CN113123145A - Plant dyeing process for improving dyeing uniformity of protein fiber yarns - Google Patents
Plant dyeing process for improving dyeing uniformity of protein fiber yarns Download PDFInfo
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- CN113123145A CN113123145A CN202110440056.9A CN202110440056A CN113123145A CN 113123145 A CN113123145 A CN 113123145A CN 202110440056 A CN202110440056 A CN 202110440056A CN 113123145 A CN113123145 A CN 113123145A
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- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
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- D06P1/34—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 natural dyestuffs
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- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- D06P1/673—Inorganic compounds
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Abstract
The invention discloses a plant dyeing process for improving the dyeing uniformity of protein fiber yarns. Firstly, carrying out surface treatment on protein fiber yarns, then attaching and grafting waterborne Polyurethane (PU) and waterborne acrylate (PA) to the surfaces of the protein fiber yarns in an auxiliary mode to aminate carbon microspheres, then grafting dopamine on the surfaces of the secondarily pretreated protein fiber yarns, and finally carrying out treatment through a softening agent and a smoothing agent in the dyeing process. Compared with the prior art, the protein fiber yarn dyeing method has the advantages that after the protein fiber yarn is dyed, the yarn surface is softer, the dyeing uniformity is improved, and the color is not easy to fade after multiple times of washing.
Description
Technical Field
The invention relates to the technical field of dyeing, in particular to a plant dyeing process for improving the dyeing uniformity of protein fiber yarns.
Background
The protein fiber yarn fiber is a natural protein fiber with excellent wearability, is in a curled shape, and basically comprises spiral macromolecules formed by connecting alpha-amino acid by amido bonds, and protein macromolecules mainly form various levels of tissues in molecules by virtue of intermolecular disulfide bonds, salt bonds, hydrogen bonds and the like.
In the dyeing process of natural dyes, because the substantivity between the dyes and fibers is low, the dye-uptake is low, the dyeing fastness is poor, and the main dyeing method of the natural dyes which have great difference due to different types and structures of the natural dyes is a mordant method which is divided into a premedium, a homo-mordant and a post-mordant. The method is characterized in that the pre-medium method is to combine the fabric with a mordant before dyeing and then dye the fabric, and is suitable for dyeing light colors and medium and light colors, but the dyeing process is complex and the process time is long; the dyeing process by the same medium method is simplest and shortest in time, but the dye-uptake rate is not high; the latter medium method is that the fabric is combined with dye and then treated with mordant, and the dyeing rate is the highest and the change of color light of the dyed fabric is the least. The fabric is dyed by a mordant method, stable coordination bonds are formed among fibers, mordants and natural pigments, the dyeing fastness can be improved, and different mordants have different colors of the dyed fabric. However, the mordant dyeing method usually needs to use a metal mordant, which causes uneven dyeing and influences the dyeing quality of the protein fiber yarn.
Technical problem to be solved
Aiming at the defects of the prior art, the plant dyeing process for improving the dyeing uniformity of the protein fiber yarns is characterized in that nano porous carbon microspheres are grafted on the protein fiber yarn fibers through multi-section treatment of the protein fiber yarns, so that the channel and diffusion speed of dye molecules diffusing into the protein fiber yarn fibers are fundamentally increased, meanwhile, more active sites exist in the protein fiber yarn fibers through introduction of a dopamine-containing graft copolymer, a mordant is directionally trapped, the indirect dye molecules are uniformly distributed on the surfaces of the protein fiber yarns, finally, the dye molecules are firmly adsorbed on the surfaces of the protein fiber yarns through treatment of a softener smoothing agent, the phenomenon of cross color is not generated, and meanwhile, the damage of the protein fiber yarns is repaired. Meanwhile, the introduction of the porous carbon microspheres and the dopamine-containing fiber yarns has toughness and elasticity on the protein fiber yarns.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a dyeing process method for improving dyeing uniformity of a protein fiber yarn shirt comprises the following steps:
(1) grafting the nano carbon microspheres: adding water of a certain mass into the water-based polyurethane PU, the water-based acrylate PA and the aminated nano carbon microspheres according to the mass ratio, performing ultrasonic dispersion for 30min, and uniformly stirring for 60-120 min. And then adding the surface activated protein fiber yarn for treatment to prepare the grafted aminated nano carbon microsphere protein fiber yarn.
