CN101876142A - A method for modifying the surface of cotton fabrics by using titanium sulfate and urea - Google Patents

Abstract

Translated fromChinese

本发明公开的一种采用硫酸钛和尿素对棉织物表面进行改性的方法，将待改性的棉织物在80℃条件下超声振荡清洗，烘干；按照质量比为3：2～10称取棉织物和硫酸钛，按照硫酸钛和尿素的摩尔比为0.1～0.5：1称取尿素，按照硫酸钛和去离子水的体积比为1：6～30将硫酸钛溶于去离子水，将尿素加入到硫酸钛溶液中搅拌得到混合溶液，将棉织物浸渍在混合溶液中10～40min，放入高温高压反应釜中，在130～160℃条件下恒温处理1.5～3h，取出棉织物，以1：30～50的浴比，在70～90℃条件下用洗涤液洗涤10～20min，用热冷水反复洗涤，烘干或自然晾干，得到改性后的棉织物。本发明方法安全无污染，生产效率高，节省原材料，改性后的棉织物具有良好的抗紫外线和抗菌性能，耐洗涤。

The invention discloses a method for modifying the surface of cotton fabrics by using titanium sulfate and urea. The cotton fabrics to be modified are cleaned by ultrasonic vibration at 80°C and dried; the mass ratio is 3:2-10 and weighed. Take cotton fabric and titanium sulfate, weigh urea according to the molar ratio of titanium sulfate and urea of 0.1-0.5:1, dissolve titanium sulfate in deionized water according to the volume ratio of titanium sulfate and deionized water of 1:6-30, Add urea into the titanium sulfate solution and stir to obtain a mixed solution, soak the cotton fabric in the mixed solution for 10-40 minutes, put it in a high-temperature and high-pressure reaction kettle, and treat it at a constant temperature of 130-160°C for 1.5-3 hours, take out the cotton fabric, With a bath ratio of 1:30-50, wash with washing liquid at 70-90°C for 10-20 minutes, repeatedly wash with hot and cold water, dry or naturally dry to obtain the modified cotton fabric. The method of the invention is safe and pollution-free, has high production efficiency, saves raw materials, and the modified cotton fabric has good anti-ultraviolet and antibacterial properties and is resistant to washing.

Description

A kind of method that adopts titanium sulfate and urea surface of cotton fabric to be carried out modification

Technical field

The invention belongs to function textile material technical field, relate to a kind of method of modifying of surface of cotton fabric, be specifically related to a kind of method that adopts titanium sulfate and urea surface of cotton fabric to be carried out modification.

Background technology

Nanometer titanic oxide material has good photocatalytic activity and electrical property, in fields such as photocatalysis, dyestuff, Industrial Catalysis, lithium rechargeable battery material and photoactivate battery, obtained using widely, but nano-titanium dioxide powder is reunited easily, cause photocatalytic activity to reduce, other performance is also had a significant impact.Therefore the high-quality nanometer titanic oxide material of synthetic single dispersion is the emphasis of people's research in recent years.Preparation nano-titanium dioxide powder method mainly contains sol-gal process, sluggish precipitation, micro emulsion method and hydro-thermal method etc. at present, wherein hydrothermal technique has shown comparatively broad development prospect, this is because reaction occurs in the airtight system, there is not the introducing of other impurity, temperature is low during preparation, the time short, the titanium dioxide nanoparticle purity height that obtains, good dispersion, uniform particles, crystal grain are grown complete, controllable shapes, and can be accessed desirable stoichiometric composition material.COTTON FABRIC enjoys people to like with its good permeability and comfort, but its uvioresistant and anti-microbial property are bad, therefore uses to be very limited.

