阅读说明：本技术 一种提高耐洗牢度的交联剂、其制备方法及防水织物 (Cross-linking agent for improving washing fastness, preparation method thereof and waterproof fabric ) 是由 董锋 周宁 姜兴盛 托马斯·沃尔特施密特 张俊峰 李天源 卓丽琼 吴建通 于 2019-11-13 设计创作，主要内容包括：本发明提供的一种提高耐洗牢度的交联剂、其制备方法及防水织物,所述交联剂包括以下质量份的组分：15-30质量份甲基氯丙烯、20-35质量份氰酸钠、10-40质量份三羟甲基丙烷,1-30质量份丙烯酸,所述交联剂的pH值为7-8。该交联剂配合防水剂,可以提高防水剂的耐洗度,增加防水织物的使用寿命,生产工艺简单,造价低,可大规模应用于工业化生产中。(The invention provides a cross-linking agent for improving washing fastness, a preparation method thereof and a waterproof fabric, wherein the cross-linking agent comprises the following components in parts by mass: 15-30 parts of methyl chloropropene, 20-35 parts of sodium cyanate, 10-40 parts of trimethylolpropane and 1-30 parts of acrylic acid, wherein the pH value of the cross-linking agent is 7-8. The cross-linking agent is matched with a waterproof agent, so that the washing fastness of the waterproof agent can be improved, the service life of a waterproof fabric is prolonged, the production process is simple, the manufacturing cost is low, and the cross-linking agent can be applied to industrial production on a large scale.)

1. The cross-linking agent for improving the washing fastness is characterized by comprising the following components in parts by mass: 15-30 parts of methyl chloropropene, 20-35 parts of sodium cyanate, 10-40 parts of trimethylolpropane and 1-30 parts of acrylic acid, wherein the pH value of the cross-linking agent is 7-8.

2. The crosslinking agent according to claim 1, further comprising water and an organic solvent, wherein the organic solvent is ethanol.

3. The cross-linking agent according to claim 1, wherein the cross-linking agent comprises the following components in parts by mass: 22 parts by mass of methyl chloropropene, 20 parts by mass of sodium cyanate, 40 parts by mass of trimethylolpropane and 30 parts by mass of acrylic acid.

4. The preparation method of the cross-linking agent for improving the washing fastness is characterized by comprising the following steps:

firstly putting 800 mass parts of 200-mass water into a reaction kettle, then putting 15-30 mass parts of methyl chloropropene and 20-35 mass parts of sodium cyanate into the reaction kettle, continuously stirring for 2-4 hours at 30-40 ℃, cooling to 15-25 ℃, then adding 10-40 mass parts of trimethylolpropane, stirring and emulsifying, cooling to 8-10 ℃, adding 1-30 mass parts of acrylic acid at 8-10 ℃, finally adding an organic solvent to obtain an emulsion, and adjusting the pH value of the emulsion to 7-8 to obtain the cross-linking agent.

5. The process according to claim 4, wherein the acrylic acid is continuously added dropwise over a period of 1 to 3 hours.

6. The method according to claim 4, wherein the organic solvent is ethanol, and the amount of ethanol added is 10 to 15g/L of the crosslinking agent.

7. The method according to claim 4, wherein the pH of the emulsion is adjusted by a pH adjusting agent comprising citric acid, sodium hydroxide and sodium citrate.

8. A waterproof fabric characterized by being waterproofed with a non-silicon fluorine-free waterproofing agent and the crosslinking agent according to any one of claims 1 to 3; the non-silicon fluorine-free waterproof agent comprises the following components in parts by mass: 20-30 parts by mass of acrylic acid, 20-30 parts by mass of glycidyl acrylate, 10-20 parts by mass of diacetone acrylamide, 1-10 parts by mass of stearic acid and 1-10 parts by mass of isocyanate; the pH value of the non-silicon fluorine-free waterproof agent is 5-7.

