Environment-friendly acidic color fixing agent as well as preparation method and application thereof

Abstract

The invention discloses an environment-friendly acidic color fixing agent and a preparation method and application thereof, and the environment-friendly acidic color fixing agent comprises the following raw materials in parts by mass: 40-60 parts of water, 10-20 parts of an organic solvent, 1-5 parts of an emulsifier, 25-30 parts of a monomer mixed solution and 1-5 parts of an initiator. The acid color fixing agent prepared by the invention has a high-molecular acrylic elastomer polymer structure, is stable in structure, and can be subjected to cross-linking reaction with hydroxyl in an acid dye, so that the bonding degree of the acid dye and a fabric is higher, the dry rubbing fastness, the wet rubbing fastness and the color fastness to washing of the acid dye are improved, and the effect is remarkable. The raw materials are wide in source, the preparation process is simple, the environment-friendly, safe and non-toxic effects are achieved, phenol and bisphenol are not contained, the environment-friendly requirements of environment-friendly organizations such as blue labels, ZDHC and OEKO-TEX Standard 100 are met, the use prospect is wide, and popularization and promotion in related industries of textiles are facilitated.

Description

Technical Field

[0001] The invention relates to an environmentally friendly acidic color fixing agent and a preparation method and application thereof, and belongs to the field of textile dyeing functional finishing agents. Background Art

[0002] Nylon products are mainly dyed with weak acid dyes or neutral dyes. Since the dye molecules contain anionic polar groups such as sulfonic acid groups and carboxylic acid groups, they usually exist in water as water-soluble sodium salts. Nylon fiber macromolecules contain a large number of amide groups and terminal amino groups. Under acidic conditions, cationic groups are formed, which can be ionically bonded with the anionic groups of the dye molecules. At the same time, the affinity between the dye and the fiber macromolecule is also large, and it can also be combined through intermolecular forces and van der Waals forces, thereby greatly increasing the adsorption of the dye, improving the color yield, and reducing the residual amount of the dye in the dye liquor. Nylon products are often washed, and household washing is generally carried out under alkaline conditions. The dye will fall off the fabric and hydrolyze due to ionization in the alkaline aqueous solution, and under the action of surfactants such as soap or washing powder, it will be dispersed in the water away from the fabric and may be contaminated on other fabrics, resulting in poor wet friction fastness and staining fastness. Therefore, nylon usually needs to be fixed with a fixing agent after being dyed with weak acid dyes or neutral dyes to improve its various wet fastnesses.

[0003] Traditional acid dye fixing agents are generally high molecular weight aromatic sulfonic acid condensates coated on the fiber surface. The advantages of this type of acid fixing agent are: the negative charge of the sulfonic acid group on the surface has a repulsive force on the acid dye in the fiber, and the acid dye fixing agent prevents the dye from coming out. The coating effect also reduces the fiber swelling, reducing the chance of the dye and water molecules combining, thereby improving the fastness. However, this type of acid fixing agent uses a large amount of aromatic materials as synthetic raw materials, resulting in the final product containing phenol, bisphenol S, bisphenol F, formaldehyde and other residues. With the improvement of people's environmental awareness, these substances have been banned or restricted by environmental protection organizations such as Blue Label, ZDHC, OEKO-TEX Standard 100, so this type of acid fixing agent can no longer meet the current environmental protection requirements. Summary of the invention

[0004] In view of the problems existing in the above-mentioned prior art, the present invention provides an environmentally friendly acidic color fixing agent and a preparation method and application thereof.

[0005] In order to achieve the above purpose, the present invention adopts an environmentally friendly acidic color fixing agent, which includes the following raw materials by weight: 40-60 parts of water, 10-20 parts of organic solvent, 1-5 parts of emulsifier, 25-30 parts of monomer mixed liquid, and 1-5 parts of initiator.

[0006] As an improvement, the organic solvent is at least one of ethanol, isopropanol, ethylene glycol, glycerol, diethylene glycol, tripropylene glycol, 2-methyl-2,4-pentanediol, propylene glycol, and dipropylene glycol.

[0007] As an improvement, the emulsifier is at least one of tetradecanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, isomeric decanol polyoxyethylene ether, sodium dodecylbenzene sulfonate, and C14-17 secondary alkyl sodium sulfonate.

