CN101363190B - Preparation of a Gemini type composite sol and its application in UV protection/antibacterial finishing - Google Patents

Abstract

The invention discloses the preparation of a Gemini-type cationic TiO ₂ /SiO ₂ composite sol and its application method in the anti-ultraviolet/antibacterial composite finishing of cotton fabrics, belonging to the technical field of textile chemical industry. The present invention selects silicon and titanium precursors, Gemini cationic compounds, water, catalysts and solvents to prepare Gemini cationic TiO ₂ /SiO ₂ composite sols for UV protection/antibacterial finishing of cotton fabrics. This composite sol has a simple synthesis process, easy-to-control reaction, high product purity, low cost, environmental protection and energy saving, particle size less than 10nm, and a uniform film formed on the fabric after finishing, which can endow the fabric with good UV shielding and antibacterial properties, and has a Its performance is not greatly affected.

Description

Preparation of a Gemini type composite sol and its application in UV protection/antibacterial finishing

technical field

The invention belongs to the technical field of textile chemical industry, and in particular relates to the preparation of a Gemini-type cationic TiO ₂ /SiO ₂ composite sol and its application in the anti-ultraviolet/antibacterial composite finishing of cotton fabrics.

Background technique

With the rapid development of science and technology and the continuous improvement of people's living standards, people's demand for clothing and other textiles is becoming more and more comfortable, healthy and safe. Cotton fabrics are favored by people because of their cheap and good quality, good hygroscopicity, and comfortable wearing. However, the poor resistance of cotton fabrics to ultraviolet rays and microorganisms makes their further widespread application encounter some challenges. Therefore, it is of certain significance to carry out anti-ultraviolet and antibacterial finishing on cotton fabrics.

At present, there are two main methods of applying nano-materials to textiles to make anti-ultraviolet or anti-bacterial functional textiles that are being researched and applied at home and abroad: one is the spinning method, that is, the nano-powder is dispersed and melted in the polyester solution, and then The method of spinning fibers. This method can achieve a good combination of nano powder and textiles, but the production process of this method is complicated, the production difficulty is high, and it can only be applied to chemical fiber textiles, not natural fiber textiles; the second is post-finishing method, that is, first The nanometer powder is made into an anti-ultraviolet finishing solution or an antibacterial finishing solution, and then the fabric is subjected to padding or coating finishing to obtain a functional fabric. This method is simple and easy to implement, but due to the adhesive relationship between the nano-powder and the textile, there is no chemical bond, and there are disadvantages such as poor washing fastness, unsustainable function and poor fabric feel. And because the nanoparticles have the characteristics of easy agglomeration, it is very difficult to uniformly disperse the nano-powders and prepare a stable finishing solution.

Sol-gel method is a new technology for fabric surface modification. The nano-sol prepared by sol-gel technology can form a thin and transparent gel film on the surface of the fabric through coating and other methods, which can effectively improve the surface properties of the fabric. Patent CN1585496A discloses a method of using sol-gel method to prepare titanium nano sol for anti-ultraviolet finishing of cotton fabrics. Using this method can endow the fabric with excellent and long-lasting anti-ultraviolet performance, and has an impact on the feel and physical and mechanical properties of the fabric. very small. Patent CN1631996A prepares a SiO ₂ /TiO ₂ composite oxide ultraviolet shielding agent, which has good dispersion performance, ultraviolet absorption ability and weather resistance, and avoids the bluish phenomenon in the application of titanium dioxide. Patent CN1614133A discloses a method for UV-proof finishing of cotton fabrics by organic solvent-modified titanium dioxide sol. Particle-specific properties. A titanium sol was prepared in CN165473A and used for antibacterial finishing of cotton fabrics. Cotton fabrics treated with the sol have excellent and long-lasting antibacterial properties, and have the effect of releasing negative ions, and have no side effects on the feel and strength of the fabrics. Patent CN101187079A discloses a fiber with antibacterial and anti-ultraviolet composite functions. This fiber is made by using nano-TiO ₂ , nano-SiO ₂ , nano-ZnO and nano-scale AgNO ₃ as fiber masterbatches and spinning at high speed by melting. , this fiber has very good anti-ultraviolet and antibacterial effects.

Contents of the invention

The object of the present invention is to provide a Gemini composite sol.

