CN112647319B

CN112647319B - Transfer dyeing reactive dye ink and application thereof

Info

Publication number: CN112647319B
Application number: CN202011328852.5A
Authority: CN
Inventors: 钟博文
Original assignee: Newtech Textile Technology Development Shanghai Co ltd
Current assignee: Newtech Textile Technology Development Shanghai Co ltd
Priority date: 2020-11-24
Filing date: 2020-11-24
Publication date: 2022-11-01
Anticipated expiration: 2040-11-24
Also published as: CN112647319A; WO2022110622A1

Abstract

The invention relates to a reactive dye ink for transfer dyeing, which comprises the following components in percentage by weight of 100 percent of the total composition: 25-80% of a paste slurry comprising, based on the total weight of the slurry, from 3-20% of guar and/or guar derivatives and from 0.1-3% of chitosan; and 2-18% of fluorine-containing double active group reactive dye which is provided with a vinyl sulfone group or a vinyl sulfone group precursor group and a fluorine-containing s-triazine group.

Description

Transfer dyeing reactive dye ink and application thereof

Technical Field

The application relates to a printing and dyeing technology in textile industry, in particular to novel transfer dyeing reactive dye ink and an application thereof, in particular to a method for dyeing fiber fabrics such as jean grey cloth.

Background

Fiber fabrics are widely used in the textile industry and in the apparel field. In addition to the conventional and common cotton fibers, various natural fibers such as hemp, ramie, flax, silk, wool, etc. are widely used as well as regenerated fibers of viscose, tencel, modal, etc. or synthetic fiber chemical fibers such as polyester, polyamide, acrylic, spandex, etc.

In order to provide rich colors and aesthetic feeling of clothes and fabrics, it is necessary to dye the fiber fabric with dyes. These dyes include, for example, various reactive dyes, indigo dyes, sulfur dyes, vat dyes, and the like. The reactive dye is an anionic dye, also called reactive dye, the molecular structure of which is composed of two parts of dye parent and reactive group, when dyeing, the dye parent is fixed on the fiber by the reaction of the reactive group in aqueous solution with hydroxyl or amino in the fiber such as cotton and wool to form covalent bond. It is popular because of its characteristics of good brilliance, convenient use and good color fastness. The vat dye needs to be reduced and dissolved into leuco sodium salt in alkaline strong reducing liquid during dyeing to dye the fiber, and then the vat dye is oxidized into insoluble dye and is fixed on the fiber through lake. Indigo is an ancient vat dye. Sulphur dyes are also commonly used for dyeing cotton fibres, which are based on dyes dissolved in alkali sulphide. Similar to vat dyes, sulfur dyes also form water-soluble form leuco dye-dyed fibers with affinity with the fibers through chemical reduction reaction, and then are tightly combined with the fibers through oxidation.

Common jeans or jean grey fabrics are on the market. It is mainly made of cotton, but can also be made of various raw material structures, such as cotton, wool, silk, hemp natural fiber blending, chemical fiber blending, elastic yarn, tight twist yarn, fancy yarn and the like. The jean fabric is produced through dyeing warp and sizing with dye and weaving. The main dyeing methods for the denim fabric comprise indigo dye, sulfur dye, vat dye and the like.

Whether the indigo dye or the sulfur dye or the vat dye is used, a large amount of inorganic salt is needed when the fiber fabric, especially jean grey cloth, is dyed, and a large amount of water is needed for full washing after dyeing, so that the residual dye on the textile is reduced. Therefore, the dyeing pollution of the traditional fiber fabric such as jean grey cloth is very serious.

Therefore, the market urgently needs an environment-friendly fiber fabric printing and dyeing process. The current solution is to adopt reactive dyes, but the production batch is not large, and the main problems are that the color and luster are not stable enough, the dyeing importance is poor, and the requirements of downstream customer garment manufacturers cannot be met. The method is directly related to the problems of high difficulty, high consumption, high cost, difficult sewage treatment and the like of the existing dyeing and sizing combination machine for producing the reactive dyeing fiber fabric.

