Dyeing method for cellulose fiber products

Abstract

Provided is a novel dyeing method that uses alkali washing under specific temperature and pH conditions, thereby making it possible to obtain a cellulosic fiber product that is dyed with a reactive dye, that has high color-fastness, that is not subject to hydrolysis during alkali treatment, and that enables a reduction of CO2 emissions. The present invention is a dyeing method for cellulosic fibers or for a fiber product that includes cellulosic fibers, the method being a batch-type or continuous-type dyeing method and including: a dyeing reaction step in which cellulosic fibers or a fiber product that includes cellulosic fibers is made to react with a reactive dye in a dyeing solution; an alkali washing step in which, after all or part of the dyeing solution has been discharged, the dyed fibers or the dyed fiber product is washed with an alkali washing solution with a pH of 10–14 and a temperature of 15–70°C; and an alkali post-washing step in which, after the alkali washing solution has been discharged, washing is performed with water.

Description

Technical Field

[0001] The present invention relates to a method for dyeing cellulose fibers or fiber products containing cellulose fibers using reactive dyes. More specifically, the present invention relates to a dyeing method using reactive dyes for cellulose fibers or fiber products containing cellulose fibers, which includes a specific washing step after the dyeing reaction step.

Background Art

[0002] In the industrial dyeing of cellulose fibers or fiber products containing cellulose fibers, when using reactive dyes, inorganic salts and an alkali agent are added as dyeing aids together with the reactive dye into the dyeing bath, and the dyeing with the reactive dye is carried out. The presence of inorganic salts is necessary to promote the absorption of the dye into the interior of the cellulose fibers, while the alkali agent is necessary to immobilize the reactive dye on the cellulose fibers. It is generally known that the addition of inorganic salts and the alkali agent to the dyeing bath is an important factor for obtaining a uniform dyed product. In such dyeing using reactive dyes, after the completion of the dyeing reaction, unreacted dyes, inorganic salts and alkali agents which are dyeing aids must be washed. The reasons are as follows: · If unreacted dyes remain, there is a risk of color fading and dye contamination of other fabrics, that is, poor dyeing fastness occurs. · Since inorganic salts play a role in exhausting the dye, the dye itself cannot be removed while the salt concentration remains high. · Since alkali is irritating to the skin, it is necessary to lower the pH of the fabric using an acid or the like and neutralize it.

[0003] Therefore, conventionally, in the washing in the dyeing method using reactive dyes, there has been a problem that many washings have to be carried out in order not to leave these chemicals on the dyed fabric. In conventional water washing, in order to discharge the dye well, washing at a high temperature (generally around 90°C, at least 75°C or higher) has been carried out. Under such circumstances, when heating a large amount of washing water to a high temperature, it is common to use steam boiled by a boiler or the like, which consumes a lot of energy. Moreover, it is necessary to spend time raising the temperature, and a lot of electricity is consumed during operation, resulting in a large amount of CO2 emissions.

[0004] In Patent Document 1 below, in a washing method using an alkaline soaping bath for a colored fiber material with a reactive dye having a sulfatoethylsulfonyl group, it is proposed to wash with a washing liquid at a temperature of 75 to 95°C, pH 9 to 10 for batch washing, and pH 9 to 12 for continuous washing. Also, in Patent Document 2 below, in the dyeing of cotton and cotton blended fabrics using reactive dyes, it is described to wash with a washing liquid added with an alkaline liquid of 45 wt% KOH: 10 to 74 wt%, 50°Bé sodium silicate: 10 to 60 wt% at 0.25 to 1 g / L at 200°F (93.3°C). In this case, the pH of the washing liquid is estimated to be around 11. Also, in Patent Document 3 below, a soaping agent suitable for washing at 70 to 75°C that can obtain an effect equivalent to soaping performed at 90°C is proposed, and as a treatment method, to wash with a washing liquid containing a soaping agent containing a water-soluble salt of a polymerized fatty acid at 70 to 75°C and having a pH of less than 10 to 12. Furthermore, in Patent Document 4 below, as a treatment method for dyed articles of disperse dyes and reactive dyes that are easily decomposed by alkali treatment, preferably nucleophilic substitution type reactive dyes, a method of treating at pH 8 or higher, preferably pH 10.0 to 13.5, temperature 50 to 85°C, preferably 60 to 80°C is proposed.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Non-Patent Document

[0006]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] In view of the above-described state of the art, the problem to be solved by the present invention is, in particular, in the washing after dyeing in a method for dyeing cellulose fibers and products thereof using a nucleophilic addition type reactive dye, while lowering the temperature of the washing liquid and increasing the pH, to obtain a cellulose fiber product dyed with a reactive dye that has a high dyeing fastness and no hydrolysis due to alkali treatment while reducing the CO2 emissions. The problem is to provide a novel dyeing method for cellulose fiber fabrics. In order to solve such problems, the inventors of the present application considered lowering the temperature of the washing water used for washing after dyeing cellulose fibers and products thereof using a reactive dye as follows.

