TWI417346B - Novel quinoneimine sulfur dye compositions, production thereof and use thereof for dyeing cellulosic material - Google Patents

Description

Novel bismuth sulfite dye composition, preparation thereof and application to dyed fiber materials

The present invention relates to novel white sulfur dye compositions for the quinone imine sulfur dye population, and to methods of preparing the same by electrochemical reduction of controlled electrochemical treatment conditions.

The quinone imine dye comprises a dye formed by the reaction of polynitrated phenol, halobenzene, indophenol or indoline with sulfur, an alkali metal sulfide or an alkali metal polysulfide in an aqueous or alcohol-containing medium. The violet, blue, green, reddish brown and black sulfur dyes specifically comprise this dye population. The resulting oligomeric or polymeric product contains organic structural repeating elements (eg, phenothiazine, buprofezin, thiazide, and phenoxazinone substructures) linked together via a disulfide bridge. These structures are described in the reference Angewandte Chemie 60 (1948), 141-147.

These sulfur dyes are dyed and they are converted into a ready-to-use white form by a number of reduction methods. On the other hand, they reduce the quinone imine functionality and cleave the disulfide bridge in a reducing manner. The resulting white compound typically has a lower molecular weight and contains a wide range of molecular weight species. They are soluble in alkaline aqueous media and can be used to dye fibrous materials.

In the presence of a suitable oxidizing agent (for example, oxygen, peroxide or bromate in air), the dye is more or less completely oxidized according to the following formula, wherein R represents an organic repeating structural unit, for example, Substructure of phenothiazine, buprofezin, thiazide and morphoxazinone.

Like a fully oxidized sulfur dye, during the actual dyeing operation, by adding an organic or inorganic reducing agent, it can be converted into a ready-to-use white form, more or less ready-to-use, previously reduced white. The sulfur dye brand is also on the market, an example is Cassulfon Carbon CMR. It is preferably produced on a large industrial scale by adding an inorganic or organic reducing agent such as sodium hydrogen sulfide or sucrose in an alkaline medium.

The disadvantages of these prior methods are the very high concentration of waste from the reducing agent used and the presence of salt burden, and the high COD and TOC burden of the dyehouse wastewater. These by-products can only be removed upstream of the wastewater treatment stage with a large amount of engineering and high cost and inability to (eg, membrane techniques).

Another environmentally friendly reduction method is known from the documents DE 1906083 and EP 10122210. DE 1906083 proposes a process for reducing dyes by a cathodic reduction reaction having a current density in an aqueous solution of between 5 mA/cm 2 and 50 mA/cm 2 . However, this method is not applicable because a commercially available pre-reduced sulfur dye which is substantially blended with other stabilizers for stabilization in the dyeing solution is exemplified because a large amount of hydrogen is released during the reduction reaction. The EP 1012210 patent specification describes a method for reducing sulfur dyes at current densities between 0.5 milliamperes per square centimeter and 5 milliamps per square centimeter.

Surprisingly, it has been found that a current density between 50 mA/cm 2 and 500 mA/cm 2 and a flow rate in the range of 0.1 m/s to 0.4 m/s can be used. A novel white sulfur dye composition which cannot be obtained by a conventional reduction reaction of an organic or inorganic reducing agent.

Accordingly, the present invention provides a novel white sulfur dye composition having a current density between 50 mA/cm 2 and 500 mA/cm 2 (between 50 mA/cm 2 and 150 mA) Preferably, the flow rate is in the range of 0.1 m/sec to 2 m/sec (preferably in the range of 0.1 m/sec to 0.4 m/sec).

The method of making the white sulfur dye composition of the present invention is novel and forms part of the subject matter of the present invention. To prevent hydrogen from escaping at these high current densities, the initial concentration is 80 g/l in the presence of a relatively high dye concentration, the initial current density is 0.5 mA/cm 2 and the concentration is continuously increased to 500 g/l and current density. The electrochemical reduction reaction was carried out to 500 mA/cm 2 . The process of the invention increases the dye concentration to 500 grams per liter.

The white sulfur dye composition of the present invention is prepared in an alkaline medium (preferably having a pH of > 9.5). Preferably, an alkaline solution of an alkali metal salt (particularly sodium hydroxide, potassium hydroxide or sodium carbonate) is used as the electrolyte for conduction. In a particularly preferred case, a dilute aqueous solution of sodium hydroxide is used. The concentration of the added conductive salt is between 0.1 moles/liter and 5 moles/liter, preferably between 0.1 moles/liter and 1.5 moles/liter.