[0008] As an improvement, the monomer mixture adopts at least two of acrylic acid, maleic anhydride, methacrylic acid, styrene, methyl methacrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, dimethylaminoethyl methacrylate, dodecyl acrylate, vinyl acetate, polyethylene glycol (PEG400) diacrylate, ethyl acrylate, and butyl acrylate.

[0009] As an improvement, the initiator is at least one of 50% hydrogen peroxide, sodium persulfate, ammonium persulfate, potassium persulfate, and azobisisobutyramidine dihydrochloride.

[0010] The second aspect of the present invention also provides a method for preparing the environmentally friendly acidic color fixing agent, comprising the following steps: adding 30-50 parts of water and a formula amount of organic solvent and emulsifier into a reaction kettle, introducing nitrogen, opening reflux, heating to 70-100°C and maintaining a constant temperature while dripping a monomer mixture and an initiator dissolved in 10 parts of water, the dripping time being 1-3 hours, and after the dripping is completed, sealing the reaction kettle, heating the reactants to 80-130°C and continuing to keep warm for 1-4 hours, cooling to 40°C, vacuum removing residual monomers for 0.5 hours, and filtering to obtain an environmentally friendly acidic color fixing agent.

[0011] The third aspect of the present invention also provides an application of the environmentally friendly acidic color fixing agent or the environmentally friendly acidic color fixing agent obtained by the preparation method in the color fixing treatment of cloth samples.

[0012] As an improvement, weigh 10g of the cloth sample, the bath ratio is 1:10, the amount of the fixing agent is 3% (owf), the pH value of the working solution is adjusted to 4-4.5 with glacial acetic acid, preheated to 40℃ before entering the cylinder, heated to 70℃ at a rate of 2℃ / min for 20 minutes, washed with water after exiting the cylinder, and dehydrated and dried.

[0013] Compared with the prior art, the acidic color fixing agent prepared by the invention has a high molecular weight acrylic elastomer polymer structure, a stable structure, and can undergo a cross-linking reaction with the hydroxyl group in the acidic dye, so that the acidic dye is more closely combined with the fabric, thereby improving the dry rubbing fastness, wet rubbing fastness and washing fastness of the acidic dye, and the effect is remarkable. The raw material source of the acidic dye is wide, the preparation process is simple, the acidic dye is environmentally friendly, safe, non-toxic, does not contain phenol, does not contain bisphenol, and meets the environmental protection requirements of environmental protection organizations such as Blue Label, ZDHC, OEKO-TEX Standard 100, etc., and the application prospect is broad, which is conducive to popularization and promotion in textile-related industries. DETAILED DESCRIPTION

[0014] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0015] Example 1

[0016] A method for preparing an environmentally friendly acidic color fixing agent comprises the following steps:

[0017] Add 40 parts of water, 15 parts of organic solvent (isopropanol), and 5 parts of emulsifier (isotridecyl alcohol polyoxyethylene ether (TO8)) into a reaction kettle, introduce nitrogen, start reflux, raise the temperature to 80°C and keep the constant temperature while dripping 25 parts of monomer mixture (10 parts of acrylic acid, 5 parts of 2-hydroxyethyl acrylate, 5 parts of styrene, 5 parts of maleic anhydride) and initiator (5 parts of sodium persulfate dissolved in 10 parts of water) for 2 hours. After the dripping is completed, seal the reaction kettle, heat the reactants to 100°C and keep the temperature for 3 hours, cool to 40°C, remove residual monomers in vacuo for 0.5 hours, and filter to obtain an environmentally friendly acidic color fixing agent.

[0018] Example 2

[0019] A method for preparing an environmentally friendly acidic color fixing agent comprises the following steps:

[0020] Add 45 parts of water, 13 parts of organic solvent (propylene glycol), and 3 parts of emulsifier (sodium dodecylbenzene sulfonate) into a reaction kettle, introduce nitrogen, start reflux, raise the temperature to 100° C. and keep the constant temperature while dripping 25 parts of monomer mixture (10 parts of acrylic acid, 10 parts of methacrylic acid, 5 parts of polyethylene glycol (PEG400) diacrylate) and initiator (4 parts of 50% hydrogen peroxide dissolved in 10 parts of water) for 1.5 hours. After the dripping is completed, seal the reaction kettle, heat the reactants to 120° C. and keep the temperature for 2 hours, cool to 40° C., remove residual monomers in vacuum for 0.5 hours, and filter to obtain an environmentally friendly acidic color fixing agent.

