CN111996815B - Preparation and dyeing of boron/silicon-containing hybrid functional protein fiber - Google Patents

Preparation and dyeing of boron/silicon-containing hybrid functional protein fiber Download PDF

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CN111996815B
CN111996815B CN202010873487.XA CN202010873487A CN111996815B CN 111996815 B CN111996815 B CN 111996815B CN 202010873487 A CN202010873487 A CN 202010873487A CN 111996815 B CN111996815 B CN 111996815B
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dyeing
fiber
silicon
boron
dye
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CN111996815A (en
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何雪梅
周天池
蔡露
冒海燕
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Yancheng Institute of Technology
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/34General 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/445Use of auxiliary substances before, during or after dyeing or printing
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/52General 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 synthetic macromolecular substances
    • D06P1/5264Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5278Polyamides; Polyimides; Polylactames; Polyalkyleneimines
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/64General 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
    • D06P1/642Compounds containing nitrogen
    • D06P1/645Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/64General 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
    • D06P1/651Compounds without nitrogen
    • D06P1/65106Oxygen-containing compounds
    • D06P1/65131Compounds containing ether or acetal groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/653Nitrogen-free carboxylic acids or their salts
    • D06P1/6536Aromatic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/655Compounds containing ammonium groups
    • D06P1/66Compounds containing ammonium groups containing quaternary ammonium groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/673Inorganic compounds
    • D06P1/67383Inorganic compounds containing silicon
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02Material containing basic nitrogen
    • D06P3/04Material containing basic nitrogen containing amide groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02Material containing basic nitrogen
    • D06P3/04Material containing basic nitrogen containing amide groups
    • D06P3/14Wool

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Coloring (AREA)
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Abstract

The invention provides preparation and dyeing of a boron/silicon-containing hybrid functional protein fiber, which comprises the steps of mixing carboxyphenylboronic acid, a cation modifier and a silicon coupling agent, and adjusting the pH value to 3-7 to prepare a modified solution; soaking the fiber into the prepared modified solution for treatment, taking out, washing and drying; dyeing the modified fiber in a dye bath consisting of natural dye, auxiliary agent, water and pH regulator by a dip dyeing method, washing and drying after dyeing to obtain the dyed boron/silicon-containing hybrid functional protein fiber; wherein the concentration of the carboxyphenylboronic acid in the modified solution is 1-10 g/L, the concentration of the cationic modifier is 1-50 g/L, and the concentration of the silicon coupling agent is 2-20 g/L. The invention enhances the effect between the fiber and the anionic natural dye, can promote the dye to dye, and effectively improves the dye uptake, color depth and dyeing fastness of the natural dye on the fiber.

Description

Preparation and dyeing of boron/silicon-containing hybrid functional protein fiber
Technical Field
The invention belongs to the technical field of modification and functional dyeing of textile fiber materials, and particularly relates to preparation and dyeing of boron/silicon-containing hybrid functional protein fibers.
Background
The dyeing and the functional processing of the textile are combined into a whole, so that the energy is saved, and the ecological sustainable development concept is met. Although the chemical dyes used in the dyeing and finishing processing of the textile have complete color spectrum and good dyeing fastness, the chemical dyes consume petroleum industrial resources, and meanwhile, the biocompatibility and the degradability of a plurality of dyes are poor, so that the industrial waste water discharge is not friendly to the environment and is not beneficial to the health.
The natural dye has excellent characteristics of good biocompatibility, antibiosis, antiphlogosis, health care, no toxicity, degradability and the like, and has important significance for realizing functional dyeing of textiles by utilizing the pigment and the function of the natural dye. However, the natural dye has the defects of poor promotion and fastness, poor functional health care performance and the like in the dyeing process.
Therefore, the art needs a dyeing method which can endow the fabric with good ultraviolet resistance and antibacterial function and effectively solve the problems of deep dyeing property and poor dyeing fastness of natural dyes.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide the preparation and dyeing of the boron/silicon-containing hybrid functional protein fiber.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation and dyeing of the boron/silicon-containing hybrid functional protein fiber comprise mixing carboxyphenylboronic acid, a cationic modifier and a silicon coupling agent, and adjusting the pH value to 3-7 to prepare a modified solution; soaking the fiber into the prepared modified solution for treatment, taking out, washing and drying; dyeing the modified fiber in a dye bath consisting of natural dye, auxiliary agent, water and pH regulator by a dip dyeing method, washing and drying after dyeing to obtain the dyed boron/silicon-containing hybrid functional protein fiber; wherein the concentration of the carboxyphenylboronic acid in the modified solution is 1-10 g/L, the concentration of the cationic modifier is 1-50 g/L, and the concentration of the silicon coupling agent is 2-20 g/L.
