CN1211525C - Bactericidal and for infrared radiation fabric or fibre and its preparation method - Google Patents

Abstract

The invention discloses a fabric or fiber with functions of sterilizing and inhibiting bacteria and far-infrared radiation and a manufacturing method thereof. It belongs to the fields of daily life, textiles and materials. This kind of fabric or fiber is composed of conventional fabric or fiber background and a film composed of particles with bactericidal and antibacterial functions and far-infrared radiation. The film is composed of oxides of titanium and oxides of transition metals, especially rare earth metals. The radio frequency magnetron reactive sputtering method is used to prepare a mixture of metal titanium and transition metals, especially rare earth metals, as a sputtering target on the fabric or fiber. Such fabrics have good medical and health effects.

Description

A kind of antibacterial and antibacterial and far-infrared radiation fabric or fiber and its preparation method

The invention relates to a fabric or fiber with bactericidal and antibacterial functions and far-infrared radiation functions and a preparation method thereof. This kind of fabric or fiber is composed of conventional fabric or fiber background and a film of particles with bactericidal and antibacterial and far-infrared radiation functions. The particle film is composed of oxides of titanium and oxides of transition metals, especially rare earth metals. composition. The particle film is prepared on a fabric or fibrous substrate using radio frequency reactive sputtering. The invention belongs to the fields of daily life, textiles and materials.

With the improvement of living standards and the development of the textile industry, people's requirements for clothing are getting higher and higher. From the past texture, color and pattern to today's health care function, people pay more and more attention to textiles with health care function after the lower level needs are met. Therefore, the development of fibers and fabrics with antibacterial and bactericidal functions Be more active.

After consulting and searching, the manufacturing methods of fabrics or fibers with bactericidal and antibacterial or far-infrared radiation functions mainly include the following:

The first category is to prepare antibacterial or fibers with far-infrared radiation functions, and then weave them into fabrics. One of these methods is to add or graft antibacterial agents or far-infrared ceramics into polymer slices, and obtain antibacterial or far-infrared radiation functional fibers through conventional spinning processes. Such as the method adopted in patent EP 360 962JP11 286 831 JP 11 189 919 DE 19 722 411 JP 03 227 408 JP 05 51 816CN1070438 to manufacture antibacterial fibers.

JP328396 CN1090353 US4999243 US5419855 CN1081475 Add far-infrared ceramic powder to the base material of synthetic fiber raw materials, and then make far-infrared health-care synthetic fiber according to conventional technology.

Also can use the fiber that itself has antibacterial property and conventional fiber to utilize general modern textile technology blending in addition, as CN1084911 any kind of fiber in cotton, fiber crops, wool, chemical fiber and stainless steel fiber, nickel fiber, copper fiber with antibacterial function Any fiber blended into antibacterial blended yarn. CN1261111 discloses an antibacterial fiber containing chitin and its derivatives, which has a strong inhibitory effect on bacteria such as Escherichia coli.

The second category is to directly arrange existing fabrics to obtain antibacterial or far-infrared fabrics. The bactericidal or antibacterial agent or far-infrared ceramics are attached to the surface of the fabric by means of impregnation, coating, electrochemical deposition or grafting, so that it has bactericidal and antibacterial or far-infrared radiation properties. Patent JP 03 85 181 JP09 327 622 JP 10 72 704 JP 11 293 559 JP 05 93 365 CN1014720 CN1041018US189499 CN1048846 CN1044964 CN1073734 CN10780 is the method of making the above-mentioned antibacterial fibers through 80. And CN1036084 is to have made the far-infrared fiber by the way of bonding.

