WO2022110622A1

WO2022110622A1 - Reactive dye ink for transfer dyeing and application thereof

Info

Publication number: WO2022110622A1
Application number: PCT/CN2021/088990
Authority: WO
Inventors: 钟博文
Original assignee: 长胜纺织科技发展(上海)有限公司
Priority date: 2020-11-24
Filing date: 2021-04-22
Publication date: 2022-06-02
Also published as: CN112647319B; CN112647319A

Abstract

A reactive dye ink for transfer dyeing comprises based on 100% of the total weight of the composition: 25-80% of a paste slurry comprising, based on the total weight of the slurry, 3-20% guar gum and/or a guar derivative, and 0.1-3% of chitosan; and 2-18% of a fluorine-containing reactive dye having a double active group, a vinyl sulfone group or a vinyl sulfone precursor group, and a monochlorotriazine group.

Description

Transfer dyeing reactive dye ink and its application

technical field

The present application relates to the printing and dyeing technology of the textile industry, more particularly to a new type of transfer dyeing reactive dye ink and its application, especially to the dyeing method of fibrous fabrics such as denim grey fabrics.

Background technique

Fiber fabrics are widely used in the textile industry and clothing field. In addition to traditional and common cotton fibers, various natural fibers such as hemp, ramie, flax, silk, wool, etc. blended with cotton, regenerated fibers such as viscose, tencel, modal, etc., or synthetic fiber chemical fibers such as polyester, nylon , acrylic fiber, spandex, etc. have been widely used.

In order to provide the rich color and beauty of garments and fabrics, the fiber fabrics need to be dyed with dyes. These dyes include, for example, various reactive dyes, indigo dyes, sulfur dyes, vat dyes, and the like. Reactive dye is an anionic dye, also known as reactive dye. Its molecular structure is composed of dye precursor and reactive group. During dyeing, the dye precursor can interact with hydroxyl groups or hydroxyl groups in cotton, wool and other fibers through reactive groups in aqueous solution. The amino group reacts to form a covalent bond that is fixed on the fiber. It is popular due to its good vividness, ease of use and good color fastness. When dyeing, vat dyes need to be reduced and dissolved into leuco sodium salts in strong alkaline reducing solution to dye fibers, and then oxidized into insoluble dye lakes and fixed on fibers. Indigo is an ancient vat dye. Sulfur dyes are also commonly used in cotton fiber dyeing, and are based on dyes dissolved in sulfide bases. Sulfur dyes are similar to vat dyes in that they also dye fibers through a chemical reduction reaction to form a water-soluble leuco form that has an affinity for fibers, and then bind tightly to fibers through an oxidation process.

Denim or denim grey is common in the market. It is mainly made of cotton, but can also use a variety of raw material structures, such as cotton, wool, silk, hemp natural fibers blended, and can also be blended with chemical fibers, as well as elastic yarn, twisted yarn, fancy yarn, etc. as raw materials. The manufacturing process of denim is relatively unique. It is a product that is first dyed and sizing with dyes, and then woven. Indigo dyes, sulfur dyes, vat dyes, etc. are mainly used for denim dyeing.

Whether it is indigo dyes, sulfur dyes or vat dyes, a large amount of inorganic salts need to be used when dyeing fiber fabrics, especially denim grey fabrics, and a large amount of water is required to be fully washed after dyeing to reduce residual dyes on the fabric. . Therefore, the dyeing pollution of traditional fiber fabrics such as denim grey fabrics is very serious.

Therefore, the market urgently needs an environmentally friendly fiber fabric printing and dyeing process. One of the current solutions is to use reactive dyes, but the production batch is not large. The main problem is that the color and shade are not stable enough, and the importance of dyeing is also poor, which cannot meet the needs of downstream customer garment manufacturers. This is also directly related to the difficulty of producing reactive dyed fiber fabrics by the existing dyeing and pulping machine, high consumption, high cost, and difficult sewage treatment.

Another type of approach is to develop modifiers to pretreat fibers. For example, CN107740295A provides a dyeing method based on a reactive dye cationic modifier for cotton fabrics, wherein the cotton fibers are modified, and the modified aqueous solution used is an aqueous glutamate solution or an aqueous phenylalanine solution.

