阅读说明：本技术 一种用于牛仔布的活性染料转移染色方法 (Reactive dye transfer dyeing method for denim ) 是由 钟博文 于 2020-12-17 设计创作，主要内容包括：本发明涉及一种用于牛仔布的活性染料转移染色方法,其包括：1)将牛仔原坯布进行退浆处理,获得牛仔坯布；2)将上染促进液施加到所述牛仔坯布的正面上,得到具有湿涂层的正面；3)采用转移染色设备的第一套印刷版辊,将活性染料墨水印刷在第一套传墨辊或传墨毯带上；4)使步骤2)中得到的具有湿涂层的正面与步骤3)中的第一套传墨辊或传墨毯带密合和压力接触,从而将活性染料墨水从第一套传墨辊或传墨毯带转移到所述正面上,并烘干,以实现牛仔坯布的正面上色；5)将上染促进液施加到所述牛仔坯布的反面上,得到具有湿涂层的反面；6)采用转移染色设备的第二套印刷版辊,将活性染料墨水印刷在第二套传墨辊或传墨毯带上；7)所述步骤5)中得到的具有湿涂层的反面与步骤6)中的第二套传墨辊或传墨毯带密合和压力接触,从而将活性染料墨水从第二套传墨辊或传墨毯带转移到所述反面上,并烘干,以实现牛仔坯布的反面上色；和8)对正面和反面都已经上色的牛仔坯布进行后处理,得到牛仔布产品。(The invention relates to a reactive dye transfer dyeing method for denim, which comprises the following steps: 1) desizing the jean grey cloth to obtain jean grey cloth; 2) applying a dye-promotion liquor to the front side of the jean grey fabric to obtain a wet coated front side; 3) printing reactive dye ink on a first set of ink transfer rollers or ink transfer blanket belts by adopting a first set of printing roller of transfer dyeing equipment; 4) closely and pressure-contacting the front side with the wet coating obtained in the step 2) with the first set of ink transfer rollers or ink transfer blanket belts in the step 3), thereby transferring the reactive dye ink from the first set of ink transfer rollers or ink transfer blanket belts to the front side, and drying to realize front side coloring of the denim fabric; 5) applying a dye-promotion liquor to the reverse side of the denim fabric, resulting in a reverse side with a wet coating; 6) printing reactive dye ink on a second set of ink transfer rollers or an ink transfer blanket belt by adopting a second set of printing plate rollers of transfer dyeing equipment; 7) the reverse side with the wet coating obtained in the step 5) is closely fit and in pressure contact with the second set of ink transfer rollers or ink transfer blanket belts in the step 6), so that the reactive dye ink is transferred from the second set of ink transfer rollers or ink transfer blanket belts to the reverse side and dried to realize the reverse side coloring of the jean blank cloth; and 8) carrying out post-treatment on the colored jean grey cloth on the front surface and the back surface to obtain the jean product.)

1. A reactive dye transfer dyeing method for denim, comprising:

1) desizing the jean grey cloth to obtain jean grey cloth;

2) applying a dye-promotion liquor to the front side of the jean grey fabric to obtain a wet coated front side;

3) printing reactive dye ink on a first set of ink transfer rollers or ink transfer blanket belts by adopting a first set of printing roller of transfer dyeing equipment;

4) closely and pressure-contacting the front side with the wet coating obtained in the step 2) with the first set of ink transfer rollers or ink transfer blanket belts in the step 3), thereby transferring the reactive dye ink from the first set of ink transfer rollers or ink transfer blanket belts to the front side, and drying to realize front side coloring of the denim fabric;

5) applying a dye-promotion liquor to the reverse side of the denim fabric, resulting in a reverse side with a wet coating;

6) printing reactive dye ink on a second set of ink transfer rollers or an ink transfer blanket belt by adopting a second set of printing plate rollers of transfer dyeing equipment;

7) the reverse side with the wet coating obtained in the step 5) is closely fit and in pressure contact with the second set of ink transfer rollers or ink transfer blanket belts in the step 6), so that the reactive dye ink is transferred from the second set of ink transfer rollers or ink transfer blanket belts to the reverse side and dried to realize the reverse side coloring of the jean blank cloth; and

8) and carrying out post-treatment on the colored jean grey cloth on the front surface and the back surface to obtain the jean product.

2. The method of claim 1, wherein the dyeing promoter liquid comprises 3-5% of a dyeing promoter, 2-5% of a binder, 1-3% of a surfactant, 0.5-2% of a leveling agent, and 0-12% of an alkaline agent, based on the total weight of the dyeing promoter liquid;

wherein the dyeing promoter is a di-reactive quaternary ammonium salt compound having an ethyl sulfone group and a monohalos-triazine group of the following formula (I):

wherein M is H or an alkali metal ion, preferably Na or K; y each independently represents H, halogen or straight-chain or branched C_1-12Alkyl of (a), preferably H; each X independently represents halogen, preferably Cl or F, more preferably Cl; and R₁And R₂Each represents a quaternary ammonium group, identical or different, selected from:

or (R)₃)₃N⁺-R₄-,

Wherein R is₃Independently of one another, represents a linear or branched C_1-12Alkyl of (a), preferably methyl, ethyl or propyl; r₄Denotes straight-chain or branched C_1-12Alkylene of (a), preferably ethylene, propylene or butylene; and R₀Represents optionally one or more substituents selected from halogen or C on the phenyl ring_1-8A substituent of the alkyl group of (1).

3. The method of claim 2, wherein M is Na or K; y represents H; x represents Cl; r₃Independently of one another, represents a linear or branched C_1-8Alkyl of (2)More preferably C_1-6Particularly preferably methyl or ethyl; r₄Denotes straight-chain or branched C_1-8Alkylene of (3), more preferably C_2-6Alkylene groups of (a), particularly preferably propylene groups; and/or the benzene ring does not contain a substituent R₀。

4. A method according to claim 2 or 3, wherein the balance of the dyeing promoter liquid is water.

5. The method of any one of claims 2-4, wherein the binder is selected from the group consisting of sodium alginate, guar gum, synthetic gums, cellulose and derivatives thereof, starch and derivatives thereof, multipolymers of acrylic acid, crotonic acid and derivatives thereof, and mixtures thereof.

6. The method of any of claims 2-5, wherein the surfactant is selected from the group consisting of polyvinylpyrrolidone, polyoxyethylenealkylamines, fatty alcohol-polyoxyethylene ethers, silicones, and mixtures thereof.

7. The method according to any one of claims 2-6, wherein the levelling agent is selected from alkali metal alkyl sulfonates such as sodium alkyl sulfonate, alkali metal fatty alcohol sulfates such as sodium higher fatty alcohol sulfate, fatty alcohol polyoxyethylene or polyoxypropylene, and mixtures thereof.

8. The method of any one of claims 1-7, wherein the reactive dye ink comprises, based on the total weight of the reactive dye ink:

25-80%, preferably 30-72%, more preferably 40-65% of a paste slurry comprising 3-20%, preferably 5-15% of guar and/or guar derivatives and 0.1-3%, preferably 0.3-2%, more preferably 0.5-1.5% of chitosan, based on the total weight of the paste slurry; and

2-18%, preferably 4-13% of a reactive dye having a double reactive group.

9. Process according to claim 8, wherein the guar derivative is selected from guar gums having a degree of substitution DS ≥ 0.15 or a degree of substitution DS ≥ 0.25, for example oxidized guar gums, such as hydroxylated or carboxylated guar gums, preferably hydroxypropyl guar or carboxymethyl guar.

10. The method according to claim 8 or 9, wherein the reactive dye having a double reactive group is a fluorine-containing double reactive group reactive dye having a vinylsulfone group or a vinylsulfone group precursor group and a monofluoro-s-triazine group.