[0008] As described above, in a dyeing processing machine, washing at a high temperature (generally around 90°C, at least 75°C) increases the CO2 emissions because of the energy and operation time required for heating up. On the other hand, if the temperature is lowered for washing, sufficient washing cannot be performed, leading to poor color fastness (fastness). Also, as described above, there is a technique in which the use of an alkali for washing can enhance the dyeing fastness. However, while an alkali has an effect of enhancing the washing effect of the dye, it is known that the alkali further reacts with the already reacted dye to cause desorption of the bond, resulting in poor fastness, or hydrolyzes the dye itself, causing discoloration and fading. In Patent Document 1, washing is carried out at a high temperature (75 to 95°C) at approximately pH 9 to 10 (dip dyeing) and pH 9 to 12 (continuous dyeing). However, the resulting effect is not high, and there is a risk of discoloration due to hydrolysis and poor fastness even in such a relatively low pH range. Furthermore, such treatment at a relatively high temperature not only has a risk of hydrolysis but also the CO2 emission amount is the same as that of the prior art. Also, in Patent Document 2, washing is carried out at about 93°C and pH of about 11. In this case, the risk of discoloration becomes higher, and the CO2 emission amount is the same as that of the prior art. Also, in Patent Document 3, although it is stated in the claims to be 75°C or lower, regarding the problem to be solved by the invention, it is described that "it is desired" to set it to a "low temperature of 70 to 75°C", and a lower temperature than that is not assumed. In the case of washing at 70 to 75°C and pH 10 to 12, the resulting effect is not high, and there is a risk of discoloration due to hydrolysis and poor fastness even in such a relatively low pH range. Also, in Patent Document 4, although it is stated in the claims to be 50 to 80°C, in all of the examples, washing is carried out at 80 to 85°C. In the case of washing at 80 to 85°C and a pH above 8, the resulting effect is not high, and there is a risk of discoloration due to hydrolysis and poor fastness even in such a relatively low pH range, and the CO2 emission amount is not significantly improved compared to that of the prior art.

[0009] On the other hand, as types of reactive groups in reactive dye species, there are "nucleophilic addition type" and "nucleophilic substitution type". In the case of the "nucleophilic addition type", it has been found that the risk of hydrolysis is particularly increased.

Means for Solving the Problems

[0010] As a result of intensive studies and repeated experiments to solve the above problems, the present inventors have unexpectedly found that in the washing after dyeing in a method for dyeing cellulose fibers and their products using a nucleophilic addition type reactive dye, by increasing the pH while lowering the temperature of the washing liquid, it is possible to reduce the CO2 emission amount, avoid hydrolysis of the dye due to alkali treatment, and obtain a uniform dyed product with high dyeing fastness and no color unevenness, thus completing the present invention.

[0011] That is, the present invention is as follows. [1] The following steps: A batch or continuous dyeing method comprising the following steps: A dyeing reaction step of reacting a cellulose fiber or a fiber product containing a cellulose fiber with a reactive dye in a dyeing solution; After discharging all or part of the dyeing solution, an alkali washing step of washing the dyed fiber or fiber product with an alkali washing solution having a pH of 10 to 14 and a temperature of 15 to 70 ° C; and An alkali post-washing step of washing with water after discharging the alkali washing solution; A method for dyeing a cellulose fiber or a fiber product containing a cellulose fiber, comprising the above steps. [2] The dyeing method according to [1], wherein in the alkali post-washing step, an acid is added to the water and neutralized with an acid-containing acid washing solution. [3] The dyeing method according to [1] or [2], having an alkali pre-washing step of washing with an aqueous solution between the dyeing reaction step and the alkali washing step. [4] The dyeing method according to any one of [1] to [3], wherein the dyeing method is a batch dyeing method, and the alkali washing solution has a pH of 10 to 13 and a temperature of 15 ° C to 70 ° C or lower. [5] The dyeing method according to any one of [1] to [3], wherein the dyeing method is a continuous dyeing method, and the alkali washing solution has a pH of 12 to 14 and a temperature of 15 ° C to 60 ° C. [6] The following formula (1): -0.07x + 13 ≤ y < -0.07x + 17 {Wherein x is a value of a temperature of 15 to 70 ° C, and y is a value of a pH of 10 to 14.} The dyeing method according to any one of [1] to [5], which satisfies the relationship. [7] The dyeing method according to any one of [1] to [6], wherein the dyeing solution is maintained at a temperature of 5 ° C or higher and 70 ° C or lower throughout the alkali washing step. [8] The dyeing method according to any one of [1] to [7], wherein the reactive dye contains a nucleophilic addition type reactive dye. [9] In the alkali pre-washing step, the dyeing method according to any one of [3] to [8], wherein washing is performed with water having a bath ratio of 1:100 or less and a temperature of 5 to 70°C.

[10] In the alkali washing step, the dyeing method according to any one of [1] to [9], wherein washing is performed with an alkali washing solution having a bath ratio of 1:100 or less and a temperature of 15 to 70°C.