9. A waterproof fabric characterized by being waterproofed with a silicone fluorine-free water repellent and the crosslinking agent according to any one of claims 1 to 3; the organic silicon fluorine-free waterproof agent comprises the following components in parts by mass: 60-70 parts by mass of an organic silicon polymer, 1-10 parts by mass of a cross-linking mixture and 1-5 parts by mass of a surfactant; the organic silicon polymer comprises amino silane and modified silicone oil, and the mass ratio of the amino silane to the modified silicone oil is 50-60: 40-50; the crosslinking mixture comprises acrylic acid and epoxy silane, and the mass ratio of the acrylic acid to the epoxy silane is 30-60: 40-70; the pH value of the organic silicon fluorine-free waterproof agent is 5-7.

10. The waterproof fabric according to any one of claims 8 or 9, wherein the waterproof fabric is a chemical fiber fabric.

Technical Field

The invention relates to the field of textiles, in particular to a cross-linking agent for improving washing fastness, a preparation method thereof and a waterproof fabric.

Background

Perfluorooctane sulfonyl compounds (PFOS) and perfluorooctanoic acid (PFOA) are trace substances present in C8 waterproofing agents, are difficult to degrade, bioaccumulate and of various toxicities, and share the common characteristics of all persistent organic pollutants, and are therefore subject to strict limitations. For the textile industry, PFOA and PFOS are mainly present in fabrics treated with fluorine-containing water-and oil-repellent finishes.

Therefore, I have developed organosilicon fluorine-free waterproof agents and non-silicon fluorine-free waterproof agents, but in the research, the waterproof effect of the two types of waterproof agents is reduced after the two types of waterproof agents are washed for many times, so that the use effect is influenced.

Disclosure of Invention

In view of the problems described in the background art, the present invention aims to provide a crosslinking agent for improving washing fastness, a preparation method thereof and a waterproof fabric. The cross-linking agent can be used together with an organic silicon fluorine-free waterproof agent and a non-silicon fluorine-free waterproof agent, so that the washing fastness is improved, and the waterproof performance of the waterproof fabric cannot be reduced after the waterproof fabric is washed for many times.

In order to achieve the above object, in a first aspect of the present invention, the inventors provide a crosslinking agent for improving wash fastness, the crosslinking agent comprising the following components in parts by mass: 15-30 parts of methyl chloropropene, 20-35 parts of sodium cyanate, 10-40 parts of trimethylolpropane and 1-30 parts of acrylic acid, wherein the pH value of the cross-linking agent is 7-8.

In a second aspect of the invention, the inventors provide a method for preparing a cross-linking agent for improving wash fastness, comprising the steps of:

firstly putting 800 mass parts of 200-mass water into a reaction kettle, then putting 15-30 mass parts of methyl chloropropene and 20-35 mass parts of sodium cyanate into the reaction kettle, continuously stirring for 2-4 hours at 30-40 ℃, cooling to 15-25 ℃, then adding 10-40 mass parts of trimethylolpropane, stirring and emulsifying, cooling to 8-10 ℃, adding 1-30 mass parts of acrylic acid at 8-10 ℃, finally adding an organic solvent to obtain an emulsion, and adjusting the pH value of the emulsion to 7-8 to obtain the cross-linking agent.

In a third aspect of the invention, the inventors provide a waterproof fabric treated with a cross-linking agent as provided in the first aspect of the invention and a non-silicon, fluorine-free, water repellant. The non-silicon fluorine-free waterproof agent comprises the following components in parts by mass: 20-30 parts of acrylic acid, 20-30 parts of glycidyl acrylate, 10-20 parts of diacetone acrylamide, 1-10 parts of stearic acid and 1-10 parts of a cross-linking agent; the pH value of the non-silicon fluorine-free waterproof agent is 5-7.