(2) Grafting dopamine: fully reacting the protein fiber yarn subjected to secondary pretreatment, dopamine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium hydrochloride and N-hydroxysuccinimide, washing with water and drying. And preparing the dopamine-grafted aminated nano carbon microsphere protein fiber yarn.
(3) Dyeing treatment: firstly, the plant dye is crushed and soaked before dyeing, so that the pigment of the dye has better solubility to water, the dye can be better dyed on the fabric, and for the dye which is difficult to dissolve in water, the dye can be extracted by repeatedly soaking for 1-2 times by using 95% ethanol solution. Secondly, adding the prepared dopamine-grafted aminated nano carbon microsphere protein fiber yarn and mordant treatment liquid into a dyeing device, and uniformly stirring, wherein the bath ratio is 1: 20-35, and pre-mediating for 30min at 70-90 ℃. Taking out the fabric, cleaning, putting the fabric into a plant dye aqueous solution, slowly heating to 130-150 ℃ at the heating rate of 1 ℃/min, dyeing for 40-60min, and taking out for washing. Fourthly, 0.1g/L neutral soaping agent 5N is used for soaping and drying at the temperature of 70 ℃).
(4) Flexible treatment: adding softening agent and smoothing agent, adjusting pH7, taking out, vacuum drying at 70-90 deg.C for 10-30min, cooling to room temperature, washing with water for 2-3 times, and vacuum drying at 40-60 deg.C.
Preferably, the water-based polyurethane PU, the water-based acrylate PA and the aminated nano carbon microspheres in the step (1) are mixed according to the mass ratio of 2: 1: 0.05-0.1
Preferably, in the step (1), the pH value is adjusted to be 6-7 by using a pH regulator, the treatment bath ratio of the activated protein fiber yarn is 1:20, the adding treatment time is 30-40min, and the treatment temperature is 45-55 ℃.
Preferably, in the step (2), the mass ratio of the protein fiber yarn, the dopamine 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium hydrochloride and the N-hydroxysuccinimide is 100:20:4:8-10, the bath ratio of the secondary pretreatment is 1: 40-1: 60, and the oscillation is carried out for 6-10 hours at the temperature of 40-50 ℃.
Preferably, the mass ratio of the protein fiber yarn, the mordant and the plant dye in the step (3) is 5:2: 4-8.
Preferably, the dyeing in the step (3) has pH of 4-6, bath ratio: 1:50, heating to 30-50 ℃, and dyeing for 1-3 hours in a heat preservation way.
Preferably, in the step (3), the content of the acidic dye is 35-40%, the content of the penetrating agent is 0.3-0.6%, and the content of the leveling agent is 1-3%. The penetrant is sodium sulfamate; the leveling agent is anhydrous sodium sulphate.
Preferably, the softening treatment in the step (4) has a pH of 7 and a treatment temperature of 30-50 ℃ for 15-30 min. Wherein the softening agent is amino silicone oil, the content of the softening agent is 2-5%, and the content of the smoothing agent is 3-10%.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
a plant dyeing process for improving the dyeing uniformity of protein fiber yarns is characterized in that grafted carbon microspheres with amino groups grafted on the surfaces are introduced to the surfaces of the protein fiber yarns, and carbonyl, carboxyl and the like exist; the groups and ammonium groups have Schiff base reaction or ammonolysis reaction, and simultaneously have rich pore structures, and the introduction of the groups can enhance the adsorption speed and the adsorption capacity of the protein fiber yarn to dye molecules, thereby fundamentally increasing the channel and the diffusion speed of dye molecules diffusing into the protein fiber yarn fibers.
A plant dyeing process for improving the dyeing uniformity of protein fiber yarns is characterized in that waterborne Polyurethane (PU) and waterborne acrylate (PA) are used for assisting in attaching and grafting aminated carbon microspheres to the surfaces of the protein fiber yarns, and the carbon microspheres can be uniformly distributed on the surfaces of the protein fiber yarns through the adhesion force and the chemical reaction of the surfaces of the carbon microspheres.