The application of nano material in textile industry at present mainly realizes by co-blended spinning and back two kinds of methods of arrangement.The shortcoming of blending method is the preparation process more complicated of nano-powder, and particle is very easily reunited, and is wrapped in fibrous inside and can not fully contacts with oxygen, moisture, and function can not be brought into play fully; Use the afterfinish method of resin binder fairly simple, but adhesive also forms parcel to nano particle, influences the performance of function, and physical and mechanical properties such as fabric feeling obviously descend.There is the scholar to form zinc oxide crystal seed on the cotton fiber surface earlier, adopts the diauxic growth method again,, obtain a certain size zinc oxide nano rod on the cotton fiber surface by the growth of hydro-thermal reaction promotion crystal; Or adopt silicon dioxide gel that COTTON FABRIC is carried out preliminary treatment, under the low-temperature hydrothermal condition, realized that by zinc nitrate and hexa reaction nano zine oxide is in the growth on the throne of the one-step method on cotton fiber surface; Or earlier nano particle is dispersed in the dressing liquid processing such as again COTTON FABRIC is flooded (rolling), preliminary drying and bake; Or the preparation nano titanic oxide sol is put in order COTTON FABRIC more earlier; Or the employing radio frequency magnetron sputtering method, at surface of cotton fabric deposition of titanium oxide function nano structure sheaf.Said method or can not to solve load layer well even inadequately, fine and close, nanoparticulate dispersed is poor, combines problems such as fastness is not high with fiber, or the instrument and equipment costliness, and processing cost is higher, can not satisfy needs of production.

Summary of the invention

The purpose of this invention is to provide a kind of method that adopts titanium sulfate and urea that surface of cotton fabric is carried out modification, providing cotton fabric uvioresistant, antibiotic function solve the existing problem that coating COTTON FABRIC washing durability is poor, gas permeability is poor, feel is bad.

The technical solution adopted in the present invention is, a kind of method that adopts titanium sulfate and urea that surface of cotton fabric is carried out modification is specifically implemented according to following steps:

Step 1: the COTTON FABRIC that will treat modification is respectively 95% absolute ethyl alcohol sonic oscillation cleaning repeatedly with deionized water and concentration under 80 ℃ of conditions, dry for standby;

Step 2: according to mass ratio is COTTON FABRIC and titanium sulfate after 3:2～10 take by weighing the processing that step 1 obtains, mol ratio according to titanium sulfate and urea is that 0.1～0.5:1 takes by weighing urea, volume ratio according to titanium sulfate and deionized water is 1:6～30, the titanium sulfate that takes by weighing is dissolved in deionized water, obtain titanium sulfate solution, the urea that takes by weighing is joined in the titanium sulfate solution, vigorous stirring, obtain mixed solution, COTTON FABRIC after the processing that takes by weighing is immersed in 10～40min in the mixed solution, the mixed solution that will be impregnated with COTTON FABRIC is put into high-temperature high-pressure reaction kettle then, be filled to 80% of reactor volume with deionized water, sealing is handled 1.5～3h with reactor constant temperature under 130～160 ℃ of conditions of good seal, and reaction finishes the back and takes out COTTON FABRIC;

Step 3: will go up the reacted COTTON FABRIC that obtains of step, and with the bath raio of 1:30～50, with cleaning solution washing 10～20min, use heat, cold water cyclic washing then under 70～90 ℃ of conditions, oven dry or dry naturally obtains the COTTON FABRIC after the modification.

Characteristics of the present invention also are,

The cleaning solution in the step 3 wherein is by the solid soap flakes of 2g/L, the water-soluble composition of soda ash of 2g/L.

The invention has the beneficial effects as follows, use titanium sulfate and urea under hydrothermal condition directly at COTTON FABRIC fiber surface load nano-titanium dioxide film, providing cotton fabric uvioresistant and antibiotic function, by control reaction temperature and time, the technological parameters such as consumption of COTTON FABRIC, titanium sulfate and urea, the best modified technique of optimization, this method is saved raw material, easy and simple to handle, the washing durability excellence.Test result shows that the COTTON FABRIC after titanium sulfate is urea-modified still has good uvioresistant and anti-microbial property through after 30 washings.

