TWI568743B - Organic - inorganic blends, fabrics containing them and methods for their preparation - Google Patents

Description

Organic-inorganic hybrid material, fabric containing the same and preparation method thereof

The present invention relates to a mixed material and a preparation method thereof, and more particularly to an organic-inorganic hybrid material having an antibacterial effect and a preparation method thereof.

In today's many functional and composite functional products, the performance requirements of textiles are getting higher and higher, not only paying attention to the style and texture of textiles, but also paying more attention to the functions of textiles. Faced with this situation, many textile production companies pay more attention to the development of functional textiles, making them comparable to natural fibers and surpassing their functions. The development of functional textiles not only gives textiles many special functions, such as: water absorption, moisture absorption, hydrophobic, oleophobic, antifouling, antibacterial, deodorant, deodorizing, aromatic, conductive, antistatic, flame retardant, heat storage and heat preservation (far Infrared), ultraviolet shielding, electromagnetic shielding, etc., but also to promote the textile fabric in the style, feel and appearance of the characteristics to meet or exceed the characteristics of natural fiber materials.

In terms of antibacterial function, the antibacterial agent can be added to the fabric to have an antibacterial effect. Currently, the commonly used antibacterial agent is a nano silver ion, which is a silver particle having a size of less than 100 nm. The methods for antibacterial processing of fabrics are mainly divided into antibacterial fiber method and post-treatment method. The antibacterial fiber method is that the antibacterial fiber is an antibacterial fiber itself, or chemically grafted and blended and woven on the fiber, and the synthetic fiber can be spun by adding an antibacterial agent during the spinning process; The post-treatment method is to carry out subsequent dyeing of the fabric. It is processed to be immersed in an antibacterial agent (for example, a nano silver suspension), and the suspension is uniformly absorbed into the fiber under pressure, and finally the dried antibacterial agent is fixed on the cloth fiber to have antibacterial property.

However, all the above methods have deficiencies. The antibacterial effect of the antibacterial fiber method is durable, washable, and weather resistant, but the processing process is complicated and the cost is high. The post-treatment method is simple in processing and low in cost. However, the antibacterial agent of the woven fabric is not washable and the antibacterial effect cannot be sustained.

In view of the above, an object of the present invention is to provide an organic-inorganic hybrid material which can have a stable antibacterial effect, a process for producing the mixed material, and an antibacterial fabric prepared from the mixed material. Mainly by using a sol-gel method (Sol-gel), a mixture of formula (II), vinyl triethoxy hydride (VTES), tetraethoxy oxane (TEOS), and nano silver is synthesized. An organic-inorganic hybrid material containing a stable structure of nano silver and used to solve the problem of unstable antibacterial properties of conventional antibacterial fabrics.

In view of the above objects, the present invention provides a method of producing an organic-inorganic hybrid material comprising providing a formula (I): Wherein A may be an aromatic group of C ₆ ; and at a predetermined pH, the formula (I), nano silver liquid and Tetraethyl orthosilicate (TEOS) are mixed to form a mixed material.

In the above, wherein the formula (I) can be formed by mixing the formula (II) with Vinyltriethoxysilane (VTES),

In the above, wherein the formula (II) can be formed by mixing the formula (III) with a diazonium salt,

Preferably, the predetermined pH may be from 2 to 4.

In the preparation method provided by the present invention, the molar ratio of the total addition of the formula (II), the vinyl triethoxy decane, the tetraethoxy decane, and the nano silver liquid may be 1:5:x:2.5. Where x can be between 2.5 and 10.

In the preparation method provided by the present invention, the molar ratio of the total addition of the formula (II), the vinyl triethoxy decane, the tetraethoxy decane, and the nano silver liquid may be 1:5:10:y, Where y can be between 1 and 2.5.

In view of the above objects, the present invention further provides a mixed material having a structure as shown in the formula (IV):

In the above, the mixed material may comprise a plurality of nano silver particles embedded in the Si-O-Si network structure.

In view of the above, the present invention still provides an antibacterial fabric comprising: a synthetic fiber fabric; and the present invention provides a blended material in which the blended material is uniformly attached to the fiber surface of the synthetic fiber fabric in a block form.

Preferably, the synthetic fiber fabric may be selected from the group consisting of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyacrylate (PA), and poly It is made of fibers of a group consisting of polyacrylonitrile (PAN), poly(vinyl chloride), and polyvinylurethane (PU).

According to the above, the organic-inorganic hybrid material provided by the present invention and the method for producing the same can have the following advantages:

(1) A method for preparing a mixed material according to an embodiment of the present invention, which is prepared by a sol-gel method, which can uniformly synthesize an organic-inorganic hybrid material.

(2) A mixed material according to an embodiment of the present invention, which comprises a stable 矽-oxygen network structure, which can coat silver ions therein and increase the mixing ratio of nano silver.

