阅读说明：本技术 一种纤维素纺织品活性染料无盐少水循环染色的方法 (Salt-free less-water circulating dyeing method for cellulose textile reactive dye ) 是由 王强 卫艺敏 王平 余圆圆 周曼 姜哲 于 2021-02-20 设计创作，主要内容包括：本发明公开了一种纤维素纺织品活性染料无盐少水循环染色的方法,属于纺织品生态染整技术领域。本发明首次使用天然疏水性低共熔溶剂体系(HDES)作为染色介质对棉进行活性染料染色。首先将制得的天然疏水性低共熔溶剂与少量染料水溶液高速混合,制备得到染液,然后将浸轧碱液后的棉织物投入染浴中进行染色。该染色方法无需添加无机盐和其他染色助剂,使用了少量水和碱剂就能达到和传统水浴相同的染色效果,并且染色介质安全、环保,染色后的染浴经简单分离处理,就能实现循环染色,真正实现了活性染料的绿色环保染色。(The invention discloses a salt-free and water-less circulating dyeing method for a cellulose textile active dye, belonging to the technical field of ecological dyeing and finishing of textiles. The invention uses a natural hydrophobic eutectic solvent system (HDES) as a dyeing medium for dyeing cotton with reactive dyes for the first time. Firstly, mixing the prepared natural hydrophobic eutectic solvent with a small amount of dye aqueous solution at a high speed to prepare dye solution, and then putting the cotton fabric soaked in the alkali liquor into a dye bath for dyeing. According to the dyeing method, inorganic salt and other dyeing auxiliaries are not required to be added, the same dyeing effect as that of the traditional water bath can be achieved by using a small amount of water and an alkaline agent, the dyeing medium is safe and environment-friendly, the dyeing bath after dyeing can be subjected to simple separation treatment to realize circular dyeing, and the green and environment-friendly dyeing of the reactive dye is really realized.)

1. A dyeing method of cellulose textile reactive dye is characterized in that the dyeing method comprises the steps of mixing hydrophobic eutectic solvent and reactive dye to obtain dye liquor, and then dyeing the cellulose textile by using the dye liquor; the hydrophobic eutectic solvent comprises a hydrogen bond donor and a hydrogen bond acceptor; the water content in the dye liquor is 60-150% o.w.f.

2. Dyeing process according to claim 1, characterized in that the hydrogen bond donor comprises thymol or tetradecanol; the hydrogen bond acceptor comprises menthol or coumarin.

3. Dyeing process according to claim 2, characterized in that the molar ratio of hydrogen bond donor and hydrogen bond acceptor is (0.5-2): 1.

4. Dyeing process according to any one of claims 1 to 3, characterized in that the mass ratio of hydrophobic eutectic solvent to reactive dye is (900- > 990): 1.

5. Dyeing process according to any one of claims 1 to 4, characterized in that the specific steps of the process are:

(1) firstly, uniformly mixing a hydrogen bond donor and a hydrogen bond acceptor to obtain a hydrophobic eutectic solvent;

(2) dissolving a reactive dye in water, and then mixing the reactive dye with the hydrophobic eutectic solvent prepared in the step (1) to obtain a dye solution;

(3) swelling the cotton fabric in a sodium carbonate aqueous solution, and then putting the cotton fabric into a dye solution for dyeing.

6. The dyeing method according to any one of claims 1 to 5, characterized in that the cellulosic textile comprises any one of cellulosic fibers or composite fibers containing cellulosic fibers, yarns, carpet-like fabrics, woven fabrics, knitted fabrics, thermal wadding, fillers, nonwoven fabrics, clothing, apparel, home textiles, ornaments, medical and hygienic articles, or special work clothes.

7. Cellulosic textile dyed by the method according to any one of claims 1 to 6.

8. A dye liquor, characterized in that the dye liquor comprises a hydrophobic eutectic solvent and a reactive dye; the hydrophobic eutectic solvent includes a hydrogen bond donor and a hydrogen bond acceptor.