Description of drawings

Fig. 1 is the urea-modified preceding stereoscan photograph of COTTON FABRIC titanium sulfate;

Fig. 2 be adopt the inventive method to the COTTON FABRIC titanium sulfate stereoscan photograph after urea-modified;

Fig. 3 is the X-ray diffraction spectrogram after adopting the inventive method to COTTON FABRIC titanium sulfate urea water heat modification;

Fig. 4 is the forward and backward ultraviolet reflection curve of spectrum of the embodiment of the invention 1 middle cotton fabric-modifying;

Fig. 5 is the forward and backward ultraviolet reflection curves of spectrum of the embodiment of the invention 2 middle cotton fabric-modifyings;

Fig. 6 is the forward and backward ultraviolet reflection curves of spectrum of the embodiment of the invention 3 middle cotton fabric-modifyings.

The specific embodiment

The present invention is described in detail below in conjunction with the drawings and specific embodiments.

The method that the present invention adopts titanium sulfate and urea that surface of cotton fabric is carried out modification, specifically implement according to following steps:

Step 1: the COTTON FABRIC that will treat modification is respectively 95% absolute ethyl alcohol sonic oscillation cleaning repeatedly, dry for standby then with deionized water and concentration under 80 ℃ of conditions;

Step 2: according to mass ratio is COTTON FABRIC and titanium sulfate after 3:2～10 take by weighing the processing that step 1 obtains, mol ratio according to titanium sulfate and urea is that 0.1～0.5:1 takes by weighing urea, according to titanium sulfate and deionized water volume ratio is 1:6～30, the titanium sulfate that takes by weighing is dissolved in deionized water, obtain titanium sulfate solution, the urea that takes by weighing is joined in the titanium sulfate solution, vigorous stirring, obtain mixed solution, COTTON FABRIC after the processing that takes by weighing is immersed in 10～40min in the mixed solution, the mixed solution that will be impregnated with COTTON FABRIC is put into high-temperature high-pressure reaction kettle then, and be filled to 80% of reactor volume with deionized water, sealing is handled 1.5～3h with reactor constant temperature under 130～160 ℃ of conditions of good seal, and reaction finishes the back and takes out COTTON FABRIC;

Step 3: will go up the reacted COTTON FABRIC that obtains of step, and with the bath raio of 1:30～50, with cleaning solution washing 10～20min, use heat, cold water cyclic washing then under 70～90 ℃ of conditions, oven dry or dry naturally obtains the COTTON FABRIC after the modification.Cleaning solution wherein is by the solid soap flakes of 2g/L, the water-soluble composition of soda ash of 2g/L.

Fig. 1 and Fig. 2 are respectively the urea-modified forward and backward stereoscan photographs of COTTON FABRIC titanium sulfate.As can be seen, COTTON FABRIC is through after the modification of titanium sulfate urea surface, and fiber surface has coated one deck nano-titanium dioxide film.Fig. 3 is the COTTON FABRIC X-ray diffraction spectrogram behind the titanium sulfate urea water heat modification.This nano-titanium dioxide film is a Detitanium-ore-type as can be seen.The crystalline structure energy gap of anatase-type nanometer titanium dioxide is greater than the crystalline structure of rutile ore type, thereby the hole-electron pair that anatase crystal is produced has corrigendum and more negative current potential, therefore for most of light-catalyzed reaction systems, the nano-titanium dioxide film of Detitanium-ore-type has advantages of high catalytic activity.

According to standard GB/T8629-2001 " textiles test with home washings and drying program " to titanium sulfate the COTTON FABRIC after urea-modified wash and drying (is selected A type washing machine for use, the 4A washing procedure, A type drying program), and according to standard GB/T18830-2009 " evaluation of ultraviolet resistance of fabric " measure the COTTON FABRIC ultraviolet resistance of titanium sulfate after urea-modified.After 30 standard washings, the COTTON FABRIC after the modification is at spectral transmittance T＜3.0% of UVB and UVA wave band, Ultraviolet Protection Factor UPF〉55, can be used as the antiultraviolet product.

Measure the COTTON FABRIC antibacterial effect of titanium sulfate after urea-modified according to standard GB/T20944.2-2007 " the evaluation part 2 of antibacterial textile performance: absorption process ".All more than 96%, the COTTON FABRIC after titanium sulfate is urea-modified has antibacterial effect to COTTON FABRIC after titanium sulfate is urea-modified to the bacteriostasis rates of staphylococcus aureus (ATCC6538) and Escherichia coli (8099).

