KR101793641B1 - New Giant Metal Polyoxides and Manufacturing Method of Functionalized Fibers or Fabrics Using the Same - Google Patents
New Giant Metal Polyoxides and Manufacturing Method of Functionalized Fibers or Fabrics Using the Same Download PDFInfo
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Abstract
The present invention relates to a novel giant metal multi-oxide and a method for producing functional fibers or fabrics using the giant metal multi-oxides. The giant metal multi-oxide according to the present invention exhibits excellent antibacterial and deodorizing effect, and the functional fiber or fabric produced by using the giant metal multi-oxide has an advantage that functionality is not deteriorated over time due to strong ionic bonding, It is useful for the development of functional fibers or fabrics having the ability to dye fibers or fabrics as well as antibacterial and deodorant effects.
Description
The present invention relates to a novel giant metal multi-oxide and a method for producing functional fibers or fabrics using the giant metal multi-oxides.
Giant metal polyoxides (hereinafter referred to as 'GMP') are formed by bundling metal polyoxides (hereinafter referred to as 'MP') into a super structure of a huge ball or ring. The history of GMP begins with "blue waters" found in Idaho Springs, Colorado, USA, or in the Valley of the Ten Thousand Smokes of Alaska. This "blue water" was reported by Carl Wilhelm Scheele in 1783 as molybdenum blue (hereinafter referred to as "MB"). MB is formed by partial oxidation of molybdenite (MoS 2 ) and has a molecular formula of Mo 3 O 8 .nH 2 O. It has been found that by reducing an aqueous molybdate (VI) solution with various reducing agents Can be obtained. [Non-Patent Document 1, Angewandte Chemie International Edition English 1995, 34, 2122]
In the mid-1990s, the MB solution was reduced by the Muller group to obtain a monocrystalline {Mo 154 } structure with a giant ring structure, and a new GMP structure was synthesized and applied. Such a GMP structure has a nanometer-sized space, for example, {Mo 132 } has a diameter of 2.7 nanometers and {Mo 154 } has a diameter of 3.7 nm. [Non-Patent Document 2] Angewandte Chemie International Edition English 1995, Nanometer size. {Mo 256 } is 5.7 nanometers in diameter and {Mo 368 } is 5.4 nanometers in diameter, similar to protein or virus size, providing important information as a model for their surface structure and characterization studies. It also has a high water solubility by forming large hydration walls due to the large amount of water present on the inner or outer surface of the GMP. In addition, since GMP can adsorb or support ions, organic or inorganic molecules in a large surface area and a nanometer-sized space, it can be applied to a field of catalyst, nanoreactor or nanosensor.
MP is a polyatomic ion mainly composed of anions, which is composed of three or more transition metal oxygen anions. These transition metal oxygen anions are connected to each other by oxygen atoms and have a large three-dimensional structure. Metal atoms mainly include a group V or VI transition metal, and have a high oxidation state. In this high oxidation state, the electron configuration is d 0 or d 1 . Examples of such metal atoms include vanadium (V), niobium (V), tantalum (V), molybdenum (VI), and tungsten (VI).
MP is largely divided into isopoly anion and heteropoly anion. The isopoly anion consists only of a transition metal and an oxide anion, and the heteropoly anion includes a heteroatom having a p or d orbital in the transition metal and an oxide anion. A typical example of a heteropoly anion is a phosphotungstate anion, in which the skeletal structure of a transition metal oxygen anion is surrounded by a heteroatom such as phosphorus or silicon and shares neighboring oxygen atoms.
In 1826, the first MP compound, ammonium phosphomolybdate ([PMo 12 O 40 ] 3- ), was found. In 1934, ammonium phosphomolybdate was found to have the same structure as the phosphotungstate anion, and this structure is called the Keggin structure. Since then, MPs with high symmetry and MPs containing organic / inorganic hybrid materials have been developed and their magnetic, optical and medical properties and application studies are known.
MP has several different basic skeletal structures, depending on the type of compound. The most well-known structure is the Keggin heteropoly anion ([X n + M 12 O 40 ] (8-n) - ) structure, which is very stable and easy to synthesize and spectroscopically confirmed. In the case of this Ketjen structure, molybdate or tungstate compounds are generally used, and tungsten or molybdenum atoms may be substituted with other transition metals, organometallic or organic groups. The Lindvvist structure is an isopolyoxy anion structure, and decabanadate, paratungstate, and molybdenum 36-polymolybdate structure is a heteropoly anion structure. The Kathryn and Dawson structures have a tetrahedral coordination structure centered on phosphorus or silicon atoms, while the Anderson structure has an octahedral coordination structure centered on aluminum atoms. In addition, several basic structures are known.
