Printing thickening agent and preparation method thereof

Abstract

The invention relates to the technical field of textile auxiliary agents, and discloses a printing thickening agent and a preparation method thereof. Comprising 120 to 170 parts of an acrylic monomer, 5 to 15 parts of fumed silica, 50 to 80 parts of an epoxy modified polyurethane prepolymer, 0 to 240 parts of a pH regulator A, 20 to 300 parts of a pH regulator B, 0.05 to 0.20 part of a cross-linking agent, 1 to 5 parts of a chelating dispersant, 100 to 160 parts of an oil-phase solvent, 15 to 25 parts of an emulsifier, 15 to 45 parts of a reverse-phase emulsifier, 0.15 to 0.25 part of an oxidant and 0.15 to 0.25 part of a reducing agent. According to the printing thickening agent provided by the invention, the obtained product is excellent in color yield, and the color paste is easy to clean; and the printed cloth sample has high softness after being washed with water.

Description

Technical Field

[0001] The invention relates to the technical field of textile auxiliaries, in particular to a printing thickener and a preparation method thereof. Background Art

[0002] Synthetic thickeners are an important branch of water-soluble polymers. They are generally used to change the rheological behavior of the thickened system, bringing better physical and chemical stability to the thickened system, while improving the storage and construction performance of the system. Therefore, they have their place in many industries.

[0003] In textile printing, anionic polyacrylic acid has the best thickening effect and is currently the most widely used thickener. The main type is polyacrylate polymers, which can greatly improve the thixotropy of printing paste, making the printed colors more vivid and full, and having excellent permeability. However, this type of thickener still has some defects, such as poor electrolyte resistance and easy penetration. Among various application performances, color yield is a very important indicator. High color yield can save dyes and greatly reduce processing costs. Therefore, thickeners with high color yield are very popular in the market. Summary of the invention

[0004] Technical problems solved by the present invention:

[0005] The invention is used to solve the problem that the existing printing thickener can improve the color yield, but the color yield has a great influence on the hand feel and the degree of improvement of the color yield is limited.

[0006] The technical solution adopted by the present invention is:

[0007] In view of the above technical problems, the object of the present invention is to provide a printing thickener and a preparation method thereof.

[0008] Specifically,

[0009] A printing thickener comprises raw material components in parts by weight, including 120-170 parts of acrylic monomers, 5-15 parts of fumed silica, 50-80 parts of epoxy-modified polyurethane prepolymers, 0-240 parts of pH adjuster A, 20-300 parts of pH adjuster B, 0.05-0.20 parts of crosslinking agents, 1-5 parts of chelating dispersants, 100-160 parts of oil phase solvents, 15-25 parts of emulsifiers, 15-45 parts of reverse emulsifiers, 0.15-0.25 parts of oxidants, and 0.15-0.25 parts of reducing agents.

[0010] According to some preferred embodiments, the acrylic monomer includes at least one of methacrylic acid, acrylic acid, and dimethacrylic acid.

[0011] According to some preferred embodiments, pH regulator A includes at least one of liquid caustic soda and ammonia water.

[0012] According to some preferred embodiments, pH regulator B includes at least one of triethylamine, N-methyldiethanolamine, triethanolamine, and allyltrimethylammonium chloride.

[0013] According to some preferred embodiments, the particle size of fumed silica is 20 - 50 nm.

[0014] According to some preferred embodiments, the crosslinking agent includes at least one of methylenebisacrylamide and N-hydroxymaleimide.

[0015] According to some preferred embodiments, the chelating dispersant includes at least one of glutamate N,N-diacetic acid, diethylenetriaminepentaacetic acid, and EDTA.

[0016] According to some preferred embodiments, the oil-phase solvent includes at least one of D40, D60, D70, 15# white oil, 68# white oil, 100# white oil, and 150# white oil.

[0017] According to some preferred embodiments, the emulsifier includes at least one of Span-80, Span-60, and 1599A.

[0018] According to some preferred embodiments, the inverse emulsifier includes at least one of Tween-80, Tween-60, AE0-9, AEO-7, TO-7, and TO-9.

[0019] According to some preferred embodiments, the oxidizing agent includes at least one of potassium persulfate, sodium persulfate, and ammonium persulfate;

[0020] According to some preferred embodiments, the reducing agent includes at least one of sodium bisulfite, sodium metabisulfite, and sodium sulfite.