[11] In the post-alkali washing step, the dyeing method according to any one of [1] to

[10] , wherein washing is performed with water having a bath ratio of 1:100 or less and a temperature of 5 to 70°C. [Advantages of the Invention]

[0012] According to the dyeing method of the present invention, particularly in the washing after dyeing in the dyeing method of cellulose fibers and their products using nucleophilic addition type reactive dyes, by increasing the pH while lowering the temperature of the washing solution, it is possible to reduce the CO2 emission amount, obtain a cellulose fiber product dyed with a reactive dye having high dyeing fastness and no hydrolysis due to alkali treatment. [Brief Description of the Drawings]

[0013]

Figure 1

Figure 2

[0014] Hereinafter, embodiments of the present invention will be described in detail. One embodiment of the present invention is The following steps: A batch type or continuous type dyeing method, comprising the following steps: A dyeing reaction step of reacting a cellulose fiber or a fiber product containing a cellulose fiber with a reactive dye in a dyeing solution; After discharging all or part of the dyeing solution, an alkali washing step of washing the dyed fiber or fiber product with an alkali washing solution having a pH of 10 to 14 and a temperature of 15 to 70°C; and After discharging the alkali washing solution, an alkali post-washing step of washing with water; A method for dyeing a cellulose fiber or a fiber product containing a cellulose fiber, which comprises the above steps.

[0015] There are no particular restrictions on the form of the cellulose fiber or the fiber product containing the cellulose fiber dyed by the dyeing method of the present embodiment, and examples include various forms such as yarns, woven fabrics, weft knitted fabrics, non-woven fabrics, and sewn products. There are also no particular restrictions on the cellulose fiber, and examples include cotton, hemp, rayon, cupra ammonium rayon, lyocell, cellulose fiber by organic solvent method, cellulose fiber by ionic liquid method, etc., but preferably cotton, rayon, cupra ammonium rayon, lyocell, cellulose fiber by organic solvent method, and more preferably cotton, rayon, cupra ammonium rayon. For the fibers other than the cellulose fiber in the fiber product containing the cellulose fiber dyed by the dyeing method of the present embodiment, they can be dyed in combination with known dyeing methods.

[0016] The dyeing method of the present embodiment is not particularly limited, and it may be printing or plain dyeing, but preferably plain dyeing. Examples of the dye reaction process in the dyeing method of the present embodiment include pad steaming method, pad batch method, dipping method, etc., but it is not particularly limited to these.

[0017] As the equipment used in each washing step of the dyeing method of the present embodiment, it may be a batch type or a continuous type, and there are no particular restrictions. As the batch type, preferably, cheese dyeing machine, skein dyeing machine, jet dyeing machine, air flow dyeing machine, beam dyeing machine, jigger dyeing machine, winch dyeing machine, rotary dyeing machine, paddle dyeing machine, mini-color dyeing machine, and more preferably a jet dyeing machine (see Figure 1). As the continuous type, preferably, open soaper type continuous water washing machine, continuous winch dyeing machine, and more preferably an open soaper type continuous water washing machine (see Figure 2).

[0018] The reactive dyes used in the dyeing method of this embodiment are preferably, for example, reactive dyes having a nucleophilic addition type reactive group, or bifunctional or polyfunctional reactive dyes having both a nucleophilic addition type and a nucleophilic substitution type reactive group. Examples of the nucleophilic addition type reactive group include reactive groups such as saturated alkane monocarboxylic acid amide type, saturated alkane dicarboxylic acid amide type, saturated alkane monocarboxylic acid type, cycloalkane carboxamide type, alkene monocarboxamide type, alkene dicarboxamide type, saturated aliphatic ketone type, saturated aliphatic sulfonic acid amide type, vinylsulfonamide type, β-saturated ethylsulfone type, vinylsulfone type, and sulfatoethylsulfonic acid type. Among them, vinylsulfone type and sulfatoethylsulfonic acid type reactive groups are preferred. Examples of the nucleophilic substitution type reactive group include reactive groups such as pyridine type, pyridazine type, pyridazone type, pyrimidine type, S-triazine type, 1,2,4-triazine type, thiazole type, benzoxazole type, benzothiazole type, quinoline type, isoquinoline type, quinoxaline type, quinazoline type, and phthalazine type. Among them, 1,2,4-triazine type is preferred.

[0019] Examples of the inorganic salts used in the dyeing reaction method include sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, or mixtures thereof, but are not particularly limited thereto. Examples of the alkali agent include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate, tripotassium phosphate, or mixtures thereof, but are not particularly limited thereto.

[0020] The dyeing method of this embodiment includes the above-described reactive dyeing step, an alkali washing step for removing residual dyes and the like after discharging the dyeing solution from the dyeing bath, and an alkali post-washing step for performing washing after discharging the alkali washing solution.

[0021] (Alkali washing step) Hereinafter, the alkali washing step will be described in detail. The dyeing method of the present embodiment is a batch-type or continuous-type dyeing method, and includes the following steps: A dyeing reaction step of reacting a cellulose fiber or a fiber product containing a cellulose fiber with a reactive dye in a dyeing solution; An alkali washing step of washing the dyed fiber or fiber product with an alkali washing solution having a pH of 10 to 14 and a temperature of 15 to 70°C after discharging all or part of the dyeing solution; and An alkali post-washing step of washing with water after discharging the alkali washing solution; It is a dyeing method for a cellulose fiber or a fiber product containing a cellulose fiber, including the above steps. In the alkali washing step, while reducing the temperature of the washing solution and increasing the pH, it is possible to obtain a cellulose fiber product dyed with a reactive dye that has a high dyeing fastness and no hydrolysis due to alkali treatment while reducing the CO2 emission amount. From the viewpoint of reducing the amount of alkali used and not imposing a burden on wastewater, a single treatment is preferable, but it may include multiple washing treatments.