(3) An antibacterial fabric according to an embodiment of the present invention, which uses the mixed material of the present invention for antibacterial processing, has excellent antibacterial effect, abrasion resistance, and high water repellency.

Figure 1 is a FT-TR analysis of a blended material provided in accordance with an embodiment of the present invention.

Fig. 2 is a ²⁹ Si-NMR analysis chart of a mixed material provided according to an embodiment of the present invention.

Fig. 3 to Fig. 5 are surface electro-optical drawings of PET fabrics, wherein the third figure is the surface electric map of the PET fabric PE ₁ -PE ₄ processed by the blended material 1; the fourth figure is the hybrid material 2 The surface electrical display of the processed PET fabric QE ₁ -QE ₄ ; the fifth figure is the surface electrical display of the PET fabric RE ₁ -RE ₄ processed by the blended material 2.

6A to 6F are the results of EDS analysis of the mixed material of the present embodiment. 6A is an elemental analysis diagram of the embodiment P ₁ of the mixed material 1; FIG. 6B is an elemental analysis diagram of the embodiment P ₄ of the mixed material 1; and FIG. 6C is an implementation of the mixed material 2 The elemental analysis chart of the aspect Q ₁ ; the 6D figure is the elemental analysis chart of the embodiment Q ₄ of the mixed material 2; the 6E figure is the elemental analysis chart of the embodiment R ₁ of the mixed material 2; It is an elemental analysis diagram of the embodiment R ₄ of the mixed material 2.

Figure 7 is a contact angle analysis diagram of a PET fabric treated with a blended material.

Figure 8 is a diagram of the light diffraction analysis of the Ag crystal structure alone.

Fig. 9 is a light diffraction analysis diagram of a mixture of a precursor (I') and TEOS and Ag.

The invention will be further described in detail by the following preferred embodiments and the accompanying drawings. It should be noted that the experimental data disclosed in the following embodiments are for explaining the technical features of the present invention, and are not intended to limit the manner in which they can be implemented.

The present invention provides an embodiment for preparing a method for preparing an organic-inorganic hybrid material containing nano silver.

First, an intermediate represented by the formula (III) is obtained: Wherein A may be an aromatic group of C ₆ , and preferably may be a phenyl group. In the present embodiment, the phenyl group will be denoted by the designation Ph.

The intermediate of formula (III) is prepared by the following steps: First, thiourea (0.3020 g; 0.004 mol), acetophenone (0.2538 g; 0.002 mol), iodine (0.2400 g; 0.02 mol) are placed in a circle. The bottom flask was stirred and heated under reflux for 4 hours, and then filtered with anhydrous diethyl ether to obtain a solid, which was dissolved in 300 ml of hot water, and then added with aqueous ammonia to precipitate a solid, such as the formula (1). Shown as follows:

Next, the intermediate (III') and the monodiazonium salt were mixed, and the diazonium salt was prepared as follows: 1.38 g (0.01 mol) of p-nitroaniline was dissolved in hydrochloric acid (HCl), and placed in an ice bath to be magnetically stirred, followed by magnetic stirring. Further, 0.69 g (0.01 mol) of sodium nitrite was slowly added dropwise, and the reaction was stirred for one hour to become a diazonium salt. 1.76 g (0.01 mol) of the intermediate (III') was added to a solution of sodium carbonate dissolved in water, and magnetically stirred to uniformly disperse in water as a coupling salt solution. Next, the diazonium salt was added to the coupling salt solution under an ice bath, and the pH was adjusted to 6 to 7 with sodium hydroxide (NaOH) for 2 hours, and then filtered and dried to obtain a powder of p-nitroso. Nitrogen dye (II'). The overall reaction process is as shown in equation (2):

Next, the precursor of the organic-inorganic hybrid material and the preparation of the mixed material were further carried out by a sol-gel method (Sol-Gel). The so-called sol-gel method (Sol-Gel) is mainly a chemically active molecule as a precursor, and is uniformly mixed in a solution and hydrolyzed and condensed to form a sol having uniform dispersion and liquid characteristics (Sol) ). The size of the colloidal particles of the sol is controlled between 1 and 1000 nm, and these colloidal particles are finally linked into a three-dimensional network structure and a gel having a solid characteristic (Gel). Controlling the pH of the solution can affect the rate of hydrolysis and condensation. The higher the pH, the higher the degree of cross-linking. On the contrary, the lower the pH, the smaller the degree of cross-linking.

