阅读说明：本技术 能够染固一浴处理的环保型酸性固色剂、制备方法及应用 (Environment-friendly acidic color fixing agent capable of being subjected to dyeing and fixing one-bath treatment, and preparation method and application thereof ) 是由 邹其光 李中全 于 2020-08-04 设计创作，主要内容包括：本发明公开一种能够染固一浴处理的环保型酸性固色剂、制备方法及应用,属于纺织印染助剂领域,按重量百分比计,包括30-70％的芳香族磺酸化合物、1-5％的阴离子聚氨酯、5-20％的分散剂和5-65％的去离子水；制备方法包括：1)将配方量的分散剂加入到搅拌釜中；2)将搅拌釜加热至60-65℃,然后搅拌50-70min加入配方量阴离子聚氨酯,加毕后搅拌20-40min；3)加入配方量芳香族磺酸化合物,在60℃搅拌25-35min；4)加入配方量去离子水,混合25-35min后,即得。本发明既可提升酸性染料染色或印花后色牢度,又可与绝大多数染色助剂同浴使用。(The invention discloses an environment-friendly acidic color fixing agent capable of being used for dyeing and fixing one-bath treatment, a preparation method and application, which belong to the field of textile printing and dyeing auxiliaries, and comprise 30-70 wt% of aromatic sulfonic acid compounds, 1-5 wt% of anionic polyurethane, 5-20 wt% of dispersing agents and 5-65 wt% of deionized water; the preparation method comprises the following steps: 1) adding the dispersant with the formula amount into a stirring kettle; 2) heating the stirring kettle to 60-65 ℃, then stirring for 50-70min, adding the anionic polyurethane with the formula amount, and stirring for 20-40min after the addition is finished; 3) adding aromatic sulfonic acid compound according to the formula amount, and stirring at 60 ℃ for 25-35 min; 4) adding deionized water according to the formula amount, and mixing for 25-35min to obtain the final product. The invention can not only improve the color fastness of acid dye after dyeing or printing, but also can be used together with most dyeing auxiliaries.)

1. An environment-friendly acidic color fixing agent capable of being used for dyeing and fixing one-bath treatment is characterized by comprising 30-70% of aromatic sulfonic acid compound, 1-5% of anionic polyurethane, 5-20% of dispersing agent and 5-65% of deionized water in percentage by weight.

2. The environment-friendly acidic color fixing agent capable of dyeing and fixing one-bath treatment according to claim 1, wherein the aromatic sulfonic acid compound is an anionic aromatic sulfonic acid compound which does not contain formaldehyde, bisphenol S and toluene.

3. The environment-friendly acidic color fixing agent capable of dyeing and fixing in one bath is prepared from phenolic compounds, epichlorohydrin and concentrated sulfuric acid under the action of a catalyst according to claim 2.

4. The environment-friendly acidic color fixing agent capable of being used for dyeing and fixing one-bath treatment according to claim 3, wherein the phenolic compound is a mixture of ethyl naphthol and hydroquinone in a molar ratio of 1:2-2: 1.

5. The environment-friendly acidic color fixing agent capable of dyeing one-bath treatment according to any one of claims 2 to 4, wherein the aromatic sulfonic acid compound is prepared by the following steps:

s1, carrying out ring-opening condensation reaction on a phenolic compound and epichlorohydrin for 3-5h at 50-60 ℃ under the action of a catalyst of trifluoromethanesulfonic acid, and then distilling under vacuum reduced pressure to remove unreacted epichlorohydrin to obtain an intermediate A;

s2, slowly dripping liquid caustic soda into the intermediate A, keeping the reaction temperature at 35-45 ℃, and after dripping is finished, keeping the temperature to react for 30-60min to obtain a viscous transparent liquid-shaped intermediate B;

s3, keeping the intermediate B at 35-45 ℃, dropwise adding concentrated sulfuric acid into the intermediate B, reacting for 1-2h, and adding a proper amount of glycolic acid after the reaction is finished to maintain the pH of a 1% solution at 4-5, thus obtaining the brown yellow transparent aromatic sulfonic acid compound.