In addition, transfer printing technology has also been used for the dyeing of fiber fabrics, forming a pattern of dyeing by printing. The water consumption of printing is usually much lower than that of traditional dyeing. In traditional dyeing (especially dip dyeing), the fabric has a longer action time in the dye bath, which enables the dye to diffuse and penetrate into the fiber more fully to complete the dyeing process. In fact, printing is a local dyeing. During printing, after the paste added in the color paste is dried to form a film, the polymer film layer will prevent the dye from diffusing into the fiber, so that the dye adheres to the surface of the fiber, and the dye is finally fixed by steaming, baking and other means. .

However, there is still room for improvement for those technical problems mentioned above, and further exploration of suitable accelerators for improving the dyeing process is also required.

SUMMARY OF THE INVENTION

In view of the above technical problems, the inventors of the present application have developed a new type of transfer dyeing reactive dye ink. The reactive dye ink uses water as a solvent, in which a specific reactive dye and a specific paste and surface tension regulator and other auxiliary agents are dissolved, which can be printed on the transfer dyeing equipment used in the transfer dyeing process of fiber fabrics The ink transfer roller or the ink transfer blanket belt, and the dye ink is transferred from the ink transfer roller or the ink transfer blanket belt to the fibers of the denim fabric during the transfer dyeing process.

The inventors of the present application found that the use of the transfer dyeing reactive dye ink according to the present invention can greatly improve the levelness of the printing surface, provide more stable color and luster, high color fixing rate and form stable dye-fiber bond , thereby greatly improving the color fastness of transfer printing. In addition, the reactive dye inks of the present invention have good rheology, permeability, storage stability and are very suitable for processing on transfer rollers or transfer blankets.

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

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

2-18%, preferably 4-13%, of fluorine-containing dual-reactive reactive dyes having vinylsulfone groups or vinylsulfone-based precursor groups and monofluoro-s-triazine groups.

Guar gum used in the dye ink of the present invention is a kind of galactomannan gum, and galactomannan is a kind of neutral polysaccharide gum, which is a plant polysaccharide gum widely used in industry. The galactomannan glue solution is a pseudoplastic fluid, and the macromolecules are entangled in a network structure in the natural state. As a common form, guar gum includes a main chain connected by (1-4)-β-D-mannose as a structural unit, and a single α-D-galactose with (1-6 ) bond to the side chain connected to the main chain. From the perspective of the whole molecule, galactose is randomly distributed on the main chain, but mostly in groups of two or three. Due to different sources, guar gum differs from other galactomannans in molecular weight and monosaccharide ratio. The molecular weight of guar gum may generally be about 500,000 to 3 million, such as 1 to 2 million, and the ratio of mannose to galactose may be about 1.2 to 2.5:1, such as 1.5 to 2:1.

The guar gum derivative suitable for use in the present invention is not particularly limited in principle, as long as it is a water-soluble cationic guar gum derivative or a water-soluble nonionic guar gum derivative. In an advantageous embodiment, the guar derivatives are selected 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, such as hydroxylated or carboxylated guar, such as hydroxypropyl guar or carboxymethyl guar.

In the dye ink of the present invention, guar gum or its derivative as a paste is very important for rheology, permeability and levelness, and it has particularly good compatibility with the fluorine-containing dual reactive group reactive dye of the present invention, At the same time, the solid effect of printing on the rubber surface of the ink transfer roller or the ink transfer blanket belt is very good.

In addition, the content of guar gum or its derivatives is also important in the dye ink of the present invention. It has been found that if the content of guar gum or its derivatives is too low, the dye penetration is strong, the surface color yield is poor, and the color is not bright enough; and if the content is too high, the levelness of the dye is poor, and the fastness after washing. poor.

There are a lot of amino groups in the chitosan molecule, and it is the only basic polysaccharide discovered so far. The inventors of the present application found that chitosan would wrap around the surface of the cotton fiber to form a film layer, thereby enabling the fabric to absorb more dyes, thereby improving the dyeing rate of the cotton fabric. The inventors have also discovered that chitosan has a synergistic gain effect when combined with guar gum or its derivatives, especially in modulating the rheology of dye inks. The dye ink of the present invention is mainly used in the transfer dyeing process. It is hoped that the uniformity of dyeing can be taken into account under the premise of less paste and high ink loading. Therefore, proper rheology is critical for the upper limit of the transfer dyeing speed and the uniformity. important key points. In conclusion, in the present invention, when combined with guar gum or its derivatives, chitosan can further improve the color absorption performance, save the amount of dye, and at the same time play a darkening and brightening effect, and can adjust the rheological change of the dye ink. Well suited for transfer dyeing processes.

