CN1624234A - A modified nano-oxide multifunctional finishing agent, its preparation method and its use - Google Patents

Abstract

This invention relates to a manufacturing method of multi-function dressing agent of modified nanometer oxide and its use. It consists of the following products: modified nanometer oxide emulsified liquid 5%-30%, penetrating agent 0.01%-1.0%, hand conditioning agent 0-5%, cross linker or grafting agent consisting of more than two 10-90g/l, catalyzer 6-15g/l, the rest is deionized water or distillation. The character is that interlinked reaction can be made between modified nanometer oxide and natural fabric cloth by the aid of cross linker or grafting agent, through regular rolling-baking-torrefying process, multi-function dressing is made in order to make the dressed cloth have the qualities of ultravioresistance and antibiotic property, improve the wash resistance and hand feeling.

Description

A modified nano-oxide multifunctional finishing agent, its preparation method and its use

technical field

The invention belongs to the technical field of textile finishing. It relates to a modified nano-oxide multifunctional finishing agent, a preparation method and an application thereof. The multifunctional finishing agent performs a cross-linking reaction on the modified nano-oxide and the natural fiber fabric through a cross-linking agent or a grafting agent, and permanently applies the modified nano-oxide to the natural fiber fabric. Baking ~ baking process. Make natural fiber fabrics have durable anti-ultraviolet and antibacterial finishing effects, and have a good hand feeling.

Background technique

With the development of the market economy, a wide variety of textiles appear in large numbers. The textile industry is no longer only satisfied with providing people with traditional warm and cold-proof textiles, but more importantly, to update products, improve product quality, develop high-grade, high-value-added multifunctional textiles, and endow textiles with new technological connotations , extend the application field, and meet the needs of the market for innovation and change.

Nanotechnology has been a key research field that countries in the world have paid more attention to in recent years. By the end of the last century, the preparation technology of nanoscale oxides has made great progress, and some nanoscale oxides have achieved industrial production. The quantum size effect and surface effect of nanomaterials make them have optical characteristics that large particle materials do not have, and have strong reflection characteristics for ultraviolet and infrared rays. Adding them to materials has anti-ultraviolet aging and heat insulation effects; Nanoparticles have strong surface catalytic activity and good antibacterial and deodorizing properties; the small size effect and macroscopic quantum tunneling effect of nanomaterials will greatly improve the strength, elasticity, water resistance, light stability and thermal stability of the material; The extremely rich residual bonds on the surface of nanomaterials make it super surface active and have a super strong adsorption and protection effect on pigment particles, which will greatly reduce the pigment attenuation caused by ultraviolet radiation. Dispersing and fixing nano-oxides on textiles can make them have various functions, such as anti-ultraviolet, antibacterial, anti-mildew and deodorizing, emitting far infrared rays, anti-radiation, anti-aging, strong color fastness and vividness, etc. Compared with other functional textiles, this kind of nano-functional textiles has obvious advantages, and can realize some unique functions, such as far-infrared functions can only be realized through nano-oxide particles; although antibacterial and other functions can also be arranged through organic functions However, organic finishing agents are often easy to age and decompose, and cannot be stored for a long time, and many organic functional finishing agents (such as antibacterial agents, etc.) are toxic, and nano-functional textiles can effectively solve these problems. Therefore, the nano-functionalization of textiles has become one of the hot spots in the research and development of the international textile industry, especially the use of nano-oxides in the traditional textile printing and dyeing industry to develop natural materials (cotton, hemp, wool, silk, etc.) with special functions. ) of textiles.

At present, the methods of applying nanoparticles to textiles that are being researched and applied at home and abroad mainly include: one is to use solution blending or melt blending methods to mix nanoparticles and polymers to prepare functional fibers and fabrics. In 1996, Japan first researched and developed this kind of anti-ultraviolet fiber and fabric fabric; Japan Cangluo Company added nano-ZnO particles to polyester fibers with special-shaped cross-sections, and the resulting synthetic fibers have the unique properties of antibacterial, anti-virus, and deodorizing. Function, but also has the effect of shielding ultraviolet rays. However, due to the serious agglomeration of nanoparticles in the fiber polymer melt, it is very easy to cause blockage or breakage of the micron-sized spinneret, and wear and tear of the fabric. This contradiction between functionality and dispersibility has become a difficulty restricting the preparation of nano-functional fibers, and this method can only be used for synthetic fiber textiles, not natural fibers. The second is to uniformly coat nanoparticles on the surface of fibers or fabrics through adhesives to make functional textiles. This method is simple in process and can achieve certain functional indicators. The production of antibacterial fabrics on the surface of fabrics has attracted people's attention. However, since the inorganic nanoparticles are not connected by chemical bonds with the fibers of the textile, the washing fastness is low, the function cannot last, and the fabric feels poor. At the same time, due to the defects and problems in the above-mentioned spinning method and coating printing and dyeing method, the product quality is poor, and it is difficult to adapt to large-scale production, so that nano-functional fabrics (especially natural fiber fabrics such as cotton) have not yet been industrialized. Therefore, how to disperse nanoparticles evenly on textiles and realize the firm combination of nanoparticles and fibers is the key technology for the development and application of nano-functional textiles.