As far as the types of bactericides or bacteriostatic agents are concerned, one is that the components with bactericidal or bacteriostatic functions are inorganic substances such as metals, metal ions or metal oxides, mainly silver-based, copper-based, titanium-based, etc. At this time, due to the different types of inorganic compounds selected, the fibers or fabrics obtained can have one or more of the above functions, and only have bactericidal and antibacterial effects. For example, the patent JP 11 189 919 introduces the production of silver-containing antibacterial fibers. method, the antibacterial rate is 99.9%, which can meet the hospital's requirements for antibacterial textiles. Patent JP 0 551 816 makes silver-containing antibacterial fiber. The biggest difference between this method and patent JP 11189919 is to have added liquid polyester. In the patent JP9 191 571, the hydrated phosphate containing silver or copper or plumbous or tin is used as an antibacterial agent, and the prepared product has a good inhibitory and killing effect on Gluconus xanthus. For example, CN1057872, which has a single effect of far-infrared radiation, relates to a secondary treatment method for increasing the far-infrared radiation function of fabrics. It coats the far-infrared ceramic paint mixed with far-infrared ceramic powder and binder on the fabric base material, which can make the coated fabric have a certain health care effect.

CN1085617 discloses a fabric coated with far-infrared radiating powder on the surface, which is formed by printing a paint composed of adhesive and far-infrared radiating powder on the fabric base material.

Another way is to use organic or macromolecular reagents with bactericidal or bacteriostatic properties, and the fibers or fabrics produced by this method basically do not have far-infrared radiation function. For example, the patent JP9194304 uses sulfur and phosphorus-containing heterocyclic compounds as active ingredients for sterilization. In fact, the preparation methods of using organic or polymer bactericides or bacteriostats are basically the same, the difference lies in the selected bactericides or bacteriostats.

In the above method, the method of preparing antibacterial or fibers with far-infrared radiation function and then weaving them into fabrics will cause some problems due to the need to add antibacterial agents or far-infrared ceramics in the polymer slices, such as adding organic antibacterial agents. Due to the high temperature melting during the spinning process, it will cause partial thermal decomposition and produce some degradation molecules. These degradation molecules will be slowly released during the wearing process, and the impact on the human body is unpredictable. The use of inorganic antibacterial agents will reduce the mechanical properties of the fibers due to the addition of inorganic particles, which will affect the normal operation of the equipment in production, cause problems such as parking, and increase the unit production cost; in addition, this type of fiber is spun into fabrics. After the garment is made, due to the mechanical defects of the fiber itself, it is easy to be damaged during wearing. For fibers with far-infrared radiation properties, the problem is the same as that of using inorganic antibacterial agents. Blending with fibers with antibacterial properties, if metal fibers are used, the weight of the fabric will be too heavy, and the wearing comfort will not be strong. At the same time, due to the high preparation cost of metal fibers with small diameters, the blending process requires modification of existing equipment. Production costs are higher. If the cost of using chitosan or chitin fiber is very high, only chitosan needs 150,000 yuan/ton. By dipping, coating, electrochemical deposition or grafting, etc., the bactericidal or bacteriostatic agent or far-infrared ceramics are attached to the surface of the fabric to make it have bactericidal and antibacterial or far-infrared radiation properties. The essence of the method is to finish the original fabric. The process of attaching bactericide or far-infrared ceramics is added in the process. No matter what kind of treatment agent is used, there are also serious environmental protection problems, especially the discharge of waste water. The bactericidal and antibacterial or far-infrared radiation performance of fabrics mainly depends on the degree of adhesion. Frequent friction will also lead to the disappearance or decline of performance. Poor air permeability and hard hand feeling are also the main problems.