As a preferable scheme of the method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber, the method comprises the following steps: the cation modifier is one or two of epoxypropyl trimethyl ammonium chloride and polyethyleneimine.
As a preferable scheme of the method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber, the method comprises the following steps: the coupling agent is one of silicon-containing coupling agents such as aminopropyl ethoxy siloxane and epoxypropyl trimethoxy siloxane.
As a preferable scheme of the method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber, the method comprises the following steps: the step of immersing the fibers into the prepared modified solution is to immerse the fibers in a constant-temperature oscillation dyeing machine at 50-90 ℃ for 1-2 hours, then wash the fabric with cold water and dry the fabric at 50 ℃.
As a preferable scheme of the method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber, the method comprises the following steps: the dye bath comprises the natural dye, an auxiliary agent, water and a pH regulator, wherein the concentration of the natural dye is 2-4% calculated as o.w.f, the pH is regulated to 1.81-10.38, and the concentration of the auxiliary agent is 2-10 g/L.
As a preferable scheme of the method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber, the method comprises the following steps: the dyeing is carried out by a dip dyeing method, wherein the bath ratio is 1: 30-40 ℃, the dyeing temperature is 30-90 ℃, and the dyeing time is 1-2 h.
As a preferable scheme of the method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber, the method comprises the following steps: the pH value of the modified solution and the pH value of the dye bath can be adjusted by one or two or three of boric acid, phosphoric acid, citric acid and acetic acid; the alkalinity adjustment is one or two of sodium hydroxide, sodium carbonate and sodium bicarbonate.
As a preferable scheme of the method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber, the method comprises the following steps: the auxiliary agent is one or two of nonionic auxiliary agents polyoxyethylene ether peregal OS-15, peregal OP-10 and peregal AEO-10; the natural dye is polyphenol natural dye.
As a preferable scheme of the method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber, the method comprises the following steps: the fiber is one of silk fiber or wool fiber.
It is still another object of the present invention to overcome the deficiencies of the prior art and to provide a method for preparing a boron/silicon containing hybrid functional protein fiber and a dyed fiber obtained by the dyeing method.
The invention has the beneficial effects that:
(1) the finishing liquid used by the invention contains boric acid groups, quaternary ammonium salt and silicon-containing nano particles, after the fibers are modified, boric acid groups, amino groups and hydroxyl groups are introduced to the surfaces of the fibers, so that the effect between the fibers and anionic natural dyes is enhanced, the dyes can be promoted to be dyed, and the dye uptake, the color depth and the dye fastness of the natural dyes on the fibers are effectively improved. According to the invention, silicon dioxide nano particles are introduced through in-situ deposition, so that the ultraviolet light absorption of the fabric is enhanced, and the introduced amino groups enable the fiber to have good antibacterial performance.
(2) The invention overcomes the defects of poor lifting property, poor washing fastness, needing of mordant for dyeing fibers and the like of the traditional natural dye, and meets the requirements of green dyeing and finishing technology; after modification, the dyeing uniformity of the natural dye on the fabric is improved, and the dyed cotton fabric has good washing fastness and an antibacterial function. The natural dye dyeing technology based on fiber modification has the advantages of uniform dyeing, simple process and convenient operation, and particularly can be used for large-scale production by using a dyeing machine, thereby having wide application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
fig. 1 is a graph of the effect of staining temperature variation on surface color depth value and UPF of curcumin staining in the practice of the present invention.