At present, there are two main methods for the application of nano-oxides on textiles: (1) Melt blending and solution blending: functional fibers are made, but this method cannot be used for natural fibers. (2) Through post-finishing methods, such as coating methods: the nano-oxides are evenly coated on the textiles through an adhesive to make functional textiles, but there is no chemical bond between the nano-oxide particles and the fibers of the textiles , the washing fastness is poor, the function is not durable, and it also affects the feel of the fabric.

The present invention uses a certain chemical method to carry out necessary chemical modification on the surface of nano-oxide and nano-composite oxide, and introduces groups such as hydroxyl, amino, and siloxy groups to make simple nanoparticles or simple nano-particles with reactive groups. Organic "clusters" improve the dispersion stability of nanoparticles in the water phase and the reactivity with natural fibers; and a method of grafting or cross-linking modified nano-oxide particles is proposed to apply to natural fibers through post-finishing On textiles, obtain a durable functional finish with a good hand feel.

The applicant and the inventor simultaneously applied for the invention patent of "modified nano-oxide, preparation method and use thereof", which provided the basis for the present invention.

Contents of the invention

The object of the present invention is to provide the above-mentioned modified nano-oxide finishing agent.

The object of the present invention is also to provide a preparation method of the above-mentioned modified nano-oxide finishing agent.

Another object of the present invention is to provide a method for the above-mentioned modified nano-oxide finishing agent to be used for permanent functional finishing of natural textiles.

The modified nano oxide finishing agent of the present invention adopts the modified nano oxide and its emulsion in the invention patent "modified nano oxide, preparation method and application thereof" applied by the inventor as the basic raw material.

The modified nano-oxide has the following structural formula:

Wherein, A is a nano-oxide, and the nano-oxide is nano-titanium oxide, nano-zinc oxide, nano-alumina, nano-iron oxide, nano-silicon oxide and their composites; R=(CH ₂ )n,n =0-4; Y is vinyl, hydroxyl, aminoalkyl, amino, epoxy, methacryloyloxyalkyl or mercapto.

Wherein, m=0-20, R"=A, H or C ₁ -C ₄ alkyl.

The emulsifier described in the modified nano oxide emulsion is polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty alcohol polyoxyethylene ether, alkyl sulfonate, etc.; emulsifier consumption 5~15g/L. Adjust pH=2~7 with acetic acid.

The modified nano-oxide can react with fibers containing hydroxyl, carboxyl or amino groups through a suitable crosslinking agent or grafting agent to form a strong covalent bond to achieve a permanent finishing effect.

The crosslinking agent or grafting agent must contain two or more reactive groups, which can be epoxy, vinyl, epichlorohydrin, isocyanate, methylol, etherified hydroxyl Methyl group, azido group, vinylsulfone group, silanol group, silicon amino group, polycarboxylic acid group, aldehyde group.

The active group Y on the modified nano oxide can react with the reactive group on the crosslinking agent or grafting agent to form a covalent bond; and, through the crosslinking agent or another reactive group on the grafting agent and The reactive group on the fiber cross-chains to form a covalent bond, so that the nano-oxide and the fiber are firmly combined.

The modified nano-oxide finishing agent of the present invention can be applied to textiles containing carboxyl, hydroxyl and amino groups, especially natural fiber textiles containing carboxyl groups, hydroxyl groups and amino groups, such as cotton, ramie, flax, silk, wool, and its form can be Yarn, knitted, woven or non-woven fabrics.