Another object of the present invention is to provide a kind of preparation method of Gemini type composite sol, this method selects Gemini cationic compound, silicon and titanium precursor, catalyst, solvent, water for use, can prepare composite sol at room temperature or lower temperature liquid.

Another object of the present invention is to provide an application of the above-mentioned composite sol in the anti-ultraviolet/antibacterial composite finishing of cotton fabrics, that is, to use the composite sol finishing solution of the present invention to impregnate or pad the fabric, and then heat-treat and finish The silica sol in the solution forms a thin film on the surface of the fiber, and anchors some titanium dioxide nanoparticles with anti-ultraviolet effect and some Gemini cations with antibacterial effect in the gel film, so that the fabric has good anti-ultraviolet and antibacterial effects.

Compared with the traditional anti-ultraviolet and antibacterial technology, the present invention has the following characteristics:

1. The preparation process of this sol-gel anti-ultraviolet/antibacterial composite finishing solution is simple, the reaction is easy to control, and it is environmentally friendly and energy-saving;

2. The particle size of the prepared composite sol is small, the film formed on the fabric is very uniform, has good ultraviolet shielding and antibacterial properties, and has little effect on the feel and physical and mechanical properties of the fabric;

3. This sol-gel anti-ultraviolet/antibacterial agent is a water-based fabric finishing solution with simple components and easy use, and is suitable for conventional finishing equipment and basic processes;

4. In particular, this method combines UV protection and antibacterial finishing, which shortens the technological process and greatly saves manpower and material resources, which is very in line with the concept requirements of modern industrial energy conservation and environmental protection.

The titanium precursor involved in the present invention is titanate such as ethyl titanate, n-propyl titanate, n-butyl titanate, tetrabutyl titanate, isobutyl titanate and isopropyl titanate; The silicon precursors involved are silicate esters such as ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate, isobutyl orthosilicate and isopropyl orthosilicate.

The Gemini cationic compound described in the present invention can be 2-dipropanolamine-two (tetradecyl dimethyl ammonium chloride), dimethylene-bis (dodecyl dimethyl ammonium bromide) , tetramethylene-bis(hexadecyl dimethyl ammonium chloride), hexamethylene-bis(hexadecyl dimethyl ammonium bromide), etc.

Catalyst among the present invention can be hydrochloric acid, formic acid, sulfuric acid, nitric acid, acetic acid etc.

The solvent in the present invention can be ethanol, propanol, isopropanol, butanol, ethylene glycol and the like.

The fabrics used in the present invention are conventional fabrics on the market, and the fabrics suitable for the present invention mainly include cotton fabrics and blended fabrics thereof.

Detailed ways

The following examples will help to further understand the present invention, but cannot limit the content of the present invention.

(1) Add 30-42 parts of solvent, 20-38 parts of silicate, 15-30 parts of water and 1-5 parts of Gemini cationic compound into the three-necked flask in sequence. Stir on a magnetic stirrer (50-600r/min) for 2-35min, and under this condition, add 1-3 parts of a catalyst with a concentration of 0.01mol/L dropwise into the above mixed solution at a speed of 20-80drop/min. After the dropwise addition, adjust the rotation speed of the magnetic stirrer (100-600r/min), and continue stirring at room temperature for 24 hours to obtain a Gemini-type cationic silica sol.

(2) Add 30-54 parts of solvent, 15-26 parts of titanate and 10-30 parts of water into the three-necked flask in sequence. Stir on a magnetic stirrer (50-600r/min) for 2-35min, and under this condition, add 5-10 parts of a catalyst with a concentration of 0.01mol/L dropwise into the mixture at a speed of 20-80drop/min. After the dropwise addition, adjust the rotation speed of the magnetic stirrer (100-600r/min), and continue stirring at room temperature for 8 hours to obtain a titanium dioxide sol.

(3) Take 1-20 parts of Gemini cationic silica sol, dissolve in 20-70 parts of deionized water, stir on a magnetic stirrer (50-900r/min) for 3-40min, under this condition, 5- 35 parts of the prepared titanium dioxide sol were added dropwise into the above mixed solution at a speed of 10-90 drop/min. After the dropwise addition, adjust the rotation speed of the magnetic stirrer (100-900r/min), and continue stirring at room temperature for 3 hours to obtain a UV-protective/antibacterial composite finishing solution of Gemini-type cationic TiO ₂ /SiO ₂ sol.