Fig. 2 is a graph showing the effect of curcumin dyeing on the surface color depth of the fabric modified at different pH values in the practice of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
In the embodiment, the silk fiber fabric is selected for dyeing, and the specific steps are as follows:
(1) mixing 1g/L carboxyphenylboronic acid, 1g/L epoxypropyltrimethylammonium chloride, 25g/L polyethyleneimine and 5g/L silicon coupling agent aminopropylethoxysiloxane, adding acetic acid to adjust the pH to 3, and adding deionized water to prepare 100mL of modified solution under the condition of magnetic stirring;
(2) immersing 2g of silk fiber into the prepared modified solution, treating for 1h in a constant-temperature oscillation dyeing machine at 50 ℃, taking out cold water to wash the fabric, and drying at 50 ℃;
(3) dyeing: the modified silk fiber is put into a dye bath consisting of 4% of curcumin, 2g/L peregal OP-10, water and acetic acid for adjusting the pH value to 4.56, and the bath ratio is 1: 30, dyeing for 1h at 30 ℃ in a constant-temperature oscillation dyeing machine, taking out, washing with water and drying.
Example 2
In the embodiment, the silk fiber fabric is selected for dyeing, and the specific steps are as follows:
(1) mixing 1g/L carboxyphenylboronic acid, 1g/L epoxypropyltrimethylammonium chloride, 25g/L polyethyleneimine and 5g/L silicon coupling agent aminopropylethoxysiloxane, adding acetic acid to adjust the pH to 3, and adding deionized water to prepare 100mL of modified solution under the condition of magnetic stirring;
(2) immersing 2g of silk fiber into the prepared modified solution, treating for 1h in a constant-temperature oscillation dyeing machine at 50 ℃, taking out cold water to wash the fabric, and drying at 50 ℃;
(3) dyeing: the modified silk fiber is put into a dye bath consisting of 4% anthocyanin, 2g/L peregal OP-10, water and acetic acid for adjusting the pH value to 4.56, wherein the bath ratio is 1: 30, dyeing for 1h at 45 ℃ in a constant-temperature oscillation dyeing machine, taking out, washing with water and drying.
Example 3
In the embodiment, the silk fiber fabric is selected for dyeing, and the specific steps are as follows:
(1) mixing 1g/L carboxyphenylboronic acid, 1g/L epoxypropyltrimethylammonium chloride, 25g/L polyethyleneimine and 5g/L silicon coupling agent aminopropylethoxysiloxane, adding acetic acid to adjust the pH to 3, and adding deionized water to prepare 100mL of modified solution under the condition of magnetic stirring;
(2) immersing 2g of silk fiber into the prepared modified solution, treating for 1h in a constant-temperature oscillation dyeing machine at 50 ℃, taking out cold water to wash the fabric, and drying at 50 ℃;
(3) dyeing: the modified silk fiber is put into a dye bath consisting of 6 percent of curcumin, 2g/L peregal OP-10, water and acetic acid for adjusting the pH value to 4.56, and the bath ratio is 1: 30, dyeing for 1h at 45 ℃ in a constant-temperature oscillation dyeing machine, taking out, washing with water and drying.
Example 4
In the embodiment, the silk fiber fabric is selected for dyeing, and the specific steps are as follows:
(1) mixing 1g/L carboxyphenylboronic acid, 1g/L epoxypropyltrimethylammonium chloride, 25g/L polyethyleneimine and 5g/L silicon coupling agent aminopropylethoxysiloxane, adding acetic acid to adjust the pH to 3, and adding deionized water to prepare 100mL of modified solution under the condition of magnetic stirring;
(2) immersing 2g of silk fiber into the prepared modified solution, treating for 1h in a constant-temperature oscillation dyeing machine at 50 ℃, taking out cold water to wash the fabric, and drying at 50 ℃;
(3) dyeing: the modified silk fiber is put into a dye bath consisting of 8 percent of curcumin, 2g/L peregal OP-10, water and acetic acid for adjusting the pH value to 4.56, and the bath ratio is 1: 30, dyeing for 1h at 45 ℃ in a constant-temperature oscillation dyeing machine, taking out, washing with water and drying.
Example 5
In the embodiment, the silk fiber fabric is selected for dyeing, and the specific steps are as follows:
(1) mixing 1g/L carboxyphenylboronic acid, 1g/L epoxypropyltrimethylammonium chloride, 25g/L polyethyleneimine and 5g/L silicon coupling agent aminopropylethoxysiloxane, adding acetic acid to adjust the pH to 3, and adding deionized water to prepare 100mL of modified solution under the condition of magnetic stirring;
(2) immersing 2g of silk fiber into the prepared modified solution, treating for 1h in a constant-temperature oscillation dyeing machine at 50 ℃, taking out cold water to wash the fabric, and drying at 50 ℃;
(3) dyeing: the modified silk fiber is put into a dye bath consisting of 10 percent of curcumin, 2g/L peregal OP-10, water and acetic acid for adjusting the pH value to 4.56, and the bath ratio is 1: 30, dyeing for 1h at 45 ℃ in a constant-temperature oscillation dyeing machine, taking out, washing with water and drying.