The paste slurry can be prepared simply by mixing guar gum or its derivatives with chitosan in water in a weight ratio. For example, 5-15% by weight of guar gum or a guar gum derivative such as hydroxypropyl guar can be placed in a container followed by the addition of a sufficient amount of distilled or deionized water. After fully stirring for 2 hours to fully dissolve, 0.5-1.5% by weight of chitosan is added, and then adjusted to 100% with distilled water or deionized water. Continue stirring until it is completely dissolved and the color of the system is uniform, which is the transfer dyeing paste slurry.

As another important component, the dye ink of the present invention must contain 2-18% of fluorine-containing dual reactive group reactive dyes, which have vinylsulfone groups or vinylsulfone-based precursor groups and monofluoro-s-triazine groups two reactive groups of the group. The dual reactive group reactive dyes according to the present invention can be represented by the following formula:

D-(B-Re) ₂ (I)

where D is a dye intermediate,

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

Re is a reactive group, which is a group containing a monofluoro-s-triazine group without a chloro-s-triazine group and a group containing a vinylsulfone group (-SO ₂ CH=CH ₂ ) or a vinylsulfone group precursor, respectively .

The dye intermediates are well known to those skilled in the art, and can also be called dye chromophores, including dye parent compounds such as azo, anthraquinone, phthalocyanine, etc., or their structural modifications. These parent compounds or forms to which reactive groups have been attached are generally commercially available, such as Huntsman's Cibacron type F reactive dyes and Levafix EN type reactive dyes (both of which have a fluorine homopolymer attached to the parent) triazine group) etc.

Such reactive dyes having vinylsulfone groups or their precursor groups and halogenated s-triazine di-reactive groups are known per se or methods for their preparation and are commercially available. Such reactive dyes have been used in the dyeing of fibrous fabrics. Common reactive dyes of this type usually contain a vinylsulfone group and a chloro-s-triazine double reactive group. However, the inventors of the present application found that if fluorine is used to replace chlorine in the structure of the s-triazine reactive group in the dye molecule, the stability of the dyed fiber can be greatly increased when it is used for printing and dyeing, and the Dyes with monochloro-s-triazine reactive groups more stable dye-fiber bonds, resulting in higher color fastness, especially when combined with pastes containing guar gum or its derivatives as described above When used in combination with slurries.

Preferably, a substituted or unsubstituted monofluoro-s-triazine group represented by the following formula (II), more preferably an unsubstituted mono-fluoro-s-triazine group, can be used as the active group. The vinyl sulfone group precursor group can then be any group that can be converted into a vinyl sulfone group under suitable media and conditions such as alkaline conditions and, for example, upon dyeing, for example as a vinyl sulfone group-containing precursor group An ester-ethylsulfone group-containing group represented by the following formula (III) can be preferably used.

in

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

R1 is an ester group selected from sulfate, carboxylate and phosphate, 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 _1-12 alkyl, preferably H.

A well-known example of a compound commonly used to introduce groups containing vinylsulfone-based precursors is para-ester (or para-(beta-ethylsulfone sulfate)aniline) or derivatives or analogs thereof.

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

In the context of this application, the term "alkyl" preferably denotes a straight-chain or branched alkyl group having 1-12, preferably 1-8 carbon atoms, and one or more H on the carbon atoms may be replaced by a halogen such as F , Cl or Br substituted. In a preferred embodiment, the alkyl group represents an unsubstituted C _1-8 alkyl group, more preferably a C _1-4 alkyl group, such as methyl, ethyl, propyl or butyl. The term "alkoxy" may then be taken to mean an alkyloxy group, wherein the alkyl group is as defined above.

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

The mono- or disubstituted amino groups are not limited in principle and are those substituted amino groups known in the dye art, including, for example, alkyl, alkoxy, aryl, amido, sulfamido, amidoalkyl, sulfamido Alkyl or hydroxyalkyl substituted amino, etc.

In the reactive dye ink of the present application, in addition to the combination of the above-mentioned specific paste slurry and specific dual reactive group reactive dye, other components and auxiliary agents may also be contained. Examples of suitable components and adjuvants include rare earth driers, stain inhibitors, dispersants, surface tension modifiers, and the like.