[0021] Example 3

[0022] A method for preparing an environmentally friendly acidic color fixing agent comprises the following steps:

[0023] Add 47 parts of water, 10 parts of organic solvent (diethylene glycol), and 3 parts of emulsifier (C14-17 sodium secondary alkyl sulfonate (SAS60)) into a reactor, introduce nitrogen, start reflux, raise the temperature to 90°C and keep the constant temperature while dripping a monomer mixture (10 parts of acrylic acid, 10 parts of styrene, and 5 parts of vinyl acetate) and an initiator (5 parts of azobisisobutyramidine dihydrochloride dissolved in 10 parts of water) for 1.5 hours. After the dripping is completed, seal the reactor, heat the reactants to 120°C and keep the temperature for 2 hours, cool to 40°C, remove residual monomers in vacuo for 0.5 hours, and filter to obtain an environmentally friendly acidic color fixing agent.

[0024] Example 4

[0025] A method for preparing an environmentally friendly acidic color fixing agent comprises the following steps:

[0026] Add 38 parts of water, 20 parts of organic solvent (tripropylene glycol), and 5 parts of emulsifier (isomeric decanol polyoxyethylene ether (XP80)) into a reaction kettle, introduce nitrogen, start reflux, raise the temperature to 100°C and keep the constant temperature while dripping a monomer mixture (10 parts of methyl methacrylate, 10 parts of 2-ethylhexyl acrylate, and 5 parts of stearyl acrylate) and an initiator (2 parts of potassium persulfate dissolved in 10 parts of water) for 2.5 hours. After the dripping is completed, seal the reaction kettle, heat the reactants to 110°C and continue to keep the temperature for 2 hours, cool to 40°C, remove residual monomers in vacuo for 0.5 hours, and filter to obtain an environmentally friendly acidic color fixing agent.

[0027] Example 5

[0028] A method for preparing an environmentally friendly acidic color fixing agent comprises the following steps:

[0029] Add 42 parts of water, 15 parts of organic solvent (2-methyl-2,4-pentanediol), and 5 parts of emulsifier (polyoxyethylene dodecaethanol (AEO9)) into the reactor, introduce nitrogen, start reflux, raise the temperature to 90°C and keep the constant temperature while dripping a monomer mixture (15 parts of acrylic acid, 5 parts of dimethylaminoethyl methacrylate, and 5 parts of dodecyl acrylate) and an initiator (3 parts of ammonium persulfate dissolved in 10 parts of water) for 2 hours. After the dripping is completed, seal the reactor, heat the reactants to 110°C and continue to keep the temperature for 3 hours, cool to 40°C, remove residual monomers in vacuo for 0.5 hours, and filter to obtain an environmentally friendly acidic color fixing agent.

[0030] Application performance test of the product of the present invention:

[0031] 1. Fabric color fixing treatment: accurately weigh 10g of fabric sample, bath ratio 1:10, dosage of color fixing agent 3% (owf), adjust the pH value of the working solution to 4-4.5 with glacial acetic acid, preheat to 40℃ and put it into the cylinder, heat to 70℃ at a rate of 2℃ / min and run for 20 minutes, wash it out of the cylinder, dehydrate and dry it for use.

[0032] 2. Determination of color fastness to washing: According to the test of GB / T 3921-2008 Textiles - Color fastness to washing with soap, sew the above-mentioned test cloth after color fixation with the standard six-fiber test cloth, add 5g / l detergent and 2g / l soda ash, put it into the vat at 60℃ for 30 minutes, wash it out of the vat, dehydrate and dry it, and compare the staining effect of the standard six-fiber test cloth. The rating is 1-5, and 5 is the best.

[0033] 3. Determination of water fastness: Liby washing powder 2g / l, bath ratio 1:50, soak the above-mentioned cloth treated with color fixation in 60℃ working solution for 30 minutes and then take it out, compare the water fastness effect, and rate it from 1 to 5, with 5 being the best.

[0034] The test results are shown in Table 1 below.

[0035] Table 1 Performance of environmentally friendly acidic color fixing agent prepared in the embodiment of the present invention

[0036] Test sample name Color fastness to washing Water fastness Example 1 Level 3-4 Level 4-5 Example 2 Level 3-4 Level 3-4 Example 3 Level 4-5 Level 3-4 Example 4 Level 4-5 Level 4-5 Example 5 Level 4-5 Level 4-5 Similar products on the market Level 3 Level 3

[0037] Analysis shows that the environmentally friendly acidic color fixing agent prepared by the present invention can make the color fastness to washing and the color fastness to water of the cloth sample after color fixing treatment not less than level 3, and even reach level 5; while the commercially available products can only maintain the color fastness to washing and the color fastness to water of the cloth sample at level 3.

[0038] The acidic color fixing agent prepared by the invention has a high molecular weight acrylic elastomer polymer structure, has a stable structure, can undergo a cross-linking reaction with a hydroxyl group in an acidic dye, so that the acidic dye is more closely combined with the fabric, thereby improving the dry rubbing fastness, wet rubbing fastness and washing fastness of the acidic dye, and has a significant effect. The raw material source of the acidic dye is wide, the preparation process is simple, the acidic dye is environmentally friendly, safe, non-toxic, does not contain phenol, does not contain bisphenol, and meets the environmental protection requirements of environmental protection organizations such as Blue Label, ZDHC, OEKO-TEX Standard 100, etc., has a broad prospect for use, and is conducive to popularization and promotion in textile-related industries.

[0039] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. An environmentally friendly acidic color fixing agent, characterized in that: The raw materials include the following by weight: 40-60 parts of water, 10-20 parts of organic solvent, 1-5 parts of emulsifier, 25-30 parts of monomer mixed solution, and 1-5 parts of initiator.

2. The environmentally friendly acidic color fixing agent according to claim 1, characterized in that: The organic solvent is at least one of ethanol, isopropanol, ethylene glycol, glycerol, diethylene glycol, tripropylene glycol, 2-methyl-2,4-pentanediol, propylene glycol and dipropylene glycol.

3. The environmentally friendly acidic color fixing agent according to claim 1, characterized in that: The emulsifier is at least one of tetradecanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, isomeric decanol polyoxyethylene ether, sodium dodecylbenzene sulfonate, and C14-17 secondary alkyl sodium sulfonate.

4. The environmentally friendly acidic color fixing agent according to claim 1, characterized in that: The monomer mixture liquid adopts at least two of acrylic acid, maleic anhydride, methacrylic acid, styrene, methyl methacrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, dimethylaminoethyl methacrylate, dodecyl acrylate, vinyl acetate, polyethylene glycol (PEG400) diacrylate, ethyl acrylate, and butyl acrylate.

5. The environmentally friendly acidic color fixing agent according to claim 1, characterized in that: The initiator is at least one of 50% hydrogen peroxide, sodium persulfate, ammonium persulfate, potassium persulfate and azobisisobutyramidine dihydrochloride.

6. A method for preparing the environmentally friendly acidic color fixing agent according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: adding 30-50 parts of water and a formula amount of an organic solvent and an emulsifier into a reaction kettle, introducing nitrogen, starting reflux, heating to 70-100° C. and keeping the temperature constant while dripping a monomer mixture and an initiator dissolved in 10 parts of water for 1-3 hours. After the dripping is completed, the reaction kettle is sealed, the reactants are heated to 80-130° C. and kept warm for 1-4 hours, cooled to 40° C., vacuum-removing residual monomers for 0.5 hours, and filtered to obtain an environmentally friendly acidic color fixing agent.

7. Use of the environmentally friendly acidic color fixing agent according to any one of claims 1 to 5 or the environmentally friendly acidic color fixing agent prepared by the preparation method according to claim 6 in color fixing treatment of cloth samples.

8. The use according to claim 7, characterized in that: Weigh 10g of fabric sample, bath ratio 1:10, dosage of fixing agent 3% (owf), adjust the pH value of the working solution to 4-4.5 with glacial acetic acid, preheat to 40℃ and put it into the cylinder, heat it to 70℃ at a rate of 2℃ / min and run it for 20 minutes, wash it out of the cylinder, dehydrate and dry it.