6. The environment-friendly acidic color fixing agent capable of dyeing and fixing one-bath treatment according to claim 1, wherein the anionic polyurethane is a hyperbranched polyurethane compound synthesized by a sulfonic acid type chain extender.

7. The environment-friendly acidic color fixing agent capable of dyeing and fixing one-bath treatment according to claim 1, wherein the dispersant is one or more of dodecylbenzene sulfonic acid, alkyl diphenyl ether disulfonate and lignosulfonate mixed in any proportion.

8. The environment-friendly acidic color fixing agent capable of dyeing and fixing one-bath treatment according to claim 7, wherein the alkyl diphenyl oxide disulfonate and the lignosulfonate are respectively one or two of sodium salt and potassium salt which are mixed in any proportion.

9. A method for preparing the environment-friendly acidic color fixing agent as defined in any one of claims 1 to 8, comprising the following steps:

1) adding the dispersant with the formula amount into a stirring kettle;

2) heating the stirring kettle to 60-65 ℃, then stirring for 50-70min, adding the anionic polyurethane with the formula amount, and stirring for 20-40min after the addition is finished;

3) adding aromatic sulfonic acid compound according to the formula amount, and stirring at 60 ℃ for 25-35 min;

4) adding deionized water according to the formula amount, and mixing for 25-35min to obtain the final product.

10. The application of the environment-friendly acidic color fixing agent of any one of claims 1 to 9 in color fixing of textiles, wherein the textiles are one of nylon, wool and silk fabrics;

wherein, polyamide fibre fixation liquid includes: the dosage of the color fixing agent is 1.0-4.0% (o.w.f), and the pH value is 3.5-5.0;

the silk color fixing solution comprises: the dosage of the color fixing agent is 0.5-2.5% (o.w.f), and the pH value is 4.0-4.5;

the wool color fixing solution comprises: the dosage of the color fixing agent is 2.0-5.0% (o.w.f), and the pH value is 4.5-5;

the specific color fixing step comprises the following steps: after dyeing is finished, directly cooling to 75-80 ℃, adding the color fixing agent, keeping the temperature for color fixing for 25-30 minutes, cooling to 45-60 ℃, draining, washing with clean water for 10-15 minutes, draining, taking out of a cylinder for dehydration, and drying.

Technical Field

The invention relates to an environment-friendly acidic color fixing agent capable of being subjected to dyeing and fixing one-bath treatment, a preparation method and application, and belongs to the field of textile printing and dyeing auxiliaries.

Background

Chinlon, silk and wool are usually dyed or printed by using acid dyes, and the dyes are mainly fixed on the fabrics by virtue of van der waals force and hydrogen bond action. Because the acid dye is anionic dye, the water solubility is good, the Van der Waals force and the hydrogen bond are not firm, and the color fastness to washing, rubbing, perspiration stain and the like of dyed chinlon, real silk and wool fabrics are poor. In order to meet various requirements, color fixing treatment is generally required to improve various color fastness of fabrics.

In the early stage, natural tannin is adopted as a color fixing agent, the color fixing effect of the color fixing agent is good, but the color fixing process is complex, a two-bath method is required for color fixing, and the fabric hand feeling after color fixing is poor. The synthetic tannin color fixing agent developed in recent years has a simple processing method, can be used for fixing color by a bath method, but cannot be treated with dyeing in a bath, and raw materials used in the production of the color fixing agent contain formaldehyde, bisphenol S and the like, for example, an acid-reaction-resistant nylon color fixing agent and application thereof (ZL201210304218.7) in Chinese patents disclose the acid-reaction-resistant nylon color fixing agent which is prepared by the following method: a phenolic substance and two aromatic sulfonic acid compounds are used for carrying out condensation reaction with formaldehyde under the action of a composite catalyst; then adding epoxy chloropropane and a modifier into the reaction system for modification; and finally, adjusting the pH value of the multi-copolymerization high-molecular aromatic sulfonic acid formaldehyde condensate obtained by modification to 2.0-4.0 by using strong acid or concentrated acid to obtain the acid-resistant reaction type chinlon color fixing agent. The color fixing agent is not beneficial to environmental protection. At present, the water consumption and sewage discharge of a printing and dyeing mill are limited, so the problems of color fixation after dyeing by acid dyes, energy conservation and emission reduction are one of the hot spots of research.