Alternatively, by adding a catalytic amount of a Bunte salt of the formula: R-S-SO ₃ Na

Wherein R represents an organic repetitive structural unit, such as a phenothiazine, a thione, a thiazide or a phenoxazinone structure, or by catalytic addition of a chemical reducing agent such as sodium dithionite or an organic sulfinic acid and/or Organic sugar prevents hydrogen from escaping. The amount can be as high as 5% by weight based on the initial amount of the sulfur dye to be used. Similarly, a Bunte salt or reducing agent was added, initially at 80 g/l and the initial current density was 0.5 mA/cm 2 and the concentration was continuously increased to 500 g/l.

Basically, all of the divided flow channels are suitable for producing the white sulfur dye compositions of the present invention. The cathode used may be not only a large-scale plate electrode but also a three-dimensional cathode.

The white sulfur dye composition of the present invention is preferably produced at 20 to 135 ° C, more preferably at 20 to 95 ° C.

If necessary, the reduction reaction can be carried out in the presence of a commercially available wetting agent such as a wood sulfonate.

The method of the invention is preferably used to reduce C.I. Leuco Sulfure Black or C.I. Vat Blue43. Basically, mixtures of different sulfur dyes can also be reduced by the process of the invention.

The reduction equivalent concentration of the reduction reaction of C.I. Leuco Sulfur Black 1 of the present invention is preferably between 150 Ah/kg and 534 Ah/kg, based on 1 kg of anhydrous solid dye.

The reduction equivalent concentration of the reduction reaction of C.I.Vat Blue43 of the present invention is between 75 Ah/kg and 225 amp/kg, based on 1 kg of anhydrous solid dye.

The composition of the various white sulfur dye mixtures is determined using HPLC techniques and materials as described in the document DE 10 120 821.

Table 1 lists the HPLC profiles of sulfur-reduced CISulfur Black 1 and samples 1 to 3 (chemically reduced at different current densities, sample 1 is reduced by the method of the invention, sample 2 is as DE 9060883 The results of the comparison, as described in the sample 3, as described in EP10122210).

Surprisingly, the use of high current densities >50 mA/cm 2 and high flow rates (which allows the dye to be transported to the electrodes in the most suitable manner) makes the species distribution of CISulfur Black 1 narrow and thus makes the molecular distribution narrower. .

Table 2 lists the HPLC profiles of sulfide-reduced CIVat Blue 43 and Examples 6 to 8 (chemically reduced at different current densities, sample 6 is reduced by the method of the invention, sample 7 is as in EP10122210 The result of the comparison).

The white sulfur dye solution of the present invention can be applied not only to the fiber by a conventional dyeing method (which utilizes a large excess of sodium hydrosulfide (NaHS)), but also to an optimum dyeing method under protective gas conditions or can be used. Electrochemical application as described in Offenlegungsschrift DE 10234825 A1. This reducing condition is only used to counteract the oxygen in the environment that is introduced into the dye liquor. This makes it possible to obtain wastewater with low salt, COD and TOC. Accordingly, the use of the white sulfur dye compositions of the present invention provides substantial ecological and economic advantages.

Alternatively, the electrochemical reduction reaction to produce the dye composition of the present invention can also be produced directly in a dyebath.

Electrolysis (eg, in a cell separated by a cation exchange membrane and containing a stainless steel cathode and a stainless steel mixed oxide coated titanium electrode as an anode) in the presence of a conducting electrolyte at a current density of 50 mA/cm 2 Up to 500 mA / cm ^ 2 (preferably between 50 mA / cm ^ 2 and 150 mA / cm ^ 2 ) and flow rate in the range of 0.1 m / s to 2 m / s (to 0.1 The dye bath is circulated through the cathode space by the material to be dyed and is percolated through the cathode space so that the dye bath is continuously regenerated by exchange with the catholyte under the conditions of preferably in the range of 0.4 m/sec. The catholyte contains a sulfur dye to be reduced (for example, CISulfur Black or CIVat Blue43), a wetting agent present when appropriate, and an electrolyte for conduction (in the case of an alkali metal salt (especially sodium hydroxide, potassium hydroxide or carbonic acid) An alkaline solution of sodium) is preferred, a dilute aqueous solution of sodium hydroxide is preferred, and a salt for conduction. The concentration of the conductive salt added is between 0.1 moles/liter and 5 moles/liter, preferably between 0.1 moles/liter and 1.5 moles/liter.