By using the modification scheme in the embodiment 1, the pH of the modified fiber is adjusted to 4.56 by 10% of curcumin, 2g/L peregal O, water and acetic acid, and the bath ratio is 1: 30, dyeing for 1h in a constant-temperature oscillation dyeing machine at 45 ℃, taking out, washing with water and drying.
Example 6
In the embodiment, the silk fiber fabric is selected for dyeing, and the specific steps are as follows:
(1) mixing 1g/L carboxyphenylboronic acid, 1g/L epoxypropyltrimethylammonium chloride, 25g/L polyethyleneimine and 5g/L silicon coupling agent aminopropylethoxysiloxane, adding acetic acid to adjust the pH to 3, and adding deionized water to prepare 100mL of modified solution under the condition of magnetic stirring;
(2) immersing 2g of silk fiber into the prepared modified solution, treating for 1h in a constant-temperature oscillation dyeing machine at 50 ℃, taking out cold water to wash the fabric, and drying at 50 ℃;
(3) dyeing: the modified silk fiber is put into a dye bath consisting of 12 percent of curcumin, 2g/L peregal OP-10, water and acetic acid for adjusting the pH value to 4.56, and the bath ratio is 1: 30, dyeing for 1h at 45 ℃ in a constant-temperature oscillation dyeing machine, taking out, washing with water and drying.
By using the modification scheme in the embodiment 1, the pH of the modified fiber is adjusted to 4.56 by 12% of curcumin, 2g/L peregal O, water and acetic acid, and the bath ratio is 1: 30, dyeing for 1h in a constant-temperature oscillation dyeing machine at 45 ℃, taking out, washing with water and drying.
The silk fabrics treated in the above examples 1-6 were tested for K/S value (K/S value represents the color depth of the fabric surface) by a DataColor tester.
And (3) dyeing the silk fabric with curcumin and anthocyanin before and after modification, and then testing the antibacterial performance. The antibacterial property of the silk is tested according to GB/T20944.3-2008, and two strains of escherichia coli (E.coli) and staphylococcus aureus (S.aureus) are adopted.
And (3) antibacterial testing: cutting silk fabric (0.75g) into small pieces, placing the small pieces and prepared bacterial liquid in a water bath kettle, and oscillating for 24 hours; the temperature of Escherichia coli and Staphylococcus aureus was set to 30 ℃ and 24 ℃ respectively while shaking. Then, the bacterial solution was diluted 1000 times with a sterilized phosphate buffer solution to prepare a test bacterial solution. After dilution, the bacterial liquid was inoculated on an agar medium and cultured at 37 ℃ for 24 hours and 48 hours for Escherichia coli and Staphylococcus aureus, respectively. The number of colonies on the swatches was then counted under low power microscope:
Y=(Nb-Nc)*100%/Wb
wherein Y is the bacteriostasis rate, Nb is the colony count cultured by the standard blank sample
Nc is the number of colonies cultured by the modified silk or unmodified silk sample
The properties of the modified natural silk dye after dyeing are shown in table 1.
TABLE 1 Natural dyes for modified Silk after dyeing
Figure BDA0002651879190000061
Figure BDA0002651879190000071
As can be seen from table 1, the color depth of the modified silk fabric dyed with curcumin and anthocyanin, which are natural dyes, is significantly thicker than that of the unmodified silk fabric. Meanwhile, after the silk fabric is modified by the method, more amino groups are introduced to the surface, and the bacteriostatic rate of staphylococcus aureus and escherichia coli of the modified fabric reaches over 80 percent, so that the modified silk fabric has a good bacteriostatic effect. The antibacterial effect of the curcumin dyed fabric is better than that of anthocyanin dyed fabric, and the surface color depth value is increased along with the increase of curcumin concentration, so that the antibacterial effect is enhanced. The inventor unexpectedly finds that when the curcumin dye concentration exceeds 10%, the surface color depth value, the uvioresistant performance and the antibacterial performance are reduced on the contrary, and probably because the dyeing of the modified silk is fixed, the adsorbable dye is fixed, and after the adsorption saturation value is exceeded, the concentration is increased, the adsorbable dye amount per gram of fiber on the fiber surface is reduced, and therefore various properties of the surface of the modified fiber are changed.