In order to solve the problems of formaldehyde and the like of the acid color fixing agent, a plurality of formaldehyde-free color fixing agents are developed at home and abroad, and the performances of the formaldehyde-free color fixing agents are different. The prior Chinese patent is a formaldehyde-free acid dye color fixing agent (ZL201610109405.8) which is synthesized by taking acrylic acid, 2-naphthol and 2-acrylamide-2-methylpropanesulfonic acid as raw materials, ammonium acetate as an initiator and nickel chloride as a catalyst. The color fixing agent can obviously improve the fastness of soaping, rubbing, sweat stain and the like of the fiber after color fixing treatment. But the adopted nickel chloride brings the trouble of exceeding the standard of the fabric nickel for the actual production; meanwhile, the usability of dyeing and color fixing in one bath is poor, the color fixing is needed to be carried out independently, the working procedures are not shortened, and the water-saving effect is achieved. According to the color fixing agent disclosed by the Chinese patent and the preparation method thereof (CN201310590513.8), hydroquinone and epoxy chloropropane are mixed in a nitrogen environment, a catalyst is added for full reaction, then a sodium hydroxide solution, toluene and concentrated sulfuric acid are sequentially added, and finally the color fixing agent is obtained. The pH value of the color fixing agent solution is controlled to be 7.5-9, which is not beneficial to dyeing and fixing one-bath treatment, and the color fixing effect is not as good as that of a formaldehyde-containing color fixing agent; meanwhile, toluene is used in the synthesis process, and the requirements of MRSL (methanol to toluene) of standards such as OEKO-TEXStandard 100 and the like are not met.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides an environment-friendly acid color fixing agent capable of being used for dyeing and fixing in one bath, which can improve the color fastness of acid dyes after dyeing or printing and can be used with most dyeing auxiliaries in one bath.

The second purpose of the invention is to provide a preparation method of the environment-friendly acidic color fixing agent.

The third purpose of the invention is to provide an application of the environment-friendly acidic color fixing agent.

In order to achieve the purpose, the environment-friendly acidic color fixing agent capable of being used for dyeing and fixing one-bath treatment comprises, by weight, 30-70% of aromatic sulfonic acid compounds, 1-5% of anionic polyurethane, 5-20% of dispersing agents and 5-65% of deionized water.

As an improvement, the aromatic sulfonic acid compound is specifically an anionic aromatic sulfonic acid compound which does not contain formaldehyde, bisphenol S and toluene.

As an improvement, the anionic aromatic sulfonic acid compound is prepared from a phenolic compound, epichlorohydrin and concentrated sulfuric acid under the action of a catalyst.

As an improvement, the phenolic compound is a mixture of ethyl naphthol and hydroquinone according to a molar ratio of 1:2-2: 1.

As an improvement, the aromatic sulfonic acid compound is prepared by the following steps:

s1, carrying out ring-opening condensation reaction on the mixed phenolic compound and epichlorohydrin for 3-5h at 50-60 ℃ under the action of a catalyst of trifluoromethanesulfonic acid, and distilling under vacuum reduced pressure to remove unreacted epichlorohydrin to obtain an intermediate A;

s2, slowly dripping liquid caustic soda into the intermediate A, keeping the reaction temperature at 35-45 ℃, and after dripping is finished, keeping the temperature to react for 30-60min to obtain a viscous transparent liquid-shaped intermediate B;

s3, keeping the intermediate B at 35-45 ℃, dropwise adding concentrated sulfuric acid into the intermediate B, reacting for 1-2h, and adding glycolic acid after the reaction is finished to maintain the pH of a 1% solution at 4-5, thus obtaining the brown yellow transparent aromatic sulfonic acid compound.

As a refinement, the anionic polyurethane is a hyperbranched polyurethane compound synthesized by sulfonic acid-type chain extenders, which can be obtained according to known routes, such as Qualitex PU from the company zhanfeng, guangdong.

As an improvement, the dispersant is one or more of dodecyl benzene sulfonic acid, alkyl diphenyl ether disulfonate and lignosulfonate mixed in any proportion.

As an improvement, the alkyl diphenyl ether disulfonate and the lignosulfonate are respectively one or two of sodium salt and potassium salt which are mixed in any proportion.