Titanium sulfate and amount of urea ratio, hydrothermal temperature and time all affect product crystalline phase, crystallization degree, pattern and particle size.When COTTON FABRIC and titanium sulfate mass ratio were 3:2～10, fiber surface can coat certain thickness film, and nano particle combines comparatively firm with cotton fiber, tangible agglomeration can not take place, and also can not deposit too many titanium dioxide granule in the solution; When less than 3:2, titanium sulfate and amount of urea are excessive, easily cause waste, and nano titanium oxide is many to be deposited on the solution bottom with Granular forms, and the fiber surface adhesion amount obviously reduces, and fastness is bad, and the fabric after the processing in use nano particle comes off easily; When greater than 3:10, though in the solution residual titanium dioxide nanoparticle seldom, the titanium dioxide amount that fiber surface adheres to does not form continuous films very little, antiultraviolet and anti-microbial property are affected.When the mol ratio of titanium sulfate and urea is 0.1～0.5:1, can obtain the anatase-phase nano titanium dioxide particle, the activity of titanium dioxide weakens along with the increase of crystal particle scale, and crystallite dimension is reduced to nanoscale can make energy gap increase, thereby makes light at hole h⁺With electronics e^-In have stronger oxidisability and reducibility, the nano particle yardstick is less than the mean free path of carrier, thereby reduced the compound of electronics and hole in the transition process; When less than 0.1:1, amount of urea is relatively large, and the solution degree of supersaturation increases in course of reaction, and forming core speeds up, the nucleus quantity that produces increases, because competition mechanism, with this understanding, grain growth is slow, grain size will be more little, but the increase of pH value of solution value is serious to the cotton fiber damage; When greater than 0.5:1, the titanium sulfate consumption is more relatively, and the solution degree of supersaturation is on the low side, predecessor titanium sulfate hydrolysis aggravation, and grain growth is accelerated, and grain size increases, and is easy to generate agglomeration.When temperature of reaction kettle is 130～160 ℃, can prepare nanoscale anatase phase titanium dioxide particle; When being higher than 160 ℃, crystal growth rate is accelerated, and nucleation process is an exothermic process, and the rising of temperature will be unfavorable for that hydrolysis carries out to the nucleation direction, make in the system nucleus quantity less relatively, and the rising of temperature also can cause can stable existence critical nucleus size increase; When being lower than 130 ℃, can not synthesizing anatase phase nano-titanium dioxide product.The hydro-thermal reaction time can be prepared the Nano titanium dioxide particle when being 1.5～3h; When greater than 3h, titanium dioxide nucleus growth time lengthening, crystal is grown up gradually, and specific area then decreases, and crystallite dimension obviously increases, fastness and serviceability that influence combines with fiber; When less than 1.5h, can not guarantee the growth of titanium dioxide nanocrystalline at short notice.

Embodiment 1

Take by weighing the COTTON FABRIC of 14.4g respectively, the titanium sulfate of 9.6g and the urea of 24g.Deionized water and ethanol solution sonic oscillation washing 30min under 50KHz power 100W condition that COTTON FABRIC is 1:1 with 80 ℃ of volume ratios of temperature, 60 ℃ of oven dry.Titanium sulfate is dissolved in the deionized water of 300ml, and adds the urea vigorous stirring, add COTTON FABRIC dipping 10min immediately; The COTTON FABRIC that dipping is good is put into the high-temperature high-pressure reaction kettle of 500ml together with the titanium sulfate urea liquid, and is filled to 80% of reactor volume with deionized water, and reactor constant temperature under 130 ℃ of conditions of good seal is handled 1.5h.After last question response finishes, with the soap flakes of 2g/L, the soda ash of 2g/L, 1:30 bath raio, under 90 ℃ of conditions, handle COTTON FABRIC 15min, then with 90 ℃ of hot water, cold water cyclic washing, 60 ℃ of oven dry.Fig. 4 is that COTTON FABRIC adopts the forward and backward ultraviolet reflection curve of spectrum of above-mentioned process modification.As can be seen, COTTON FABRIC after the modification is through after 30 washings, (280～315nm) ultraviolet average reflectances drop to 3.9% by 34.8% to the UVB wave band, promptly ultraviolet absorbability has been improved approximately 31%, and (315～400nm) ultraviolet average absorption abilities have improved 14.4% to the UVA wave band.

