KR20050020783A - Functional fiber sheet - Google Patents

Abstract

A fibrous sheet coated with a physically vapor deposited film, wherein the vapor deposited film is made transparent so that colors and patterns on the fiber sheet are expressed, further imparting electrical conductivity to the vapor deposited film, and also improving the productivity of the vapor deposited film. It also enables selective blocking of infrared and ultraviolet radiation. In a fiber sheet comprising synthetic fibers, one or both surfaces are coated with a physical vapor deposited film containing a metal oxide, the metal oxide having a small amount of valence lower than a normal oxide as a main component and a normal oxide as a secondary component. An amount of the low valence oxide is 0.1-20% by weight of the total amount of the metal oxide, and the thickness of the physical vapor deposited film is 5-500 nm.

Description

Functional Fiber Sheets {FUNCTIONAL FIBER SHEET}

The present invention relates to a functional fiber sheet physically coated with a vapor deposition film containing titanium oxide and other metal oxides.

On the surface of the fiber sheet containing synthetic fibers such as woven fabrics, knitted fabrics, nonwoven fabrics, and the like, metallic materials are formed using physical vapor deposition methods such as vacuum vapor deposition, ion beam method, sputtering method, and the like. Alternatively, it has been known that by forming a metal oxide thin film, it is possible to provide fiber sheets of various functional types such as electrical conductivity, heat shielding, thermal insulation, antifouling, antibacterial, corrosion resistance and the like. However, when the fiber sheet is coated with a vapor deposition film of a metal such as stainless steel, titanium, chromium, or copper, the color and pattern on the fiber sheet are covered by the vapor deposition film and the metallic color, and there is a lack of variety in terms of fashion. There was a problem. On the other hand, when a vapor deposition film containing a metal oxide such as titanium oxide is formed, since the oxide constitutes a normal oxide containing -divalent oxygen, the vapor deposition film is made transparent by controlling the thickness of the film, thereby causing color and pattern. And so on. On the other hand, there is a problem that the electrical conductivity is insufficient compared to the metallic vapor deposition film, low heat shielding, and further reduced productivity.

In addition, the formation of the vapor deposition layer is made of a multi-layer structure consisting of three layers of TiO _2, Ag, TiO _2, has a vapor deposition layer selectively blocking ultraviolet and infrared radiation and at the same time known nopindago the visible light transmission. However, the vapor deposition film was not practical because it was easily peeled off in repeated washing, and furthermore, there was a problem in that the metal was oxidized and deteriorated in use.

The present invention relates to a functional fiber sheet obtained by coating a fiber sheet with a physical vapor deposition film and changing the components of the physical vapor deposition film, wherein a transparent vapor deposition film is formed to express colors and patterns on the fiber sheet. Further, the vapor deposition film may be provided with functions such as electrical conductivity, infrared radiation protection, ultraviolet radiation protection, and the like, and productivity may be increased at the time of vapor deposition.

1 is a cross-sectional view of the sputtering apparatus according to the first embodiment.

2 is a graph showing the light transmittance of a vapor deposited film.

3 is a graph showing the light reflectance of a vapor deposited film.

The fibrous sheet according to the present invention comprises synthetic fibers, one or both surfaces of which are physically coated with a vapor deposition film containing a metal oxide, wherein the metal oxide has an oxide having a lower valency than that of the main oxide, which is a main component. It is characterized by consisting of a mixture containing a small amount.

Synthetic fibers used in the present invention include thermoplastic synthetic fibers used for the use of ordinary knits and fabrics, and may include polyester fibers, nylon fibers, acrylic fibers and polyimide fibers. In particular, polyester fibers are preferred in view of low moisture content, easy physical vapor deposition of metals and metallic oxides, and excellent durability of the deposited film. The synthetic fibers may be in the form of staples or filaments. Staples or filaments are used without modification in nonwoven fabrics, but when used as structural yarn for woven or knitted goods, filament yarns such as monofilament yarns and multifilament yarns are preferred.

