JP4058996B2 - Functional fiber and method for producing the same - Google Patents

Description

【００７７】
【表２】

【図面の簡単な説明】
【図１】図１は、本発明に用いられるプラズマ放電処理装置に設置されるプラズマ放電処理容器の一例を示す概略図である。
【図２】図２は、本発明に用いられるプラズマ放電処理装置に設置されるプラズマ放電処理容器の別の一例を示す概略図である。
【図３】図３（ａ）（ｂ）は、各々、本発明に用いられるプラズマ放電処理装置の円筒型のロール電極の一例を示す概略図である。
【図４】図４（ａ）（ｂ）は、各々、本発明に用いられるプラズマ放電処理装置の円筒型の固定電極の一例を示す概略図である。
【図５】図５（ａ）（ｂ）は、各々、本発明に用いられるプラズマ放電処理装置の角柱型の固定電極の一例を示す概略図である。
【図６】図６は、本発明に用いられるプラズマ放電処理装置の一例を示す概略図である。
【図７】図７は、本発明に用いられるプラズマ放電処理装置の別の一例を示す概略図である。
【図８】図８は、本発明に用いられるプラズマ放電処理装置の別の一例を示す概略図である。
【符号の説明】
２５、２５ｃ、２５Ｃ ・・・ロール電極
２６、２６ｃ、２６Ｃ、３６、３６ｃ、３６Ｃ、１０３、１０４ ・・・電極
２５ａ、２５Ａ、２６ａ、２６Ａ、３５ａ、３６ａ、３６Ａ
・・・金属等の導電性母材
２５ｂ、２６ｂ、３５ｂ、３６ｂ ・・・セラミック被覆処理誘電体
２５Ｂ、２６Ｂ、３６Ｂ ・・・ライニング処理誘電体
３１、１０２ ・・・プラズマ放電処理容器
４１、１０５ ・・・電源
５１ ・・・ガス発生装置
５２ ・・・給気口
５３ ・・・排気口
６０ ・・・電極冷却ユニット
６１ ・・・元巻き基材
６５、６６、１０７、１０８ ・・・ニップローラ
６４、６７ ・・・ガイドローラ
１００、Ｆ ・・・基材
１０６ ・・・アース
１１０ ・・・搬送ベルト
１１１ ・・・搬送台[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a functional fiber and a method for producing the same. More specifically, the present invention relates to a functional fiber having one or more functions of electromagnetic wave shielding properties, infrared shielding properties, ultraviolet shielding properties, conductivity, and water repellency, and a method for producing the same.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
In recent years, with the rapid spread of OA devices such as personal computers and word processors, and information communication devices such as mobile phones, the effects of electromagnetic waves generated from these electronic devices on the human body and medical treatments such as pacemakers embedded in the human body There is concern about malfunction of the equipment.
[0003]
In recent years, environmental problems such as global warming have attracted attention, and energy saving measures are important. As one of such energy saving measures, there is a measure to increase the air conditioning efficiency of the building. For example, a window that is an opening of a building transmits infrared rays from the outside in summer, lowering the cooling efficiency of the building, while absorbing the warm air in the building and releasing it as infrared rays in the winter, heating efficiency Will lower. On the other hand, in order to increase the cooling / heating efficiency, it is conceivable to cover the window with a textile product such as a curtain. In this case, it is more effective if an infrared shielding effect can be imparted to the textile.
[0004]
Furthermore, an increase in the amount of ultraviolet rays reached due to destruction of the ozone layer is a problem, and it is required to effectively avoid ultraviolet rays on a daily basis. For example, it is required to provide a hat, a parasol, clothes, and the like with an ultraviolet shielding effect that is greater than that inherent in the fibers constituting the hat.
In addition, in daily life, it is required to impart water repellency and antistatic functions to fibers or textiles.
[0005]
With regard to these, for example, in the case of imparting electromagnetic wave shielding properties to the fiber, the fiber (cloth) is plated with metal, sputtered, etc., and inserted between the materials constituting the clothing, or the fabric is attached to the outer surface of the clothing. It is known to do. In addition, when imparting infrared shielding properties or ultraviolet shielding properties to fibers or fiber products, a compound having a property of absorbing light of each wavelength is kneaded into the fiber itself, or the compound is added to the fibers or fiber products. A method of impregnating and applying a solution or a dispersion liquid is known. Also, the same method as described above is known for the purpose of imparting water repellency and preventing static electricity.
[0006]
However, when the fiber is treated by, for example, plating or sputtering, a metallic luster is generated on the fiber surface, and the hue of the base fabric is limited. Furthermore, since high temperature treatment is required, there is a problem that the properties and shapes of fibers that can be treated are limited.
In addition, the method of kneading the compound with the fiber also has a problem that it can be applied only to the synthetic fiber. In addition, since methods such as impregnation and coating use a solvent, there are problems of environmental burdens and limitations on target fibers.
[0007]
The present invention has been made in order to solve the above-mentioned problems of the prior art, and a functional fiber having functions such as electromagnetic wave shielding properties, infrared shielding properties, ultraviolet shielding properties, water repellency, and conductivity, and a method for producing the same. Is to provide.
[0008]
OBJECT OF THE INVENTION
An object of this invention is to provide the functional fiber which has functions, such as electromagnetic wave shielding, infrared shielding, ultraviolet shielding, electroconductivity, and water repellency, and its manufacturing method.
[0009]
SUMMARY OF THE INVENTION
The functional fiber according to the present invention is
Under a pressure at or near atmospheric pressure, a reactive gas is put into a plasma state by discharging between the opposing electrodes, and the reactive gas is exposed to the reactive gas in the plasma state by exposing the fiber to the reactive gas in the plasma state. Has a thin film layer formed in contact with each other.
[0010]
The functional fiber preferably has one or more functions of electromagnetic shielding properties, infrared shielding properties, ultraviolet shielding properties, conductivity, and water repellency.
The method for producing a functional fiber according to the present invention includes a reactive gas in a plasma state by discharging between opposing electrodes under atmospheric pressure or a pressure near atmospheric pressure, and the reactive gas in the plasma state. It is characterized in that a reactive gas is brought into contact with the fiber surface to form a thin film layer.