In addition, the invention also provides a preparation method of the environment-friendly acidic color fixing agent, which comprises the following steps:

1) adding the dispersant with the formula amount into a stirring kettle;

2) heating the stirring kettle to 60-65 ℃, then stirring for 50-70min, adding the anionic polyurethane with the formula amount, and stirring for 20-40min after the addition is finished;

3) adding aromatic sulfonic acid compound according to the formula amount, and stirring at 60 ℃ for 25-35 min;

4) adding deionized water according to the formula amount, and mixing for 25-35min to obtain the final product.

Finally, the invention also provides an application of the environment-friendly acidic color fixing agent in color fixing of textiles, wherein the textiles are one of chinlon, wool and silk fabrics;

wherein, polyamide fibre fixation liquid includes: the dosage of the color fixing agent is 1.0-4.0% (o.w.f), and the pH value is 3.5-5.0;

the silk color fixing solution comprises: the dosage of the color fixing agent is 0.5-2.5% (o.w.f), and the pH value is 4.0-4.5;

the wool color fixing solution comprises: the dosage of the color fixing agent is 2.0-5.0% (o.w.f), and the pH value is 4.5-5;

the specific color fixing step comprises the following steps: after dyeing is finished, directly cooling to 75-80 ℃, adding the color fixing agent, keeping the temperature for color fixing for 25-30 minutes, cooling to 45-60 ℃, draining, washing with clean water for 10-15 minutes, draining, taking out of a cylinder for dehydration, and drying.

Compared with the prior art, the invention has the beneficial effects that:

1. according to the environment-friendly acidic color fixing agent capable of being used for dyeing and fixing one-bath treatment, formaldehyde is preferably not used in raw materials, and the fabric does not contain or release formaldehyde after being treated; meanwhile, forbidden raw materials such as bisphenol S and the like are not used, and the requirements of ecological textiles are met.

2. The environment-friendly acidic color fixing agent capable of being subjected to dyeing and fixing one-bath treatment contains epoxy groups, the epoxy groups with high activity are easy to open loops, a large number of amino groups, carbamate groups and other groups exist in polyurethane molecules, and the epoxy groups are easy to form covalent bond hinge combination with active hydrogen groups contained in chinlon, silk, wool fibers and acidic dye molecules, so that the molecular weight of a generated product is increased, the activity is weakened, and the binding force of the dye and fabrics is improved; the polyurethane is baked at high temperature, the deblocked isocyanate group reacts with the active group, and the film forming property of the color fixing agent is improved; the polyurethane has a large molecular weight, and can cover the dye, completely coat the water-soluble group of the dye, play a role as an adhesive and a coating, and bond and seal the acid dye in a transparent thin layer. The binding capacity of the acid dye and the fiber is improved through the three modes, so that the color fixing effect of the invention is improved.

3. The sulfonic group in the environment-friendly acidic color fixing agent capable of being subjected to dyeing and fixing one-bath treatment can provide excellent water dispersibility of the color fixing agent, has stronger repulsion to acidic dye, prevents less dye from migrating into working solution, and improves the color retention of fabrics; secondly, the dispersing agent containing sulfonic group has strong dispersibility, and is preferentially combined with level dyeing of fatty amine polyoxyethylene ether and the like in a dye bath, so that the phenomenon that the dispersing agent is combined with a color fixing agent to generate insoluble substances to generate color fixing spots is avoided. Therefore, the use stability of the fixing agent is obviously improved.

4. The strong crosslinking effect of the anionic polyurethane assists in enhancing the color fixing and washing resisting effects of the aromatic sulfonic acid compound in the use process of the environment-friendly acidic color fixing agent, and the existence of the dispersant can improve the stability of the product, so that the effective use of the product is ensured. Therefore, the color fixing effect and the service performance of the color fixing agent are further improved by the mutual synergistic effect of the three components after compounding.

5. The environment-friendly acid color fixing agent can reduce the total steps of dyeing and color fixing (the traditional two-bath two-step process is optimized into one-bath one-step process), reduce the sewage amount, ensure the good printing and dyeing processability of the fabric, realize the green processing of the textile and reduce the pollution to the environment.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention.