Washing-free plush thickening agent and preparation method thereof

Abstract

The invention relates to the technical field of textile auxiliary agents, and discloses a washing-free plush thickening agent and a preparation method of the washing-free plush thickening agent. Comprising 100 to 170 parts of an acrylic monomer, 1 to 10 parts of a special monomer, 20 to 60 parts of organosilicon modified hyaluronic acid, 0 to 200 parts of a pH regulator, 0.01 to 0.10 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 initiator and 0.15 to 0.25 part of a reducing agent. According to the washing-free plush thickening agent provided by the invention, the color yield of a product can be improved, and the thickening capability under the condition of low dosage can be realized; the acid and alkali resistance of the system can be improved, and the flexibility of the system can also be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of textile auxiliaries, and more specifically, to a waterless plush thickener and a preparation method thereof. Background Art

[0002] Synthetic thickeners are the thickener varieties with the largest sales volume and the widest application range in the market. Such thickeners are generally microchemically cross-linked polymers, which absorb water and expand into a paste to play a thickening role. Polyacrylic acid thickeners are the most widely used synthetic thickeners at present, and such thickeners have the advantages of rapid thickening, low cost, and low dosage.

[0003] There are two thickening mechanisms for polyacrylic acid thickeners: neutralization thickening and hydrogen bond binding thickening. One is that there are negative charges on the main chain of polyacrylic acid after neutralization, resulting in a certain charge repulsion within the molecule and forming a network structure in the solution. The other is that the carboxyl groups of polyacrylic acid ionize and form hydrogen bonds with water molecules to cooperate with the network structure to achieve the thickening purpose.

[0004] In the textile printing industry, polyacrylic acid thickeners are usually important components in printing pastes. Adding thickeners can make the printed products have high color yield, clear outlines, bright and full colors, excellent screen penetration and thixotropy. In the dyeing process, synthetic thickeners are also applied. In the plush dyeing process, thickeners are usually used to increase the viscosity of dyeing to improve the liquor uptake of plush fabrics, so as to increase the dyeing depth and save dyes.

[0005] With the continuous improvement of environmental protection requirements, the importance of sewage treatment in printing and dyeing factories has been significantly improved. Traditional printing and dyeing processes require multiple water washes to remove the thickeners on the fabric surface, so the amount of wastewater generated is quite large, bringing high sewage treatment costs. Facing this problem, the waterless process is a good solution. The core of the waterless process is liquid disperse dyes. Traditional dyes are made into finer nanoscale particles through grinding and other methods and then dispersed in water. The fastness of this kind of dye is significantly better than that of traditional dyes, and the fastness is still very high without the need for water washing steps. In the plush waterless dyeing process, in addition to liquid disperse dyes, new requirements are also put forward for thickeners: such as high color yield, high color fastness, excellent thickening ability at extremely low thickener dosages, and soft handfeel. Summary of the Invention

[0006] Technical problems to be solved by the present invention:

[0007] To solve the defects that there are fewer waterless processes for existing thickeners, and the thickening ability and softness are insufficient.

[0008] Technical solutions adopted by the present invention:

[0009] In view of the above technical problems, the object of the present invention is to provide a water-free washable plush thickener and a preparation method thereof.

[0010] Specifically,

[0011] A water-free plush thickener. The raw material components, measured by weight, include 100-170 parts of acrylic acid monomers, 1-10 parts of special monomers, 20-60 parts of silicone-modified hyaluronic acid, 0-200 parts of pH regulators, 0.01-0.10 parts of cross-linking 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 initiators, and 0.15-0.25 parts of reducing agents.

[0012] According to some preferred embodiments, the acrylic monomer includes at least one of methacrylic acid, acrylic acid, and dimethacrylic acid.

[0013] According to some preferred embodiments, the special monomer includes at least one of triethylene aminoethyl methacrylate chloride and methacryloylpropyl trimethyl ammonium chloride.

