WO2019214185A1 - 一浴法阳离子改性活性染料染色的整理方法 - Google Patents

一浴法阳离子改性活性染料染色的整理方法 Download PDF

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WO2019214185A1
WO2019214185A1 PCT/CN2018/113623 CN2018113623W WO2019214185A1 WO 2019214185 A1 WO2019214185 A1 WO 2019214185A1 CN 2018113623 W CN2018113623 W CN 2018113623W WO 2019214185 A1 WO2019214185 A1 WO 2019214185A1
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fabric
reactive dye
dyeing
reactive
soaping
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PCT/CN2018/113623
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English (en)
French (fr)
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阎克路
王磊
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东华大学
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6426—Heterocyclic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/655—Compounds containing ammonium groups
    • D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673—Inorganic compounds
    • D06P1/67333—Salts or hydroxides
    • D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341

Definitions

  • the invention belongs to the field of textile printing and dyeing, and relates to a method for dyeing salt-free padding or dip dyeing which satisfies the requirement of fixing rate and apparent color yield in one step of cationization, and particularly relates to a method for finishing dyeing of cationically modified reactive dye by one-bath method .
  • Cotton fabrics have excellent characteristics such as comfortable wearing, moisture absorption, warmth retention, good air permeability and easy cleaning, which are favored by more and more consumers.
  • Reactive dyes have the advantages of bright color, complete chromatogram and good dye fastness. Therefore, it is widely used in the dyeing of cotton and other cellulosic fiber fabrics.
  • the dyeing of the reactive dye is affected.
  • the dyeing needs to add a large amount of salt to promote dyeing and alkali fixation, resulting in a large amount of unfixed or hydrolyzed in the wastewater.
  • Reactive dyes and salts cause serious pollution to the environment.
  • the specific two-step process is as follows: firstly, the cotton fabric is treated with a cationic modifier by dipping or padding, and hydrogen is used at this time.
  • the sodium cation completes the cationization reaction, and then is subjected to baking, pickling neutralization and water washing to obtain a cationized cotton fabric; the cationized cotton fabric is dyed by a salt-free dyeing or pad dyeing method to obtain a reactive dye-dyed fabric.
  • the cationic modifier and the reactive dye react with the hydroxyl groups on the cotton fabric, the corresponding cationization and reactive dye fixing processes are carried out in sequence, and there is no competition between the two. Relationship, will not compete for the hydroxyl on the cotton fabric.
  • the two-step process is long and requires a lot of energy and water resources, which is not conducive to industrial production.
  • the fixing rate of the cotton fabric reactive dye dyeing process can reach about 70-80%.
  • the fixing rate of the cotton fabric reactive dyeing process using the cationization two-step method is improved, the addition of a large amount of electrolyte may cause environmental pollution.
  • the two-step process of cationization requires a large amount of energy and water resources, which is not conducive to industrial production.
  • the technical problem to be solved by the present invention is to provide a method for dyeing salt-free padding or dip dyeing which satisfies the requirements of fixing rate and apparent color yield, and specifically relates to a one-bath cationically modified reactive dye.
  • Dyeing method for padding or dip dyeing is a one-step cationization method, which not only saves time and shortens the process, but also saves a lot of water and energy, and the apparent color yield and the fixation rate are higher than the salt-assisted dyeing method, and the effect is the same as the cationization two-step method.
  • a one-bath method for cation-modified reactive dyeing finishing a dyeing solution containing a cationic modifier and a reactive dye on a cellulose fiber fabric by a pad dyeing or dip dyeing process, and then performing soaping to obtain a reactive dye-dyed fabric, wherein
  • the padding process is adopted, the cellulose fiber fabric is steamed, baked or cold-rolled before being soaped;
  • the cationic modifier is a molecule having a reactive group and a positively charged group in a molecular structure and having a number average molecular weight of 100 to 30,000, and the reactive group is an epoxy group, a s-triazine, a pyridine, and an olefin.
  • One or more, positively charged groups include one or more of a quaternary ammonium salt and an ammonium chloride structure.
  • the padding solution comprises 10 to 150 g/L of a cationic modifier, 5 to 40 g/L of a reactive dye, 10 to 70 g/L of an alkali agent, 30 to 150 g/L of urea, and a balance. Ionic water.
  • the cationic modifier is specifically 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltriethylammonium chloride, 3-chloro-2. - Hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltriethylammonium chloride, monochlorotriazine-type quaternary ammonium salt compound, azetidine cation compound, choline chloride And a mixture of one or more of polyepoxychloropropane amides.
  • the reactive dye is a s-triazine, pyrimidine, vinyl sulfone or phosphonic acid type reactive dye.
  • the alkali agent is a mixture of one or more of sodium hydroxide, sodium hydrogencarbonate and sodium carbonate.
  • the type of the alkali agent is not limited thereto, and includes potassium hydroxide, potassium hydrogencarbonate, potassium carbonate, potassium phosphate, potassium silicate, sodium silicate or sodium phosphate.
  • the process of the padding process is: padding the cellulose fiber fabric by padding to ensure the liquid rate of the fabric is 60-100% by weight;
  • the process of the dyeing process is: The cellulose fiber fabric is treated by dip dyeing and dyed at 60-90 ° C for 30-90 min.
  • the cellulose fiber fabric comprises cotton, hemp, viscose, tencel and modal fabric.
  • the steaming or baking is carried out directly or after the pad-treated fabric is dried.
  • the steaming refers to steaming of 100 to 180 ° C for 1 to 15 minutes; the baking is 100 to 180 ° C for 1 to 15 minutes; the cold rolling pile is 15 to 15 Stacked at 35 ° C for 6 ⁇ 18h.
  • the steaming, baking or cold rolling stack temperature and time are set in this range.
  • the main purpose is to ensure the reaction of the cationic modifier and the reactive dye with the cotton fabric. If the temperature is too high or the time is too long, the covalent bond formed between the reactive dye and the cotton fabric will be broken, resulting in a decrease in the K/S value and the fixing rate; if the temperature is too low or the time is too short, it is not suitable for the reactive dye and cotton. The reaction between the fabrics gives a lower K/S value and a higher fixation rate.
  • the invention firstly proposes to improve the dyeing effect of reactive dyes by using a one-bath cationic modification reactive dyeing process.
  • the process combines the solidification of cationic modification and reactive dyes in one step, greatly shortening the process flow and saving energy.
  • This process (referred to as the one-step process) is different from the two-step process in which the fabric is first cationized and then dyed with reactive dyes.
  • a cotton fabric is firstly cationically modified to obtain a cationized cotton fabric by a two-step process, and then the reactive dye dyeing solution is padded, and the reactive dye is fixed to the cationized cotton fabric in a steaming process.