In a fourth aspect of the present invention, the inventors provide a waterproof fabric which is subjected to a waterproofing treatment with a silicone fluorine-free waterproofing agent and the crosslinking agent provided in the first aspect of the present invention; the organic silicon fluorine-free waterproof agent comprises the following components in parts by mass: 60-70 parts by mass of organic silicon polymer, 1-10 parts by mass of cross-linking agent and 1-5 parts by mass of surfactant; the organic silicon polymer comprises amino silane and modified silicone oil, and the mass ratio of the amino silane to the modified silicone oil is 50-60: 40-50; the cross-linking agent comprises acrylic acid and epoxy silane, and the mass ratio of the acrylic acid to the epoxy silane is 30-60: 40-70; the pH value of the organic silicon fluorine-free waterproof agent is 5-7.

Different from the prior art, the invention at least comprises the following beneficial effects: the cross-linking agent for improving the washing fastness and the preparation method thereof provided by the invention have the advantages that the cross-linking agent is matched with a waterproof agent, the washing fastness of the waterproof agent can be improved, the service life of a waterproof fabric is prolonged, the production process is simple, the manufacturing cost is low, and the cross-linking agent can be applied to industrial production in a large scale.

Detailed Description

In order to explain technical contents, structural features, and objects and effects of the technical means in detail, the following detailed description is given with reference to specific embodiments.

First, a crosslinking agent for improving wash fastness according to a first aspect of the present invention is described, which comprises the following components in parts by mass: 15-30 parts of methyl chloropropene, 20-35 parts of sodium cyanate, 10-40 parts of trimethylolpropane and 1-30 parts of acrylic acid, wherein the pH value of the cross-linking agent is 7-8.

The inventor finds that the proportion of the methyl chloropropene, the sodium cyanate and the trimethylolpropane can influence the crosslinking effect of the crosslinking agent in research. The methyl chloropropene and the sodium cyanate can promote the crosslinking reaction of the chemical fiber fabric and the waterproof agent; acrylic acid is the binder.

Preferably, the cross-linking agent further comprises water and an organic solvent, and the organic solvent is ethanol.

The water content in the waterproof agent is increased or decreased according to the needs, so that the components can be emulsified. The organic solvent is used for assisting dissolution.

Preferably, the cross-linking agent comprises the following components in parts by mass: 22 parts by mass of methyl chloropropene, 20 parts by mass of sodium cyanate, 40 parts by mass of trimethylolpropane and 30 parts by mass of acrylic acid.

Next, a method for producing a crosslinking agent according to the second aspect of the present invention is explained, comprising the steps of:

firstly putting 800 mass parts of 200-mass water into a reaction kettle, then putting 15-30 mass parts of methyl chloropropene and 20-35 mass parts of sodium cyanate into the reaction kettle, continuously stirring for 2-4 hours at 30-40 ℃, cooling to 15-25 ℃, then adding 10-40 mass parts of trimethylolpropane, stirring and emulsifying, cooling to 8-10 ℃, adding 1-30 mass parts of acrylic acid at 8-20 ℃, finally adding an organic solvent to obtain an emulsion, and adjusting the pH value of the emulsion to 7-8 to obtain the cross-linking agent.

Preferably, the acrylic acid is continuously added dropwise over 1 to 3 hours.

Preferably, the organic solvent is ethanol, and the addition amount of the ethanol is 10-15g/L of the crosslinking agent.

Preferably, the pH value of the emulsion is adjusted by a pH adjusting agent, and the pH adjusting auxiliary agent comprises citric acid, sodium hydroxide and sodium citrate.

Next, a waterproof fabric according to a third aspect of the present invention is described, which is treated with the crosslinking agent provided in the first aspect of the present invention and a non-silicon fluorine-free water repellent agent. The non-silicon fluorine-free waterproof agent comprises the following components in parts by mass: 20-30 parts by mass of acrylic acid, 20-30 parts by mass of glycidyl acrylate, 10-20 parts by mass of diacetone acrylamide, 1-10 parts by mass of stearic acid and 1-10 parts by mass of isocyanate; the pH value of the non-silicon fluorine-free waterproof agent is 5-7.