The fiber material ready to be used for dyeing is placed in a dye bath.

The dyeing process consists of the following stages: reduction and heating stages The dyeing and cooling stages are dyed, washed and dried by oxidation of the sulfur dye.

The coloring evaluation of the dye obtained by the white sulfur dye of the present invention shows that the ratio of the waste having no affinity for the fiber is remarkably lower than that of the white sulfur dye which is generally obtained by using a chemical reducing agent. This allows the electrochemically produced white sulfur dye composition to have a more pure hue and a shift in color tone. It was observed that C.I. Sulfur Black 1 made the hue significantly bluer, redder and purer. Similarly, these reactions were also observed in the electrochemical reduction reaction of C.I.Vat Blue43.

According to DIN 6174 and DIN 5033, the dyeing was evaluated by coloring as determined by color trajectory.

The L value as shown in the following Table 3, in the electrochemical reduction reaction for increasing the current density in the method according to the invention, achieves the same color intensity with a smaller amount of dye.

The color depth and hue can be described by the color trajectory measurement using dye (10% sulfide staining) by the relationship between the dye concentration and current density used. Taking C.I.Vat Blue 43 as an example, the hue is significantly shifted depending on the current density used (redder at higher current density), which is shown in Table 4.

In addition to the hue characteristics, the sulfur dye of the present invention has a dye paste amount of up to 10% lower than that of the white sulfur dye solution obtained by chemical means, and therefore, the amount of the raw material is as low as at most 10%.

The electrochemically reduced white quinone imine sulfur dye composition of the present invention can be stabilized by being separated as a solid material. Accordingly, the present invention also provides a reduced form of the reduced sulfhydryl imine dye of the present invention by reducing the pH to <9 and/or drying the electrochemically reduced white quinone imine sulfur dye solution. The method. The separation in the form of a solid material in the present invention includes lowering the pH to <9, which can be carried out by adding an organic acid, a mineral acid and carbon dioxide to the reduced solution. Further, the reduced sulfur dye solution can be adjusted to pH <9 by adding water, thereby precipitating the dye. The product of the invention is then obtained by filtration and subsequent drying. The resulting filtrate can be oxidized and thus significantly reduces the amount of COD. The residual sulfur content of the anhydrous sulfur dye thus obtained is <10% by weight, based on the total amount.

A second way of separating the solid white quinone imide dye involves completely drying the reduced solution. Drying can be carried out using conventional drying systems and equipment (e.g., evaporators), for example, by spray drying or film drying, the dried product can be further comminuted to the desired particle size to convert the anhydrous reduced alkali soluble product into Such as pellets, powder or tablet form. Mixtures with appropriate adjuvants can also be obtained by mixing. Lyophilization is another way.

The reducing equivalent concentration of the anhydrous white sulfur dye obtained by this method is, for example, CILeuco Sulfur Black 1 between 150 Ah/kg and 534 Ah/kg, and CIVat Blue 43 as an example, between 75 Ah/kg and Between 225 Ah/kg, this is based on 1 kg of anhydrous solid dye. The white sulfur dye is considered to be an anhydrous product at a water content of < 5% by weight (preferably <2% by weight), based on the total product.

The process proposes a very simple way of obtaining the white sulfur dye of the invention, which is stabilized in a very high concentration (not added with other sulfides and other adjuvants) and consists essentially of a sulfide-free white sulfur dye. A substance that, when precipitated at a relatively low pH, is salt-free and has no fiber affinity. The content is still <1% by weight and preferably <0.5% by weight, based on the entire product. The resulting dye has significant stability to the oxidation of the environment.

The concentration of the white sulfur dye solution used to separate the product of the present invention may range from 20 to 600 grams per liter. The product of the present invention, once dissolved in water and suitably blended with a base, can be used to dye fibrous materials or leather. The anhydrous white sulfur dye composition of the present invention can be applied to the fiber after dissolution, not only by conventional dyeing (operating with an excess of chemical reducing agent), but also by using an optimized dyeing formulation under protective gas. It can be applied electrochemically (this is described in Offenlengungsschrift DE 10234825 A1). This reducing condition is only used to counteract the oxygen in the environment that is introduced into the dye liquor. Therefore, the use of the white sulfur dye composition of the present invention has substantially ecological and economic advantages. The colour properties of the product correspond to the properties of the samples described in the application DE 102004040601.4.

The invention is illustrated by the following examples.