11. The method of claim 10, wherein the fluorine-containing double reactive group reactive dye is represented by the following formula:

D-(B-Re)₂ (I)

wherein D is a dye intermediate,

b is a single bond or a linking group, such as-NH-, and

re is an active group which is a group containing a monofluoros-triazinyl group but not a chlorotriazinyl group and a group containing a vinylsulfonyl group (-SO)₂CH＝CH₂) Or a group of vinylsulfonyl precursors.

12. The method of claim 11, wherein the reactive group is selected from a substituted or unsubstituted monofluoros-triazine group represented by the following formula (II), and a vinylsulfone group or a vinylsulfone precursor represented by the following formula (III):

wherein M is H or an alkali metal ion, preferably Na or K; r1 is an ester group selected from the group consisting of sulfates, carboxylates and phosphates, preferably a sulfate group (-OSO)₃-) according to the formula (I); r2 is H, hydroxy, alkyl, alkoxy, amino or mono or di substituted amino; and Y each independently represents H, halogen or straight-chain or branched C_1-12Alkyl of (3), preferably H.

13. The method according to any one of claims 10-12, wherein the group of the vinylsulfone-based precursor is derived from p- (β -ethylsulfone sulfate) aniline.

Technical Field

The invention relates to a printing and dyeing technology in textile industry, in particular to a method for transfer dyeing of denim by using reactive dyes, which can remarkably improve the affinity between the dyes and denim fibers, reduce the residual amount of the dyes, improve the utilization rate of the dyes, and promote energy conservation and consumption reduction.

Background

The classic jean is a coarse twill fabric which is formed by interweaving pure cotton indigo dyed yarns serving as warp yarns, undyed pure cotton white yarns serving as weft yarns and three-over-one-under-one right-oblique tissues. With the development of textile technology, the raw materials of denim fabric are blended with other fibers besides the main cotton fiber, including natural fibers such as hemp, ramie, flax, silk, wool, viscose, tencel, modal, etc., and chemical fibers such as terylene, chinlon, acrylon, spandex, etc.

The jean is produced through dyeing warp and sizing with indigo and weaving. The indigo dyeing of the denim warp yarn comprises three types of rope dyeing, sheet dyeing and suspension ring dyeing, wherein the former two types are connected with sizing, and the latter dyeing is carried out for sizing. Classic denim is usually dyed with indigo dyes and sulphur dyes.

Indigo dye is the most commonly used dye in the denim dyeing process, and about 6 million tons of the indigo dye is used in the world every year. The indigo dye belongs to a reducing dye, is blue powder, is insoluble in water or a general organic solvent, can be dissolved in concentrated sulfuric acid, molten phenol, hot aniline or concentrated acetic acid solution, has a melting point of 390-392 ℃, generates purple sublimation gas when heated to 170 ℃, and cannot be decomposed. Indigo is a water-soluble leuco body in the alkaline sodium hydrosulfite solution, and the leuco acid of the indigo is a white substance slightly soluble in water. Compared with the common vat dye, the indigo dyeing rate is slower, and the phenomenon of insufficient dyeing can occur. In addition, due to the poor bleeding property of the indigo dye, the yarn dyed by the indigo dye shows ring dyeing effect, namely, a remarkable white core area is left in the center of the yarn, and the surface of the fabric is exposed white and clear after the manufactured jeans are stone-milled or rinsed, and the style is unique.

The sulfur dye is an organic compound containing nitro and amino, has a structure similar to that of vat dye, forms a water-soluble leuco body with affinity with the fiber through chemical reduction reaction to dye the fiber, and is tightly combined with the fiber through oxidation process.

Both indigo dyes and sulphur dyes require the use of large amounts of inorganic salts and require extensive washing with water after dyeing to reduce residual dye on the fabric. Generally, waste water of a water washing process of a common denim processing enterprise contains a large amount of inorganic salt and dye, which increases the Chemical Oxygen Demand (COD) of the waste water. It is reported that COD in the wastewater is as high as about 2200-. Therefore, the dyeing process of the denim is not friendly to the environment, and the production cost of the denim is increased along with the stricter environmental protection policy.

In addition, the stability of the dyeing process is poor, and the dyeing process is greatly affected by seasons and environments, and slight changes in conditions cause changes in color and tone, resulting in poor reproducibility. Moreover, the common commercial indigo dye is difficult to dye deep and bright colors, has poor color fastness, especially poor color fastness to rubbing and washing, and is easy to dye other fabrics in the washing process.

In recent years, with the diversification of living needs of people, the market is pursuing multicolor environment-friendly printing and dyeing of denim, and some mixed-color denim dyed by reactive dyes is produced. The reactive dye is an anionic dye, also called reactive dye, the molecule of which contains chemically active groups and can react with fibers such as cotton, wool and the like in aqueous solution to form a co-bond. It is popular because of its characteristics of good brilliance, convenient use and good color fastness. However, the reactive dyes are very easy to hydrolyze while being covalently bonded to the fibers, so that there is a problem that the dye uptake and fixation rate are low. In the traditional dyeing process, a large amount of inorganic salt is usually required to be added to shield negative charge aggregation on the surface of the fiber and improve the dye adsorption performance. But doing so can produce high salt content wastewater that can impact the environment or cause wastewater treatment problems.

In view of the problems in the prior art, the inventor of the present invention has developed a method for transfer dyeing of reactive dyes for denim, which can significantly improve the affinity between the reactive dyes and denim fibers, thereby stabilizing the dyeing quality, increasing the wash fastness, the rubbing resistance and the weather fastness, reducing the residual amount of the dyes, improving the utilization rate of the dyes, simultaneously promoting energy saving and consumption reduction, and reducing the environmental pressure.

Disclosure of Invention

In one aspect, the present invention provides a reactive dye transfer dyeing method for denim, which comprises:

1) desizing the jean grey cloth to obtain jean grey cloth;

2) applying a dye-promotion liquor to the front side of the jean grey fabric to obtain a wet coated front side;

3) printing reactive dye ink on a first set of ink transfer rollers or ink transfer blanket belts by adopting a first set of printing roller of transfer dyeing equipment;

4) closely and pressure-contacting the front side with the wet coating obtained in the step 2) with the first set of ink transfer rollers or ink transfer blanket belts in the step 3), thereby transferring the reactive dye ink from the first set of ink transfer rollers or ink transfer blanket belts to the front side, and drying to realize front side coloring of the denim fabric;

5) applying a dye-promotion liquor to the reverse side of the denim fabric, resulting in a reverse side with a wet coating;

6) printing reactive dye ink on a second set of ink transfer rollers or an ink transfer blanket belt by adopting a second set of printing plate rollers of transfer dyeing equipment;

7) the reverse side with the wet coating obtained in the step 5) is closely fit and in pressure contact with the second set of ink transfer rollers or ink transfer blanket belts in the step 6), so that the reactive dye ink is transferred from the second set of ink transfer rollers or ink transfer blanket belts to the reverse side and dried to realize the reverse side coloring of the jean blank cloth; and

8) and carrying out post-treatment on the colored jean grey cloth on the front surface and the back surface to obtain the jean product.

The desizing treatment involved in step 1) is known in the art. Because cotton fiber commensals, raw cotton pigments and the like contained in the jean grey cloth have adverse effects on the transfer dyeing effect and stability of the jean, the desizing treatment eliminates the adverse effects, thereby improving the water absorption performance of the jean and being beneficial to dye uptake and penetration. For example, the denim gray fabric may be padded in a desizing enzyme solution at about 40-80 ℃ and preferably about 50-60 ℃ for about 2-5 hours and preferably about 3-4 hours, and then washed with hot water at about 60 ℃ or higher, e.g., about 90 ℃, and then washed with water at normal temperature and dried to obtain the denim gray fabric.