[0021] According to some preferred embodiments, the preparation method of the epoxy-modified polyurethane prepolymer is as follows: polyol and diisocyanate are added into a reaction vessel, and reacted at 70-90 °C for 1-4 h to obtain a prepolymer; a chain extender is added to the prepolymer and reacted for 0.5-2 h to obtain a polyurethane prepolymer; epichlorohydrin and a catalyst are added to the polyurethane prepolymer, and reacted at 60-80 °C for 2-5 h, and then filtered, washed, and dried to obtain the epoxy-modified polyurethane prepolymer. The polyol is a polyether polyol or a polyester polyol. The polyether polyol is selected from polyethylene glycol or polypropylene glycol, and the polyester polyol is selected from polyethylene adipate or polycarbonate polyol. The diisocyanate is selected from toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, etc. The chain extender is ethylene glycol or 1,4-butanediol. The catalyst is triethylamine. The ratio of polyol, diisocyanate, chain extender, epichlorohydrin, and catalyst is 40-80:20-40:3-10:10-20:2-10.

[0022] Second, the present invention provides a preparation method of the foregoing printing thickener, comprising the following steps:

[0023] (1) Add water into a reactor, and then add acrylic monomers, and start stirring until completely dispersed;

[0024] (2) Sequentially dropwise add pH regulator A and pH regulator B to step (1) until the pH value reaches 5.5-6.5;

[0025] (3) Add a chelating dispersant, a crosslinking agent, an oxidant, fumed silica, and an epoxy-modified polyurethane prepolymer to the neutralized acrylate solution in step (2), and continue stirring until completely dissolved to obtain an aqueous solution;

[0026] (4) Stir the oil-phase solvent and emulsifier evenly and then emulsify at high speed to obtain an oil-phase solution; maintain the emulsification power, slowly add the aqueous solution in step (3) to the oil-phase solution, and continue to emulsify at high speed for 15-20 min. The temperature is controlled below 35 °C during this process;

[0027] (5) Prepare a reducing agent solution by dissolving the reducing agent in 20-30 times of water and stirring evenly for standby.

[0028] (6) Pass nitrogen into step (4) for 20-30 min, and then slowly dropwise add the reducing agent mixed solution, control the dropping time to be 3-10 min. After the system temperature rises, control the temperature at 50-55 °C, continue to keep warm for 1-3 h, and then cool down to room temperature;

[0029] (7) Filter the material obtained in step (6) through a 200-mesh filter screen;

[0030] (8) The material obtained in step (7) is added with an inverse emulsifier and stirred for 20 - 30 min to obtain the finished thickener.

[0031] The beneficial effects achieved by the present invention:

[0032] (1) The printing thickener provided by the present invention adds organic amine, resulting in excellent color development of the product and easy cleaning of the color paste.

[0033] (2) The printing thickener provided by the present invention does not use acrylamide monomer, so that the printed cloth sample has higher softness after washing.

[0034] (3) The printing thickener provided by the present invention adds fumed silica. Due to its high specific surface area and a large number of hydroxyl groups on the surface, it can form a network structure with the thickener system, thereby increasing the viscosity of the system. At the same time, it can also form a stable suspension in the system to avoid the problem of sedimentation.

[0035] (4) The printing thickener provided by the present invention adds an epoxy-modified polyurethane prepolymer. Its soft segment (polyether) and hard segment (epoxy, isocyanate) can maintain the necessary viscosity of the system while endowing the product with good handle and softness. The epoxy groups therein react with the acrylic monomers in the system to form a crosslinked network structure. In addition, the groups it has can interact with the pigments to promote the dispersion of the pigments.

[0036] (5) The printing thickener provided by the present invention adopts a low-temperature polymerization process and extends the polymerization time, which can not only avoid yellowing but also make the monomers react more fully to obtain higher thickening ability. Description of the Drawings

[0037] Figure 1 It is a physical picture of color development comparison for Example 1 and Comparative Examples 1 - 4. Detailed Embodiments

[0038] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Those not specified in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. Reagents or instruments not specified by the manufacturer are all conventional products that can be obtained through commercial purchase.

[0039] Example 1

[0040] (1) Add 90 g of water to the reactor, and then add 150 g of acrylic acid and stir for 5 min until completely dispersed.

[0041] (2) Drop about 200 g of liquid caustic soda and 50 g of triethanolamine into step (1) in sequence until the pH value reaches between 5.5 and 6.5.