The plant dyeing process for improving the dyeing uniformity of the protein fiber yarns is characterized in that dopamine is grafted on the surfaces of the protein fiber yarns, the dopamine has good biocompatibility and biodegradability, and degradation products do not have any harmful effect on organisms and the environment. Catechol, polyfunctional amine and imine in the chemical structure can be used as the initial point of covalent bond modification and also can be used as anchor bolts of metal ions in a mordant, stable coordination bonds are formed among fibers, the mordant and natural pigments, the color fastness can be improved, and the aim of uniform dyeing can be achieved through the anchor bolt effect of dopamine.
The utility model provides a promote plant dyeing technology of protein fiber yarn dyeing homogeneity, the porous carbon microballon of grafting amino and dopamine own structure have certain intensity and toughness to protein fiber yarn protein fibre has certain repairing effect, make firm the adsorbing of dyestuff molecule on protein fiber yarn's surface not produce the phenomenon of cross color through the processing of softener and smoothing agent in the whole process design, repair the damage of protein fiber yarn simultaneously, and it is more smooth to have attached the feeling, and efficiency such as difficult balling-up.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: the dyeing process for improving the dyeing uniformity of the protein fiber yarn sweater comprises the following steps:
(1) grafting the nano carbon microspheres: adding water of a certain mass into the water-based polyurethane PU, the water-based acrylate PA and the aminated nano carbon microspheres according to the mass ratio, performing ultrasonic dispersion for 30min, and uniformly stirring for 60-120 min. And then adding the surface activated protein fiber yarn for treatment to prepare the grafted aminated nano carbon microsphere protein fiber yarn.
(2) Grafting and dopamine insertion: fully reacting the pretreated protein fiber yarn, dopamine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium hydrochloride and N-hydroxysuccinimide according to the mass ratio of 100:20:4:8-10, washing with water, and drying. In the prepared dopamine-grafted aminated nano carbon microsphere protein fiber yarn, the bath ratio is 1: 40-1: 60, the yarn is oscillated at 40-50 ℃ for 6-10 h, and the yarn is fully washed and dried. And preparing the dopamine-grafted aminated nano carbon microsphere protein fiber yarn.
(3) Dyeing treatment: firstly, the plant dye is crushed and soaked before dyeing, so that the pigment of the dye has better solubility to water, the dye can be better dyed on the fabric, and for the dye which is difficult to dissolve in water, the dye can be extracted by repeatedly soaking for 1-2 times by using 95% ethanol solution. Secondly, adding the prepared dopamine-grafted aminated nano carbon microsphere protein fiber yarn and mordant treatment liquid into a dyeing device, and uniformly stirring, wherein the bath ratio is 1: 20-35, and pre-mediating for 30min at 70-90 ℃. Taking out the fabric, cleaning, putting the fabric into a plant dye aqueous solution, slowly heating to 130-150 ℃ at the heating rate of 1 ℃/min, dyeing for 40-60min, and taking out for washing. And (4) soaping and drying at 70 ℃ by using 0.1g/L neutral soaping agent 5N (the mass ratio of the protein fiber yarn to the mordant to the vegetable dye is 5:2: 4-8).
(4) Flexible treatment: adding a softening agent and a smoothing agent, adjusting the pH value to 7, continuing heat preservation for 15-30 minutes, taking out, vacuum drying at 70-90 ℃ for 10-30 minutes, cooling to room temperature, washing for 2-3 times, and vacuum drying the protein fiber yarn sweater yarn at 40-60 ℃ (wherein the softening agent is amino silicone oil, the content of the softening agent is 2-5%, and the content of the smoothing agent is 3-10%).
Example 1
(1) The water-based polyurethane PU, the water-based acrylate PA and the aminated nano carbon microspheres are mixed according to the mass ratio of 2: 1: 0.05 adding water with a certain mass, ultrasonically dispersing for 30min, and uniformly stirring for 60 min. Adjusting pH to 6-7 with pH regulator at a bath ratio of 1:20, adding for 30min, and treating at 45 deg.C. And preparing the grafted aminated nano carbon microsphere protein fiber yarn.