The preparation method of the precursor is as follows: the p-nitroazo dye (II') is dissolved in ethanol (EtOH) and mixed with vinyl triethoxy decane (VTES) in a specific ratio, and sol-condensed in a constant temperature stirring device. The reaction method (Sol-Gel) was carried out for 4 hours to obtain a precursor (I') as shown in the formula (3):

Next, the mixed material is prepared as follows: the precursor (I') is adjusted in solution to adjust the pH of the solution to 2 to 4, and two kinds of mixed materials are separately prepared according to a certain ratio: only mixed with the nano silver liquid, and The nano silver liquid and the tetraethoxy decane (TEOS) are mixed, and both are reacted in a sol-gel method for 2 hours in a constant temperature stirring device, and then the mixed material 1 and the mixed material 2 are respectively obtained, and the reaction formula is as follows Show:

In general, the nano silver liquid is a solution having a suspension of nano silver metal, which can be purchased from a commercially available manufacturer or can be prepared by itself. Preferably, the nano silver liquid of the present invention is prepared by itself, and the size of the nano silver particles can be controlled to be below 100 nm. The preparation method is as follows: silver nitrate (1.7 g; 0.01 mol) is dissolved as 8.5 mL of water as a precursor solution; reducing agent glucose (3.6 g; 0.02 mol), protective agent (Polyvinylpyrrolidone, PVP) (2 g) is 25.5 mL. The water is dissolved and the pH is adjusted to 11 using sodium hydroxide (NaOH). The glucose-PVP-NaOH aqueous solution was gradually dropped at 60 ° C, and the stirring was continued for 15 minutes to prepare a nano silver preparation liquid.

According to the present invention, the organic-inorganic hybrid material 1 containing nano silver and the mixed material 2 are produced according to the method for producing the above organic-inorganic hybrid material. Wherein, the mixed material 2 comprises the chemical structure represented by the formula (IV): Wherein A is a benzene ring. The mixed material 2 further contains a plurality of nano silver fine particles embedded in the Si-O-Si network structure. Therefore, the mixed material 2 can be understood as a mixture of an organic (p-nitroazo dye (II')) and an inorganic (VTES, TEOS).

In order to test and achieve an optimum preparation ratio of the mixed material, the preparation method of the organic-inorganic hybrid material provided by the present invention, wherein the p-nitroazo dye (II'), VTES, TEOS and nano silver are prepared The ratio is divided into two experimental groups, Q ₁ -Q ₄ and R ₁ -R ₄ . The molar ratio of the p-nitroazo dye (II'), VTES, TEOS and nano silver added in the Q group is 1:5:x:2.5, wherein the x system is between 2.5 and 10; The molar ratio of the p-nitroazo dye (II'), VTES, TEOS, and nanosilver of the R group is 1:5:10:y, wherein the y is between 1 and 2.5. Further, the mixed material 1 (i.e., not mixed with TEOS) was used as a control P, which was classified into P ₁ -P _{4 in} accordance with the molar ratio of the addition of the p-nitroazo dye (II'), VTES, and nano silver. Refer to Table 1 below for the proportion of each component in the respective embodiments of the mixed material 1 and the mixed material 2.

In order to further test the physicochemical properties of the mixed materials prepared by the present invention, the above three groups of the four embodiments were subjected to special functional group analysis. The specific functional groups in this example were analyzed using a Fourier infrared spectrometer (FT-IR, model: FTS-40, Bio rad Digilab).

In the infrared analysis, the intermediate (III') was analyzed by infrared spectroscopy, and the position of the absorption peak of the functional group characteristic was observed from the experimental results (not shown), and the stretching of the NH group on the intermediate (III') structure was known. The absorption peak of the vibration characteristic appeared at 3433 cm ^-1 of the spectrum, and the absorption peak of the stretching vibration characteristic of the CH group appeared at 2970 cm ^-1 . The synthesized p-nitroazo dye (II') was analyzed by infrared spectroscopy, and it was found that the functional group characteristic absorption peak position on the dye structure showed that the characteristic absorption peak of the NH group on the dye structure appeared at position 3332 cm ^{-1 .} At the same time, the absorption peak of the stretching vibration characteristic of the CH group on the dye structure appeared at 2972 cm ^-1 . Mixing timber through infrared spectroscopy, near 3480cm ^-1 NH group has an absorption peak, 2934cm ^-1 CH groups near the near 1638cm ^-1 and an absorption peak phenyl group, there are in the vicinity of 1100cm ^-1 Si-O in The group absorbs the peak.