  • the cationic modification of cotton fabric and the fixing of reactive dyes are carried out in two steps. Although both cationic modifiers and reactive dyes react with hydroxyl groups on cotton fabrics, their corresponding cationization and reactive dye fixing processes It is carried out in sequence, so there is no competition between the two. In the one-bath cationic modification reactive dye dyeing process used in the present invention, the fixation of the cationic modification and the reactive dye is carried out in one step, and both of them react with the hydroxyl groups on the cotton fabric, so there is a Competitive relationship.
  • the present invention uses Gauss software to calculate the reaction thermodynamics and kinetic data of cationic modifier and cotton fabric, and the reaction thermodynamics of reactive dyes and cotton fabrics. And kinetic data.
  • the reaction scheme below lists the reaction processes of reactants R1, R2, R3, transition states TS1, TS2, and products P1, P2, as follows:
  • R1 is used to indicate the cationic modifier
  • R2 is the reactive dye
  • R3 is the cotton fabric
  • TS1 and TS2 are the transition states of the reaction, respectively
  • P1 and P2 are the products.
  • the Gaussian calculation results show that the CO bond is from the reactant R1.
  • the reaction mechanism is that the oxygen atom in R3 attacks the carbon atom in R1 which is connected to the oxygen and has no branching, and a nucleophilic reaction occurs to form the product P1.
  • the Gaussian calculation results show that the C-Cl bond is from the reactant R2.
  • the free energy is -74.1205KJ ⁇ mol -1 , and the more Gibbs free energy is negative, the more likely the chemical reaction will occur.
  • the reaction activation energy (Ea) of R1 and R3 is 125.7208 KJ ⁇ mol -1
  • the reaction activation energy (Ea) of R2 and R3 is 172.1007 KJ ⁇ mol -1 .
  • the lower the activation activation energy the easier the chemical reaction is.
  • the reactivity of the cationic modifier and the cotton fabric is stronger than that of the reactive dye and the cotton fabric. In the one bath cation-modified reactive dye padding process, the cationic modifier will preferentially react with the cotton fabric.
  • the reaction time increases, the zeta potential of the fabric slowly changes from negative to positive, so the attraction band The adsorption and fixation of the negatively charged reactive dye on the fabric, thereby increasing the apparent color yield and fixing rate of the fabric.
  • the treatment liquid is adsorbed on the cotton fabric to ensure that the fabric has a liquid filling rate of 60% by weight, and then the fabric after the padding treatment is directly steamed, and finally The soap is washed to obtain a reactive dye-dyed fabric, wherein the treatment liquid comprises 100 g/L of 2,3-epoxypropyltrimethylammonium chloride, 15 g/L of s-triazine reactive dye, 20 g/L of sodium hydroxide, 80g / L urea and the balance of deionized water, wherein steaming means 100 ° C saturated steam steaming for 15min, soaping includes the following five stages: 1) room temperature rinse 3min; 2) 40 ° C warm water wash 1min; 3) 1g / L soaping agent D-301 90 ° C soaping 5 min; 4) 40 ° C warm water wash 3 min; 5) room temperature rinse 1-5 min.
  • the treatment liquid comprises 100 g/L of 2,3-epoxypropyltrimethylammonium chloride, 15 g/
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 14.7 and a fixing ratio of 80.8%.
  • One-bath method for cationically-modified reactive dyeing using a padding method, adsorbing the treatment liquid on the hemp fabric, ensuring that the fabric has a liquid-trapping rate of 70% by weight, and then directly steaming the fabric after the padding treatment, and finally Performing soaping to obtain a reactive dye-dyed fabric
  • the treatment liquid comprises 80 g/L of 2,3-epoxypropyltriethylammonium chloride, 25 g/L of s-triazine reactive dye, 50 g/L of sodium hydrogencarbonate, 30g / L urea and the balance of deionized water
  • steaming refers to 160 ° C saturated steam steaming 1min
  • soaping includes the following five stages: 1) room temperature rinse 5min; 2) 40 ° C warm water wash 3min; 3) 2g / L soaping agent D-301 92 ° C soaping 6 min; 4) 50 ° C warm water wash 1 min; 5) room temperature rinse 1 min.
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 18.8 and a fixing ratio of 83.2%.
  • One-bath method for cationically modified reactive dyeing using the method of padding, adsorbing the treatment liquid on the viscose fiber fabric to ensure that the fabric has a liquid rate of 80% by weight, and then directly baking the fabric after the padding treatment Finally, soaping is performed to obtain a reactive dye-dyed fabric, wherein the treatment liquid comprises 130 g/L of 3-chloro-2-hydroxypropyltrimethylammonium chloride, 35 g/L of pyrimidine reactive dye, 40 g/L of sodium carbonate, 90g / L urea and the balance of deionized water, wherein baking refers to baking at 100 ° C for 15min, soaping includes the following five stages: 1) room temperature rinse 1min; 2) 40 ° C warm water wash 2min; 3) 3g / L soap Lotion D-301 97 ° C soaping 5 min; 4) 60 ° C warm water wash 3 min; 5) room temperature rinse for 12 min.
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 23.1 and a fixing ratio of 93.2%.
  • One-bath method for cationically-modified reactive dyeing using a padding method, adsorbing the treatment liquid on the Tencel fabric to ensure that the fabric has a liquid-carrying rate of 90% by weight, and then directly baking the fabric after the padding treatment. Finally, soaping is carried out to obtain a reactive dye-dyed fabric, wherein the treatment liquid comprises 150 g/L of 3-chloro-2-hydroxypropyltriethylammonium chloride, 40 g/L of pyrimidine reactive dye, and 30 g/L of sodium hydroxide.
  • baking refers to baking at 120 ° C for 3 min
  • the soaping comprises the following five stages: 1) rinsing at room temperature for 2 min; 2) Washing at 50 ° C for 1 min; 3) 4 g / L soaping agent D-301 94 ° C soaping 7 min; 4) 50 ° C warm water wash 4 min; 5) room temperature rinse for 3 min.
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 24.6 and a fixing ratio of 95.3%.
