CN110735333B - Novel dyeing-color fixing method of micromolecular natural dye - Google Patents
Novel dyeing-color fixing method of micromolecular natural dye Download PDFInfo
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- CN110735333B CN110735333B CN201911103977.5A CN201911103977A CN110735333B CN 110735333 B CN110735333 B CN 110735333B CN 201911103977 A CN201911103977 A CN 201911103977A CN 110735333 B CN110735333 B CN 110735333B
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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
- 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
- D06P1/34—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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- 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
- D06P1/0032—Determining dye recipes and dyeing parameters; Colour matching or monitoring
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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
- 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
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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
- 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
- D06P1/67383—Inorganic compounds containing silicon
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Abstract
The invention belongs to the technical field of textile printing and dyeing, and particularly relates to a dyeing-color fixing method of a micromolecular natural dye. Because the micromolecule natural dye has low molecular weight and lacks groups combined with fibers, the micromolecule natural dye cannot be fixed on the fibers and only can float on the surface, and the micromolecule natural dye can fade after being simply soaped, so that direct dyeing cannot be realized. The method introduces soluble quantum dots into the dyeing bath of the micromolecular natural dye, utilizes the quantum dots to influence the dyeing process of the micromolecular natural dye, and changes the aggregation state of the dye, thereby improving the fixation of the dye on the fabric, reducing the color fading and further improving the color fastness of the dye on the fabric.
Description
Technical Field
The invention belongs to the technical field of textile printing and dyeing, relates to a dyeing method of natural dye, and particularly relates to a novel dyeing-color fixing method of micromolecular natural dye.
Background
Natural dyes have gained popularity in recent years due to their natural, environmentally friendly characteristics. However, natural plant dyes have poor affinity to fibers, are difficult to dye, have poor color fastness indexes, and are also important reasons for replacing natural dyes with synthetic dyes. The micromolecule natural dye can hardly be directly dyed on the fiber, and the mordant dyeing technology is mainly used, namely, the action mode of the micromolecule natural dye and the fiber is changed by utilizing metal ion complexation, so that the mordant dyeing of the natural dye is carried out. The mordant dyeing mode of natural dye can be divided into front mordant, back mordant and one-bath.
At present, mordants with excellent properties such as chromium, copper and the like can not/can not be used on textiles due to ecological environment protection requirements, namely prohibition/limitation of heavy metal ions. Thus, scientists are also improving the fastness of natural dyes on fabrics by using non-banned metal dye mediators or developing new methods. For example, the Chinese patent CN109235076A Natural dye dyeing technology for Cashmere fabrics adopts the mode of alum one-bath mordanting and protein derivative adding to improve the natural dye dyeing technology for Cashmere fabrics, the dye solution comprises the protein derivative and a plurality of surfactants besides aluminum metal ions, 1, 6-hexanediol is added during dyeing, and the temperature is kept for 40-60 min, and the process steps are more. The Chinese patent CN109056392A, a dyeing method of natural dye, adopts a method of firstly plasma and then padding chitosan solution to improve the dyeing fastness and depth of natural dye and textile, needs a low-temperature plasma treatment instrument, and is not suitable for industrialized popularization. In patent CN108589334A, liquid ammonia is used as a medium in the preparation of deep-color cellulose dyed by natural vegetable dye, the natural vegetable dye is added into the liquid ammonia, and color fixing treatment is carried out in a color fixing agent-silicon-based non-aqueous medium mixed system after dyeing of the cellulose fiber. The production process has high requirements on equipment and is extremely complex. In patent CN104088167A, namely a method for improving color depth and light fastness of natural dye dyed fabric, polyvinylpyrrolidone is treated on the surface of the fabric, and nanometer ZnO is generated in situ after dyeing, so that the color depth and the light fastness of the natural dye dyed fabric are improved, but the process is too complex and difficult to control.
