A low-temperature soaping agent for cotton active dyes and a preparation method thereof

Abstract

The application discloses a low-temperature soaping agent for cotton active dyes and a preparation method thereof. The soaping agent comprises the following components in percentage by weight based on the total weight: 40-60% of modified acrylic acid copolymer, 5-15% of surfactant, 20-40% of dispersant, 0.5-5% of alkali agent and 0.5-5% of additive. The soaping agent can achieve the effect of traditional soaping at 60 DEG C, has excellent soaping fastness and stain-proof performance, and is environment-friendly and stable.

Description

Technical Field

[0001] This invention relates to the field of textile auxiliaries, and more particularly to a low-temperature soaping agent for cotton reactive dyes and its preparation method. Background Technology

[0002] Currently, reactive dyes are diverse in type and structure, exhibiting significant differences in dyeing rates and failing to fully react with fibers. During the dyeing and fixation process, the reactive groups in the reactive dyes are replaced by hydroxyl groups, resulting in hydrolyzed dyes. Unfixed and hydrolyzed dyes possess diffusion and adsorption properties very similar to reactive dyes, readily adsorbing onto the fiber surface. In the dye bath, unfixed and hydrolyzed dyes partially bind to the fibers, easily leading to bleeding and re-staining, thus affecting the dyeing effect.

[0003] Traditional soap washing requires 20 minutes at 95-98℃, which is energy-intensive. Research on low-temperature soaping agents has yielded some results. For example, patent CN109914133A discloses a low-temperature soaping agent and method for preventing staining of reactive dyes. The key to achieving low-temperature soaping in this patent is the addition of 10-15% oxidizing substances (such as potassium chlorate, sodium persulfate, potassium persulfate, etc.). Although this lowers the soaping temperature, the oxidizing substances can easily cause discoloration and damage to the fabric. Another example is patent CN115679725A, which discloses a low-temperature soaping agent and process for dyed fabrics, also prepared by adding 10-20 parts of peroxide, with a soaping temperature of 70-90℃. Clearly, these types of low-temperature soaping agents have limitations in their key raw materials. More importantly, products containing oxides and peroxides themselves pose serious safety concerns. Patent CN114232365A discloses a method for producing an acidic soap detergent, which involves copolymerizing maleic anhydride and acrylic acid and compounding with polyvinylpyrrolidone to prevent the redeposition of oligomers in the dye bath. However, polyvinylpyrrolidone is listed as a Group 3 carcinogen by the International Agency for Research on Cancer of the World Health Organization.

[0004] Therefore, developing environmentally friendly, safe, and low-energy-consumption soap products will inevitably be a future trend, with a broad market and positive practical significance. Summary of the Invention

[0005] The purpose of this invention is to provide a low-temperature soaping agent for cotton reactive dyes that exhibits excellent washing fastness, dry / wet rubbing fastness, removal of loose dye, and anti-staining properties, and is also environmentally friendly and stable. Another purpose of this invention is to provide a method for preparing this low-temperature soaping agent for cotton reactive dyes.

[0006] The concept of low temperature mentioned in this invention refers to a temperature lower than 98°C, which is the traditional soap washing temperature. In this invention, it specifically refers to a soap washing temperature of 55-65°C.

[0007] One aspect of the present invention provides a low-temperature soaping agent for cotton reactive dyes, comprising, by total weight, the following components:

[0008]

[0009] Another aspect of the present invention provides a method for preparing the above-mentioned low-temperature soaping agent for cotton reactive dyes, which includes the following steps:

[0010] (a) The amide-containing compound shown in formula (I), vinylpyridine, and a reactive surfactant are added to a mixed solution of deionized water and ethanol. The mixture is heated to 55-65°C while stirring and maintained for 20-30 minutes. Then, an aqueous solution of acrylic acid and an initiator is added dropwise over 2-3 hours while maintaining the temperature at 80-85°C. After the addition is complete, the temperature is maintained at 80-85°C for another 2-3 hours. The mixture is cooled to room temperature, and the pH is adjusted to 7-8 to obtain the modified acrylic acid copolymer.

[0011] (b) The above modified acrylic copolymer, surfactant, dispersant, alkali agent and additive are mixed evenly in a weight ratio of (45-120):(8-30):(30-80):(1-10):(1-10).

[0012] The present invention has the following excellent technical effects: the low-temperature soaping agent for cotton reactive dyes of the present invention can achieve the effect of traditional soaping when soaping at a low temperature of 60°C, and has excellent soaping fastness and anti-staining performance, and is environmentally friendly and has good stability. Detailed Implementation

[0013] In one embodiment, the low-temperature soaping agent for cotton reactive dyes of the present invention comprises, by total weight, the following components:

[0014]

[0015] In a preferred embodiment, the modified acrylic copolymer is a linear copolymer polymerized from acrylic acid, an amide-containing compound of formula (I), vinylpyridine, and a reactive surfactant.

