阅读说明：本技术 一种非硅无氟防水剂、其制备方法及防水织物 (non-silicon fluorine-free waterproof agent, 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：本发明提供的一种不含硅和氟的防水剂及其制备方式,所述非硅无氟防水剂包括以下质量份的组分：20-30质量份丙烯酸、20-30质量份丙烯酸缩水甘油酯、10-20质量份双丙酮丙烯酸酰胺、1-10质量份硬脂酸,1-10质量份的交联剂,所述非硅无氟防水剂的pH值为5-7。该防水剂的防水性能好,对环境友好,生产工艺简单,造价低,可大规模应用于工业化生产中。使用该防水剂的织物,防水等级可达到5级。(The non-silicon and fluorine-containing waterproof agents comprise, 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, and the pH value of the non-silicon and fluorine-free waterproof agent is 5-7.)

The non-silicon fluorine-free waterproof agent is characterized by comprising, 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 crosslinking agent, wherein the pH value of the non-silicon fluorine-free waterproof agent is 5-7.

2. The non-silicon fluorine-free waterproofing agent according to claim 1, further comprising 200-300 parts by mass of water and an organic solvent, wherein the content of the organic solvent is 10-15 g/L.

3. The non-silicon, fluorine-free water repellent agent according to claim 1, wherein said crosslinking agent is isocyanate.

The preparation method of non-silicon fluorine-free waterproof agents is characterized by comprising the following steps:

firstly, putting water into a reaction kettle, then putting acrylic acid, glycidyl acrylate and a cross-linking agent into the reaction kettle, continuously stirring, and reacting for 2-6 hours at the temperature of 80-110 ℃; then cooling to 40-45 ℃, adding diacetone acrylamide and stearic acid, continuously stirring, and reacting for 1-3 hours at 80-110 ℃; finally adding an organic solvent 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 cross-linking agent 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 organic solvent is 10-15g/L of non-silicon fluorine-free waterproof agent.

5. The method of claim 4, wherein the organic solvent is ethanol.

6. The method of claim 4, wherein the cross-linking agent is an isocyanate.

7. The method of claim 4, wherein the pH of the emulsion is adjusted using a solution of citric acid, sodium hydroxide, or sodium citrate.

A waterproof fabric of , wherein said waterproof fabric is waterproofed with the non-silicon, fluorine-free waterproofing agent of any of claims 1 to 3 to .

9. The waterproof fabric of claim 8, wherein the waterproof fabric is prepared by the steps of:

working solution is prepared by diluting the non-silicon fluorine-free water repellent of any in claims 1-3 to 10-40g/L,

dipping rolling, namely soaking the fabric in the working solution for 10 to 90s and then rolling the fabric for times by using a padder, wherein the pressure of the padder is 1 to 2Kg/cm²The liquid carrying rate is 65-100%,

and (3) drying, namely drying the dipped padded fabric for 60-180 seconds at 150-180 ℃ to obtain the waterproof fabric.

10. The waterproof fabric of claim 7, wherein said fabric is a chemical fiber fabric.

Technical Field

The invention relates to the field of textiles, in particular to non-silicon fluorine-free waterproof agents, a preparation method thereof and waterproof fabrics.

Background

Perfluorooctane sulfonyl compounds (PFOS) and perfluorooctanoic acid (PFOA) are trace substances existing in C8 waterproof agents, have difficult degradation, bioaccumulation and various toxicities, and have common characteristics of all persistent organic pollutants, so that the PFOA and PFOA are strictly limited, and the PFOA and PFOS mainly exist in fabrics treated by fluorine-containing waterproof and oilproof finishing agents in the textile industry.

Disclosure of Invention

In view of the problems in the background art, the invention aims to provide kinds of silicon-free and fluorine-free waterproof agents and a preparation method thereof, wherein the waterproof agents are good in waterproof performance, environment-friendly, simple in production process and low in manufacturing cost, and can be applied to industrial production in a large scale to prepare fabrics using the waterproof agents.

In order to achieve the above object, in th aspect of the present invention, the inventors provide kinds of non-silicon fluorine-free water repellent, which comprises, by mass, 20 to 30 parts of acrylic acid, 20 to 30 parts of glycidyl acrylate, 10 to 20 parts of diacetone acrylamide, 1 to 10 parts of stearic acid, and 1 to 10 parts of a crosslinking agent, and has a pH of 5 to 7.