Preparation Example 1 (Sample 1)

An aqueous suspension of the C.I. Sulfur Black 1 press cake produced in this case was electrolyzed using a flow cell separated by a cation exchange membrane (Nafion 424). A small amount of dye is used at the beginning and gradually increases during the electrolysis period. At the beginning of the reaction, 156.9 g of CISulfur Black 1 regarded as anhydrous was used in 2 liters of water containing 8 ml of 50% aqueous sodium hydroxide solution and 4 ml of Primasol NF wetting agent, and the amount was gradually increased to 2271 g. The anhydrous CISulfur Black 1 is in a total volume of 5.815 liters. The anionic electrolyte used was an aqueous solution of sodium hydroxide (1 mol/l). This electrolytic reaction was carried out for 3510 minutes using a current density of 100 mA/cm 2 and a flow rate of 0.2 m/sec. After the electrolysis reaction, the amount of reducing equivalent which can be determined is 4.2, which corresponds to a charge amount of 378 Ah/kg of dye. The solution thus obtained can be used for dyeing without additional addition or addition of a very small amount of reducing agent.

The HPLC chromatogram of the reaction product is shown in Figure 1.

Preparation Example 2 (Sample 2)

The C.I. Sulfur Black 1 suspension was electrolyzed at a current density of 20 mA/cm 2 using a flow cell separated by a cation exchange membrane (Nafion 424) as described in DE 1906083.

The HPLC chromatogram of the reaction product is shown in Figure 2.

Preparation Example 3 (Sample 3)

The C.I. Sulfur Black 1 suspension was electrolyzed at a current density of 0.48 mA/cm 2 using a flow cell separated by a cation exchange membrane (Nafion 424) as described in DE 10122210.

The HPLC chromatogram of the reaction product is shown in Figure 3.

Preparation Example 4 (Sample 4)

An aqueous suspension of the C.I. Sulfur Black 1 press cake produced in this case was electrolyzed using a flow cell separated by a cation exchange membrane (Nafion 424). At the beginning of the reaction, 337 g of CISulfur Black 1 regarded as anhydrous was used in 4 liters of water containing 16 ml of 50% aqueous sodium hydroxide, and gradually increased to 1740 g over a period of 1320 minutes. The CISulfur Black 1 is contained in a total volume of 6.8 liters, and 126 grams to 253 grams of CISulfur Black 1 is considered to be anhydrous. Electrolysis was started at a current density of 0.83 mA/cm 2 using a flow rate of 0.2 m/sec and continued up to 100 mA/cm 2 , which increased the concentration of the white dye. After the electrolysis reaction, the amount of reducing equivalent which can be determined is 5.67, which corresponds to a charge amount of 504 Ah/kg of dye. The composition of the solution thus obtained was the same as that of the dye solution prepared in Preparation Example 1.

The HPLC chromatogram of the reaction product is shown in Figure 1.

This reaction product can be isolated as a solid material in the following manner: Method 1: The dye solution is heated at 130 ° C and maintained at 130 ° C for 12 hours until a dry residue is obtained. 34 grams of anhydrous black product was isolated which was readily and completely soluble in water and was used for dyeing.

Method 2: 100 g of a white dye solution was blended with carbon dioxide at 60 ° C until pH < 9 and the dye was completely precipitated. The precipitated dye was filtered off under an argon atmosphere and dried at 80 ° C under reduced pressure. 22 grams of anhydrous black product was isolated which was readily and completely soluble in dilute aqueous sodium hydroxide solution and was used for dyeing.

Preparation Example 5 (Sample 6)

An aqueous suspension of the CIVat Blue 43 press cake produced in this case was electrolyzed using a flow cell separated by a cation exchange membrane (Nafion 424). At the beginning of the reaction, 50.0 g of CIVat Blue 43 regarded as anhydrous was used in an inclusion of 8 ml 50 Aqueous sodium hydroxide solution and 4 ml of Primasol NF wetting agent in 3 liters of water. Increasing the amount to 400 g was considered anhydrous and C.I.Vat Blue 43 was in a total volume of 4.6 liters. The anionic electrolyte used was an aqueous solution of sodium hydroxide (1 mol/L). This electrolytic reaction was carried out for 650 minutes using a current density of 100 mA/cm 2 and a flow rate of 0.2 m/sec. After the electrolysis reaction, the amount of reducing equivalent which can be determined is 3, which corresponds to a charge amount of 221.5 Ah/kg of dye. The solution thus obtained can be used for dyeing without additional addition or addition of a very small amount of reducing agent.