Rare earth driers can not only speed up the drying speed of reactive dye inks in water-based systems and improve production efficiency, but also have an auxiliary role in deepening and brightening reactive dyes. The rare earth drier can be selected from carboxylate 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, ≤10 microns, ≤8 microns, or 5 microns. The rare earth drier can 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 from, for example, a methylene naphthalene sulfonic acid dispersant, or a phenolic condensate sulfonate dispersant, or a fatty alcohol polyoxyethylene ether silane type dispersant. The dispersant may be used in an amount of 1-10%, such as 1.5-7%, preferably 2-5%, based on the total weight of the dye ink.

The surface tension modifier is not particularly limited, and can be, for example, a nonionic surfactant, such as BYK-DYNWET 800 from BYK, Efka 3570N from BASF, or Hydropalat 140 from Corning. The surface tension modifier may be used in an amount of 0.1-10%, such as 0.1-5% or 0.5-2%, based on the total weight of the dye ink. By adding an appropriate amount of surface tension modifier, the surface tension of the reactive dye ink can be further adjusted to be less than the critical surface tension of the transfer roller or the transfer blanket in the transfer dyeing equipment, so that the ink can be clearly printed on the transfer roller or The surface of the ink blanket belt.

Anti-dyeing agent is used to control the dyeing process, which can prevent dyes from coloring and form patterns on fabrics or during printing and dyeing. Examples of suitable resists include resist salt S (based primarily on sodium m-nitrobenzenesulfonate) and resist salt H (based on primarily ammonium phenylhydrazine sulfonate), and the like. The resist 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 and the specific dual reactive reactive dyes and other suitable components and auxiliaries mentioned above, the balance of water is included in the composition. The composition was adjusted to 100% by weight with water.

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

In a specific embodiment, the fluorine-containing dual reactive group reactive dye can be mixed with other components and auxiliary agents optionally dissolved in water, and then optionally filtered and then added to the paste slurry. If necessary, the fluorine-containing double reactive group reactive dye can be made into a paste with water in a container first.

The reactive dye ink prepared according to the present invention has a viscosity of 50-4000 mPa·s, preferably 100-3000 mPa·s, and a surface tension of 20-50 mN/m, preferably 25-40 mN/m. The ink of the present invention generally uses the surface of a rubber blanket or a rubber roller as a transfer temporary carrier, and the surface tension of rubber is relatively low, for example, the critical surface tension of polyurethane rubber is about 29, and the critical surface tension of butyl rubber is about 27. The surface tension of styrene-butadiene rubber is about 48, so when printing and dyeing fiber fabrics, especially denim grey fabrics, such viscosity and surface tension are especially suitable for applying ink on ink transfer rollers or ink transfer blankets. , thereby improving workability.

In particular, compared with indigo dyes, sulfur dyes or vat dyes, the reactive dye ink of the present invention can significantly reduce pollution when dyeing fiber fabrics, especially denim grey fabrics, and improves the lack of color, luster and light when dyeing denim grey fabrics with commercially available reactive dyes Stability and dyeing importance are also poor issues.

Another aspect of the present application relates to a dyeing method for fiber fabrics, especially denim grey fabrics, comprising the following steps:

1) Evenly coat the dyeing accelerator on the fiber fabric to be dyed;

2) The reactive dye ink as described above is applied on the transfer roller or the transfer blanket or belt by transfer dyeing equipment;

3) The fiber fabric in step 1) is brought into pressure contact with the ink transfer roller or ink transfer blanket or belt in step 2), thereby realizing the dyeing of the fiber fabric.

As required, the fiber fabric can also be subjected to desizing treatment before step 1). For example, the fabric can be stacked in the desizing enzyme solution at 50-60°C for 3-4 hours, then washed with hot water at a higher temperature such as above 60°C (such as 90°C), then washed with normal temperature water, and dried. After drying, it becomes the fiber fabric to be dyed.

In an exemplary embodiment, in step 2), the dyeing accelerator liquid may be coated on the desizing surface of the fiber fabric by an anilox coating method through an anilox pre-treatment device.

After going through the dyeing of step 3), the fabric or fabric can be further dried, and the other side of the fabric or fabric can be prepared for dyeing as required. Repeat steps 1) to 3), thereby achieving the dyeing of the other side of the fabric or fabric. The dyeing of the two sides can be the same color on both sides or different colors on both sides.