On the other hand, the metal atoms called "addenda atoms" are mainly molybdenum, tungsten, vanadium, and the like. When two or more metal atoms are included in the framework structure, they are referred to as 'mixed-adenide clusters'. The ligand (mainly oxide anion) coordinated to this metal atom forms a bridged skeleton structure with each other, and the oxide anion may be substituted with a sulfur, bromine atom, nitro, or alkoxy group. Typical components of the skeletal structure are the polyhedral units, which are the central metal with 4-7 coordination. These units share the edges or vertices of the entire skeletal structure. PO 4 , SiO 4 , AsO 4, etc.), 6 coordination (Anderson structure, octahedral, Al (OH) 6 , TeO 6 ), 8 coordination (square anti-prism, [(CeO 8 ) W 10 O 28 ] 8- ), 12 coordination (twentieth side, [(UO 12 ) Mo 12 O 30 ] 8- ) . Also interesting in the MP structure is that it generally has structural isomers. Keggin structures have five isomeric structures, four of which are rotated by 60 ° in the M 3 O 13 units.
The large size and structure of the MP described above represent various characteristics. The ability to provide water and organic solvents solubility, thermal stability, low toxicity, ability to provide electrons and oxygen transfer, strong absorption at ultraviolet-near-sight (<400 nm), structural retention during reduction, , Protons, metal cations, etc.). Especially, it is applied for catalysis and photocatalysis. [
GMP with various structures has been synthesized so far and its structure has been revealed. Due to various characteristics of GMP mentioned above, the application field of GMP is wide. In addition, the characteristics of GMP depend not only on the inherent three-dimensional super structure but also on the type and properties of the metal constituting the structure. Therefore, the development of a new GMP with a variety of metal atoms is of great interest, as it can improve the properties of existing MPs and potentially lead to completely new properties.
As a result of efforts to develop giant metal multi-oxide (GMP) having a new structure, the present inventors have found that cobalt (II), copper (II), iron (II) having novel structure of giant ring super structure having excellent antibacterial and deodorizing function ), Manganese (II), nickel (II), zinc (II) and palladium (II) giant molybdate-vanadate were synthesized and showed excellent antimicrobial and deodorizing properties when introduced into functional fibers or fabrics Thereby completing the present invention.
Accordingly, it is an object of the present invention to provide a giant metal multi-oxide (GMP) having a novel structure.
It is still another object of the present invention to provide a method for producing the giant metal multiple oxide (GMP).
It is still another object of the present invention to provide a method for producing a functional fiber or fabric using the giant metal multiple oxide (GMP).
Finally, it is another object of the present invention to provide functional fibers or fabrics comprising giant metal multioxide (GMP) in cationized fibers or fabrics and various applications using them.
In order to solve the above problems, the present invention provides a giant metal multi-oxide (GMP) represented by the following formula (1)
[Chemical Formula 1]
Na 8 X 12 Mo 72 V 32 S 12 O 388 H 112 · yH 2 O
(Wherein X is at least one metal selected from the group consisting of Co, Cu, Fe, Mn, Ni, Zn, and Pd, and y is a real number of 100 to 300 in terms of the number of water)
The present invention also provides a method for preparing a molybdenum-vanadium aqueous solution, comprising the steps of: (a) adding an aqueous solution of vanadyl sulfate hydrate to sodium molybdate hydrate under acidic conditions to prepare a molybdenum-vanadium aqueous solution; (b) adding a metal hydrate selected from the group consisting of cobalt hydrate, copper hydrate, iron hydrate, manganese hydrate, nickel hydrate, zinc hydrate and palladium compound to the molybdenum vanadium aqueous solution to prepare a composite metal solution; And (c) recovering crystals of the giant metal multi-oxide represented by Formula 1 produced by crystallizing the composite metal solution; (GMP), wherein the giant metal multi-oxide (GMP)
The present invention also relates to a method of making a fiber or fabric comprising: (a) cationizing a fiber or fabric; And (b) adding at least one selected from the giant metal multi-oxides represented by Formula 1 to the cationized fiber or fabric; And a method of producing the functional fiber or fabric.