Such desizing enzyme solutions are known in the art. An exemplary desizing enzyme solution may comprise about 0.5-1.0% and preferably about 0.6-0.8% desizing enzyme, about 0.5-1.0% and preferably about 0.6-0.9% alkali metal chloride-containing salt, about 0.1-0.5% and preferably 0.2-0.3% nonionic surfactant, and deionized water, based on the total weight of the desizing enzyme solution.

Such desizing enzymes are known in the art and are commercially available, including, for example, mesophilic alpha-amylases or wide-temperature alpha-amylases. The chlorine-containing alkali metal salt is, for example, NaCl or the like. The nonionic surfactants are those known in the art and include, for example, fatty alcohol polyoxyethylene ethers, sorbitan fatty acid esters, polyoxyethylene polyoxypropylene block polymers, polyoxyethylene compound combinations, and the like.

In addition to the above components, the desizing enzyme solution may contain conventional additives known in the art, such as, but not limited to, preservatives (e.g., benzoic, sorbic, dehydroacetic, or diacetic preservatives), activators (e.g., sodium chloride or calcium chloride), and the like.

The application steps involved in step 2) are known in the art. For example, the pre-anilox roller treatment apparatus shown in fig. 1, which is the apparatus shown in application No. 201611223321.3, can be used to apply a dye-uptake promoting solution to the front side of the denim fabric by means of anilox roller coating, resulting in a wet coated front side. Wherein the amount of the dyeing promoting liquid is such that the liquid carrying rate of the jean grey cloth is more than 20%, such as 25-50%. Wherein the anilox roll may comprise a laser engraved chrome plated anilox roll or a ceramic anilox roll, which may have a thread count of about 60-200 threads/cm, preferably 80-160 threads/cm.

Hereinafter, the process of applying the dye-uptake promoting liquid to the jean grey fabric in steps 2) and 5) will be described with reference to fig. 1.

The pretreatment apparatus shown in fig. 1 includes a pressure-bearing main roll 1, and a fabric is wrapped around the pressure-bearing main roll 1. Two sides of the pressure-bearing main roller 1 are respectively provided with an anilox roller coating head device which mainly comprises an anilox roller 2, a closed scraper 3, a material receiving groove 4 and an anilox roller feeding mechanism. The left and right anilox roller coating head devices have the same structure. The pressure-bearing main roller 1 is fixed on a frame. One side of each anilox roller 2 is opposite to the pressure-bearing main roller 1, and the other side is provided with a closed type scraper 3. The outer diameter of the pressure-bearing main roller 1 is larger than that of the anilox roller 2. The pressure-bearing main roller 1 and the anilox roller 2 are horizontally arranged, and the axes are on the same straight line. During sizing, two anilox rolls 2 are brought into contact with a pressure-bearing main roll 1 with a suitable pressure by means of air cylinders. The pressure-bearing main roller 1 is driven to rotate by a pressure-bearing main roller motor, the anilox roller motor does not work at the moment, the two anilox rollers 2 are driven to rotate only by the rotation of the pressure-bearing main roller 1, and the rotation of the pressure-bearing main roller 1 is driven to the anilox rollers under the action of the one-way bearing of the anilox rollers 2 at the moment. Meanwhile, the closed scraper is contacted/separated with/from the anilox roller through the scraper driving mechanism, and the scraper body, the roller body and the corresponding sealing component are matched to form a closed cavity in a contact state. The required dye-uptake promoting liquid can be injected into the closed cavity from an injection port arranged on the closed scraper by using a pump. In addition, the closed scraper is provided with a sealable discharge port for discharging the dye promotion liquid in the cavity. And the dyeing promoting liquid in the cavity is coated on the fabric through the anilox roller along with the rotation of the pressure-bearing main roller and the anilox roller. During production pauses, the two anilox rolls 2 are separated from the pressure-bearing main roll 1 by means of air cylinders. At this time, the anilox roller is driven to rotate by an anilox roller motor so as to be cleaned quickly.

The dye-uptake enhancing fluid is the dye-uptake enhancing composition disclosed in application No. 202011328829.6, which is incorporated herein by reference in its entirety.

Specifically, the dyeing promoter composition comprises 3-5% of a dyeing promoter, 2-5% of a binder, 1-3% of a surfactant, 0.5-2% of a leveling agent, and 0-12% of an alkaline agent, based on the total weight of the dyeing promoter composition. The balance of the dyeing promoter composition includes additives, conditioners, salts, dispersants, solvents, and the like known in the art. Preferably, the balance of the dyeing promoter composition is a dispersant or solvent, such as water.

The dyeing promoter is a double-active group quaternary ammonium salt compound with an ethyl sulfone group and a monohalogen s-triazine group, and has the following structural formula (I):

wherein M is H or an alkali metal ion, preferably Na or K;

y each independently represents H, halogen, straight-chain or branched C_1-12Alkyl, preferably H;

each X independently represents halogen, preferably Cl or F, more preferably Cl; and

R₁and R₂Each represents a quaternary ammonium group, identical or different, selected from:

or (R)₃)₃N⁺-R₄-,

Wherein R is₃Independently of one another, represents a linear or branched C_1-12Alkyl, preferably methyl, ethyl or propyl, R₄Denotes straight-chain or branched C_1-12Alkylene, preferably ethylene, propylene or butylene, and R₀Represents optionally one or more (e.g. 1, 2, 3 or 4) substituents on the phenyl ring selected from halogen or C_1-8A substituent of an alkyl group.

In the context of the present application, the term "alkali metal" denotes a metal element of main group I of the periodic table of the elements, including Li, Na and K, etc., preferably Na or K.

In the context of the present application, the term "alkyl" preferably denotes straight-chain or branched alkyl having 1 to 12, preferably 1 to 8 or 1 to 4, carbon atoms, and one or more H on a carbon atom may be substituted by halogen, such as F, Cl or Br. In a preferred embodiment, said alkyl group represents unsubstituted C_1-8More preferably C_1-4Such as methyl, ethyl, propyl or butyl.

In the context of the present application, the term "halogen" preferably comprises F, Cl and Br, more preferably represents Cl.

Radical R₀Represents optionally one or more substituents selected from halogen or C on the phenyl ring_1-8A substituent of the alkyl group of (1). In a preferred embodiment, the individual phenyl rings of the formula (I) have no substituents R₀I.e. the phenyl ring is unsubstituted.

According to the invention, in preferred compounds of formula (I): m is Na or K; y represents H; x represents Cl; r₃Independently of one another, represents a linear or branched C_1-8More preferably C_1-6Particularly preferably methyl or ethyl; r₄Denotes straight-chain or branched C_1-8Alkylene of (3), more preferably C_2-6Alkylene groups of (a), particularly preferably propylene groups; and/or the benzene ring does not contain a substituent R₀。

The compounds of formula (I) as described above may be prepared by a process comprising the steps of:

(1) one or more R is selected from optionally substituted by one or more R₀The group-substituted m-phenylhydroxyalkyl trialkyl ammonium salt, p-phenylhydroxyalkyl trialkyl ammonium salt or trialkyl ammonium salt of hydroxyalkyl trialkyl ammonium salt are subjected to ring closure reaction under alkaline conditions to obtain corresponding epoxy derivatives;

(2) carrying out ammoniation reaction on the epoxy derivative obtained in the step (1) to obtain a corresponding amino derivative; and

(3) reacting the amine derivative obtained in step (2) with 1,3, 5-trihalos-triazine and optionally substituted with one or more R₀Reaction of a group-substituted p- (beta-sulfate ethyl sulfone) aniline.

The binder is generally used as a dispersion medium and may be composed, for example, of vegetable oils, mineral oils, organic solvents, various natural and synthetic resins and small amounts of waxes. In a preferred embodiment, the binder may be selected from sodium alginate, guar gum, synthetic gums, cellulose and its derivatives, starch and its derivatives, multipolymers of acrylic or crotonic acid and its derivatives, or mixtures thereof.