Next, please refer to Fig. 1, which is an FT-TR analysis chart of the mixed material provided according to the present invention. In the first part (A), the P ₁ -P ₄ of the mixed material 1 as a control group was analyzed by infrared spectroscopy, and a peak of vibration absorption of the benzene ring group was observed in the vicinity of 1652 cm ^-1 , and with Ag As the concentration increases, the absorption intensity increases. At the vicinity of 1109 cm ^-1 , the absorption peak of Si-O group increases with the increase of Ag concentration, so that the content of Ag promotes the precursor (I' ) The bond is becoming more complete. In the first part (B), the experimental group Q ₁ -Q ₄ of the mixed material 2 was analyzed by infrared spectroscopy, and the absorption peak of the Si-O group at the vicinity of 1091 cm ^{-1 was} found to increase with the increase of the concentration, indicating As the concentration of TEOS increases, the extent of the network structure also increases. In the first part (C), the experimental group R ₁ -R ₄ of the mixed material 2 was analyzed by infrared spectroscopy. At 3431 cm ^-1 , the absorption peak of the NH group was found to increase significantly with the Ag concentration, around 1641 cm ^-1 . The absorption peak of the phenyl group also increased with the concentration of Ag. The absorption peak of the Si-O group at around 1072 cm ^{-1 was} found to increase with increasing concentration, but the amplitude was not large.

Next, the mixed material 1 and the mixed material 2 were subjected to structural analysis, and a ²⁹ Si-NMR spectrum was measured by a superconducting nuclear magnetic resonance apparatus 500 NMR (BRUKER AVANCE 500 Solution-NMR), and recorded.

It can be seen from ²⁹ Si-NMR that there are T ³ , Q ³ , Q ⁴ absorption peaks, wherein T ^{3 is} at δ: -78.47 ppm; Q ^{3 is} at δ: -100.37 ppm; Q ^{4 is} at δ: -109.22 ppm; The T ³ absorption peak is the structure of the absorption peak of Si-O-Si after VTES hydrolysis, and the Si tetra-bond has an unreacted Si-R functional group such as R-Si (-OSi≡) ₃ type, Q the structure ³ is bonded to some of Si four remaining, a Si-OR of unreacted functional groups, such as (RO) Si (-OSi≡) ₃ type, the structure of all of Q ⁴ Si are bonded four complete reaction of The Si-O functional group exists as a Si (-OSi≡) ₄ type.

Please refer to Fig. 2, which is a ²⁹ Si-NMR analysis chart of the mixed material provided according to the present invention. When the current precursor (I') is fixedly mixed with Ag in a polycondensation reaction, the obtained composite material 1 is subjected to P ₂ ²⁹ Si-NMR nuclear magnetic resonance spectroscopy analysis, and the result of FIG. 2 (A) is obtained. It is known that the noise peak of the analysis chart is more significant, and a significant T ³ absorption peak appears at δ: -78.89 ppm. It is speculated that the mixed material 1 still exists in the form of R-Si(-OSi≡) ₃ . It indicates that the Si-O-Si network structure has not been formed in the mixed material process.

²⁹ Si-NMR nuclear magnetic resonance spectroscopy analysis of the mixture prepared by changing the ratio of Ag to different concentrations of TEOS, as shown in part (B) of Figure 2, except for the formation of the network of the mixed material, except for the appearance of T ^{In addition to the 3} absorption peaks, there are also absorption peaks of Q ³ and Q ⁴ . In the experimental group Q ₁ -Q _{4 of the} mixed material 2, the T ³ absorption peak appeared at about δ: -79.51 ppm and the absorption peak decreased with the increase of TEOS concentration. It can be inferred that the network structure of the mixed material increases with concentration. The formation of the Si-O-Si network structure causes the R-Si(-OSi≡) ₃ structure to decrease, and the T ³ absorption peak decreases. In the embodiment 2, Q ₁ and Q _{2 of the} mixed material 2 were found to have an absorption peak Q ³ in the vicinity of δ: -99.29 ppm, but gradually disappeared with increasing concentration, and increased with TEOS concentration. Then, only the Q ⁴ absorption peak appears near the absorption peak δ: -110.03 ppm, and the noise peak of the absorption peak tends to decrease as the TEOS concentration increases, indicating that the Si-O-Si network structure of the mixed material 2 is formed. The formation is more complete.

The synthetic fiber 1 and the mixed material 2 prepared by the above-described organic-inorganic hybrid material preparation method provided by the present invention are respectively subjected to dyeing and weaving treatment to provide an antibacterial fabric. Among them, the synthetic fiber fabric can be selected from polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyacrylate (PA), polyacrylonitrile (Polyacrylonitrile). , PAN), polyvinyl chloride (poly(vinyl chloride), PVC), and polyurethane (PU) composed of fibers of the group. Preferably, this embodiment utilizes PET fibers and PTT fibers to prepare an antimicrobial fabric. The PET fiber weaving size used in this example was (124 × 80) / (150d / 144f × 150d / 144f); and the PTT fiber specification was (183 × 152) / (75d / 72f × 75d / 72f).