The present invention also relates to a cationic fiber or fabric comprising at least one selected from the group consisting of the giant metal multiple oxides (GMP) represented by Formula 1 or a giant metal multiple oxide (GMP) and silver, copper, tin, zinc and palladium And at least one metal selected from the group consisting of the metals.
Finally, the present invention provides paper, clothes or quasi-drugs made using the functional fibers or fabrics.
The novel giant metal multi-oxide (GMP) according to the present invention exhibits excellent antibacterial and deodorant effect and can be utilized as a functional fiber or fabric having excellent antibacterial and deodorizing effect when it is introduced into a fiber or a fabric. Such functional fiber or textile products can be widely used as high value-added natural clothes or blend fibers or fabrics, and can be utilized as sterilizing and deodorizing clothes mainly by using as underwear, shoe insole, wallpaper and air filter. In addition, since it is a strong ionic bond rather than a mechanical adsorption method, when it is applied to a fiber or a fabric, its functionality does not deteriorate over time and the original characteristics of the fiber or the fabric are not changed at all. In particular, the novel giant metal multi-oxides of the present invention are characterized by their inherent color and their ability to dye fibers or fabrics without going through a separate dyeing step.
1 is a photograph of a solid crystal and an aqueous solution of zinc (II) molybdate-vanadate (Na 8 Zn 12 Mo 72 V 32 S 12 O 388 H 112 .yH 2 O).
2 is a Fourier transform infrared (FT-IR) spectroscopic spectrum of zinc (II) molybdate-vanadate (Na 8 Zn 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O).
3 is an ultraviolet-visible (UV-Vis) spectral spectrum of zinc (II) molybdate-vanadate (Na 8 Zn 12 Mo 72 V 32 S 12 O 388 H 112 .yH 2 O).
Fig. 4 is a photograph of Example 8 of the present invention for cellulosic fabrics prior to 1) treatment, 2) cationized cellulosic fabric, and 3) zinc (II) molybdate-vanadate added cellulose fabric.
5 is a scanning electron microscope (SEM) image of a cellulose fabric prior to 1) treatment, 2) a cationized cellulosic fabric, 3) a zinc (II) molybdate-vanadate- It is a photograph.
6 is an antibacterial test report for the functional fabric of the present invention.
7 is a deodorant test report for the functional fabric of the present invention.
The present invention provides a novel giant metal multiple oxide (GMP) and a method for producing the giant metal multiple oxide. The giant metal multi-oxide characterized by the present invention can be represented by the following formula (1).
[Chemical Formula 1]
Na 8 X 12 Mo 72 V 32 S 12 O 388 H 112 · yH 2 O
(Wherein X is at least one metal selected from the group consisting of Co, Cu, Fe, Mn, Ni, Zn, and Pd, and y is a real number of 100 to 300 in terms of the number of water)
The giant metal multi-oxide (GMP) of the present invention is a compound of a novel structure which has not been known until now and has excellent antimicrobial and deodorizing effect. Especially, it has an excellent effect on a house dust mite known as a cause of various dermatitis such as atopy.
The present invention also relates to a process for preparing the giant metal multi-oxide (GMP), comprising the steps of: (a) adding an aqueous vanadyl sulfate hydrate solution to sodium molybdate hydrate under acidic conditions to prepare a molybdenum-vanadium aqueous solution; (b) preparing a composite metal solution by adding at least one hydrate selected from the group consisting of cobalt hydrate, copper hydrate, iron hydrate, manganese hydrate, nickel hydrate, zinc hydrate and palladium hydrate to the molybdenum vanadium aqueous solution step; And (c) recovering crystals of the giant metal multi-oxide represented by
The metal hydrate used in the method for producing giant metal multiple oxides according to the present invention is a compound commonly used in the art, and the present invention does not have any particular limitation in its selection. The cobalt hydrate may be cobalt chloride hexahydrate (CoCl 2 .6H 2 O) or cobalt sulfate cobalt (CoSO 4 .7H 2 O). The copper hydrate may be copper chloride dihydrate (CuCl 2 .2H 2 O) or copper sulfate pentahydrate (CuSO 4 .5H 2 O). The iron hydrate may be iron chloride heptahydrate (FeCl 2 .4H 2 O) or iron sulfate heptahydrate (FeSO 4 .7H 2 O). The manganese hydrate may be manganese chloride tetrahydrate (MnCl 2 .4H 2 O) or manganese sulfate hydrate (MnSO 4 .H 2 O). The nickel hydrate may be nickel chloride hexahydrate (NiCl 2 .6H 2 O) or nickel sulfate hexahydrate (NiSO 4 .6H 2 O). The zinc hydrate may be zinc sulfate heptahydrate (ZnSO 4 .7H 2 O). The palladium hydrate may be palladium chloride (PdCl 2 ) or palladium sulfate (PdSO 4 ). The compound specifically exemplified above is merely an example of a readily obtainable component. In addition, any metal chloride flame or sulfate salt hydrate including Co, Cu, Fe, Mn, Ni, Zn and / or Pd The present invention is applicable to the present invention.