The surfactant may be selected from polyvinylpyrrolidone, polyoxyethylenealkylamine, fatty alcohol-polyoxyethylene ether, silicone or a mixture thereof.

The levelling agent may be selected from alkali metal alkyl sulphonates such as sodium alkyl sulphonate, or alkali metal fatty alcohol sulphates such as sodium higher fatty alcohol sulphate, or fatty alcohol polyoxyethylene or polyoxypropylene or mixtures thereof.

The alkaline agent can be selected from amine compounds and alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide.

The inventor finds that the double-active-group quaternary ammonium salt simultaneously having the monohalogen s-triazine and the ethyl sulfone groups not only has excellent fixation reaction characteristics on cotton fibers, but also has remarkable ecological advantages compared with the traditional dyeing method when the double-active-group quaternary ammonium salt is used as a dyeing promoter to modify and dye denim grey cloth. For example, after the compound of formula (I) of the present invention is used as a dyeing promoter, the conventional salt as a dyeing promoter can be greatly reduced or even completely eliminated while the dyeability of the fiber fabric can be maintained or even improved. Thus, the expense, handling difficulties and disposal problems associated with salt addition can be eliminated. In addition, after the dyeing promoter disclosed by the invention is treated, the dye can be completely combined on cotton fiber tissues to realize high apparent color yield, so that the dye is utilized to the maximum extent, and the use of the dye is obviously reduced. Furthermore, the resulting textile can be dyed uniformly and with good dyefastness, thereby also reducing the need for fixing alkaline agents.

Thus, in preferred embodiments of the present invention, preferred dye booster compositions may also contain other suitable salts such as sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate. However, as one of the benefits of the present invention, in a preferred embodiment, the use of alkali agents such as alkali metal hydroxides, and alkali agents selected from amine compounds such as organic amines including alkylamines such as triethylamine, and the like, and the use of other organic ammonium salts than the quaternary ammonium salt compound of formula (I) that are susceptible to contamination may be reduced (e.g., less than 5%, 2%, 1%, or even 0.5% by weight of the accelerator composition) and even eliminated from the dyeing accelerator composition.

The transfer dyeing equipment used in step 3) is known in the art and may be, for example, the transfer dyeing equipment shown in fig. 2, which is the equipment shown in application No. 201710048416.4, through which a first set of printing rolls prints reactive dye ink on a first set of ink transfer rollers or blanket belts. Wherein, the printing plate roller can comprise a gravure plate roller, a flexible plate roller or a rotary screen. The surface material of the ink transfer roller or the ink transfer blanket belt is a rubber coating layer having a thickness of 3-15mm, the rubber is polyurethane rubber, nitrile rubber, styrene-butadiene rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, ethylene propylene rubber or the like having a surface hardness of shore 45-90 degrees, the surface tension of these rubbers is low, for example, the critical surface tension of polyurethane rubber is about 29, the critical surface tension of butyl rubber is about 27, and the surface tension of styrene-butadiene rubber is about 48, so that such viscosity and surface tension are particularly suitable for applying reactive dye ink to the ink transfer roller or the ink transfer blanket belt when transfer dyeing denim fabric, thereby improving workability.

Hereinafter, the transfer dyeing apparatus described in the implementation of steps 3),4),6) and 7) will be described with reference to fig. 2. The transfer dyeing apparatus mainly comprises a central roll 1 and at least one dyeing section set device 5. The dyeing unit adopts a satellite structure, and at least one dyeing part sleeve device shares a central roller as a back pressure roller. The central roller 1 is fixedly connected to the frame 12 by a bearing. The center roller 1 may be driven to rotate by a variable frequency motor 13. The center roll 1 may be a hard material roll whose surface is coated with rubber. At least one (e.g., 2-8, 6 shown in fig. 2 a) dyeing unit set 5 is distributed around the circumference of the central roller 1. Each dyeing unit set 5 is independently provided with its advance towards the central roll 1 by a respective advancing means, for example an advancing cylinder 506. The pushing cylinders 506 are mounted on the body of each dyeing unit set 5, for example, on the frame 501 of the body. Optionally, the transfer dyeing apparatus may further comprise a guide roll 4. At least one guide roll is provided in the vicinity of the entrance and exit of the fabric to be dyed, respectively, in contact with the central roll. The guide roll 4 guides the fabric 2 into or out of the press section between the central roll 1 and the dyeing stack arrangement 5. Drying boxes 7 can be arranged among the dyeing part sleeve devices 5 and are used for ensuring the drying of the ink after the ink printing, and preventing the phenomenon of staining and color mixing among multiple times of registration. The transfer dyeing apparatus may further comprise an in-line central roll washing system 15 arranged in the non-pressurized section of the central roll 1 and the dyeing stack arrangement 5. The online central roller cleaning system 15 comprises a cleaning device, a water scraping knife and an oven, wherein after the surface of the central roller 1 is cleaned by the cleaning device, the water on the surface of the central roller 1 is scraped by the water scraping knife, and then the surface of the central roller is dried by the oven, so that the continuous circulation application is realized. The cleaning device may include a showerhead and a brush. The transfer dyeing apparatus may further include a high-definition image detection unit 900, and the high-definition image detection unit 900 may employ a high-speed camera. The high-speed camera shoots the dyed pattern and sends the pattern to the central control unit for processing, and then image signals are displayed through the liquid crystal display, so that the image signals are provided for operators to monitor the quality of the printed matter in real time, and the yield is improved.

Fig. 2b shows a dyeing section set 5 of the transfer dyeing apparatus according to this embodiment of the present invention. The dye house assembly 5 may include the aforementioned propulsion devices (e.g., propulsion cylinder 506), ink fountain assembly 510, full cliche plate roller 511, ink transfer roller 512, and pressure applicator assembly. The ink fountain assembly 510, the full cliche plate roller 511, the ink transfer roller 512, and the pressure applicator assembly are mounted within the frame 501. The ink transfer roller 512 is located between the full-blanket cylinder 511 and the center roller 1, and can be brought into contact with the full-blanket cylinder 511. The respective axial ends of the ink transfer roller 512 and the full cliche plate roller 511 can be mounted into a mounting block 502 in the frame 501. The mounting block 502 is slidable on a slide provided in the frame 501, so that, under the thrust action of the thrust cylinder 506, the mounting block 502 is moved towards the central roller 1, bringing the distributor roller 512 into contact with the fabric to be dyed on the central roller 1. Here, the propulsion cylinder 506 may also provide pressure of the ink transfer roller 512 against the fabric to be dyed on the central roller 1. The pressure applicator assembly can be used to provide an adjustable pressure of the distributor roller 512 against the full cliche plate roller 511. The pressure applying assembly is used for adjusting the ink amount to control the color difference, and the pressure is mainly used for sticking out the ink amount in the net holes of the anilox roller. In the illustrated embodiment, the pressure applicator assembly includes an actuator 509 and an eccentric sleeve 503. The actuator 509 comprises a cylinder and a piston rod. The cylinder is pivotally connected to the mounting block 502. The actuator 509 may be of a hydraulic type, a pneumatic type or an electric type. In the case of an actuator 509 of the hydraulic or pneumatic type, the length of extension of the piston rod may be adjusted by adjusting the fluid pressure within the chamber of the cylinder. The actuator 509 may be a servo actuator, such as a servo electric cylinder. The pressure applicator assembly may also include a swing arm 508 and a link 516. The swing arm 508 is pivotably connected to the mounting block 502 by a swing arm pivot 504. The swing arm 508 includes a first end and a second end. A first end of the swing arm 508 is pivotally connected to an extended end of a piston rod of an actuator 509 by a pin. A second end of the swing arm 508 is pivotally connected to one end of a link 516 by a pin. The other end of link 516 is pivotally connected to eccentric sleeve 503. The dyeing department set device can also comprise a pressure lock 517 for locking the pressure between the distributor roller 512 and the full-bottom printing plate roller 511, so as to avoid the micro-jump of the pressure value caused by the surface unevenness of the fabric 2 in the production process. The pressure lock may comprise a variable length member having one end pivotally connected to the eccentric bushing 503 and the other end pivotally secured to the mounting block 502.