The rapid development of nanotechnology in recent years has led to the application of natural dyes in two directions: the first is in the direction of sensitized cells, such as patent CN103280325A sensitized solar cells based on natural organic dyes and ZnO single crystal nano arrays. Secondly, by utilizing the fluorescence effect, organic dye molecules (ruthenium or osmium complexes) are doped in the monodisperse silicon dioxide nanospheres and are used for preparing a fluorescence probe for marking, for example, the invention patent CN101457139A utilizes the photoelectric conversion effect of polypyrrole complexes of VIII group metals; zhu et al (Zhu L, Yin Y, Wang C F, et al. journal of Materials Chemistry C,2013,1(32),4925.) A carbon dot solution synthesized from plant leaves is added to an ink jet printer as an ink to draw a pattern, and an image can be clearly seen under ultraviolet rays, and also the fluorescence color developing property thereof is utilized. The application of the ultra-small quantum dots in small molecular natural dyes to dye fibers changes the dyeing property of the fibers, and no report is found at present.
Disclosure of Invention
The invention aims to provide a novel dyeing-color fixing method of micromolecular natural dye, which can improve the dye uptake and the color fastness of the micromolecular natural dye.
Natural small molecular dye due to its molecular weightLow, small molecule, and lack of groups combined with fiber, can not fix on fiber, can only float on fiber, will fade with simple soaping, therefore can not dye directly. Testing K/S values of the dyed fabrics/fibers before and after soaping by using a computer testing color matching instrument, and calculating the retention rate N of the K/S values by using a formula (1)K/SBy NK/STo characterize the fading of the fabric/fiber during dyeing.
The water-soluble quantum dot is a nano-grade particle, can be divided into carbon quantum dot and silicon carbon quantum dot according to the source, has the size less than 10nm, and can form a stable solution in water, and active groups (amino, hydroxyl, carboxyl and the like) point to a water phase. By the action of the dye and the natural dye with small molecules, the original single or small amount of associated dye small molecules can be gathered to form dye aggregates with larger size. The dye is not easy to fall off from the fiber due to the change of the aggregation state while the property of the dye is not changed.
The technical scheme adopted for solving the technical problems is that water-soluble quantum dots (carbon quantum dots and silicon-carbon quantum dots) are introduced into a dyeing bath of micromolecular natural dye, the micromolecular natural dye is influenced to be dyed by the water-soluble quantum dots, and the aggregation state of the dye is changed, so that the fixation of the dye on the fabric is improved, the fading is reduced, and the color fastness of the dye on the fabric is improved.
The dyeing-fixing method provided by the invention can be used for treating the water-soluble quantum dots and the micromolecular natural dye in one bath; the fabric/fiber can be treated by adopting water-soluble quantum dots, and then dyed by micromolecular natural dye; the method can be that the micromolecule natural dye firstly dyes the fabric/fiber, and then the dyed fiber is treated by the water-soluble quantum dots.
The specific method and the formula are as follows:
one-bath method: adding the water-soluble quantum dot solution into the micromolecular natural dye solution, mixing uniformly to prepare dye solution, and dyeing the fabric/fiber.
The dyeing formula is as follows: the bath ratio is 1: 10-50; dyeing temperature is 40-80 ℃; dyeing time is 5-60 min; soaping, washing and drying to obtain a dyeing sample.
The pretreatment method comprises the following steps: firstly, the fabric/fiber is treated by water-soluble quantum dot solution, and then the small molecular natural dye is dyed.
The pretreatment formula comprises: the bath ratio is 1: 10-50; the treatment temperature is 20-30 ℃; the treatment time is 1-5 min; and (5) wringing.
The dyeing formula comprises the following components: the bath ratio is 1: 10-50; dyeing temperature is 40-80 ℃; dyeing time is 5-60 min; soaping, washing and drying to obtain a dyeing sample.
③ the post-processing method: firstly, dyeing by using micromolecular natural dye, and then treating the dyed fabric/fiber by using a water-soluble quantum dot solution.
The dyeing formula comprises the following components: the bath ratio is 1: 10-50; dyeing temperature is 40-80 ℃; dyeing time is 5-60 min; and (5) wringing.
The post-treatment formula comprises: the bath ratio is 1: 10-50; the treatment temperature is 20-30 ℃; the treatment time is 1-5 min; soaping, washing and drying to obtain a dyeing sample.
Compares the K/S retention rate N after soaping in the dyeing process in the three methodsK/SWherein the one-bath dyeing is NK/SMore than 80 percent, and the color and luster before and after the color and luster are not obviously changed. Pretreatment dyeing NK/SMore than 70 percent, and the color and luster before and after the color and luster are not obviously changed. Method of post-dyeing treatment NK/SMore than 50 percent, and the color changes from front to back.