9. The dye liquor as claimed in claim 8, characterized in that the mass ratio of the hydrophobic eutectic solvent to the reactive dye in the dye liquor is (900- > 990): 1.

10. Use of a dye liquor according to claim 8 or 9 for dyeing.

Technical Field

The invention relates to a salt-free and water-less circulating dyeing method for a cellulose textile active dye, belonging to the technical field of ecological dyeing and finishing of textiles.

Background

The cotton fabric is popular with people because of the characteristics of comfortable wearing, soft material, good air permeability, excellent dyeing performance and the like, and becomes the natural fiber for spinning with the largest consumption. At present, cotton fabrics are mainly dyed by reactive dyes, and are an important production link in the textile printing and dyeing industry. The reactive dye can be combined with the cellulose fiber in a covalent bond mode, so that dyed fabrics have better color fastness, and the reactive dye has the advantages of various types, complete chromatogram, bright color, simple dyeing process and the like, and gradually replaces direct dye, sulfur dye and vat dye to become the main dye for dyeing the cellulose fiber. However, reactive dyes have many disadvantages when used in conventional water baths: (1) the molecular structure of the reactive dye contains water-soluble groups which can be ionized into dye anions in water, cellulose fibers generally have negative charges in a dye bath, and electrostatic repulsion exists between the fibers and the dye, so that the dye-uptake rate of the dye is low, a large amount of neutral electrolyte needs to be added for dyeing promotion, a large amount of electrolyte (such as anhydrous sodium sulphate) is contained in dyeing wastewater, and the treatment difficulty of the dyeing wastewater is increased. (2) The reaction of the active groups on the reactive dye and the fiber needs to be carried out under the alkaline condition, the reactive dye is easy to hydrolyze in a dye bath and can fall off during subsequent water washing and soaping, so that a great amount of hydrolyzed dye is contained in the dyeing wastewater. With the increasing shortage of water resources and the enhancement of environmental protection consciousness of people, the defects of reactive dye dyeing are overcome, the discharge of printing and dyeing wastewater is reduced, and the development of a novel dyeing technology with less water and no salt is a new trend for the development of the current printing and dyeing industry. At present, researches on little water/no water dyeing mainly include supercritical carbon dioxide dyeing, organic solvent dyeing, liquid ammonia dyeing and vacuum sublimation dyeing.

The supercritical carbon dioxide dyeing technology has been studied for more than 30 years and is always a hotspot of non-aqueous medium dyeing research. Although the supercritical carbon dioxide dyeing has many advantages, the dyeing method is applicable to few dyes and fibers, has high requirements on equipment and operators, and has not been applied on an industrial scale. The organic solvent is used as a dyeing medium instead of water, so that the dye hydrolysis can be avoided to a certain extent, the high dye uptake and the high color fixing rate are realized, but the organic solvent can generate new environmental, ecological and safety problems in the dyeing process, the solvent recovery cost is high, and the industrial production can not be realized. The liquid ammonia dyeing has the problems of low color fixing rate, poor color fastness and the like, and the equipment requirement is high; the vacuum sublimation dyeing technology has high requirements on equipment and serious pollution, and cannot be further developed. Therefore, the key point for solving the dyeing problem of the reactive dye is to find an anhydrous/anhydrous dyeing technology which is green, environment-friendly, safe, economical and capable of circularly dyeing.

Disclosure of Invention

[ problem ] to provide a method for producing a semiconductor device

The invention aims to solve the technical problem of providing a method which does not need to use inorganic salt and other dyeing auxiliaries, is environment-friendly, safe and economical, can circularly dye and is suitable for dyeing cellulose textiles by using reactive dyes.

