A printing material liquid, its preparation method and application in printing and dyeing

Abstract

The present invention relates to the technical field of textile printing and dyeing, and particularly relates to a printing paste liquid, a preparation method thereof and an application in printing and dyeing; the printing paste liquid comprises the following raw materials in parts by weight: 60-70 parts of modified acrylic emulsion, 2-2.4 parts of thickener, 0.5-1.5 parts of dispersant, 4-5 parts of stabilizer, 0.5-1 part of humectant, 1-2 parts of curing agent, 0.2-0.4 part of defoamer, 3-5 parts of dye and 50-60 parts of water. The printing paste liquid prepared by the present invention significantly improves the quality of printing patterns, and also enhances the rubbing fastness and washing fastness of printed fabrics.

Description

Technical Field

[0001] The present invention relates to the technical field of textile printing and dyeing, and particularly relates to a printing paste and its preparation method and application in printing and dyeing. Background Art

[0002] As an important part of the textile printing and dyeing industry, the printing technology has been continuously developing and innovating for a long time. Traditional printing methods, such as manual screen printing, roller printing, etc., although meeting the market demand to a certain extent, still have many deficiencies in terms of color fastness, pattern clarity, and production efficiency. With the progress of technology and the enhancement of environmental awareness, developing a new type of printing paste and its preparation method and exploring its application in printing and dyeing have become important topics in the textile printing and dyeing industry.

[0003] The preparation of traditional printing paste usually involves the mixing of various dyes, auxiliaries, and thickeners. The selection and proportion of these components directly affect the printing effect. However, there are some problems in the preparation and use of traditional printing paste, such as easy diffusion of dyes, uneven penetration, unclear printing patterns, and insufficiently bright colors. Based on this, the present invention provides a printing paste and its preparation method and application in printing and dyeing. Summary of the Invention

[0004] The purpose of the present invention is to provide a printing paste and its preparation method and application in printing and dyeing, solve the above technical problems, improve the quality of printing patterns, and also enhance the rubbing fastness and washing fastness of printed fabrics.

[0005] On the one hand, the present invention provides a printing paste, which comprises the following raw materials in parts by weight: 60 - 70 parts of modified acrylic emulsion, 2 - 2.4 parts of thickener, 0.5 - 1.5 parts of dispersant, 4 - 5 parts of stabilizer, 0.5 - 1 part of moisturizer, 1 - 2 parts of curing agent, 0.2 - 0.4 parts of defoamer, 3 - 5 parts of dye, and 50 - 60 parts of water.

[0006] Further, the preparation method of the modified acrylic emulsion includes: mixing acrylic acid, methyl methacrylate, n-butyl acrylate monomers with deionized water, adding sodium dodecyl sulfate and nonylphenol polyoxyethylene ether and then continuing to stir to obtain a mixed solution, and then adding rare earth doped nano-TiO 2 Perform ultrasonic dispersion for 30 - 40 min, gradually heat up to 75 - 79 °C, adjust the pH to 4 - 6, then add ammonium persulfate, heat up to 82 - 84 °C, keep the temperature for reaction for 4 - 5 h and then cool to room temperature, and adjust the pH to 8 with ammonia water to obtain.

[0007] Further, the acrylic acid, methyl methacrylate, n-butyl acrylate monomers, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, rare earth doped nano-TiO2 The weight ratio of [substance] to ammonium persulfate is (2 - 3):(12 - 14):(20 - 22):(40 - 50):(0.5 - 1):(1 - 1.2):(0.2 - 0.4):(4 - 5).

[0008] Furthermore, the rare earth - doped nano - TiO 2 The preparation method includes: ultrasonically dispersing silane coupling agent KH - 550 for 120 - 140 min in an ethanol - aqueous solution, adjusting the pH to 3 - 4 with glacial acetic acid to obtain a silane coupling agent solution; adding nano - TiO 2 to absolute ethanol, ultrasonically dispersing for 50 - 70 min, adding cerium nitrate, slowly dripping the silane coupling agent solution, adjusting the pH to 9 - 10 with ammonia water, heating to 65 - 75 °C, stirring and reacting for 2 - 2.2 h, cooling, centrifuging, washing with water, and then drying to obtain.

[0009] Furthermore, the weight ratio of the silane coupling agent KH - 550, ethanol - aqueous solution, nano - TiO 2 absolute ethanol and cerium nitrate is (6 - 8):(30 - 40):(25 - 35):(15 - 20):(4 - 5).

