阅读说明：本技术 一种反应型自分散彩色乳胶的制备方法 (Preparation method of reaction type self-dispersion color latex ) 是由 付少海 杨義 李敏 王春霞 张丽平 于 2020-07-23 设计创作，主要内容包括：本发明公开了一种反应型自分散彩色乳胶的制备方法,属于精细化工和材料科学领域。所述方法是对聚甲基丙烯酸缩水甘油酯PGMA微球进行氨基化改性,得到PGMA-NH<Sub>2</Sub>微球,再在PGMA-NH<Sub>2</Sub>微球表面接枝活性染料,使得染料分子和PGMA-NH<Sub>2</Sub>微球以共价键连接,得到反应型自分散彩色乳胶；所述氨基化改性是指在PGMA微球表面接枝多氨基化合物。本发明利用活性染料的反应性将染料分子固着在微球表面,不会影响染料的色泽,同时,活性染料和微球通过共价键连接,使得制备得到的彩色乳胶的稳定性较好。本发明公开了一种以活性染料为着色剂制备的自分散彩色乳胶,并应用于纺织品印花。(The invention discloses a preparation method of reactive self-dispersing color latex, belonging to the fields of fine chemical engineering and material science. The method is to carry out amination modification on Poly Glycidyl Methacrylate (PGMA) microspheres to obtain PGMA-NH 2 Microspheres, followed by PGMA-NH 2 Grafting reactive dye on the surface of the microsphere to ensure that the dye molecules and PGMA-NH 2 Connecting the microspheres by covalent bonds to obtain reactive self-dispersing color latex; the amination modification refers to grafting a polyamino compound on the surface of the PGMA microsphere. The invention utilizes the reactivity of the reactive dye to fix the dye molecules on the surface of the microsphereMeanwhile, the reactive dye and the microspheres are connected through covalent bonds, so that the prepared color latex has good stability. The invention discloses a self-dispersed color latex prepared by taking reactive dye as a coloring agent, and the self-dispersed color latex is applied to textile printing.)

1. The method for preparing the reactive self-dispersing color latex is characterized in that the method is to carry out amination modification on polyglycidyl methacrylate (PGMA) microspheres to obtain PGMA-NH₂Microspheres, followed by PGMA-NH₂Grafting reactive dye on the surface of the microsphere to ensure that the dye molecules and PGMA-NH₂Connecting the microspheres by covalent bonds to obtain reactive self-dispersing color latex; the amination modification refers to grafting a polyamino compound on the surface of the PGMA microsphere.

2. The method according to claim 1, wherein the amino modification agent used in the amination modification is one selected from the group consisting of hexamethylenediamine, decamethylenediamine, polyethyleneimine and branched polyethyleneimine.

3. The method of claim 1 or 2, wherein the reactive dye is a s-triazine reactive dye selected from the group consisting of reactive bright yellow X-6G, reactive yellow X-R, reactive bright yellow X-7G, reactive yellow X-RG, reactive orange X-GN, reactive red X-3B, reactive bright red X-8B, reactive blue X-3G, reactive bright blue X-BR, reactive blue X-R, reactive bright yellow K-6G, reactive yellow K-RN, reactive gold K-3RP, reactive gold K-2RA, reactive bright orange K-7G, reactive red K-3B, reactive red K-7B, reactive bright red K-2G, reactive bright red K-2BP, reactive red K-G, reactive violet K-3R, reactive violet K-2R, One of reactive blue K-3G, reactive brilliant blue K-GR, reactive deep blue K-R, reactive turquoise blue K-GL and reactive brilliant blue K-3R.

4. The method of any one of claims 1 to 3, wherein the reaction conditions for the amination modification of the PGMA microspheres are as follows: the addition amount of the polyamino compound is 1-50% of the mass of the PGMA microspheres, the reaction temperature is 60-80 ℃, and the reaction time is 4-10 h.

5. The method of any one of claims 1 to 4, wherein the reaction is carried out in PGMA-NH₂The reaction conditions for grafting the reactive dye on the surface of the microsphere are as follows: the addition amount of the reactive dye is PGMA-NH₂0.1-15% of the microsphere, 7-10 of pH value, 25-80 ℃ of reaction temperature and 0.5-3h of reaction time.

6. A colored latex prepared by the method of any one of claims 1 to 5.

7. Use of the colored emulsion of claim 6 for textile printing.

8. A cotton fabric printing method is characterized by comprising the following steps: the cotton fabric is firstly subjected to carboxylation modification and then printed by the colored latex of claim 6.

9. The printing process according to claim 8, wherein the fabric is carboxylated prior to the cotton fabric printing process.

10. Printing process according to claim 8 or 9, characterized in that it comprises the following steps:

(1) preparing modified cotton fabric: using citric acid or glutaric acid as a modifier, preparing a modifier solution with the mass of 0.1-10 wt% relative to the mass of the cotton fabric, soaking the cotton fabric in the solution, carrying out two-time soaking and two-time rolling with the liquid carrying rate of 50-100%, drying at 30-80 ℃, and then baking at 130-170 ℃ for 1-6min to obtain the modified cotton fabric;

(2) preparing a printed fabric: the prepared color latex is adopted, the modified cotton fabric is directly printed after being mixed with the thickening agent, and the printed cotton fabric is obtained after drying at 30-80 ℃ and baking at 130-170 ℃ for 1-6 min.