The synthetic fiber fabric adopts a two-dip two-pressure method, which uses the undyed synthetic fiber to be soaped, rinsed with water, dried in an oven, and placed in a clean synthetic fiber cloth into the nano silver-containing mixture of the present invention. In the material, after the first soaking for about 5-10 minutes, put it into the pressing machine for the first pressure suction (pressure absorption rate 80%); after the second soaking for about 5-10 minutes, carry out the second The secondary pressure suction (pressure absorption rate of 80%) completes the processing step of dyeing and antibacterial. Then, the processed synthetic fiber fabric is pre-dried at 70 ° C for 2 minutes. The bell was subjected to a thermal baking treatment: the thermal baking condition of the PET fiber was 180 ° C for 120 seconds, and the thermal baking condition of the PTT fiber was 160 ° C for 120 seconds.

Four embodiments of the mixed material 1 prepared by the present invention P ₁ -P ₄ , eight embodiments of the mixed material 2 Q ₁ -Q ₄ , R ₁ -R ₄ , and the implementation of the respective treated PET fiber fabrics aspects respectively _{PE 1 -PE 4, QE 1 -QE} 4, RE ₁ -RE ₄ and FIG. The following functional tests were then performed on the fabric aspects treated with the blended material.

Fabric surface observation

The processed dyed fabric was observed on a XL-40 FEG field emission scanning electron microscope (Philips XL40 FE-SEM) to observe the surface of the dyed fabric. At the same time, energy-dispersive X-ray spectroscopy (EDS) analysis technology was performed.

The results are shown in Figures 3 to 5, which are the surface electrograms of PET fabrics. Figure 3 is a surface electrical display of PET fabric PE ₁ -PE ₄ processed by the blended material 1; and Fig. ₄ is a surface electrical display of the PET fabric QE ₁ -QE ₄ processed by the blended material 2; 5 is a surface electro-optical display of PET fabric RE ₁ -RE ₄ processed by the blended material 2. The inventors observed the adhesion of the dye on the surface of the fabric by means of a scanning electron microscope. It is known from the electrographic display that the mixed material is attached to the surface of the fiber in a block form instead of covering the surface of the fiber with a film as in the conventional method. Further, the mixed material increases in a block shape attached to the fiber substantially as the TEOS concentration increases. Fig. 3 (A)-(D) are electric patterns of PET fabrics in which a mixture of Ag is changed but TEOS is not added. Since the network structure has not been formed, the block structure attached to the fibers is less. The number of nano-silver particles on the treated fabric increases with the proportion of Ag. Figure 4 (A)-(D) shows the proportion of Ag in the fixed mixture 2, and the TEOS ratio is changed to process the PET fabric. It can be clearly seen that the block structure of the fiber surface is more than the TEOS. It can be seen that the addition of TEOS contributes to the construction of the network structure, and in addition, it is found that the block structure of the fiber surface increases as the TEOS increases. Fig. 5 (A) - (D) is an electric pattern of a PET fabric processed by changing the ratio of Ag of the mixed material 2, and it can be seen from the figure that the silver nanoparticle of the fiber surface increases as the proportion of Ag increases.

The EDS analysis technique was carried out while observing the surface of the fabric with an electron microscope. When EDS is combined with an imaging tool such as an electron microscope, an area of as small as nanometers can be provided for elemental analysis. The impact of the electron beam on the sample produces characteristic X-rays of the sample element, and the EDS analysis can be used to determine the elemental composition of a single point or to map the lateral distribution of the elements of the imaged area.

Please refer to Table 2 and Figures 6A to 6F, which are the results of the EDS analysis of the mixed material of the present embodiment. 6A is an elemental analysis diagram of the embodiment P ₁ of the mixed material 1; FIG. 6B is an elemental analysis diagram of the embodiment P ₄ of the mixed material 1; and FIG. 6C is an implementation of the mixed material 2 The elemental analysis chart of the aspect Q ₁ ; the 6D figure is the elemental analysis chart of the embodiment Q ₄ of the mixed material 2; the 6E figure is the elemental analysis chart of the embodiment R ₁ of the mixed material 2; It is an elemental analysis diagram of the embodiment R ₄ of the mixed material 2. For the embodiment P ₁ -P ₄ , it can be seen from Table 2, Figure 6A and Figure 6B that the silver content in the fabric increases as the amount of Ag increases. For the mixed material implementations Q ₁ -Q ₄ , the results of Table 2, 6C and 6D show that the content of lanthanum increases with the increase of TEOS concentration, because TEOS contains more ruthenium atoms. The content of the lanthanum element of the mixed material is increased, and the silver is gradually decreased as the TEOS concentration increases. For mixing timber embodiment aspect R ₁ -R _4, Table 2, results of the first and second FIG. 6E 6F may be learned FIG silver content rises with the increase of the amount of Ag.

Determination of colorability and levelness of fabrics

In order to understand the colorability and the uniform dyeing degree of the antibacterial fabric provided by the present invention, the coloring property and the leveling property were measured. The coloring property can be determined by comparing the color difference between the dyed fabric and the blank test cloth to indicate the color shade of the dyed fabric, and using the microcomputer color difference meter to obtain the coloring ΔE value of the dyed fabric; The difference between the maximum value and the minimum value of ΔE measured in the same piece of dyed cloth can be known as the degree of uniformity.