The method of the invention selects one-bath dyeing preferentially, the water-soluble quantum dot solution is added into the micromolecule natural dye solution, and the mixture is mixed evenly to prepare dye liquor for dyeing the fabrics/fibers.
The dyeing formula is as follows: the bath ratio is 1: 10-50; dyeing temperature is 40-80 ℃; dyeing time is 5-60 min; soaping, washing and drying to obtain a dyeing sample.
The quantum dot solution provided by the invention is a water-soluble quantum dot solution, the solubility of the quantum dot solution in water is good, and the size of the quantum dot is less than 10 nm. The carbon quantum dot solution or the silicon-carbon quantum dot solution can be used.
The carbon quantum dot solution provided by the invention is prepared by the following specific steps: mixing sodium citrate or sodium ascorbate with an alkaline agent, reacting at 150-200 ℃ for 1-5h, cooling to room temperature, purifying, performing ultrafiltration, and adding deionized water to dilute by 0-50 times according to volume.
Wherein the alkaline agent is sodium hydroxide, ammonium bicarbonate or urea. The molar ratio of the alkaline agent to the sodium citrate or the sodium ascorbate is 1:20-30
The silicon-carbon quantum dot solution provided by the invention is prepared by the following specific steps: hydrolyzing the silane coupling agent in water at 50-60 ℃ for 20-50 min, then adding a reducing agent, stirring for 30-50 min, and adding deionized water to dilute by 0-50 times according to volume.
Wherein the molar ratio of the silane coupling agent to the reducing agent is 50-20: 1. The related silane coupling agent is one or a mixture of more than two of KH550 (gamma-aminopropyltriethoxysilane), KH560 (gamma-glycidoxypropyltrimethoxysilane) and KH570 (gamma-methacryloxypropyltrimethoxysilane). The reducing agent is one of ascorbic acid, sodium ascorbate, citric acid and sodium citrate.
The micromolecular natural dye has the molecular weight of less than 500, lacks a group directly dyed with fabrics/fibers in the structure, can obtain relatively stable color through metal medium complexation, is difficult to directly dye on the fabrics/fibers, and is particularly characterized in that the direct dyeing is all loose color, and the K/S value retention rate N after the soap washing is dyedK/SLess than 20%, and discoloration was severe.
The micromolecule natural dye provided by the invention is derived from natural plant extracts and can be one of sappan wood extracts (mainly containing hematoxylin and hematoxylin oxide), madder extracts (mainly containing alizarin), honeysuckle extracts (mainly containing luteolin) and tea extracts (mainly containing catechin). The fabric/fiber can be real silk, wool, or real silk wool blended fabric, or real silk wool interwoven fabric.
The invention has the beneficial effects that:
(1) the micromolecule natural dye can be dyed on the fabric/fiber without using metal medium ions,K/S retention ratio NK/SHigher and more stable color and luster obtained by dyeing.
(2) The chemicals related in the scheme provided by the invention only contain carbon, silicon and oxygen elements or sodium elements, and are ecological and environment-friendly.
(3) The dyeing-color fixing process provided by the invention is similar to the metal mordant dyeing method in operation, additional equipment and process are not needed, workers are not needed to be trained, and the industrial popularization is facilitated.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
Silicon carbon quantum dot solution 1
The molar ratio of KH550 to ascorbic acid is 50: 1. Hydrolyzing silane coupling agent KH550 (industrial product) in deionized water at 50 deg.C for 20min, adding reducing agent ascorbic acid, and stirring for 30 min. Preparing the silicon-carbon quantum dot solution 1, wherein the particle size of the quantum dot is 2.2 +/-0.4 nm.
Silicon carbon quantum dot solution 2
The molar ratio of KH560 to sodium ascorbate was 42: 1. Hydrolyzing silane coupling agent KH560 (industrial product) in 55 deg.C water for 50min, adding reducing agent sodium ascorbate, stirring for 50min, adding deionized water to dilute the solution to 20 times of original volume to obtain silicon-carbon quantum dot solution 2 with quantum dot particle size of 1.8 + -0.4 nm.