[0011]
In the method for producing a functional fiber according to the present invention, a high-frequency voltage exceeding 100 kHz is provided between the opposing electrodes, and 1 W / cm. ² It is preferable to form a thin film layer by bringing the reactive power into contact with the fiber surface by supplying the above electric power to discharge, bringing the reactive gas into a plasma state, and exposing the fiber to the plasma-like reactive gas. .
[0012]
In the present invention, the high-frequency voltage is preferably a continuous sine wave.
In the method for producing a functional fiber according to the present invention, the fiber is a long fiber, the long fiber is transported between the electrodes, and the reactive gas is the electrode. It is preferable that a reactive gas is brought into contact with the surface of the long fiber to form a thin film layer by being introduced in between.
[0013]
The fibers are preferably transported between the electrodes in a state of being placed on a transport table.
It is desirable that the transfer table also serves as one of the opposing electrodes.
Further, in the method for producing a functional fiber according to the present invention, a reactive gas in a plasma state is blown between the slit-shaped or cylindrical electrodes on the fiber to thereby cause the fiber to react with the plasma-like reactive gas. It is also desirable to be exposed to
[0014]
In the method for producing a functional fiber according to the present invention, by using a metal-containing reactive gas as the reactive gas, the fiber has any one of electromagnetic shielding properties, infrared shielding properties, ultraviolet shielding properties, and electrical conductivity. It is preferable to provide one or more functions.
In the method for producing a functional fiber according to the present invention, it is preferable to impart water repellency to the fiber by using an organic fluorine compound-containing reactive gas as the reactive gas.
[0015]
In the method for producing a functional fiber according to the present invention, the fiber is continuously given any two or more functions of electromagnetic wave shielding property, infrared ray shielding property, ultraviolet ray shielding property, conductivity, and water repellency. Is also desirable.
In the method for producing a functional fiber according to the present invention, a mixed gas containing the reactive gas and an inert gas between the electrodes, the inert gas being contained in an amount of 90 to 99.99% by volume. It is preferable to introduce a mixed gas.
[0016]
The metal-containing reactive gas preferably contains an organometallic compound. The organometallic compound is preferably selected from metal alkoxides, alkylated metals, and metal complexes.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described.
The functional fiber according to the present invention causes a reactive gas to be in a plasma state by discharging between opposing electrodes under atmospheric pressure or a pressure near atmospheric pressure, and exposes the fiber to the reactive gas in the plasma state. Is characterized in that it has a thin film layer formed by contacting a reactive gas on the fiber surface. Here, the thin film layer may be uniformly formed on the entire fiber surface, or may be intermittently formed on the fiber surface. In order to maintain various functions described later at a high level with high durability. Is preferably the former.
[0018]
In the present invention, by forming a specific thin film layer on the fiber surface in this way, functions such as electromagnetic wave shielding properties, infrared shielding properties, ultraviolet shielding properties, electrical conductivity, water repellency, etc. can be imparted to the fibers. In addition, since the method for imparting these functions is performed under atmospheric pressure or a pressure in the vicinity of atmospheric pressure, and processing at a low temperature is possible at that time, the fiber material used in the present invention is not limited. .
[0019]
That is, the fiber used in the present invention is not particularly limited, and any of artificial fibers and natural fibers can be used.
Specifically, for example, regenerated fibers such as rayon and copper ammonia rayon;
Synthetic fibers such as acrylic, nylon, polyester, vinylon, polyvinyl chloride, polypropylene, polyethylene, polyurethane, fluorine fiber, acetate;
Animal and plant fibers such as silk, wool, cotton and hemp; inorganic fibers such as glass fiber, carbon fiber, metal fiber and ceramic fiber;
[0020]
Moreover, as a form of the fiber used for this invention, what was processed into the form of the twisted yarn which twisted the said various fibers into the thread form, the woven fabric, the knitted fabric, and the nonwoven fabric (henceforth also called a fabric). Furthermore, what processed these in the elongate shape etc. are mentioned preferably.
Furthermore, in the present invention, since it is possible to process a three-dimensional object by devising the shape of the processing apparatus, the fiber is a textile product such as a three-dimensional shape clothing or clothing in which a cloth is processed such as sewing. It may be.
[0021]
Next, the plasma discharge processing apparatus used in the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view showing an example of a plasma discharge treatment container of a plasma discharge treatment apparatus suitable for imparting a function to a long fiber. In this plasma discharge processing container, an example is shown in which a roll electrode also serving as a transport roll (transport table) and a counter electrode are formed.
[0022]
In this way, it is preferable that the transfer table also serves as one of the counter electrodes, because the apparatus can be simplified and improved in efficiency.
In FIG. 1, a discharge is caused between a roll electrode 25 that is an earth electrode and a fixed electrode 26 that is an application electrode disposed at an opposite position under a pressure at or near atmospheric pressure, and a reaction occurs between the electrodes. A reactive gas is introduced into the plasma state and exposed to the reactive gas in the plasma state by exposing a long fiber wound around the roll electrode 25, such as a twisted yarn or a fabric, to the surface of the fiber. Functionality is imparted to the fiber by contacting the gas to form a thin film layer.
[0023]
In addition, although the atmospheric pressure vicinity means the pressure of 100 hPa-1500 hPa here, in order to acquire the effect as described in this invention preferably, it is preferable that it is the range of 850 hPa-1150 hPa.
In FIG. 1, a long fiber (hereinafter also simply referred to as a substrate) F is conveyed while being wound around a roll electrode 25 that rotates in a conveying direction (clockwise in the figure). The fixed electrode 26 is composed of a plurality of cylinders, and is installed facing the roll electrode 25. The substrate F wound around the roll electrode 25 is pressed by the nip rollers 65 and 66, regulated by the guide roller 64, transported to the discharge treatment space secured by the plasma discharge treatment vessel 31, subjected to discharge plasma treatment, and then Then, it is conveyed to the next process via the guide roller 67. Further, the partition plate 54 is disposed in the vicinity of the nip rollers 65 and 66 to suppress the air accompanying the base material F from entering the plasma discharge processing container 31.