The above (a) preparation step is carried out under acidic conditions, generally at a pH of 1 to 3. In order to adjust the acidic conditions, the conditions can be satisfied by diluting the aqueous concentrated sulfuric acid solution (0.5 M).
The amount of the metal hydrate to be used in the step (b) is preferably 0.8 to 0.9 weight ratio based on the weight of the solid content of molybdenum-vanadium based on the solid content. The step (b) is carried out at a temperature of 20 ° C to 80 ° C, preferably 60 ° C to 80 ° C.
The crystallization method of the step (c) may be performed by a crystallization method commonly used in the art, for example, by allowing the solution prepared in the above step to stand at room temperature to recover and recover crystals . The present invention is not particularly limited as to such a crystallization method.
The present invention also relates to a method of making a fiber or fabric comprising: (a) cationizing a fiber or fabric; And (b) adding a giant metal multioxide to the cationized fiber or fabric; ≪ RTI ID = 0.0 > a < / RTI > functional fiber or fabric.
The present invention also relates to a method of manufacturing a functional fiber or fabric to which a giant metal multi-oxide is added, as a manufacturing step after the step (b), wherein at least one selected from the group consisting of silver, copper, tin, zinc and palladium The method may further include adding a salt of a functional metal. In this case, the functionality such as antibacterial and deodorization can be greatly improved.
The fibers used in the present invention include natural fibers, artificial fibers, or blend fibers thereof, and there is no particular limitation on the selection of the fibers of the present invention. Natural fibers include, for example, flax, ramie, mulberry, cotton, silk, wool, cashmere and the like. Examples of the synthetic fiber include cellulose, amide and the like. The fibers of step (a) are preferably anionized through pretreatment before cationization.
The cationization is an important chemical process required to produce the final functional fiber or fabric. In the present invention, the cationization of the present invention is a reversed multiple negative charge of the present invention which is the core of functionalization through cationization of the fiber with a stable cationic compound Giant metal multi-oxides were added in ion-bonded form through highly stable electrostatic interactions. The introduction of the giant metal oxides having a strong oxidizing power has made it possible to develop fibers or fabrics having excellent antibacterial and deodorizing effects. In addition, it shows excellent characteristics of removing house dust mite, mechanical stability (resistance to warping, resistance to shrinkage, increase in pressure persistence, etc.).
Further, in the present invention, by adding a salt of one or more metals selected from the group consisting of silver, copper, tin, zinc and palladium to the giant metal multiple oxide, the antibacterial and deodorizing effect of the functional fiber or fabric can be maximized .
In addition, the present invention can be applied to fibers or fabrics using the inherent dark color of the giant metal oxides, thereby providing antibacterial and deodorizing effects as well as multifunctional fibers capable of dyeing with antibacterial and deodorizing effects in one step Or to develop textiles.
The method for producing the functional fiber or fabric described above will be described in more detail as follows.
In order to impart functionality to the fiber or fabric, a step of cationizing the fiber or fabric is required. The cationization of the fibers or fabrics can be carried out using various cationic reagents. For example, cationic reagents such as 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHTAC) and 2-chloroethyldiethylamine hydrochloride (DEAECl.HCl) with stable cationic properties can be used. The cationization of fibers or fabrics using cationic reagents can also be carried out using various methods known in the art, such as the warming method (also referred to as exhaustion method) or the cold pad-batch method .
It is more preferable that the fiber or the fabric is subjected to anionization process before the cationization process because it is easy to introduce a cation. The anionization process can be easily carried out using various known methods.
Then, a functional fiber or fabric having strong ionic bonding can be produced by adding a giant metal multi-oxide (GMP) having anion to the cationized fiber produced in the present invention.