Silicon carbon quantum dot solution 3
The molar ratio of the silane coupling agent KH570 to the citric acid was 35: 1. Hydrolyzing silane coupling agent KH570 (industrial product) in 60 deg.C water for 30min, adding reducing agent citric acid, stirring for 40min, and adding deionized water to dilute the solution to 31 times of original volume. Preparing the silicon-carbon quantum dot solution 3, wherein the particle size of the quantum dot is 1.5 +/-0.4 nm.
Silicon carbon quantum dot solution 4
The molar ratio is as follows: KH 570: KH 560: sodium citrate 10:10: 1. Hydrolyzing silane coupling agent KH570 (industrial product) in water at 57 deg.C for 39min, adding reducing agent sodium citrate, stirring for 35min, adding deionized water to dilute the solution to 51 times of the original volume, wherein the particle size of the quantum dot is 2.6 + -0.4 nm.
Carbon quantum dots 1
Mixing sodium citrate and ammonium bicarbonate, reacting at 150 ℃ for 5h, cooling to room temperature, purifying, ultrafiltering by using a dialysis bag, and adding deionized water to dilute to 11 times of the original volume. The molar ratio is as follows: sodium citrate: ammonium bicarbonate 30: 1. The quantum dot particle size is less than 10 nm.
Carbon quantum dots 2
Mixing sodium citrate and ammonium bicarbonate, reacting at 200 ℃ for 1h, cooling to room temperature, purifying, performing ultrafiltration by using an ultrafiltration membrane, and adding deionized water to dilute to 26 times of the original volume. The molar ratio is as follows: sodium citrate: ammonium bicarbonate 20: 1. The particle size of the quantum dots is less than 10 nm.
Example 2
Small molecule natural dyes: lignum sappan extract (hematoxylin and hematoxylin oxide as main ingredients)
Fabric: two pieces of real silk woven fabric
Adding the silicon-carbon quantum dot solution 1 (the quantum dot stock solution prepared in example 1) into a hematoxylin dye solution, mixing uniformly to prepare a dye solution, and dyeing the fabric.
The dyeing formula is as follows:
the concentration of the hematoxylin dye is 0.5g/L, the concentration of the silicon-carbon quantum dots is 0.5g/L, and the bath ratio is 1: 10; the dyeing temperature is 40 ℃; dyeing for 10min to obtain two fabrics 1 and 2.
Drying the fabric 1, measuring the K/S value of 1.4014, and determining the color characteristic value: l64.23, a 19.55, b 17.78;
soaping, washing and drying the fabric 2, measuring the K/S value of the fabric to be 1.364, and measuring the color characteristic value: l64.47, a 19.18, b 17.59.
Retention ratio of K/S N after washing with dyeing soapK/S97% and no change in color before and after.
Comparative example 1
Direct dyeing with small molecular natural dye (without silicon carbon quantum dots and other substances)
Small molecule natural dyes: lignum sappan extract (hematoxylin and hematoxylin oxide as main ingredients)
Fabric: two pieces of real silk woven fabric
The dyeing formula is as follows:
the concentration of the hematoxylin dye is 0.5g/L, and the bath ratio is 1: 10; the dyeing temperature is 40 ℃; dyeing for 10min to obtain two fabrics 3 and 4.
Drying the fabric 3, measuring the K/S value of 1.4961, and determining the color characteristic value: l76.49, a 11.66, b 37.98;
soaping, washing and drying the fabric 4, measuring the K/S value of the fabric to be 0.1905, and measuring the color characteristic value: l82.64, a 6.17, b 6.71.
Retention ratio of K/S N after washing with dyeing soapK/S13 percent and the color change before and after the color change is obvious.
Comparative example 2
Dyeing with small molecular natural dye coupling agent (adding coupling agent KH550)
Small molecule natural dyes: lignum sappan extract (hematoxylin and hematoxylin oxide as main ingredients)
Fabric: two pieces of real silk woven fabric
The dyeing formula is as follows:
the concentration of the hematoxylin dye is 0.5g/L, the coupling agent KH5500.5g/L and the bath ratio is 1: 10; the dyeing temperature is 40 ℃; dyeing for 10min to obtain two fabrics 5 and 6 with colored film on the surface.