(2) Fully reacting and washing the pretreated protein fiber yarn, dopamine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium hydrochloride and N-hydroxysuccinimide according to the mass ratio of 100:20:4:8, oscillating for 6 hours at 40 ℃ at the bath ratio of 1:40, fully washing and drying. And preparing the grafted aminated nano carbon microsphere protein fiber yarn containing the block graft copolymer.
(3) Dyeing: the madder plant dye is crushed and soaked before dyeing, so that the pigment of the dye has better solubility to water, the dye can be better dyed on the fabric, and for the dye which is difficult to dissolve in water, the dye can be extracted by repeatedly soaking for 1-2 times by using 95% ethanol solution. Secondly, adding the prepared dopamine-grafted aminated nano carbon microsphere protein fiber yarn and an alum treatment solution into a dyeing device, and uniformly stirring, wherein the bath ratio is 1:20, pre-medium at 70 ℃ for 30 min. Thirdly, the fabric is taken out and cleaned, is put into the plant dye water solution, is slowly heated to 130 ℃ at the heating rate of 1 ℃/min, is dyed for 40-60min and is taken out and washed. And (4) soaping and drying at 70 ℃ by using 0.1g/L neutral soaping agent 5N (the mass ratio of the protein fiber yarn to the alum to the madder plant dye is 5:2: 4).
(4) Flexible treatment: adding a softening agent and a smoothing agent, adjusting the pH value to 7, carrying out heat preservation treatment for 15-30 minutes, taking out, carrying out vacuum drying at 70 ℃ for 10-30 minutes, cooling to room temperature, washing for 3 times, and carrying out vacuum drying on the protein fiber yarn sweater thread at 40 ℃ (wherein the softening agent is amino silicone oil, the content of the softening agent is 2-5%, and the content of the smoothing agent is 3-10%).
Example 2
(1) The water-based polyurethane PU, the water-based acrylate PA and the aminated nano carbon microspheres are mixed according to the mass ratio of 2: 1: 0.07 adding water with certain mass, ultrasonically dispersing for 30min, and uniformly stirring for 80 min. Adjusting pH to 6-7 with pH regulator at a bath ratio of 1:20, adding for 35min, and treating at 50 deg.C. And preparing the grafted aminated nano carbon microsphere protein fiber yarn.
(2) Fully reacting and washing the pretreated protein fiber yarn, dopamine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium hydrochloride and N-hydroxysuccinimide according to a mass ratio of 100:20:4:9, oscillating for 8 hours at 40-50 ℃ at a bath ratio of 1:50, fully washing and drying. And preparing the grafted aminated nano carbon microsphere protein fiber yarn containing the block graft copolymer.
(3) Dyeing: firstly, the hematoxylin plant dye is crushed and soaked before dyeing, so that the pigment of the dye has better solubility to water, the dye can be better dyed on the fabric, and for the dye which is difficult to dissolve in water, the dye can be extracted by repeatedly soaking for 1-2 times by using 95% ethanol solution. Secondly, adding the prepared dopamine-grafted aminated nano carbon microsphere protein fiber yarn and the treating solution of the melanterite into a dyeing device, and uniformly stirring, wherein the bath ratio is 1: 25, pre-medium at 75 ℃ for 30 min. Thirdly, the fabric is taken out and cleaned, is put into the plant dye water solution, is slowly heated to 135 ℃ at the heating rate of 1 ℃/min, is dyed for 60min and is taken out and washed. And (iv) soaping and drying at 70 ℃ by using 0.1g/L neutral soaping agent 5N (the mass ratio of the protein fiber yarn to the copperas to the hematoxylin plant dye is 5:2: 5).