It can be seen from Table 3 that in terms of coloring property, the antibacterial fabric of the present invention increases as the concentration of the mixed material increases, and the ΔE value in the leveling property can reach the standard range acceptable for the rating, and the mixed material processing cloth The level dyeability is less than 1, which is in the standard range. In Table 3, PE ₁ -PE ₄ is a PET fabric in which a mixed ratio of silver is added, and the color of the dyed woven fabric is darkened by the silver particles, so that the coloring property increases as the concentration of silver ions increases. Due to the uneven distribution of silver particles, the level of dyeability increases as the concentration of silver increases. The QE ₁ -QE ₄ in Table 3 is a PET processing cloth in which the mixed Ag concentration and the TEOS concentration ratio are mixed. Due to the formation of the bulk structure of the mixed material, the uniformity increases with the increase of the network structure, and the network structure The formation of the mixed material reduces the fineness of the mixed material and causes a slight decrease in colorability. In Table 3, RE ₁ -RE ₄ is a PET fabric of a mixed material having a fixed TEOS concentration and a varying Ag concentration ratio, and it can be found that the coloring property increases as the silver ion concentration increases, and the leveling property increases as the Ag concentration increases.

Washable and abrasion resistant test of fabric

The water-resistant washing test of the fabric of this example was tested according to the conventional test method CNS1494L48A3 test method, and the test specifications were as follows: dyed cloth*1 (10 cm×5 cm); white cloth*1 (5 cm×5 cm); condition: soap 5 g/ L, sodium carbonate 2 g / L, 10 stainless steel balls, liquid amount 100 ml, treated at 60 ° C × 30 minutes. The abrasion resistance test of the present embodiment is carried out according to the conventional CNS 1499L3032 test method, and the test cloth rules are as follows: dyed cloth *1 (22 cm × 3 cm); white cloth * 1 (5 cm × 5 cm); condition: type B (study) Type) Abrasion Tester (HT-8031) was rubbed 100 times.

As can be seen from Table 4, the dry rub resistance of the fabric processed by the blended material is roughly 4 grades, the wet rub fastness is roughly 3-4 grades, and the pollution rating is slightly lower than the fade grade. . The dyeing fastness rating of each dyed fabric has a fade grade of 4-5, and the pollution rating is roughly 4-5. As can also be seen from the table, the fabrics which have not been treated with the blended materials described in one embodiment of the present invention are lower in the water washable or abrasion resistant rating than the dyed fabrics.

Table 4: Analysis of abrasion resistance and wash fastness of dyed and untreated fabrics

Gas permeability analysis

The fabric of this example was analyzed for gas permeability in accordance with the ASTM D737-2004 test method. The conditions were as follows: an area of 38 cm ² and a pressure difference of 125 Pa.

It can be seen from Table 5 that the permeability of the fabric containing the blended material is somewhat reduced, because the ratio of TEOS to Ag rises to form a network structure and fill the gap between the fabrics, so that the breathability is inferior to that of the original fabric. In Table 5, PE ₁ -PE ₄ is a PET fabric in which a mixture of Ag varying concentration ratios is added. Since TEOS is not added to form a network structure, the gas permeability is reduced compared with the mixed material with TEOS added. In Table 5, QE ₁ -QE ₄ is a PET fabric of a mixed material having a fixed Ag concentration and a varying TEOS concentration ratio. Due to the formation of a network structure, the gap between the fabrics is filled, and the gas permeability is inferior to that of the TEOS-mixed material. In Table 5, the PET fabric in which the RE ₁ -RE ₄ is a fixed TEOS concentration and the Ag concentration is changed, it is found that the gas permeability has little effect on the change in the Ag ratio.

Contact angle measurement

The fabric of this example was measured for its contact angle by a static contact angle analyzer (model: CAM100, Sigma). The contact angle meter was used to determine the initial contact angle of the fabric with water droplets after the mixed material treatment. The larger the initial contact angle, the better the water repellency of the fabric and the worse the wetting ability.