[0016]

[0017] R1 is H, CH3, or pyridinyl;

[0018] R2 is H or phenyl;

[0019] Preferably, the amide-containing compound represented by formula (I) includes, but is not limited to, vinylformamide, vinylacetamide, vinylpyridine amide, acetamido-1-styrene, and other compounds having carbonyl and amino groups.

[0020] Preferably, the molecular weight of the modified acrylic copolymer is 8000-10000.

[0021] Preferably, the weight ratio of the acrylic acid, the amide-containing compound of formula (I), the vinylpyridine, and the reactive surfactant is 1:(1.0-1.6):(0.3-0.6):(0.02-0.05).

[0022] Preferably, the reactive surfactant is selected from one or more of sodium fatty alcohol ether vinyl sulfonate, sodium 2-acrylamido-2-methylpropane sulfonate, and sodium allyloxyhydroxypropyl sulfonate.

[0023] In one embodiment, the surfactant includes, but is not limited to, lecithin, hydrogenated lecithin, soy lecithin, or mixtures thereof.

[0024] In one embodiment, the dispersant includes diethyl aminomalonate hydrochloride, polyethyleneimine, polyacrylamide, and fatty acid C. 11 -C 17 Soaps, carbomer 690, poloxamer 188, or mixtures thereof.

[0025] In one embodiment, the alkali agent includes triethanolamine, diethanolamine, ethylenediamine, sodium hydroxylamine carboxylate, sodium aminocarboxylate, or mixtures thereof.

[0026] In one embodiment, the additive includes maleic rosin alcohol esters, rosin amine polyoxyethylene ethers, disproportionated rosin sodium salts, hydrogenated acrylate rosin esters, or mixtures thereof.

[0027] In one embodiment, the preparation method of the low-temperature soaping agent for cotton reactive dyes of the present invention includes the following preferred steps:

[0028] a) Add the amide-containing compound shown in formula (I), vinylpyridine, and a reactive surfactant to a mixed solution of deionized water and ethanol, and heat to 55-65°C while stirring, maintaining the temperature for 20-30 minutes. Then, add the aqueous solution of acrylic acid and initiator dropwise over 2-3 hours while controlling the temperature at 80-85°C. After the addition is complete, continue to maintain the temperature at 80-85°C for 2-3 hours. Cool to room temperature and adjust the pH to 7-8 to obtain the modified acrylic acid copolymer;

[0029] b) Mix the above modified acrylic copolymer, surfactant, dispersant, alkali agent and additives in a weight ratio of (45-120):(8-30):(30-80):(1-10):(1-10) until homogeneous.

[0030] In step a) above, the weight ratio of deionized water to ethanol is approximately 10:1, such as approximately 9-11:1 or 8-12:1, without any particular limitation; the initiator can be a conventional initiator such as ammonium persulfate, without any particular limitation.

[0031] This invention allows for the control of the molecular weight of the copolymer by adjusting the weight ratio between reactants. When combined with other components, the product exhibits high stability, high wash fastness at low temperatures, good dry and wet rubbing fastness, and outstanding anti-staining effect. Overall, it achieves the same effect as traditional 98℃ soap washing.

[0032] Example

[0033] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0034] The performance of the low-temperature soaping agent for cotton reactive dyes prepared in the various embodiments of the present invention was verified by the following tests.

[0035] 1. Fabric: Pure cotton fabric (commercially available)

[0036] 2. Soap washing process

[0037] conventional process

[0038] Dyed cotton fabric → 98℃ soap wash for 20 minutes (1-2g / L soap) → cold water wash → dehydration → tumble dry

[0039] Low temperature process

[0040] Dyed cotton fabric → 60℃ soap wash for 20 minutes (1-2g / L soap detergent) → cold water wash → dehydration → tumble dry

[0041] 3. Performance Testing

[0042] 3.1 Stability

[0043] Place the product in a sealed sample bottle and leave it at room temperature for 6 months. Observe whether the product separates into layers or whether any precipitates appear.

[0044] 3.2 Friction fastness

[0045] The rubbing fastness was determined according to GB / T 3920-2008 Textiles - Tests for Color Fastness to Rubbing. The higher the grade, the better the fastness to dry and wet rubbing.

[0046] 3.3 Wash fastness

[0047] The test was conducted according to test method C(3) in GB / T 3921-2008, "Tests on color fastness of textiles - color fastness to washing". The higher the value, the better the washing fastness.

[0048] 3.4 Performance in removing excess color

[0049] The fabric was dyed a dark color with reactive red, washed with water, and then washed with water and soap (2g / L) at 60℃ for 5-10 minutes. The residual liquid from boiling the fabric was used as a reference, and the absorbance was measured at the maximum absorption wavelength of the dye using a spectrophotometer. The darker the color and the greater the absorbance, the better the removal of floating dye, indicating a stronger removal performance.