In the present invention, a thin film containing a metal oxide such as titanium oxide is formed on one or both surfaces of the fiber sheet by physical vapor deposition, preferably sputtering, such as vacuum vapor deposition, ion beam, sputtering, or the like. . The metal oxide is composed of a mixture of a normal oxide containing oxygen in a -divalent state as a main component, a small amount of oxide having a lower valence than a normal oxide as a secondary component, an oxide having a lower valence, and the like. For example, in titanium oxide, tetravalent oxide TiO ₂ is a normal oxide, and oxides having a low valence include Ti0 which is a divalent oxide and Ti ₂ O ₃ which is a _trivalent oxide. Therefore, the vapor deposition film of titanium oxide is formed by a mixture of the above normal valence oxide (tetravalent oxide) and low valence oxide (divalent or trivalent oxide).

In physical vapor deposition such as sputtering, while the metal is sputter-vaporized in a closed chamber containing a small amount of argon gas, it is oxidized by a small amount of oxygen supplied to the chamber and adsorbed to the fiber sheet. When the amount of oxygen supplied reaches an appropriate amount for producing the normal oxide, only the normal oxide is produced, and at the same time, there is an effect of greatly reducing the amount of metal oxidized and evaporated on the surface of the target metal.

In contrast, when the amount of oxygen supplied is less than the amount needed to produce normal oxides, oxides of lower valences are produced together with the normal oxides, which are absorbed in mixed form on the fiber sheet, and furthermore, the target surface is Since it does not oxidize, the amount of evaporated metal does not decrease and prevents a decrease in productivity. Therefore, by forming the vapor deposition film containing the mixture, by further adjusting the thickness of the vapor deposition film, it is possible to maintain the transparency while providing a function such as electrical conductivity, heat shielding. Further, in the above sputtering state, productivity is improved to a higher level by mixing a small amount of nitrogen gas together with argon gas and oxygen.

In order to determine the amount of oxygen so that less oxygen is supplied than is needed for the production of normal oxides, the specific brightness of the metal emitted by the evaporated metal as it passes through the plasma that occurs with sputtering, i.e. It is preferable that the luminance is maintained at a constant level by determining the luminance and adjusting the amount of oxygen supplied. For example, if the metal is titanium, when titanium passes through the plasma by sputter evaporation, visible light with a wavelength of 453 nm is emitted, and in the absence of oxygen, the evaporation rate is kept at its maximum and the brightness is the strongest. do. When excess oxygen is supplied, the evaporation rate is kept to a minimum, and the brightness decreases. Thus, by controlling the amount of oxygen supplied at the basic brightness, it is possible to control the amount of oxide having a low valence. Moreover, light may use any required intensity index associated with it instead of light itself.

The mixture of oxides having valences lower than those of the normal oxides, ie, oxides having low valences, is preferably from 0.1 to 20% by weight of the total oxides. When the amount of this mixture is less than 0.1% by weight, functions such as electrical conductivity and heat shielding are not obtained, and further, productivity is significantly lowered. Conversely, if it is 20% by weight or more, the metallic color is evident, moreover, the visible light transmittance is insufficient and the fiber sheet property is lost. In addition, the thickness of the above-mentioned physical vapor deposited film is preferably 5 to 500 nm, particularly 3 to 300 nm. Below 5 nm, functions of electrical conductivity, heat shielding, infrared radiation shielding, ultraviolet radiation shielding, etc. cannot be obtained, and above 500 nm, structural fibers, colors, patterns, etc. of the fiber sheet do not appear, and in terms of cost, It is difficult to anticipate normal use.

In addition, the transparency of the physically vapor deposited film is preferably 30% or more for visible light transmittance of 550 nm wavelength, and at 30% or less, the color and pattern on the surface of the fiber sheet and the fiber are no longer visible, and the fiber The attributes of the sheet will be lost. In addition, the transmittance of infrared radiation and ultraviolet radiation is determined by the amount of the mixture of oxides having low valences, but when the infrared radiation shielding includes an object, the amount of the mixture is increased and the infrared radiation transmittance is less than 70% at a wavelength of 1000 nm. It is desirable to suppress this. In addition, when the ultraviolet radiation shielding includes an object, it is desirable to lower the amount of the mixture and to suppress the ultraviolet radiation transmittance to 50% or less at 400 nm wavelength.

Example 1

A fiber sheet and a fabric using polyester fiber multifilament yarn as weft and warp are used, and a transparent coating of titanium oxide having a thickness of 5 to 500 nm, preferably 30 to 300 nm is formed on the surface by sputtering.