Drying the fabric 5, carrying out color spot, measuring the K/S value of 1.9866, and carrying out color characteristic value: l54.8, a 20.42, b 9.39;
6 soaping, washing, drying, having color spots and uneven color distribution, measuring the K/S value of 1.1665, and obtaining the color characteristic value: l64.52, a 23.22, b 9.66.
Comparative example 2'
Micromolecular natural dye chitosan dyeing
Preparing a chitosan solution (with glacial acetic acid as a solvent) with the mass percentage concentration of 1 percent
Small molecule natural dyes: lignum sappan extract (hematoxylin and hematoxylin oxide as main ingredients)
Fabric: two pieces of real silk woven fabric
Adding the chitosan solution into the hematoxylin dye solution, mixing uniformly to prepare dye solution, and dyeing the fabric.
The dyeing formula is as follows:
the concentration of the hematoxylin dye is 0.5g/L, the concentration of the chitosan is 0.5g/L, and the bath ratio is 1: 10; the dyeing temperature is 40 ℃; dyeing for 10min to obtain two fabrics 7 and 8.
Drying the fabric 7, measuring the K/S value of 2.037, and determining the color characteristic value: l66.95, a 8.96, b 29.57;
soaping, washing and drying the fabric 8, measuring the K/S value of the fabric to be 1.0032, and measuring the color characteristic value: l80.72, a 7.12, b 21.75.
Retention ratio of K/S N after washing with dyeing soapK/S49 percent and more obvious color change before and after.
Example 3
Small molecule natural dyes: radix Rubiae extract (alizarin as main ingredient)
Fabric: two pieces of wool knitted fabric
The carbon quantum dot solution 1 (the diluted quantum dot solution in example 1) is used for treating wool fabric, and then the wool fabric is added into the madder dye solution for dyeing.
The pretreatment formula comprises: the concentration of the carbon quantum dots is 1g/L, and the bath ratio is 1: 10; the treatment temperature is 20 ℃; the treatment time is 1 min; and (5) wringing.
The dyeing formula comprises the following components: the concentration of the madder dye is 1g/L, and the bath ratio is 1: 20; the dyeing temperature is 50 ℃; dyeing time is 30 min; two pieces of fabric 9, 10 are obtained.
Drying the fabric 9, measuring the K/S value of 1.8763, and determining the color characteristic value: l61.42, a 18.48, b 22.27;
soaping, washing and drying the fabric 10, measuring the K/S value of the fabric to be 1.4264, and measuring the color characteristic value: l63.07, a 15.04, b 18.42.
Retention ratio of K/S N after washing with dyeing soapK/S76% and no obvious change in color before and after.
Comparative example 3
Small molecule natural dyes: radix Rubiae extract (alizarin as main ingredient)
Fabric: two pieces of wool knitted fabric
The dyeing formula without adding carbon quantum dots is as follows:
the concentration of the madder dye is 1g/L, and the bath ratio is 1: 20; the dyeing temperature is 50 ℃; dyeing for 30min to obtain two fabrics 11 and 12.
Drying the fabric 11, measuring the K/S value of 1.5442, and determining the color characteristic value: l74.18, a 12.46, b 30.53;
soaping, washing and drying the fabric 12, measuring the K/S value of the fabric to be 0.2007, and measuring the color characteristic value: l70.32, a 14.50, b 23.41.
Retention ratio of K/S N after washing with dyeing soapK/S13 percent and the color change before and after the color change is obvious.
Example 4
Small molecule natural dyes: flos Lonicerae extract (luteolin as main ingredient)
Fabric: two wool tops
Wool tops were treated with the honeysuckle dye and then treated with carbon quantum dot solution 2 (diluted quantum dot solution from example 1).
The dyeing formula comprises the following components: 2g/L of honeysuckle dye, and the bath ratio is 1: 50; the dyeing temperature is 80 ℃; dyeing time is 30 min; and (5) wringing.
The post-treatment formula comprises: the concentration of the carbon quantum dots 2 is 2g/L, and the bath ratio is 1: 50; the treatment temperature is 30 ℃; the treatment time is 5 min; two wool tops 13, 14 are obtained.