The object of the present invention is to provide a fabric or fiber with bactericidal and antibacterial functions and far-infrared radiation function and its manufacturing method. This kind of fiber or fabric is prepared by magnetron reactive sputtering in vacuum technology. The particle film generated by sputtering contains not only oxides of titanium, but also oxides of rare earths or transition metals that can generate far-infrared rays. Therefore, It has the functions of bactericidal and antibacterial and far-infrared radiation. Compared with the technology mentioned above, the fabric or fiber with antibacterial and far-infrared radiation functions prepared by magnetron reactive sputtering has no reduction in fiber strength, good air permeability and hand feeling, and avoids the problem of wastewater treatment in finishing production. Low production cost. In addition, due to the simultaneous sputtering of titanium oxides and rare earth or transition metal oxides, there is a synergistic effect between the two, that is, the photocatalytic oxidation performance of rare earth or transition metal oxides on titanium oxides is The antibacterial or bactericidal performance is promoted, which can significantly improve the photocatalytic oxidation performance; and the titanium oxide can promote the far-infrared radiation performance of the rare earth or transition metal oxide, which can significantly improve the far-infrared radiation ability. The fiber or fabric prepared in this way can be widely used in sterile environments, and the far-infrared radiation performance of rare earth or transition metal oxides has certain health care and warming effects on the human body.

The invention will be further developed and illustrated by the following detailed description and illustrations.

The invention discloses a fabric or fiber with functions of sterilizing and inhibiting bacteria and far-infrared radiation and a manufacturing method thereof. This fiber or fabric consists of two layers, one layer being the fabric or fiber itself, which is the matrix of the particle film mentioned below. The fibers or fabrics referred to here can be natural fibers, such as cotton, hemp, wool, rabbit hair, etc., or synthetic fibers, such as acrylic, polyester, nylon, spandex, polypropylene, or artificial fibers, such as viscose. fiber. The other layer is a dense or porous film composed of particles with antibacterial and bactericidal functions or emitting far-infrared rays. This layer of particle film contains at least one component, namely titanium oxide, and transition metals, especially rare earths. Metal oxides, in transition metals, especially rare earth metals, selenium, tungsten, manganese, iron, cobalt, tellurium, antimony, nickel, copper, zinc, aluminum, zirconium, vanadium, barium, indium, tin, silver, niobium, Technetium, ruthenium, rhodium, palladium, rare earth metals (metal lanthanum La, metal cerium Ce, metal praseodymium Pr, metal neodymium Nd, metal samarium Sm, metal gadolinium Gd, yttrium, promethium, europium, terbium, dysprosium, holmium, erbium, thulium ) can be one of the components. In this layer of granular film, titanium oxide forms a film in the form of dense particles, and transition metals, especially rare earth metals, are doped in it. The ratio of the two mainly depends on the speed and ratio of coating. These particles are porous and have a particle size between 0.003-0.9 microns. The distance between the particles is between 0.001-1 micron, and there are irregular holes inside the particles, the diameter of which is between 0.1-100 nanometers.

In the present invention, the preparation of the particle film is accomplished by vacuum technology equipment, such as chemical vapor deposition, physical vapor deposition, electron beam evaporation, activation reaction evaporation, ion beam technology, ionized group beam (ICB) technology, direct current and alternating current Reactive magnetron sputtering, etc., especially reactive magnetron sputtering equipment, especially the reactive magnetron sputtering equipment that has been applied for a utility model to the State Intellectual Property Office and completed by the inventor. In the preparation process of reactive magnetron sputtering, when preparing the film, the fabric or fiber is on the other side of the sputtering target, which can be stationary or constantly moving, such as rotating, advancing, etc. Fabrics and fibers need to clean the oil on the surface before sputtering. The cleaning method can be a solution containing a surfactant or an organic solvent. The granular film prepared in this way has good antibacterial and bactericidal properties and far-infrared radiation properties. It has a good killing and inhibiting effect on Gram-positive bacteria and Gram-negative bacteria. At room temperature, due to the excitation of visible light, it can emit far-infrared rays with a wavelength of 8-25 μm, and the normal specific emissivity of far-infrared rays is 88- 90%. At the same time, it has good air permeability and moisture permeability.