The reactive dye ink comprises the following components by weight:

25-80%, preferably 30-72%, more preferably 40-65% of a paste slurry comprising 3-20%, preferably 5-15% guar and/or guar derivatives and 0.1-3%, preferably 0.3-2%, more preferably 0.5-1.5% chitosan, by total weight of the paste slurry; and

2-18%, preferably 4-13% of a reactive dye having a double reactive group.

The guar gum is a galactomannan gum, which is a neutral polysaccharide gum and is a vegetable polysaccharide gum with wide industrial uses. The galactomannan glue solution is a pseudoplastic fluid, and macromolecules are in a winding net structure in a natural state. As a common form, guar gum comprises a main chain formed by connecting (1-4) -beta-D-mannose as a structural unit and a side chain which is formed by single alpha-D-galactose and is connected with the main chain by a (1-6) bond. From the whole molecule, galactose is randomly distributed in the main chain, but is more in groups of two or three. Guar gum differs from other galactomannans in molecular weight and monosaccharide ratio due to the different sources. The molecular weight of guar gum may typically be about 50-300 million, such as 100-200 million, and the ratio of mannose to galactose may be about 1.2-2.5:1, such as about 1.5-2: 1.

The guar gum derivative suitable for use in the present invention is not particularly limited as long as it is a water-soluble cationic guar gum derivative or a water-soluble nonionic guar gum derivative. In one embodiment, the guar derivatives are selected from guar gums having a degree of substitution DS ≥ 0.15 or ≥ 0.25, such guar derivatives including oxidized guar gums, for example hydroxylated or carboxylated guar gums, such as hydroxypropyl guar or carboxymethyl guar. Guar gum or its derivatives are very important as a paste for rheology, permeability and levelling property, and it is particularly well compatible with the fluorine-containing double reactive group reactive dye of the present invention, and at the same time, the setting effect printed on the rubber surface of the ink transfer roller or ink transfer blanket tape is very good.

Furthermore, the content of guar gum or derivatives thereof is also important in the reactive dye inks of the present invention. It has been found that if the guar gum or its derivatives are present in too low a content, the dye penetration is strong, the surface colour yield is poor and the colour is not bright enough; if the content is too high, the level-dyeing property of the dye is poor, and the fastness after washing is poor.

The chitosan molecule has a large number of amino groups and is the only basic polysaccharide discovered so far. The inventor finds that chitosan can wrap the surface of cotton fibers to form a film layer, so that the fabric can absorb more dyes, and the dye uptake of cotton fabrics is improved. The inventors have also found that chitosan has a synergistic effect when combined with guar gum or a derivative thereof, in particular in terms of adjusting the rheology of dye inks. The dye ink is mainly applied to a transfer dyeing process, and is expected to simultaneously take the dyeing uniformity into consideration on the premise of less paste and high ink loading, so that the proper rheological property is a key point which is crucial to the upper limit and the uniformity of the transfer dyeing speed. In summary, in the present invention, when combined with guar gum or its derivatives, chitosan can further improve the color absorbing performance, save the dye amount and simultaneously achieve the effects of darkening and brightening, and can adjust the rheological property of the dye ink to be better suitable for the transfer dyeing process.

The paste slurry can be simply prepared by mixing a weight ratio of guar or guar derivative with chitosan in water. For example, 5-15% by weight guar or guar derivative may be placed in a container, sufficient distilled or deionized water added, stirred well for about 1-2 hours to dissolve well, then 0.5-1.5% by weight chitosan added, then adjusted to 100% with distilled or deionized water, and stirred further until completely dissolved and uniform in color, to form a transfer dye paste slurry.

The reactive dyes having a double reactive group may be those known in the art, such as H-E type developed by ICI company containing a bis-monochlorotriazine reactive group, or Drimarene XN and the like by Clariant company, Sumifix Supra series type of reactive dyes developed by Sumitomo company containing a bis-reactive group of monochlorotriazine and vinyl sulfone, or ME type dyes developed by Shanghai Dynasty eight factories, or Basilen FM type dyes developed by BASF company, or Megafix B type dyes developed by Shanghai Vandazida chemical company, and the like.

In a preferred embodiment, the reactive dye having a double reactive group is a fluorine-containing double reactive group reactive dye disclosed in patent application No. 202011328852.5, which is incorporated herein by reference in its entirety.

Specifically, the fluorine-containing double active group reactive dye has a vinylsulfone group or a vinylsulfone group precursor group and a monofluoro-s-triazine group, which can be represented by the following formula:

D-(B-Re)₂(I)

wherein D is a dye intermediate,

b is a single bond or a linking group, such as-NH-, and

re is an active group which is a group containing a monofluoros-triazinyl group but not a chlorotriazinyl group and a group containing a vinylsulfonyl group (-SO)₂CH＝CH₂) Or a group of vinylsulfonyl precursors.

The dye intermediate is known in the art and may also be referred to as a dye chromophore, and includes, for example, dye parent compounds such as azo, anthraquinone, phthalocyanine and the like, or structural modifications thereof. These parent compounds, or forms to which the reactive group has been attached, are generally commercially available, for example, Henschel's Cibacron F-type reactive dye, or Liyuan's Lily FL-type reactive dye, or Levafix's EN-type reactive dye (all of which have attached a monofluoro-s-triazine group to the parent), and the like.

Such reactive dyes comprising a vinylsulfone or a precursor thereof and a halos-triazine double reactive group are known per se or processes for their preparation and are commercially available. Such reactive dyes have been used in the dyeing of fiber fabrics. Common reactive dyes of this type generally contain a vinylsulfone group and a monochlorotriazine double reactive group. However, the inventors have found that the substitution of fluorine for chlorine in the s-triazine reactive group structure of the dye molecule results in a greatly increased stability of the dyed fibers when used for printing, resulting in a more stable dye-fiber bond than dyes containing a monochlorotriazine reactive group, and thus in higher color fastness, particularly when used in combination with a paste slurry comprising guar gum or a derivative thereof as described above.

Preferably, a substituted or unsubstituted monofluoros-triazine group, more preferably an unsubstituted monofluoros-triazine group, represented by the following formula (II) can be used as the reactive group. The vinylsulfonyl precursor group may then be any group which can be converted into a vinylsulfonyl group in a suitable medium and under conditions, such as basic conditions, for example during dyeing, for example as vinylsulfonyl precursor a group containing an esterethylsulfonyl group as shown in the following formula (III) may preferably be used.

Wherein M is H or an alkali metal ion, preferably Na or K;

r1 is an ester group selected from the group consisting of sulfates, carboxylates and phosphates, preferably a sulfate group (-OSO)₃-)；

R2 is H, hydroxy, alkyl, alkoxy, amino or mono or di substituted amino;

y each independently represents H, halogen or straight-chain or branched C_1-12Alkyl of (3), preferably H.

An example of a known compound commonly used for introducing a group containing a vinylsulfone group-containing precursor is a para-ester (or para (. beta. -ethylsulfone sulfate) aniline) or a derivative or analog thereof.

In the context of the present application, the term "alkali metal" denotes a metal element of main group I of the periodic table of the elements, including Li, Na and K, etc., preferably Na or K.

In the context of the present application, the term "alkyl" preferably denotes a compound having 1 to 12, preferablyStraight or branched alkyl of 1 to 8 carbon atoms is selected and one or more H on a carbon atom may be substituted with a halogen such as F, Cl or Br. In a preferred embodiment, said alkyl group represents unsubstituted C_1-8More preferably C_1-4Such as methyl, ethyl, propyl or butyl. The term "alkoxy" is alkyloxy, wherein alkyl is as defined above.