[0024]
The air entrained at this time is preferably suppressed to 1% by volume or less, more preferably 0.1% by volume or less, with respect to the total volume of the gas in the plasma discharge treatment vessel 31. This can be achieved by the nip rollers 65 and 66.
A mixed gas (an organic gas containing an inert gas and a reactive gas) used for the discharge plasma treatment is introduced into the plasma discharge treatment vessel 31 from the air supply port 52, and the treated gas is introduced from the exhaust port 53. Exhausted.
[0025]
FIG. 2 shows an example in which the cylindrical counter electrode 26 of FIG. 1 is changed to a prismatic type. Since the prismatic electrode 36 has the effect of extending the discharge range, it is preferably used in the present invention.
In the present invention, the discharge electric field is a high frequency voltage exceeding 100 kHz between the opposing electrodes, and 1 W / cm. ² It is preferable to supply the above power. The upper limit of the frequency of the high frequency voltage applied between the electrodes is preferably 150 MHz or less. In addition, the lower limit value of the frequency of the high-frequency voltage is usually desirably more than 100 kHz, preferably 200 kHz or more, more preferably 800 kHz or more.
[0026]
Moreover, the lower limit value of the power supplied between the electrodes is usually 1 W / cm. ² Or more, preferably 1.2 W / cm ² The upper limit is preferably 50 W / cm. ² Or less, more preferably 20 W / cm ² The following is desirable. Here, the voltage application area at the electrode (/ cm ² ) Means an area in a range where discharge occurs.
[0027]
A dense thin film layer can be formed along the fine structure of the fiber surface by applying such an electric field to bring the reactive gas into a plasma state and processing the long fibers. Further, it is possible to impart functions to long fibers with high production efficiency.
The high-frequency voltage applied between the electrodes may be an intermittent pulse wave or a continuous sine wave. However, in order to obtain the effect of the present invention, a continuous sine wave is sufficient. Preferably there is.
[0028]
The electrode used in the plasma discharge treatment apparatus is preferably a metal base material coated with a dielectric. It is desirable to coat a dielectric on at least one side of the opposed application electrode and the ground electrode, and more preferably coat both the opposed application electrode and the ground electrode with a dielectric. The dielectric is preferably an inorganic material having a relative dielectric constant of 6 to 45. Examples of such a dielectric include ceramics such as alumina and silicon nitride, or glass such as silicate glass and borate glass. A lining material is preferred.
[0029]
In addition, when the substrate is placed between the electrodes or transported between the electrodes and exposed to plasma, not only the roll electrode specification that allows the substrate to be transported in contact with one electrode, but also the dielectric surface is polished. By finishing and making the surface roughness Rmax (JIS B0601) of the electrode 10 μm or less, the thickness of the dielectric and the gap between the electrodes can be kept constant, and the discharge state can be stabilized. Furthermore, the durability of the electrode can be greatly improved by covering a high-precision inorganic dielectric that is not porous and eliminates distortion and cracking due to thermal shrinkage differences and residual stress.
[0030]
In addition, when manufacturing electrodes with a dielectric coating on a metal base at high temperatures, at least the dielectric on the side in contact with the substrate should be polished and the difference in thermal expansion between the metal base and dielectric of the electrode It is preferable to make it as small as possible. Therefore, when manufacturing the electrode, as a layer capable of absorbing stress on the surface of the base material, lining the inorganic material by controlling the amount of bubbles mixed in, preferably by a melting method known as cocoon as the material By using the obtained glass, the amount of bubbles mixed in the lowermost layer in contact with the conductive metal base material is set to 20 to 30% by volume, and the subsequent layer and the subsequent layers are set to 5% by volume or less. Electrodes can be manufactured.
[0031]
As another method for coating the base material of the electrode with a dielectric, ceramic spraying is performed so that the porosity is 10% by volume or less, and further, a sealing treatment is performed with an inorganic material that is cured by a sol-gel reaction. Is preferred. Here, in order to promote the sol-gel reaction, heat curing or UV curing is preferable. Further, when the sealing liquid is diluted and coating and curing are repeated several times in succession, the mineralization is further improved, and there is no deterioration. An electrode is obtained.
[0032]
3A and 3B are schematic views showing examples of the above-described cylindrical roll electrodes, and FIGS. 4A and 4B are examples of electrodes fixed in a cylindrical shape. FIG. 5A and FIG. 5B are schematic views each showing an example of an electrode fixed in a prismatic shape.
3 (a) and 3 (b), a roll electrode 25c, which is a ground electrode, is a ceramic coating process in which ceramic is thermally sprayed on a conductive base material 25a such as metal and then sealed with an inorganic material. It is comprised by the combination which coat | covered the dielectric material 25b. A ceramic-coated dielectric is coated with 1 mm of a single piece, manufactured to have a roll diameter of 200 mm after coating, and grounded to ground. Or you may comprise with the roll electrode 25C of the combination which coat | covered the lining process dielectric material 25B which provided the inorganic material by lining to the electroconductive base materials 25A, such as a metal. As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass and the like are preferably used. Of these, borate glass is more preferred because it is easy to process. Examples of the conductive base materials 25a and 25A such as metals include metals such as silver, platinum, stainless steel, aluminum, and iron. Stainless steel is preferable from the viewpoint of processing. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is more preferable because it is easily processed. In the present embodiment, the base material of the roll electrode is a stainless jacket roll base material having a cooling means using cooling water (not shown).
[0033]
4 (a), 4 (b), 5 (a), and 5 (b) show a fixed electrode 26c, an electrode 26C, an electrode 36c, and an electrode 36C as application electrodes, and the roll electrode 25c and the roll electrode described above. It is configured in the same combination as 25C. That is, a hollow stainless steel pipe is covered with the same dielectric as described above, and can be cooled with cooling water during discharge. In addition, it manufactured so that it might become (phi) 12mm or (phi) 15mm after the coating | cover of a ceramic coating process dielectric material, and the 14 said electrodes are installed along the periphery of the said roll electrode.
[0034]
The power source for applying a voltage to the application electrode is not particularly limited, but a high frequency power source (200 kHz) manufactured by Pearl Industry, a high frequency power source (800 kHz) manufactured by Pearl Industry, a high frequency power source manufactured by JEOL (13.56 MHz), and a high frequency power source manufactured by Pearl Industry. (150 MHz) can be used.