Example 7
Mixing 1g/L carboxyphenylboronic acid, 1g/L epoxypropyltrimethylammonium chloride, 25g/L polyethyleneimine and 5g/L silicon coupling agent aminopropylethoxysiloxane, adjusting the pH value to 3 with acetic acid, and preparing 100mL of modified solution under the condition of magnetic stirring. And (3) immersing 2g of silk fiber into the prepared modified solution, treating for 1h in a constant-temperature oscillation dyeing machine at 50 ℃, taking out, washing and drying. The modified silk fiber is treated by using 4% of curcumin, 2g/L peregal O and dye liquor pH under the condition that the bath ratio is 1: 30, and testing the K/S value and UPF index change of the surface of the silk fiber after dyeing at 30 ℃, 45 ℃, 60 ℃, 75 ℃ and 90 ℃ respectively by using a constant-temperature oscillation dyeing machine.
It can be seen from fig. 1 that the K/S of the surface of the dyed fabric increases with increasing temperature, reaching a maximum at a temperature of 45 c. Therefore, the invention obviously improves the K/S value of the natural dye dyed fabric and improves the uvioresistant performance. Above this temperature, the K/S value decreases, which is disadvantageous in that natural dyes are generally poor in heat resistance stability and easily deactivated at high temperatures, and therefore, high temperature dyeing is not suitable.
Example 8
Mixing 1g/L carboxyphenylboronic acid, 1g/L epoxypropyltrimethylammonium chloride, 25g/L polyethyleneimine and 5g/L silicon coupling agent aminopropylethoxysiloxane, adjusting the pH value to 3 with acetic acid, and preparing 100mL of modified solution under the condition of magnetic stirring. And (3) immersing 2g of silk fiber into the prepared modified solution, treating for 1h in a constant-temperature oscillation dyeing machine at 50 ℃, taking out, washing and drying. The modified silk fiber is treated by 8% of curcumin and 2g/L of peregal O, and the pH value of the dye liquor is adjusted to be 1.81, 2.56, 3.29, 4.56, 5.72, 6.8, 7.96 and 9.15 by using 0.04mol/L of triacid mixed liquor (phosphoric acid, acetic acid and boric acid, the concentration is 0.04mol/L) and 0.2mol/L of LNaOH respectively, wherein the bath ratio is 1: 30, dyeing at 45 ℃ by using a constant-temperature oscillation dyeing machine.
As can be seen from FIG. 2, the surface color depth value of the modified silk fibers dyed with curcumin is higher than that of the unmodified silk fibers, and the K/S is highest at a pH of 4.56. Above this value, the greater the pH, the lower the surface color depth. The modified fabric has higher K/S value in the range from acidity to alkalinity, which shows that the modified fiber has enhanced dye adsorption performance.
Example 9
On the basis of example 5, the other conditions are the same, and the influence of different modifier formulas on various properties of the natural silk dye after dyeing is researched, and the table 2 shows.
TABLE 2
Figure BDA0002651879190000081
As can be seen from Table 2, an increase in carboxyphenylboronic acid concentration increases deposition of cationic polymer on the fiber surface, which helps to adsorb dye molecules, but above 10g/L causes a decrease in surface K/S and UPF. When the content of the carboxyl phenylboronic acid exceeds a certain value, more negatively charged groups can be introduced on the surface of the fiber, so that the negatively charged groups occupy active sites on the surface of the fiber, and the adsorption of dye molecules is not facilitated, so that the K/S is reduced. When the cationic modifier exceeds 25g/L, the thickness of a film formed on the surface of the fiber by the cationic polymer increases, and the diffusion of dye molecules into the fiber is not facilitated. The silicon coupling agent is increased, a Si-O reticular film is introduced on the surface of the fiber, the surface area of the fiber is increased, dye adsorption is facilitated, but too much increase in the using amount results in increase in the thickness of the formed film, which in turn hinders dye permeation and is not beneficial to adsorption of dye molecules.