[0042] (3) To the acrylate solution neutralized in step (2), add 3.5 g of diethylenetriaminepentaacetic acid, 0.10 g of methylenebisacrylamide, 0.15 g of potassium persulfate, 10 g of fumed silica, and 65 g of epoxy-modified polyurethane prepolymer, and continue stirring until completely dissolved to obtain an aqueous solution. The preparation method of the epoxy-modified polyurethane prepolymer is as follows: Add polyethylene glycol and toluene diisocyanate into a reaction vessel, react at 80 °C for 3 h, then at the same temperature, add ethylene glycol and react for 1 h. Then add epichlorohydrin and triethylamine, react at 75 °C for 2 h, and then obtain the product through filtration, washing, and drying. The ratio of polyethylene glycol, toluene diisocyanate, ethylene glycol, epichlorohydrin, and triethylamine is 80:35:6:13:6.

[0043] (4) Stir 160 g of D70 and 15 g of SPAN-60 evenly and then emulsify at high speed to obtain an oil-phase solution. While maintaining the emulsification power, slowly add the aqueous solution in step (3) to the oil-phase solution, control the temperature below 35 °C, and continue high-speed emulsification for 15 - 20 min to obtain a pre-emulsion.

[0044] (5) Dissolve 0.20 g of sodium bisulfite in 6 g of water, stir evenly, and set aside.

[0045] (6) Pass nitrogen into step (4) for 25 min, then slowly dropwise add the solution in (5), control the dropping time to be 3 - 10 min, and control the temperature at 50 - 55 °C. After dropping, continue to keep warm for 1 - 2 h.

[0046] (7) Filter the material obtained in step (6) through a 200-mesh filter screen.

[0047] (8) Add 30 g of Tween-80 to the material obtained in step (7), and stir for 20 - 30 min to obtain the finished thickener.

[0048] Control Example 1

[0049] (1) Add 90 g of water to a reactor, then add 130 g of acrylic acid and 20 g of acrylamide, and start stirring until completely dispersed.

[0050] (2) Dropwise add about 200 g of liquid alkali to step (1) until the pH value reaches between 5.5 and 6.5;

[0051] (3) To the acrylate solution neutralized in step (2), add 43.5 g of diethylenetriaminepentaacetic acid, 0.10 g of methylenebisacrylamide, 0.15 g of potassium persulfate, and continue stirring until completely dissolved to obtain an aqueous solution;

[0052] (4) Stir 160 g of D70 and 15 g of SPAN-60 evenly, and then perform high-speed emulsification to obtain an oil-phase solution; while maintaining the emulsification power, slowly add the aqueous-phase solution in step (3) to the oil-phase solution, control the temperature below 35 °C, and continue high-speed emulsification for 15 - 20 min to obtain a pre-emulsion;

[0053] (5) Dissolve 0.20 g of sodium bisulfite in 6 g of water, stir evenly, and set aside.

[0054] (6) Pass nitrogen into step (4) for 25 min, then slowly add the solution in (5), control the dropping time to be 5 min, and control the temperature at 50 - 55 °C. After the dropping is completed, continue to keep warm for 2 h, and then cool down to room temperature;

[0055] (7) Filter the material obtained in step (6) through a 200-mesh filter screen.

[0056] (8) Add 30 g of Tween-60 to the material obtained in step (7), and stir for 20 - 30 min to obtain the finished thickener.

[0057] Control Example 2

[0058] (1) Add 90 g of water to the reactor, then add 130 g of acrylic acid and 20 g of acrylamide, and start stirring until completely dispersed.

[0059] (2) Drop about 200 g of liquid alkali into step (1) until the pH value reaches between 5.5 and 6.5.

[0060] (3) Add 43.5 g of diethylenetriaminepentaacetic acid, 0.10 g of methylenebisacrylamide, and 0.15 g of potassium persulfate to the neutralized acrylate solution in step (2), and continue stirring until completely dissolved to obtain an aqueous-phase solution.

[0061] (4) Stir 160 g of D70 and 15 g of SPAN-60 evenly, and then perform high-speed emulsification to obtain an oil-phase solution. While maintaining the emulsification power, slowly add the aqueous-phase solution in step (3) to the oil-phase solution, control the temperature below 35 °C, and continue high-speed emulsification for 15 - 20 min to obtain a pre-emulsion.

[0062] (5) Dissolve 0.20 g of sodium bisulfite in 6 g of water, stir evenly, and set aside.