  • One-bath method for cationically modified reactive dyeing using a padding method, adsorbing the treatment liquid on the modal fabric to ensure that the fabric has a liquid rate of 100% by weight, and then directly baking the fabric after the padding treatment, and finally Performing soaping to obtain a reactive dye-dyed fabric
  • the treatment liquid comprises 60 g/L of 2-chloro-4,6-diamino-1,3,5-triazine, 5 g/L of vinylsulfone reactive dye, 10 g/L a mixture of sodium bicarbonate and sodium carbonate (mass ratio 1:3), 110 g/L urea and the balance of deionized water
  • baking refers to baking at 180 ° C for 1 min
  • the soaping comprises the following five stages: 1) room temperature Rinse for 4 min; 2) Wash at 60 ° C for 5 min; 3) 1 g/L soap lotion D-301 93 ° C for 10 min; 4) 40 ° C warm water for 5 min; 5) Rinse at
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 8.6 and a fixing ratio of 75.5%.
  • the treatment liquid is adsorbed on the cotton and hemp blended fabric (mass ratio 1:1) fabric to ensure the fabric liquid rate is 60wt%, and then dip The rolled fabric is directly steamed, and finally soaped to obtain a reactive dye padded fabric, wherein the treatment liquid comprises 30 g/L of N-dimethylazetidine chloride and 10 g/L of vinylsulfone reactive dye.
  • soaping includes the following Five stages: 1) rinsing at room temperature for 1 min; 2) washing at 40 ° C for 3 min; 3) 3 g/L soaping agent D-301 98 ° C soaping for 5 min; 4) 40 ° C warm water washing for 4 min; 5) rinsing at room temperature for 5 min.
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 11.6 and a fixing ratio of 81.6%.
  • One-bath method for cation-modified reactive dyeing using a padding method, adsorbing the treatment liquid on the cotton fabric to ensure that the fabric has a liquid rate of 100% by weight, and then drying the fabric after the padding treatment for baking Finally, soaping is performed to obtain a reactive dye padded fabric, wherein the treatment liquid comprises 10 g/L choline chloride, 5 g/L phosphonic acid type reactive dye, 50 g/L sodium hydroxide, a mixture of sodium hydrogencarbonate and sodium carbonate ( The mass ratio is 1:1:3), 150g/L urea and the balance of deionized water, wherein baking refers to baking at 150 ° C for 1.5 min, and the soaping includes the following five stages: 1) rinsing at room temperature for 4 min; 2) 50 °C warm water wash 4min; 3) 3g / L soap lotion D-301 95 3 ° C soaping 10min; 4) 50 ° C warm water wash 5min; 5) room temperature rinse 5min.
  • the treatment liquid comprises 10 g
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 10.9 and a fixing ratio of 80.3%.
  • One bath method of cationically modified reactive dyeing method using the method of padding, adsorbing the treatment liquid on the fabric of viscose fiber and Tencel blend (mass ratio 1:1) to ensure the liquid carrying rate of the fabric is 80 wt%.
  • the fabric after the padding treatment is dried, steamed, and finally soaped to obtain a reactive dye padded fabric, wherein the treatment liquid comprises 100 g/L polyepichlorohydrin dimethylamine and 35 g/L phosphonic acid type activity.
  • Dye 30g / L sodium hydroxide, 30g / L urea and the balance of deionized water, wherein steaming means 100 ° C saturated steam steaming 10min, soaping includes the following five stages: 1) room temperature rinse 3min; 2) Washed at 60 ° C for 1 min; 3) 4 g / L soaping agent D-301 90 ° C soaping 10 min; 4) 60 ° C warm water wash 2 min; 5) room temperature rinse 4 min.
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 22.2 and a fixing ratio of 90.5%.
  • the treatment liquid is adsorbed on the fabric of Tencel and modal blend (mass ratio 1:1) to ensure the fabric liquid rate is 70wt%, and then The fabric after the padding treatment is steamed after drying, and finally soaped to obtain a reactive dye padded fabric, wherein the treatment liquid comprises 120 g/L of 2,3-epoxypropyltrimethylammonium chloride and 2, a mixture of 3-epoxypropyltriethylammonium chloride (mass ratio of 2:3), 30 g/L of s-triazine reactive dye, 10 g/L of sodium hydroxide, 150 g/L of urea and the balance of deionized water
  • the steaming refers to steaming at 130 ° C for 3 min.
  • the soaping includes the following five stages: 1) rinsing at room temperature for 5 min; 2) washing at 50 ° C for 2 min; 3) 4 g/L soaping agent D-301 98 ° C soap Wash for 5 min; 4) wash at 40 ° C for 2 min in warm water; 5) rinse at room temperature for 3 min.
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 20.3 and a fixing ratio of 89.8%.
  • the treatment liquid is adsorbed on the fabric of cotton, hemp and viscose fiber blending (mass ratio 1:1:1) to ensure the liquid rate of the fabric. 60wt%, the fabric after the padding treatment is dried, steamed, and finally soaped to obtain a reactive dye padded fabric, wherein the treatment liquid comprises 50 g/L of 3-chloro-2-hydroxypropyltrimethyl Mixture of ammonium chloride and 3-chloro-2-hydroxypropyltriethylammonium chloride (mass ratio 1:1), 20 g/L s-triazine reactive dye, 40 g/L sodium bicarbonate, 50 g/L urea And the balance of deionized water, wherein steaming refers to steaming at 120 ° C for 3 min, the soaping includes the following five stages: 1) rinsing at room temperature for 5 min; 2) washing at 50 ° C for 5 min; 3) 2 g / L soaping D
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 16.9 and a fixing ratio of 84.2%.
  • One-bath method for cation-modified reactive dyeing using the method of padding, finishing the treatment liquid on the viscose fiber, Tencel and modal blend (quality ratio 1:1:1) fabric to ensure the fabric with liquid The ratio is 100 wt%, and the fabric after the padding treatment is dried, then baked, and finally soaped to obtain a reactive dye padded fabric, wherein the treatment liquid comprises 90 g/L 2 -chloro-4,6-diamino-1.
  • baking refers to baking at 140 ° C for 2min, soaping includes the following five stages: 1) room temperature rinse 1min; 2) 60 ° C warm water wash 3min; 3) 3g / L Soaping agent D-301 was soaped at 96 ° C for 5 min; 4) washed at 60 ° C for 1 min in warm water; 5) rinsed at room temperature for 1 min.
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 15.8 and a fixing ratio of 82.8%.
  • One bath cation-modified reactive dyeing method using the method of padding, adsorbing the treatment liquid on the viscose fiber, Tencel and modal blended fabric (mass ratio 1:1:1) to ensure the fabric liquid rate 70wt%, the padded treated fabric is directly subjected to cold-rolled pile, and finally soap-washed to obtain a reactive dye-dyed fabric, wherein the treatment liquid comprises 70 g/L 2 -chloro-4,6-diamino-1,3 , a mixture of 5-triazine, N-dimethylazetidine chloride and choline chloride (mass ratio 2:1:1), 5 g/L s-triazine reactive dye, 20 g/L hydrogencarbonate Sodium, 60g/L urea and the balance of deionized water, wherein the cold-rolled pile refers to stacking at 15 ° C for 6 h.