[ technical solution ] A

Eutectic Solvents (DES) are generally composed of two or more compounds, which are a combination of Hydrogen Bond Donors (HBD) and Hydrogen Bond Acceptors (HBA), capable of joining to each other by hydrogen bonding. Most DES studied before 2015 were hydrophilic, which greatly limited their practical application due to miscibility with water. It is against this large background that hydrophobic eutectic solvents appear. The natural hydrophobic eutectic solvent system (HDES) is used as a dyeing medium for dyeing cotton with reactive dye for the first time, and the adopted natural hydrophobic eutectic solvent is prepared from natural component terpene, and is biodegradable, nontoxic, green and environment-friendly. Generally consisting of a hydrogen bond donor and a hydrogen bond acceptor. A small amount of dye water solution and HDES form a semi-stable emulsion system, the low-water salt-free dyeing of the reactive dye is realized on the premise of not using inorganic salt and other dyeing auxiliaries, and due to the hydrophobicity of the HDES, the circular dyeing can be realized by simply separating and treating the dyed dye bath, so that the sewage discharge is greatly reduced.

The first purpose of the invention is to provide a dyeing method of cellulose textile reactive dye, the dyeing method is that hydrophobic eutectic solvent and reactive dye are mixed to obtain dye liquor, and then the cellulose textile is dyed by the dye liquor; the hydrophobic eutectic solvent comprises a hydrogen bond donor and a hydrogen bond acceptor; the water content in the dye liquor is 60-150% o.w.f, wherein the o.w.f refers to the mass percentage relative to the gram weight of the fabric, and the unit is g/g.

In one embodiment of the present invention, the dyeing process does not require the use of inorganic salts and other dyeing aids.

In one embodiment of the invention, the hydrogen bond donor comprises thymol or tetradecanol; the hydrogen bond acceptor comprises menthol or coumarin.

In one embodiment of the invention, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is (0.5-2): 1.

In one embodiment of the invention, the mass ratio of the hydrophobic eutectic solvent to the reactive dye is (990-930): 1.

In one embodiment of the invention, the cotton fabric is soaked in a sodium carbonate aqueous solution to swell the fibers, then the cotton fabric is dyed at a certain liquid carrying rate, and the cotton fabric is dyed at room temperature and then is subjected to temperature rise for fixation.

In one embodiment of the present invention, the method specifically comprises the following steps:

(1) firstly, uniformly mixing a hydrogen bond donor and a hydrogen bond acceptor to obtain a hydrophobic eutectic solvent;

(2) dissolving a reactive dye in water, and then mixing the reactive dye with the hydrophobic eutectic solvent prepared in the step (1) to obtain a dye solution;

(3) swelling the cotton fabric in a sodium carbonate aqueous solution, and then putting the cotton fabric into a dye solution for dyeing.

In one embodiment of the present invention, in the step (1), the hydrogen bond donor is thymol, the hydrogen bond acceptor is menthol, the molar ratio of menthol to thymol is 1:1-2:1, the temperature is 40-60 ℃, and the time is 40-60 min.

In one embodiment of the present invention, the mixing speed of the aqueous dye solution and the menthol-thymol in the step (2) is 10000-14000 rpm.

In one embodiment of the present invention, in the step (2), the bath ratio is 1:20 to 1:40, and the water content in the system is 60% o.w.f to 140% o.w.f, preferably 100% to 120% o.w.f.

In one embodiment of the present invention, in the step (2), the amount of the reactive dye is not particularly limited, and may be determined according to the requirement of the actual dyeing depth, and the reactive dye is a vinylsulfone-based reactive dye, an s-triazine-based dye, or a di-reactive group-based dye; wherein the vinyl sulfone reactive dye is active blue 19, the s-triazine reactive dye is active yellow 3, and the double-active group dye is active red 195.

In one embodiment of the invention, in the step (3), the concentration of sodium carbonate is 20-100g/L, the swelling time is 40-70min, and the liquid carrying rate of the cotton fabric is 60-140%; the concentration of the sodium carbonate is preferably 60g/L, and the liquid carrying rate of the cotton fabric is preferably 100%.

In one embodiment of the present invention, in the step (3), the dyeing process is: dyeing at room temperature for 30min, and heating to 50-70 deg.C for fixing color for 10-60 min; the heating rate is 2 ℃/min, the fixation temperature is preferably 60 ℃, and the fixation time is preferably 30 min.