The present invention also provides a functional fiber or fabric comprising a giant metal multioxide (GMP) in said cationized fiber or fabric. The functional fiber or fabric is stably bonded to giant metal multi-oxide (GMP) through an ionic bond, and exhibits excellent deodorizing and antibacterial activity through its strong oxidative activity. In addition, it is possible to produce paper, clothes, etc. using the above-mentioned fibers or fabrics, and also to be used as quasi-drugs such as dressings and bands. Specifically, it can be used for various applications such as sterilization and deodorizing clothing by utilizing not only high value-added natural clothes or blend fibers or fabrics but also underwear, shoe insole, wallpaper, air filter and the like.
Hereinafter, the present invention will be described in detail in the following examples, but the scope of protection of the present invention is not limited to the following examples.
Example 1: Synthesis of cobalt (II) molybdate-vanadate (Na 8 Co 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O)
4.84 g of sodium molybdate dihydrate (Na 2 MoO 4 .2H 2 O) and 16 mL (0.5 M) of dilute sulfuric acid were placed in an Erlenmeyer flask, and 70 mL of 5.06 g of vanadyl sulfate aqueous solution was added thereto while stirring. At this time, the Erlenmeyer flask was closed with a stopper and stirred at room temperature for 30 minutes. The solution was dark purple. To this was added 4.15 g of cobalt hexahydrate (CoCl 2 .6H 2 O) and the mixture was stirred at room temperature or under heating for 30 minutes. The Erlenmeyer flask was kept at room temperature with the stopper plug closed to crystallize. After 5 days, the crystals were filtered, washed with cold water and dried in air to give 4.1 g of purple-black solid crystals (yield 82%).
Example 2: Synthesis of copper (II) molybdate-vanadate (Na 8 Cu 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O)
4.84 g of sodium molybdate dihydrate (Na 2 MoO 4 .2H 2 O) and 16 mL (0.5 M) of dilute sulfuric acid were placed in an Erlenmeyer flask, and 70 mL of 5.06 g of vanadyl sulfate aqueous solution was added thereto while stirring. At this time, the Erlenmeyer flask was closed with a stopper and stirred at room temperature for 30 minutes. The solution was dark purple. To this was added 3.0 g of copper dihydrate (CuCl 2 .2H 2 O) and the mixture was stirred at room temperature or under heating for 30 minutes. The Erlenmeyer flask was kept at room temperature with the stopper plug closed to crystallize. After 5 days, the crystals were filtered, washed with cold water and dried in air to obtain 3.9 g of a purple-black solid crystal (yield 78%).
Example 3: Synthesis of iron (II) molybdate-vanadate (Na 8 Fe 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O)
4.84 g of sodium molybdate dihydrate (Na 2 MoO 4 .2H 2 O) and 16 mL (0.5 M) of dilute sulfuric acid were placed in an Erlenmeyer flask, and 70 mL of 5.06 g of vanadyl sulfate aqueous solution was added thereto while stirring. At this time, the Erlenmeyer flask was closed with a stopper and stirred at room temperature for 30 minutes. The solution was dark purple. To this was added 3.47 g of iron oxide (FeCl 2 .4H 2 O) and the mixture was stirred at room temperature or under heating for 30 minutes. The Erlenmeyer flask was kept at room temperature with the stopper plug closed to crystallize. After 5 days, the crystals were filtered, washed with cold water and dried in air to obtain 4.0 g of a purple-black solid crystal (yield 80%).
Example 4: Synthesis of manganese (II) molybdate-vanadate (Na 8 Mn 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O)
4.84 g of sodium molybdate dihydrate (Na 2 MoO 4 .2H 2 O) and 16 mL (0.5 M) of dilute sulfuric acid were placed in an Erlenmeyer flask, and 70 mL of 5.06 g of vanadyl sulfate aqueous solution was added thereto while stirring. At this time, the Erlenmeyer flask was closed with a stopper and stirred at room temperature for 30 minutes. The solution was dark purple. 3.45 g of manganese heptahydrate (MnCl 2 .4H 2 O) was added thereto, and the mixture was stirred at room temperature or under heating for 30 minutes. The Erlenmeyer flask was kept at room temperature with the stopper plug closed to crystallize. After 5 days, the crystals were filtered, washed with cold water and dried in air to obtain 3.8 g of a purple-black solid crystal (yield 76%).