In the context of the present application, the term "aryl" preferably denotes an aromatic radical having 5 to 12, preferably 6 to 10, carbon atoms, preferably phenyl or alkylphenyl.

The mono-or disubstituted amino groups are in principle not restricted and are those substituted amino groups known in the dye art, including for example alkyl, alkoxy, aryl, amido, thioamido, amidoalkyl, thioamidoalkyl or hydroxyalkyl substituted amino groups and the like.

In addition to the combination of the above-described specific paste slurry with the specific dual reactive group reactive dye, the reactive dye ink may further comprise other components and adjuvants known in the art, including, for example, but not limited to, rare earth driers, resists, dispersants, surface tension modifiers, and balance water, and the like.

The rare earth drier can accelerate the drying speed of the reactive dye ink of a water-based system and improve the production efficiency, and the rare earth has the auxiliary effect of deepening and brightening the reactive dye. The rare earth drier may be selected from carboxylates of rare earth elements, such as rare earth isooctanoate or rare earth naphthenate. The fineness of the rare earth drier is not limited, and can be, for example, less than or equal to 10 micrometers, less than or equal to 8 micrometers or 5 micrometers. The rare earth drier may be used in an amount of 0.2 to 3%, such as 0.5 to 1%, based on the total weight of the dye ink.

The dye-proofing agent is used for controlling a dyeing process, and is a substance capable of preventing dyes from being colored to form patterns on fiber fabrics or in a printing and dyeing process. Examples of suitable stain blocking agents include the stain blocking salt S (based primarily on sodium m-nitrobenzenesulfonate) and the stain blocking salt H (based primarily on ammonium phenylhydrazine sulfonate), among others. The dye-proofing agent may be used in an amount of 0.2 to 3% and preferably 0.5 to 1% based on the total weight of the dye ink.

The dispersant may be selected, for example, from methylene naphthalene sulphonic acid dispersants, or phenolic condensate sulphonate dispersants, or fatty alcohol polyoxyethylene ether silane type dispersants. The dispersant may be used in an amount of 1 to 10%, preferably 1.5 to 7%, more preferably 2 to 5%, based on the total weight of the dye ink.

The surface tension modifier is not particularly limited and may be, for example, a nonionic surfactant such as BYK-DYNFET 800 of Picker, Germany, or Efka3570N of Pasteur, or Hydropalat 140 of Corning. The surface tension adjusting agent may be used in an amount of 0.1 to 10%, preferably 0.1 to 5%, more preferably 0.5 to 2%, based on the total weight of the dye ink. The surface tension of the reactive dye ink can be further adjusted to be less than the critical surface tension of the ink transfer roller or ink transfer belt in the transfer dyeing apparatus by adding an appropriate amount of a surface tension adjusting agent so that the ink can be clearly printed on the surface of the ink transfer roller or ink transfer belt.

The reactive dye ink can be prepared by mixing and stirring uniformly the fluorine-containing double-reactive-group reactive dye as described above with the paste slurry and optionally other components and auxiliaries.

In one embodiment, the fluorine-containing double reactive dye may be mixed with other optional components and auxiliaries dissolved in water, and then added to the paste slurry, optionally after filtration. If necessary, the fluorine-containing double-active group reactive dye can be firstly mixed into paste in a container by water.

The reactive dye ink has a viscosity of about 50 to 4000mPa.s, preferably about 100 to 3000mPa.s, and a surface tension of about 20 to 50mN/m, preferably about 25 to 40 mN/m.

The reactive dye ink of the present invention generally uses the surface of a rubber blanket belt or a rubber roller as a transfer temporary carrier, and the surface tension of rubber is low, such as the critical surface tension of polyurethane rubber of about 29, the critical surface tension of butyl rubber of about 27, and the surface tension of styrene butadiene rubber of about 48, so that such viscosity and surface tension are particularly suitable for applying the ink to a transfer roller or an ink transfer blanket when transfer dyeing denim fabric, thereby improving processability.

Particularly, compared with indigo dye, sulfur dye or vat dye dyeing, the reactive dye ink provided by the invention can obviously reduce pollution when used for dyeing denim grey cloth, and solves the problems of unstable color and luster and poor dyeing importance when the denim grey cloth is dyed by using commercially available reactive dye.

The contacting step in step 4) is known in the art, and may be carried out under a line pressure of 10 to 80kg/cm and a vehicle speed of 5 to 60 m/min. The drying step is also known in the art and may be performed, for example, using hot air or infrared radiation.

The application step involved in step 5) and the dye-accelerating liquid used therein are the same as those in step 2). For example, the dye-uptake promoting solution can be applied to the reverse side of the denim fabric by means of anilox roll coating by means of a second anilox roll in an anilox roll pre-treatment apparatus, resulting in a reverse side with a wet coating.

The reactive dye ink used in step 6) may be the same or different in color from the reactive dye ink used in step 3), as determined by the dyeing requirements of the same or different colors on both sides, and different colors may be obtained by varying the D dye precursor in the reactive dye molecule, as is known to those skilled in the art. The transfer dyeing equipment employed therein is also known in the art and may be the same as that employed in step 3).

The contacting and drying steps involved in step 7) are the same as in step 4).

The post-treatment steps involved in step 8) are known in the art and include, for example, fixing, washing, and setting. The fixation may include steaming fixation or baking fixation. The water washing generally includes cold water washing, hot water washing (40-50 ℃) to remove salt, alkali and unfixed dye, soaping, hot water washing (70-95 ℃, <10min) to further remove dye solution adhered to the fiber, and cold water washing in this order, followed by drying and setting with a setting machine. Optionally, neutralization may be performed in an acetic acid bath prior to soaping to prevent dye hydrolysis during soaping, to avoid negative effects of residual alkaline electrolytes, and the like.

The method for the transfer dyeing of denim fabric of the invention is characterized in that: a combination of the specific dye-uptake accelerating liquid and the specific reactive dye ink is adopted. The jean grey cloth is modified by the dyeing promoting liquid, so that the affinity between the fiber and the reactive dye can be effectively improved, deeper chroma can be obtained without adding salt during dyeing, and pollution caused by washing is greatly reduced; the reactive dye ink contains a reactive dye with vinyl sulfone and monofluoro-s-triazine double-active groups, wherein the vinyl sulfone group and fiber undergo nucleophilic addition reaction, the monofluoro-s-triazine group also partially participates in reaction, and due to the synergistic effect of the two active groups, the reactivity of the whole dye is improved, and a stable dye-fiber bonding bond is formed, so that higher color fastness is brought, meanwhile, the requirements on the dyeing temperature, the using amount of an alkaline agent and a dyeing accelerant are low, the compatibility of three primary colors is good, the reproducibility is good, and the dyeing rate and the fixation rate of dyeing are obviously improved compared with those of the dye with a single active group.

The method adopts a transfer dyeing mode completely different from the traditional jean production process, the dyeing mode only dyes the surface layer of the jean, and the internal part and the invisible part of the fiber do not need to be filled with dye, so that the dyeing according to the requirement is realized, the beneficial effects of proper dye-uptake and high fixation rate are realized, meanwhile, the dye consumption and the water consumption are obviously saved, and the wastewater quantity is obviously reduced.

Drawings

Fig. 1 is a general axial end view of an anilox roller pretreatment device applied in steps 2) and 5) of the method of the invention.

FIGS. 2a and 2b are a schematic drawing of the transfer dyeing apparatus as a whole and a schematic drawing of the transfer dyeing kit, respectively, applied in steps 3),4) and 6), 7) of the process according to the invention.

FIGS. 3a and 3b are respectively a nuclear magnetic resonance spectrum and an infrared spectrum of the dyeing promoter used in example 1.