Drying the wool tops 13, measuring the K/S value of the wool tops to be 2.3028, and determining the color characteristic value: l81.49, a 0.66, b 13.98;
soaping the wool top 14, washing with water, drying, measuring the K/S value of 1.2205, and measuring the color characteristic value: l82.31, a 0.73, b 13.79.
Retention ratio of K/S N after washing with dyeing soapK/S53 percent, and the color of the front and the back is not obviously changed.
Comparative example 4
Small molecule natural dyes: flos Lonicerae extract (luteolin as main ingredient)
Fabric: two wool tops
The dyeing formula without adding carbon quantum dots is as follows:
the concentration of the honeysuckle dye is 2g/L, and the bath ratio is 1: 50; the dyeing temperature is 80 ℃; dyeing time is 30 min; two pieces of fabric 15, 16 are obtained.
Drying the fabric 15, measuring the K/S value of 1.7961, and determining the color characteristic value: l76.56, a 2.71, b 15.36;
washing 16 fabrics with soap, washing with water, drying, measuring the K/S value of 0.2905, and measuring the color characteristic value: l72.31, a 0.54, b 14.12.
Retention ratio of K/S N after washing with dyeing soapK/S16 percent and the color change before and after the color change is obvious.
Example 5
Small molecule natural dyes: tea extract (catechin as main ingredient)
Fabric: two parts of silk yarn
Adding the silicon-carbon quantum dot solution 2 (the diluted quantum dot solution in the embodiment 1) into the tea dye solution, mixing uniformly to prepare a dye solution, and dyeing the real silk yarns.
The dyeing formula is as follows:
the concentration of the tea dye is 3g/L, the concentration of the silicon-carbon quantum dots is 2g/L, and the bath ratio is 1: 50; the dyeing temperature is 80 ℃; dyeing time is 40min, and two parts of yarns 17 and 18 are obtained.
Drying the yarn 17, measuring the K/S value of 3.1015, and determining the color characteristic value: l55.06, a 18.87, b 6.1;
soaping the yarn 18, washing with water, drying, measuring the K/S value of 2.9770, and measuring the color characteristic value: l55.47, a 19.18, b 6.59.
Retention ratio of K/S N after washing with dyeing soapK/S96% and no change in color before and after.
Comparative example 5
Small molecule natural dyes: tea extract (catechin as main ingredient)
Fabric: two parts of silk yarn
The dyeing formula is as follows without adding silicon-carbon quantum dots:
the concentration of the tea dye is 3g/L, and the bath ratio is 1: 50; the dyeing temperature is 80 ℃; dyeing time 40min, two yarns 19, 20 are obtained.
Drying the yarn 19, measuring the K/S value of 2.8437, and determining the color characteristic value: l53.76, a 16.33, b 7.80;
and (3) soaping, washing and drying the yarn 20, measuring the K/S value of the yarn to be 0.2559, and measuring the color characteristic value: l40.91, a 7.42, b 7.55.
Retention of K/S after dyed soapingNK/S9 percent and more obvious color change before and after.
Example 6
Small molecule natural dyes: lignum sappan extract (hematoxylin and hematoxylin oxide as main ingredients)
Fabric: weaving two pieces of silk and wool blended machine
Adding the silicon-carbon quantum dot solution 3 (the diluted quantum dot solution in the embodiment 1) into the hematoxylin dye solution, mixing uniformly to prepare dye solution, and dyeing the fabric.
The dyeing formula is as follows:
the concentration of the hematoxylin dye is 0.5g/L, the concentration of the silicon-carbon quantum dots is 3g/L, and the bath ratio is 1: 30; the dyeing temperature is 60 ℃; dyeing for 5min to obtain two fabrics 21 and 22.
Drying the fabric 21, measuring the K/S value of 2.1014, and determining the color characteristic value: l75.05, a 14.27, b 16.97;
soaping the fabric 22, washing with water, drying, measuring the K/S value of 2.0173, and measuring the color characteristic value: l74.71, a 15.56, b 16.39.
Retention ratio of K/S N after washing with dyeing soapK/S96% and no change in color before and after.