A preparation method of a non-silicon fluorine-free waterproof agent comprises the following steps:

firstly, putting water into a reaction kettle, then putting acrylic acid, glycidyl acrylate and isocyanate into the reaction kettle, continuously stirring, and reacting for 2-6 hours at the temperature of 80-110 ℃; cooling to 40-45 ℃, adding diacetone acrylamide and stearic acid, continuously stirring, and reacting for 1-3 hours at 80-110 ℃; finally, adding ethanol for assisting dissolution to obtain an emulsion, and adjusting the pH value of the emulsion to 5-7 to obtain a non-silicon fluorine-free waterproof agent;

the mass ratio of the acrylic acid to the glycidyl acrylate to the isocyanate to the diacetone acrylamide to the stearic acid to the water is 20-30: 20-30: 1-10: 10-20:1-10: 200-300, wherein the content of the ethanol is 10-15g/L of the non-silicon fluorine-free waterproof agent.

Finally, a waterproof fabric of a fourth aspect of the present invention is explained, which is subjected to a waterproofing treatment with a silicone fluorine-free waterproofing agent and the crosslinking agent provided in the first aspect of the present invention; the organic silicon fluorine-free waterproof agent comprises the following components in parts by mass: 60-70 parts by mass of an organic silicon polymer, 1-10 parts by mass of a cross-linking mixture and 1-5 parts by mass of a surfactant; the organic silicon polymer comprises amino silane and modified silicone oil, and the mass ratio of the amino silane to the modified silicone oil is 50-60: 40-50; the crosslinking mixture comprises acrylic acid and epoxy silane, and the mass ratio of the acrylic acid to the epoxy silane is 30-60: 40-70; the pH value of the organic silicon fluorine-free waterproof agent is 5-7.

A preparation method of an organosilicon fluorine-free waterproof agent comprises the following steps:

firstly, putting water into a reaction kettle, then sequentially putting 60-70 parts by mass of organic silicon polymer, 1-10 parts by mass of cross-linked mixture and 1-5 parts by mass of surfactant into the reaction kettle, and stirring and emulsifying to obtain emulsion; adjusting the temperature of the emulsion to 55-70 ℃, adding ethanol for assisting dissolution, adjusting the pH value of the emulsion to 5-7, and keeping the temperature at 70-80 ℃ for 2-3h to obtain the organic silicon fluorine-free waterproof agent;

the organic silicon polymer comprises aminopropyltriethoxysilane and carboxyl silicone oil, and the mass ratio of the aminopropyltriethoxysilane to the carboxyl silicone oil is 50-60: 40-50; the crosslinking mixture comprises acrylic acid and vinyl triethoxysilane, and the mass ratio of the acrylic acid to the vinyl triethoxysilane is 30-60: 40-70; the surfactant comprises AEO-9, AEO-1303 and AEO-1307, wherein the mass ratio of the AEO-9 to the AEO-1303 to the AEO-1307 is 2:1: 1; the addition amount of the ethanol is 10-15g/L of non-silicon fluorine-free waterproofing agent.

The waterproof function of the fabric is determined by the surface appearance and the surface energy of the fabric. When the roughness of the fabric surface is low, the contact angle of liquid on the fabric surface is increased, and the residence time and the residual amount of the liquid on the fabric surface can be reduced to a certain extent. And the lower the free energy of the fabric surface, the lower the adhesive force, the larger the contact angle of the liquid on the fabric surface. The components in the water repellent agent are low surface energy polymers, so that the surface energy of the fabric surface using the water repellent agent can be effectively reduced, and the effective water repellent effect is achieved. Meanwhile, the cross-linking agent provided by the invention can be tightly combined with the fabric by matching with a waterproof agent.