Another approach is to develop modifiers to pretreat the fibers. For example, CN107740295a provides a dyeing method based on cotton fabric reactive dye cationic modifier, wherein cotton fiber is subjected to modification treatment, and the used modification aqueous solution is glutamate aqueous solution or phenylalanine aqueous solution.

In addition, transfer printing technology has also been used for dyeing of fiber fabrics, forming a mode of dyeing by printing. The water consumption of printing is usually much lower than for traditional dyeing. In traditional dyeing (especially dip dyeing), the fabric has longer action time in a dye bath, so that the dye can be fully diffused and penetrated into the fiber to complete the dyeing process. Whereas in practice printing is a partial dyeing. During printing, after the paste added in the color paste is dried to form a film, the macromolecular film layer can prevent the dye from diffusing into the fiber, so that the dye is attached to the surface of the fiber, and finally the fixation of the dye is realized through steaming, baking and other means.

However, there is still room for improvement with respect to those technical problems mentioned above, and there is also a need to further explore suitable accelerators for improving the dyeing process.

Disclosure of Invention

In view of the above technical problems, the inventors of the present application developed a novel transfer-dyeing reactive dye ink. The reactive dye ink uses water as a solvent, wherein a specific reactive dye and a specific thickener, a surface tension regulator and other auxiliary agents are dissolved, and the reactive dye ink can be printed on an ink transfer roller or an ink transfer blanket belt of transfer dyeing equipment used in a transfer dyeing process of fiber fabric, and the dye ink is transferred to fibers of jean grey cloth from the ink transfer roller or the ink transfer blanket belt in the transfer dyeing process.

The inventor of the application finds that the level-dyeing property of the printing surface can be greatly improved, more stable color and luster can be provided, the fixation rate is high, and a stable dye-fiber bonding bond is formed by adopting the transfer dyeing reactive dye ink, so that the color fastness of the transfer printing is greatly improved. In addition, the reactive dye inks of the present invention have good rheology, penetration, storage stability and are well suited for handling on ink transfer rollers or blankets.

Accordingly, a first aspect of the present application relates to a transfer-dyeing reactive dye ink comprising, based on 100% by weight of the total composition:

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, based on the total weight of the slurry; and

2-18%, preferably 4-13% of fluorine-containing double active group reactive dye, which has vinylsulfone group or vinylsulfone group precursor group and monofluoro-s-triazine group.

The guar gum used in the dye inks of the present invention is a galactomannan gum, which is a neutral polysaccharide gum, a plant polysaccharide gum having a wide range of 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. Guar gum may typically have a molecular weight of about 50 to 300, such as 100 to 200, ten thousand, and a mannose to galactose ratio of about 1.2 to 2.5:1, e.g., 1.5 to 2:1.

The guar gum derivatives suitable for use in the present invention are in principle not particularly limited as long as they are water-soluble cationic guar gum derivatives or water-soluble nonionic guar gum derivatives. In an advantageous embodiment, the guar derivatives are chosen from guar gums with a degree of substitution DS ≧ 0.15 or a degree of substitution DS ≧ 0.25. Such guar derivatives include oxidized guar, for example hydroxylated or carboxylated guar, such as hydroxypropyl guar or carboxymethyl guar.

In the dye ink of the present invention, guar gum or a derivative thereof is very important as a paste for rheology, permeability and leveling property, and it is particularly well compatible with the fluorine-containing double active 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 a derivative thereof is also important in the dye ink 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 presence of a large number of amino groups in the chitosan molecule is the only basic polysaccharide discovered to date. The inventor of the application 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 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 guar gum or a derivative thereof and chitosan in water in a weight ratio. For example, 5-15% by weight guar or guar derivatives such as hydroxypropyl guar may be placed in a container followed by sufficient distilled or deionized water. Stirring for 2 hr to dissolve, adding 0.5-1.5 wt% chitosan, and adjusting to 100% with distilled water or deionized water. And continuously stirring until the dye is completely dissolved and the system has uniform color, thus obtaining the transfer dyeing paste slurry.

As another important component, the dye ink of the present invention must contain 2 to 18% of a fluorine-containing double reactive group reactive dye having two reactive groups of a vinylsulfone group or a vinylsulfone group precursor group and a monofluoro-s-triazine group. The double reactive group reactive dyes according to the present invention 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.