(4) Use this composite finishing solution to carry out anti-ultraviolet/antibacterial composite finishing on woven fabrics by dipping, one dipping and one rolling or two dipping and two rolling methods, and use the dipping method to carry out anti-ultraviolet/antibacterial composite finishing on knitted fabrics. The concentration is 0.5-5% (o.w.f), the treatment temperature is 50-80°C, and the treatment time is 30-50min. The concentration of the composite finishing solution in the way of padding is 1-8%, and the excess rolling rate is 60-100%. After finishing, the fabric is prebaked at 60-80°C, and then baked at 120-200°C for 3-15 minutes.

(5) Test methods, specifically as follows:

① Anti-ultraviolet performance test

The UV transmittance of the fabric is tested by spectrophotometer method, and the UV transmittance (also known as the transmittance, which refers to the ratio of the UV transmitted radiation flux with the sample to the UV transmitted radiation flux without the sample) is used to measure the UV transmittance of the fabric. As an evaluation index of anti-ultraviolet performance.

②Antibacterial performance test

The antibacterial performance is tested according to AATCC 100-2004 standard.

③Strength test

Refer to GB/T 3923.1-1997 "Textile Fabric Tensile Properties Part 1: Determination of Breaking Strength and Elongation at Break Strip Method" test.

④Whiteness measurement

WSD-III whiteness meter measures the whiteness of fabrics, expressed in Henry whiteness value.

(6) Embodiment

Example 1 Preparation of Gemini-type cationic TiO ₂ /SiO ₂ composite sol

40 parts of ethanol, 30 parts of ethyl orthosilicate, 27 parts of water and 1 part of dimethylene-bis(hexadecyldimethylammonium chloride) were sequentially added to the three-necked flask. Stirring on a magnetic stirrer at 500r/min for 15min, under this condition, 2 parts of hydrochloric acid with a concentration of 0.01mol/L was added dropwise to the above mixture at a speed of 40drop/min. After the dropwise addition, adjust the rotating speed of the magnetic stirrer to 500r/min, and stir continuously at room temperature for 24h to obtain a Gemini-type silica sol.

50 parts of ethanol, 25 parts of tetrabutyl titanate, and 20 parts of water were sequentially added to the three-necked flask. Stirring on a magnetic stirrer at 600r/min for 15min, under this condition, 5 parts of hydrochloric acid with a concentration of 0.01mol/L was added dropwise to the above mixture at a speed of 40drop/min. After the dropwise addition, the rotating speed of the magnetic stirrer was adjusted to 500 r/min, and the stirring was continued at room temperature for 8 hours to obtain a titanium dioxide sol.

Take 15 parts of Gemini-type cationic silica sol, dissolve in 65 parts of deionized water, stir on a magnetic stirrer at 800r/min for 3-40min, under this condition, mix 20 parts of the prepared titanium dioxide sol at 60drop/min Speed dropwise into the above mixture. After the dropwise addition, adjust the rotating speed of the magnetic stirrer (800r/min, and continue stirring at room temperature for 3 hours to obtain a UV-protective/antibacterial composite finishing solution of Gemini-type cationic _TiO2 / _SiO2 sol.

Example 2 Anti-ultraviolet/antibacterial finishing of pure cotton woven fabric by dipping method

The cloth sample is selected as pure cotton plain woven fabric (20tex×20tex) through desizing, scouring and bleaching.

The specific process is as follows:

Take 2g of pure cotton plain woven fabric (20tex×20tex) after desizing, scouring and bleaching, put it into Gemini type composite TiO ₂ /SiO ₂ composite sol for 60min, and dry the finished fabric in a blast oven at 60°C Dry, then bake at 150°C for 3 minutes.

The ultraviolet light transmittance of the cotton fabric finished by the above method is close to 15.5% in the UVA wave band, the UVB wave band is close to 2.5%, and the UVC wave band is close to 1%, that is, the fabric has a good anti-ultraviolet effect; The antibacterial rates of the sample to Staphylococcus aureus and Escherichia coli were 92.1% and 90.5%, respectively, that is, the fabric has a better antibacterial effect. The strength of the fabric sample before and after treatment changed from 798N to 753N, and the whiteness changed from 93.89 to 93.25, which means that the finishing process has little effect on the strength and whiteness of the fabric.