(4) Flexible treatment: adding a softening agent and a smoothing agent, adjusting the pH value of 7, adjusting the pH value of 7, continuously preserving heat for 20 minutes, taking out, vacuum drying for 20 minutes at 70-90 ℃, cooling to room temperature, washing for 2 times, and vacuum drying the protein fiber yarn sweater yarn at 40-60 ℃ (wherein the softening agent is amino silicone oil, the content of the softening agent is 2-5%, and the content of the smoothing agent is 3-10%).
Example 3
(1) The water-based polyurethane PU, the water-based acrylate PA and the aminated nano carbon microspheres are mixed according to the mass ratio of 2: 1: 0.08 adding water with a certain mass, ultrasonically dispersing for 30min, and uniformly stirring for 100 min. Adjusting pH to 7 with pH regulator at a bath ratio of 1:20, adding for 40min, and treating at 50 deg.C. And preparing the grafted aminated nano carbon microsphere protein fiber yarn.
(2) Fully reacting and washing the pretreated protein fiber yarn, dopamine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium hydrochloride and N-hydroxysuccinimide according to a mass ratio of 100:20:4:9, oscillating for 9 hours at 40-50 ℃ at a bath ratio of 1:50, fully washing and drying. And preparing the grafted aminated nano carbon microsphere protein fiber yarn containing the block graft copolymer.
(3) The gallnut plant dye is crushed and soaked before dyeing, so that the pigment of the dye has better solubility to water, the dye can be better dyed on the fabric, and the dye which is difficult to dissolve in water can be repeatedly soaked for 1-2 times by using 95% ethanol solution to extract the dye. Secondly, adding the prepared dopamine-grafted aminated nano carbon microsphere protein fiber yarn and a treatment solution into a dyeing device, and uniformly stirring, wherein the bath ratio is 1:40, pre-medium for 30min at 85 ℃. Thirdly, the fabric is taken out and cleaned, is put into the plant dye water solution, is slowly heated to 140 ℃ at the heating rate of 1 ℃/min, is dyed for 60min and is taken out and washed. And (4) soaping and drying at 70 ℃ by using 0.1g/L neutral soaping agent 5N (the mass ratio of the protein fiber yarn to the plant ash to the Chinese gall vegetable dye is 5:2: 6).
(4) Flexible treatment: adding a softening agent and a smoothing agent, adjusting the pH value to 7, continuing heat preservation for 30 minutes, taking out, vacuum drying for 30 minutes at 80 ℃, cooling to room temperature, washing for 3 times, and vacuum drying the protein fiber yarn sweater thread at 50 ℃ (wherein the softening agent is amino silicone oil, the content of the softening agent is 2-5%, and the content of the smoothing agent is 3-10%).
Example 4
(1) The water-based polyurethane PU, the water-based acrylate PA and the aminated nano carbon microspheres are mixed according to the mass ratio of 2: 1: 0.09 adding water with certain mass, ultrasonically dispersing for 30min, and uniformly stirring for 100 min. Adjusting pH to 7 with pH regulator at a bath ratio of 1:20, adding for 40min, and treating at 55 deg.C. And preparing the grafted aminated nano carbon microsphere protein fiber yarn.
(2) Fully reacting and washing the pretreated protein fiber yarn, dopamine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium hydrochloride and N-hydroxysuccinimide according to the mass ratio of 100:20:4:10, oscillating at 50 ℃ for 9 hours at the bath ratio of 1:50, fully washing and drying. And preparing the grafted aminated nano carbon microsphere protein fiber yarn containing the block graft copolymer.
(3) Firstly, the plant dye is crushed and soaked before dyeing, so that the pigment of the dye has better solubility to water, the dye can be better dyed on the fabric, and for the dye which is difficult to dissolve in water, the dye can be extracted by repeatedly soaking for 1-2 times by using 95% ethanol solution. Secondly, adding the prepared dopamine-grafted aminated nano carbon microsphere protein fiber yarn and the treating solution of the melanterite into a dyeing device, and uniformly stirring, wherein the bath ratio is 1: 45, pre-medium at 85 ℃ for 30 min. Thirdly, the fabric is taken out and cleaned, is put into the plant dye water solution, is slowly heated to 140 ℃ at the heating rate of 1 ℃/min, is dyed for 60min and is taken out and washed. And (4) soaping and drying at 70 ℃ by using 0.1g/L neutral soaping agent 5N (the mass ratio of the protein fiber yarn to the melanterite to the turmeric vegetable dye is 5:2: 7).