The results are shown in Tables 6 and 7, which are the contact angle analysis charts of the PET fabric treated with the mixed materials. It can be seen from Table 6 that the contact angles before and after washing are increased as the concentration changes. Figure 7 (A) shows the contact angle of the PET fiber with a change in concentration of Ag, PE ₁ = 123 °, PE ₂ = 124 °, PE ₃ = 124 °, PE ₄ = 126 °, the contact angle after washing of _{PE 1 = 114 °, PE 2} = 118 °, PE 3 = 115 °, PE 4 = 117 °, the PE ₁ -PE ₄ may be found to increase the concentration of Ag were processed fabric of fibers The contact angle has little effect and its contact angle is slightly lower than other blended materials with TEOS added. In section (B) of Figure 7, it is shown that the PET fabric treated with the blended material having a fixed Ag concentration and a change in TEOS, the contact angle before washing is QE ₁ = 125 °, QE ₂ = 126 °, QE, respectively. ₃ = 133 °, QE ₄ = 134 °, contact angle after washing is QE ₁ = 118 °, QE ₂ = 119 °, QE ₃ = 121 °, QE ₄ = 124 °, due to the addition of TEOS will increase the contact angle and dial The water effect makes the fabric have a higher contact angle than the blended fabric without TEOS. Next, it can be seen from the section (C) of Fig. 7 that the PET fabrics with the TEOS concentration and the Ag ratio changed, the contact angles before washing with water are RE ₁ = 132°, RE ₂ = 131°, RE ₃ =130°, RE ₄ =134°, and the contact angles after washing are RE ₁ =127°, RE ₂ =125°, RE ₃ =123°, RE ₄ =126°, which can be found by RE ₁ -RE ₄ The increase in Ag concentration has no effect on the contact angle of the processed fabric.

Water repellency analysis

The dyed fabrics were placed in a circular frame of 6 inches in diameter, and then sprayed onto the dyed fabric by means of 250 ml of water through a funnel. After about 20-25 seconds, the water droplets on the surface of the fabric were bounced off. To determine the water level.

Please refer to Table 7. In Table 7, PE ₁ -PE ₄ is a PET fabric having a mixture of varying concentrations of Ag, which has a lower water repellency than the fabric to which TEOS is added. In Table 7, the fabric QE ₁ -QE ₄ is a PET fabric treated with a mixture of fixed Ag concentration and TEOS concentration ratio. Since the addition of TEOS increases the contact angle and water repellency, the water repellency rating is The situation in which TEOS concentration increases and rises. Further, RE ₁ -RE ₄ is a PET fabric processed by a blended material having a fixed concentration of TEOS and a concentration ratio of Ag, and similarly, as a result of the contact angle test, when the proportion of Ag is increased, the water repellency is not affected.

Light diffraction analysis

The fabric of this example was further subjected to analysis of the crystal configuration of the mixed material by an X-ray diffraction spectrometer (Rigaku, D/MAX 2500V). The test conditions are as follows: Cu-Kα radiation source, voltage: 40 kV, current: 100 mA, scanning speed: 30/min, scanning range: 15° to 80°.

Please refer to Fig. 8 and Fig. 9. Fig. 8 is a light diffraction analysis diagram of the crystal structure of Ag alone, and Fig. 9 is a light diffraction of the mixture of precursor (I') and TEOS and Ag. Shoot the analysis chart. Figure 8 is a control group, from which it can be seen that where 2 θ = 38.12 °, 2 θ = 44.32 °, 2 θ = 64.46 °, 2 θ = 77.40 °, 2 θ = 81.54 °, respectively corresponds to The (111), (200), (220), (311), and (222) crystal faces of the face-centered cubic packing (FCC) crystal structure. And it can be seen from FIG. 9, the light diffraction analysis of Q ₄ as precursor (I ') of the mixing timber, and Ag TEOS, known mixing timber diffraction peaks appear at 2 θ = 25 °, 2 θ = 38.12 °, 2 θ = 44.32 ° , 2 θ = 64.46 °, 2 θ = 77.40 °, 2 θ = 81.54 °. It can be inferred that the diffraction peak near 2θ=25° may be the diffraction peak of the dye, and the other diffraction peaks are the diffraction peaks of the silver metal in the mixed material. This phenomenon is roughly consistent with the literature data, but it is seen from the figure. The noise peak of the mixed material may be due to the fact that the dye is amorphous and the diffraction peak is less obvious, and does not affect the determination of the Ag crystal structure content in the dye.

Antibacterial performance analysis

The treated fabric of the present example was subjected to an antibacterial analysis of the fabric. Peibu original timber and mixed by the treated PET fabric embodiment aspect RE ₁ -RE ₄ antibacterial test for Staphylococcus gold, wherein the test conditions and parameters are as follows:

1. The concentration of the inoculum is within 1.0~3.0 E+5 (number of bacteria/ml) and the test is established.

2. Ma = number of bacteria in the control group immediately after scouring; Mb = number of bacteria in the control group after 18 hours of culture; Mc = number of cultured cells in the sample group at 18 hours.

3. Proliferation value = logMb-logMa, proliferation value ≧ 1.0 indicates that the experiment was established.

4. Antibacterial activity value = (logMb-logMa) - (logMc-logMo); bactericidal activity value = logMa-logMc

5. According to the standard antibacterial test specification JIS L1902: When the bacteriostatic activity value is 2.0 or more, it indicates a deodorizing effect, and when the bactericidal activity value is 0 or more, it indicates that the sample has a bacteriostatic effect.