[0010] Furthermore, the mass ratio of water to ethanol in the ethanol - aqueous solution is 1:1.

[0011] Furthermore, the thickener is ACRACONC FN 01.

[0012] Furthermore, the dispersant is Dispers740W.

[0013] Furthermore, the stabilizer is sodium citrate.

[0014] Furthermore, the humectant includes at least one of urea, ethylene glycol, and glycerol.

[0015] Furthermore, the curing agent includes ARADUR38 - 1 or ARADUR3986.

[0016] Furthermore, the defoamer is Z - 2875.

[0017] On the other hand, the present invention also provides a method for preparing a printing liquid, the steps including: adding a defoamer, a dispersant, a humectant, a stabilizer, and water to the modified acrylic emulsion while stirring, stirring and dispersing; then adding a thickener, a curing agent, and a dye, and stirring and dispersing evenly.

[0018] On the other hand, the present invention also provides the application of this printing liquid in fabric printing and dyeing.

[0019] The beneficial effects of the present invention are as follows:

[0020] In the present invention, the high chemical stability of titanium dioxide is utilized to achieve its long-term stability in the modified acrylic emulsion. The introduction of titanium dioxide endows the modified acrylic emulsion with stronger ability to absorb and reflect ultraviolet rays, thereby reducing the damaging effect of ultraviolet rays on the printing ink liquid, which helps to maintain the vividness and color fastness of the printed pattern and extend the service life of the printed fabric. Moreover, a chemical bond can be formed between titanium dioxide and the acrylic resin, making it not easy to fall off or wear, thus improving the color fastness of the printing ink liquid.

[0021] In the present invention, rare earth-doped nano-TiO 2 For the modified acrylic emulsion, the doping of rare earth elements may change the optical properties of titanium dioxide, thereby affecting its coloring performance; the rare earth element cerium has a special electronic structure and chemical activity, and can form complex complexes with dye molecules, thus increasing the dye uptake percentage; in addition, the doping of rare earth cerium may also improve the adsorption and diffusion properties of dyes on fibers, making the printed pattern more vivid and the color shade pure.

[0022] In the present invention, further on the basis of rare earth-doped nano-TiO 2 silane coupling agent KH-550 is added, which improves the adhesion and dispersibility of the material on the fiber surface. The modification treatment helps to reduce the shedding and fading of dyes during washing, thereby enhancing the wash resistance and color fastness of the printed fabric. In addition, the silane coupling agent can also improve the interaction force between the fiber and the dye, making the printed pattern more durable and stable.

[0023] The present invention uses rare earth-doped nano-TiO 2 modified acrylic emulsion as raw material. The surface effect and quantum size effect of nano-TiO 2 can also enhance the interaction force between dye molecules and fibers, thereby improving the color fastness of the printed fabric. One end of the silane coupling agent binds to the hydroxyl groups on the surface of nano-TiO 2 and the other end binds to the hydroxyl groups or amino groups and other functional groups on the fiber surface, thus forming a firmly bound system. Moreover, the doping of rare earth and the cooperation of silane coupling agent KH-550 further enhance the dyeing fastness of the printed fabric, including rubbing fastness and wash fastness. Specific Embodiments

[0024] The technical solutions of the present invention will be described clearly and completely below. Obviously, the described embodiments are some but not all of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention. It should be noted that all raw materials can be obtained commercially. In the embodiments of the present invention, the dye is taken as Disperse Red H-B as an example for illustration.

[0025] Example 1

[0026] This example provides a printing liquid, which comprises the following raw materials in parts by weight: 65 parts of modified acrylic emulsion, 2.2 parts of thickener, 1 part of dispersant, 4.5 parts of stabilizer, 0.75 part of humectant, 1.5 parts of curing agent, 0.3 part of defoamer, 4 parts of dye and 55 parts of water;

[0027] Among them, the preparation method of the modified acrylic emulsion includes:

[0028] (1) Prepare rare earth-doped nano-TiO 2 The preparation method includes: ultrasonically dispersing silane coupling agent KH-550 in an ethanol aqueous solution for 130 min, adjusting the pH to 3.5 with glacial acetic acid to obtain a silane coupling agent solution; adding nano-TiO 2 to anhydrous ethanol, ultrasonically dispersing for 60 min, adding cerium nitrate, slowly dropping the silane coupling agent solution, adjusting the pH to 9.5 with ammonia water, raising the temperature to 70 °C, stirring and reacting for 2.1 h, cooling, centrifuging, washing with water, and drying at 60 °C to obtain; the weight ratio of silane coupling agent KH-550, ethanol aqueous solution, nano-TiO 2 , anhydrous ethanol and cerium nitrate is 7:35:30:17.5:4.5; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:1;