[0063] (6) Pass nitrogen into step (4) for 25 min, then add the solution in (5), control the dropping time to be 1 min, and control the temperature at 65 - 75 °C. Keep warm for 1 h, and then cool down to room temperature.

[0064] (7) Filter the material obtained in step (6) through a 200-mesh filter screen.

[0065] (8) Add the material obtained in step (7) to 30 g of Tween-60 and stir for 20 - 30 min to obtain the finished thickener.

[0066] Control Example 3

[0067] (1) Add 90 g of water to the reactor, then add 150 g of acrylic acid and stir for 5 min until completely dispersed.

[0068] (2) Dropwise add about 200 g of liquid alkali and 50 g of triethanolamine to step (1) in sequence until the pH value reaches between 5.5 and 6.5.

[0069] (3) Add 3.5 g of diethylenetriaminepentaacetic acid, 0.10 g of methylenebisacrylamide, 0.15 g of potassium persulfate, and 65 g of epoxy-modified polyurethane prepolymer to the neutralized acrylate solution in step (2), and continue to stir until completely dissolved to obtain the aqueous solution. The preparation method of the epoxy-modified polyurethane prepolymer is the same as that in Example 1.

[0070] (4) Stir 160 g of D70 and 15 g of SPAN-60 evenly and then emulsify at high speed to obtain the oil-phase solution. While maintaining the emulsification power, slowly add the aqueous solution in step (3) to the oil-phase solution, control the temperature below 35 °C, and continue to emulsify at high speed for 15 - 20 min to obtain the pre-emulsion.

[0071] (5) Dissolve 0.20 g of sodium bisulfite in 6 g of water, stir evenly, and set aside.

[0072] (6) Pass nitrogen into step (4) for 25 min, then slowly dropwise add the solution in (5), control the dropping time to be 3 - 10 min, and control the temperature at 50 - 55 °C. After the dropping is completed, continue to keep warm for 1 - 2 h.

[0073] (7) Filter the material obtained in step (6) through a 200-mesh filter screen.

[0074] (8) Add the material obtained in step (7) to 30 g of Tween-80 and stir for 20 - 30 min to obtain the finished thickener.

[0075] Control Example 4

[0076] (1) Add 90 g of water to the reactor, then add 150 g of acrylic acid and stir for 5 min until completely dispersed.

[0077] (2) Dropwise add about 200 g of liquid alkali and 50 g of triethanolamine to step (1) in sequence until the pH value reaches between 5.5 and 6.5.

[0078] (3) To the acrylate solution neutralized in step (2), add 3.5 g of diethylenetriaminepentaacetic acid, 0.10 g of methylenebisacrylamide, 0.15 g of potassium persulfate, and 10 g of fumed silica, and continue stirring until completely dissolved to obtain an aqueous solution.

[0079] (4) Stir 160 g of D70 and 15 g of SPAN-60 evenly and then emulsify at high speed to obtain an oil-phase solution. While maintaining the emulsification power, slowly add the aqueous solution in step (3) to the oil-phase solution, control the temperature below 35 °C, and continue high-speed emulsification for 15 - 20 min to obtain a pre-emulsion.

[0080] (5) Dissolve 0.20 g of sodium bisulfite in 6 g of water, stir evenly, and set aside.

[0081] (6) Pass nitrogen into step (4) for 25 min, then slowly add the solution in (5), control the addition time to be 3 - 10 min, and control the temperature at 50 - 55 °C. After the addition is complete, continue to keep warm for 1 - 2 h.

[0082] (7) Filter the material obtained in step (6) through a 200-mesh sieve.

[0083] (8) Add 30 g of Tween-80 to the material obtained in step (7), stir for 20 - 30 min to obtain the finished thickener.

[0084] Test Examples

[0085] Take the thickeners prepared in Example 1 and Comparative Examples 1 - 4 as samples, test the thickening ability of the thickener for printing color paste, add the same printing color paste additives, thicken the color paste with the same amount of thickener, and at the same time test different dosages of the thickener. Use a 200-mesh screen to scrape the cloth, dry at 100 °C, set the shape at 180 °C for 5 min, wash with water, and then dry. Test the thickening ability, color obtained, and hand feeling.

[0086] The printing color paste additives include the following components in parts by weight: a certain amount of thickener, 1% of disperse dye, and use the same method for preparing the color paste. Use a DV-II type rotary viscometer, 7# rotor, and a rotation speed of 6 r / min for testing. The viscosity size is in mPa·s. The larger the viscosity data, the better the thickening effect. The K / S value is an important index for color evaluation. The larger the K / S value, the deeper the surface color. The results are shown in Table 1.

