Ammonium chloride), 4.20g softener HS and the remaining amount of water are mixed, and grind in a vertical continuous zirconia equipment for 45 minutes to obtain 100g of water-based disperse dye yellow 54-C.

Comparative example 6: 35.00g yellow 54, 2.10g Tween 80, 1.05g glycidyltrimethylammonium chloride (2,3-epoxypropyltrimethylammonium chloride), 1.00g anionic diffusing agent MF , 4.20g softener HS is mixed with the remaining amount of water, and ground in a vertical continuous zirconia equipment for 40 minutes to obtain 100g of water-based disperse dye yellow 54-D.

Comparative Example 7: Mix 35.00g blue 60, 1.00g diffusing agent MF, 2.10g quaternary ammonium salt cationic surfactant 1227, 1.05g non-ionic alkyl glycoside APG1214, 4.20g softener HS and the balance of water. Grind in continuous zirconia equipment for 40 minutes to obtain 100 g of water-based disperse dye blue 60-B.

(2) Preparation and dyeing method of dyeing solution

Example 21: 1) Dye solution preparation: 3.5Kg water-based disperse dye red 92 (Example 1) and 96.5Kg water were mixed to prepare a red dye solution; 2) Padding and drying: the polyester fabric was continuously flat The red dye solution is dipped on the rolling trolley, and the rolling rate is controlled to 85%; after the dipping is completed, it is dried on a continuous drying equipment at a drying temperature of 110°C and a drying time of 150 seconds; 3) High temperature Dye fixation: After the drying is completed, high-temperature treatment is performed on the continuous baking machine to complete the dyeing and fixing of the disperse dyes on the polyester fiber. The baking temperature is 190℃, and the baking time is 1 minute; 4) Post-treatment and baking Drying: After the baking is completed, the polyester is washed with hot water in a continuous washing equipment at a washing temperature of 75°C and a washing time of 5 minutes; after the washing is completed, the polyester fabric is conventionally dried to obtain a red polyester dyed fabric.

Example 22: 1) Dye solution preparation: 2.5Kg of water-based disperse dye red 92 (Example 2) and 97.5Kg of water were mixed to prepare a red dye solution. The remaining steps and process condition control are the same as in Example 21.

Example 23: 1) Dye solution preparation: 2.5Kg of water-based disperse dye red 343 (Example 4) and 97.5Kg of water were mixed to prepare a red dye solution. The remaining steps and process condition control are the same as in Example 21.

Example 24: 1) Dye solution preparation: 2.5Kg of water-based disperse dye red 343 (Example 5) and 97.5Kg of water were mixed to prepare a red dye solution. The remaining steps and process condition control are the same as in Example 21.

Example 25: 1) Dye solution preparation: 2.5Kg of water-based disperse dye blue 291:1 (Example 20) and 97.5Kg of water were mixed to prepare a blue dye solution. The remaining steps and process condition control are the same as in Example 21.

Comparative Example 8: 1) Dye solution preparation: 2.5Kg of water-based disperse dye yellow 211-A (Comparative Example 1) and 97.5Kg of water were mixed to prepare a yellow dye solution. The remaining steps and process condition control are the same as in Example 21.

Comparative Example 9: 1) Dye solution preparation: 2.5Kg of water-based disperse dye Orange 44-A (Comparative Example 2) and 97.5Kg of water were mixed to prepare an orange dye solution. The remaining steps and process condition control are the same as in Example 21.

Comparative Example 10: 1) Dye solution preparation: 2.5Kg of water-based disperse dye red 92-B (Comparative Example 3) and 97.5Kg of water were mixed to prepare a yellow dye solution. The remaining steps and process condition control are the same as in Example 21.

Comparative Example 11: 1) Dye solution preparation: 2.5Kg of water-based disperse dye yellow 54-B (Comparative Example 4) and 97.5Kg of water were mixed to prepare a yellow dye solution. The remaining steps and process condition control are the same as in Example 21.

Comparative Example 12: 1) Dye solution preparation: 2.5Kg of water-based disperse dye yellow 54-C (Comparative Example 5) and 97.5Kg of water were mixed to prepare a yellow dye solution. The remaining steps and process condition control are the same as in Example 21.

Performance test of water-based nano-disperse dyes: see Table 4 for test results.

1) Average particle size: Test the average particle size of water-based nano-disperse dyes on a laser particle size analyzer. The figure number description of the dye particle size test chart is shown in Table 4, and the test results are shown in Figure 1 to Figure 18.

2) Centrifugal stability: Take 5ml of the water-based nano-disperse dye to be tested, centrifuge at 3000 rpm for 30 minutes at room temperature, and observe the degree of delamination or sedimentation of the water-based nano-disperse dye.

3) Storage stability: Put 10g sample in a 25ml glass reagent bottle, put it in a (50±2℃) constant temperature drying oven for 14h, take it out and place it at room temperature (20±2℃) for 30 days, observe the liquid dye Delamination or settlement phenomenon.

Continuous dyeing performance test of water-based disperse dyes: see Table 5 and Table 6 for test results.

