A bisphenol S-free acidic color fixing agent and preparation method thereof

Abstract

The present invention belongs to the technical field of fabric color fixing agents and provides a novel acidic color fixing agent free of bisphenol S and a preparation method thereof; the acidic color fixing agent is composed of the following components in parts by weight: 15-25 parts of water, 10-15 parts of phenol, 15-25 parts of dimethylacetamide, 2-5 parts of sodium sulfite, 10-15 parts of acetic acid, 5-7 parts of concentrated sulfuric acid, 15-20 parts of acrylic acid, 2-5 parts of ethylene glycol dimethyl ether, and 1-3 parts of sorbitol; the preparation method comprises the following steps: mixing a formula amount of phenol, dimethylacetamide, acrylic acid, acetic acid, and sodium sulfite, heating, adding concentrated sulfuric acid to react, cooling, adding a formula amount of water, and adding a formula amount of ethylene glycol dimethyl ether and sorbitol to obtain the product. Compared with the prior art, the present invention does not contain bisphenol S, has a good color fixing effect, can effectively improve various fastnesses such as water fastness, perspiration fastness, and seawater resistance, has little effect on the color change of the fabric after treatment, and has good tolerance to hardness ions.

Description

Technical Field

[0001] The invention belongs to the technical field of fabric color fixing agents, and particularly relates to a bisphenol S-free acidic color fixing agent and a preparation method thereof. Background Art

[0002] Nylon fabric has a soft feel and good wear resistance. It is widely used and is usually dyed with acid dyes.

[0003] After acid dyes are dyed onto nylon fabrics, due to the small number of amino groups at the ends of nylon fibers, the dyed dyes mostly rely on van der Waals forces and hydrogen bonds to bind to the fabric, resulting in poor fastness. Acid dyes also contain water-soluble sulfonic acid and carboxyl groups, which make the dyes easily washed off. Furthermore, the more sulfonic acid groups there are, the worse the wet fastness of the fabric will be. Therefore, generally, medium to dark nylon dyed fabrics require color fixation treatment. The general color fixation principles currently used in this field can be divided into the following two points:

[0004] (1) The phenolic resin in the fixing agent forms a film on the nylon surface under high temperature conditions to prevent the dye from diffusing outward;

[0005] (2) The repulsive force between the sulfonic acid anions of the fixing agent and the dye anions is used to prevent the dye from diffusing from the inside of the fiber to the outside.

[0006] That is, the vast majority of acidic color fixing agents on the market are phenolic resin type color fixing agents with sulfonic acid groups, and phenolic resins are mostly synthesized from bisphenols, which are not conducive to environmental protection.

[0007] CN107724124A discloses a method for preparing a nylon fabric fixing agent. The agent is composed of the following raw materials by weight: 20-30 parts bisphenol S, 20-30 parts epichlorohydrin, 5-10 parts catalyst, 20-25 parts fatty alcohol polyoxyethylene ether, 3-5 parts octadecyl dimethylamine oxide, 5-9 parts hydroxypropyl methylcellulose, 5-10 parts acrylate, 10-20 parts ethanol, and 30-50 parts deionized water. The nylon fabric fixing agent of this invention achieves a wash fastness of grade 4-5 and a rubbing fastness of grade 4-5 after dyeing the fabric. However, the addition of bisphenol S is toxic and environmentally unfriendly.

[0008] CN116536944A discloses a sun-resistant dye-fixing agent comprising 500-550 parts of epichlorohydrin, 550-600 parts of diethylenetrimonium chloride, 250-300 parts of 1,4-dioxane, 150-200 parts of a secondary alkyl amine, 70-80 parts of an initiator, 95-105 parts of polysulfone, 60-70 parts of polyphenylene sulfide, 95-105 parts of aniline, 95-105 parts of dicyandiamide, and 95-105 parts of 2-hydroxy-4-octyloxybenzophenone. The combination of 1,4-dioxane with dicyandiamide and aniline strengthens the covalent bond with the fiber, making it less susceptible to breakage. This also enhances the dye's wash fastness (grade 5-6) and rubbing fastness (grade 3-4), as well as UV resistance. This demonstrates that improving the fastness of dye-fixing agents is a common research topic in the field.