Such dye intermediates are well known to those skilled in the art and may also be referred to as dye chromophores, including 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 dyes and Levafix EN-type reactive dyes (both of which have been attached to the parent with a monofluoro-s-triazine group) and the like.

Such reactive dyes having a vinylsulfone group or a precursor group 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 of the present application 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 having 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 disubstituted amino, and

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

An example of a well-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 straight-chain or branched alkyl having 1 to 12, preferably 1 to 8, 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. The term "alkoxy" may then be regarded as an alkyloxy group, 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 the reactive dye ink of the present application, in addition to the combination of the above-mentioned specific paste slurry and the specific double reactive group reactive dye, other components and auxiliaries may be contained. Examples of suitable components and adjuvants include rare earth driers, resists, dispersants, surface tension modifiers, and the like.

The rare earth drier can accelerate the drying speed of the reactive dye ink of a water-based system, 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 0.2-3%, such as 0.5-1%, 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%, such as 1.5 to 7%, 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 Efka 3570N of Pasteur, or Hydropalat 140 of Corning. The surface tension modifier may be used in an amount of 0.1 to 10%, such as 0.1 to 5% or 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 dye-proofing agent is used for controlling the dyeing process and can prevent dye from coloring to form a pattern substance on a fiber fabric or in the 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 0.2-3%, such as 0.5-1%, based on the total weight of the dye ink.

In addition to the combination of the paste slurry with the specific double-reactive dye and the appropriate other components and auxiliaries mentioned above, the composition comprises the balance water. The composition was adjusted to 100 wt% with water.

Yet another aspect of the present application relates to a method for preparing a reactive dye ink, which comprises mixing a fluorine-containing double reactive dye as described above with a paste slurry and optionally other components and auxiliaries, followed by stirring them uniformly.

In one embodiment, the fluorochemical double reactive dye may be mixed with optional other components and adjuvants 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 a paste in a container by using water.

The reactive dye inks prepared according to the invention have a viscosity of from 50 to 4000 mPas, preferably from 100 to 3000 mPas, and a surface tension of from 20 to 50mN/m, preferably from 25 to 40mN/m. The 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 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 when printing and dyeing fiber fabric, especially when carrying out transfer dyeing on jean grey cloth, such viscosity and surface tension are particularly suitable for applying the ink on a transfer roller or a transfer blanket, thereby improving the 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 fiber fabrics, particularly jean grey cloth, and solves the problems of unstable color and luster and poor dyeing importance when the jean grey cloth is dyed by using commercially available reactive dye.

A further aspect of the present application relates to a process for dyeing a fibrous fabric, in particular a denim blank, comprising the steps of:

1) Uniformly coating a dyeing accelerant on a fiber fabric to be dyed;

2) Applying the reactive dye ink as described above to a transfer roller or blanket or belt by means of a transfer dyeing apparatus;

3) Contacting the fibrous web of step 1) with the ink transfer roller or ink transfer blanket or belt of step 2) under pressure, thereby effecting dyeing of the fibrous web.

According to requirements, the fiber fabric can be subjected to desizing treatment before the step 1). For example, the fabric can be padded in desizing enzyme liquid at 50-60 ℃ and then piled for 3-4 hours, and then washed by hot water at higher temperature, such as above 60 ℃ (such as 90 ℃), washed by normal temperature water, and dried to obtain the fiber fabric to be dyed.

In one exemplary embodiment, in step 2), the dye-uptake promoter liquid may be applied to the optionally desized surface of the fibrous web by means of an anilox roller pre-treatment device by means of anilox roller coating.

After being subjected to the dyeing of step 3), the fabric or face fabric may be further dried and the other side of the fabric or face fabric prepared for dyeing as desired. Repeating steps 1) to 3), thereby achieving dyeing of the other side of the fabric or textile. The dyeing of the two sides can be double-sided homochromatic or double-sided heterochromatic.

The apparatus suitable for the transfer dyeing of the present application is not particularly limited, and for example, a transfer dyeing apparatus described in patent CN201710048416.4, or a paperless transfer printing machine described in patent CN201710048399.4, or a horizontal cylinder transfer printing machine described in patent CN201710504257.4, or a vertical double-sided cylinder transfer printing machine described in patent CN201710504264.4, or a satellite cylinder transfer printing machine described in patent CN201710504256.X, etc. may be used.