[0022] The alkali washing solution is an aqueous solution having a pH of 10 to 14 and a temperature of 15 to 70°C containing one or more alkalis, and can be selected from the viewpoints of the ease of hydrolysis of the dye used, the washing treatment time, and the required wet fastness. From the viewpoint of CO2 emission amount, and since the risk of hydrolysis increases as the temperature is higher, its pH is preferably 15 to 60°C, more preferably 15 to 50°C. Also, since it is easier to control and the detergency is higher when the pH range is higher when adding an alkali, its pH is preferably 10.5 to 14, more preferably 11 to 14.

[0023] When the alkali washing solution is treated in a batch type, since the treatment time is long and the risk of hydrolysis increases, it is preferably an aqueous solution having a pH of 10 to 13 and a temperature of 15 to 70°C. When treated in a continuous type, although the treatment time is short and the risk of insufficient washing increases, when the temperature is high, steam containing an alkali is generated, which poses a risk to workability. Therefore, it is preferably a pH of 12 to 14 and a temperature of 15 to 60°C.

[0024] Furthermore, in order to eliminate the influence of hydrolysis by the alkaline cleaning solution at a high temperature and to eliminate insufficient cleaning by the alkaline cleaning solution at a low temperature, the alkaline cleaning solution preferably satisfies the following formula (1): -0.07x + 13 ≤ y < -0.07x + 17 {In the formula, x is a value of temperature from 15 to 70 °C, and y is a value of pH from 10 to 14.} It is an aqueous solution that satisfies the relationship.

[0025] The alkaline cleaning solution may contain components such as a dispersant, a wetting agent, an in-bath softener, an in-bath smoothing agent, an emulsifier, and a soaping agent as desired. The alkali contained in the alkaline cleaning solution is not particularly limited, and examples include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate, tripotassium phosphate, or a mixture thereof. Preferably, they are sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and more preferably sodium carbonate and sodium hydroxide.

[0026] (Alkaline post-washing step) Hereinafter, the alkaline post-washing method will be described in detail. The dyeing method of the present embodiment includes an alkaline post-washing step of adding an alkaline post-washing solution and washing after discharging all or part of the alkaline cleaning solution. The alkaline post-washing step is a step of treating with water, which is the alkaline post-washing solution, to wash the alkali used in the alkaline cleaning solution. It may be a single treatment, but since the remaining alkali may cause serious claims such as skin damage or inhibit the functional processing in the subsequent finishing step, it is preferably included in multiple washing treatments.

[0027] From the viewpoint of suppressing the CO2 emission amount by setting the water, which is the alkaline post-washing solution, to a low temperature, the temperature is preferably 5 °C to 70 °C, more preferably 5 °C to 50 °C. However, since the low temperature is easily affected by the ambient temperature, it is even more preferably 15 °C to 50 °C.

[0028] In the water which is the post-alkali cleaning liquid, an acid may be added in order to eliminate the residual alkali. There is no restriction on the acid to be used, and any of citric acid, malic acid, acetic acid, formic acid, sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, etc. may be used, but preferably those with less corrosiveness to metals, and more preferably formic acid, acetic acid, citric acid, or malic acid. Further, the water which is the post-alkali cleaning liquid may contain components such as a dispersant, a wetting agent, an in-bath softener, an in-bath smoothing agent, an emulsifier, a soaping agent, etc. as desired.

[0029] (Pre-alkali cleaning step) Between the dyeing reaction step and the alkali cleaning step, a pre-alkali cleaning step of washing with an aqueous solution can be provided. Adding the pre-alkali cleaning step can exclude high-concentration salts having a dye exhaustion effect, and is desirable from the viewpoint of enhancing the cleaning effect of the alkali cleaning step.

[0030] The water which is the pre-alkali cleaning liquid is not particularly restricted, and may contain components such as a dispersant, a wetting agent, an in-bath softener, an in-bath smoothing agent, an emulsifier, a soaping agent, etc. as desired, but it is preferably water from the viewpoint of excluding salts.

[0031] From the viewpoint of suppressing the CO2 emission amount by lowering the temperature of the water which is the pre-alkali cleaning liquid, the temperature is preferably 5°C to 70°C, more preferably 5°C to 50°C, but since a low temperature is easily affected by the air temperature and stable dyeing is difficult to perform, it is even more preferably 15°C to 50°C.

[0032] The bath ratios of the alkali cleaning step, the post-alkali cleaning step, and the pre-alkali cleaning step depend on the machine for cleaning. When the processing amount is large in a continuous cleaning machine, the bath ratio becomes higher than 1:1. When the bath ratio becomes high, the CO2 emission amount required for heating the cleaning liquid increases, so preferably it is 1:100 or less, and more preferably 1:30 or less.

Examples

[0033] Examples and comparative examples are given below to specifically illustrate the present invention, but the present invention is not limited to the examples. In addition, the calculation of the CO2 emission reduction amount and various evaluations of each yarn or fiber product were performed by the following methods.