[0029] (2) Prepare the modified acrylic emulsion: mix acrylic acid, methyl methacrylate, n-butyl acrylate monomers and deionized water, add sodium dodecyl sulfate and nonylphenol polyoxyethylene ether, and continue stirring to obtain a mixed solution, then add rare earth-doped nano-TiO 2 for ultrasonic dispersion for 35 min, gradually raise the temperature to 77 °C, adjust the pH to 5, then add ammonium persulfate, raise the temperature to 83 °C, keep the temperature for reaction for 4.5 h, then cool to room temperature, and adjust the pH to 8 with ammonia water to obtain; the weight ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomers, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, rare earth-doped nano-TiO 2 and ammonium persulfate is 2.5:13:21:45:0.75:1.1:0.3:4.5;

[0030] Among them, the thickener is ACRACONC FN 01; the dispersant is Dispers740W; the stabilizer is sodium citrate; the humectant is ethylene glycol; the curing agent is ARADUR38-1; the defoamer is Z-2875.

[0031] The preparation method of the printing material liquid comprises the steps of: adding an antifoaming agent, a dispersant, a humectant, a stabilizer and water to a modified acrylic emulsion in sequence while stirring, and stirring and dispersing; then adding a thickener, a curing agent and a dye, and stirring and dispersing evenly.

[0032] Example 2

[0033] This example provides a printing material liquid, which comprises the following raw materials in parts by weight: 60 parts of modified acrylic emulsion, 2 parts of thickener, 0.5 part of dispersant, 4 parts of stabilizer, 0.5 part of humectant, 1 part of curing agent, 0.2 part of antifoaming agent, 3 parts of dye and 50 parts of water;

[0034] Among them, the preparation method of the modified acrylic emulsion comprises:

[0035] (1) Prepare rare earth doped nano-TiO 2 The preparation method comprises: ultrasonically dispersing silane coupling agent KH-550 in an ethanol aqueous solution for 120 min, adjusting the pH to 3 with glacial acetic acid to obtain a silane coupling agent solution; adding nano-TiO 2 to anhydrous ethanol, ultrasonically dispersing for 50 min, adding cerium nitrate, slowly dropping the silane coupling agent solution, adjusting the pH to 9 with ammonia water, raising the temperature to 65 °C, stirring and reacting for 2 h, cooling, centrifuging, washing with water, and drying at 60 °C to obtain; the weight ratio of silane coupling agent KH-550, ethanol aqueous solution, nano-TiO 2 , anhydrous ethanol and cerium nitrate is 6:30:25:15:4; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:1;

[0036] (2) Prepare a modified acrylic emulsion: mix acrylic acid, methyl methacrylate, n-butyl acrylate monomers and deionized water, add sodium dodecyl sulfate and nonylphenol polyoxyethylene ether, and continue stirring to obtain a mixed solution, then add rare earth doped nano-TiO 2 for ultrasonic dispersion for 30 min, gradually raise the temperature to 75 °C, adjust the pH to 4, then add ammonium persulfate, raise the temperature to 82 °C, keep the temperature for reaction for 4 h, then cool to room temperature, and adjust the pH to 8 with ammonia water to obtain; the weight ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomers, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, rare earth doped nano-TiO 2 and ammonium persulfate is 2:12:20:40:0.5:1:0.2:4;

[0037] Among them, the thickener is ACRACONC FN 01; the dispersant is Dispers740W; the stabilizer is sodium citrate; the humectant is urea; the curing agent is ARADUR3986; the antifoaming agent is Z-2875.

[0038] The preparation method of the printing material liquid comprises the following steps: adding an antifoaming agent, a dispersant, a moisturizing agent, a stabilizer and water to the modified acrylic emulsion in sequence while stirring, and stirring and dispersing; then adding a thickening agent, a curing agent and a dye, and stirring and dispersing evenly.