Example 5: Synthesis of nickel (II) molybdate-vanadate (Na 8 Ni 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O)
4.84 g of sodium molybdate dihydrate (Na 2 MoO 4 .2H 2 O) and 16 mL (0.5 M) of dilute sulfuric acid were placed in an Erlenmeyer flask, and 70 mL of 5.06 g of vanadyl sulfate aqueous solution was added thereto while stirring. At this time, the Erlenmeyer flask was closed with a stopper and stirred at room temperature for 30 minutes. The solution was dark purple. To this was added 4.15 g of nickel hexahydrate (NiCl 2 .6H 2 O) and the mixture was stirred at room temperature or under heating for 30 minutes. The Erlenmeyer flask was kept at room temperature with the stopper plug closed to crystallize. After 5 days, the crystals were filtered, washed with cold water and dried in air to obtain 3.7 g of a purple-black solid crystal (yield 74%).
Example 6: Synthesis of zinc (II) molybdate-vanadate (Na 8 Zn 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O)
4.84 g of sodium molybdate dihydrate (Na 2 MoO 4 .2H 2 O) and 16 mL (0.5 M) of dilute sulfuric acid were placed in an Erlenmeyer flask, and 70 mL of 5.06 g of vanadyl sulfate aqueous solution was added thereto while stirring. At this time, the Erlenmeyer flask was closed with a stopper and stirred at room temperature for 30 minutes. The solution was dark purple. 5.02 g of zinc sulfate heptahydrate (ZnSO 4 .7H 2 O) was added thereto, and the mixture was stirred at room temperature or under heating for 30 minutes. The Erlenmeyer flask was kept at room temperature with the stopper plug closed to crystallize. After 5 days, the crystals were filtered, washed with cold water and dried in air to obtain 4.2 g of a purple-black solid crystal (yield 84%).
A photograph of the zinc (II) molybdate-vanadate solid crystal and aqueous solution prepared in Example 6 is shown in FIG. In addition, Fourier transform infrared (FT-IR) spectroscopy of zinc (II) molybdate-vanadate (Na 8 Zn 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O) and ultraviolet- -Vis) spectral spectrum is shown in FIG. 2 and FIG.
Example 7: Synthesis of palladium (II) molybdate-vanadate (Na 8 Pd 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O)
4.84 g of sodium molybdate dihydrate (Na 2 MoO 4 .2H 2 O) and 16 mL (0.5 M) of dilute sulfuric acid were placed in an Erlenmeyer flask, and 70 mL of 5.06 g of vanadyl sulfate aqueous solution was added thereto while stirring. At this time, the Erlenmeyer flask was closed with a stopper and stirred at room temperature for 30 minutes. The solution was dark purple. 3.1 g of palladium (PdCl 2 ) was added thereto, and the mixture was stirred at room temperature or under heating for 30 minutes. The Erlenmeyer flask was kept at room temperature with the stopper plug closed to crystallize. After 5 days, the crystals were filtered, washed with cold water and dried in air to obtain 3.9 g of a purple-black solid crystal (yield 78%).
Example 8: Preparation of functional fabric
Step 1: The cationization step
40 g of cotton fabric was prepared for functional fabric production. In order to cationize the fabric, 40 g of sodium hydroxide, 96 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHTAC; product name CR2000, Dow) and 0.1 g of sodium roryl sulfate as anionic surfactant The solution was prepared by mixing. The prepared cotton fabric was soaked in 0.8 L of the prepared mixed solution. After 10 hours, the cationized cotton fabric was washed with water, washed with 4% acetic acid solution, again with water and dried in air at room temperature.
Step 2: Step of adding a giant metal multiple oxide
2-1) Addition of cobalt (II) molybdate-vanadate
To a solution of 2.5 g of cobalt (II) molybdate-vanadate (Na 8 Co 12 Mo 72 V 32 S 12 O 388 H 112 .yH 2 O) crystals in 0.5 L of water was added the cationized The cotton fabric was soaked and shook for 30 minutes. The fabric was then removed from the solution and rinsed with water to remove excess giant metal multiple oxides to obtain a functional fabric with cobalt (II) molybdate-vanadate bonded.
2-2) Copper (II) molybdate-vanadate
To a solution obtained by dissolving 2.5 g of copper (II) molybdate-vanadate (Na 8 Cu 12 Mo 72 V 32 S 12 O 388 H 112 .yH 2 O) crystals in 0.5 L of water was added the cationized The cotton fabric was soaked and shook for 30 minutes. The fabric was then removed from the solution and rinsed with water to remove excess giant metal multiple oxides to obtain a functional fabric with copper (II) molybdate-vanadate bonded thereto.