[0014] According to some preferred embodiments, the organosilicon-modified hyaluronic acid is obtained by APTES-modified hyaluronic acid. That is, hyaluronic acid forms a solution of 5 to 10 mg / mL, and then APTES in an amount of 10 to 15 wt% is added thereto, the temperature is raised to 60 to 85°C, and stirred for 1 to 3 hours. After the reaction, the intermediate is filtered and washed to obtain the intermediate, and then the intermediate is dispersed into a liquid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide are added during the stirring process, and the stirring is continued for 2 to 4 hours. The mass ratio of the intermediate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide is 1:0.3 to 0.5:0.2 to 0.4. After reacting at room temperature for 3 to 7 hours, the organosilicon-modified hyaluronic acid is obtained by centrifugation and washing.

[0015] According to some preferred embodiments, the pH adjuster includes at least one of aqueous ammonia, triethylamine, N-methyldiethanolamine, triethanolamine, and triallyl ammonium chloride.

[0016] According to some preferred embodiments, the cross-linking agent includes at least one of methylenebisacrylamide and N-hydroxyacrylamide.

[0017] According to some preferred embodiments, the chelating dispersant includes at least one of glutamic acid N,N-diacetic acid, diethylenetriaminepentaacetic acid, EDTA, and diethylenetriaminepenta(methylenephosphonic acid).

[0018] According to some preferred embodiments, the oil-phase solvent includes at least one of D40, D60, D70, No. 15 white oil, No. 68 white oil, No. 100 white oil, and No. 150 white oil.

[0019] According to some preferred embodiments, the emulsifier includes at least one of Span-80, Span-60, and 1599A.

[0020] 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.

[0021] According to some preferred embodiments, the initiator includes at least one of potassium persulfate, sodium persulfate, and ammonium persulfate.

[0022] According to some preferred embodiments, the reducing agent includes at least one of sodium bisulfite, sodium metabisulfite, and sodium sulfite.

[0023] Second, the present invention provides a preparation method of the waterless plush thickener mentioned above, including the following steps:

[0024] (1) Add water to the reactor, then add acrylic acid monomer, and start stirring until it is completely dispersed;

[0025] (2) Sequentially dropwise add a pH regulator to step (1) until the pH value reaches 5.5 - 6.5;

[0026] (3) Add organosilicon-modified hyaluronic acid, special monomer, chelating dispersant, crosslinking agent, and oxidant to the neutralized acrylate solution in step (2), and continue stirring until it is completely dissolved to obtain an aqueous solution;

[0027] (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 high-speed emulsification for 15 - 20 min. Control the temperature below 35°C during this process;

[0028] (5) Prepare a reducing agent solution by dissolving the reducing agent in 20 - 30 times of water, stirring evenly, and setting aside.

[0029] (6) Pass nitrogen into step (4) for 60 - 90 min, then slowly dropwise add the reducing agent mixed solution, control the dropping time to be 1 - 3 min. After the system temperature rises, control the temperature at 60 - 80°C, continue to keep warm for 0.5 - 1.5 h, and then cool down to room temperature;

[0030] (7) Filter the material obtained in step (6) through a 200-mesh filter screen;

[0031] (8) The material obtained in step (7) is added with an inverse emulsifier and stirred for 20 - 30 min to obtain the finished thickener.

[0032] Beneficial effects achieved by the present invention:

[0033] (1) The water - wash - free plush thickener provided by the present invention can improve the color yield of the product and achieve the thickening ability at low dosages by introducing special monomers. Meanwhile, the cationic functional groups contained therein can improve the softness and antistatic effect of the product.

[0034] (2) The water - wash - free plush thickener provided by the present invention can enhance the consistency of the system and improve the coloring ability by introducing hyaluronic acid. After the organosilicon modification treatment, it can not only improve the acid and alkali resistance of the system, but also ensure the stability of hyaluronic acid in the pH environment and improve the flexibility of the system.