Drawings

FIG. 1 is an infrared spectrum of a fluorine-containing double reactive dye solid synthesized in example 1.

FIG. 2 is an infrared spectrum of a solid of the reactive dye containing fluorine double reactive groups synthesized in example 2.

The following examples are intended to illustrate various embodiments of the invention, but should not be construed as limiting the invention in any way.

Examples

While specific embodiments of the invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the scope of the invention as defined in the appended claims.

Test method

The fixation test described in the examples below was carried out according to the method of determination of the fixation of the prints described in GB/T2391-2014 "determination of the fixation of reactive dyes".

The test of dry rubbing fastness and wet rubbing fastness is carried out according to GB/T3920-2008 'textile, color fastness test, rubbing color fastness'.

The test of light fastness and soaping resistance color fastness is carried out according to GB/T14575-2009 comprehensive color fastness of textile color fastness test.

The PVI value test and the water holding capacity test of the paste slurry are carried out according to Zhong Xiang, song Xinrong, chen Zhen and Chen Lingling test method for basic performance of textile printing paste [ J ] Chinese fiber inspection, 2017 (03): 97-100 ].

Example 1

Polyurethane rubber is used as a surface material of an ink transfer roller or an ink transfer blanket belt in the transfer dyeing equipment described in patent CN201710048416.4, and a gravure plate is used as a plate roller.

The formula of the transfer dyeing reactive dye ink comprises the following components in percentage by weight:

composition of	By weight%
		Paste slurry	50％
Fluorine-containing double-active-group reactive dye	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	Adjusting to 100 percent

(1) Preparation of paste slurry:

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.

(2) Synthesis of fluorine-containing double-active-group reactive dye

1) 1 molar part of 1-amino-8-naphthol-3,6-disulfonic acid is placed in deionized water for pulping for 1 hour, then the pH =6.5 +/-0.2 is adjusted by NaOH to dissolve the 1-amino-8-naphthol-3,6-disulfonic acid, and the dissolved 1-amino-8-naphthol-5363-disulfonic acid is cooled to about 0-5 ℃ for storage for later use.

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

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 part by mol of concentrated hydrochloric acid was added thereto, and 1 part by mol of NaN0 was slowly dropped₂The prepared 30% solution is diazotized and detected by starch KI test paper to ensure that the nitrous acid is slightly excessive. After the end of the dropwise addition, stirring was carried out at 0.5 ℃ for 1h, and then excess nitrous acid was eliminated with sulfamic acid.

4) Slowly adding the liquid obtained in the step 3) intoCooling to about 10 ℃ in the liquid obtained in the step 2). With NaHC0₃The pH =6.5 ± 0.2 was adjusted, and the reaction was carried out for 4 hours with stirring, so as to obtain the fluorine-containing double reactive group reactive dye used in the present example, and the infrared spectrum of the dried sample is shown in fig. 1.

(3) Preparing reactive dye ink:

firstly, adding a small amount of cold water with the weight percent of about 2% and the prepared 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 obtained was 900 mPas, and the surface tension was 27mN/m.

The denim printing and dyeing cloth is obtained by adopting the transfer dyeing method described in Chinese patent CN201710048417.9 to carry out printing and dyeing operation.

The color fixing rate of the prepared fluorine-containing double-active-group reactive dye is 95 percent; the prepared jean dyed fabric has dry rubbing color fastness of 4-5 grade, wet rubbing color fastness of 3.5-4 grade, light fastness of 5 grade and soaping color fastness of 4-5 grade.

Example 2

Butyl rubber is used as a surface material of an ink transfer roller or an ink transfer blanket belt in the horizontal type rotary screen transfer printing machine in the patent CN201710504257.4, and a rotary screen is used as a plate roller.

(1) Preparation of paste slurry:

15% by weight of guar gum based on the total weight of the paste slurry was placed in a container, 70% by weight of distilled or deionized water was added, and stirred well for 2h. After the chitosan is fully dissolved, 1.5 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.