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

Description of drawings

FIG. 1 is the infrared spectrum of the solid fluorine-containing dual reactive group reactive dye synthesized in Example 1. FIG.

Fig. 2 is the infrared spectrogram of the fluorine-containing dual reactive group reactive dye solid synthesized in Example 2.

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

Example

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

testing method

The color fixing rate test described in the following examples is carried out according to the determination method of the printing color fixing rate in GB/T 2391-2014 "Determination of the color fixing rate of reactive dyes".

Dry rubbing fastness and wet rubbing fastness test are carried out according to GB/T 3920-2008 "Textiles. Color fastness test. Color fastness to rubbing".

Light fastness and color fastness to soaping are tested according to GB/T 14575-2009 "Comprehensive Color Fastness of Textile Color Fastness Test".

The PVI value test and water retention test of the paste slurry are based on "Zhong Xiang, Song Xinrong, Chen Zhen, Chen Lingling. Test method for basic properties of textile printing paste [J]. China Fiber Inspection, 2017(03):97-100 ."conduct.

Example 1

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

The formula of transfer dyeing reactive dye ink is as follows according to weight percentage:

(1) Preparation of paste slurry:

Put 5% by weight of hydroxypropyl guar gum with a degree of substitution DS≥0.15 based on the total weight of the paste slurry into a container, add 70% by weight of distilled water or deionized water, and fully stir for 2 hours. After fully dissolving, add 1% by weight of chitosan, adjust it to 100% with distilled water or deionized water, and continue stirring until it is completely dissolved and the color of the system is uniform.

(2) Synthesis of fluorine-containing dual reactive group reactive dyes

1) After placing 1 molar portion of 1-amino-8-naphthol-3,6-disulfonic acid in deionized water for 1 hour, adjust pH=6.5±0.2 with NaOH, dissolve it, and cool it down Store at about 0°C-5°C for later use.

2) 1-amino-8-naphthol-3,6-disulfonic acid solution mixes in the Cibacron F type reactive dye filter cake of Huntsman after the purification of 1 molar portion for use and in step 1), drips NaHCO ₃ to pH=4.5±0.2. Under the condition of 30°C-40°C, stir at a low speed to react for 3 hours, use an amino reagent to detect the end point, and cool the obtained liquid to about 10°C and store it for use.

3) After stirring and beating 1 mole part of p-(β-ethylsulfone sulfate)aniline in deionized water for 1 hour, add ice to cool down to 0-10°C. Add 1 mol part of concentrated hydrochloric acid, slowly dropwise add 1 mol part of NaN0 ₂ to prepare a 30% solution, carry out diazotization, and detect with starch KI test paper to ensure a slight excess of nitrous acid. After the dropwise addition, the mixture was stirred at 0.5° C. for 1 h, and then excess nitrous acid was eliminated with sulfamic acid.

4) The liquid obtained in step 3) is slowly added to the liquid obtained in step 2) which is cooled to about 10°C. Adjust pH=6.5±0.2 with NaHCO ₃ and react under stirring for 4 h to obtain the fluorine-containing dual reactive group reactive dye used in this example. The infrared spectrum of the dried sample is shown in Figure 1 .

(3) Preparation of reactive dye ink:

First, add a small amount of cold water of about 2% by weight and the prepared reactive dye in the container, and adjust it into a paste; then add a mixture of dissolved anti-dyeing salt S, dispersant, and surface tension regulator according to the dosage shown in the table above. Add about 15% by weight of warm water at 85°C to fully dissolve the reactive dye, add it to the prepared paste after filtration, adjust it to 100% by weight with water and stir evenly to obtain reactive dye ink. The obtained reactive dye ink had a viscosity of 900 mPa·s and a surface tension of 27 mN/m.

The printing and dyeing operation is carried out by using the transfer dyeing method described in Chinese patent CN201710048417.9 to obtain denim printing and dyeing cloth.

The color fastness of the prepared fluorine-containing dual reactive group reactive dyes is 95%; the color fastness to dry rubbing of the prepared denim dyed fabric is 4-5, the color fastness to wet rubbing is 3.5-4, and the light fastness is 5 The color fastness to soaping is 4-5.

Example 2

The butyl rubber is used as the surface material of the ink transfer roller or the ink transfer blanket belt in the horizontal rotary screen transfer printing machine described in the patent CN201710504257.4, and the rotary screen is used as the plate roller.