The fabric or fiber of the present invention is produced by:

1. Cleaning: Soak the fabric with an organic solvent with a boiling point of 60-190°C or an aqueous solution containing anionic or nonionic surfactants for 5 minutes to 75 minutes, and its weight should be 0.5 to 10 times the weight of the fabric. Stir and wash with deionized water for more than or equal to three times, the amount of water used each time is 0.5 to 2.5 times the amount of solvent, and dry for 1-24 hours at a drying temperature of 120-180°C. The cleaning solution can be placed in a general container or in an ultrasonic cleaner, which has a better cleaning effect.

2. Sputtering: Send the cleaned and dried fabric into the sputtering reactor, fix the metal alloy or metal powder at an appropriate distance on the opposite side of the fabric, pass cooling water and working gas, first perform pre-sputtering, and then adjust to the working pressure sputtering film growth. Take it out after sputtering and it can be used for clothing manufacture.

(1) The sputtering conditions are: the target material is metal as the sputtering target, and one of the metals must be titanium. In the entire target material, the content of titanium should not be less than 30%, and the other metals are selenium and tungsten. , manganese, iron, cobalt, tellurium, antimony, nickel, copper, zinc, aluminum, zirconium, vanadium, barium, indium, tin, silver, niobium, technetium, ruthenium, rhodium, palladium, rare earth metals (metal lanthanum La, metal cerium Ce, metal praseodymium Pr, metal neodymium Nd, metal samarium Sm, metal gadolinium Gd, yttrium, promethium, europium, terbium, dysprosium, holmium, erbium, thulium) one or two kinds, the content of each of which is between 0 Between -70%. Such targets can exist in the form of alloys, can also be mixed together in the form of powders, and can also be single metal substances in which transition or rare earth metals are evenly and symmetrically placed on the titanium target. The thickness is 0.1-80mm. Make a circle, its size is the same as the base size of the fixed target, and its diameter is 2-50 centimeters.

(2) The power supply is a radio frequency power supply, the frequency is 13.56 MHz, the power acting on the target is 0.1-25W/cm ² , and the two electrodes are respectively connected to the target base and the fabric base.

(3) The pressure in the sputtering chamber is 0.0001~50Pa, and the sputtering time is 1~180min. The gas introduced during sputtering is He, Ne, Ar, Kr, O ₂ or a mixture of the above gases, and one of the components must be Oxygen, the content of which is between 0.05-95%, other gases account for the rest, which can be any combination of He, Ne, Ar, and Kr in any proportion.

(4). Two ways can be used in the sputtering process: 1) Always feed the above gas; 2) First feed one of the above pure or 2-4 mixed gases, adjust the pressure and start sputtering for 1-10 After 10 minutes, gradually change the amount of gas introduced, adjust the pressure in the reaction chamber (0.001~50Pa) to keep the glow discharge in the chamber, and continue the sputtering process. The adjustment of the above-mentioned pressure can be done by changing the amount of gas introduced, controlling and adjusting the pressure and power in the chamber, maintaining the glow discharge, and maintaining the best experimental parameters until the sputtering is completed.

(5) The gas flow control is between 1~1500sccm. Control instruments can use manual valves or mass flow controllers. Such as KF mass flow controller.

(6) When sputtering, pre-sputtering is required first. Insert a metal baffle between the two electrodes, perform pre-sputtering at a pressure of 0.001~50Pa, and a power per unit area of 0.1~25W, and clean the target surface for 1-20 minutes. To improve the purity and adhesion of the film, the baffle is then removed for sputtering. Both the base fabric and the target must be cooled with water during sputtering.

(7) The placement of the target and the fabric is as follows: the target surface and the fabric plane must be parallel, and the distance between them is 1-15 cm. This distance can be adjusted by rotating an external control knob during sputtering.

Example 1:

1 Cleaning Soak 100*100cm PET fabric in 500ml of acetone for 60 minutes, stir for 1 minute every 10 minutes, take it out, blow dry, repeat soaking 3 times, and then use 500ml deionized water to wash 3 times, soaking for 10 minutes each time, Stir for 1 minute and dry with hot air. Put it into an oven and dry it for 2 hours at a temperature of 120°C. Let cool and set aside.