  • the soaping includes the following five stages: 1) rinsing at room temperature for 1 min; 2) washing at 60 ° C for 3 min; 3) 3g / L soaping agent D-301 96 ° C soaping 5min; 4) 60 ° C warm water wash 1min; 5) room temperature rinse 1min.
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 10.2 and a fixing ratio of 78.5%.
  • the method of dyeing the cationically modified reactive dye by one bath method using the method of padding, adsorbing the treatment liquid on the cotton fabric, ensuring that the liquid rate of the fabric is 90 wt%, and then directly drying the fabric after the padding treatment. Finally, soaping is performed to obtain a reactive dye-dyed fabric, wherein the treatment liquid comprises 90 g/ L of 3-chloro-2-hydroxypropyltrimethylammonium chloride, 15 g/L of phosphonic acid-type reactive dye, and 40 g/L of sodium carbonate.
  • soaping includes the following five stages: 1) room temperature rinse 1min; 2) 60 ° C warm water wash 3min; 3) 3g / L soaping agent D-301 96 ° C soaping 5 min; 4) 60 ° C warm water wash 1 min; 5) room temperature rinse 1 min.
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 15.8 and a fixing ratio of 82.2%.
  • One-bath method for cationically modified reactive dyeing using a padding method, finishing the treatment liquid on the cotton fabric to ensure that the fabric has a liquid rate of 100% by weight, and then drying the fabric after the padding treatment for cold rolling The pile is finally soaped to obtain a reactive dye-dyed fabric, wherein the treatment liquid comprises 100 g/L of 3-chloro-2-hydroxypropyltrimethylammonium chloride, 30 g/L of pyrimidine reactive dye, and 60 g/L of sodium hydroxide.
  • the cold-rolled pile refers to stacking at 25 ° C for 16 h
  • the soaping includes the following five stages: 1) rinsing at room temperature for 3 min; 2) washing at 60 ° C for 3 min; 3) 3 g / L soaping agent D-301 96 ° C soaping 5 min; 4) 60 ° C warm water wash 1 min; 5) room temperature rinse for 3 min.
  • the final prepared reactive dye padded fabric was tested with a DataColor tester for K/S values (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final prepared reactive dye inkjet printing.
  • the fabric had a K/S value of 21.9 and a fixing ratio of 90.1%.
  • One-bath method for cationically modified reactive dyeing using a dip dyeing method, the viscose fiber fabric is dipped in a treatment liquid at a certain temperature for a period of time, and finally soaping to obtain a reactive dye-dyed fabric, wherein the treatment liquid includes 120 g/ L 3-chloro-2-hydroxypropyltrimethylammonium chloride, 30 g/L pyrimidine reactive dye, 60 g/L sodium hydroxide, 30 g/L urea and the balance of deionized water, wherein the dip temperature is 90 ° C The time is 90min.
  • the soaping includes the following five stages: 1) rinsing at room temperature for 1 min; 2) washing at 40 ° C for 3 min; 3) 3 g/L soaping agent D-301 97 ° C soaping for 3 min; 4) 60 ° C warm water washing 3 min; 5) Rinse at room temperature for 10 min.
  • the final reactive dyed fabric was tested with a DataColor tester to test the K/S value (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final reactive dye inkjet printed fabric.
  • K/S value was 22.1 and the fixation rate was 92.2%.
  • One-bath method for cationically modified reactive dyeing using a dip dyeing method, the cotton fabric is dipped in a treatment liquid at a certain temperature for a period of time, and finally soaping to obtain a reactive dye-impregnated fabric, wherein the treatment liquid includes 30 g/L of chlorine Choline, 10g/L pyrimidine reactive dye, 10g/L sodium carbonate, 60g/L urea and the balance of deionized water, wherein the dip temperature is 60 ° C, the time is 30 min, soaping includes the following five stages: 1) Rinse at room temperature for 1 min; 2) wash at 40 °C for 5 min; 3) 3 g/L soaping agent D-301 97 °C for 5 min; 4) 60 ° C warm water for 5 min; 5) rinse at room temperature for 10 min.
  • the treatment liquid includes 30 g/L of chlorine Choline, 10g/L pyrimidine reactive dye, 10g/L sodium carbonate, 60g/L urea and the balance of dei
  • the final reactive dyed fabric was tested with a DataColor tester to test the K/S value (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final reactive dye inkjet printed fabric.
  • K/S value was 11.1 and the fixation rate was 81.2%.
  • One-bath method for cationically modified reactive dyeing using a dip dyeing method, the cotton fabric is dipped in a treatment liquid at a certain temperature for a period of time, and finally soaping to obtain a reactive dye-impregnated fabric
  • the treatment liquid includes 90 g/L of 3 -Chloro-2-hydroxypropyltrimethylammonium chloride, 20 g/L phosphonic acid reactive dye, 30 g/L sodium hydroxide, 90 g/L urea and the balance of deionized water, wherein the dip temperature is 75 ° C,
  • the time is 60min
  • the soaping includes the following five stages: 1) rinsing at room temperature for 3 min; 2) washing at 40 ° C for 3 min; 3) 3 g/L soaping agent D-301 97 ° C soaping for 5 min; 4) washing at 60 ° C for 5 min. ; 5) Rinse at room temperature for 15 min.
  • the final reactive dyed fabric was tested with a DataColor tester to test the K/S value (K/S value represents the apparent color yield of the fabric), and then the fixing rate was measured to determine the final reactive dye inkjet printed fabric.
  • K/S value was 17.9 and the fixation rate was 87.7%.