[0034] (1) Calculation of CO2 emission amount Measure the power consumption and steam consumption required for the operation of the dyeing machine and use the following formula: W = E × α + S × β {In the formula, W: CO2 emission amount (kgCO2e), E: power consumption (MJ), S: steam consumption (MJ), α: CO2 unit of electricity (kg-CO2e / MJ), β: CO2 unit of steam (kg-CO2e / MJ).} The CO2 emission amount (kg-CO2e) was determined. Here, α and β are the CO2 units of electricity and steam (kg-CO2e / MJ) at a certain point in time, and are the values published by the Ministry of the Environment. The CO2 unit at a certain point in time is not particularly limited, but the CO2 unit described in Non-Patent Document 1 (Reference Material 2 Formulas for Calculating Greenhouse Gas Emission Amounts and List of Emission Coefficients (https: / / www.env.go.jp / earth / ondanka / suishin_g / 3rd_edition / ref2.pdf)) can be exemplified. For example, in the case of α which is the unit of electricity, it is 0.1542 (kg-CO2e / MJ), and in the case of β which is the unit of steam, it is 0.0600 (kg-CO2e / MJ). In the following examples, the CO2 emission amount (kg-CO2e) was determined using the unit of α = 0.1542 (kg-CO2e / MJ) and β = 0.0600 (kg-CO2e / MJ). Also, among the comparative examples of each dyeing method, material type, and amount of dye used, those using the conventional water washing method were regarded as "blank", and when the CO2 emission amount (kg-CO2e) decreased compared to the blank, it was determined as "improved", and when there was no change, it was evaluated as "equivalent".

[0035] (2) Color fading For the dyed textile products, color measurement was carried out using a spectrophotometer (manufactured by Gretagmacbeth, model Color-Eye7000A) under the conditions of a D56 light source and a viewing angle of 10 degrees, and the L* values in the CIE1976L*a*b* color space were obtained respectively. Also, among each dyeing method, material type, and comparative example of dye usage, those using the conventional water washing method were taken as "blank", and the following formula: ΔL* value = L* value of blank - L* value of the measured object was used to calculate the ΔL* value. When the ΔL* value is 0.5 or less, it can be judged that there is no color fading and it is good. Also, when the ΔL* value is more than 0.5 and 1.0 or less, it was judged as "slightly deteriorated", and when it is more than 1.0, it was judged as "deteriorated".

[0036] (3) Perspiration fastness A perspiration fastness test was conducted according to the test method for dyeing fastness to perspiration specified in JIS L 0848. Also, as the attached white cloth, a multi-fiber woven fabric woven in a vertical pattern using 8 types of fibers (cotton, nylon, acetate, wool, rayon, acrylic, silk, and polyester) compliant with JIS L 0803 was used. Also, among each dyeing method, material type, and comparative example of dye usage, those using the conventional water washing method were taken as "blank", and when the total of the acid perspiration fastness and the alkali perspiration fastness is larger compared to the blank, it was judged as "improved", when they are the same, it was judged as "equivalent", and when it is smaller, it was judged as "deteriorated".

[0037] (4) Dyeing substrates Also, in the examples and comparative examples, cupra knitted fabric and cotton knitted fabric were used as the dyeing substrates. They were obtained as follows respectively. The cupra knitted fabric was prepared as follows. Using a 24-gauge single-feed test tube knitting machine (manufactured by Eiko Sangyo Co., Ltd., model NCR-ES), 5 parts of single-feed knitted fabric made of 167 dtex cupra fiber, which is a regenerated cellulose fiber, were treated in a bath prepared by dissolving 0.1 part of sodium carbonate and 0.1 part of surfactant Scorell (manufactured by Kitahiro Chemical Co., Ltd.) in 100 parts of water at a liquid temperature of 90 °C for 30 minutes, followed by dehydration and drying to obtain a cupra knitted fabric dyeing substrate. The cotton knitted fabric was prepared as follows. A general-purpose smooth knitted fabric made of cotton was scoured and bleached, and the fabric before dyeing of unsilked cotton knitted fabric was obtained and treated as the object to be dyed. The cupra fabric was prepared as follows. A fabric before cupra dyeing was obtained by scouring a woven fabric in which 110 dtex cupra fiber was weft-inserted into 84 dtex cupra fiber of the warped warp using a loom, and it was treated as the object to be dyed.

[0038] [Comparative Example 1a] Dyeing process: Dyeing was carried out using a mini-color dyeing machine (manufactured by Texsam Giken Co., Ltd., UR·MINI-COLOR type) as a batch-type dyeing method. First, the reaction process of dyeing was carried out. 140 parts of water at 20 °C was put into a stainless steel pot with a diameter of 72 mm and a height of 110 mm. After 5 parts of cupra fabric was put in as the object to be dyed, a total of 5 parts of reactive dyes having a nucleophilic addition type reactive group (0.125 part of Remazol BrRed BB 150% (manufactured by Dystar Japan Co., Ltd.), 0.0625 part of Remazol BrYellow GL 150% (manufactured by Dystar Japan Co., Ltd.), and 0.0625 part of KPZOL BLACK B 150 POWDER (manufactured by Kowa Chemical Industry Co., Ltd.)) were put in. Then, after raising the liquid temperature to 60 °C, 7.5 parts of sodium sulfate was added. After exhausting the dye, 2.25 parts of sodium carbonate was added, and then it was held at a liquid temperature of 60 °C for 30 minutes to react the dye. Then, 120 parts of the dyeing solution was taken out to obtain a dyed product before the washing process. Next, as the washing process, a total of 4 washing processes were carried out. In addition, in each process, for the temperature rising operation, the initial temperature was 15 °C and the temperature was raised at a rate of 3 °C / min. The initial temperature and the temperature rising rate were the same in all the following examples and comparative examples. First washing process: 70 parts of water was added, and after raising the temperature to 20 °C, it was held for 10 minutes for washing, and then 70 parts of the washing solution was taken out. Second washing process: 70 parts of a solution in which 0.25 part of acetic acid was dissolved in water was added, and after raising the temperature to 20 °C, it was held for 10 minutes for washing, and then 70 parts of the washing solution was taken out. Third washing step: 70 parts of water was added, the temperature was raised to 90 °C, and then it was held for 10 minutes for washing. After that, 70 parts of the washing solution was taken out. Fourth washing step: 70 parts of water was added, the temperature was raised to 20 °C, and then it was held for 10 minutes for washing. The dyed fabric was taken out and dehydrated and dried by a known method to obtain a dyed product after the washing step. For the dyed product after the washing step, color fading and perspiration fastness were evaluated. Also, the CO2 emissions in the dyeing step and the washing step were calculated.