Comparative example 6
Small molecule natural dyes: lignum sappan extract (hematoxylin and hematoxylin oxide as main ingredients)
Fabric: weaving two pieces of silk and wool blended machine
The dyeing formula is as follows without adding silicon-carbon quantum dot solution:
the concentration of the hematoxylin dye is 0.5g/L, and the bath ratio is 1: 30; the dyeing temperature is 60 ℃; dyeing time is 5min, and two fabrics 23 and 24 are obtained.
Drying the fabric 23, measuring the K/S value of 1.9481, and determining the color characteristic value: l73.61, a 16.92, b 15.34;
soaping the fabric 24, washing with water, drying, measuring the K/S value of 0.2013, and measuring the color characteristic value: l54.24, a 15.63, b 17.90.
Retention ratio of K/S N after washing with dyeing soapK/S10 percent and the color change before and after the color change is obvious.
Example 7
Small molecule natural dyes: lignum sappan extract (hematoxylin and hematoxylin oxide as main ingredients)
Fabric: two blocks of true silk skein
Adding the silicon-carbon quantum dot solution 4 (the diluted quantum dot solution in the embodiment 1) into the hematoxylin dye solution, mixing uniformly to prepare dye solution, and dyeing the skein.
The dyeing formula is as follows:
the concentration of the hematoxylin dye is 1g/L, the concentration of the silicon-carbon quantum dots is 5g/L, and the bath ratio is 1: 50; the dyeing temperature is 80 ℃; dyeing time is 60min, and two skeins 25 and 26 are obtained.
And (3) drying the skein 25, measuring the K/S value of the skein to be 1.6981, and determining the color characteristic value: l71.15, a 8.27, b 31.89;
soaping the skein 26, washing, drying, measuring the K/S value of 1.4436, and measuring the color characteristic value: l71.22, a 7.93, b 26.03.
Retention ratio of K/S N after washing with dyeing soapK/S85% and no change in color before and after.
Comparative example 7
Small molecule natural dyes: lignum sappan extract (hematoxylin and hematoxylin oxide as main ingredients)
Fabric: two blocks of true silk skein
The dyeing formula is as follows without adding silicon-carbon quantum dot solution:
the concentration of the hematoxylin dye is 1g/L, and the bath ratio is 1: 50; the dyeing temperature is 80 ℃; dyeing time is 60min, and two skeins 27 and 28 are obtained.
Drying the fabric 27, measuring the K/S value of 1.1986, and determining the color characteristic value: l62.59, a 20.63, b 11.71;
soaping, washing and drying the fabric 28, measuring the K/S value of the fabric to be 0.1979, and measuring the color characteristic value: l43.35, a 25.30, b 10.06.
Retention ratio of K/S N after washing with dyeing soapK/S16 percent and the color change before and after the color change is obvious.
The color comparison data for the specific examples and comparative examples are shown in table 1.
TABLE 1K/S values and color characterization values for dyed fabrics
Experimental results show that the method provided by the invention greatly improves the dyeing effect of the micromolecule natural dye on the fabric/fiber, and the K/S retention rate N is maintained after the dyeing soap washingK/SHigher and more stable color and luster obtained by dyeing. In the comparative example, the small-molecule natural dye was directly dyed (without any other auxiliary agent), and the K/S retention rate N was maintained after the dyeing soap washingK/SThe color is low, the color is almost faded after dyeing and soaping, and the color is unstable; when the coupling agent is adopted as the auxiliary agent for dyeing in the comparative example, the coupling agent is hydrolyzed violently in water to form a membranous color block which is adsorbed on the surface of the fabric, so that the dyeing is uneven, color spots are formed, and the dyeing is not suitable for dyeing application; comparative example K/S Retention ratio N after washing of dyeing soap when dyeing was carried out using chitosan as an auxiliary agentK/SLower, the color changes. The novel dyeing-color fixing method of the micromolecule natural dye provided by the invention has good dyeing effect on fabrics and good application prospect.
Claims (11)
1. The dyeing-color fixing method of the micromolecule natural dye is characterized by comprising the following steps: introducing water-soluble quantum dots into a dyeing bath of the micromolecular natural dye, and using the water-soluble quantum dots to influence the dyeing process of the micromolecular natural dye;
the water-soluble quantum dots are water-soluble carbon quantum dots or water-soluble silicon-carbon quantum dots;
the molecular weight of the small molecular natural dye is less than 500, and the structure lacks a group for directly dyeing fabrics/fibers.