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Abstract

本发明涉及一浴法阳离子改性活性染料染色的整理方法，通过轧染或浸染工艺将含阳离子改性剂和活性染料的处理液整理在纤维素纤维织物上后进行皂洗得到活性染料染色织物，其中，采用轧染工艺时，纤维素纤维织物在进行皂洗前进行汽蒸、焙烘或冷轧堆；阳离子改性剂为分子结构中含有反应性基团和正电荷基团且数均分子量为100-30000的分子，其反应性基团为环氧基团、均三嗪、吡啶和烯烃中的一种或多种，正电荷基团包括季铵盐和氯化铵结构中的一种或多种。本发明方法将棉织物阳离子改性和活性染料的固色合为一步进行，缩短了工艺流程，提高了织物的表观得色量和固色率，且在染色过程中避免了无机盐的加入，从而避免了对环境的污染。

Description

一浴法阳离子改性活性染料染色的整理方法 技术领域
本发明属于纺织印染领域，涉及一种阳离子化一步法满足固色率和表观得色量要求的无盐轧染或浸染的染色方法，具体涉及一浴法阳离子改性活性染料染色的整理方法。
背景技术
棉织物具有穿着舒适、吸湿性、保暖性、透气性好、容易清洗等优良特性，受到越来越多消费者的青睐。活性染料具有颜色鲜艳、色谱齐全和染色牢度好等优点。因此，其被广泛应用在棉及其它纤维素纤维织物的染色中。但是，由于棉纤维和带负电的活性染料之间存在着库伦斥力，影响活性染料的上染，染色需要加入大量的盐促染和加入碱固色，导致废水中含有大量的未固色或水解的活性染料和盐，对环境造成严重的污染。
为了提高活性染料的上染率和固色率，通常有两种方法：一种是染浴中加入大量的盐，屏蔽棉织物和活性染料之间的库伦斥力，再加入碱提高活性染料与纤维素羟基的固色反应，从而提高活性染料的上染率以及固色率；另外一种是两步法工艺：对先对棉织物进行阳离子改性，以提高对活性染料上染的电荷引力而提高上染率，再进行无盐染色。将阳离子改性方法应用到活性染料染色中时，其工艺流程长，能耗大，具体两步法工艺如下：首先通过浸渍或者浸轧的方式用阳离子改性剂处理棉织物，此时使用氢氧化钠完成阳离子化反应，再经过焙烘以及酸洗中和和水洗干燥后得到阳离子化棉织物；阳离子化棉织物再通过活性染料无盐浸染或者轧染的方式染色，得到活性染料染色织物。上述两步法工艺过程中，虽然阳离子改性剂和活性染料都会与棉织物上的羟基发生反应，但是其对应的阳离子化和活性染料固色过程是依次进行的，两者之间不存在竞争关系，不会争夺棉织物上的羟基。两步法工艺流程长，需要消耗大量的能源以及水资源，不利于工业化生产。
目前，通过加入大量电解质的方法，棉织物活性染料染色工艺的固色率可以达到70～80％左右。采用阳离子化二步法的棉织物活性染料染色工艺固色率虽然有所提高，但是，大量电解质的加入会对环境造成污染。而阳离子化的两步法工 艺流程长，需要消耗大量的能源以及水资源，不利于工业化生产。
因此，研究开发一种固色率高、表观得色量性能优异、工艺流程短且无污染的一浴法阳离子改性活性染料染色的整理方法成为目前亟待解决的技术问题。
发明内容
本发明所要解决的技术问题是提供一种阳离子化一步法满足固色率和表观得色量要求的无盐轧染或浸染的染色方法，具体是涉及一种一浴法阳离子改性活性染料轧染或浸染的染色方法。本发明技术是阳离子化一步法，不仅节省了时间缩短工艺节约大量水和能源，而且表观得色量以及固色率高于加盐促染的方法，与阳离子化两步法效果相同。
为了达到上述目的，本发明采用的技术方案为：
一浴法阳离子改性活性染料染色的整理方法，通过轧染或浸染工艺将含阳离子改性剂和活性染料的染液整理在纤维素纤维织物上后，进行皂洗得到活性染料染色织物，其中，采用轧染工艺时，纤维素纤维织物在进行皂洗前进行汽蒸、焙烘或冷轧堆；
所述阳离子改性剂为分子结构中含有反应性基团和正电荷基团且数均分子量为100-30000的分子，其反应性基团为环氧基团、均三嗪、吡啶和烯烃中的一种或多种，正电荷基团包括季铵盐和氯化铵结构中的一种或多种。
作为优选的技术方案：
如上所述的整理方法，所述轧染液包括10～150g/L阳离子改性剂﹑5～40g/L活性染料﹑10～70g/L碱剂、30～150g/L尿素和余量的去离子水。
如上所述的整理方法，所述阳离子改性剂具体为2,3-环氧丙基三甲基氯化铵﹑2,3-环氧丙基三乙基氯化铵﹑3-氯-2-羟丙基三甲基氯化铵﹑3-氯-2-羟丙基三乙基氯化铵﹑一氯均三嗪型季铵盐化合物﹑氮杂环丁烷阳离子化合物、氯化胆碱和聚环氧氯丙烷胺化物中的一种或几种的混合物。
如上所述的整理方法，所述活性染料为均三嗪﹑嘧啶、乙烯砜或膦酸型活性染料。
如上所述的整理方法，所述碱剂为氢氧化钠﹑碳酸氢钠和碳酸钠中的一种或几种的混合物。碱剂种类不限于此，还包括氢氧化钾、碳酸氢钾、碳酸钾、磷酸钾、硅酸钾、硅酸钠或磷酸钠。
如上所述的整理方法，所述轧染工艺的过程为：使用浸轧的方式对纤维素纤维织物进行轧染处理，保证织物带液率为60～100wt％；所述浸染工艺的过程为：使用浸染的方式对纤维素纤维织物进行处理，在60～90℃浸染30～90min。
如上所述的整理方法，所述纤维素纤维织物包括棉、麻、黏胶纤维、天丝和莫代尔织物。
如上所述的整理方法，所述汽蒸或焙烘直接进行或者将浸轧处理后的织物烘干后进行。
如上所述的整理方法，所述汽蒸是指100～180℃饱和蒸汽汽蒸1～15min；所述烘焙是指100～180℃焙烘1～15min；所述冷轧堆是指在15～35℃堆置6～18h。汽蒸、焙烘或冷轧堆温度和时间设置在这个范围主要的目的是为了保证阳离子改性剂以及活性染料同棉织物的反应。温度过高或时间过长，会使活性染料和棉织物之间形成的共价键发生断裂，导致K/S值和固色率下降；温度过低或时间过短，不利于活性染料和棉织物之间的反应，得到的K/S值和固色率较低。
发明机理：
本发明首次提出利用一浴法阳离子改性活性染料染色工艺提高活性染料的染色效果。该工艺将阳离子改性和活性染料的固色合为一步进行，极大地缩短了工艺流程，节约了能源。该工艺(简称一步法工艺)同织物先阳离子化后再染色活性染料的两步法工艺相比，其化学反应过程不一样。现有技术采用两步法工艺为棉织物先经阳离子改性得到阳离子化的棉织物，然后浸轧活性染料染液，在汽蒸过程中使活性染料同阳离子化的棉织物发生固着。棉织物的阳离子改性和活性染料的固色是分为两步进行的，虽然阳离子改性剂和活性染料都会与棉织物上的羟基发生反应，但是其对应的阳离子化和活性染料固色过程是依次进行的，因此，两者之间并不存在着竞争关系。本发明采用的一浴法阳离子改性活性染料染色工艺中，阳离子改性和活性染料的固色合为一步进行，并且他们两者都会同棉织物上的羟基发生反应，因此两者之间存在着竞争关系。为了探究一步法中阳离子改性剂和活性染料同棉织物的反应过程，本发明使用高斯软件分别计算出阳离子改性剂同棉织物的反应热力学和动力学数据以及活性染料同棉织物的反应热力学和动力学数据。下述反应结构式列出了反应物R1、R2、R3，过渡态TS1、TS2以及产物P1、P2的反应过程，如下所示：