In a second aspect of the present invention, the inventors provide a method for preparing non-silicon fluorine-free water repellents, comprising the steps of:

firstly, putting water into a reaction kettle, then putting acrylic acid, glycidyl acrylate and a cross-linking agent into the reaction kettle, uniformly mixing, and reacting for 2-6 hours at the temperature of 80-110 ℃; cooling to 40-45 ℃, adding diacetone acrylamide and stearic acid, mixing uniformly, and reacting for 1-3 hours at 80-110 ℃; finally, adding an organic solvent 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 cross-linking agent 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 organic solvent is 10-15g/L of non-silicon fluorine-free waterproof agent.

In a third aspect of the present invention, the inventors provide waterproof fabrics treated with the non-silicon, fluorine-free water repellant provided by aspect of the present invention.

The waterproof agents without silicon and fluorine and the preparation method thereof have the advantages of good waterproof performance, capability of fully permeating fabric fibers, environmental friendliness, simple production process and low cost, and can be applied to industrial production on a large scale, and the waterproof grade of the fabric using the waterproof agent can reach 5 grade.

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.

Diacetone acrylamide has two reactive groups: n-substituted amide and ketone are easy to copolymerize with other ethylene and monomer, so that ketone carbonyl group is introduced into polymer, and the chemical property of ketone carbonyl group can make polymer produce cross-linking grafting reaction.

First, parts by mass of a non-silicon fluorine-free water repellent according to of the present invention, which comprises 20 to 30 parts by mass of acrylic acid, 20 to 30 parts by mass of glycidyl acrylate, 10 to 20 parts by mass of diacetone acrylamide, 1 to 10 parts by mass of stearic acid, and 1 to 10 parts by mass of a crosslinking agent, and has a pH of 5 to 7, will be described.

Preferably, the water-free fluorine-free water repellent further comprises 200-300 parts by mass of water and an organic solvent, wherein the content of the organic solvent is 10-15g/L of the non-silicon fluorine-free water repellent.

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 crosslinking agent is an isocyanate.

Preferably, the pH of the emulsion is adjusted using citric acid, sodium hydroxide, or sodium citrate solutions.

Next, a description will be given of a method for producing kinds of non-silicon fluorine-free water repellent according to a second aspect of the present invention, comprising the steps of:

firstly, putting water into a reaction kettle, then putting acrylic acid, glycidyl acrylate and a cross-linking agent 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 an organic solvent 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 cross-linking agent 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 organic solvent is 10-15g/L of non-silicon fluorine-free waterproof agent.

Preferably, the organic solvent is ethanol.

Preferably, the crosslinking agent is an isocyanate.

Next, kinds of waterproof fabrics according to the third aspect of the present invention are described, which are subjected to a waterproof treatment with the non-silicon fluorine-free waterproofing agent according to the aspect of the present invention.

The preparation method of the waterproof fabric comprises the following steps:

working solution preparation, namely diluting the non-silicon fluorine-free water repellent prepared by the aspect of the invention into working solution with the concentration of 10-40g/L,

dipping rolling, namely soaking the fabric in the working solution for 10 to 90s and then rolling the fabric for times by using a padder, wherein the pressure of the padder is 1 to 2Kg/cm²The liquid carrying rate is 65-100%,

and (3) drying, namely drying the dipped padded fabric for 60-180 seconds at 150-180 ℃ to obtain the waterproof fabric.

The water-proof function of the fabric is determined by the surface appearance and the surface energy of the fabric, the surface roughness of the fabric is low, the liquid contact angle of the surface of the fabric is increased, the retention time and the residual amount of liquid on the surface of the fabric can be reduced from to a certain extent, the free energy of the surface of the fabric is low, the adhesive force is small, and the contact angle of the liquid on the solid surface is larger.

Meanwhile, the waterproof agent can fully permeate into the fabric fiber, and the waterproof performance is improved.

Preferably, the fabric is a chemical fiber fabric.

The concentration of the working solution is controlled to be 10-40g/L, and the inventor finds that when the concentration is more than 40g/L, the waterproof agent can form a coating on the surface of the fabric, so that the softness of the fabric is influenced; the concentration is less than 10g/L, the content of the waterproof agent in the fabric is too small, and a good waterproof effect cannot be achieved.