2-3) Addition of iron (II) molybdate-vanadate
To a solution of 2.5 g of iron (II) molybdate-vanadate (Na 8 Fe 12 Mo 72 V 32 S 12 O 388 H 112 .yH 2 O) crystals in 0.5 L of water was added the cationized The cotton fabric was soaked and shook for 30 minutes. The fabric was then removed from the solution and rinsed with water to remove excess giant metal multiple oxides to obtain a functional fabric with iron (II) molybdate-vanadate bonded.
2-4) Manganese (II) Molybdate-Vanadate
To a solution of 2.5 g of manganese (II) molybdate-vanadate (Na 8 Mn 12 Mo 72 V 32 S 12 O 388 H 112 .yH 2 O) crystals in 0.5 L of water was added the cationized The cotton fabric was soaked and shook for 30 minutes. The fabric was then removed from the solution and washed with water to remove excess giant metal multiple oxides to obtain a functional fabric with manganese (II) molybdate-vanadate bonded.
2-5) Addition of nickel (II) molybdate-vanadate
To a solution of 2.5 g of nickel (II) molybdate-vanadate (Na 8 Ni 12 Mo 72 V 32 S 12 O 388 H 112 .yH 2 O) crystals in 0.5 L of water was added the cationized The cotton fabric was soaked and shook for 30 minutes. The fabric was then removed from the solution and rinsed with water to remove excess giant metal multi-oxide, resulting in a functional fabric with nickel (II) molybdate-vanadate bonded.
2-6) Addition of zinc (II) molybdate-vanadate
To a solution of 2.5 g of zinc (II) molybdate-vanadate (Na 8 Zn 12 Mo 72 V 32 S 12 O 388 H 112 .yH 2 O) crystals in 0.5 L of water was added the cationized The cotton fabric was soaked and shook for 30 minutes. The fabric was then removed from the solution and rinsed with water to remove excess giant metal multiple oxides to obtain a functional fabric with zinc (II) molybdate-vanadate bonded.
2-7) Palladium (II) molybdate-vanadate
To the solution obtained by dissolving 2.5 g of the palladium (II) molybdate-vanadate (Na 8 Pd 12 Mo 72 V 32 S 12 O 388 H 112 .yH 2 O) crystal in 0.5 L of water was added the cationized The cotton fabric was soaked and shook for 30 minutes. The fabric was then removed from the solution and rinsed with water to remove excess giant metal multiple oxides to yield a functional fabric with palladium (II) molybdate-vanadate bonded.
FIG. 4 is a photograph of the fabric according to each step for manufacturing the functional fabric according to the eighth embodiment.
It was also confirmed stepwise by scanning electron microscopy (SEM) photograph whether the giant metal multi-oxide and metal salt were successfully adsorbed to the fiber or fabric. The scanning electron microscope of FIG. 5 confirmed that the giant metal multi-oxide (GMP) and the metal salt were successfully adsorbed on the fabric surface.
[Experimental Example]
Experimental Example 1: Confirmation of structure of giant metal multiple oxide (GMP)
In order to confirm the structure of the giant metal multi-oxide (GMP) of the present invention, the stretching or bending vibration energy of each functional group was confirmed by Fourier transform infrared spectroscopy, and each compound was confirmed by Fourier transform infrared (FT-IR) spectroscopy.
The measurement results are as follows.
1) Fourier Transform Infrared Spectroscopy (FT-IR): See Figure 2
Zinc (II) molybdate-vanadate (Na 8 Zn 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O):
1181 (w), 1100 (s ), 1053 (w) (SO 4), 959 (w) (V = O, Mo = O), 784 (vs), 691 (w), 615 (s) cm -1
2) ultraviolet-visible (UV-Vis / water) spectroscopy: see Figure 3
Zinc (II) molybdate-vanadate (Na 8 Zn 12 Mo 72 V 32 S 12 O 388 H 112 yH 2 O):
? = 511 (vs), 690 (w), 850 (w) nm
Experimental Example 2: Antibacterial effect of giant metal multiple oxide
In order to confirm the antimicrobial effect of the functionalized fabric treated with the giant metal oxides of the present invention, the experiment was commissioned to the Korea Clothing Testing Institute.
This experiment was performed in accordance with KS K 0693-2006. Staphylococcus aureus 6538 and pneumococci (Klebsiella pneumoniae ATCC 4352) were used as the isolates. Test groups and control specimens were inoculated and cultured as a control strain and then shaken in a certain amount of liquid to extract the cultured bacteria. When the number of bacteria present in the liquid was measured, the rate of bacterial reduction in the antimicrobial test group was calculated.