[0009] Therefore, the main problems in nylon acid fixation in the industry are:

[0010] (1) Fixatives generally contain bisphenol S, which cannot meet environmental protection requirements;

[0011] (2) The color fixing agent has the problem of unsatisfactory improvement of color fastness and large color change;

[0012] (3) Acidic fixing agents are not resistant to hardness ions and are prone to causing color fixation spots due to water hardness problems;

[0013] Therefore, how to provide an acidic fixing agent that has the advantages of high fastness, no color change and resistance to hardness ions, while ensuring that it is bisphenol S-free and meets environmental protection requirements, is one of the key issues in this field. Summary of the Invention

[0014] The present invention addresses the environmental issues caused by the use of highly polluting bisphenol raw materials in the production of color fixing agents in the prior art, as well as the demand in the art for high fastness, no color change and resistance to hardness ions, and provides a bisphenol S-free acidic color fixing agent and a preparation method thereof.

[0015] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0016] A bisphenol S-free acidic dye fixing agent, comprising the following components:

[0017] Water, phenol, dimethylacetamide, sodium sulfite, concentrated sulfuric acid, acetic acid, acrylic acid, ethylene glycol dimethyl ether, and sorbitol;

[0018] The acidic fixing agent does not contain bisphenol S.

[0019] Preferably, the acidic fixing agent is composed of the following components in parts by weight:

[0020] 15-25 parts of water, 10-15 parts of phenol, 15-25 parts of dimethylacetamide, 2-5 parts of sodium sulfite, 10-15 parts of acetic acid, 5-7 parts of concentrated sulfuric acid, 15-20 parts of acrylic acid, 2-5 parts of ethylene glycol dimethyl ether and 1-3 parts of sorbitol.

[0021] Further preferably, the acidic fixing agent is composed of the following components in parts by weight:

[0022] 17-23 parts of water, 11-15 parts of phenol, 16-24 parts of dimethylacetamide, 2-4 parts of sodium sulfite, 12-15 parts of acetic acid, 5-7 parts of concentrated sulfuric acid, 16-18 parts of acrylic acid, 2-5 parts of ethylene glycol dimethyl ether and 1-3 parts of sorbitol.

[0023] More preferably, the acidic fixing agent is composed of the following components in parts by weight:

[0024] 19-22 parts of water, 12-14 parts of phenol, 18-24 parts of dimethylacetamide, 2-3 parts of sodium sulfite, 12-14 parts of acetic acid, 5-7 parts of concentrated sulfuric acid, 16-18 parts of acrylic acid, 3-5 parts of ethylene glycol dimethyl ether and 2-3 parts of sorbitol.

[0025] Most preferably, the acidic fixing agent is composed of the following components in parts by weight:

[0026] 20 parts of water, 13 parts of phenol, 20 parts of dimethylacetamide, 2 parts of sodium sulfite, 13 parts of acetic acid, 7 parts of concentrated sulfuric acid, 17 parts of acrylic acid, 3 parts of ethylene glycol dimethyl ether and 2 parts of sorbitol.

[0027] The present invention also provides a method for preparing the above-mentioned acidic color fixing agent, comprising the following steps:

[0028] Mix phenol, dimethylacetamide, acrylic acid, acetic acid and sodium sulfite in a formula amount, heat, add concentrated sulfuric acid to react, cool, add water in a formula amount, add ethylene glycol dimethyl ether and sorbitol in a formula amount, and obtain the product.

[0029] Preferably, the heating temperature is 70-90°C.

[0030] Preferably, the reaction temperature does not exceed 100° C., and the reaction time is 2-4 hours.

[0031] Preferably, the target temperature of the cooling is 50-60°C.

[0032] Preferably, after adding the formulated amount of water, stirring is continued for 30-60 minutes.

[0033] Preferably, after adding the formulated amounts of ethylene glycol dimethyl ether and sorbitol, stirring is continued for 40-80 minutes.

[0034] The present invention also provides an acidic color fixing agent prepared by the above preparation method.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) Does not contain bisphenol S, meeting environmental protection requirements;

[0037] (2) Good color fixing effect, which can effectively improve various fastnesses such as washing fastness, perspiration fastness, and seawater resistance;

[0038] (3) The color change of the fabric after treatment is minimal and basically does not affect the original color of the fabric;

[0039] (4) It has good tolerance to hardness ions and is not prone to color spots caused by water quality problems. DETAILED DESCRIPTION

[0040] It is worth noting that the raw materials used in the present invention are all common commercially available products, and their sources are not specifically limited.