Figure PCTCN2018113623-appb-000001
为了简化计算过程，用R1来表示阳离子改性剂，R2表示活性染料，R3表示棉织物，其中TS1和TS2分别为反应的过渡态，P1和P2表示生成物。对于R1和R3的反应，高斯计算结果显示C-O键由反应物R1的
Figure PCTCN2018113623-appb-000002
增大为过渡态TS1中的
Figure PCTCN2018113623-appb-000003
O-H键由反应物R3的
Figure PCTCN2018113623-appb-000004
增大为过渡态TS1中的
Figure PCTCN2018113623-appb-000005
新生成的C-O键由过渡态TS1中的
Figure PCTCN2018113623-appb-000006
减少为生成物P1中的
Figure PCTCN2018113623-appb-000007
新生成的O-H键由过渡态TS1中的
Figure PCTCN2018113623-appb-000008
减少为生成物P1中的
Figure PCTCN2018113623-appb-000009
因此，对于R1和R3的反应，其反应机理是R3中的氧原子进攻R1中与氧相连并且没有支链的碳原子，发生亲核反应生成产物P1。对于R2和R3的反应，高斯计算结果显示C-Cl键由反应物R2的
Figure PCTCN2018113623-appb-000010
增大为过渡态TS2中的
Figure PCTCN2018113623-appb-000011
O-H键由反应物R3的
Figure PCTCN2018113623-appb-000012
增大为过渡态TS2中的
Figure PCTCN2018113623-appb-000013
新生成的C-O键由过渡态TS2中的
Figure PCTCN2018113623-appb-000014
减少为生成物P2中的
Figure PCTCN2018113623-appb-000015
因此，对于R2和R3的反应，其反应机理是R3中的氧原子进攻R2中与氯相连的碳原子，发生亲核反应生成产物P2。b3lyp/6-31g方法计算的阳离子改性剂以及活性染料同棉织物的反应热力学和动力学数据如下表所示：
Figure PCTCN2018113623-appb-000016
从表中可以看出，R1和R3的反应焓(ΔH)为-121.6814KJ·mol -1，R2和R3的反应焓为-69.9570KJ·mol -1，相比R2和R3的反应，R1和R3的反应发出更多的热量。吉布斯自由能(ΔG)为负值时，预示着化学反应能够自发进行， 相比R2和R3反应的吉布斯自由能为-53.6521KJ·mol -1，R1和R3反应的吉布斯自由能为-74.1205KJ·mol -1，吉布斯自由能负的越多，有可能化学反应越容易发生。R1和R3的反应活化能(Ea)为125.7208KJ·mol -1，R2和R3的反应活化能(Ea)为172.1007KJ·mol -1，反应活化能越低预示着化学反应越容易进行。综上所述，阳离子改性剂和棉织物的反应性是要强于活性染料和棉织物的反应性。在一浴法阳离子改性活性染料轧染工艺中，阳离子改性剂会优先与棉织物发生反应，随着反应时间的增加，织物的zeta电位慢慢的由负变为正，于是就吸引带负电的活性染料在织物上的吸附以及固色，从而提高织物的表观得色量以及固色率。
有益效果：
(1)本发明的一浴法阳离子改性活性染料染色的方法，在实际应用中，由于其将棉织物阳离子改性和活性染料的固色合为一步进行，极大的缩短了工艺流程，提高了织物的表观得色量和固色率；
(2)本发明的一浴法阳离子改性活性染料染色的方法，该方法在整个染色过程中避免了无机盐的加入，从而减轻了废水中盐的含量，避免了对环境的污染。
具体实施方式
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在棉织物上，保证织物带液率为60wt％，再将浸轧处理后的织物直接进行汽蒸，最后进行皂洗得到活性染料轧染织物，其中，处理液包括100g/L的2,3-环氧丙基三甲基氯化铵﹑15g/L均三嗪活性染料﹑20g/L氢氧化钠、80g/L尿素和余量的去离子水，其中汽蒸是指100℃饱和蒸汽汽蒸15min，皂洗包括如下五个阶段：1)室温冲洗3min；2)40℃温水洗1min；3)1g/L皂洗剂D-301 90℃皂洗5min；4)40℃温水洗3min；5)室温冲洗1-5min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表 织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为14.7，固色率为80.8％。
实施例2
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在麻织物上，保证织物带液率为70wt％，再将浸轧处理后的织物直接进行汽蒸，最后进行皂洗得到活性染料轧染织物，其中，处理液包括80g/L的2,3-环氧丙基三乙基氯化铵﹑25g/L均三嗪活性染料﹑50g/L碳酸氢钠、30g/L尿素和余量的去离子水，其中汽蒸是指160℃饱和蒸汽汽蒸1min，皂洗包括如下五个阶段：1)室温冲洗5min；2)40℃温水洗3min；3)2g/L皂洗剂D-301 92℃皂洗6min；4)50℃温水洗1min；5)室温冲洗1min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为18.8，固色率为83.2％。
实施例3
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在黏胶纤维织物上，保证织物带液率为80wt％，再将浸轧处理后的织物直接进行焙烘，最后进行皂洗得到活性染料轧染织物，其中，处理液包括130g/L的3-氯-2-羟丙基三甲基氯化铵﹑35g/L嘧啶活性染料﹑40g/L碳酸钠、90g/L尿素和余量的去离子水，其中烘焙是指100℃焙烘15min，皂洗包括如下五个阶段：1)室温冲洗1min；2)40℃温水洗2min；3)3g/L皂洗剂D-301 97℃皂洗5min；4)60℃温水洗3min；5)室温冲洗12min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为23.1，固色率为93.2％。
实施例4
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在天丝织物上，保证织物带液率为90wt％，再将浸轧处理后的织物直接进行焙烘，最后进行皂洗得到活性染料轧染织物，其中，处理液包括150g/L的3-氯-2-羟丙基三乙基氯化铵﹑40g/L嘧啶活性染料﹑30g/L氢氧化钠与碳酸氢钠的混合物(质 量比为1:2)、100g/L尿素和余量的去离子水，其中烘焙是指120℃焙烘3min，皂洗包括如下五个阶段：1)室温冲洗2min；2)50℃温水洗1min；3)4g/L皂洗剂D-301 94℃皂洗7min；4)50℃温水洗4min；5)室温冲洗3min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为24.6，固色率为95.3％。