[0035] (3) The water - wash - free plush thickener provided by the present invention can wholly or partly replace ammonia water by introducing organic amine as a neutralizing base, thereby improving the hand feeling of the product.

[0036] (4) The cross - linker provided by the present invention is used to introduce cross - linking sites during the polymerization process, thereby forming a three - dimensional network structure, further increasing the viscosity of the polymer, and thus enabling it to maintain good stability. Specific embodiments

[0037] 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. For those conditions not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0038] Example 1

[0039] (1) Add 130 g of water to the reactor, and then add 150 g of acrylic acid and stir for 5 min until completely dispersed.

[0040] (2) Drop about 110 g of ammonia water and 40 g of N - methyldiethanolamine into step (1) in sequence until the pH value reaches between 5.5 and 6.5.

[0041] (3) Add 50 g of organosilicon - modified hyaluronic acid, 5 g of chlorotrimethylvinylammonium methacrylate, 2.5 g of diethylenetriamine pentamethylenephosphonic acid, 0.02 g of methylene bisacrylamide, and 0.25 g of potassium persulfate to the neutralized acrylate solution in step (2), and continue stirring until completely dissolved to obtain the aqueous solution.

[0042] Silicone-modified hyaluronic acid: Hyaluronic acid was made into a 10 mg / mL solution, and then APTES with a dosage of 15 wt% was added thereto. The temperature was raised to 80 °C and stirred for 2 h. After the reaction, it was subjected to suction filtration and washing to obtain an intermediate. Then the intermediate was dispersed into a liquid, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added during stirring. Stirring was continued for 3 h. The mass ratio of the intermediate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide was 1:0.5:0.3. After reacting at room temperature for 6 h, it was centrifuged and washed to obtain silicone-modified hyaluronic acid.

[0043] (4) 160 g of D70 and 18 g of SPAN-60 were stirred evenly and then emulsified at high speed to obtain an oil-phase solution; while maintaining the emulsification power, the aqueous-phase solution in step (3) was slowly added to the oil-phase solution, the temperature was controlled below 35 °C, and high-speed emulsification was continued for 15 - 20 min to obtain a pre-emulsion.

[0044] (5) 0.25 g of sodium bisulfite was dissolved in 7 g of water, stirred evenly, and reserved.

[0045] (6) Nitrogen was passed through the solution in step (4) for 60 minutes, and then the solution in (5) was slowly added dropwise, the dropping time was controlled to be 3 - 10 min, and the temperature was controlled at 60 - 70 °C. After the dropping was completed, it was kept warm for 0.5 h and then cooled to room temperature.

[0046] (7) The material obtained in step (6) was filtered through a 200-mesh filter screen.

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

[0048] Comparative Example 1

[0049] (1) 130 g of water was added to a reactor, and then 130 g of acrylic acid and 20 g of acrylamide were added. Stirring was started until it was completely dispersed.

[0050] (2) Approximately 140 g of ammonia water was added dropwise to step (1) until the pH value reached between 5.5 and 6.5.

[0051] (3) To the neutralized acrylate solution in step (2), 2.5 g of diethylenetriamine pentamethylenephosphonic acid, 0.02 g of methylene bisacrylamide, and 0.25 g of potassium persulfate were added, and stirring was continued until it was completely dissolved to obtain an aqueous-phase solution.

[0052] (4) to (8) were the same as in Example 1.

[0053] Comparative Example 2

[0054] The difference between this comparative example and Example 1 is that silicone-modified hyaluronic acid was not added.

[0055] Comparative Example 3

[0056] The difference between this comparative example and Example 1 is that triethylammonium ethyl methacrylate chloride was not added.

[0057] Test Example

[0058] Using the thickeners prepared in Example 1 and Comparative Examples 1-3 as samples, the thickening ability of the thickener for the dyeing solution was measured. The same amount of disperse dye was added, and the same amount of thickener was added for comparison of the thickening ability. The dyeing solution included the following components in parts by weight: a certain amount of thickener, 3% liquid disperse dye. Using the same method for preparing the dyeing solution, a DV-II type rotational viscometer, a 2# rotor, and a rotation speed of 10 r / min were used for testing, and the viscosity was measured in mPa·s. The greater the viscosity data, the better the thickening effect. The results are shown in Table 1.