Note: 6.2.0 E+2 means 200, 1.3 E+4 means 13000, and so on.

Please refer to Table 8, which is an analysis of the antibacterial properties of fabrics treated with the blended materials. As shown in Table 8, the inoculum was analyzed and compared with the number of colonies after 18 hours, NA indicates the same fabric which was not treated with the mixed material, and RE ₁ -RE ₄ was the embodiment of the fabric. As can be seen from the table, the antibacterial activity value and the bactericidal activity value of RE ₁ -RE ₄ in the embodiment of the fabric increased as the ratio of Ag increased. According to the standard antibacterial test specification JIS L1902: When the bacteriostatic activity value is 2.0 or more, it indicates a deodorizing effect, and when the bactericidal activity value is 0 or more, it indicates that the sample has a bacteriostatic effect. As can be seen from the table, the antibacterial activity value of the fabric embodiment RE ₁ -RE ₄ is between 2.8 and 3.3, while the bactericidal activity value is between 5.2 and 5.6, and the fabric RE ₁ -RE ₄ The sterilization rate is higher than 99%, between 99.576% and 99.941%, and has very good antibacterial properties. The fabric without the place is not antibacterial. Furthermore, PE ₁ -PE ₄ and QE ₁ -QE ₄ embodiment aspect of fabrics have to undergo analysis antibacterial properties, sterilization rate which is also higher than 99% (not shown), through the display of the embodiment of the embodiment of the present invention after the mixing process timber The fabric can achieve a high degree of antibacterial effect.

In combination with the above functionality test, the mixed material containing nano silver prepared by the method for preparing an organic-inorganic hybrid material provided by the present invention, and the synthetic fiber fabric processed by the mixed material can have good water repellency. Excellent characteristics such as high contact angle, high antibacterial property, water wash resistance and abrasion resistance.

The method for preparing an organic-inorganic hybrid material provided by the invention can successfully mix an organic dye with an inorganic cerium oxide compound and a nano silver ion to form a mixed material by a sol-gel method.

The mixed material provided by the invention can form a stable network structure of Si-O-Si, and stably coat the nano silver ions therein.

The invention provides a fiber fabric treated by a mixed material, wherein the mixed material is attached to the surface of the fiber in a block shape, and silver ions can be firmly embedded in the fiber, and as the Ag concentration is increased, the Ag particles attached to the surface of the fiber are more many.

The invention provides a fiber fabric treated by a mixed material, which has excellent characteristics such as good water repellency, high contact angle, high antibacterial property, water washing resistance, abrasion resistance and the like.

The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of the invention are intended to be included in the scope of the appended claims.

Claims (9)

An organic-inorganic hybrid material for use in the preparation of an antibacterial fabric, wherein the organic-inorganic hybrid material is produced in the following steps: provided as shown in formula (I): Wherein A is an aromatic group of C ₆ ; and at a predetermined pH, a mixture of (I), one nano silver, and Tetraethyl orthosilicate (TEOS) is formed to form a composition comprising the formula (IV) The organic-inorganic hybrid material of the structure shown: Wherein the organic-inorganic hybrid material is uniformly attached to the surface of the fiber of a synthetic fiber fabric in a block form; and the sterilization rate of an antibacterial fabric is greater than 99%. The use according to claim 1, wherein the formula (I) is formed by mixing the formula (II) with vinyl triethoxysilane (VTES), The use according to claim 2, wherein the formula (II) is formed by mixing the formula (III) with a diazonium salt, The use of claim 1, wherein the predetermined pH is from 2 to 4. The use according to claim 2, wherein the total molar ratio of the formula (II), the vinyl triethoxy decane, the tetraethoxy decane, and the nano silver liquid is 1:5:x: 2.5, where x is between 2.5 and 10. The use according to claim 2, wherein the total molar ratio of the formula (II), the vinyl triethoxy decane, the tetraethoxy decane, and the nano silver liquid is 1:5:10: y, where y is between 1 and 2.5. The use of the first aspect of the invention, wherein the synthetic fiber fabric is selected from the group consisting of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and poly Made of acrylate (PA), polyacrylonitrile (PAN), polyvinyl chloride (PVC), and polyurethane (PU) . An antibacterial fabric comprising: a synthetic fiber fabric; and an organic-inorganic hybrid material uniformly attached to the fiber surface of the synthetic fiber fabric in a block form, wherein the organic-inorganic hybrid material is mixed (I) : It is prepared by a nano silver liquid and Tetraethyl orthosilicate (TEOS), and the sterilization rate of the antibacterial fabric is more than 99%. The antibacterial fabric of claim 8, wherein the synthetic fiber fabric is selected from the group consisting of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), Fiber made of polyacrylate (PA), polyacrylonitrile (PAN), polyvinyl chloride (PVC), and polyurethane (PU) to make.