FIG. 6 is a conceptual diagram showing an example of a plasma discharge treatment apparatus used in the present invention. In FIG. 6, the portion of the plasma discharge processing vessel 31 is the same as that shown in FIG. 2, but a gas generator 51, a power source 41, an electrode cooling unit 60, and the like are further arranged as the device configuration. As a coolant for the electrode cooling unit 60, an insulating material such as distilled water or oil is used.
[0035]
The electrodes 25 and 36 shown in FIG. 6 are the same as those shown in FIGS. 3, 4, 5, etc., and the gap between the opposing electrodes is set to about 1 mm, for example.
The distance between the electrodes is determined in consideration of the thickness of the solid dielectric placed on the base material of the electrodes, the magnitude of the applied voltage, the purpose of using plasma, and the like. The shortest distance between the solid dielectric and the electrode when a solid dielectric is placed on one of the electrodes, and the distance between the solid dielectrics when a solid dielectric is placed on both of the electrodes is uniform in any case From the viewpoint of discharging, a range of 0.5 mm to 20 mm is preferable, and a range of 0.5 mm to 1.5 mm is particularly preferable.
[0036]
A roll electrode 25 and a fixed electrode 36 are arranged in a predetermined position in the plasma discharge processing container 31, and the mixed gas generated by the gas generator 51 is controlled in flow rate, and the plasma discharge processing container is supplied from the air supply port 52. The plasma discharge treatment vessel 31 is filled with a mixed gas used for the plasma treatment and exhausted from the exhaust port 53.
Next, a voltage is applied to the electrode 36 by the power source 41, and the roll electrode 25 is grounded to the ground to generate discharge plasma. Here, the base material F is supplied from the roll-shaped original winding base material 61, and the electrodes in the plasma discharge treatment vessel 31 are in a single-sided contact state (in contact with the roll electrode 25) via the guide roller 64. The substrate F is subjected to a discharge treatment by discharge plasma during conveyance, and then conveyed to the next step via the guide roller 67. Here, the substrate F is subjected to discharge treatment only on the surface not in contact with the roll electrode 25.
[0037]
The value of the voltage applied to the electrode 36 fixed from the power supply 41 is determined as appropriate. For example, the voltage is about 0.5 to 10 kV, and the power supply frequency is adjusted to more than 100 kHz and 150 MHz or less. As for the method of applying power, either a continuous sine wave continuous oscillation mode called a continuous mode or an intermittent oscillation mode called ON / OFF intermittently called a pulse mode may be adopted, but the continuous mode is better. A denser and better quality film can be obtained.
[0038]
The plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (R) glass or the like, but may be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and ceramic spraying may be performed on the metal frame to achieve insulation.
[0039]
Moreover, in order to suppress the influence on the base material at the time of discharge plasma processing to the minimum, the temperature of the base material at the time of discharge plasma processing is normal temperature (here, normal temperature means 15 to 25 degreeC)-. It is preferable to adjust to a temperature of less than 200 ° C, and more preferably to adjust in the range of room temperature to 100 ° C. In order to adjust to the above temperature range, the discharge plasma treatment may be performed while cooling the electrode and the substrate with a cooling means as necessary.
[0040]
FIG. 7 shows another example of the plasma discharge treatment apparatus, which is suitable for imparting functions to long fibers, particularly twisted yarns. When plasma discharge treatment is performed on a thin base material such as a twisted yarn, it is desirable that the entire surface be uniformly treated regardless of the front and back surfaces in consideration of subsequent processing. For this reason, in this case, with respect to the transport of the base material during the plasma discharge treatment, a transport means that does not bring the base material into close contact with a transport base or the like is preferable. For example, in the plasma discharge processing apparatus of FIG. 7, the substrate (twisted yarn) 100 is provided before and after the counter electrode when performing plasma discharge processing through the electrodes 103 and 104 facing each other in the processing unit 102. By gripping the base material with the nip rolls 107 and 108, the base material is not in close contact with the transport table or the like during the plasma discharge treatment. In FIG. 7, the power source 105 is connected to one of the electrodes 103 and 104, and the electrode 104 is grounded by a ground 106. The electrode 104 may also serve as a transport table. In FIG. 7, flat electrodes are used as the electrodes 103 and 104, but one or both electrodes may be a cylindrical electrode, a prismatic electrode, a roll electrode, a dome electrode, or the like.
[0041]
FIG. 8 shows another example of the plasma discharge treatment apparatus, which is suitable for imparting a function to a three-dimensional textile product such as clothing or clothing in which a cloth is processed such as sewing. That is, when a thin film layer is formed on the surface of a base material such as a three-dimensional fiber product that cannot be placed between electrodes, a reactive gas that has been preliminarily made into a plasma state is sprayed onto the surface of the base material to form the thin film layer Is.
[0042]
In the plasma discharge processing apparatus of FIG. 8, 100 is a base material, 35a is a dielectric, 35b is a metal base material, and 105 is a power source. The mixed gas is introduced from above into a slit-like discharge space provided between plate-like electrodes in which a metal base material 35 b is coated with a dielectric 35 a, and a high frequency voltage is applied by a power source 105, thereby causing the reaction. A thin film layer is formed on the surface of the base material 100 by making the reactive gas into a plasma state and injecting the reactive gas in the plasma state onto the surface of the base material 100. In this case, a transport base 111 is placed on a transport belt 110 such as a belt conveyor or a roller conveyor, and a thin film layer is continuously formed on the base material 100 while the base material 100 is transported on the transport base. Can be made. This device is particularly effective when, for example, an ultraviolet shielding function is imparted to a three-dimensional sewing product such as a hat.
[0043]
Moreover, the discharge space provided between electrodes can also be made into cylindrical shape as another aspect of the apparatus of the said FIG.
The discharge electrode used in the present invention is preferably adjusted so that the maximum height (Rmax) of the surface roughness defined by JIS B0601 of the electrode is 10 μm or less, more preferably Rmax. Is 8 μm or less, and more preferably 7 μm or less. Further, the center line average surface roughness (Ra) defined by JIS B0601 of the electrode is preferably 0.5 μm or less, more preferably 0.1 μm or less.