[0041] Example 1 A bisphenol S-free acidic color fixing agent and its preparation method

[0042] 20 parts of water, 13 parts of phenol, 20 parts of dimethylacetamide, 2 parts of sodium sulfite, 13 parts of acetic acid, 7 parts of concentrated sulfuric acid, 17 parts of acrylic acid, 3 parts of ethylene glycol dimethyl ether and 2 parts of sorbitol;

[0043] The preparation method is as follows:

[0044] Mix the formulated amounts of phenol, dimethylacetamide, acrylic acid, acetic acid and sodium sulfite, heat to 80°C, add concentrated sulfuric acid to control the temperature in the range of 80-90°C and react for 3 hours, cool to 55°C, add the formulated amount of water and stir for 45 minutes, add the formulated amount of ethylene glycol dimethyl ether and sorbitol and stir for 50 minutes to obtain the product.

[0045] Example 2 A bisphenol S-free acidic color fixing agent and its preparation method

[0046] The acidic color fixing agent raw materials and dosage used in this embodiment are as follows:

[0047] 15 parts of water, 10 parts of phenol, 15 parts of dimethylacetamide, 2 parts of sodium sulfite, 10 parts of acetic acid, 5 parts of concentrated sulfuric acid, 15 parts of acrylic acid, 2 parts of ethylene glycol dimethyl ether and 1 part of sorbitol;

[0048] The preparation method is as follows:

[0049] Mix the formulated amounts of phenol, dimethylacetamide, acrylic acid, acetic acid and sodium sulfite, heat to 70°C, add concentrated sulfuric acid to control the temperature range at 80-90°C and react for 4 hours, cool to 50°C, add the formulated amount of water and stir for 30 minutes, add the formulated amount of ethylene glycol dimethyl ether and sorbitol and stir for 40 minutes to obtain the product.

[0050] Example 3 A bisphenol S-free acidic color fixing agent and its preparation method

[0051] The acidic color fixing agent raw materials and dosage used in this embodiment are as follows:

[0052] 25 parts of water, 15 parts of phenol, 25 parts of dimethylacetamide, 5 parts of sodium sulfite, 15 parts of acetic acid, 7 parts of concentrated sulfuric acid, 20 parts of acrylic acid, 5 parts of ethylene glycol dimethyl ether and 3 parts of sorbitol;

[0053] The preparation method is as follows:

[0054] Mix the formulated amounts of phenol, dimethylacetamide, acrylic acid, acetic acid and sodium sulfite, heat to 90°C, add concentrated sulfuric acid to control the temperature in the range of 80-90°C and react for 2 hours, cool to 60°C, add the formulated amount of water and stir for 60 minutes, add the formulated amount of ethylene glycol dimethyl ether and sorbitol and stir for 80 minutes to obtain the product.

[0055] Example 4 A bisphenol S-free acidic color fixing agent and its preparation method

[0056] The acidic color fixing agent raw materials and dosage used in this embodiment are as follows:

[0057] 17 parts of water, 15 parts of phenol, 16 parts of dimethylacetamide, 4 parts of sodium sulfite, 12 parts of acetic acid, 5 parts of concentrated sulfuric acid, 16 parts of acrylic acid, 5 parts of ethylene glycol dimethyl ether and 1 part of sorbitol;

[0058] The preparation method is as follows:

[0059] Mix the formulated amounts of phenol, dimethylacetamide, acrylic acid, acetic acid and sodium sulfite, heat to 75°C, add concentrated sulfuric acid to control the temperature range at 80-90°C and react for 2.5 hours, cool to 55°C, add the formulated amount of water and stir for 40 minutes, add the formulated amount of ethylene glycol dimethyl ether and sorbitol and stir for 70 minutes to obtain the product.

[0060] Example 5 A bisphenol S-free acidic color fixing agent and its preparation method

[0061] The acidic color fixing agent raw materials and dosage used in this embodiment are as follows:

[0062] 23 parts of water, 11 parts of phenol, 24 parts of dimethylacetamide, 2 parts of sodium sulfite, 15 parts of acetic acid, 7 parts of concentrated sulfuric acid, 18 parts of acrylic acid, 2 parts of ethylene glycol dimethyl ether and 3 parts of sorbitol.