[0059] Table 1

[0060]

[0061] Adjust the dyeing solution to the same viscosity, and compare the color yield and handle of the dyed fabric samples. The K / S value is an important index for color evaluation. The larger the K / S value, the darker the surface color. The process flow is as follows: sizing (viscosity adjusted to 200-400 cp) → padding → steaming (130 °C × 30 min) → cold washing → drying → comparing the handle and color yield. The results are shown in Table 2.

[0062] Table 2

[0063]

[0064] 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 can have various modifications and changes. Any modifications, equivalent replacements, improvements, 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 water-free plush thickener, characterized in that: The raw material components are calculated by weight and include 100-170 parts of acrylic acid monomer, 1-10 parts of special monomer, 20-60 parts of silicone-modified hyaluronic acid, 0-200 parts of pH adjuster, 0.01-0.10 parts of cross-linking agent, 1-5 parts of chelating dispersant, 100-160 parts of oil phase solvent, 15-25 parts of emulsifier, 15-45 parts of reverse emulsifier, 0.15-0.25 parts of initiator and 0.15-0.25 parts of reducing agent.

2. The wash-free plush thickener according to claim 1, characterized in that: The special monomer includes at least one of triethylene aminoethyl methacrylate chloride and methacryloylpropyl trimethyl ammonium chloride; and / or the acrylic monomer includes at least one of methacrylic acid, acrylic acid, and dimethacrylic acid.

3. The wash-free plush thickener according to claim 1, characterized in that: The pH adjuster includes at least one of ammonia water, triethylamine, N-methyldiethanolamine, triethanolamine, and triallyl ammonium chloride.

4. The wash-free plush thickener according to claim 1, characterized in that: The cross-linking agent includes at least one of methylene bisacrylamide and N-hydroxyacrylamide.

5. The wash-free plush thickener according to claim 1, characterized in that: The chelating dispersant includes at least one of glutamic acid N,N-diacetic acid, diethylenetriaminepentaacetic acid, EDTA, and diethylenetriaminepenta(methylenephosphonic acid).

6. The wash-free plush 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 wash-free plush thickener according to claim 1, characterized in that: The initiator 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 wash-free plush thickener according to any one of claims 1 to 7, characterized in that: The preparation method of the silicone-modified hyaluronic acid is as follows: APTES is added to a hyaluronic acid solution, the temperature is raised for reaction, an intermediate is obtained by suction filtration and washing, the intermediate is dispersed into a liquid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide are added, the reaction is stirred, and the silicone-modified hyaluronic acid is obtained by centrifugation and washing.

9. The wash-free plush thickener according to claim 8, characterized in that: The concentration of the hyaluronic acid solution is 5 to 10 mg / mL; and / or, the amount of APTES added is 10 to 15 wt% of the hyaluronic acid; and / or, the mass ratio of the intermediate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide is 1:0.3 to 0.5:0.2 to 0.

4.

10. A method for preparing a wash-free plush thickener as claimed in any one of claims 1 to 9, characterized in that: The steps include: (1) adding water into a reactor, and then adding acrylic acid monomer, and performing dispersion treatment; (2) adding a pH adjusting agent dropwise to step (1); (3) adding organosilicon-modified hyaluronic acid, special monomer, chelating dispersant, crosslinking agent and initiator to the acrylate solution neutralized in step (2), and continuing stirring until the acrylate solution is completely dissolved 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, the system is heated and maintained for a period of time, and then the temperature is cooled to room temperature; (7) filtering the material obtained in step (6); (8) Add an inverse emulsifier to the material obtained in step (7), stir, and obtain a finished thickener.

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