[0087]

[0088] The color comparison diagrams of Example 1 and Comparative Examples 1 - 4 are shown in Figure 1 .

[0089] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A printing thickener, wherein the raw material components are measured by weight, including 120-170 parts of acrylic monomers, 5-15 parts of fumed silica, 50-80 parts of epoxy-modified polyurethane prepolymers, 0-240 parts of pH adjuster A, 20-300 parts of pH adjuster B, 0.05-0.20 parts of crosslinking agents, 1-5 parts of chelating dispersants, 100-160 parts of oil phase solvents, 15-25 parts of emulsifiers, 15-45 parts of reverse emulsifiers, 0.15-0.25 parts of oxidants, and 0.15-0.25 parts of reducing agents.

2. The printing thickener according to claim 1, characterized in that The acrylic monomer includes at least one of methacrylic acid, acrylic acid, and dimethacrylic acid.

3. The printing thickener according to claim 1, characterized in that The pH adjuster A includes at least one of liquid alkali and ammonia water; and / or the pH adjuster B includes at least one of triethylamine, N-methyldiethanolamine, triethanolamine, and triallyl ammonium chloride.

4. The printing thickener according to claim 1, characterized in that The particle size of fumed silica is 20 to 50 nm.

5. The printing thickener according to claim 1, characterized in that The cross-linking agent includes at least one of methylenebisacrylamide and N-hydroxyacrylamide; and / or the chelating dispersant includes at least one of glutamic acid N,N-diacetic acid, diethylenetriaminepentaacetic acid, and EDTA.

6. The printing thickener according to claim 1, characterized in that The oil phase solvent includes at least one of D40, D60, D70, 15# white oil, 68# white oil, 100# white oil, and 150# white oil; and / or, the emulsifier includes at least one of Span-80, Span-60, and 1599A; and / or, the reverse emulsifier includes at least one of Tween-80, Tween-60, AE0-9, AEO-7, TO-7, and TO-9.

7. The printing thickener according to claim 1, characterized in that The oxidizing agent includes at least one of potassium persulfate, sodium persulfate, and ammonium persulfate; and / or the reducing agent includes at least one of sodium bisulfite, sodium pyrosulfite, and sodium sulfite.

8. The printing thickener according to any one of claims 1 to 7, characterized in that The preparation method of the epoxy modified polyurethane prepolymer comprises the following steps: adding polyol and diisocyanate into a reaction container, reacting to obtain a prepolymer; adding a chain extender into the prepolymer, reacting to obtain a polyurethane prepolymer; adding epichlorohydrin and a catalyst into the polyurethane prepolymer, reacting, filtering, washing and drying to obtain the epoxy modified polyurethane prepolymer.

9. The printing thickener according to claim 8, characterized in that The polyol is a polyether polyol or a polyester polyol; and / or the diisocyanate is selected from at least one of toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and isophorone diisocyanate; and / or the chain extender is ethylene glycol or 1,4-butanediol; and / or the catalyst is triethylamine; the ratio of the polyol, the diisocyanate, the chain extender, the epichlorohydrin and the catalyst is 40-80:20-40:3-10:10-20:2-10.

10. A method for preparing a printing thickener according to any one of claims 1 to 9, characterized in that: The steps include: (1) adding water into a reactor, and then adding an acrylic acid monomer, and dispersing the mixture by stirring; (2) sequentially adding pH adjuster A and pH adjuster B to step (1); (3) adding a chelating dispersant, a crosslinking agent, an oxidant, fumed silica, and an epoxy-modified polyurethane prepolymer to the acrylate solution neutralized in step (2), and continuing to stir to obtain an aqueous solution; (4) stirring the oil phase solvent and the emulsifier uniformly and then emulsifying them to obtain an oil phase solution; maintaining the emulsification power, slowly adding the aqueous phase solution in step (3) to the oil phase solution and continuing the emulsification; (5) preparing a reducing agent solution for standby use; (6) nitrogen is passed through step (4), and then the reducing agent mixed solution is slowly added dropwise. After the system is heated up, the temperature is controlled, the temperature is continued to be kept, and the temperature is cooled to room temperature; (7) filtering the material obtained in step (6); (8) Add a reverse emulsifier to the material obtained in step (7) to obtain a finished thickener.

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