FIG. 4 is an infrared spectrum of a fluorine-containing double reactive dye used in example 2.

FIGS. 5a and 5b are respectively a nuclear magnetic resonance spectrum and an infrared spectrum of the dyeing promoter used in example 3.

FIG. 6 is an infrared spectrum of a fluorine-containing double reactive dye used in example 4.

Examples

The invention is further illustrated by way of examples. It should be noted that these examples should not be construed as limiting the invention.

The test methods referred to in the examples are as follows:

and (3) fixation rate: according to the measuring method of the printing fixation rate in GB/T2391-2014 'determination of the fixation rate of reactive dyes';

dry and wet crockfastness: testing is carried out according to GB/T3920-;

light fastness and soaping color fastness: the test is carried out according to GB/T14575 + 2009 comprehensive color fastness of textile color fastness test.

Example 1: transfer dyeing jean grey fabric of pure cotton herringbone oblique jean fabric:

specification: 10 × 10/72 × 44;

weight: 10 OZ;

breadth: 58-60 inches

Comprises the following components: 100% cotton.

The denim fabric is subjected to transfer dyeing by a method comprising the following steps:

1) desizing treatment: padding the jean grey cloth in desizing enzyme liquid which contains 0.6 percent of medium-temperature alpha-amylase, 0.6 percent of NaCl and 0.2 percent of fatty alcohol-polyoxyethylene ether and is complemented to 100 percent by deionized water for 3 hours at 50 ℃, then washing with 90 ℃ hot water, washing with normal-temperature water, and drying to obtain the jean grey cloth to be printed.

2) Applying a dyeing promoter liquid on the front side: uniformly coating a dyeing promoting liquid on the front side of the jean grey cloth by a laser engraved chromium-plated anilox roller with the line number of 200 lines/cm in the anilox roller pretreatment device shown in the attached drawing 1 in an anilox roller coating mode to obtain a front side with a wet coating; wherein the dye-uptake accelerating liquid comprises 3% of a dye-accelerating agent, 5% of guar gum, 1% of polyvinylpyrrolidone, 0.5% of sodium alkylsulfonate, 8% of a 1: a mixture of sodium carbonate and sodium bicarbonate at a 1 molar ratio and the balance to 100% deionized water.

Wherein the dyeing promoter has the following formula and its nuclear magnetic resonance spectrum and infrared spectrum are shown in FIGS. 3a and 3 b:

wherein X is Cl, and the like,

R₁and R₂Respectively as follows:

the dyeing promoter is synthesized as follows:

1 molar part by mass of a 40% aqueous NaOH solution was added dropwise to 1 molar part by mass of each of 1 molar part by mass of m-xylylene trimethylammonium hydrochloride (purchased from Sigma-Aldrich, analytical grade) and 1 molar part by mass of hydroxypropyl trimethylammonium hydrochloride (purchased from Sigma-Aldrich, analytical grade) placed in a reaction vessel with stirring at room temperature. After the dropwise addition is completed, the reaction is continued for 30 to 60 minutes. NaCl formed in the reaction was filtered off, and the pH of the solution was adjusted to 6.5 to 7 with hydrochloric acid, whereby the corresponding epoxy derivatives were obtained, respectively. Then, an excess of 32% strength concentrated aqueous ammonia was added dropwise to each of the two above-described reaction vessels containing the freshly prepared epoxy derivative. After the dropwise addition is finished, the reaction is continued for 3-4 h. Then removing excessive ammonia in vacuum at 80 ℃ to obtain two corresponding amino derivatives with yield of more than 85%. Subsequently, an acetone solution containing 1,3, 5-monochlorotriazine and p- (. beta. -sulfatoethylsulfone) aniline is slowly added dropwise to the above-mentioned amino derivative of m-xylylene trimethylammonium hydrochloride at 0-5 ℃ in a uniformly stirred environment, optionally with Na₂CO₃The pH value of the reaction is regulated and controlled to be 6.5 by the aqueous solution until the reaction is finished to obtain a primary product. At this point, Na is no longer added₂CO₃The pH value of the aqueous solution is kept unchanged at 6.5. Heating the reaction system containing the primary product to 35-40 deg.C, and adding dropwise the amino derivative of hydroxypropyl trimethylammonium hydrochloride while stirring, wherein Na is still used₂CO₃And regulating and controlling the pH value of the reaction to be 6.5 by using an aqueous solution until the reaction is finished to obtain the denim fabric dyeing promoter. At this time, Na is not added₂CO₃The pH of the aqueous solution was maintained at 6.5.

3) Delivery of reactive dye ink: printing reactive dye ink on a first set of ink transfer rollers using a first set of printing rollers of the transfer dyeing apparatus of FIG. 2; the formula of the reactive dye ink is as follows:

composition of	By weight%
		Paste slurry	50％
Reactive dyes	12％
		Rare earth drier (naphthenic acid rare earth, fineness is less than or equal to 5 microns)	0.5％
Anti-staining salt S	1％
		Dispersant (methylene naphthalene sulfonic acid dispersant)	4％
Surface tension regulator (BYK-DYNFET 800, Pyk, Germany)	1％
		Distilled water	To 100 percent

Wherein the paste slurry is formulated as follows: hydroxypropyl guar with a degree of substitution DS of 0.15 or more in an amount of 5 wt% based on the total weight of the paste slurry was placed in a container, and 70 wt% of distilled or deionized water was added and stirred well for 2 hours. After the chitosan is fully dissolved, 1 weight percent of chitosan is added, the mixture is adjusted to 100 percent by distilled water or deionized water, and the stirring is continued until the chitosan is fully dissolved and the color of the system is uniform.

Wherein the reactive dye is Procion Blue HERD double-reactive-group reactive dye produced by ICI company.

Wherein, the reactive dye ink is prepared as follows: firstly, adding a small amount of cold water with the weight percent of about 2% and the reactive dye into a container, and blending into paste; then adding the mixed solution of the dissolved dye-resistant salt S, the dispersant and the surface tension regulator according to the dosage shown in the table, adding warm water with the temperature of about 85 ℃ of about 15 weight percent to fully dissolve the reactive dye, adding the mixture into the prepared paste slurry after filtering, adjusting the weight percent of the mixture to be 100 percent by water, and uniformly stirring the mixture to obtain the reactive dye ink. The viscosity of the reactive dye ink is 900mPa.s, and the surface tension is 27 mN/m.

4) Coloring on the front side: and (3) closely fitting the front side with the wet coating obtained in the step 2) with the first set of ink transfer rollers or ink transfer blanket belts in the step 3) and contacting the front side with the first set of ink transfer rollers or ink transfer blanket belts under the line pressure of 80kg/cm, so that the reactive dye ink is transferred onto the front side of the jean grey cloth from the first set of ink transfer rollers or ink transfer blanket belts, and then is dried under the infrared irradiation, so that the front side of the jean grey cloth is colored.

5) Back side application of dyeing promoter solution: uniformly coating the same dyeing promoting liquid as the dyeing promoting liquid in the step 2) on the reverse side of the jean blank cloth by using a laser engraved chromium plating second anilox roller with the line number of 200 lines/cm in the anilox roller pretreatment device shown in the attached drawing 1 in an anilox roller coating mode to obtain the reverse side with a wet coating.

6) Delivery of reactive dye ink: the same reactive dye ink as in step 3 was printed on a second set of ink transfer rollers or blanket belts by means of a second set of printing plate rollers of the transfer dyeing apparatus of fig. 2.

7) Coloring the back side: and (3) closely fitting the reverse side with the wet coating obtained in the step 5) with the second set of ink transfer rollers or ink transfer blanket belts in the step 6) and contacting the reverse side with a line pressure of 10kg/cm, so that the reactive dye ink is transferred from the second set of ink transfer rollers or ink transfer blanket belts to the reverse side of the jean blank cloth, and then drying the jean blank cloth under infrared irradiation to realize the reverse side coloring of the jean blank cloth.