组成composition	重量％weight%
糊料浆液paste slurry	65％65%
含氟双活性基活性染料Fluorine-containing dual reactive group reactive dyes	5％5%
稀土催干剂(环烷酸稀土，细度≤5微米)Rare earth drier (rare earth naphthenate, fineness ≤ 5 microns)	0.5％0.5%
防染盐S Anti-staining salt S	1％1%
分散剂(酚醛缩合物磺酸盐分散剂)Dispersant (phenolic condensate sulfonate dispersant)	3％3%
表面张力调节剂(巴斯夫公司的Efka 3570N)Surface tension modifier (BASF's Efka 3570N)	0.5％0.5%
蒸馏水distilled water	调整到100％Adjust to 100%

(1) Preparation of paste slurry:

Put 15% by weight of guar gum based on the total weight of the paste slurry into a container, add 70% by weight of distilled water or deionized water, and stir well for 2h. After fully dissolving, add 1.5% by weight of chitosan, adjust it to 100% with distilled water or deionized water, and continue stirring until it is completely dissolved and the color of the system is uniform.

(2) Synthesis of fluorine-containing dual reactive group reactive dyes

Synthesize fluorine-containing double reactive group reactive dyes as described in Example 1, wherein Levafix EN type reactive dyes of DyStar Company are used instead of Huntsman's Cibacron F type reactive dyes, and the prepared fluorine-containing double reactive group reactive dyes are dried The infrared spectrum of the post sample is shown in Figure 2.

(3) Preparation of reactive dye ink:

The reactive dye ink was formulated as described in Example 1 using the weight ratios stated in the formula table. The viscosity of the obtained reactive dye ink was 3000 mPa·s, and the surface tension was 25 mN/m.

The fixation rate of the prepared fluorine-containing dual reactive group reactive dyes was 92%; the dry rubbing fastness of the prepared denim dyed fabric was 4-5, the wet rubbing fastness was 3.5-4, and the light fastness was 5. The color fastness to soaping is 4-5.

Example 3

Styrene-butadiene rubber is used as the surface material of the ink transfer roller or ink transfer blanket belt in the paperless transfer printing machine described in the patent CN201710048399.4, and it is printed with flexographic printing equipment.

The formula of transfer dyeing reactive dye ink is as follows in weight percentage:

组成composition	重量％weight%
糊料浆液paste slurry	40％40%
含氟双活性基活性染料Fluorine-containing dual reactive group reactive dyes	10％10%
稀土催干剂(异辛酸稀土，细度≤5微米)Rare earth drier (rare earth isooctanoate, fineness ≤ 5 microns)	1％1%
防染盐SAnti-staining salt S	0.5％0.5%
分散剂(脂肪醇聚氧乙烯醚硅烷型分散剂)Dispersant (fatty alcohol polyoxyethylene ether silane type dispersant)	2％2%
表面张力调节剂(科宁公司的Hydropalat 140)Surface tension modifier (Hydropalat 140 from Corning)	1％1%
蒸馏水distilled water	调整到100％Adjust to 100%

(1) Preparation of paste slurry:

Put 8 wt % of carboxymethyl guar gum with DS=1.1 based on the total weight of the paste slurry into a container, add 70 wt % of distilled water or deionized water, and fully stir for 2 h. After fully dissolving, 0.5% by weight of chitosan was added, adjusted to 100% with distilled water or deionized water, and stirring was continued until it was completely dissolved and the color of the system was uniform.

(2) Synthesis of fluorine-containing dual reactive group reactive dyes

Fluorine-containing dual-reactive reactive dyes were synthesized as described in Example 1. (3) Preparation of reactive dye ink:

The reactive dye ink was formulated as described in Example 1 using the weight ratios stated in the formula table. The obtained reactive dye ink had a viscosity of 100 mPa·s and a surface tension of 40 mN/m.

The printing and dyeing operation is carried out by using the transfer dyeing method described in Chinese patent CN201710048417.9 to obtain a denim printing and dyeing cloth.

The fixation rate of the prepared fluorine-containing dual reactive group reactive dyes is 95%; the prepared denim dyed fabric has a dry rubbing fastness of 4-5, wet rubbing fastness of 3.5-4, and a light fastness of 5. The color fastness to soaping is 4-5.