[0044]
Next, the mixed gas used in the present invention will be described.
In producing the functional fiber according to the present invention using the plasma discharge treatment apparatus described above, the gas used is preferably a mixed gas containing an inert gas and a reactive gas for imparting a function. Can be mentioned.
Examples of the inert gas include Group 18 elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. In order to obtain the effects described in the present invention, helium Argon is preferably used.
[0045]
Such an inert gas is preferably contained in the mixed gas in an amount of 90 to 99.99% by volume, more preferably 95 to 99.9% by volume, when the total mixed gas is 100% by volume. It is desirable to make it contain in the quantity.
Since the reactive gas varies depending on the function to be imparted to the fiber, that is, the thin film layer formed on the fiber surface, they will be described in more detail below.
[0046]
<Electromagnetic wave shielding, conductivity>
(Electromagnetic wave shielding)
In order to impart electromagnetic shielding properties to the fiber, it is preferable to provide a thin film layer on the fiber surface that lowers the surface specific resistance of the fiber. Specifically, the surface resistivity value of the fiber after providing the thin film layer is preferably 1 × 10Ω or less, but the electromagnetic wave shielding property cannot be accurately evaluated only with such a surface resistivity value. .
[0047]
Therefore, it is necessary to evaluate the electromagnetic wave shielding property by another more appropriate method. Here, as an electromagnetic wave shielding evaluation method, the “KEC method” by the Kansai Electronics Industry Promotion Center (KEC) is generally known. In this KEC method, an electromagnetic wave having a specific frequency is transmitted in a shield box, and an electric field and a magnetic field passing through the sample are received on the other side, and the electromagnetic wave shielding effect is expressed by an attenuation rate (dB) by passing through the sample obtained according to the following equation. The greater the attenuation factor, the higher the electromagnetic wave shielding effect. If the electric field is about 20 dB or more and the magnetic field is about 10 dB or more, it can be said that there is an effect of shielding electromagnetic waves generated from OA equipment or the like.
[0048]
Attenuation rate (dB) = 20 log (Ei / Et) (1)
Ei: Incident electric field strength [V / m] (incident magnetic field strength [G] in the case of a magnetic field)
Et: Conducted electric field strength [V / m] (in the case of magnetic field, conducted magnetic field strength [G])
(Conductivity, antistatic)
When imparting electrical conductivity to the fiber, it is preferable to provide a thin film layer on the fiber surface that lowers the surface specific resistance of the fiber. Specifically, the surface specific resistance value of the fiber after providing the thin film layer is 1 × 10. ¹¹ It is preferable to set it to Ω or less. When the antistatic function is imparted to the fiber, the surface specific resistance value is 1 × 10 ¹¹ Ω ～ 1 × 10 ¹³ It may be in the range of Ω.
[0049]
In order to give the fiber such a function, it is effective to provide a thin film layer composed of various metal-containing layers on the fiber surface. As such a metal-containing layer, specifically, for example, metal such as chromium, aluminum, copper, gold, silver, nickel, iron, indium, titanium, zinc oxide, tin oxide, indium oxide, titanium oxide, A layer mainly containing a metal oxide such as bismuth oxide, tantalum oxide, tungsten oxide, or zinc oxide can be given. These may be one kind, or two or more kinds may be appropriately mixed. For example, an indium tin oxide conductive film (indium oxide conductive film doped with tin, ITO), a tin oxide conductive film doped with antimony or fluorine (ATO), AZO in which zinc oxide is doped with aluminum, and the like are good electromagnetic waves. Provides shielding.
[0050]
Moreover, these metal content layers can also be laminated | stacked suitably. For example, titanium nitride film / ITO film / titanium nitride film, titanium oxide film / silver film / titanium oxide film, zinc oxide film / silver film / zinc oxide film, tin oxide film / silver film / tin oxide film, etc. 5 layer types such as titanium oxide film / silver film / titanium oxide film / silver film / titanium oxide film, zinc oxide film / silver film / zinc oxide film / silver film / zinc oxide film, and other configurations may be mentioned as appropriate. it can.
[0051]
<Infrared shielding>
In order to impart infrared shielding properties to the fiber, it is desirable to set the transmittance of light of 700 nm or more to 20% or less. In particular, the transmittance of light of 1200 nm or more is preferably 20% or less. In this case, the thin film layer formed on the fiber surface may absorb or reflect light. In order to impart such a function to the fiber, it is preferable to form a thin film layer composed of the following metal-containing layer on the fiber surface. Examples of the metal-containing layer include those formed of aluminum, copper, gold, silver, chromium, nickel, indium, palladium, tin, alloys thereof, or oxides. These are not limited to a single layer but may be a multilayer. Specifically, for example, a metal oxide containing indium oxide and / or tin oxide as a main component is particularly suitable because it has a capability of absorbing infrared light in a wavelength region longer than 1200 nm with high efficiency. The thickness of the metal-containing layer is 30 to 600 mm, preferably 50 to 300 mm.
[0052]
<Ultraviolet shielding>
In order to impart ultraviolet shielding properties to the fiber, it is preferable to set the light transmittance of 460 nm or less to 20% or less. In particular, the transmittance of light of 400 nm or less is preferably 20% or less. In this case, the thin film layer formed on the fiber surface may absorb or reflect light. In order to impart such a function to the fiber, it is preferable to form a thin film layer composed of the following metal-containing layer on the fiber surface. Examples of the metal-containing layer include, as main components, metals such as silicon, titanium, vanadium, chromium, manganese, iron, cobalt, gallium, germanium, zirconium, nickel, silver, gold, copper, indium, tin, hafnium, and palladium. Layer, zinc oxide, lanthanum oxide, cerium oxide, iron oxide, cobalt oxide, nickel oxide, titanium oxide, aluminum oxide, silicon oxide, potassium titanate, barium titanate, barium oxide, barium sulfate, zirconium dioxide, stannic acid A layer made of a metal oxide such as cadmium can be given. Of these, titanium dioxide and zinc oxide are preferably used. Moreover, ITO, ATO, etc. can also be used suitably.