[0063] The preparation method is as follows:

[0064] Mix the formulated amounts of phenol, dimethylacetamide, acrylic acid, acetic acid and sodium sulfite, heat to 85°C, add concentrated sulfuric acid to control the temperature range at 80-90°C and react for 3 hours, cool to 55°C, add the formulated amount of water and stir for 50 minutes, add the formulated amount of ethylene glycol dimethyl ether and sorbitol and stir for 50 minutes to obtain the product.

[0065] Comparative Example 1: A bisphenol S-free acidic color fixing agent and its preparation method

[0066] The difference between this comparative example and Example 1 is that the amount of the acidic color fixing agent raw material used is different:

[0067] 26 parts of water, 8 parts of phenol, 26 parts of dimethylacetamide, 1 part of sodium sulfite, 16 parts of acetic acid, 3 parts of concentrated sulfuric acid, 22 parts of acrylic acid, 1 part of ethylene glycol dimethyl ether and 4 parts of sorbitol;

[0068] Comparative Example 2: A bisphenol S-free acidic color fixing agent and its preparation method

[0069] The difference between this comparative example and Example 1 is that the amount of the acidic color fixing agent raw material used is different:

[0070] 14 parts of water, 17 parts of phenol, 14 parts of dimethylacetamide, 6 parts of sodium sulfite, 8 parts of acetic acid, 8 parts of concentrated sulfuric acid, 14 parts of acrylic acid, 6 parts of ethylene glycol dimethyl ether and 0.8 parts of sorbitol;

[0071] Comparative Example 3: A Bisphenol S-free Acidic Fixing Agent and Its Preparation Method

[0072] The only difference between this comparative example and Example 1 is that sorbitol is replaced by a mixture of equal mass, wherein the mixture contains sorbitol and xylitol in a mass ratio of 1:1.

[0073] Test Example 1 Test of Bisphenol S Content in Samples:

[0074] Test method: Refer to USA EPA 3550 2007

[0075] The results are shown in Table 1:

[0076] Table 1 Test results of bisphenol S content in different fixing agent samples:

[0077]

[0078] Test Example 2: Color fixation effect test:

[0079] Formula: different concentrations of % (owf) of fixing agent;

[0080] Bath ratio: 1:10;

[0081] Fabric: Acid LD black 5% (owf) dyed fabric;

[0082] Process: Fix at 80℃ for 20 minutes → Rinse with cold water → Dehydrate and dry → Test the fabric for water fastness, perspiration fastness and seawater fastness.

[0083] (1) Washing fastness test:

[0084] Test method: AATCC 61-2A

[0085] The blank sample does not contain any fixing agent;

[0086] The results are shown in Table 2:

[0087] Table 2 Washing fastness test results of fabrics treated with different fixing agents

[0088]

[0089] As can be seen from the table above, Examples 1-5 provided by the present invention have good water fastness, and at a concentration of 2% (owf), the water fastness is above grade 4 / 4-5, which is significantly higher than the color fixing agent provided in the comparative example and the market sample.

[0090] (2) Perspiration (alkaline) fastness test:

[0091] Test method: According to ISO 105 E4

[0092] The results are shown in Table 3:

[0093] Table 3 Test results of perspiration (alkali) fastness of fabrics treated with different fixing agents

[0094]

[0095] As can be seen from the table above, Examples 1-5 provided by the present invention have good perspiration (alkali) fastness, and the water washing fastness at a concentration of 2% (owf) is above level 4, which is significantly higher than the fixing agent provided in the comparative example and the market sample.

[0096] (3) Seawater fastness test:

[0097] Test method: According to ISO 105 E02

[0098] The results are shown in Table 4:

[0099] Table 4 Test results of seawater fastness of fabrics treated with different fixing agents:

[0100]

[0101] As can be seen from the table above, Examples 1-5 provided by the present invention have good seawater fastness, and at a concentration of 2% (owf), the water washing fastness is above 4 / 4-5, which is significantly higher than the color fixing agent provided in the comparative example and the market sample.