[0039] [Comparative Examples 1b - 1c, Examples 1a - 1d] Dyeing step: 5 parts of cupra knitted fabric was used as the fabric to be dyed, and the dye was reacted with the dye and method of Comparative Example 1a. The liquid was taken out to obtain a dyed product before the washing step. Next, as the washing step, the washing solution and temperature were changed as shown in Table 1 below, and washing, dehydration, and drying were performed in the same procedure as in Comparative Example 1a to obtain a dyed product after the washing step. The evaluation of color fading, perspiration fastness, and CO2 emissions was compared with that of Comparative Example 1a. The comparison results are summarized in Table 2 below.

[0040] [Comparative Examples 2a, 2b, Examples 2a, 2b] Dyeing step: 5 parts of cotton knitted fabric was used as the fabric to be dyed, and the dye was reacted with the dye and method of Comparative Example 1a except that 5 parts of cotton knitted fabric was used. The liquid was taken out to obtain a dyed product before the washing step. Next, as the washing step, the washing solution and temperature were changed as shown in Table 1 below, and washing, dehydration, and drying were performed in the same procedure as in Comparative Example 1a to obtain a dyed product after the washing step. The evaluation results of color fading, perspiration fastness, and CO2 emissions and the comparison results are summarized in Table 2 below.

[0041] [Comparative Example 3a] Dyeing step: 5 parts of cotton knitted fabric was used as the fabric to be dyed, and the dye was reacted with the dye and method of Comparative Example 1a except that 5 parts of cotton knitted fabric was used. The liquid was taken out to obtain a dyed product before the washing step. Next, as the washing step, a total of 6 washing treatments were performed. First washing step: 70 parts of water were added, the temperature was raised to 20 °C, and then it was held for 10 minutes for washing. After that, 70 parts of the washing liquid were taken out. Second washing step: 70 parts of a solution in which 0.4 part of acetic acid was dissolved in water were added, the temperature was raised to 30 °C, and then it was held for 10 minutes for washing. After that, 70 parts of the washing liquid were taken out. Third washing step: 70 parts of a liquid containing 0.2 part of the soaping agent Maisanol KHM (Meisei Chemical Industry Co., Ltd.) were added, the temperature was raised to 90 °C, and then it was held for 10 minutes for washing. After that, 70 parts of the washing liquid were taken out. Fourth washing step: 70 parts of water were added, the temperature was raised to 20 °C, and then it was held for 10 minutes for washing. After that, 70 parts of the washing liquid were taken out. Fifth washing step: 70 parts of water were added, the temperature was raised to 20 °C, and then it was held for 10 minutes for washing. After that, 70 parts of the washing liquid were taken out. Sixth washing step: 70 parts of water were added, the temperature was raised to 20 °C, and then it was held for 10 minutes for washing. The dyed fabric was taken out and dehydrated and dried by a known method to obtain a dyed product after the washing step. For the dyed product after the washing step, color fading and sweat fastness were evaluated. Also, the CO2 emissions in the dyeing step and the washing step were calculated.

[0042] [Comparative Examples 3b - 3d, Examples 3a - 3g] Dyeing step: 5 parts of cotton knitted fabric were used as the fabric to be dyed, and the dye was reacted with the dye and method of Comparative Example 1a. The liquid was taken out to obtain a dyed product before the washing step. Next, as the washing step, the washing liquid and temperature were changed as shown in Table 1 below, and washing, dehydration, and drying were performed in the same procedure as Comparative Example 3a to obtain a dyed product after the washing step. The evaluation of color fading, sweat fastness, and CO2 emissions was compared with Comparative Example 3a. The comparison results are summarized in Table 2 below.

[0043] [Comparative Example 4a, Examples 4a, 4b] Dyeing step: 5 parts of cupra knitted fabric were used as the fabric to be dyed. A total of 0.25 parts of reactive dyes having a nucleophilic addition type reactive group and a nucleophilic substitution type reactive group (0.125 part of Remazol Red RGB (manufactured by Dystar Japan Co., Ltd.), 0.0675 part of Remazol GoldYellow RGB (manufactured by Dystar Japan Co., Ltd.), and 0.0675 part of Remazol Navy RGB (manufactured by Dystar Japan Co., Ltd.)) were used, and the dyes were reacted by the method of Comparative Example 1a except for this. The liquid was taken out to obtain a dyed product before the washing step. Next, as the washing step, the washing liquid and temperature were changed as shown in Table 1 below, and washing, dehydration, and drying were performed in the same procedure as in Comparative Example 1a to obtain a dyed product after the washing step. The evaluation of color fading, perspiration fastness, and CO2 emission amount and the comparison results are summarized in Table 2 below.