After the modification, boric acid groups, active groups such as hydroxyl, amino and the like are introduced on the surface of the fiber, and the deposition of nano silicon dioxide particles is contained, so that the color depth and the color fastness of natural dye on the fiber are effectively improved. The silicon dioxide nano particles are introduced, so that the ultraviolet light absorption of the fabric is enhanced, and the introduced quaternary ammonium salt enables the fiber to have good antibacterial performance. By using the cationic modifier to bring more positive charges into the fiber surface, the silicon coupling agent can be hydrolyzed to form Si-O-Si alkyl groups to form a net-shaped film.
The carboxyl phenylboronic acid is also a cross-linking agent at the same time, can be connected with the cationic modifier and the siloxane to be deposited on the surface of the fiber, and the carboxyl phenylboronic acid, the cationic modifier and the siloxane are combined to act, so that the effect between the fiber and the anionic natural dye is improved and enhanced, the dye can be promoted to be dyed, and the dye uptake, the color depth and the dye fastness of the natural dye on the fiber are effectively improved.
The invention aims to provide a natural dye dyeing method which can achieve higher dyeing depth and obtain better color fastness, ultraviolet resistance and antibacterial performance by dyeing natural dyes on fabrics without adding mordant. The finishing liquid used by the invention contains boric acid groups, quaternary ammonium salt and silicon-containing nano particles, after the fibers are modified, boric acid groups, amino groups, hydroxyl groups and other groups are introduced to the surfaces of the fibers, so that the effect between the fibers and anionic natural dyes is enhanced, the dyes can be promoted to be dyed, and the dye uptake, the color depth and the dye fastness of the natural dyes on the fibers are effectively improved. Silica nanoparticles are introduced through in-situ deposition, so that the ultraviolet light absorption of the fabric is enhanced, and the introduced amino groups enable the fiber to have good antibacterial performance. The process is simple and convenient to operate and has wide application prospect.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

Claims (6)

1. A method for preparing and dyeing boron/silicon-containing hybrid functional protein fiber is characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
mixing carboxyl phenylboronic acid, a cationic modifier and a silicon coupling agent, and adjusting the pH value to 3-7 to prepare a modified solution;
soaking the fiber into the prepared modified solution for treatment, taking out, washing and drying;
dyeing the modified fiber in a dye bath consisting of natural dye, auxiliary agent, water and pH regulator by a dip dyeing method, washing and drying after dyeing to obtain the dyed boron/silicon hybrid functional protein fiber, wherein the concentration of the natural dye is 4-10% in terms of o.w.f, the pH is regulated to 1.81-4.56, the concentration of the auxiliary agent is 2-10 g/L, and the natural dye is curcumin;
wherein the concentration of the carboxyphenylboronic acid in the modified solution is 1-10 g/L, the concentration of the cationic modifier is 1-25 g/L, and the concentration of the silicon coupling agent is 2-20 g/L;
the cationic modifier is one or two of epoxypropyl trimethyl ammonium chloride and polyethyleneimine;
the auxiliary agent is one or two of nonionic auxiliary agents polyoxyethylene ether peregal OS-15, peregal OP-10 and peregal AEO-10;
the silicon coupling agent is epoxypropyl trimethoxy siloxane.
2. The method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber according to claim 1, wherein the method comprises the following steps: the step of immersing the fibers into the prepared modified solution is to immerse the fibers in a constant-temperature oscillation dyeing machine at 50-90 ℃ for 1-2 hours, then wash the fabric with cold water and dry the fabric at 50 ℃.
3. The method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber according to claim 1, wherein the method comprises the following steps: the dyeing is carried out by a dip dyeing method, wherein the bath ratio is 1: 30-40 ℃, the dyeing temperature is 30-90 ℃, and the dyeing time is 1-2 h.
4. The method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber according to claim 1, wherein the method comprises the following steps: the pH value of the modified solution and the pH value of the dye bath are adjusted in an acidic manner by one or two or three of boric acid, phosphoric acid, citric acid and acetic acid; the alkalinity adjustment is one or two of sodium hydroxide, sodium carbonate and sodium bicarbonate.
5. The method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber according to claim 1, wherein the method comprises the following steps: the fiber is one of silk fiber or wool fiber.
6. A dyed fiber prepared by the method for preparing and dyeing the boron/silicon-containing hybrid functional protein fiber according to any one of claims 1 to 5.
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