[0102] Test Example 3 Color fixation and color change test:

[0103] Formula: different concentrations of % (owf) of fixing agent;

[0104] Bath ratio: 1:10;

[0105] Fabric: Acid AFN dye 2% (owf) dyed fabric;

[0106] Process: Fix at 80℃ for 20 minutes → rinse with cold water → dehydrate and dry → test the total color difference of the fabric (△E).

[0107] The results are shown in Table 5:

[0108] Table 5 Color change test results of fabrics treated with different acidic fixing agents

[0109]

[0110] As can be seen from the above table, Examples 1-5 provided by the present invention have a stable fabric color change effect. On the blue nylon fabric, the color change of the fabric treated with the acidic color fixing agent provided by the present invention is significantly smaller than that of the comparative examples 1-3, market sample 1, and market sample 2, and there is basically no color change.

[0111] Test Example 4: Test on hardness ion tolerance:

[0112] Formula: Fixing agent 10g / L + different hardness ppm;

[0113] Test method: Take 1g of the color fixing agent to be tested in a 100ml glass beaker, then add pre-prepared water of different hardness to 100g, stir evenly and let it stand for 20 minutes to observe the stability of the prepared working solution.

[0114] The results are shown in Table 6:

[0115] Table 6 Test results of different fixing agents' tolerance to hardness ions

[0116]

[0117] As can be seen from the above table, market samples 1 and 2 do not have obvious hardness ion tolerance, and obvious bottom particle precipitation appeared at 10000ppm. However, Examples 1-5 provided by the present invention all showed very good hardness ion tolerance under the three test conditions. Compared with Comparative Examples 1-3, the present invention achieves better hardness ion tolerance through specific raw material dosage and composition.

[0118] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A bisphenol S-free acidic color fixing agent, characterized in that: It is composed of the following components in parts by weight: 15-25 parts of water, 10-15 parts of phenol, 15-25 parts of dimethylacetamide, 2-5 parts of sodium sulfite, 10-15 parts of acetic acid, 5-7 parts of concentrated sulfuric acid, 15-20 parts of acrylic acid, 2-5 parts of ethylene glycol dimethyl ether and 1-3 parts of sorbitol; The preparation method of the acidic fixing agent comprises the following steps: Mix phenol, dimethylacetamide, acrylic acid, acetic acid and sodium sulfite in a formula amount, heat, add concentrated sulfuric acid to react, cool, add water in a formula amount, add ethylene glycol dimethyl ether and sorbitol in a formula amount, and obtain the product; The heating temperature is 70-90°C; the reaction temperature is 80-90°C.

2. The acidic color fixing agent according to claim 1, characterized in that It is composed of the following components in parts by weight: 17-23 parts of water, 11-15 parts of phenol, 16-24 parts of dimethylacetamide, 2-4 parts of sodium sulfite, 12-15 parts of acetic acid, 5-7 parts of concentrated sulfuric acid, 16-18 parts of acrylic acid, 2-5 parts of ethylene glycol dimethyl ether and 1-3 parts of sorbitol.

3. The acidic color fixing agent according to claim 1, characterized in that It is composed of the following components in parts by weight: 20 parts of water, 13 parts of phenol, 20 parts of dimethylacetamide, 2 parts of sodium sulfite, 13 parts of acetic acid, 7 parts of concentrated sulfuric acid, 17 parts of acrylic acid, 3 parts of ethylene glycol dimethyl ether and 2 parts of sorbitol.

4. The method for preparing the acidic color fixing agent according to any one of claims 1 to 3, characterized in that: The following steps are involved: Mix phenol, dimethylacetamide, acrylic acid, acetic acid and sodium sulfite in a formula amount, heat, add concentrated sulfuric acid to react, cool, add water in a formula amount, add ethylene glycol dimethyl ether and sorbitol in a formula amount, and obtain the product; The heating temperature is 70-90°C; the reaction temperature is 80-90°C.

5. The preparation method according to claim 4, characterized in that: The target temperature of the cooling is 50-60°C.

6. The preparation method according to claim 4, wherein: After adding the formulated amount of water, stir for 30-60 minutes; after adding the formulated amount of ethylene glycol dimethyl ether and sorbitol, stir for 40-80 minutes.

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