The modified nano-oxide finishing agent of the present invention is composed of the following substances in weight percent: 5-30 g/L of modified nano-oxide emulsion, 0.01-1 g/L of penetrating agent, 0-5 g/L of hand feel regulator, containing two More than 10-90g/L of cross-linking agent or grafting agent of active groups, 6-15g/L of catalyst, and deionized water or distilled water as the rest.

The crosslinking agent or grafting agent must contain two or more reactive groups, such as 2D resin, modified (etherified) 2D resin, crosslinking agent BH, glutaraldehyde, glyoxal, Cross-linking agent BTCA, water-soluble amino resin U-51, modified amino silicone oil or hydroxyl silicone oil. The handle regulator is aminoorganosilane, hydrogen-containing organosilane, silicone body or water-soluble polyurethane. The penetrant is dioctyl sulfosuccinate sodium salt, penetrant M or penetrant JFC. Described catalyst is organic acid, as citric acid, tartaric acid, acetic acid, acrylic acid, Lewis (Lewis) acid, as magnesium chloride, zinc nitrate, zinc sulfate, aluminum sulfate, sodium fluoborate, and the compound of organic acid and Lewis acid , Basic salts, such as sodium bicarbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium carbonate, potassium bicarbonate, potassium carbonate, or organic tin, such as tin laurate.

The preparation method of the above-mentioned modified nano-oxide finishing agent of the present invention is as follows: the above-mentioned modified nano-oxide emulsion, penetrating agent, hand feel regulator, crosslinking agent or grafting agent containing more than two active groups, Add it to the required amount of deionized water or distilled water, stir and mix at 10-40°C, and then add the required amount of catalyst before use. Among them, the crosslinking agent or grafting agent containing two or more active groups is 10-90g/L, the modified nano-oxide emulsion is 5-30g/L, the penetrating agent is 0.01-1.0g/L, and the hand feel regulator is 0-5g /L and catalyst 6~15g/L.

The multifunctional finishing agent of the present invention can process natural fiber textiles containing carboxyl, hydroxyl and amino groups, such as cotton, ramie, silk or wool, and its form can be yarn, knitted fabric, woven fabric or non-woven fabric.

For processing natural fiber fabrics such as cotton fabrics, ramie fabrics, linen fabrics, and silk fabrics, rolling-drying-baking processes can be used, the fabrics are dipped twice and rolled twice, the excess rolling rate is 50-100%, and pre-baked at 80-100°C for 3 ~6 minutes, bake at 120~160°C for 2~5 minutes.

The finished fabric is tested, and the anti-ultraviolet performance (the shielding rate to UVA and UVB) is greater than 99%, and the ultraviolet protection factor of the fabric reaches more than 45-50. According to the FZ/T 01021-92 fabric antibacterial performance test method, it has obvious antibacterial effect on typical Gram-positive bacteria and Gram-negative bacteria, and the antibacterial efficiency is over 90%. Finished fabric can withstand standard washing more than 50 times.

Detailed ways

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

Example 1 Preparation of modified nano-titanium dioxide

1. Scatter

Mix 20 grams of rutile phase nano-titanium dioxide, 70 milliliters of organic solvent ethylene glycol and 15 grams of dispersant polyvinylpyrrolidone, and disperse with a high-speed disperser at a speed of 10,000 to 30,000 rpm, while vibrating with ultrasonic waves for 30 to 60 minutes.

2. Modification

Add 20 grams of surface modifier γ-aminopropyltriethoxysilane to the above dispersion system, stir for 10 minutes, add 40 ml of water, stir for 30 minutes, heat up to 80-100°C, and react for 2-4 hours.

3. Emulsification

Add 3 grams of emulsifier Pingping O to the above reactants, adjust the pH value with acetic acid to make pH = 4-6, stirring speed 1000-3000 rpm, time 30-60 minutes, temperature 20-60°C.

Example 2 Preparation of Modified Composite Nano Oxide

1. Scatter

Mix nano-oxides in different proportions, such as nano-ZnO and nano-TiO ₂ in a weight ratio of 1-3:3-1, take 20 grams of mixed nano-oxides, 70 milliliters of glycerol, 10 grams of polyvinylpyrrolidone, polyethylene glycol Alcohol (M=400) 2 grams is dispersed with a high-speed disperser at a speed of 10,000 to 30,000 rpm, while ultrasonically oscillating for 30 to 60 minutes.

2. Modification

Add 15 grams of surface modifier γ-glycidoxymethoxysilane to the above dispersion system, stir for 10 minutes, add 30 ml of water, stir for 30 minutes, heat up to 80-100°C, and react for 2-4 hours .