[0039] Example 3

[0040] This example provides a printing material liquid, which comprises the following raw materials in parts by weight: 70 parts of modified acrylic emulsion, 2.4 parts of thickening agent, 1.5 parts of dispersant, 5 parts of stabilizer, 1 part of moisturizing agent, 2 parts of curing agent, 0.4 part of antifoaming agent, 5 parts of dye and 60 parts of water;

[0041] Among them, the preparation method of the modified acrylic emulsion comprises:

[0042] (1) Prepare rare earth-doped nano-TiO 2 The preparation method of comprises: ultrasonically dispersing silane coupling agent KH-550 in an ethanol aqueous solution for 140 min, adjusting the pH to 4 with glacial acetic acid to obtain a silane coupling agent solution; adding nano-TiO 2 to anhydrous ethanol, ultrasonically dispersing for 70 min, adding cerium nitrate, slowly dropping the silane coupling agent solution, adjusting the pH to 10 with ammonia water, heating to 75 °C, stirring and reacting for 2.2 h, cooling, centrifuging, washing with water, and drying at 60 °C to obtain; the weight part ratio of silane coupling agent KH-550, ethanol aqueous solution, nano-TiO 2 , anhydrous ethanol and cerium nitrate is 8:40:35:20:5; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:1;

[0043] (2) Prepare the modified acrylic emulsion: mix acrylic acid, methyl methacrylate, n-butyl acrylate monomers and deionized water, add sodium dodecyl sulfate and nonylphenol polyoxyethylene ether, and continue stirring to obtain a mixed solution, then add rare earth-doped nano-TiO 2 for ultrasonic dispersion for 40 min, gradually heat up to 79 °C, adjust the pH to 6, then add ammonium persulfate, heat up to 84 °C, keep warm and react for 5 h, then cool to room temperature, and adjust the pH to 8 with ammonia water to obtain; the weight part ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomers, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, rare earth-doped nano-TiO 2 and ammonium persulfate is 3:14:22:50:1:1.2:0.4:5;

[0044] Among them, the thickening agent is ACRACONC FN 01; the dispersant is Dispers740W; the stabilizer is sodium citrate; the moisturizing agent is glycerol; the curing agent is ARADUR38-1; the antifoaming agent is Z-2875.

[0045] The preparation method of the printing material liquid comprises the following steps: adding an antifoaming agent, a dispersant, a humectant, a stabilizer and water to the modified acrylic emulsion in sequence while stirring, and stirring and dispersing; then adding a thickener, a curing agent and a dye, and stirring and dispersing evenly.

[0046] Example 4

[0047] This example provides a printing material liquid, which comprises the following raw materials in parts by weight: 60 parts of modified acrylic emulsion, 2.4 parts of thickener, 0.5 part of dispersant, 5 parts of stabilizer, 0.5 part of humectant, 2 parts of curing agent, 0.2 part of antifoaming agent, 5 parts of dye and 50 parts of water;

[0048] Among them, the preparation method of the modified acrylic emulsion comprises:

[0049] (1) Prepare rare earth doped nano-TiO 2 The preparation method of includes: ultrasonically dispersing silane coupling agent KH-550 in an ethanol aqueous solution for 140 min, adjusting the pH to 3 with glacial acetic acid to obtain a silane coupling agent solution; adding nano-TiO 2 to anhydrous ethanol, ultrasonically dispersing for 70 min, adding cerium nitrate, slowly dropping the silane coupling agent solution, adjusting the pH to 9 with ammonia water, heating to 75 °C, stirring and reacting for 2 h, cooling, centrifuging, washing with water, and drying at 60 °C to obtain; the weight ratio of silane coupling agent KH-550, ethanol aqueous solution, nano-TiO 2 , anhydrous ethanol and cerium nitrate is 8:30:35:15:4; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:1;

[0050] (2) Prepare the modified acrylic emulsion: mix acrylic acid, methyl methacrylate, n-butyl acrylate monomers and deionized water, add sodium dodecyl sulfate and nonylphenol polyoxyethylene ether, and continue stirring to obtain a mixed solution, then add rare earth doped nano-TiO 2 for ultrasonic dispersion for 40 min, gradually heat to 75 °C, adjust the pH to 6, then add ammonium persulfate, heat to 82 °C, keep the temperature for reaction for 5 h, then cool to room temperature, and adjust the pH to 8 with ammonia water to obtain; the weight ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomers, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, rare earth doped nano-TiO 2 and ammonium persulfate is 2:14:20:50:0.5:1.2:0.2:5;

[0051] Among them, the thickener is ACRACONC FN 01; the dispersant is Dispers740W; the stabilizer is sodium citrate; the humectant is ethylene glycol; the curing agent is ARADUR38-1; the antifoaming agent is Z-2875.