[0053]
It is preferable to attach the metal-containing layer to the fiber surface with a film thickness of 100 mm or more because the light having a wavelength of 250 to 400 nm in the ultraviolet region is well reflected. However, when the film thickness is 2000 mm or more, the texture of the functional fiber may become slightly hard. As the reactive gas used for imparting the above functions to the fiber, it is preferable to use a reactive gas containing a hydride, halide, or organometallic compound of various metals described above. In addition, as an organometallic compound, a metal alkoxide, an alkylated metal, and a metal complex are mentioned preferably.
[0054]
Specific examples of the various metal hydrides, halides, and organometallic compounds include, for example, aluminum trichloride, trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutylaluminum, diisobutylaluminum, triethylaluminum, Diethylaluminum hydride, trimethylaluminum; Tetramethoxygermanium, Tetraethoxygermanium; Pentamethoxytantalum, Pentaethoxytantalum; Molybdenum hexacarnivor; Bor, iron pentacarnivor; nickel tetracarnibol, nickel acetate, nickel bromide, ni chloride Kel, nickel formate, nickel hydroxide, nickel iodide, nickel nitrate, nickel sulfate; chromium hexacarnivol; acetylacetonate copper, hexafluoroacetylacetonate copper, bisdipivaloylmethanate copper; zirconium tetra Acetylacetonate, zirconium tetrabisdipivaloylmethanate, t-tetrabutoxyzirconium, zirconium chloride, zirconium fluoride, zirconium hydroxide, zirconium iodide, zirconium acetate; gold chloride, chloroauric acid, gold bromide , Gold chloride, gold trichloride, gold oxide, gold hydroxide; silver acetylacetonate, silver acetate, silver bromide, silver odor oxide, silver carbonate, silver chloride, silver chloride, silver nitrate, silver oxide; Indium, indium oxide, basic indium acetate; barium tetrabisdipi Roylmethanate, barium acetylacetonate, barium hexafluoroacetylacetonate, barium acetate, barium bromide, barium bromide, barium carbonate, barium chloride, barium fluoride, barium hydroxide, barium nitrate; tetraethyltin, tetramethyltin , Di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, dimethyltin, diisopropyltin, dibutyltin, diethoxytin Dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate, tin dichloride, tin tetrachloride; Examples include, but are not limited to, ropoxy titanium, titanium tetrabisdipivaloylmethanate, tetrapropoxy titanium, tetradimethylamino titanium; iridium acetylacetonate.
[0055]
When the compound is introduced between electrodes serving as discharge spaces, it may be in a gas, liquid, or fixed state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, and in the case of liquid or solid, it may be used after being vaporized by means such as heating, decompression or ultrasonic irradiation, or may be used after being dissolved in an appropriate solvent. .
<Water repellency>
When imparting water repellency to the fiber, it is preferable to form a thin film layer mainly composed of a fluorine compound on the fiber surface.
[0056]
As the reactive gas for forming such a thin film layer, it is effective to use a reactive gas containing an organic fluorine compound.
As the organic fluorine compound, a fluorocarbon gas, a fluorinated hydrocarbon gas or the like is preferably used. Examples of the fluorocarbon gas include carbon tetrafluoride and carbon hexafluoride, specifically, tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, octafluorocyclobutane, and the like. Examples of the fluorinated hydrocarbon gas include difluoromethane, tetrafluoroethane, tetrafluoropropylene, and trifluoride propylene.
[0057]
Further, a halogenated fluoride compound such as trichloromethane monochloride, methane difluoride methane, or cyclobutane tetrachloride, or a fluorine-substituted product of an organic compound such as alcohol, acid, or ketone may be used. Although it can, it is not limited to these. These compounds may have an ethylenically unsaturated group in the molecule. Further, the above compounds may be used alone or in combination.
[0058]
Further, when the organic fluorine compound according to the present invention is a gas at normal temperature and normal pressure, it can be used as it is as a component of the mixed gas, so that the method of the present invention can be most easily performed. However, when the organic fluorine compound is liquid or solid at normal temperature and normal pressure, it may be vaporized by a method such as heating or decompression, or it may be dissolved in an appropriate solvent.
[0059]
The various reactive gases are preferably from 0.01 to 10% by volume, more preferably from 0.1 to 5%, based on the entire mixed gas, from the viewpoint of forming a uniform thin film layer on the fiber surface by plasma discharge treatment. It is preferable to make it contain in the quantity of volume%. By using the mixed gas containing the reactive gas in the above amount, a thin film layer having a thickness of 0.1 nm to 1000 nm can be formed on the fiber surface.
[0060]
In addition, it is desirable that the gas mixture further contains a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, nitrogen dioxide, nitrogen monoxide, hydrogen, and nitrogen as a reactive gas. In this case, together with the above various reactive gases, the content is preferably 0.01 to 10% by volume, more preferably 0.1 to 5% by volume. Thereby, the reaction is promoted, the hardness of the thin film is remarkably improved, and a dense and high-quality thin film can be formed. In particular, it is preferable to add oxygen or hydrogen.
[0061]
In addition to performing each function to the functional fiber independently, a plurality of functions can be combined to continuously impart two or more functions. Specifically, for example, two or more plasma discharge treatment devices described above may be installed in succession to continuously treat the fibers. Moreover, it is also possible to mix the reactive gas and perform a plurality of function imparting processes at once, and the configuration is not limited.
[0062]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the functional fiber which has functions, such as electromagnetic wave shielding, infrared shielding, ultraviolet shielding, electroconductivity, and water repellency, and its manufacturing method can be provided.
In the present invention, various functions are imparted by forming a thin film layer in a form along the fine structure of the fiber surface, so that the unevenness of the fiber surface is filled like conventional plating or sputtering. The original texture and feel of the fiber are maintained.
[0063]
Moreover, since a thin film layer is formed by depositing very densely on the fiber surface, durability is good and the effect is not easily removed even after washing.
[0064]
【Example】
Evaluation of each functionality of the functional fiber prepared by plasma discharge treatment and the untreated product as a comparative control was performed by the following method.