In one embodiment of the present invention, the cellulose textile includes any one of cellulose fibers or composite fibers containing cellulose fibers, yarns, carpet-like fabrics, woven fabrics, knitted fabrics, thermal insulating batting, fillers, nonwoven fabrics, clothing accessories, home textiles, ornaments, medical and health products, or special work clothes.

In one embodiment of the invention, the cellulose fibers comprise natural cellulose fibers and man-made cellulose fibers.

The second purpose of the invention is to provide a cellulose textile dyed by the method.

A third object of the present invention is to provide a dye liquor comprising a hydrophobic eutectic solvent and a reactive dye; the hydrophobic eutectic solvent includes a hydrogen bond donor and a hydrogen bond acceptor.

In one embodiment of the invention, the mass ratio of the hydrophobic eutectic solvent to the reactive dye in the dye solution is (900- & 990): 1.

In one embodiment of the invention, the water content in the dye liquor accounts for 1-10% of the total dye liquor by mass percent.

In one embodiment of the invention, the dye liquor is an emulsion.

In one embodiment of the invention, the dye liquor is prepared by mixing an aqueous dye solution with a natural hydrophobic eutectic solvent at high speed to obtain a semi-stable emulsion system.

Preferably, the mass ratio of the dye aqueous solution to the hydrophobic eutectic solvent is 1: 19 at 12000 rpm.

In one embodiment of the invention, the dye liquor is a dye liquor capable of circularly dyeing, the dyeing residual liquor is kept stand, a small amount of residual dye aqueous solution is removed, and a clear non-aqueous medium is obtained, namely, the circularly dyeing is realized.

The fourth purpose of the invention is to provide the application of the dye liquor in dyeing.

The invention has the beneficial effects that:

(1) the invention adopts the hydrophobic eutectic solvent as the dyeing medium for the first time, compared with the existing other non-aqueous dyeing media (such as dimethyl sulfoxide, dimethyl carbonate and decamethylcyclopentasiloxane), the components of the deep-dyeing deep.

(2) The dyeing system adopted by the invention can achieve the equivalent dyeing effect of the traditional water bath dyeing without adding any inorganic salt or dyeing auxiliary agent, thereby greatly reducing the wastewater pollution.

(3) The dyeing method only needs trace water, saves a large amount of dyeing water and greatly reduces the discharge of dyeing wastewater compared with the traditional water bath dyeing.

(4) The dye bath after dyeing can recover the hydrophobic eutectic solvent through simple separation operation and carry out circular dyeing, thereby greatly saving the cost and being beneficial to industrial popularization.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.

1. K/S value: the staining depth K/S of the samples was determined under D65 light source and 10 ℃ field of view.

2. Fastness to rubbing: the assay was performed with reference to GB/T3920-.

3. Fastness to soaping: the assay was performed with reference to GB/T3921-.

Example 1:

firstly, menthol and thymol are mixed for 1h under magnetic stirring at 50 ℃ according to the molar ratio of 1:1 to obtain clear and uniform thymol-menthol liquid. Dissolving 2% o.w.f reactive red 195 in 140% o.w.f water at a dyeing bath ratio of 1:20, and mixing the formed reactive red dye aqueous solution and thymol-menthol at high speed of 12000rpm to prepare a dye solution; wherein, menthol-thymol: the mass ratio of the dye was 930: 1. Swelling 1g of cotton fabric in 40g/L sodium carbonate solution for 1h at room temperature, controlling the liquid carrying rate of the cotton fabric to be 120%, putting the cotton fabric into a dye bath, dyeing the cotton fabric for 1h at 25 ℃ in an infrared dyeing machine after a dyeing tank is sealed, then heating to 60 ℃ for fixation for 50min, taking out the fabric after dyeing is finished, washing with cold water, then soaping, washing with hot water and drying. The bath ratio is 1:30, the using amount of sodium carbonate is 2g/L during soaping, the using amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, the time is 10min, and dyes adsorbed and unfixed on the cotton fabrics are removed.