[0052] The preparation method of the printing material liquid comprises the following steps: adding an antifoaming agent, a dispersant, a humectant, a stabilizer and water to the modified acrylic emulsion in sequence while stirring, and stirring and dispersing; then adding a thickener, a curing agent and a dye, and stirring and dispersing evenly.

[0053] Comparative Example 1

[0054] This comparative example provides a printing material liquid, which comprises the following raw materials in parts by weight: 65 parts of modified acrylic emulsion, 2.2 parts of thickener, 1 part of dispersant, 4.5 parts of stabilizer, 0.75 part of humectant, 1.5 parts of curing agent, 0.3 part of antifoaming agent, 4 parts of dye and 55 parts of water;

[0055] Among them, the preparation method of the modified acrylic emulsion comprises:

[0056] (1) Prepare rare earth-doped nano-TiO 2 The preparation method of includes: ultrasonically dispersing silane coupling agent KH-560 in an ethanol aqueous solution for 130 min, adjusting the pH to 3.5 with glacial acetic acid to obtain a silane coupling agent solution; adding nano-TiO 2 to anhydrous ethanol, ultrasonically dispersing for 60 min, adding cerium nitrate, slowly dropping the silane coupling agent solution, adjusting the pH to 9.5 with ammonia water, heating to 70 °C, stirring and reacting for 2.1 h, cooling, centrifuging, washing with water, and drying at 60 °C to obtain; the weight ratio of silane coupling agent KH-560, ethanol aqueous solution, nano-TiO 2 , anhydrous ethanol and cerium nitrate is 7:35:30:17.5:4.5; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:1;

[0057] (2) Prepare the modified acrylic emulsion: mix acrylic acid, methyl methacrylate, n-butyl acrylate monomers and deionized water, add sodium dodecyl sulfate and nonylphenol polyoxyethylene ether, and continue stirring to obtain a mixed solution, then add rare earth-doped nano-TiO 2 for ultrasonic dispersion for 35 min, gradually heat up to 77 °C, adjust the pH to 5, then add ammonium persulfate, heat up to 83 °C, keep the temperature for reaction for 4.5 h, then cool to room temperature, and adjust the pH to 8 with ammonia water to obtain; the weight ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomers, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, rare earth-doped nano-TiO 2 and ammonium persulfate is 2.5:13:21:45:0.75:1.1:0.3:4.5;

[0058] Among them, the thickener is ACRACONC FN 01; the dispersant is Dispers740W; the stabilizer is sodium citrate; the humectant is ethylene glycol; the curing agent is ARADUR38-1; the antifoaming agent is Z-2875.

[0059] The preparation method of the printing material liquid comprises the steps of: adding an antifoaming agent, a dispersing agent, a humectant, a stabilizer and water to a modified acrylic emulsion in sequence while stirring, and stirring and dispersing; then adding a thickening agent, a curing agent and a dye, and stirring and dispersing uniformly.

[0060] Comparative Example 2

[0061] This comparative example provides a printing material liquid, which comprises the following raw materials in parts by weight: 65 parts of modified acrylic emulsion, 2.2 parts of thickening agent, 1 part of dispersing agent, 4.5 parts of stabilizer, 0.75 part of humectant, 1.5 parts of curing agent, 0.3 part of antifoaming agent, 4 parts of dye and 55 parts of water;

[0062] Among them, the preparation method of the modified acrylic emulsion comprises:

[0063] (1) Prepare rare earth-doped nano-TiO 2 The preparation method of is as follows: ultrasonically disperse silane coupling agent KH-570 in an ethanol aqueous solution for 130 min, adjust the pH to 3.5 with glacial acetic acid to obtain a silane coupling agent solution; add nano-TiO 2 to absolute ethanol, ultrasonically disperse for 60 min, add cerium nitrate, slowly drop the silane coupling agent solution, adjust the pH to 9.5 with ammonia water, raise the temperature to 70 °C, stir and react for 2.1 h, cool, centrifuge, wash with water, and then dry at 60 °C to obtain; the weight part ratio of silane coupling agent KH-570, ethanol aqueous solution, nano-TiO 2 , absolute ethanol and cerium nitrate is 7:35:30:17.5:4.5; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:1;

[0064] (2) Prepare a modified acrylic emulsion: mix acrylic acid, methyl methacrylate, n-butyl acrylate monomers and deionized water, add sodium dodecyl sulfate and nonylphenol polyoxyethylene ether, and continue stirring to obtain a mixed solution, then add rare earth-doped nano-TiO 2 for ultrasonic dispersion for 35 min, gradually raise the temperature to 77 °C, adjust the pH to 5, then add ammonium persulfate, raise the temperature to 83 °C, keep the temperature for reaction for 4.5 h, then cool to room temperature, and adjust the pH to 8 with ammonia water to obtain; the weight part ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomers, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, rare earth-doped nano-TiO 2 and ammonium persulfate is 2.5:13:21:45:0.75:1.1:0.3:4.5;

[0065] Among them, the thickening agent is ACRACONC FN 01; the dispersant is Dispers740W; the stabilizer is sodium citrate; the humectant is ethylene glycol; the curing agent is ARADUR38-1; the defoaming agent is Z-2875.