(2) Synthesis of fluorine-containing double-active-group reactive dye

The fluorine-containing double reactive group reactive dye was synthesized as described in example 1, wherein a Levafix EN type reactive dye of desmedia was used instead of a Cibacron F type reactive dye of hensman, and the infrared spectrum of the dried sample of the prepared fluorine-containing double reactive group reactive dye was as shown in fig. 2.

(3) Preparing reactive dye ink:

reactive dye inks were formulated as described in example 1, using the weight ratios described in the formulation tables. The viscosity of the reactive dye ink obtained was 3000 mPas, and the surface tension was 25mN/m.

The denim dyed fabric is obtained by adopting the transfer dyeing method described in Chinese patent CN201710048417.9 to carry out printing and dyeing operation.

The color fixing rate of the prepared fluorine-containing double-active-group reactive dye is 92 percent; the prepared jean dyed fabric has dry rubbing fastness of 4-5 grade, wet rubbing fastness of 3.5-4 grade, light fastness of 5 grade and soaping resistance color fastness of 4-5 grade.

Example 3

Styrene butadiene rubber is used as a surface material of an ink transfer roller or an ink transfer blanket belt in the paperless transfer printing machine in the patent CN201710048399.4, and is printed by using flexography equipment.

(1) Preparation of paste slurry:

8 wt% of DS =1.1 carboxymethyl guar based on the total weight of the paste slurry was placed in a container, 70 wt% distilled or deionized water was added, and stirred well for 2h. After the chitosan is fully dissolved, 0.5 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.

(2) Synthesis of fluorine-containing double-active-group reactive dye

The fluorine-containing double reactive group reactive dye was synthesized as described in example 1. And (3) preparing reactive dye ink:

reactive dye inks were formulated as described in example 1, using the weight ratios described in the formula tables. The viscosity of the reactive dye ink was 100 mPas, and the surface tension was 40mN/m.

The color fixing rate of the prepared fluorine-containing double-active-group reactive dye is 95 percent; the prepared jean dyed fabric has dry rubbing fastness of 4-5 grade, wet rubbing fastness of 3.5-4 grade, light fastness of 5 grade and soaping resistance color fastness of 4-5 grade.

Example 4

A reactive dye ink was formulated according to the procedure described in example 1, wherein 5 different versions of the paste slurry were formulated at different guar and chitosan weight percentages as shown in Table 1 below, based on the total weight of the paste slurry. The transfer dyeing operation was then carried out according to the equipment and process described in example 1, comparing the effect of the denim dyeing quality.

Table 1. Effect of different guar and chitosan formulations in the paste slurry on the quality effect of the denim dyed fabric.

In addition, the paste of example 1 was compared with the paste of the prior art as shown in Table 2 below.

TABLE 2 comparison of the quality effects of different pastes.

According to the comparison, the reactive dye ink prepared by adopting the paste slurry obtained by compounding the specific guar gum or the guar gum derivative and the proper amount of chitosan has remarkable performance advantages and is suitable for the transfer dyeing process.

Example 5

A reactive dye ink was prepared according to the procedure described in example 1, except that an equivalent amount of a commercially available dye product was used instead of the fluorine-containing bisactive-based dye prepared in example 1. The transfer dyeing operation was then carried out according to the equipment and process described in example 1, comparing the effect of the denim dyeing quality. The results are shown in table 3 below.

TABLE 3 comparison of different reactive dyes

Compared with the commercially available reactive dye containing vinyl sulfone group or a double-reactive dye product containing monochlorotriazine and vinyl sulfone group, the fluorine-containing double-reactive dye has better fixation rate effect, so that the reactive dye ink more meeting the requirements of the transfer dyeing process can be provided.

Claims

1. A transfer-dyeing reactive dye ink comprising, based on 100% by weight of the total composition:

25-80% of a paste slurry comprising, based on the total weight of the slurry, from 5 to 15% of guar and/or guar derivatives selected from oxidized guar with a degree of substitution DS ≧ 0.15 and selected from hydroxylated or carboxylated guar, and from 0.5 to 3% of chitosan; and

2-18% of fluorine-containing double active group reactive dye, which has vinyl sulfone group or vinyl sulfone group precursor group and fluorine-containing s-triazine group.