1) Color fastness to rubbing: Measure and rank according to GB/T 3920-2008 "Textile Color Fastness Test and Color Fastness to Rubbing".

^{2) Fabric softness: Test the bending rigidity B value (gf.cm 2} /cm) and the average friction coefficient MIU value in accordance with FZ/T 01054.1-1999 "General Rules for Testing Methods of Fabric Style". The larger the B value, the harder the bending and the harder the fabric feel; the larger the MIU value, the harder the compression and the harder sliding, and the softer the fabric feel.

3) Absorbance: Test the absorbance value at the maximum absorption wavelength on a visible light spectrophotometer. The larger the absorbance value, the more the amount of dye in the wastewater from the washing residue, which can indirectly characterize the COD value of the wastewater.

It can be seen from Table 4 that the water-based nano-disperse dye prepared by the present invention has a small particle size, and the average particle size of the dye particles ranges from 100nm to 574nm, and the centrifugal stability test and the storage stability test have not been tested. Delamination occurs. The prepared water-based nano-disperse dyes have high-efficiency grinding efficiency and shorter grinding time. The prepared water-based nano-disperse dye has nano-level characteristics, has good stability, and does not appear delamination.

Comparative Example 1 uses yellow 211 ground with only cationic surfactants. Its particle size is larger, with an average particle size of 1819 nm. Delamination and sedimentation have occurred in both the centrifugal stability test and the storage stability test. Even if only the cationic surfactant is used as the abrasive, it is difficult to grind the dye to a nanometer level, and its polishing performance is far lower than that of Example 7 of the present invention.

Comparative Example 2 uses orange 44 milled with only amphoteric surfactants. Its particle size is larger. The average particle size of the orange 44-A dye is 2874nm, and the results show signs of separation after centrifugal stability test and storage stability test. Layers and settlement phenomena. Even if only the amphoteric surfactant is used as the abrasive, it is difficult to grind the dye to nanometer level, and its abrasive performance is far lower than that of Example 11 of the present invention.

Comparative Example 3 is a dye solution mixed with softener HS and water-based disperse dye (the ground dye in Example 1, without softener), and then mechanically stirred for a short period of time, although its average particle size is also small ( 655nm), but due to the short stirring time between the water-based disperse dye and the softener HS, the water-based disperse dye and the softener HS cannot form a sufficient interaction. The centrifugal stability test and the storage stability test both appear delamination And settlement phenomena.

Comparative Example 4 is Yellow 54 ground with non-ionic surfactants and cationic surfactants that are not optimized by the present invention. Its particle size is relatively large, with an average particle size of 1360nm. It appears after centrifugal stability test and storage stability test. Delamination and settlement phenomena.

Comparative Example 5 is yellow 54 ground with non-ionic surfactants and cationic surfactants that are not optimized by the present invention. Its particle size is relatively large, with an average particle size of 3627nm. It appears after centrifugal stability test and storage stability test. Delamination and settlement phenomena.

The results of Comparative Example 6 and Comparative Example 7 show that when anionic surfactants are present, agglomeration and agglomeration are prone to occur due to electrostatic effects, and the dyes cannot be ground and dispersed, showing obvious agglomeration (like mud, no fluidity). .

Mix 30.00g of red 92, 1.68g of diffusing agent MF, 0.84g of B001 and the remaining amount of water, and grind in a vertical continuous zirconia equipment for 35 minutes to obtain 100g of water-based nano-disperse dye red 92, which shows obvious agglomeration and cannot Preparation of disperse dyes.

It can be seen from Table 5 and Table 6 that the water-based disperse dye continuous dyeing polyester fabric prepared by the disclosed technology of the present invention has excellent rubbing fastness for both the unwashed fabric and the washed fabric; the dry rubbing fastness of the unwashed fabric is up to Grade 5, wet rubbing fastness reaches 4-5 grades. The dry rubbing fastness of the washed fabric is up to grade 5, and the wet rubbing fastness is up to grade 5. These properties are better than those of the comparative example, that is, the rubbing fastness of the unwashed fabric and the washed fabric of the comparative example is lower, indicating that the surface of the fabric has a large amount of unfixed dye, and it is still difficult to remove the fiber well after washing with mild hot water. The floating dyes on the surface have low rubbing fastness in dry and wet states. In addition, because the continuous dyeing polyester fabric of water-based disperse dyes prepared by the disclosed technology of the present invention has less dye-fixing power on the surface, the absorbance of the washing residue is low, which indicates that the amount of dye in the wastewater is small, and the chroma is low. The COD value will be lower. In the comparative example, because there are more unfixed dyes on the surface of the dye, more unfixed dyes are washed off during washing, resulting in an increase in the amount of dye in the wastewater, and an increase in the absorbance of the washing residue, which will increase the COD value of the wastewater. The color fastness of the disclosed technology of the present invention needs to increase the burden of post-dyeing treatment, which will inevitably produce more waste water. The water washing COD of the present invention is less than 50 ppm. In addition, comparing the flexural rigidity (B value) and average friction coefficient (MIU value) of the embodiment and the comparative example, it can be seen that when the water-based disperse dye prepared by the disclosed technology of the present invention contains a silicone softener, its B value and MIU value Both are lower, indicating that the dyed fabric feels soft and easy to be slipped, and the softness of the fabric feel becomes better. When the comparative example contains silicone softener, although the amount of softener is higher than that of the examples, its B value and MIU value are higher, and the fabric feel softness is slightly worse. This is because the dyes and auxiliaries in the present invention (including Softener) can form stable micro-nano particles and a stable collection of dyes and auxiliaries. The excellent stability of water-based nano-level dyes can make the dyes/auxiliaries and polyester fabrics form good adsorption and fixation, and the fabrics are well obtained. The uniformity of dyeing, there are no color spots and color blocks on the surface of the fabric. In the comparative example, although the dye and the auxiliary agent can also interact, it is difficult to prepare micro-nano particles and water-based nano-dispersed dyes with excellent stability due to the low grinding and dispersing efficiency of the auxiliary agent on the dye. The interaction between the silicone softener and the dye in the ratio is weak, so it will weaken the good adsorption and diffusion of the silicone softener on the surface of the fiber, and the surface of the fabric will have uneven dyeing color and a small amount of color points and color blocks. .