According to standard GB/T8629-2001 to titanium sulfate the COTTON FABRIC after urea-modified wash and dryly (select A type washing machine for use, the 4A washing procedure, A type drying program), and according to standard GB/T18830-2009 measure the COTTON FABRIC ultraviolet resistance of titanium sulfate after urea-modified.After 30 washings, the COTTON FABRIC after the modification is at the spectral transmittance T=2.9% of UVB and UVA wave band, Ultraviolet Protection Factor UPF=56.According to the COTTON FABRIC antibacterial effect after standard GB/T20944.2-2007 mensuration titanium sulfate is urea-modified.COTTON FABRIC after the modification is 96.2% to the bacteriostasis rate of staphylococcus aureus (ATCC6538), is 97.3% to the bacteriostasis rates of Escherichia coli (8099), has antibacterial effect.

Embodiment 2

Take by weighing the COTTON FABRIC of 14.4g respectively, the titanium sulfate of 48g and the urea of 24g.Deionized water and ethanol solution sonic oscillation washing 30min under 50KHz power 100W condition that COTTON FABRIC is 1:1 with 80 ℃ of volume ratios of temperature, 60 ℃ of oven dry.Titanium sulfate is dissolved in the deionized water of 300ml, and adds the urea vigorous stirring, add COTTON FABRIC dipping 40min immediately; The COTTON FABRIC that dipping is good is put into the high-temperature high-pressure reaction kettle of 500ml together with titanium sulfate solution, and is filled to 80% of reactor volume with deionized water, and the reactor of good seal is handled 3h under 160 ℃ of conditions.After last question response finishes, with the soap flakes of 2g/L, the soda ash of 2g/L, 1:30 bath raio, under 90 ℃ of conditions, handle COTTON FABRIC 15min, then with 90 ℃ of hot water, cold water cyclic washing, 60 ℃ of oven dry.Fig. 5 is that COTTON FABRIC adopts the forward and backward ultraviolet reflection curve of spectrum of above-mentioned process modification.As can be seen, the COTTON FABRIC after the modification is through after 30 washings, and (280～315nm) ultraviolet average absorption abilities have improved 31.3%, and (315～400nm) ultraviolet average absorption abilities have improved 27.1% to the UVA wave band to the UVB wave band.But because treatment temperature is higher, the fabric intensity damage is bigger.

According to standard GB/T8629-2001 to titanium sulfate the COTTON FABRIC after urea-modified wash and dryly (select A type washing machine for use, the 4A washing procedure, A type drying program), and according to standard GB/T18830-2009 measure the COTTON FABRIC ultraviolet resistance of titanium sulfate after urea-modified.After 30 washings, the COTTON FABRIC after the modification is at the spectral transmittance T=2.8% of UVB and UVA wave band, Ultraviolet Protection Factor UPF=58.According to the COTTON FABRIC antibacterial effect after standard GB/T20944.2-2007 mensuration titanium sulfate is urea-modified.COTTON FABRIC after the modification is 98.4% to the bacteriostasis rate of staphylococcus aureus (ATCC6538), is 99.2% to the bacteriostasis rates of Escherichia coli (8099), has antibacterial effect.