The HPLC chromatogram of the reaction product is shown in Figure 6.

Method of separation as a solid material: 100 g of the dye solution was blended with carbon dioxide at 60 ° C until pH < 9 and the dye was completely precipitated. The precipitated dye was filtered off under an argon atmosphere and dried at 80 ° C under reduced pressure. 15 g of anhydrous dark blue product was isolated which was easily and completely dissolved in a dilute aqueous solution of sodium hydroxide and was used for dyeing.

Preparation Example 6 (Sample 7)

The C.I.Vat Blue 43 suspension was electrolyzed at a current density of 10 mA/cm 2 using a flow cell separated by a cation exchange membrane (Nafion 424) as described in EP 101222104.

The HPLC chromatogram of the reaction product is shown in Figure 7.

Preparation Example 7

A solution of 100 g of Leuco Sulfur Black 1 (prepared according to Preparation 4 of the application of DE 102004040601.4) having a dye concentration of 330 g/l was heated to 130 ° C and maintained at 130 ° C for 12 hours until a dry residue was obtained. 34 grams of anhydrous black product was isolated which was readily and completely soluble in water and was used for dyeing.

Preparation Example 8

A solution of 100 g of Leuco Sulfur Black 1 having a dye concentration of 330 g/l (prepared according to Preparation 4 of the application of DE 102004040601.4) was blended with carbon dioxide at 60 ° C until pH < 9 and the dye was completely precipitated. The precipitated dye was filtered off under an argon atmosphere and dried at 80 ° C under reduced pressure. 22 grams of anhydrous black product was isolated which was readily and completely soluble in dilute aqueous sodium hydroxide solution and was used for dyeing.

Preparation Example 9

A solution of 100 g of C.I.Vat Blue 43 having a dye concentration of 250 g/l (prepared according to Preparation 5 of the application of DE 102004040601.4) was blended with carbon dioxide at 60 ° C until pH < 9 and the dye was completely precipitated. The precipitated dye was filtered off under an argon atmosphere and dried at 80 ° C under reduced pressure. 15 g of anhydrous dark blue product was isolated which was easily and completely dissolved in a dilute aqueous solution of sodium hydroxide and was used for dyeing.

dyeing

Dyeing solution by conventional exhaust dyeing method containing 16% CISulfur Black 1 or 10% CIVat Blue 43 white dye solution (prepared according to Preparation Examples 1-5), 2 g / liter anionic wetting agent, 2 ml / liter 38 °Be caustic soda, 10 ml / liter of Sulfhydrate F150%, 5 ml / liter of Stabilisal S liq., 30 g / liter of sodium sulphate and about 50 ml of completely ionic water, so that the total liquid is 100 ml, which is in the process of dyeing In the method of bleaching cotton at a bath ratio of 10:1, an initial temperature of 50 ° C, heating to 95 ° C at 2 ° C / min for 45 minutes and then cooling to 60 ° C at 3 ° C / min, for example, forming a loop Knitted cotton fabric. After the treatment, the fabric was rinsed with completely ion-free cold water for about 5 minutes and then oxidized. Here, the dyed fabric was treated at a bath ratio of 10:1 with 1% hydrogen peroxide 35% and 2% acetic acid at pH 4.5 at 70 ° C for 15 minutes. Alternatively, the reaction to oxidize to a solid sulfur dye can be carried out by blowing air at 60 ° C for 2 hours.

The dyed fabric is then immersed in completely ion-free hot water for 3 to 5 minutes, then in completely ion-free cold water for up to 5 minutes, extruded and dried.

Electrochemical dyeing uses the following tanks for electrolytic reaction: the tank is separated by a cation exchange membrane and has a capacity of 25 ml. It has three sets of cylindrical stainless steel cathodes with a total surface area of 2 square meters, coated with stainless steel mixed oxide. The titanium electrode, 0.1 M NaOH as the catholyte and the following anolyte, the anolyte contains 540 g of CISulfur Black 1 (33% aqueous paste form), 52 ml of wetting agent, 210 ml of 50% sodium hydroxide An aqueous solution and a tank of 1.56 kg of NaCl were used for the electrolysis reaction, wherein the initial stage contained a battery current of 25 amps, a battery voltage of about 8 volts at 25 amps, and a current density of 125 milliamps per square centimeter. In this method, the dyebath is circulated through the material to be dyed (69 cotton yarns, mass 2700 g, pretreated for dyeing) at about 35 liters/kg, and is sucked through the cathode space as an effusion stream, so that the dyebath It is continuously exchanged with the catholyte for regeneration.