2 The sputtering target is a circle with a diameter of 10 cm and a thickness of 2 mm. 99.9% titanium is evenly placed on top of which Zr accounts for 10% of the area of the titanium target. The power used is a radio frequency power supply with a frequency of 13.56 MHz, and the two electrodes are respectively connected to the target base and the fabric base. The distance between the target and the substrate was adjusted to be 6 cm, Ar was introduced during sputtering, and the mass flow rate of O ₂ (volume ratio: 10:1) was 20 sccm. Adjust the vacuum system so that the pressure in the sputtering chamber is 0.01Pa, insert a metal baffle between the two electrodes, perform pre-sputtering at a power per unit area of 1.5W, clean the target surface for 10 minutes, then remove the metal baffle, and adjust the vacuum chamber The pressure is 0.1Pa, the sputtering power per unit area is 1.5W, and the sputtering time is 40min. During the process, the above-mentioned mixed gas is always passed through.

The properties of the film-coated fabric prepared by sputtering are as follows: For the above-mentioned fabricated fabric, after fluorescent lamp irradiation at a height of one meter for two hours, to the representative strain Staphylococcus aureus of Gram-positive bacteria and Gram-negative bacteria, Escherichia coli (standard sample of Beijing Institute of Biological Products, concentration 900 million/ml) has good killing and inhibiting effect. The plaque diameter was 1.5 cm. The far-infrared emission wavelength range is 8-15 μm, and the normal specific emissivity of far-infrared rays is 88-90%. The microscopic morphology of the particle film is a rough multi-branched elongated particle structure with a diameter of less than 1 micron and holes with a diameter of about 50 nanometers.

Example 2:

1 Cleaning Soak 100*100cm PET fabric in 500ml acetone-ethanol mixed solvent (volume ratio 2:1) for 60 minutes, stir for 1 minute every 10 minutes, take it out and dry it, repeat soaking 3 times, and then use 500ml deionized Wash with water 3 times, soak for 10 minutes each time, stir for 1 minute, and dry with hot air. Put it into an oven and dry it for 2 hours at a temperature of 120°C. Let cool and set aside.

2 The sputtering target is a circle with a diameter of 10 cm and a thickness of 2 mm. A mixture of Zn and Ce (weight ratio 1:1) is evenly placed on top of 99.9% metal titanium, accounting for 10% of the titanium target area. The power used is a radio frequency power supply with a frequency of 13.56 MHz, and the two electrodes are respectively connected to the target base and the fabric base. The distance between the target and the substrate was adjusted to be 6 cm, Ar was introduced during sputtering, and the mass flow rate of O ₂ (volume ratio: 10:0.5) was 30 sccm. Adjust the vacuum system so that the pressure in the sputtering chamber is 0.01Pa, insert a metal baffle between the two electrodes, perform pre-sputtering at a power per unit area of 1.5W, clean the target surface for 10 minutes, then remove the metal baffle, and adjust the vacuum chamber The pressure is 0.1Pa, the sputtering power per unit area is 1.5W, and the sputtering time is 40min. During the process, the above-mentioned mixed gas is always passed through.

The properties of the film-coated fabric prepared by sputtering are as follows: For the above-mentioned fabricated fabric, after fluorescent lamp irradiation at a height of one meter for two hours, to the representative strain Staphylococcus aureus of Gram-positive bacteria and Gram-negative bacteria, Escherichia coli (standard sample of Beijing Institute of Biological Products, concentration 900 million/ml) has good killing and inhibiting effects. The diameter of the antibacterial plaque was 1.3 cm. The far-infrared emission wavelength range is 8-25 μm, and the normal specific emissivity of far-infrared rays is 90%. The microscopic morphology of the particle film is a rough multi-branched elongated particle structure with a diameter of less than 1 micron and holes with a diameter of about 50 nanometers.