3. Emulsification

Add 4 grams of emulsifier EL to the above reactants, adjust the pH value with acetic acid to make pH=4~7, stirring speed 1000~3000 rpm, time 30~60 minutes, temperature 20~60°C.

Example 3 Preparation of modified nano zinc oxide

1. Scatter

Mix 20 grams of nano-zinc oxide, 70 milliliters of organic solvent diethylene glycol and 10 grams of dispersant polyacrylamide, disperse with a high-speed disperser at a speed of 10,000 to 30,000 rpm, and oscillate with ultrasonic waves for 30 to 60 minutes.

2. Modification

Add 20 grams of the surface modifier γ-methacryloxypropyltrimethoxysilane to the above dispersion system, stir for 10 minutes, add 30 ml of water, stir for 30 minutes, heat up to 80-100°C, and react for 2- 4 hours.

3. Emulsification

Add 3 grams of emulsifier OP to the above reactants, adjust the pH value with acetic acid to make pH = 4-6, stirring speed 1000-3000 rpm, time 30-60 minutes, temperature 20-60°C.

Example 4 Anti-ultraviolet finishing pure cotton fabric processing

Finishing solution prescription:

Embodiment 1 finishing agent 7.5g/L

Modified 2D resin 80g/L

MgCl ₂ 0.1g/L

Penetrant 0.05~0.1g/L

Finishing process:

Pure cotton dyed plain cloth, count 30×30, density 68×68. Two dipping and two padding finishing solutions, the liquid rolling rate is 80-100%, pre-baked at 100-105°C for 2-5 minutes, baked at 120-150°C for 2-4 minutes, washed with water, and dried. The finishing effect can be seen in Table 1.

        Table 1 Anti-ultraviolet properties of pure cotton fabrics after anti-ultraviolet finishing

Test results

Sample No. Processing Conditions

                                                                                                   

UVB 3.02%

1 control fabric

UPF＝34

UVA 2.95%

UVB 1.15%

2 Finishing the fabric

UPF ≥ 50

UVA 1.07%

Note: Test according to GB/T 18830-2002 Test method for UV protection performance of fabrics.

              Example 5 Processing of antibacterial functional ramie fabric

Finishing solution prescription:

Example 3 finishing agent 7.5g/L

Fixparet FR-ECO 80g/L

MgCl ₂ 5g/L

Penetrant 0.05-0.1g/L

Finishing process:

Pure ramie fabric, count 36×36, density 54×54, after desizing and bleaching treatment. Two-dipping and two-rolling finishing solution, the rolling rate is 70-80%, pre-baked at 60°C for 3 minutes, baked at 120-150°C for 2-4 minutes, washed with water, soaped, washed with water, and dried.

The finishing effect can be seen in Table 2.

Table 2 Antibacterial performance of antibacterial ramie fabric

Total number of colonies (×10 ⁴ /mL) Bacteria reduced by hundreds

Treatment conditions Strains

                                                                                                           

Untreated fabric Escherichia coli 2.63

Finishing fabric Escherichia coli 0.17 0.02 98.6

                                 

Untreated fabric 2.51

cocci

                                 

Finishing Fabric 1.33 0.119 93.8

cocci

Note: Test according to FZ/T 01021-92 test method for antibacterial performance of fabrics.

                            Example 6 Multi-functional finishing of pure cotton fabric processing

(1) Finishing liquid prescription:

Example 2 finishing agent 7.5g/L

Grafting agent U-51 15g/L

Penetrant 0.05-0.1g/L

(2) Finishing process:

Pure cotton dyed plain cloth, count 30×40, density 100×60. Two dipping and two padding finishing solutions, the liquid rolling rate is 80-100%, pre-baked at 100-105°C for 2-5 minutes, baked at 120-150°C for 2-4 minutes, washed with water, and dried.

The finishing effect tests of multifunctional fabrics are shown in Table 3 and Table 4.

            Table 3 The UV resistance of multifunctionally finished cotton fabrics

Test results

Sample No. Processing Conditions

                                                                                                                                                          

1 Control fabric UVB 3.02% UPF＝34

UVA 2.95%

UVB 0.92%

2 TiO ₂ :ZnO=3:1 UPF≥50

UVA 0.85%

UVB 0.94%

3 TiO ₂ :ZnO=1:3 UPF≥50

UVA 0.92%

Note: Test according to FZ/T 01021-92 test method for antibacterial performance of fabrics.