This dyeing procedure consists of several stages: 1. Reduction and heating stages: During this stage, the dye bath is brought to the desired dyeing temperature and simultaneously applied to the current density required for the dye reduction reaction.

2. Dyeing and cooling stages: The actual dyeing procedure was carried out at 80 °C.

3. Finish: Oxidation with hydrogen peroxide, rinsing and drying.

The dye obtained in this manner had an L value of 27.11, an s value of +0.66, and a b value of -1.95.

Figure 1: HPLC chromatogram of the reaction product of Preparation Example 1 (j = 100 mA/cm 2 ).

Figure 2: HPLC chart of the reaction product of Preparation Example 2 (j = 20 mA / cm ^ 2 ).

Figure 3: HPLC chart of the reaction product of Preparation Example 3 (j = 0.48 mA / cm ^ 2 ).

Figure 4: HPLC chromatogram of the reaction product of Preparation 4.

Figure 5: HPLC chromatogram of the reaction product of C.I. Sulfur Black 1 (sulfide reduced).

Figure 6: HPLC chart of the reaction product of Preparation Example 5 (j = 100 mA/cm 2 ).

Figure 7: HPLC chromatogram of the reaction product of Preparation Example 7 (j = 10 mA/cm 2 ).

Figure 8: HPLC chromatogram of the reaction product of C.I.Vat Blue 43 (sulfide reduced).

Claims (18)

A quinone imine white sulfur dye composition obtainable at a current density of greater than 50 mA/cm 2 to 500 mA/cm 2 and a flow rate in the range of 0.1 m/s to 2 m/sec. The imine white sulfur dye composition of claim 1, wherein the current density is greater than 50 mA/cm 2 to 150 mA/cm 2 and the flow rate is in the range of 0.1 m/s to 0.4 m/s. Under the conditions. A mixture of various imine white sulfur dye compositions as claimed in claim 1 of the patent application. A method for preparing a quinone imine white sulfur dye composition as claimed in claim 1 which comprises an initial concentration of 20 g/l and an initial current density of 0.5 mA/cm 2 and continuously increasing the concentration to 600 g/ Rise and current density to 500 mA / cm ^ 2 . The method of claim 4, further comprising adding a catalytic amount of a Bunte salt of the formula RS-SO ₃ Na, wherein R represents an organic repetitive structural unit such as a phenothiazine, a thione or a thioxanthene or a sub-structure of morphoxazinone, or by catalytic addition of a chemical reducing agent such as sodium dithionite or organic sulfinic acid and/or organic sugar. The method of claim 4, wherein the large dish or three-dimensional electrode is used for the divided electrolytic cell. The method of claim 4, wherein the alkaline solution of the alkali metal salt is used as the electrolyte for conduction. For example, the method of claim 4, wherein the electrolysis is carried out at 20 It is carried out in a temperature range of 135 °C. The method of claim 4, wherein the electrolysis is carried out at a temperature ranging from 20 to 95 °C. For example, the imine white sulfur dye composition of claim 1 of the patent range, wherein when CISulfur Black 1 is used as the dye raw material, the reducing equivalent concentration is between 150 Ah/kg and 534 Ah/kg, and 1 kg of dry solid sulfur Dye meter. A method for producing a solid form of reduced quinone imine white sulfur dye composition as claimed in claim 1 which is electrochemically reduced by reducing the pH to ≦9 and/or drying A sulfur dye solution is used. The imine white sulfur dye composition of claim 1, wherein when CIVat Blue 43 is used as the dye raw material, the reducing equivalent concentration is between 75 Ah/kg and 225 Ah/kg, and 1 kg of dry solid dye is used. meter. A dye preparation comprising the quinone imine white sulfur dye composition of claim 1 of the patent application. A solid dye preparation comprising the quinone imine white sulfur dye composition of claim 1 which has a water content (based on the entire product) of 5% by weight. A solid dye preparation as claimed in claim 14 has a water content (based on the entire product) of 2% by weight. A method of dyeing and printing a fibrous material comprising the use of the quinone imine white sulfur dye composition of claim 1 of the patent application. A method of dyeing a fibrous material comprising performing an electrochemical reduction reaction to obtain a quinone imine white sulfur dye composition of claim 1 in a dye bath directly. An application of a quinone imine white sulfur dye composition as claimed in claim 1 for dyeing and printing of fibrous materials.