[0050] 3.5 Anti-fouling performance

[0051] 1) Preparation of hydrolyzed reactive dye: Weigh 0.1g of reactive red dye and dissolve it in 1L of water, and adjust the pH value to 6-7.

[0052] 2) Stain resistance test: White pure cotton fabric, liquor ratio 1:20, soap detergent 2g / L, using the above-mentioned hydrolyzed reactive dye as solvent, heated to 60℃ for 20min at a heating rate of 2℃ / min, and blank solution test was performed at the same time. After drying, the color difference between the two samples was evaluated using a gray scale. The higher the value, the better the stain resistance.

[0053] 3.6 Determination of molecular weight

[0054] The determination was performed using a Waters gel permeation chromatograph (model: Breeze 1515).

[0055] Example 1

[0056] 120 parts by weight of vinylacetamide (Shanghai Yuanye), 40 parts by weight of vinylpyridine (Nantong Runfeng), and 3 parts by weight of sodium vinyl sulfonate SW102 (Guangzhou Sanwang) were added to 826 parts by weight of deionized water and 75 parts by weight of ethanol. The mixture was stirred and heated to 55-65°C and maintained for 20 minutes. Then, 100 parts by weight of acrylic acid (Wanhua Chemical) and an initiator ammonium persulfate aqueous solution were added dropwise over 2-3 hours, maintaining the temperature at 80-85°C. After the addition was complete, the mixture was kept at 80-85°C for another 3 hours. The mixture was cooled to room temperature, and the pH was adjusted to 7-8 with sodium hydroxide aqueous solution to obtain a modified acrylic acid copolymer. The molecular weight was determined to be 8703.

[0057] The above-mentioned 60 parts by weight of modified acrylic copolymer, 35 parts by weight of polyethyleneimine (Hubei Handafei), 10 parts by weight of lecithin (Anhui Zhongchuang), 3 parts by weight of triethanolamine (Huaxi Chemical), and 3 parts by weight of disproportionated sodium rosin (Hongshun Chemical) are mixed evenly to obtain the final product.

[0058] Example 2

[0059] 140 parts by weight of vinylacetamide (Shanghai Yuanye), 50 parts by weight of vinylpyridine (Nantong Runfeng), and 4 parts by weight of sodium vinyl sulfonate SW102 (Guangzhou Sanwang) were added to 836 parts by weight of deionized water and 84 parts by weight of ethanol. The mixture was stirred and heated to 55-65°C and maintained for 30 minutes. Then, 100 parts by weight of acrylic acid (Wanhua Chemical) and an initiator ammonium persulfate aqueous solution were added dropwise over 2-3 hours, maintaining the temperature at 80-85°C. After the addition was complete, the mixture was kept at 80-85°C for another 3 hours. The mixture was cooled to room temperature, and the pH was adjusted to 7-8 with sodium hydroxide aqueous solution to obtain a modified acrylic acid copolymer. The molecular weight was determined to be 9415.

[0060] The above-mentioned 80 parts by weight of modified acrylic copolymer, 50 parts by weight of carbomer 690 (Wuhan Desheng), 15 parts by weight of soybean lecithin (Anhui Zhongchuang), 4 parts by weight of ethylenediamine (Wanhua Chemical), and 4 parts by weight of hydrogenated rosin acrylate (Hongshun Chemical) are mixed evenly to obtain the final product.

[0061] Example 3

[0062] 135 parts by weight of vinylpyridine amide (Shanghai Yuanye), 40 parts by weight of vinylpyridine (Nantong Runfeng), and 4 parts by weight of sodium 2-acrylamido-2-methylpropanesulfonate (Qingxin Hanke Chemical) were added to 806 parts by weight of deionized water and 80.5 parts by weight of ethanol. The mixture was stirred and heated to 55-65°C and maintained for 30 minutes. Then, 100 parts by weight of acrylic acid (Wanhua Chemical) and an initiator ammonium persulfate aqueous solution were added dropwise over 2-3 hours, maintaining the temperature at 80-85°C. After the addition was complete, the mixture was kept at 80-85°C for another 3 hours. The mixture was cooled to room temperature, and the pH was adjusted to 7-8 with sodium hydroxide aqueous solution to obtain a modified acrylic acid copolymer. The molecular weight was determined to be 9303.

[0063] The above-mentioned 70 parts by weight of modified acrylic copolymer, 45 parts by weight of polyacrylamide (Zibo Laner), 18 parts by weight of lecithin (Anhui Zhongchuang), 1 part by weight of sodium amino acid (Wanhua Chemical), and 1 part by weight of maleic rosin alcohol ester (Jining Letian) are mixed evenly to obtain the final product.