(4) Flexible treatment: adding a softening agent and a smoothing agent, adjusting the pH value to 7, continuing heat preservation for 30 minutes, taking out, vacuum drying for 30 minutes at 90 ℃, cooling to room temperature, washing for 3 times, and vacuum drying the protein fiber yarn sweater thread at 60 ℃ (wherein the softening agent is amino silicone oil, the content of the softening agent is 2-5%, and the content of the smoothing agent is 3-10%).
Example 5
(1) The water-based polyurethane PU, the water-based acrylate PA and the aminated nano carbon microspheres are mixed according to the mass ratio of 2: 1: 0.1 adding water with a certain mass, ultrasonically dispersing for 30min, and uniformly stirring for 120 min. Adjusting pH to 7 with pH regulator at a bath ratio of 1:20, adding for 40min, and treating at 55 deg.C. And preparing the grafted aminated nano carbon microsphere protein fiber yarn.
(2) Fully reacting and washing the pretreated protein fiber yarn, dopamine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium hydrochloride and N-hydroxysuccinimide according to the mass ratio of 100:20:4:10, oscillating for 10 hours at 450 ℃ at the bath ratio of 1:60, fully washing and drying. And preparing the grafted aminated nano carbon microsphere protein fiber yarn containing the block graft copolymer.
(3) Firstly, the indigo plant dye is crushed and soaked before dyeing, so that the pigment of the dye has better solubility to water, the dye can be better dyed on the fabric, and for the dye which is difficult to dissolve in water, the dye can be extracted by repeatedly soaking for 1-2 times by using 95% ethanol solution. Secondly, adding the prepared dopamine-grafted aminated nano carbon microsphere protein fiber yarn and an alum treatment solution into a dyeing device, and uniformly stirring, wherein the bath ratio is 1:50, pre-medium for 30min at 70-90 ℃. Thirdly, the fabric is taken out and cleaned, is put into the plant dye water solution, is slowly heated to 150 ℃ at the heating rate of 1 ℃/min, is dyed for 40-60min and is taken out and washed. And (4) soaping and drying at 70 ℃ by using 0.1g/L neutral soaping agent 5N (the mass ratio of the protein fiber yarn to the alum to the natural indigo plant dye is 5:2: 8).
(4) Flexible treatment: adding a softening agent and a smoothing agent, adjusting the pH value to 7, continuing heat preservation for 30 minutes, taking out, vacuum drying for 30 minutes at 90 ℃, cooling to room temperature, washing for 3 times, and vacuum drying the protein fiber yarn sweater thread at 60 ℃ (wherein the softening agent is amino silicone oil, the content of the softening agent is 2-5%, and the content of the smoothing agent is 3-10%).
Comparative example 1
(1) The water-based polyurethane PU, the water-based acrylate PA and the aminated nano carbon microspheres are mixed according to the mass ratio of 2: 1: 0.05 adding water with a certain mass, ultrasonically dispersing for 30min, and uniformly stirring for 60 min. Adjusting pH to 6 with pH regulator at a bath ratio of 1:20, adding for 30min, and treating at 45-55 deg.C. And preparing the grafted aminated nano carbon microsphere protein fiber yarn.
(2) The madder plant dye is crushed and soaked before dyeing, so that the pigment of the dye has better solubility to water, the dye can be better dyed on the fabric, and for the dye which is difficult to dissolve in water, the dye can be extracted by repeatedly soaking for 1-2 times by using 95% ethanol solution. Secondly, adding the prepared dopamine-grafted aminated nano carbon microsphere protein fiber yarn and an alum treatment solution into a dyeing device, and uniformly stirring, wherein the bath ratio is 1:20, pre-medium at 70 ℃ for 30 min. Thirdly, the fabric is taken out and cleaned, is put into the plant dye water solution, is slowly heated to 130 ℃ at the heating rate of 1 ℃/min, is dyed for 40min and is taken out and washed. And (4) soaping and drying at 70 ℃ by using 0.1g/L neutral soaping agent 5N (the mass ratio of the protein fiber yarn to the alum to the madder plant dye is 5:2: 4).