[0044] [Comparative Examples 5a - 5c, Examples 5a, 5b] Dyeing step: 5 parts of cotton knitted fabric as the material to be dyed were reacted with the dye and method of Comparative Example 4a, the liquid was taken out to obtain a dyed product before the washing step. Next, as the washing step, the washing liquid and temperature were changed as shown in Table 1 below, and washing, dehydration, and drying were performed in the same procedure as in Comparative Example 3a to obtain a dyed product after the washing step. The evaluation of color fading, perspiration fastness, and CO2 emission amount and the comparison results are summarized in Table 2 below.

[0045] [Comparative Example 6a] Dyeing step: Pad - steam dyeing was performed as a continuous dyeing method. First, the reaction step of dyeing was carried out. 10 parts of cupra fabric as the material to be dyed were impregnated in an aqueous solution containing 5 parts of reactive dye Remazol BrRed BB 150% (manufactured by Dystar Japan Co., Ltd.) having a nucleophilic addition type reactive group, 5 parts of sodium sulfate, and 1 part of sodium hydroxide in 100 parts of water, and padding treatment with a pickup rate of 80% by mangle was repeated twice with the same solution. Then, using a press machine applicable to the press dimensional change rate of JIS L1096H method, the test piece and filter paper were set on the bottom ironing board, the top ironing board was lowered to 20 mm above the test piece, and steaming treatment was carried out by blowing steam at 490 kPa set at 100°C for 90 seconds to complete the reaction step of dyeing and obtain a dyed product before the washing step. Next, as a washing process, a total of five washing treatments were performed. First washing process: After impregnating 100 parts of water warmed to 30°C for 10 seconds, the process of squeezing to a pickup rate of 80% with a mangle was repeated twice with the same solution to perform washing. Second washing process: After impregnating 100 parts of an aqueous solution containing 0.02 part of citric acid warmed to 80°C and 0.02 part of the soaping agent Maisanol KHM (Meisei Chemical Industry Co., Ltd.) for 10 seconds, the process of squeezing to a pickup rate of 80% with a mangle was repeated twice with the same solution to perform washing. Third washing process: It was carried out in the same manner as the second washing process. Fourth washing process: After impregnating 100 parts of water warmed to 30°C for 10 seconds, the process of squeezing to a pickup rate of 80% with a mangle was repeated twice with the same solution to perform washing. Fifth washing process: It was carried out in the same manner as the fourth washing process. Finally, drying was performed by a known method to obtain a dyed product after the washing process.

[0046] [Example 6b] Dyeing process: 10 parts of cupra fabric as the fabric to be dyed were dyed with the same dye and method as in Example 6a to obtain a dyed product before the washing process. Next, as a washing process, the washing liquid and temperature were changed as shown in Table 1 below, and washing, dehydration, and drying were performed in the same procedure as in Comparative Example 6a to obtain a dyed product after the washing process. The evaluation of color fading, perspiration fastness, and CO2 emissions was compared with Comparative Example 6a. The comparison results are summarized in Table 2 below.

[0047]

Table 1

[0048]

Table 2

[0049] In Comparative Examples 1a to 1c and Examples 1a to 1d, which are batch-type dyeing methods, the fabric to be dyed is a cupra knitted fabric, the dye type is a nucleophilic addition reaction dye, and the sample group has 4 washing times. In Examples 1a to 1d, compared with Comparative Example 1a without alkali washing, it can be confirmed that there is no hydrolysis, the perspiration fastness is improved, and the CO2 emissions are reduced. In Comparative Example 1b without alkali washing, although low-temperature dyeing at a low temperature is carried out, it is deteriorated compared with Comparative Example 1a. In Comparative Example 1c, although there is an alkali washing step, the temperature range is 90 °C, hydrolysis occurs, the color fades, and it can be confirmed that the fastness is also deteriorated.

[0050] In Comparative Examples 2a to 2b and Examples 2a to 2b, which are batch-type dyeing methods, the fabric to be dyed is a cotton knitted fabric, the dye type is a nucleophilic addition reaction dye, and the sample group has 4 washing times. In Example 2a, compared with Comparative Example 2a without alkali washing, it can be confirmed that there is no hydrolysis, the perspiration fastness is improved, and the CO2 emissions are reduced. In Example 2b, it is 70 °C and pH 11. Although the CO2 emissions are reduced and the fastness is equivalent, color fading due to hydrolysis was confirmed. In Comparative Example 2b, although there is an alkali washing step, the temperature range is 90 °C, and even though the pH range is as low as 9.4, deterioration of the fastness due to hydrolysis has occurred.