[0064] Example 4

[0065] 140 parts by weight of vinylpyridine amide (Shanghai Yuanye), 55 parts by weight of vinylpyridine (Nantong Runfeng), and 4 parts by weight of sodium 2-acrylamido-2-methylpropanesulfonate (Qingxin Hanke Chemical) were added to 847 parts by weight of deionized water and 85 parts by weight of ethanol. The mixture was stirred and heated to 55-65°C and maintained for 30 minutes. Then, 100 parts by weight of acrylic acid (Wanhua Chemical) and an initiator ammonium persulfate aqueous solution were added dropwise over 2-3 hours, maintaining the temperature at 80-85°C. After the addition was complete, the mixture was kept at 80-85°C for another 3 hours. The mixture was cooled to room temperature, and the pH was adjusted to 7-8 with sodium hydroxide aqueous solution to obtain a modified acrylic acid copolymer. The molecular weight was determined to be 9603.

[0066] The above-mentioned 75 parts by weight of modified acrylic copolymer, 45 parts by weight of diethyl aminomalonic acid hydrochloride (Hanhong Technology), 15 parts by weight of soybean lecithin (Anhui Zhongchuang), 5 parts by weight of sodium hydroxylamine carboxylate (Wuhan Ruihe), and 5 parts by weight of rosin amine polyoxyethylene ether (Wuhan Ruihe) are mixed evenly to obtain the final product.

[0067] The application effects of each embodiment are compared in Table 1.

[0068] Table 1 Comparison of the application effects of different cotton soaps

[0069]

[0070] Table 1 shows the application effects of the low-temperature soaping agents prepared in Examples 1-4 of this invention. The soaping fastness at 60℃ is high, with good dry and wet rubbing fastness, and outstanding anti-staining effect. Overall, it can achieve the effect of traditional 98℃ soaping. The low-temperature soaping performance is significantly better than market products.

[0071] Although the present invention has been disclosed above with reference to embodiments, it is not intended to limit the scope of protection of the present invention. Any modifications and refinements made by those skilled in the art without departing from the concept and scope of the present invention shall fall within the scope of protection of the present invention.

Claims

1. A low-temperature soaping agent for cotton reactive dyes, comprising the following components by total weight: 40-60% by weight of modified acrylic copolymer Surfactant 5-15% by weight Dispersant 20-40% by weight Alkali agent 0.5-5% by weight Additives 0.5-5% by weight The modified acrylic copolymer is polymerized from acrylic acid, an amide-containing compound, vinylpyridine, and a reactive surfactant. The amide-containing compound is selected from vinylformamide, vinylacetamide, and vinylpyridine amide. The reactive surfactant is selected from one or more of sodium fatty alcohol ether vinyl sulfonate, sodium 2-acrylamido-2-methylpropane sulfonate, and sodium allyloxyhydroxypropyl sulfonate. The modified acrylic copolymer has a molecular weight of 8000-10000. The weight ratio of acrylic acid, amide-containing compounds, vinylpyridine, and reactive surfactants is 1:(1.0-1.6):(0.3-0.6):(0.02-0.05). The additive is selected from one or more of maleic rosin alcohol esters, rosin amine polyoxyethylene ethers, disproportionated rosin sodium, and hydrogenated acrylate rosin esters.

2. The low-temperature soaping agent for cotton reactive dyes as described in claim 1, characterized in that, The surfactant is selected from one or more of lecithin, hydrogenated lecithin, and soybean lecithin.

3. The low-temperature soaping agent for cotton reactive dyes as described in claim 1, characterized in that, The dispersant is selected from diethyl aminomalonate hydrochloride, polyethyleneimine, polyacrylamide, and fatty acid C. 11 -C 17 Soaps, carbomer 690 and poloxamer 188, or one or more of these.

4. The low-temperature soaping agent for cotton reactive dyes as described in claim 1, characterized in that, The alkaline agent is selected from one or more of triethanolamine, diethanolamine, ethylenediamine, and sodium aminocarboxylate.

5. The preparation method of the low-temperature soaping agent for cotton reactive dyes as described in any one of claims 1-4, comprising the following steps: a) Add the amide-containing compound, vinylpyridine, and reactive surfactant to a mixed solution of deionized water and ethanol, and heat to 55-65°C while stirring and maintain for 20-30 minutes. Then, add acrylic acid and initiator aqueous solution dropwise over 2-3 hours while controlling the temperature at 80-85°C. After the dropwise addition is completed, continue to maintain the temperature at 80-85°C for 2-3 hours, cool to room temperature, and adjust the pH to 7-8 to obtain the modified acrylic acid copolymer. b) Mix the above modified acrylic copolymer, surfactant, dispersant, alkali agent and additives in a weight ratio of (45-120):(8-30):(30-80):(1-10):(1-10) until homogeneous.

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