Technical Field

The invention relates to a preparation method of a reactive self-dispersing colored latex, belonging to the fields of fine chemical engineering and material science.

Background

In the textile industry, printing textiles is a main way to increase the added value of products and realize the functions and high-grade of the textiles. At present, there are two main types of printing for fabrics: pigment printing and dye printing. The printing specificity of the dye is high, the production process is complex, the production cost is high, and the environmental pollution is serious. The pigment printing coloring process has short flow and obvious advantages of energy conservation and emission reduction, and nearly 50 percent of printed fabrics in the market are from pigment printing according to incomplete statistics. However, the traditional pigment molecules have large particle size and low surface energy, and a large amount of dispersant needs to be added for dispersion in the using process, so that the environment is seriously damaged. At present, the pigment dispersion stability is mainly improved by the following ways: (1) the coating method improves the dispersion stability of the pigment by means of coating the pigment with a polymer. (2) The grinding method is mainly characterized in that large-particle pigments are ground into superfine pigments under the action of mechanical force, and a dispersing agent is used for auxiliary dispersion, so that the aim of improving the dispersion stability is fulfilled. For example, chinese patent No. cn201810651236.x discloses a method for preparing nano-coated organic pigment powder. The surface of the pigment molecule is coated and modified by adopting a sol-gel method, and the covering power, the weather resistance and the dispersibility of the coated organic pigment are obviously improved. Chinese patent 201710402410.2 discloses a method for pulverizing superfine fluorescent pigment. After being crushed, the particle size of the pigment is between 1 and 2 microns, and the pigment shows better dispersion stability.

Although the dispersion stability of the pigment can be improved to some extent by the above method, the processing cost is greatly increased by the coating and grinding at the later stage. In addition, there are some limitations in improving dispersion stability in the above two methods. For example, with physical coatings, the polymer layer can affect the shade of the pigment; the adoption of grinding dispersion has high cost and complex process, and cannot get rid of the dependence on the dispersing agent. Therefore, the development of self-dispersed color latexes that can be used for textile printing is a major approach to solving the above problems.

Disclosure of Invention

In order to solve the problems, the invention fixes dye molecules on the surface of the microsphere by utilizing the reactivity of the reactive dye, the color of the dye cannot be influenced, and meanwhile, the reactive dye and the microsphere are connected through a covalent bond, so that the prepared colored latex has better stability. The invention discloses a self-dispersed color latex prepared by taking reactive dye as a coloring agent, and the self-dispersed color latex is applied to textile printing.

The invention provides a method for preparing reactive self-dispersing color latex, which is characterized in that polyglycidyl methacrylate (PGMA) microspheres are subjected to amination modification to obtain PGMA-NH₂Microspheres, followed by PGMA-NH₂Grafting reactive dye on the surface of the microsphere to ensure that the dye molecules and PGMA-NH₂Connecting the microspheres by covalent bonds to obtain reactive self-dispersing color latex; the amination modification refers to grafting a polyamino compound on the surface of the PGMA microsphere.

In one embodiment of the present invention, the amino modification reagent used in the amination modification is selected from one of hexamethylenediamine, heptamethylenediamine, polyethyleneimine, and branched polyethyleneimine (Mn 600-.

In one embodiment of the invention, the reactive dye is a reactive dye of s-triazine, selected from the group consisting of reactive bright yellow X-6G, reactive yellow X-R, reactive bright yellow X-7G, reactive yellow X-RG, reactive orange X-GN, reactive red X-3B, reactive bright red X-8B, reactive blue X-3G, reactive bright blue X-BR, reactive blue X-R, reactive bright yellow K-6G, reactive yellow K-RN, reactive gold K-3RP, reactive gold K-2RA, reactive bright orange K-7G, reactive red K-3B, reactive red K-7B, reactive red K-2G, reactive bright red K-2BP, reactive red K-G, reactive violet K-3R, reactive violet K-2R, reactive blue K-3G, reactive blue X-R, reactive bright yellow X-7G, reactive yellow K-R, reactive yellow K-RN, reactive yellow K-, One of active brilliant blue K-GR, active brilliant blue K-R, active turquoise blue K-GL and active brilliant blue K-3R.

In one embodiment of the present invention, the reaction conditions for the amination modification of the PGMA microspheres are as follows: the addition amount of the polyamino compound is 1-50% (w/w, g/g) of the mass of the PGMA microspheres, the reaction temperature is 60-80 ℃, and the reaction time is 4-10 h.

In one embodiment of the invention, the reaction is carried out in PGMA-NH₂The reaction conditions for grafting the reactive dye on the surface of the microsphere are as follows: the addition amount of the reactive dye is PGMA-NH₂0.1-15% (w/w, g/g) of the microsphere mass, the pH value of 7-10, the reaction temperature of 25-80 ℃ and the reaction time of 0.5-3 h.