[0051] In Comparative Examples 3a to 3d and Examples 3a to 3g, which are batch-type dyeing methods, the fabric to be dyed is a cotton knitted fabric, the dye type is a nucleophilic addition reaction dye, and the sample group has 6 washing times. In Examples 3a, 3c, 3d, 3f, and 3g, compared with Comparative Examples 3a and 3b without alkali washing, it can be confirmed that there is no hydrolysis, the perspiration fastness is improved, and the CO2 emissions are reduced. In Example 3b, it is 70 °C and pH 12.5, and in Example 3e, it is 50 °C and pH 13.6. Although color fading due to hydrolysis was confirmed, the CO2 emissions are reduced. In Comparative Example 3b, there is no alkali washing step, the temperature range is 70 °C, and compared with Comparative Example 3a, although the CO2 emissions are reduced, the fastness is deteriorated due to insufficient washing. In Comparative Example 3c, although there is an alkaline washing step, the pH is 14.2 at 30°C, exceeding pH 14. Compared with Comparative Example 3a, although the CO2 emissions are reduced, the fastness significantly deteriorates due to hydrolysis. In Comparative Example 3d, although there is an alkaline washing step, the pH is 9.8 at 60°C, below pH 10. Compared with Comparative Example 3a, although the CO2 emissions are reduced, the fastness significantly deteriorates due to insufficient washing.

[0052] In Comparative Example 4a, Example 4a, and Example 4b, which are in a batch dyeing method, with the dyed fabric being a cupra knitted fabric, and the dye type being a reactive dye having both nucleophilic addition and nucleophilic substitution reactive groups, and a sample group with 4 washing times. In Example 4a, compared with Comparative Example 4a without alkaline washing, there is no hydrolysis, the perspiration fastness is improved, and it can be confirmed that the CO2 emissions are reduced. In Example 4b, the pH is 13.1 at 60°C, and although color fading due to hydrolysis is confirmed, the CO2 emissions are reduced.

[0053] In Comparative Examples 5a to 5c and Examples 5a to 5b, which are in a batch dyeing method, with the dyed fabric being a cotton knitted fabric, and the dye type being a reactive dye having both nucleophilic addition and nucleophilic substitution reactive groups, and a sample group with 6 washing times. In both Examples 5a and 5b, compared with Comparative Example 5a without alkaline washing, there is no hydrolysis, the perspiration fastness is improved, and it can be confirmed that the CO2 emissions are reduced. In Comparative Example 5b, although there is an alkaline washing step, the pH is 14.4 at 30°C, exceeding pH 14. Compared with Comparative Example 3a, although the CO2 emissions are reduced, the fastness significantly deteriorates due to hydrolysis. In Comparative Example 5c, although there is an alkaline washing step, the pH is 9.8 at 60°C, below pH 10. Compared with Comparative Example 3a, although the CO2 emissions are reduced, the fastness significantly deteriorates due to insufficient washing.

[0054] In the continuous dyeing method, the dyed fabric is a cupra fabric, the dye type is a nucleophilic addition type reactive dye, and it is Comparative Example 6a and Example 6a of a sample group with 5 washing times. In Example 6a, compared with Comparative Example 6a without alkali washing, it can be confirmed that there is no hydrolysis, the perspiration fastness is equivalent, and the CO2 emissions are reduced.

Industrial Applicability

[0055] According to the present invention, particularly in the post-dyeing washing in the dyeing method of cellulose fibers and their products using nucleophilic addition type reactive dyes, by increasing the pH while lowering the temperature of the washing liquid, it is possible to reduce the CO2 emissions while achieving high dyeing fastness and obtaining a cellulose fiber product dyed with a reactive dye without hydrolysis due to alkali treatment. Therefore, the present invention can be preferably used in the dyeing of cellulose fibers and their products using reactive dyes.

Explanation of Signs

[0056] 1 Jet dyeing machine 2 Reserve tank 3 Heat exchanger 4 Nozzle 5 Fabric 6 Dyeing bath 7 Reaction process machine: Pad steaming dyeing machine 8 Fabric before dyeing (reaction process, washing process) 9 Dyeing bath 10 Mangle 11 Steam box 12 Washing process machine: Open soaper type continuous water washing machine 13 Cylinder dryer 14 Fabric after dyeing (reaction process, washing process)

Claims

1. The following steps: A batch or continuous dyeing process comprising the following steps: a dyeing reaction step of reacting a cellulose-based fiber or a textile product containing a cellulose-based fiber with a reactive dye in a dyeing solution; After the dyeing solution is completely or partially discharged, the dyed fiber or textile product is washed with an alkaline washing solution having a pH of 10.5 to 14 and a temperature of 15 to 50° C.; and an alkaline post-cleaning step of discharging the alkaline cleaning solution and then cleaning with water; and The following formula (1): -0.07x+13≦y<-0.07x+17 A method for dyeing a cellulose-based fiber or a textile product containing a cellulose-based fiber, which satisfies the relationship: {wherein x is a temperature value of 15 to 50° C., and y is a pH value of 10.5 to 14.}

2. The dyeing method according to claim 1 , wherein in the post-alkali washing step, an acid is added to the water and neutralized with an acid-containing pickling solution.

3. The dyeing method according to claim 1 or 2, further comprising an alkaline pre-washing step of washing with an aqueous solution between the dyeing reaction step and the alkaline washing step.

4. The dyeing method according to claim 1 or 2, wherein the reactive dye comprises a nucleophilic addition type reactive dye.

5. The dyeing method according to claim 1 or 2, wherein in the alkaline washing step, washing is performed with an alkaline washing solution having a bath ratio of 1:100 or less and a temperature of 15 to 50°C.

6. The dyeing method according to claim 1 or 2, wherein in the alkali post-washing step, washing is performed with water having a liquor ratio of 1:100 or less and a temperature of 5 to 50° C.

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