(3) Flexible treatment: adding a softening agent and a smoothing agent, adjusting the pH value to 7, continuing heat preservation for 15 minutes, taking out, vacuum drying at 70 ℃ for 10 minutes, cooling to room temperature, washing for 3 times, and vacuum drying the protein fiber yarn sweater thread at 40 ℃ (wherein the softening agent is amino silicone oil, the content of the softening agent is 2-5%, and the content of the smoothing agent is 3-10%).
Comparative example 2
(1) Fully reacting and washing the pretreated protein fiber yarn, dopamine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium hydrochloride and N-hydroxysuccinimide according to the mass ratio of 100:20:4:8, oscillating for 6 hours at 40 ℃ at the bath ratio of 1:40, fully washing and drying. And preparing the grafted aminated nano carbon microsphere protein fiber yarn containing the block graft copolymer.
(2) Dyeing: the madder plant dye is crushed and soaked before dyeing, so that the pigment of the dye has better solubility to water, the dye can be better dyed on the fabric, and for the dye which is difficult to dissolve in water, the dye can be extracted by repeatedly soaking for 1-2 times by using 95% ethanol solution. Secondly, adding the prepared dopamine-grafted aminated nano carbon microsphere protein fiber yarn and an alum treatment solution into a dyeing device, and uniformly stirring, wherein the bath ratio is 1:20, pre-medium at 70 ℃ for 30 min. Thirdly, the fabric is taken out and cleaned, is put into the plant dye water solution, is slowly heated to 130 ℃ at the heating rate of 1 ℃/min, is dyed for 40-60min and is taken out and washed. And (4) soaping and drying at 70 ℃ by using 0.1g/L neutral soaping agent 5N (the mass ratio of the protein fiber yarn to the alum to the madder plant dye is 5:2: 4).
(3) Flexible treatment: adding a softening agent and a smoothing agent, adjusting the pH value to 7, continuing heat preservation for 15-30 minutes, taking out, vacuum drying at 70 ℃ for 10 minutes, cooling to room temperature, washing for 3 times, and vacuum drying the protein fiber yarn sweater thread at 40 ℃ (wherein the softening agent is amino silicone oil, the content of the softening agent is 2-5%, and the content of the smoothing agent is 3-10%).
The results of the effect test of the examples and the comparative examples after dyeing the protein fiber yarn are as follows:
the inventor obtains through a large amount of experiments that this method can master the more even of dyestuff diffusion, when the dyestuff dyes on the protein fiber yarn, can not destroy the softness of protein fiber yarn, can make protein fiber yarn keep original softness, can not become stiff, and can not fade through washing many times.
In conclusion, the dyeing method can enable the dye to be softer, and after the protein fiber yarn is dyed, the surface of the protein fiber yarn is softer and is not easy to fade.
The above is only one embodiment of the present invention, and it should be noted that, for those skilled in the art, several similar modifications and improvements can be made without departing from the inventive concept of the present invention, and these should also be considered as within the protection scope of the present invention.