<Evaluation method>
(1) Electromagnetic wave shielding performance
Electric field shielding performance and magnetic field shielding performance were evaluated based on a measurement method by KEC (Kansai Electronics Industry Promotion Center). The measurement was performed in the range of 10 to 1000 MHz, and the degree of the electromagnetic wave shielding effect was expressed by the attenuation rate obtained from the above equation (1).
(2) Antistatic performance
The object to be measured was left to stand in an air-conditioned room at 23 ° C. and 20% RH for 2 days, and then the surface specific resistance value was measured using a teraohm meter (model VE-30, manufactured by Kawaguchi Electric Co., Ltd.). The electrode used for the measurement was 1 cm × 5 cm in contact with the sample, and the distance between the electrodes was 1 cm.
(3) Infrared shielding performance
The infrared transmittance (%) in wavelength regions 700 to 850 nm, 850 to 1000 nm, and 1000 to 1200 nm was measured with a U-3400 spectroanalyzer (manufactured by Hitachi, Ltd.), and the value obtained by subtracting the value from 100 was determined as the infrared shielding rate. (%).
(4) UV shielding performance
The UV transmittance (%) in the wavelength regions of 250 to 280 nm, 280 to 320 nm, and 320 to 400 nm was measured with a U-3400 spectroanalyzer (manufactured by Hitachi, Ltd.), and the value obtained by subtracting the value from 100 was determined as the ultraviolet shielding rate. (%).
(5) Water repellency
The water droplet contact angle was measured using a contact angle meter G-1 manufactured by Elma.
(6) Durability
Each created functional fiber was washed 20 times by a washing method suitable for the fiber of the substrate, and each performance was re-evaluated.
[0065]
[Example 1]
Addition of electromagnetic shielding
A polyester taffeta (white) having a warp density of 115 yarns / inch and a weft yarn density of 95 yarns / inch using polyester 75 denier / 48 filaments for both the warp and weft yarns, the discharge treatment container shown in FIG. 2 with the plasma discharge treatment of FIG. Using a device applied to the device, a plasma discharge treatment was performed using a mixture gas having the following composition to form a copper-containing thin film layer on the fiber surface.
[0066]
In FIG. 2, the roll electrode 25 is coated with 1 mm of alumina by ceramic spraying on a stainless jacket roll base material (cooling means is not shown in FIG. 2) having cooling means by cooling water, After that, a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, then cured by ultraviolet irradiation, sealed, and a surface having a smooth surface and a dielectric having a Rmax of 5 μm (relative dielectric constant 10). An electrode 25 was manufactured and grounded. On the other hand, as an applied electrode, a hollow rectangular stainless steel pipe was covered with the same dielectric as described above under the same conditions to form an opposing electrode group. However, the power supply used for plasma generation is a high frequency power supply JRF-10000 manufactured by JEOL Ltd. with a frequency of 13.56 MHz and 20 W / cm. ² Was supplied.
<Mixed gas>
The composition of the mixed gas used for the plasma discharge treatment is shown below.
[0067]
Inert gas: Argon 98.25% by volume
Reactive gas 1: Hydrogen gas 1.5% by volume
Reactive gas 2: Copper acetylacetonate 0.25% by volume
Note that copper acetylacetonate was sublimated to form a reactive gas.
The polyester cloth after the plasma discharge treatment and the electromagnetic wave shielding performance after washing the polyester cloth 20 times were evaluated. The results are shown in Table 1.
[0068]
[Example 2]
Addition of conductivity (antistatic effect)
A mixed gas having the following composition was used, and the plasma discharge treatment was performed on the back surface of a commercially available acrylic sweater in the same manner as in Example 1 except that the plasma discharge treatment apparatus shown in FIG. 8 was used. Formed.
<Mixed gas>
Inert gas: Argon 98.25% by volume
Reactive gas 1: Hydrogen gas 1.5% by volume
Reactive gas 2: Tetraethylsilane 0.25 vol%
When the surface specific resistance value of the back surface (treated surface) of the sweater after the plasma discharge treatment was measured, it was about 2.5 × 10 ⁹ Ω. When this sweater was actually attached and detached, generation of static electricity was suppressed as compared with the untreated one. In addition, there was no particular change in the texture, and there was no problem with the touch. In addition, the surface resistivity after 20 washes is approximately 8.5 × 10 ⁹ Ω. The results are shown in Table 2.
[0069]
[Example 3]
Infrared shielding
The same polyester taffeta as that used in Example 1 was subjected to plasma discharge treatment in the same manner as in Example 1 except that a mixed gas having the following composition was used to form a tin oxide layer.
<Mixed gas>
Inert gas: Argon 98.25% by volume
Reactive gas 1: Hydrogen gas 1.5% by volume
Reactive gas 2: Tetraethyltin 0.25 volume%
When the transmittance of this polyester cloth was measured, the transmittance at 1200 nm or more was 10% or less, and the transmittance at 700 nm to 1200 nm was 20% or less, showing a good infrared shielding effect. Moreover, the transmittance | permeability in 700 nm-1200 nm after 20 times of washing was also 20% or less. The results are shown in Table 2.
[0070]
[Example 4]
Providing UV shielding
A mixed gas having the following composition was used, and a plasma discharge treatment was applied to a normal thick wool yarn made of 100% commercially available merino wool in the same manner as in Example 1 except that the plasma discharge treatment apparatus shown in FIG. 7 was used. And a titanium oxide film was applied.
<Mixed gas>
Inert gas: Argon 98.25% by volume
Reactive gas 1: Hydrogen gas 1.5% by volume
Reactive gas 2: Triethyltitanium 0.25% by volume
Using the treated yarn, a knitted knitted stall 50cm x 120cm was created, and the transmittance of this stall was measured. The spectral transmittance at a wavelength of 400nm or less was about 20% or less, and a good ultraviolet shielding effect. showed that. Also, the texture of the wool was not particularly problematic and no change in color tone was felt. Further, the spectral transmittance at a wavelength of 400 nm or less after washing 20 times was about 20% or less. The results are shown in Table 2.
[0071]
[Example 5]
Add water repellency
Using a mixed gas having the following composition and using the plasma discharge treatment apparatus shown in FIG. 8, a plasma discharge treatment was performed on the back surface of an apron made of a commercially available cotton broad material in the same manner as in Example 1 to obtain a fluorine compound. Layers were formed.