Claims (10)

1. A method for preparing a fabric or fiber with bactericidal and antibacterial functions and far-infrared radiation, characterized in that it comprises the following steps: sending the cleaned and dried fabric or fiber into a sputtering reactor, fixing metal alloy or metal powder At an appropriate distance on the opposite side of the fabric, pass cooling water and a working gas whose component must be oxygen, first perform pre-sputtering, and then adjust to the working pressure for sputtering to form a film containing titanium oxide and transition metal oxide . 2. according to the described preparation method of claim 1, it is characterized in that: the fabric after said cleaning and drying here both can be that natural fiber, chemical synthetic fiber, man-made fiber are woven separately, also can be natural fiber, chemical synthesis Fiber, man-made fiber blended fabric. The fiber after cleaning and drying mentioned here both can be natural fiber, chemical synthetic fiber, also can be man-made fiber. 3. according to the described preparation method of claim 1, it is characterized in that: use metal as sputtering target, a kind of metal must be titanium, in the whole target material, the content of titanium should not be less than 30%, other metal Selenium, tungsten, manganese, iron, cobalt, tellurium, antimony, nickel, copper, zinc, aluminum, zirconium, vanadium, barium, indium, tin, silver, niobium, technetium, ruthenium, rhodium, palladium, metal lanthanum La, metal One or two of cerium Ce, metal praseodymium Pr, metal neodymium Nd, metal samarium Sm, metal gadolinium Gd, yttrium, promethium, europium, terbium, dysprosium, holmium, erbium, and thulium, the content of each of which is between 0 Between -70%. Such targets can exist in the form of alloys or mixed together in the form of powders, or metal powders or sheets of transition or rare earth metals placed uniformly and symmetrically on the titanium target, with a thickness of 0.1- 80mm. 4. The preparation method according to claim 1, characterized in that: the power source used during sputtering is a radio frequency power source with a frequency of 13.56 MHz and a power of 0.1-25 W/cm ² . 5. The preparation method according to claim 1, characterized in that: the pressure in the sputtering chamber is 0.0001-50Pa, and the sputtering time is 1-180min. 6. according to the described preparation method of claim 1, it is characterized in that: working gas is He, Ne, Ar, Kr, _O Or the mixed gas in the above-mentioned gas, wherein one component must be oxygen, and its content is between 0.05 -95%, other gases account for the rest, which can be any combination of He, Ne, Ar, Kr in any proportion. 7. According to the preparation method of claim 1, it is characterized in that: the working gas in claim 6 is always fed into the sputtering process, and the amount of the fed gas is changed by using a manual valve or a mass flow controller to control and adjust the amount of gas in the chamber. Pressure and power, maintain the glow discharge, maintain the pressure in claim 5, and the gas flow is between 1~1500sccm. 8. The preparation method according to claim 1, characterized in that: pre-sputtering is carried out before sputtering, that is, a metal baffle is inserted between the two electrodes, and the cleaning is performed at a pressure of 0.001~50Pa and a power per unit area of 0.1~25W Target surface 1-20 minutes. 9. according to the described preparation method of claim 1, it is characterized in that: during sputtering, the target surface in claim 3 and the fabric or fiber in claim 2 need to be parallel, and its spacing is 1-15 centimeters, and this distance can be in Rotate an external control knob to adjust during sputtering. 10. The fabric or fiber with bactericidal and antibacterial and far-infrared radiation functions prepared by the preparation method according to claim 1 is characterized in that: this fiber or fabric is made of two layers, and one layer is the fabric or fiber itself The other layer is a dense or porous film formed by particles with antibacterial and bactericidal functions or emitting far-infrared functions. This layer of particle film is produced according to the preparation method described in claim 1, that is, the sputtering process. Titanium oxide forms a film in the form of dense particles, and transition metals, especially rare earth metals, are doped in it. These particles are porous, with a particle size between 0.003-0.9 microns. The spacing is between 0.001-1 micron, and there are irregular holes inside the particles, with a diameter between 0.1-100 nanometers.