8) And (3) post-treatment: steaming and fixing color at 102 ℃ for 10min, then washing with water (cold water washing- >50 ℃ hot water washing for 10min) -, soaping (95 ℃, 10min) -, hot water washing (95 ℃, 5min) -, cold water washing, and then drying and shaping by a shaping machine.

The dry rubbing fastness of the prepared pure cotton jean dyed fabric is 4-5 grade, the wet rubbing fastness is 3.5-4 grade, the light fastness is 5 grade, and the color fixing rate of the dye ink is 85 percent.

Example 2: transfer dyeing of pure cotton herringbone oblique jean fabric

In this example 2, transfer dyeing of pure cotton denim fabric was carried out using the same procedure as in example 1, except that the Procion Blue HERD type reactive dye was replaced by a fluorine-containing double reactive dye prepared as follows:

1) 1 molar part of 1-amino-8-naphthol-3, 6-disulfonic acid is placed in deionized water for pulping for 1 hour, the pH value is adjusted to 6.5 +/-0.2 by NaOH to be dissolved, and the solution is cooled to about 0-5 ℃ for storage for later use;

2) 1 molar part of purified Cibacron F type active dye Cibacron Blue F-R filter cake of Henscman and the 1-amino-8-naphthol-3, 6-disulfonic acid solution in the step 1) are mixed, and NaHC0 is dripped₃To pH 4.5 ± 0.2. Stirring at low speed at 30-40 deg.C for reaction for 3h, measuring the end point with amino reagent, cooling the obtained liquid to about 10 deg.C, and storing;

3) stirring and pulping 1 molar part of p- (beta-ethyl sulfone sulfate) aniline in deionized water for 1h, adding ice, and cooling to O-10 ℃.1 molar part of concentrated hydrochloric acid was added thereto, and 1 molar part of NaN0 was slowly added dropwise₂The prepared 30% solution is diazotized and detected by starch KI test paper to ensure that the nitrous acid is slightly excessive. After the dropwise addition is finished, stirring for 1h at the temperature of 0.5 ℃, and then eliminating redundant nitrous acid by using sulfamic acid; and

4) slowly adding the liquid obtained in the step 3) into the liquid obtained in the step 2) after the temperature is reduced to about 10 ℃. With NaHC0₃The pH was adjusted to 6.5 ± 0.2, and the reaction was carried out for 4 hours with stirring, so as to obtain the fluorine-containing double active group reactive dye used in this example, and the infrared spectrum of the dried sample is shown in fig. 4.

The jean dyed fabric of the prepared pure cotton jean dyed fabric is determined by the method to have the dry rubbing fastness of 4-5 grades, the wet rubbing fastness of 4-5 grades and the light fastness of 5 grades, and the color fixing rate of the dye ink is 95 percent.

Example 3: transfer dyeing of stretch cotton jean fabric

In this example 3, the same procedure as in example 1 was used to perform transfer dyeing of stretch cotton denim fabric, except as follows:

stretch cotton jean fabric:

specification: 7X 16/70D;

breadth: 50-52 inches;

weight: 11.5 OZ;

comprises the following components: 97% cotton and 3% spandex.

The desizing enzyme solution used contained 0.8% of alpha-amylase, 0.9% of NaCl and 0.3% of sorbitan fatty acid ester and was made up to 100% with deionized water.

The adopted dyeing promoting liquid comprises 5% of dyeing promoter, 2% of synthetic dragon glue, 3% of polysilicone, 3% of sodium alcohol sulfate and the balance of deionized water to 100%; wherein the dyeing promoter is as follows and its nuclear magnetic resonance spectrum and infrared spectrum are shown in FIGS. 5a and 5 b:

wherein X is Cl; and R₁And R₂All are as follows:

the dyeing promoter is synthesized as follows: to 1 part by mol of each p-methylol trimethylammonium hydrochloride (purchased from Sigma-Aldrich, analytical grade) placed in two reaction kettles, 1 part by mol of a 40% NaOH aqueous solution was added dropwise with stirring at room temperature. The reaction was continued for 30-60 minutes after the addition was complete. NaCl generated in the reaction is filtered, and the pH value of the solution is adjusted to 6.5-7 by hydrochloric acid to obtain 2 parts of the same epoxy derivative. Then separately charged with the ring under stirring at room temperatureThe oxygen derivative reaction kettle is dripped into excessive concentrated ammonia water with 32% concentration. After the dropwise addition is finished, the reaction is continued for 3-4 h. Excess ammonia was then removed in vacuo at 80 ℃ to give two identical amino derivatives of p-methylol trimethylammonium hydrochloride. Then, slowly dripping acetone solution of 1,3, 5-monochlorotriazine and p- (beta-sulfate ethyl sulfone) aniline with a molar ratio of 1:1 into the obtained amino derivative by stirring uniformly at 0-5 ℃, wherein Na is used for Na any time₂CO₃And regulating the pH value of the reaction to be 6.5 by using an aqueous solution until the reaction is finished to obtain a primary product. At this point, Na is no longer added₂CO₃The pH value of the aqueous solution is kept constant at 6.5. Heating the reaction system containing the primary product to 35-40 deg.C, and adding a second portion of the resulting amine derivative dropwise while stirring, wherein Na is still used₂CO₃And regulating the pH value of the reaction to be 6.5 by using an aqueous solution until the reaction is finished to obtain the dyeing promoter. At this time, Na is not added₂CO₃The pH value of the aqueous solution is still kept at 6.5.

The anilox roller adopted in the step 2) is a ceramic anilox roller with the line number of 60 lines/cm.

The formula of the adopted reactive dye ink is as follows:

composition of	By weight%
		Paste slurry	65％
Reactive dyes	5％
		Rare earth drier (rare earth naphthenate, fineness less than or equal to5 micron)	0.5％
Anti-staining salt S	1％
		Dispersant (phenolic condensate sulfonate dispersant)	3％
Surface tension modifier (Efka 3570N of Basff corporation)	0.5％
		Distilled water	To 100 percent

Wherein the reactive dye is Sumifix Supra reactive dye (Sumifix Supra Navy Blue 2GF) of Sumifix corporation of Japan.

The roller adopted in the step 3) is a circular screen; the surface material of the ink transfer blanket belt is a rubber coating layer with the thickness of 6mm, and the rubber is chlorosulfonated polyethylene rubber with the surface hardness of 55 Shore degrees.

The fixation adopted is baking fixation.

The dry rubbing fastness of the prepared stretch cotton denim dyed fabric is 4-5 grade, the wet rubbing fastness is 3.5-4 grade, the light fastness is 5 grade, and the color fixing rate of the dye ink is 88 percent.

Example 4: transfer dyeing of stretch cotton jean fabric

In this example 4, the transfer dyeing of stretch cotton denim fabric was performed by the same procedure as in example 3, except that the semifix Supra reactive dye of sumitomo corporation was replaced with a fluorine-containing double reactive group reactive dye, which was synthesized as described in example 2, wherein a livingsu FL type dye (livingsu blue FL-RN) of livingsu corporation was used instead of a Cibacron F type reactive dye of hensman, and an infrared spectrum of a sample after drying of the prepared fluorine-containing double reactive group reactive dye was shown in fig. 6.

The dry rubbing fastness of the prepared stretch cotton denim dyed fabric is 4-5 grade, the wet rubbing fastness is 4-4.5 grade, the light fastness is 5 grade, and the color fixing rate of the dye ink is 95 percent.

The technical solutions of the above embodiments are preferred embodiments of the present invention, and several modifications and changes can be made without departing from the principle of the present invention, and these modifications and changes should also be considered as being within the protection scope of the present invention.