Example 3 Anti-ultraviolet/antibacterial finishing of pure cotton woven fabrics by padding method

The cloth sample is selected as pure cotton poplin woven fabric (40tex×40tex) through desizing, scouring and bleaching.

The specific process is as follows:

Get 2g pure cotton poplin woven fabric (40tex * 40tex) through desizing, scouring, bleaching, put into Gemini type composite TiO ₂ /SiO ₂ Composite sol adopts the mode of two dips and two rollings, and the excess rate of rolling is 65%, The finished fabric was dried in a blast oven at 60°C, and then baked at 150°C for 3 minutes.

The ultraviolet light transmittance of the cotton fabric finished by the above method is close to 15% in the UVA wave band, the UVB wave band is close to 2%, and the UVC wave band is close to 1%, that is, the fabric has a good anti-ultraviolet effect; The antibacterial rates of the sample to Staphylococcus aureus and Escherichia coli were 93.1% and 90.5%, respectively, that is, the fabric has a better antibacterial effect. The strength of the cloth sample before and after treatment changed from 812N to 777N, and the whiteness changed from 93.72 to 92.87.

Example 4 Anti-ultraviolet/antibacterial finishing of pure cotton knitted fabric by dipping method

The selected cloth sample is a combed cotton fabric (27.8tex) after desizing, scouring and bleaching.

Take 2g of the desizing, scouring and bleaching cotton combed knitted fabric (27.8tex) into the Gemini type composite TiO ₂ /SiO ₂ composite sol for 60min, and dry the finished fabric in a blast oven at 60°C Dry, then bake at 150°C for 3 minutes.

The ultraviolet light transmittance of the cotton fabric finished by the above method is close to 15.8% in the UVA wave band, the UVB wave band is close to 1.6%, and the UVC wave band is close to 1.2%, that is, the fabric has a good anti-ultraviolet effect; The antibacterial rates of the sample to Staphylococcus aureus and Escherichia coli were 96.8% and 95.5%, respectively, that is to say, the fabric has a better anti-ultraviolet effect. The strength of the fabric sample before and after treatment changed from 754N to 721N, and the whiteness changed from 93.74 to 93.35, which had little effect on the strength and whiteness of the fabric.

Claims (1)

1. the preparation method of a Gemini type complex sol: it is characterized in that adopting following method preparation:

(1) in three-neck flask, adds solvent 30-42 part, esters of silicon acis 20-38 part, water 15-30 part and Gemini cationic compound 1-5 part successively; Speed with 50-600r/min on magnetic stirring apparatus stirs 2-35min; Be that the catalyst of 0.01mol/L is added drop-wise in the above-mentioned mixed liquor with the speed of 20-80drop/min with 1-3 part concentration with this understanding; After being added dropwise to complete; The rotating speed of adjustment magnetic stirring apparatus is 100-600r/min, and at room temperature continuous stirring 24h promptly obtains a kind of Gemini type cationic colloidal silica;

(2) in three-neck flask, add solvent 30-54 part, titanate esters 15-26 part, water 10-30 part successively; Speed with 50-600r/min on magnetic stirring apparatus stirs 2-35min; Be that the catalyst of 0.01mol/L is added drop-wise in the above-mentioned mixed liquor with the speed of 20-80drop/min with 5-10 part concentration with this understanding, after being added dropwise to complete, the rotating speed of adjustment magnetic stirring apparatus is 100-600r/min; At room temperature continuous stirring 8h promptly obtains a kind of TiO 2 sol;

(3) get the cationic Ludox of Gemini of 1-20 part; Be dissolved in the deionized water of 20-70 part, on magnetic stirring apparatus, stir 3-40min, with this understanding the TiO 2 sol that makes of the 5-35 part speed with 10-90drop/min is added drop-wise in the above-mentioned mixed liquor with the speed of 50-900r/min; After being added dropwise to complete; The rotating speed of adjustment magnetic stirring apparatus is 100-900r/min, and at room temperature continuous stirring 3h promptly obtains a kind of Gemini type CATION TiO ₂/ SiO ₂The antiultraviolet of colloidal sol/antibiotic composite finishing liquid.