2. The reactive dye ink according to claim 1, wherein the reactive dye ink comprises 30 to 72% of the paste slurry, based on 100% by weight of the total composition.

3. The reactive dye ink according to claim 1, wherein the reactive dye ink comprises 40 to 65% of paste slurry, based on 100% of the total weight of the composition.

4. A reactive dye ink according to claim 1 characterised in that the paste slurry comprises 0.5 to 2% chitosan based on the total weight of the slurry.

5. A reactive dye ink according to claim 1 characterised in that the paste slurry comprises 0.5 to 1.5% chitosan based on the total weight of the slurry.

6. The reactive dye ink according to claim 1, wherein the reactive dye ink comprises 4-13% of the fluorine-containing double reactive group reactive dye based on 100% of the total weight of the composition.

7. The reactive dye ink according to claim 1, characterized in that the guar derivatives are chosen from oxidized guar with a degree of substitution DS ≥ 0.25.

8. The reactive dye ink according to claim 1, characterized in that the oxidized guar is selected from hydroxypropyl guar or carboxymethyl guar.

9. The reactive dye ink according to any one of the preceding claims 1 to 8, characterized in that 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, and

10. The reactive dye ink of claim 9, wherein B is-NH-.

11. The reactive dye ink according to claim 9, wherein the reactive group is selected from a substituted or unsubstituted monofluoros-triazine group represented by the following formula (II), and a vinyl sulfone group or a vinyl sulfone group precursor represented by the following formula (III):

wherein

M is H or an alkali metal ion,

r1 is an ester group selected from the group consisting of a sulfate ester, a carboxylate ester and a phosphate ester,

r2 is H, hydroxy, alkyl, alkoxy, amino or mono-or disubstituted amino, and

y each independently represents H, halogen or straight or branched C_1-12Alkyl group of (1).

12. The reactive dye ink of claim 11, wherein R1 is a sulfate group (-OSO)₃-)。

13. The reactive dye ink of claim 11, wherein M is Na or K.

14. A reactive dye ink according to claim 11, wherein each Y independently represents H.

15. The reactive dye ink according to claim 9, wherein the group of the vinylsulfone-based precursor is derived from p- (β -ethylsulfone sulfate) aniline.

16. Reactive dye ink according to any one of the preceding claims 1 to 8, characterized in that it further comprises components and auxiliaries selected from: rare earth drier, dye-resisting agent, dispersant and surface tension regulator.

17. Reactive dye ink according to any of the preceding claims 1 to 8, characterized in that it comprises, based on its total weight: 0.2-3% of rare earth drier; 1-10% of a dispersant; 0.1-10% of a surface tension modifier; and/or 0.2-3% of a stain-proofing agent.

18. The reactive dye ink according to claim 17, comprising based on its total weight: 0.5-1% of rare earth drier.

19. The reactive dye ink according to claim 17, comprising based on its total weight: 1.5-7% of dispersing agent.

20. The reactive dye ink according to claim 17, comprising based on its total weight: 2-5% of dispersing agent.

21. The reactive dye ink according to claim 17, comprising based on its total weight: 0.1-5% of surface tension regulator.

22. The reactive dye ink according to claim 17, comprising based on its total weight: 0.5-2% of surface tension regulator.

23. The reactive dye ink according to claim 17, comprising based on its total weight: 0.5-1% of a dye-proofing agent.

24. Reactive dye ink according to any of the preceding claims 1 to 8, characterized in that the viscosity of the reactive dye ink is 50-4000 mPa-s and/or the surface tension is 20-50mN/m.

25. The reactive dye ink of claim 24, wherein the reactive dye ink has a viscosity of 100 to 3000 mPa-s.

26. The reactive dye ink of claim 24, wherein the reactive dye ink has a surface tension of 25mN/m to 40mN/m.

27. The dyeing method for the fiber fabric comprises the following steps:

1) Uniformly coating a dyeing accelerant on a fiber fabric to be dyed;

2) Applying a reactive dye ink according to any one of claims 1 to 26 to a transfer roller or blanket or belt by means of a transfer dyeing apparatus;

28. The dyeing process according to claim 27, characterized in that the fibrous fabric is a denim fabric.