Claims (10)
1. A plant dyeing method for improving the dyeing uniformity of protein fiber yarns is characterized by comprising the following steps:
(1) grafting the nano carbon microspheres: adding the waterborne polyurethane PU, the waterborne acrylate PA and the aminated nano carbon microspheres into water with certain mass, ultrasonically dispersing for 30min, and uniformly stirring for 60-120 min; then adding the protein fiber yarn with activated surface to prepare grafted aminated nano carbon microsphere protein fiber yarn;
(2) grafting dopamine: carrying out secondary surface activation pretreatment on the protein fiber yarn in the step (1), then fully reacting with dopamine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium salt and N-hydroxysuccinimide, washing with water, and drying to prepare the protein fiber yarn containing the dopamine grafted aminated nano carbon microsphere;
(3) dyeing treatment: crushing and soaking the plant dye before dyeing, and repeatedly soaking the dye which is insoluble in water for 1-2 times by using a 95% ethanol solution to extract the dye; adding the dopamine-containing grafted aminated nano carbon microsphere protein fiber yarn prepared in the step (2) and mordant treatment liquid into a dyeing device, and uniformly stirring, wherein the bath ratio is 1: 20-35, pre-medium for 30min at 70-90 ℃; taking out the fabric, cleaning, putting the fabric into a plant dye aqueous solution, slowly heating to 130-150 ℃ at the heating rate of 1 ℃/min, dyeing for 40-60min, and taking out for washing; fourthly, 0.1g/L neutral soaping agent 5N is used for soaping and drying at 70 ℃;
(4) flexible treatment: adding softening agent and smoothing agent, adjusting pH to 7, treating at 30-50 deg.C for 15-30min, taking out, vacuum drying at 70-90 deg.C for 10-30min, cooling to room temperature, washing with water for 2-3 times, and vacuum drying at 40-60 deg.C.
2. The plant dyeing method for improving dyeing uniformity of protein fiber yarns according to claim 1, wherein the preparation of the aminated nano carbon microspheres in the step (1) specifically comprises the following steps: placing the nano carbon microspheres with the particle size of 5-10nm into liquid-phase ammonium persulfate with the concentration of 30-50%, and soaking for 2 h at 25 ℃ to obtain the aminated nano carbon microspheres.
3. The plant dyeing method for improving the dyeing uniformity of the protein fiber yarn according to claim 1, wherein the method for treating the protein fiber yarn with the activated surface in the step (1) specifically comprises the following steps: weighing 3-6% of protease by mass, putting into water, adjusting pH to 6-7, putting into protein fiber yarn for treatment at a bath ratio of 1:20, and treating at 45-55 deg.C for 30-40min to obtain surface activated protein fiber yarn.
4. The plant dyeing method for improving dyeing uniformity of protein fiber yarns according to claim 1, wherein the mass ratio of the aqueous polyurethane PU, the aqueous acrylate PA and the aminated nano carbon microspheres in the step (1) is 2: 1: 0.05-0.1.
5. The plant dyeing method for improving dyeing uniformity of protein fiber yarns according to claim 1, wherein the method for performing secondary surface activation pretreatment on the protein fiber yarns in the step (2) specifically comprises the following steps: weighing 7-10% of protease by mass, putting into water, adjusting pH to 6-7, adding the grafted aminated nano carbon microsphere protein fiber yarn at a bath ratio of 1:30, and treating at 55-65 deg.C for 60-120 min.
6. The plant dyeing method for improving dyeing uniformity of protein fiber yarns according to claim 1, wherein in the step (2), the mass ratio of the protein fiber yarns, dopamine 1-ethyl- (3-dimethylaminopropyl) carbodiimide sodium hydrochloride and N-hydroxysuccinimide is 100:20:4:8-10, the bath ratio is 1: 40-1: 60, and the plant dyeing method is oscillated at 40-50 ℃ for 6-10 hours.
7. The plant dyeing method for improving dyeing uniformity of protein fiber yarns according to claim 1, wherein the mass ratio of the protein fiber yarns, the mordant and the plant dye in the step (3) is 5:2: 4-8.
8. The plant dyeing method for improving dyeing uniformity of protein fiber yarns according to claim 1, wherein in the step (3), the dyeing pH is 4-6, the bath ratio is 1:50, the temperature is increased to 30-50 ℃, and the temperature is kept for dyeing for 1-3 hours.
9. The plant dyeing method for improving dyeing uniformity of protein fiber yarns according to claim 1, wherein in the step (3), the content of the acidic dye is 35-40%, the content of the penetrating agent is 0.3-0.6%, the content of the leveling agent is 1-3%, the penetrating agent is sodium sulfamate, and the leveling agent is anhydrous sodium sulphate.
10. The plant dyeing method for improving dyeing uniformity of protein fiber yarns according to claim 1, wherein the softening agent in the step (4) is amino silicone oil, the content of the softening agent is 2-5%, and the content of the smoothing agent is 3-10%.
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