The K/S value of the cotton fabric dyed by the method is 11.9, the color difference delta E is 0.62, the dry rubbing fastness of the dyed fabric is grade 5, the wet rubbing fastness is grade 4-5, and the soaping fastness is grade 5.

Example 2:

firstly, menthol and thymol are mixed for 1h under magnetic stirring at 50 ℃ according to the molar ratio of 1:1 to obtain clear and uniform thymol-menthol liquid. Dissolving 2% o.w.f reactive red 195 in 100% o.w.f water at a dyeing bath ratio of 1:20, and mixing the formed reactive red dye aqueous solution and thymol-menthol at high speed of 12000rpm to prepare a dye solution; wherein, menthol-thymol: the mass ratio of the dye was 950: 1. Swelling 1g of cotton fabric in 40g/L sodium carbonate solution for 1h at room temperature, controlling the liquid carrying rate of the cotton fabric to be 100%, putting the cotton fabric into a dye bath, dyeing the cotton fabric for 1h at 25 ℃ in an infrared dyeing machine after a dyeing tank is sealed, then heating to 60 ℃ for fixation for 50min, taking out the fabric after dyeing is finished, washing with cold water, then soaping, washing with hot water and drying. The bath ratio is 1:30, the using amount of sodium carbonate is 2g/L during soaping, the using amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, the time is 10min, and dyes adsorbed and unfixed on the cotton fabrics are removed.

The K/S value of the cotton fabric dyed by the method is 13.9, the color difference delta E is 0.5, the dry rubbing fastness of the dyed fabric is grade 5, the wet rubbing fastness is grade 4-5, and the soaping fastness is grade 5.

Example 3:

firstly, menthol and thymol are mixed for 1h under magnetic stirring at 50 ℃ according to the molar ratio of 1:1 to obtain clear and uniform thymol-menthol liquid. Dissolving 2% o.w.f reactive red 195 in 100% o.w.f water at a dyeing bath ratio of 1:20, and mixing the formed reactive red dye aqueous solution and thymol-menthol at high speed of 12000rpm to prepare a dye solution; wherein, menthol-thymol: the mass ratio of the dye was 950: 1. Swelling 1g of cotton fabric in 60g/L sodium carbonate solution for 1h at room temperature, controlling the liquid carrying rate of the cotton fabric to be 100%, putting the cotton fabric into a dye bath, dyeing the cotton fabric in an infrared dyeing machine for 40min after a dyeing tank is sealed, then heating to 60 ℃ for fixation for 30min, taking out the fabric after dyeing is finished, washing with cold water, then soaping, washing with hot water, and drying. The bath ratio is 1:30, the using amount of sodium carbonate is 2g/L during soaping, the using amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, the time is 10min, and dyes adsorbed and unfixed on the cotton fabrics are removed.

The K/S value of the cotton fabric dyed by the method is 12.5, the color difference delta E is 0.4, the dry rubbing fastness of the dyed fabric is grade 5, the wet rubbing fastness is grade 4-5, and the soaping fastness is grade 5.

Example 4:

firstly, menthol and thymol are mixed for 1h under magnetic stirring at 50 ℃ according to the molar ratio of 1:1 to obtain clear and uniform thymol-menthol liquid. Dissolving 2% o.w.f reactive red 195 in 100% o.w.f water at a dyeing bath ratio of 1:20, and mixing the formed dye aqueous solution and thymol-menthol at high speed at 12000rpm to prepare a dye solution; wherein, menthol-thymol: the mass ratio of the dye was 950: 1. Swelling 3g of cotton fabric in 60g/L sodium carbonate solution for 1h at room temperature, controlling the liquid carrying rate of the cotton fabric to be 100%, putting the cotton fabric into a dye bath, dyeing the cotton fabric in an infrared dyeing machine for 40min after a dyeing tank is sealed, then heating to 60 ℃ for fixation for 30min, taking out the fabric after dyeing is finished, washing with cold water, then soaping, washing with hot water, and drying. The bath ratio is 1:30, the using amount of sodium carbonate is 2g/L during soaping, the using amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, the time is 10min, and dyes adsorbed and unfixed on the cotton fabrics are removed.