[0066] The preparation method of the printing material liquid comprises the steps of: adding a defoaming agent, a dispersant, a humectant, a stabilizer and water to the modified acrylic emulsion in sequence while stirring, and stirring and dispersing; then adding a thickening agent, a curing agent and a dye, and stirring and dispersing evenly.

[0067] Comparative Example 3

[0068] This comparative example provides a printing material liquid, which comprises the following raw materials in parts by weight: 65 parts of modified acrylic emulsion, 2.2 parts of thickening agent, 1 part of dispersant, 4.5 parts of stabilizer, 0.75 part of humectant, 1.5 parts of curing agent, 0.3 part of defoaming agent, 4 parts of dye and 55 parts of water;

[0069] Among them, the preparation method of the modified acrylic emulsion comprises:

[0070] (1) Prepare rare earth doped nano-TiO 2 The preparation method comprises: ultrasonically dispersing silane coupling agent KH-550 in an ethanol aqueous solution for 130 min, adjusting the pH to 3.5 with glacial acetic acid to obtain a silane coupling agent solution; adding nano-TiO 2 to anhydrous ethanol and ultrasonically dispersing for 60 min, slowly dropping the silane coupling agent solution, adjusting the pH to 9.5 with ammonia water, heating to 70 °C and then stirring and reacting for 2.1 h, cooling, centrifuging, washing with water, and drying at 60 °C to obtain; the weight ratio of silane coupling agent KH-550, ethanol aqueous solution, nano-TiO 2 and anhydrous ethanol is 7:35:30:17.5; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:1;

[0071] (2) Prepare the modified acrylic emulsion: mix acrylic acid, methyl methacrylate, n-butyl acrylate monomers and deionized water, add sodium dodecyl sulfate and nonylphenol polyoxyethylene ether and continue stirring to obtain a mixed solution, then add rare earth doped nano-TiO 2 and ultrasonically disperse for 35 min, gradually heat to 77 °C, adjust the pH to 5, then add ammonium persulfate, heat to 83 °C, keep warm and react for 4.5 h and then cool to room temperature, and adjust the pH to 8 with ammonia water to obtain; the weight ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomers, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, rare earth doped nano-TiO 2 and ammonium persulfate is 2.5:13:21:45:0.75:1.1:0.3:4.5;

[0072] Among them, the thickener is ACRACONC FN 01; the dispersant is Dispers740W; the stabilizer is sodium citrate; the humectant is ethylene glycol; the curing agent is ARADUR38-1; the defoamer is Z-2875.

[0073] The preparation method of the printing paste liquid comprises the steps of: adding a defoamer, a dispersant, a humectant, a stabilizer and water to the modified acrylic emulsion in sequence while stirring, and stirring and dispersing; then adding a thickener, a curing agent and a dye, and stirring and dispersing evenly.

[0074] Comparative Example 4

[0075] This comparative example provides a printing paste liquid, which comprises the following raw materials in parts by weight: 65 parts of modified acrylic emulsion, 2.2 parts of thickener, 1 part of dispersant, 4.5 parts of stabilizer, 0.75 part of humectant, 1.5 parts of curing agent, 0.3 part of defoamer, 4 parts of dye and 55 parts of water;

[0076] Among them, the preparation method of the modified acrylic emulsion comprises:

[0077] (1) Prepare rare earth doped nano-TiO 2 The preparation method of is as follows: adding nano-TiO 2 to absolute ethanol, ultrasonically dispersing for 60 min, adding cerium nitrate, adjusting the pH to 9.5 with ammonia water, heating to 70 °C, stirring and reacting for 2.1 h, cooling, centrifuging, washing with water, and drying at 60 °C to obtain; the weight ratio of nano-TiO 2 , absolute ethanol and cerium nitrate is 30:17.5:4.5;