Embodiment 3

Take by weighing the COTTON FABRIC of 14.4g respectively, the titanium sulfate of 24g and the urea of 24g.Deionized water and ethanol solution sonic oscillation washing 30min under 50KHz power 100W condition that COTTON FABRIC is 1:1 with 80 ℃ of volume ratios of temperature, 60 ℃ of oven dry.Titanium sulfate is dissolved in the deionized water of 300ml, and adds the urea vigorous stirring, add COTTON FABRIC dipping 40min immediately; The COTTON FABRIC that dipping is good is put into the high-temperature high-pressure reaction kettle of 500ml together with titanium sulfate solution, and is filled to 80% of reactor volume with deionized water, and the reactor of good seal is handled 2h under 140 ℃ of conditions.After last question response finishes, with the soap flakes of 2g/L, the soda ash of 2g/L, 1:30 bath raio, under 90 ℃ of conditions, handle COTTON FABRIC 15min, then with 90 ℃ of hot water, cold water cyclic washing, 60 ℃ of oven dry.Fig. 6 is that COTTON FABRIC adopts the forward and backward ultraviolet reflection curve of spectrum of above-mentioned process modification.As can be seen, the COTTON FABRIC after the modification is through after 30 washings, and (280～315nm) ultraviolet average absorption abilities have improved 27.6%, and (315～400nm) ultraviolet average absorption abilities have improved 15.7% to the UVA wave band to the UVB wave band.

According to standard GB/T8629-2001 to titanium sulfate the COTTON FABRIC after urea-modified wash and dryly (select A type washing machine for use, the 4A washing procedure, A type drying program), and according to standard GB/T18830-2009 measure the COTTON FABRIC ultraviolet resistance of titanium sulfate after urea-modified.After 30 washings, the COTTON FABRIC after the modification is at the spectral transmittance T=2.9% of UVB and UVA wave band, Ultraviolet Protection Factor UPF=56.According to the COTTON FABRIC antibacterial effect after standard GB/T20944.2-2007 mensuration titanium sulfate is urea-modified.COTTON FABRIC after the modification is 97.9% to the bacteriostasis rate of staphylococcus aureus (ATCC6538), is 99.0% to the bacteriostasis rates of Escherichia coli (8099), has antibacterial effect.

The inventive method, use titanium sulfate and urea under hydrothermal condition directly at COTTON FABRIC fiber surface load nano-titanium dioxide film, studied COTTON FABRIC, titanium sulfate and amount of urea, parameters such as reaction temperature and time are to the influence of load effect, optimization optimization process technology.Test result shows that the COTTON FABRIC after the modification has good uvioresistant and anti-microbial property, and wash resistant.This process safety is pollution-free, and the production efficiency height is easy and simple to handle, saves raw material, simultaneously to fabric feeling and not obviously influence of wearability such as ventilative.

Claims (2)

1. one kind is adopted titanium sulfate and urea to the method that surface of cotton fabric carries out modification, it is characterized in that, specifically implements according to following steps:

Step 1: the COTTON FABRIC that will treat modification is respectively 95% absolute ethyl alcohol sonic oscillation cleaning repeatedly with deionized water and concentration under 80 ℃ of conditions, dry for standby;

Step 2: according to mass ratio is COTTON FABRIC and titanium sulfate after 3:2～10 take by weighing the processing that step 1 obtains, mol ratio according to titanium sulfate and urea is that 0.1～0.5:1 takes by weighing urea, volume ratio according to titanium sulfate and deionized water is 1:6～30, the titanium sulfate that takes by weighing is dissolved in deionized water, obtain titanium sulfate solution, the urea that takes by weighing is joined in the titanium sulfate solution, vigorous stirring, obtain mixed solution, COTTON FABRIC after the processing that takes by weighing is immersed in 10～40min in the mixed solution, the mixed solution that will be impregnated with COTTON FABRIC is put into high-temperature high-pressure reaction kettle then, be filled to 80% of reactor volume with deionized water, sealing is handled 1.5～3h with reactor constant temperature under 130～160 ℃ of conditions of good seal, and reaction finishes the back and takes out COTTON FABRIC;

Step 3: will go up the reacted COTTON FABRIC that obtains of step, and with the bath raio of 1:30～50, with cleaning solution washing 10～20min, use heat, cold water cyclic washing then under 70～90 ℃ of conditions, oven dry or dry naturally obtains the COTTON FABRIC after the modification.

2. employing titanium sulfate according to claim 1 and urea is characterized in that the method that surface of cotton fabric carries out modification, and the cleaning solution in the described step 3 is by the solid soap flakes of 2g/L, the water-soluble composition of soda ash of 2g/L.

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