实施例5
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在莫代尔织物上，保证织物带液率为100wt％，再将浸轧处理后的织物直接进行焙烘，最后进行皂洗得到活性染料轧染织物，其中，处理液包括60g/L的2-氯-4,6-二氨基-1,3,5-三嗪﹑5g/L乙烯砜活性染料﹑10g/L碳酸氢钠与碳酸钠的混合物(质量比为1:3)、110g/L尿素和余量的去离子水，其中烘焙是指180℃焙烘1min，皂洗包括如下五个阶段：1)室温冲洗4min；2)60℃温水洗5min；3)1g/L皂洗剂D-301 93℃皂洗10min；4)40℃温水洗5min；5)室温冲洗4min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为8.6，固色率为75.5％。
实施例6
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在棉和麻混纺(质量比1:1)的织物上，保证织物带液率为60wt％，再将浸轧处理后的织物直接进行汽蒸，最后进行皂洗得到活性染料轧染织物，其中，处理液包括30g/L的N-二甲基氮杂环丁烷氯化物﹑10g/L乙烯砜活性染料﹑70g/L氢氧化钠与碳酸钠的混合物(质量比为3:2)、140g/L尿素和余量的去离子水，其中汽蒸是指180℃饱和蒸汽汽蒸1min，皂洗包括如下五个阶段：1)室温冲洗1min；2)40℃温水洗3min；3)3g/L皂洗剂D-301 98℃皂洗5min；4)40℃温水洗4min；5)室温冲洗5min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为11.6，固色率为81.6％。
实施例7
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在棉织物上，保证织物带液率为100wt％，再将浸轧处理后的织物烘干后进行焙烘，最后进行皂洗得到活性染料轧染织物，其中，处理液包括10g/L氯化胆碱﹑5g/L膦酸型活性染料﹑50g/L氢氧化钠﹑碳酸氢钠与碳酸钠的混合物(质量比为1:1:3)、150g/L尿素和余量的去离子水，其中烘焙是指150℃焙烘1.5min，皂洗包括如下五个阶段：1)室温冲洗4min；2)50℃温水洗4min；3)3g/L皂洗剂D-301 95 3℃皂洗10min；4)50℃温水洗5min；5)室温冲洗5min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为10.9，固色率为80.3％。
实施例8
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在粘胶纤维和天丝混纺(质量比1:1)的织物上，保证织物带液率为80wt％，再将浸轧处理后的织物烘干后进行汽蒸，最后进行皂洗得到活性染料轧染织物，其中，处理液包括100g/L聚环氧氯丙烷二甲胺﹑35g/L膦酸型活性染料﹑30g/L氢氧化钠、30g/L尿素和余量的去离子水，其中汽蒸是指100℃饱和蒸汽汽蒸10min，皂洗包括如下五个阶段：1)室温冲洗3min；2)60℃温水洗1min；3)4g/L皂洗剂D-301 90℃皂洗10min；4)60℃温水洗2min；5)室温冲洗4min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为22.2，固色率为90.5％。
实施例9
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在天丝和莫代尔混纺(质量比1:1)的织物上，保证织物带液率为70wt％，再将浸轧处理后的织物烘干后进行汽蒸，最后进行皂洗得到活性染料轧染织物，其中，处理液包括120g/L的2,3-环氧丙基三甲基氯化铵与2,3-环氧丙基三乙基氯化铵的混合物(质量比为2:3)﹑30g/L均三嗪活性染料﹑10g/L氢氧化钠、150g/L尿素和余量的去离子水，其中汽蒸是指130℃饱和蒸汽汽蒸3min，皂洗包括如下 五个阶段：1)室温冲洗5min；2)50℃温水洗2min；3)4g/L皂洗剂D-301 98℃皂洗5min；4)40℃温水洗2min；5)室温冲洗3min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为20.3，固色率为89.8％。
实施例10
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在棉、麻和粘胶纤维混纺(质量比1:1:1)的织物上，保证织物带液率为60wt％，再将浸轧处理后的织物烘干后进行汽蒸，最后进行皂洗得到活性染料轧染织物，其中，处理液包括50g/L的3-氯-2-羟丙基三甲基氯化铵和3-氯-2-羟丙基三乙基氯化铵的混合物(质量比为1:1)﹑20g/L均三嗪活性染料﹑40g/L碳酸氢钠、50g/L尿素和余量的去离子水，其中汽蒸是指120℃饱和蒸汽汽蒸3min，皂洗包括如下五个阶段：1)室温冲洗5min；2)50℃温水洗5min；3)2g/L皂洗剂D-301 90℃皂洗10min；4)40℃温水洗5min；5)室温冲洗2min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为16.9，固色率为84.2％。
实施例11
一浴法阳离子改性活性染料染色的整理方法，使用浸轧的方式，将处理液整理在粘胶纤维、天丝和莫代尔混纺(质量比1:1:1)的织物上，保证织物带液率为100wt％，再将浸轧处理后的织物烘干后进行焙烘，最后进行皂洗得到活性染料轧染织物，其中，处理液包括90g/L_2-氯-4,6-二氨基-1,3,5-三嗪﹑N-二甲基氮杂环丁烷氯化物以及氯化胆碱的混合物(质量比为2:1:1)﹑20g/L嘧啶活性染料﹑30g/L碳酸钠、30g/L尿素和余量的去离子水，其中烘焙是指140℃焙烘2min，皂洗包括如下五个阶段：1)室温冲洗1min；2)60℃温水洗3min；3)3g/L皂洗剂D-301 96℃皂洗5min；4)60℃温水洗1min；5)室温冲洗1min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为15.8，固色率为82.8％。
实施例12