The K/S value of the cotton fabric dyed by the method is 12.7, the color difference delta E is 0.3, the dry rubbing fastness of the dyed fabric is grade 5, the wet rubbing fastness is grade 4-5, and the soaping fastness is grade 5.

Example 5:

firstly, menthol and thymol are mixed for 1h under magnetic stirring at 50 ℃ according to the molar ratio of 1:1 to obtain clear and uniform thymol-menthol liquid. Dissolving 2% o.w.f active blue 19 in 100% o.w.f water at a dyeing bath ratio of 1:20, and mixing the formed active blue dye aqueous solution and thymol-menthol at high speed of 12000rpm to prepare a dye solution; wherein, menthol-thymol: the mass ratio of the dye was 950: 1. Swelling 1g of cotton fabric in 60g/L sodium carbonate solution for 1h at room temperature, controlling the liquid carrying rate of the cotton fabric to be 100%, putting the cotton fabric into a dye bath, dyeing the cotton fabric in an infrared dyeing machine for 40min after a dyeing tank is sealed, then heating to 60 ℃ for fixation for 30min, taking out the fabric after dyeing is finished, washing with cold water, then soaping, washing with hot water, and drying. The bath ratio is 1:30, the using amount of sodium carbonate is 2g/L during soaping, the using amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, the time is 10min, and dyes adsorbed and unfixed on the cotton fabrics are removed.

The cotton fabric dyed according to the method has the K/S value of 12.9, the color difference delta E of 0.58, the dry rubbing fastness of 5 grade, the wet rubbing fastness of 4-5 grade and the soaping fastness of 5 grade.

Example 6:

firstly, menthol and thymol are mixed for 1h under magnetic stirring at 50 ℃ according to the molar ratio of 1:1 to obtain clear and uniform thymol-menthol liquid. Dissolving 2% o.w.f of active yellow 3 in 100% o.w.f of water, wherein the dyeing bath ratio is 1:20, and mixing the formed active yellow dye aqueous solution and thymol-menthol at high speed under 12000rpm to prepare a dye solution; wherein, menthol-thymol: the mass ratio of the dye was 950: 1. Swelling 1g of cotton fabric in 60g/L sodium carbonate solution for 1h at room temperature, controlling the liquid carrying rate of the cotton fabric to be 100%, putting the cotton fabric into a dye bath, dyeing the cotton fabric in an infrared dyeing machine for 40min after a dyeing tank is sealed, then heating to 60 ℃ for fixation for 30min, taking out the fabric after dyeing is finished, washing with cold water, then soaping, washing with hot water, and drying. The bath ratio is 1:30, the using amount of sodium carbonate is 2g/L during soaping, the using amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, the time is 10min, and dyes adsorbed and unfixed on the cotton fabrics are removed.

The K/S value of the cotton fabric dyed by the method is 7.5, the color difference delta E is 0.34, the dry rubbing fastness of the dyed fabric is grade 5, the wet rubbing fastness is grade 4-5, and the soaping fastness is grade 5.