[0078] (2) Prepare the modified acrylic emulsion: mixing acrylic acid, methyl methacrylate, n-butyl acrylate monomers and deionized water, adding sodium dodecyl sulfate and nonylphenol polyoxyethylene ether, and continuing to stir to obtain a mixed solution, then adding rare earth doped nano-TiO 2 for ultrasonic dispersion for 35 min, gradually heating to 77 °C, adjusting the pH to 5, adding ammonium persulfate, heating to 83 °C, holding the temperature and reacting for 4.5 h, then cooling to room temperature, and adjusting the pH to 8 with ammonia water to obtain; the weight ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomers, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, rare earth doped nano-TiO 2 and ammonium persulfate is 2.5:13:21:45:0.75:1.1:0.3:4.5;

[0079] Among them, the thickener is ACRACONC FN 01; the dispersant is Dispers740W; the stabilizer is sodium citrate; the humectant is ethylene glycol; the curing agent is ARADUR38-1; the defoamer is Z-2875.

[0080] The preparation method of the printing material liquid comprises the following steps: adding an antifoaming agent, a dispersant, a humectant, a stabilizer and water to the modified acrylic emulsion in sequence while stirring, and stirring and dispersing; then adding a thickener, a curing agent and a dye, and stirring and dispersing evenly.

[0081] Comparative Example 5

[0082] This comparative example provides a printing material liquid, which comprises the following raw materials in parts by weight: 65 parts of modified acrylic emulsion, 2.2 parts of thickener, 1 part of dispersant, 4.5 parts of stabilizer, 0.75 part of humectant, 1.5 parts of curing agent, 0.3 part of antifoaming agent, 4 parts of dye and 55 parts of water;

[0083] Among them, the preparation method of the modified acrylic emulsion comprises:

[0084] Mix acrylic acid, methyl methacrylate, n-butyl acrylate monomers and deionized water, add sodium dodecyl sulfate and nonylphenol polyoxyethylene ether, and continue stirring to obtain a mixed solution. Subsequently, add nano-TiO 2 Perform ultrasonic dispersion for 35 min, gradually raise the temperature to 77 °C, adjust the pH to 5, then add ammonium persulfate, raise the temperature to 83 °C, keep the temperature for reaction for 4.5 h, then cool to room temperature, and adjust the pH to 8 with ammonia water to obtain; the weight ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomers, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, nano-TiO 2 and ammonium persulfate is 2.5:13:21:45:0.75:1.1:0.3:4.5;

[0085] Among them, the thickener is ACRACONC FN 01; the dispersant is Dispers740W; the stabilizer is sodium citrate; the humectant is ethylene glycol; the curing agent is ARADUR38-1; the antifoaming agent is Z-2875.

[0086] The preparation method of the printing material liquid comprises the following steps: adding an antifoaming agent, a dispersant, a humectant, a stabilizer and water to the modified acrylic emulsion in sequence while stirring, and stirring and dispersing; then adding a thickener, a curing agent and a dye, and stirring and dispersing evenly.

[0087] Comparative Example 6

[0088] This comparative example provides a printing material liquid, which comprises the following raw materials in parts by weight: 65 parts of acrylic emulsion, 2.2 parts of thickener, 1 part of dispersant, 4.5 parts of stabilizer, 0.75 part of humectant, 1.5 parts of curing agent, 0.3 part of antifoaming agent, 4 parts of dye and 55 parts of water;

[0089] Among them, the preparation method of the acrylic emulsion comprises:

[0090] Mix acrylic acid, methyl methacrylate, and n-butyl acrylate monomers with deionized water. After adding sodium dodecyl sulfate and nonylphenol polyoxyethylene ether, continue stirring to obtain a mixed solution. Ultrasonically disperse for 35 min, gradually heat up to 77 °C, adjust the pH to 5, then add ammonium persulfate, heat up to 83 °C, keep the temperature for reaction for 4.5 h, and then cool down to room temperature. Adjust the pH to 8 with ammonia water to obtain the product. The weight ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomer, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, and ammonium persulfate is 2.5:13:21:45:0.75:1.1:4.5;

[0091] Among them, the thickener is ACRACONC FN 01; the dispersant is Dispers740W; the stabilizer is sodium citrate; the humectant is ethylene glycol; the curing agent is ARADUR38-1; the defoamer is Z-2875.

[0092] The preparation method of the printing material liquid includes the steps of: adding a defoamer, a dispersant, a humectant, a stabilizer, and water to the acrylic emulsion while stirring, and stirring and dispersing; then adding a thickener, a curing agent, and a dye, and stirring and dispersing evenly.