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在粘胶纤维、天丝和莫代尔混纺(质量比1:1:1)的织物上，保证织物带液率为70wt％，再将浸轧处理后的织物直接进行冷轧堆，最后进行皂洗得到活性染料轧染织物，其中，处理液包括70g/L_2-氯-4,6-二氨基-1,3,5-三嗪﹑N-二甲基氮杂环丁烷氯化物以及氯化胆碱的混合物(质量比为2:1:1)﹑5g/L均三嗪活性染料﹑20g/L碳酸氢钠、60g/L尿素和余量的去离子水，其中冷轧堆是指15℃堆置6h，皂洗包括如下五个阶段：1)室温冲洗1min；2)60℃温水洗3min；3)3g/L皂洗剂D-301 96℃皂洗5min；4)60℃温水洗1min；5)室温冲洗1min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为10.2，固色率为78.5％。
实施例13
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液吸附在棉织物上，保证织物带液率为90wt％，再将浸轧处理后的织物直接进行冷轧堆，最后进行皂洗得到活性染料轧染织物，其中，处理液包括90g/ L 3-氯-2-羟丙基三甲基氯化铵﹑15g/L膦酸型活性染料﹑40g/L碳酸钠、30g/L尿素和余量的去离子水，其中冷轧堆是指15℃堆置18h，皂洗包括如下五个阶段：1)室温冲洗1min；2)60℃温水洗3min；3)3g/L皂洗剂D-301 96℃皂洗5min；4)60℃温水洗1min；5)室温冲洗1min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为15.8，固色率为82.2％。
实施例14
一浴法阳离子改性活性染料染色的方法，使用浸轧的方式，将处理液整理在棉织物上，保证织物带液率为100wt％，再将浸轧处理后的织物烘干后进行冷轧堆，最后进行皂洗得到活性染料轧染织物，其中，处理液包括100g/L 3-氯-2-羟丙基三甲基氯化铵﹑30g/L嘧啶活性染料﹑60g/L氢氧化钠、100g/L尿素和余量的去离子水，其中冷轧堆是指25℃堆置16h，皂洗包括如下五个阶段：1)室 温冲洗3min；2)60℃温水洗3min；3)3g/L皂洗剂D-301 96℃皂洗5min；4)60℃温水洗1min；5)室温冲洗3min。
最终制得的活性染料轧染织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为21.9，固色率为90.1％。
实施例15
一浴法阳离子改性活性染料染色的方法，使用浸染的方式，粘胶纤维织物在一定温度的处理液中浸染一段时间，最后进行皂洗得到活性染料轧染织物，其中，处理液包括120g/L的3-氯-2-羟丙基三甲基氯化铵﹑30g/L嘧啶活性染料﹑60g/L氢氧化钠、30g/L尿素和余量的去离子水，其中浸染温度为90℃，时间为90min，皂洗包括如下五个阶段：1)室温冲洗1min；2)40℃温水洗3min；3)3g/L皂洗剂D-301 97℃皂洗3min；4)60℃温水洗3min；5)室温冲洗10min。
最终制得的活性染料染色织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为22.1，固色率为92.2％。
实施例16
一浴法阳离子改性活性染料染色的方法，使用浸染的方式，棉织物在一定温度的处理液中浸染一段时间，最后进行皂洗得到活性染料浸染织物，其中，处理液包括30g/L的氯化胆碱﹑10g/L嘧啶活性染料﹑10g/L碳酸钠、60g/L尿素和余量的去离子水，其中浸染温度为60℃，时间为30min，皂洗包括如下五个阶段：1)室温冲洗1min；2)40℃温水洗5min；3)3g/L皂洗剂D-301 97℃皂洗5min；4)60℃温水洗5min；5)室温冲洗10min。
最终制得的活性染料染色织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为11.1，固色率为81.2％。
实施例17
一浴法阳离子改性活性染料染色的方法，使用浸染的方式，棉织物在一定温度的处理液中浸染一段时间，最后进行皂洗得到活性染料浸染织物，其中，处理液包括90g/L的3-氯-2-羟丙基三甲基氯化铵﹑20g/L膦酸型活性染料﹑30g/L 氢氧化钠、90g/L尿素和余量的去离子水，其中浸染温度为75℃，时间为60min，皂洗包括如下五个阶段：1)室温冲洗3min；2)40℃温水洗3min；3)3g/L皂洗剂D-301 97℃皂洗5min；4)60℃温水洗5min；5)室温冲洗15min。
最终制得的活性染料染色织物用DataColor测试仪测试K/S值(K/S值代表织物表观得色量)，再测其固色率，测得最终制得的活性染料喷墨印花织物的K/S值为17.9，固色率为87.7％。

Claims (9)

  1. 一浴法阳离子改性活性染料染色的整理方法，其特征是：通过轧染或浸染工艺将含阳离子改性剂和活性染料的处理液整理在纤维素纤维织物上后进行皂洗得到活性染料染色织物，其中，采用轧染工艺时，纤维素纤维织物在进行皂洗前进行汽蒸、焙烘或冷轧堆；
    所述阳离子改性剂为分子结构中含有反应性基团和正电荷基团且数均分子量为100-30000的分子，其反应性基团为环氧基团、均三嗪、吡啶和烯烃中的一种或多种，正电荷基团包括季铵盐和氯化铵结构中的一种或多种。
  2. 根据权利要求1所述的整理方法，其特征在于，所述处理液包括10～150g/L阳离子改性剂﹑5～40g/L活性染料﹑10～70g/L碱剂、30～150g/L尿素和余量的去离子水。
  3. 根据权利要求1或2所述的整理方法，其特征在于，所述阳离子改性剂具体为2,3-环氧丙基三甲基氯化铵﹑2,3-环氧丙基三乙基氯化铵﹑3-氯-2-羟丙基三甲基氯化铵﹑3-氯-2-羟丙基三乙基氯化铵﹑一氯均三嗪型季铵盐化合物﹑氮杂环丁烷阳离子化合物、氯化胆碱和聚环氧氯丙烷胺化物中的一种或几种的混合物。
  4. 根据权利要求3所述的整理方法，其特征在于，所述活性染料为均三嗪﹑嘧啶、乙烯砜或膦酸型活性染料。
  5. 根据权利要求2所述的整理方法，其特征在于，所述碱剂为氢氧化钠﹑碳酸氢钠和碳酸钠中的一种或几种的混合物。
  6. 根据权利要求1所述的整理方法，其特征在于，轧染工艺的过程为：使用浸轧的方式对纤维素纤维织物进行轧染处理，保证织物带液率为60～100wt％；浸染工艺的过程为：使用浸染的方式对纤维素纤维织物进行处理，在60～90℃浸染30～90min。
  7. 根据权利要求6所述的整理方法，其特征在于，所述纤维素纤维织物包括棉、麻、黏胶纤维、天丝和莫代尔织物。
  8. 根据权利要求6所述的整理方法，其特征在于，所述汽蒸、焙烘或冷轧堆直接进行或者将浸轧处理后的织物烘干后进行。
  9. 根据权利要求8所述的整理方法，其特征在于，所述汽蒸是指100～180℃饱和蒸汽汽蒸1～15min；所述烘焙是指100～180℃焙烘1～15min；所述 冷轧堆是指在15～35℃堆置6～18h。
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