According to the test report of FIG. 6, it can be confirmed that the functional fabric of the present invention has a bacterial reduction rate of 99.9% or more.
Experimental Example 3: Effect of mite-fighting by a test tube method
At the other end, a test material (functional fabric of the present invention) and a attractant capable of attracting a tick were put together and sealed at the other end with the medium containing the tick in the one end with the test tube laid, . After 48 hours in the sealed state, the number of mites present in the test group was measured. These experimental results are shown in Table 1 below.
Test
As can be seen from the results shown in Table 1, the functional fabric of the present invention exhibited excellent mite avoidance rate of 99.9%. Accordingly, it can be seen that the functional fabric of the present invention inhibits the growth of house dust mite, which is a major cause of atopy, allergies, bronchial asthma, rhinitis, and the like, thereby blocking the root cause of various diseases.
Experimental Example 4: Deodorizing effect of giant metal multi-oxide
In order to confirm the deodorizing effect of the functional fabric treated with the giant metal multi-oxide of the present invention, the experiment was commissioned to the Korea Clothing Testing Institute.
In this experiment, the deodorizing effect was tested using ammonia gas by gas detection method. The initial concentration of ammonia was 500 ㎍ / mL. 30 minutes, 60 minutes, 90 minutes and 120 minutes, the deodorization rate was calculated by the following equation (1). The deodorization rates shown in the test report of FIG. 7 are summarized and shown in Table 2 below.
[Equation 1]
Claims (11)
[Chemical Formula 1]
Na 8 X 12 Mo 72 V 32 S 12 O 388 H 112 · yH 2 O
(Wherein X is a metal of Cu or Mn and y is a real number of 100 to 300 in terms of the number of water)
(b) adding a copper hydrate or manganese hydrate to the molybdenum vanadium aqueous solution and heating the molybdenum vanadium aqueous solution to a temperature of 60 ° C to 80 ° C to prepare a composite metal solution; And
(c) recovering crystals of the giant metal multi-oxide represented by the following formula (1) produced by crystallizing the composite metal solution;
≪ / RTI > wherein the giant metal multi-oxide is formed from a metal oxide.
[Chemical Formula 1]
Na 8 X 12 Mo 72 V 32 S 12 O 388 H 112 · yH 2 O
(Wherein X is a metal of Cu or Mn and y is a real number of 100 to 300 in terms of the number of water)
The copper hydrate is a copper chloride dihydrate (CuCl 2 .2H 2 O) or copper sulfate pentahydrate (CuSO 4 .5H 2 O)
Wherein the manganese hydrate is manganese chloride tetrahydrate (MnCl 2 .4H 2 O) or manganese sulfate hydrate (MnSO 4 .H 2 O).
(b) adding the giant metal multiple oxide of claim 1 to the cationized fiber or fabric;
≪ / RTI > characterized in that the functional fibers or fabrics are produced by a process comprising the steps of:
Characterized in that the cationization is carried out using a cationic reagent selected from the group consisting of 2-chloroethyldiethylamine hydrochloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and mixtures thereof. ≪ / RTI >
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Citations (2)
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| WO2004018655A2 (en) | 2002-08-26 | 2004-03-04 | Neuronova Ab | Method for culturing stem cells |
| KR101391987B1 (en) * | 2012-03-08 | 2014-05-07 | 국승원 | Manufacturing Method of Functionalized Fibers or Fabrics with Metal Polyoxides |
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| KR101124555B1 (en) | 2011-08-25 | 2012-06-12 | 국승원 | New Metal Polyoxides and Its Use in the Same Manufacturing Method of Functionalized Fibers or Fabricacturing Method of Functionalized Fibers or Fabrics |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004018655A2 (en) | 2002-08-26 | 2004-03-04 | Neuronova Ab | Method for culturing stem cells |
| KR101391987B1 (en) * | 2012-03-08 | 2014-05-07 | 국승원 | Manufacturing Method of Functionalized Fibers or Fabrics with Metal Polyoxides |
Non-Patent Citations (2)
| Title |
|---|
| ANGEW. CHEM. INT . ED. 2005, 44, 3857 -3861* |
| JOURNAL OF ENVIRONMENTAL SCIENCE AND ENGINEERING A 1 (2012) 956-966* |
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