Example 7:

firstly, menthol and thymol are mixed for 1h under magnetic stirring at 50 ℃ according to the molar ratio of 1:1 to obtain clear and uniform thymol-menthol liquid. Respectively dissolving 2% o.w.f reactive red 195, reactive blue 19 and reactive yellow 3 in 100% o.w.f water at a dyeing bath ratio of 1:20, and mixing the formed reactive red dye aqueous solution with thymol-menthol at a high speed of 12000rpm to prepare a dye solution; wherein, menthol-thymol: the mass ratio of the dye was 950: 1. Swelling 3 pieces of 1g of cotton fabric in 60g/L sodium carbonate solution for 1h at room temperature, controlling the liquid carrying rate of the cotton fabric to be 100%, respectively putting the cotton fabric into 3 dye baths, dyeing the cotton fabric in an infrared dyeing machine for 40min at 30 ℃ after the dye baths are sealed, then heating the cotton fabric to 60 ℃ for fixation for 30min, taking the cotton fabric out after dyeing is finished, washing the cotton fabric with cold water, then soaping the cotton fabric, washing the cotton fabric with hot water and drying the cotton fabric. The bath ratio is 1:30, the using amount of sodium carbonate is 2g/L during soaping, the using amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, the time is 10min, and dyes adsorbed and unfixed on the cotton fabrics are removed. The dyed dye bath is simply separated to obtain menthol-thymol, then the same amount of dye and water and a small amount of lost menthol-thymol are added into the solvent, and the dyeing step is repeated for 5 times.

After dyeing for many times according to the method, the K/S value and the color difference of a cloth sample dyed by 3 dyes are similar to those of the first dyeing, and the rubbing fastness and the washing fastness are the same as those of the first dyeing.

Example 8:

cotton fabric was dyed according to the method of example 1 except that the water content in the dye liquor was adjusted to 60% o.w.f, 80% o.w.f, 100% o.w.f, 120% o.w.f, 140% o.w.f, and the other conditions were the same as in example 1, and the results are shown in table 1.

TABLE 1

As can be seen from table 1, the water content is preferably between 100% and 120% o.w.f.

Example 9:

cotton fabric was dyed according to the method of example 1, except that thymol was replaced with tetradecanol and other conditions were the same as in example 1, to produce cotton fabric having a K/S value of 14.70 and a color difference Δ E of 0.94.

Example 10:

cotton fabric was dyed according to the method of example 1, except that menthol was replaced with coumarin under the same conditions as in example 1, to produce a cotton fabric having a K/S value of 13.58 and a color difference Δ E of 0.64.

Example 11: dye liquor

A dye liquor comprises a hydrophobic eutectic solvent and a reactive dye, wherein the mass ratio of the hydrophobic eutectic solvent to the reactive dye is 950: 1; the hydrophobic eutectic solvent consists of menthol and thymol; the molar ratio of the menthol to the thymol is 1: 1. The preparation method of the dye solution comprises the following steps:

firstly, menthol and thymol are mixed for 1h under magnetic stirring at 50 ℃ according to the molar ratio of 1:1 to obtain clear and uniform thymol-menthol liquid. Dissolving 2% o.w.f active blue 19 in 100% o.w.f water at a dyeing bath ratio of 1:20, and mixing the formed dye aqueous solution and thymol-menthol at high speed of 12000rpm to prepare a dye solution; wherein, menthol-thymol: the mass ratio of the dye was 950: 1.

Comparative example 1:

0.02g of reactive red 195 is put into 20ml of water to be dissolved to obtain a dye bath, 1g of cotton fabric is put into the dye bath and dyed at room temperature, the temperature is raised to 60 ℃ at the speed of 2 ℃/min, 0.8g of sodium sulfate is added after dyeing is carried out for 10 minutes, 0.4g of sodium carbonate is added after dyeing is continued for 30 minutes, and color fixing is carried out for one hour. And after dyeing is finished, taking out the fabric, washing with cold water, then soaping, washing with hot water and drying. The bath ratio is 1:30, the using amount of sodium carbonate is 2g/L during soaping, the using amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, the time is 10min, and dyes adsorbed and unfixed on the cotton fabrics are removed.

The K/S value of the cotton fabric dyed by the method is 12.6, the color difference delta E is 0.27, the dry rubbing fastness of the dyed fabric is grade 5, the wet rubbing fastness is grade 4-5, and the soaping fastness is grade 5.