2. The dyeing-fixing method of small-molecule natural dyes according to claim 1, characterized in that the method is: the water-soluble quantum dots and the micromolecular natural dye are treated and dyed in the same bath, or the water-soluble quantum dots are firstly adopted to treat the fabric/fiber and then dyed with the micromolecular natural dye, or the water-soluble quantum dots are adopted to treat the dyed fabric/fiber after the micromolecular natural dye dyes the fabric/fiber.
3. The dyeing-fixing method of natural small-molecule dyes according to claim 2, characterized in that a one-bath method is used, in particular: adding a water-soluble quantum dot solution into a micromolecular natural dye solution, uniformly mixing to prepare a dye solution, and dyeing fabrics/fibers; the dyeing formula comprises a bath ratio of 1: 10-50, a dyeing temperature of 40-80 ℃, a dyeing time of 5-60 min, soaping, washing and drying to obtain a dyeing sample.
4. The dyeing-fixing method of natural small-molecule dyes according to claim 2, characterized in that a pretreatment method is used, said method being in particular: firstly, treating the fabric/fiber with a water-soluble quantum dot solution, and then dyeing with a micromolecular natural dye; the pretreatment formula comprises the steps of carrying out the treatment for 1 to 10-50 ℃ at a bath ratio of 1 to 20-30 ℃ for 1-5 min, and wringing; the dyeing formula comprises a bath ratio of 1: 10-50, a dyeing temperature of 40-80 ℃, a dyeing time of 5-60 min, soaping, washing and drying to obtain a dyeing sample.
5. The dyeing-fixing method of natural small-molecule dyes according to claim 2, characterized in that a post-treatment method is used, said method being in particular: dyeing with micromolecular natural dye, and treating the dyed fabric/fiber with water-soluble quantum dot solution; the dyeing formula is that the bath ratio is 1: 10-50, the dyeing temperature is 40-80 ℃, the dyeing time is 5-60 min, and the dyeing is wrung; the post-treatment formula comprises a bath ratio of 1: 10-50, a treatment temperature of 20-30 ℃, a treatment time of 1-5 min, soaping, washing and drying to obtain a dyeing sample.
6. The method for dyeing-fixing of natural small molecule dyes according to claim 1 wherein the water soluble quantum dots are less than 10nm in size.
7. The dyeing-fixing method of the small-molecule natural dye according to claim 1, characterized in that the preparation method of the carbon quantum dots comprises the following steps: mixing sodium citrate or sodium ascorbate with an alkaline agent, reacting at 150-200 ℃ for 1-5h, cooling to room temperature, purifying, performing ultrafiltration, and adding deionized water to dilute by 0-50 times according to volume, wherein the alkaline agent is one of sodium hydroxide, ammonium bicarbonate and urea, and the molar ratio of the alkaline agent to the sodium citrate or sodium ascorbate is 1: 20-30.
8. The dyeing-fixing method of the small-molecule natural dye according to claim 1, wherein the preparation method of the silicon-carbon quantum dots comprises the following steps: hydrolyzing the silane coupling agent in water at 50-60 ℃ for 20-50 min, then adding a reducing agent, stirring for 30-50 min, and adding deionized water to dilute by 0-50 times according to volume.
9. The dyeing-fixing method of the small-molecule natural dye according to claim 8, wherein the molar ratio of the silane coupling agent to the reducing agent is 50-20: 1; the silane coupling agent is one or a mixture of more than two of gamma-aminopropyl triethoxysilane (KH550), gamma-glycidoxypropyl trimethoxysilane (KH560) or gamma-methacryloxypropyl trimethoxysilane (KH 570); the reducing agent is one of ascorbic acid, sodium ascorbate, citric acid and sodium citrate.
10. The dyeing-fixing method of the small-molecule natural dye according to claim 1, wherein the small-molecule natural dye is derived from a natural plant extract, specifically one of a sappan wood extract, a madder root extract, a honeysuckle flower extract or a tea leaf extract.
11. The method for dyeing-fixing natural small-molecule dye according to claim 2, wherein the fabric/fiber is one of real silk, wool, real silk and wool blended fabric and real silk and wool interwoven fabric.
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