In one embodiment of the invention, the method comprises the steps of:

(1) preparation of PGMA copolymer microspheres: 10-40g of Glycidyl Methacrylate (GMA) and 1-50% of polyvinylpyrrolidone (PVP) relative to the mass fraction of the monomers are first dissolved in 300mL of 100-one organic solvent. Then adding an initiator accounting for 0.2-10% of the mass fraction of the monomer, reacting for 5-24h at 60-90 ℃ to obtain Poly Glycidyl Methacrylate (PGMA) microsphere dispersion liquid, and centrifuging and washing to obtain pure PGMA microspheres with the particle size of 100-500 nm;

(2)PGMA-NH₂preparing microspheres: then 0.5-10g of PGMA microspheres are dispersed in water, 1-50% of polyamino compound is added relative to the mass dispersion of the PGMA microspheres, and reaction is carried out for 4-10h at 60-80 ℃ to obtain PGMA-NH with the surface amination and the grain diameter of 100-500nm₂Microspheres;

(3) color latex (PGMA-NH)₂Preparation of-X-3B) relative to PGMA-NH₂Adding 0.1-15% of s-triazine reactive dye into the microsphere dispersion, adjusting the pH value to 7-10, dyeing at 25-80 ℃ for 0.5-3h, filtering, and centrifugally drying to obtain the color latex with the particle size of 100-500 nm.

In an embodiment of the present invention, the organic solvent is one of methanol and ethanol.

In one embodiment of the present invention, the initiator comprises one of a water-soluble initiator or an oil-soluble initiator; the water-soluble initiator comprises potassium persulfate and ammonium persulfate; oil-soluble initiators include azobisisobutylamidine hydrochloride, azobisisobutyronitrile, benzoyl peroxide.

In one embodiment of the present invention, the pH adjuster is one of sodium carbonate, sodium bicarbonate, and sodium hydroxide.

The invention provides a colored latex prepared by the method.

The invention provides an application of the color emulsion in printing.

In one embodiment of the invention, the printing comprises direct printing of the fabric.

The invention also provides a printing method of the fabric, which comprises the following steps: firstly, carrying out carboxylation modification on cotton fabrics, and then printing by adopting the colored latex.

In one embodiment of the invention, before the cotton fabric printing method, the cotton fabric can be subjected to carboxylation modification to increase the surface carboxyl content of the cotton fabric and increase the color fastness of the color emulsion.

In one embodiment of the invention, the cotton fabric printing method comprises the following steps:

(1) preparing modified cotton fabric: using citric acid or glutaric acid as a modifier to prepare a modifier solution with the mass of 0.1-10 wt% relative to the mass of the cotton fabric, soaking the cotton fabric in the solution, carrying out two-time soaking and two-time rolling with the liquid carrying rate of 50-100%, drying at 30-80 ℃, and then baking at 130-170 ℃ for 1-6min to obtain the modified cotton fabric.

(2) Preparing a printed fabric: the prepared color latex is adopted, the modified cotton fabric is directly printed after being mixed with the thickening agent, and the printed cotton fabric is obtained after drying at 30-80 ℃ and baking at 130-170 ℃ for 1-6 min.

The invention has the beneficial effects that:

(1) the surface of the polymer microsphere is charged with negative charges after the dye is grafted, and the colored latex has better self-dispersion performance and stability due to electrostatic repulsion and water solubility of the dye;

(2) at present, most of the existing color latex particles are coated by microcapsules, dyes and polymers are combined by physical acting force, and the color latex particles are connected by covalent bonds and have better stability; on the other hand, in the prior art, dyes are physically coated, and the polymer layer can influence the color light of the pigments; the dye is attached to the surface of the microsphere, and the color of the grafted color latex is not affected;

(3) the color latex prepared by the invention is used for printing cotton fabrics, and the obtained printed fabrics have good hand feeling and color fastness.

Drawings

FIG. 1 shows PGMA and PGMA-NH₂And the morphology and particle size of the colored latex.

FIG. 2 is (a) thermal stability of a colored latex; (b) storage stability; (c) centrifuge stability and (d) self-dispersion stability.

FIG. 3 is a graph showing color properties of a colored latex.

FIG. 4 is a graph of color vividness of a color latex printed fabric.

FIG. 5 shows (a) infrared of a colored latex; (b) PGMA; (c) PGMA-NH₂；(d)PGMA-NH₂-energy spectrum of X-3B.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.

Particle size and PDI test methods: the prepared 0.1g of colored latex particles were dispersed in 100mL of deionized water, and the particle size and PDI of the latex particles were measured using a particle size tester.

The stability test method comprises the following steps: the prepared colored latex particles were tested for thermal stability, centrifugal stability, and storage stability. Respectively dispersing the color latex particles into deionized water, and calculating the change rate of the particle size of the color latex particles at the centrifugal speed of 1000-5000 revolutions into the centrifugal stability; the color latex particles are placed for 30 minutes at the temperature of 30-90 ℃, and then the thermal stability is calculated as the change rate of the particle size of the color latex particles; the change rate of the particle size of the colored latex particles was calculated as the standing stability after standing at room temperature for 7 to 30 days.