Comparative example 2:

0.02g of reactive blue 19 is put into 20ml of water to be dissolved to obtain a dye bath, 1g of cotton fabric is put into the dye bath and dyed at room temperature, the temperature is raised to 60 ℃ at the speed of 2 ℃/min, 0.8g of sodium sulfate is added after dyeing is carried out for 10 minutes, 0.4g of sodium carbonate is added after dyeing is continued for 30 minutes, and color fixing is carried out for one hour. And after dyeing is finished, taking out the fabric, washing with cold water, then soaping, washing with hot water and drying. The bath ratio is 1:30, the using amount of sodium carbonate is 2g/L during soaping, the using amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, the time is 10min, and dyes adsorbed and unfixed on the cotton fabrics are removed.

The K/S value of the cotton fabric dyed by the method is 13.1, the color difference delta E is 0.34, the dry rubbing fastness of the dyed fabric is grade 5, the wet rubbing fastness is grade 4, and the soaping fastness is grade 5.

Comparative example 3:

0.02g of reactive yellow 3 is put into 20ml of water to be dissolved to obtain a dye bath, 1g of cotton fabric is put into the dye bath and dyed at room temperature, the temperature is raised to 60 ℃ at the speed of 2 ℃/min, 0.8g of sodium sulfate is added after dyeing is carried out for 10 minutes, 0.4g of sodium carbonate is added after dyeing is continued for 30 minutes, and color fixing is carried out for one hour. And after dyeing is finished, taking out the fabric, washing with cold water, then soaping, washing with hot water and drying. The bath ratio is 1:30, the amount of sodium carbonate is 2g/L, the amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, and the time is 10 min. And removing the dye adsorbed and not fixed on the cotton fabric.

The K/S value of the cotton fabric dyed by the method is 7.3, the color difference delta E is 0.46, the dry rubbing fastness of the dyed fabric is grade 5, the wet rubbing fastness is grade 4-5, and the soaping fastness is grade 4-5.

The once dyed cotton fabric and the cotton fabric dyed repeatedly can achieve the color depth and color fastness of conventional water bath dyeing under the same concentration, and salt-free and water-free cyclic dyeing of the reactive dye can be realized.

Comparative example 4:

dyeing of cotton fabric with reference to the method of example 1, except that the hydrophobic eutectic solvent is replaced by a hydrophilic eutectic solvent, the other parameters being the same as in example 1, the method comprising in particular the following steps:

choline chloride and urea are firstly mixed for 1h at 50 ℃ by magnetic stirring according to the molar ratio of 1:2 to obtain clear uniform liquid. Dissolving 2% o.w.f reactive red 195 in 20ml choline chloride-urea, wherein the dyeing bath ratio is 1:20, and preparing into a dye solution. Swelling 1g of cotton fabric in 40g/L sodium carbonate solution for 1h at room temperature, controlling the liquid carrying rate of the cotton fabric to be 120%, putting the cotton fabric into a dye bath, dyeing the cotton fabric for 1h at 25 ℃ in an infrared dyeing machine after a dyeing tank is sealed, then heating to 60 ℃ for fixation for 50min, taking out the fabric after dyeing is finished, washing with cold water, then soaping, washing with hot water and drying. The bath ratio is 1:30, the using amount of sodium carbonate is 2g/L during soaping, the using amount of soap flakes is 2g/L, the soaping temperature is 95 ℃, the time is 10min, and dyes adsorbed and unfixed on the cotton fabrics are removed. The surface of the prepared cotton fabric has no color, which indicates that the reactive dye for the cotton fabric cannot be dyed in a choline chloride-urea system.

The results for the samples of the examples and comparative examples are as follows:

TABLE 2

As can be seen from the results in Table 2, the control results of examples 1, 5 and 6 show that the better dyeing effect can be obtained in the menthol-thymol system for different reactive dyes, and the control results of example 1 and comparative example 1 show that the same effect as the conventional dyeing can be obtained in the menthol-thymol system without adding inorganic salt. Comparative example 4 shows that reactive dyes cannot be dyed in a hydrophilic eutectic solvent system.

Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.