<Mixed gas>
Inert gas: Argon 98.25% by volume
Reactive gas 1: Hydrogen gas 1.5% by volume
Reactive gas 2: Carbon tetrafluoride 0.25% by volume
When the water droplet contact angle on the back surface (treated surface) of the apron after the plasma discharge treatment was measured, the water droplet contact angle was about 103 degrees, indicating a water repellent effect. Moreover, the water droplet contact angle after 20 washes was about 98 degrees. The result Table 2 Shown in
[0072]
[Comparative Example 1]
Using polyester taffeta (white) as a base material in Examples 1 and 3, electromagnetic wave shielding performance and infrared shielding performance were evaluated. Table 1 shows the evaluation results of the electromagnetic wave shielding performance, and Table 2 shows the evaluation results of the infrared shielding performance.
[0073]
[Comparative Example 2]
Using a commercially available acrylic sweater as a base material in Example 2, the antistatic performance of the back surface was evaluated. The results are shown in Table 2.
[0074]
[Comparative Example 3]
A knitted knitted stall 50 cm × 120 cm was prepared using 100% commercially available merino wool as a base material in Example 4 and evaluated for ultraviolet shielding performance. The results are shown in Table 2.
[0075]
[Comparative Example 4]
Using a commercially available cotton broad apron as a base material in Example 5, the water droplet contact angle on the back surface was measured to evaluate the water repellency. The results are shown in Table 2.
[0076]
[Table 1]

[0077]
[Table 2]

[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of a plasma discharge treatment vessel installed in a plasma discharge treatment apparatus used in the present invention.
FIG. 2 is a schematic view showing another example of a plasma discharge treatment vessel installed in the plasma discharge treatment apparatus used in the present invention.
FIGS. 3A and 3B are schematic views showing examples of cylindrical roll electrodes of the plasma discharge treatment apparatus used in the present invention, respectively.
4 (a) and 4 (b) are schematic views showing examples of cylindrical fixed electrodes of the plasma discharge processing apparatus used in the present invention.
FIGS. 5A and 5B are schematic views showing examples of prismatic fixed electrodes of the plasma discharge processing apparatus used in the present invention, respectively.
FIG. 6 is a schematic view showing an example of a plasma discharge treatment apparatus used in the present invention.
FIG. 7 is a schematic view showing another example of a plasma discharge treatment apparatus used in the present invention.
FIG. 8 is a schematic view showing another example of a plasma discharge treatment apparatus used in the present invention.
[Explanation of symbols]
25, 25c, 25C ... Roll electrode
26, 26c, 26C, 36, 36c, 36C, 103, 104 ... Electrodes
25a, 25A, 26a, 26A, 35a, 36a, 36A
... Conductive base materials such as metals
25b, 26b, 35b, 36b ... Ceramic-coated dielectric
25B, 26B, 36B ... Lined dielectric
31, 102 ... Plasma discharge treatment vessel
41, 105 ... Power supply
51 ・ ・ ・ Gas generator
52 ・ ・ ・ Air supply port
53 ・ ・ ・ Exhaust port
60 ・ ・ ・ Electrode cooling unit
61 ... Original winding base material
65, 66, 107, 108 ... nip rollers
64, 67 ・ ・ ・ Guide rollers
100, F ... base material
106 ・ ・ ・ Earth
110 ・ ・ ・ Conveyor belt
111 ・ ・ ・ Transport table

Claims (11)

Under a pressure of atmospheric pressure or near atmospheric pressure, a high-frequency voltage exceeding 100 kHz and a power of 1 W / cm ² or more are supplied between the electrodes facing each other to discharge the plasma, thereby generating a metal-containing reactive gas. A functional fiber manufacturing method in which a thin film layer is formed by bringing a metal-containing reactive gas into contact with the fiber surface by exposing the fiber to the plasma-containing metal-containing reactive gas. The manufacturing method of the functional fiber characterized by including any one or more metal content layers among following (1)-(3):
(1) A metal-containing layer made of tin-doped indium oxide, antimony-doped tin oxide, or aluminum-doped zinc oxide that imparts electromagnetic wave shielding properties;
(2) a metal-containing layer comprising a metal oxide mainly composed of indium oxide and / or tin oxide, which imparts infrared shielding properties;
(3) A metal-containing layer made of titanium dioxide, zinc oxide, tin-doped indium oxide, or antimony-doped tin oxide that imparts ultraviolet shielding properties.   2. The method for producing a functional fiber according to claim 1, wherein an electrode obtained by spraying ceramics on a metal base material so as to have a porosity of 10% by volume or less is used as the electrode.   The method for producing a functional fiber according to claim 1 or 2, wherein the high-frequency voltage is a continuous sine wave.   The fiber is a long fiber, the long fiber is transported between the electrodes, and the metal-containing reactive gas is introduced between the electrodes, whereby the long fiber The method for producing a functional fiber according to claim 1, wherein a metal-containing reactive gas is brought into contact with the fiber surface to form a thin film layer.   The method for producing a functional fiber according to any one of claims 1 to 4, wherein the fiber is transported between the electrodes in a state of being placed on a transport table.   The method for producing a functional fiber according to claim 5, wherein the transport table also serves as one of the facing electrodes.   2. The fiber is exposed to the plasma-like metal-containing reactive gas by spraying a metal-containing reactive gas in a plasma state between slit-like or cylindrical electrodes on the fiber. The manufacturing method of the functional fiber in any one of -6.   The functional fiber according to any one of claims 1 to 7, wherein two or more functions among electromagnetic shielding properties, infrared shielding properties, and ultraviolet shielding properties are continuously imparted to the fibers. Method.   A mixed gas containing the metal-containing reactive gas and an inert gas between the electrodes, wherein the mixed gas containing the inert gas in an amount of 90 to 99.99% by volume is introduced. The manufacturing method of the functional fiber in any one of Claims 1-8.   The method for producing a functional fiber according to claim 1, wherein the metal-containing reactive gas contains an organometallic compound.   The method for producing a functional fiber according to claim 10, wherein the organometallic compound is selected from a metal alkoxide, an alkylated metal, and a metal complex.

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