[0093] Test example: Use the printing material liquids prepared in the foregoing Examples 1-4 and Comparative Examples 1-6 to print and dye fabrics, and perform the following tests on the obtained printed and dyed fabrics:

[0094] Fabric apparent color depth: The fabric color depth is represented by the K / S value and is measured using an SF600X Datacolor colorimeter and color matching instrument;

[0095] Friction fastness test: It is measured according to GB / T3920-2008 "Textiles - Colorfastness tests - Colorfastness to rubbing". The rating is determined using an SF600X Datacolor colorimeter and color matching instrument;

[0096] Soaping fastness test: It is measured according to GB / T3920-2008 "Textiles - Colorfastness tests - Colorfastness to rubbing". The rating is determined using an SF600X Datacolor colorimeter and color matching instrument.

[0097] The results are shown in Table 1 below.

[0098] Table 1 Performance test

[0099]

[0100]

[0101] Finally, it should be noted that the above embodiments are only used to illustrate the present invention rather than to limit the technical solutions described in the present invention; those of ordinary skill in the art should understand that the present invention can still be modified or equivalently replaced; and all technical solutions and their improvements that do not depart from the spirit and scope of the present invention should be covered by the scope of the claims of the present invention.

Claims

1. A printing liquid, characterized in that: The invention comprises the following raw materials in parts by weight: 60-70 parts of modified acrylic emulsion, 2-2.4 parts of thickener, 0.5-1.5 parts of dispersant, 4-5 parts of stabilizer, 0.5-1 parts of humectant, 1-2 parts of curing agent, 0.2-0.4 parts of defoaming agent, 3-5 parts of dye and 50-60 parts of water; The preparation method of the modified acrylic emulsion comprises: mixing acrylic acid, methyl methacrylate, n-butyl acrylate monomers with deionized water, adding sodium dodecyl sulfate and nonylphenol polyoxyethylene ether and continuing to stir to obtain a mixed solution, then adding rare earth-doped nano-TiO2 for ultrasonic dispersion for 30-40 minutes, gradually heating to 75-79° C., adjusting the pH to 4-6, then adding ammonium persulfate, heating to 82-84° C., keeping the temperature for reaction for 4-5 hours, then cooling to room temperature, and adjusting the pH to 8 with ammonia water to obtain the modified acrylic emulsion; The weight ratio of acrylic acid, methyl methacrylate, n-butyl acrylate monomer, deionized water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, rare earth doped nano-TiO2 and ammonium persulfate is (2-3): (12-14): (20-22): (40-50): (0.5-1): (1-1.2): (0.2-0.4): (4-5); The preparation method of rare earth doped nano TiO2 comprises: dispersing silane coupling agent KH-550 in ethanol aqueous solution by ultrasonic for 120-140 minutes, adjusting the pH to 3-4 with glacial acetic acid to obtain a silane coupling agent solution; adding nano TiO2 to anhydrous ethanol for ultrasonic dispersion for 50-70 minutes, adding cerium nitrate, slowly dripping the silane coupling agent solution, adjusting the pH to 9-10 with ammonia water, heating to 65-75° C., stirring for reaction for 2-2.2 hours, cooling, centrifuging, washing with water and drying to obtain the product; The weight ratio of the silane coupling agent KH-550, ethanol aqueous solution, nano-TiO2, anhydrous ethanol and cerium nitrate is (6-8): (30-40): (25-35): (15-20): (4-5).

2. A printing liquid according to claim 1, characterized in that: The mass ratio of water to ethanol in the ethanol aqueous solution is 1:

1.

3. A printing liquid according to claim 1, characterized in that: The thickener is ACRACONC FN 01; the dispersant is Dispers740W; and the stabilizer is sodium citrate.

4. A printing liquid according to claim 1, characterized in that: The moisturizing agent includes at least one of urea, ethylene glycol and glycerin; the curing agent includes ARADUR38-1 or ARADUR3986; and the defoaming agent is Z-2875.

5. A method for preparing a printing liquid as claimed in any one of claims 1 to 4, characterized in that the steps include: Add defoamer, dispersant, humectant, stabilizer and water to the modified acrylic emulsion in sequence while stirring, and disperse by stirring; then add thickener, curing agent and dye, and disperse by stirring evenly.

6. Use of the printing liquid as described in any one of claims 1 to 4 in textile printing and dyeing.

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