Example 4

The reactive dye ink is prepared according to the steps described in Example 1, wherein the paste slurries of 5 different schemes are prepared according to the weight percentages of different guar gums and chitosan shown in Table 1 below, and the weight percentages are based on the paste slurries. of the total weight of the slurry. Subsequently, the transfer dyeing operation was carried out according to the equipment and process described in Example 1, and the quality effect of the denim dyed fabric was compared.

Table 1. Effects of different ratios of guar gum and chitosan in the paste slurry on the quality effect of denim dyed fabrics.

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

Table 2. Comparison of quality effects of different pastes.

It can be seen from the above comparison that, according to the present invention, the paste slurry obtained by compounding a specific guar gum or a guar gum derivative and an appropriate amount of chitosan is used to prepare a reactive dye ink, which has significant performance advantages and is suitable for this application. Invention of the transfer dyeing process.

Example 5

The reactive dye ink was prepared according to the steps described in Example 1, except that the fluorine-containing dual reactive dyes prepared in Example 1 were replaced with the same amount of commercially available dye products. Subsequently, the transfer dyeing operation was carried out according to the equipment and process described in Example 1, and the quality effect of the denim dyed fabric was compared. The results are shown in Table 3 below.

Table 3. Comparison of different reactive dyes

It can be seen from the above comparison that, compared with the commercially available reactive dyes containing vinyl sulfone groups or the dual reactive dye products containing monochloro-s-triazine and vinyl sulfone groups, the fluorine-containing dual reactive dyes according to the present invention have better performance. Fixing rate effect, which can provide reactive dye inks that better meet the needs of the transfer dyeing process.

Claims

Transfer dyeing reactive dye inks comprising, by weight of the total composition 100%:

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

2-18%, preferably 4-13%, of a fluorine-containing dual-reactive reactive dye having a vinylsulfone group or a vinylsulfone-based precursor group and a monofluoro-s-triazine group.
The reactive dye ink according to claim 1, wherein the guar gum derivatives are selected from guar gums with a degree of substitution DS≥0.15 or a degree of substitution DS≥0.25, such as oxidized guar gum, such as hydroxylated or Carboxylated guar, preferably hydroxypropyl guar or carboxymethyl guar.
The reactive dye ink according to any one of the preceding claims, wherein the fluorine-containing dual reactive group reactive dye is represented by the following formula:

D-(B-Re) 2 (I)

where D is a dye intermediate,

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

Re is a reactive group, which is a group containing a monofluoro-s-triazine group without a chloro-s-triazine group and a group containing a vinylsulfone group (-SO 2 CH=CH 2 ) or a vinylsulfone group precursor, respectively .
The reactive dye ink according to any one of the preceding claims, wherein the reactive group is selected from the group consisting of substituted or unsubstituted monofluoro-s-triazine groups represented by the following formula (II), and vinylsulfone group or a group of a vinylsulfone-based precursor represented by the following formula (III):

in

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

R1 is an ester group selected from sulfate, carboxylate and phosphate, 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 1-12 alkyl, preferably H.
The reactive dye ink according to claim 3 or 4, wherein the group of the vinylsulfone-based precursor is derived from p-(β-ethylsulfone sulfate)aniline.
The reactive dye ink according to any one of the preceding claims, characterized in that it further comprises components and auxiliary agents selected from the group consisting of rare earth driers, dye resists, dispersants, surface tension regulators, and the like.
The reactive dye ink according to any one of the preceding claims, characterized in that, based on its total weight, the reactive dye ink comprises: 0.2-3%, such as 0.5-1%, of rare earth drier; 1-10%, such as 1.5-7%, preferably 2-5% of dispersants; 0.1-10%, such as 0.1-5% or 0.5-2% of surface tension modifiers; and/or 0.2-3%, such as 0.5-1% Anti-stain.
The reactive dye ink according to any one of the preceding claims, characterized in that the reactive dye ink has a viscosity of 50-4000 mPa·s, preferably 100-3000 mPa·s and/or a surface tension of 20-50 mN/m , preferably 25-40mN/m.
The dyeing method for fiber fabrics, especially denim grey fabrics, includes the following steps:

1) Evenly coat the dyeing accelerator on the fiber fabric to be dyed;

2) applying the reactive dye ink as described in any one of claims 1-8 on an ink transfer roller or an ink transfer blanket or belt by transfer dyeing equipment;

3) The fiber fabric in step 1) is brought into pressure contact with the ink transfer roller or ink transfer blanket or belt in step 2), thereby realizing the dyeing of the fiber fabric.