             Table 4 Antibacterial performance of multifunctionally finished cotton fabrics

Total number of colonies (×10 ⁴

% reduction in bacteria

Treatment conditions Strains

Training 22 rate (%)

0 contacts

Hour

Untreated fabric Escherichia coli 2.63

TiO ₂ : ZnO=1:3 Escherichia coli 0.35 0 100

TiO ₂ :ZnO=3:1 Escherichia coli 0.55 0.07 95.6

Untreated fabric Staphylococcus aureus 2.51

TiO ₂ : ZnO=1:3 Staphylococcus aureus 0.31 0.10 92.9

TiO ₂ : ZnO=3:1 Staphylococcus aureus 1.69 0.21 90.0

Note: Test according to FZ/T 01021-92 test method for antibacterial performance of fabrics.

Claims (7)

1, a kind of modified nanometer dxide multifunction finishing agent, it is characterized in that forming by following product: modified nano oxide compound emulsion 5%～30%, bleeding agent 0.01～1.0%, feel conditioning agent 0～5%, the crosslinking agent that contains two above active groups or grafting agent 10～90g/L, catalyst 6～15g/L, all the other are deionized water or distilled water;

Described modified nano oxide compound has the compound of following molecular formula:

Wherein, A is a nano-oxide, and described nano-oxide is nano-titanium oxide, nano zine oxide, nano aluminium oxide, nano-sized iron oxide, nano silicon oxide and their compound thereof; R=(CH ₂) _n, n=0～4; Y is vinyl, hydroxyl, aminoalkyl, amino, epoxy radicals, methacryl oxyalkyl or sulfydryl,

Wherein, m=0～20, R "=A, H or C ₁~ C ₄Alkyl;

Described bleeding agent is aerosol-OT salt, penetrant m or penetrating agent JFC; Described crosslinking agent or grafting agent are 2D resin, modification 2D resin, water soluble amino resin U-51, modified amino silicon oil or hydroxy silicon oil; Described feel conditioning agent is amino-organosilanes, hydrogeneous organosilan, silicone body or soluble polyurethane.

2, a kind of modified nanometer dxide multifunction finishing agent preparation method as claimed in claim 1, it is characterized in that the material of following weight percentage is mixed: modified nano oxide compound emulsion 5%～30%, bleeding agent 0.01～1.0%, feel conditioning agent 0～5%, the crosslinking agent that contains two above active groups or grafting agent 10～90g/L, all the other are deionized water or distilled water; Described catalyst adds before use, and consumption is 6～15g/L;

Described modified nano oxide compound emulsion, bleeding agent, feel conditioning agent, the crosslinking agent that contains two above active groups or grafting agent are according to claim 1; Described catalyst is organic acid, lewis acid, organic acid and lewis acidic compound, basic salt or organotin.

3, a kind of modified nanometer dxide multifunction finishing agent preparation method as claimed in claim 2 is characterized in that described organic acid is citric acid, tartaric acid, acetic acid or acrylic acid; Described lewis acid is magnesium chloride, zinc nitrate, zinc sulfate, aluminum sulfate or sodium fluoborate; Described basic salt is sodium bicarbonate, sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium carbonate, saleratus or potash.

4, the purposes of a kind of modified nanometer dxide multifunction finishing agent as claimed in claim 1 is characterized in that being used for natural fabric is carried out durable uvioresistant, antibiotic and multi-functional arrangement with good hand feeling.

5, the purposes of a kind of modified nanometer dxide multifunction finishing agent as claimed in claim 4 is characterized in that described natural fabric is cotton, ramie, silk or the wool of yarn, knitted fabric, woven fabric or bondedfibre fabric form.

6, the purposes of a kind of modified nanometer dxide multifunction finishing agent as claimed in claim 4, it is characterized in that modified nano oxide compound and natural fabric being carried out the interlinkage reaction by crosslinking agent or grafting agent, with the modified nano oxide compound persistence be applied on the natural fabric, and undertaken by the rolling～dry by the fire of routine～roasting technology.

7, the purposes of a kind of modified nanometer dxide multifunction finishing agent as claimed in claim 6, it is characterized in that described rolling～dry by the fire～roasting technology is: fabric two is soaked two roll, pick-up 80～100%, 80～100 ℃ of preliminary dryings 3～6 minutes, 120～160 ℃ bake washing in 2～5 minutes, soap washing, oven dry.