The technology of the present invention can be used in the printing and dyeing of pure polyester and polyester/spandex fabrics, and can also be applied in water-based watercolor markers, such as mixing 20.0g of red 92 water-based disperse dye (Example 2) with 80.0g of water, Obtained 100.0g of water-based watercolor marker ink, which has the advantage of smooth writing.

Claims

A water-based nano-disperse dye, characterized in that: the preparation method of the water-based nano-disperse dye comprises the following steps: the original dye, a surfactant mixture and water are mixed and then ground to obtain a water-based nano-disperse dye; or The dye, the surfactant mixture, the organic silicon softener and water are mixed and ground to obtain a water-based nano-dispersed dye; the surfactant mixture is composed of a cationic surfactant and an amphoteric surfactant.
The water-based nano-disperse dye according to claim 1, wherein the particle size of the solids in the water-based nano-disperse dye is 100 nm to 600 nm.
The water-based nano-disperse dye according to claim 2, wherein the mass ratio of the cationic surfactant and the amphoteric surfactant is 1: (0.5-2); the cationic surfactant is an amine salt type cationic One or more of surfactants and quaternary ammonium salt-type cationic surfactants; the amphoteric surfactants are betaine-type amphoteric surfactants, sulfobetaine-type amphoteric surfactants, and amino acid-type amphoteric surfactants One or more of imidazoline-type amphoteric surfactants.
The water-based nano-disperse dye according to claim 3, wherein the cationic surfactant has one or more of the following structures:

(A-1)

(A-2)

(A-3)

In the formula: R 1 is monostearic acid substituent, coconut oleic acid substituent, lauric acid substituent, oleic acid substituent; R 2 is -C 12 H 25 , -C 16 H 33 , and R 3 is methyl, Ethyl hydroxyethyl; R 4 is -C 17 H 33 , -C 17 H 35 ; R 5 is ethyl, benzyl, hydroxyethyl; X is chlorine, bromine;

The amphoteric surfactant has one or more of the following structures:

(B-1)

(B-2)

(B-3)

(B-4)

In the formula: R 6 is -C 14-18 alkyl.
The water-based nano-disperse dye according to claim 1, wherein the grinding time is 30 minutes to 45 minutes.
The water-based nano-disperse dye according to claim 1, characterized in that: in the water-based nano-disperse dye, the mass percentage of the original dye is 30-60%, and the amount of the surfactant mixture is 8-15% of the original dye. The amount of silicone softener is 0-15% of the original dye quality, and the balance is water.
A dyeing finishing solution. The preparation method of the dye finishing solution includes the following steps:

(1) Mix the original dye, surfactant mixture and water and then grind to obtain water-based nano disperse dye; or mix the original dye, surfactant mixture, silicone softener and water and grind to obtain water-based nano disperse dye ; The surfactant mixture is composed of a cationic surfactant and an amphoteric surfactant;

(2) Mix the water-based nano-disperse dye of step (1) with water to obtain a dyeing finishing solution.
A dyed polyester fabric, the preparation method of the dyed polyester fabric includes the following steps:

(1) Mix the original dye, surfactant mixture and water and then grind to obtain water-based nano disperse dye; or mix the original dye, surfactant mixture, silicone softener and water and grind to obtain water-based nano disperse dye ; The surfactant mixture is composed of a cationic surfactant and an amphoteric surfactant;

(2) Mix the water-based nano-disperse dye of step (1) with water to obtain a dyeing finishing solution;

(3) Dyeing the polyester fabric with the dyeing finishing solution in step (2) after padding, and then baking, washing, and drying to obtain a dyed polyester fabric.
The dyed polyester fabric according to claim 8, characterized in that: in the water-based nano-disperse dyes, the mass percentage of the original dye is 30-60%, and the amount of surfactant mixture is 8-15% of the original dye. The amount of softener is 0-15% of the original dye quality, and the balance is water.
The use of the water-based nano-disperse dye of claim 1 or the dyeing finishing solution of claim 7 in the dyeing of polyester fabrics or the preparation of water-based watercolor markers.