1 shows an example of a sputtering apparatus. The sealable chamber 10 is separated by a horizontal separator 11 into a lower sputtering chamber 12 and an upper fiber chamber 13, and in the center of the lower sputtering chamber 12, a flat plate target made of titanium. 14 is fixed to a targer source 15 located in the air, and the target 14 is cooled from the bottom by coolant passing through the target source 15. The anode 16 is attached to the upper left and right sides of the target 14, and a DC voltage of 200 to 1000 V is applied by the DC power supply 17 between the anode 16 and the target 14.

A water-cooled cylinder 18 is provided horizontally above the anode 13 and, moreover, freely rotates. In the upper left of the cylinder is placed a fiber sheet sending shaft 19 and in the upper right, a fiber sheet winding shaft 20 which is relatively horizontal, moreover they are free to rotate. Thus, the fiber sheet F before the treatment wound around the sending shaft 19 is pulled, wound around the water-cooled cylinder 18 through the guide roller 21 on the upper left side, and guide roller 22 on the upper right side. Wound around the winding shaft 20. Moreover, a vacuum pump 23, an argon gas supply gas bomb 24 and an oxygen gas supply gas cylinder 25 are relatively connected to the chamber 10.

In the above arrangement, the sending shaft 19, the winding shaft 20 and the water-cooled cylinder 18 rotate, and the fiber F is sent at a fixed speed counterclockwise while cooling on the water-cooled cylinder 14 The surface temperature is kept below 60 ° C. On the other hand, the vacuum pump 23 is forcibly reduced in the internal pressure to about 1.3 × 10 ⁻³ Pa in the chamber 10, and then the argon gas and oxygen gas supply gas valves from the argon gas supply gas cylinder 24 are pressed. Oxygen from (25) is relatively adjusted to adjust the internal pressure of the chamber 10 to about 1 × 10 ⁻² Pa, and sputtering is then performed. Titanium released from the target 14 reacts with oxygen to form titanium oxide, which adheres to the fiber sheet F to form a transparent physical vapor deposited film.

This time, sputtering is performed while observing the brightness of the evaporated titanium passing through the plasma on the target 14. In the meantime, by adjusting the amount of oxygen sent from the oxygen gas supply gas cylinder 25 to the chamber 10, the intensity of the evaporated titanium or other intended intensity index associated with the intensity is fixed level determined by the previous test. To control. Since titanium oxide comprises a mixture of a normal oxide and a low valence oxide, the mixture is formed in an amount of 0.1 to 20% by weight of the low valence oxide relative to the total amount of the metal oxide, and is absorbed onto the fiber sheet F. . Furthermore, the thickness of the physically vapor-deposited film containing titanium oxide is 5 to 500 nm by controlling the moving speed of the fiber sheet F. FIG.

In this embodiment, by increasing the amount of oxygen supplied to the chamber 10, furthermore, by lowering the setting for the brightness, the normal oxides increase, the low valence oxides decrease, and the transparency of the physically vapor deposited film increases. On the other hand, by lowering the amount of oxygen supplied, further increasing the setting for the brightness, the normal oxide is reduced, the oxide with low valence is increased, the transparency of the physical vapor deposited film is reduced and the color of the metal is stronger. Further, by the adjustment of the brightness, the infrared radiation transmittance or the ultraviolet radiation transmittance is suppressed to 70% or less, while the transmittance of visible light can be maintained at 20% or more.

By using a warp-knit fabric comprising polyester fiber multifilament yarn as the fiber sheet, and also by sputtering as described above, a fiber sheet having electrical conductivity and heat shielding properties is provided. Furthermore, a knitted fabric having an attribute of 30% or more of visible light transmittance and 70% or less of infrared radiation transmittance or ultraviolet radiation transmittance is provided.

Furthermore, by using a spun-bonded nonwoven fabric comprising polyester filament as the fiber sheet, and also by performing the above-described sputtering, the properties of the twisted nonwoven fabric further having electrical conductivity and heat shielding properties And a fiber sheet having a visible light transmittance of 30% or more, an infrared radiation transmittance of 70% or less, and an ultraviolet radiation transmittance.

Example 2

By using the sputtering apparatus of FIG. 1, sputtering is performed on one side of the fiber sheet, a woven fabric, a knitted fabric, a nonwoven fabric, or the like is formed to form the above physically vapor deposited film, and then the fiber sheet is temporarily Remove, and then reattach to the sputtering apparatus by changing the front and back sides, and then sputtering on the other side as described above, and having the above physically vapor-deposited film on both front and back sides, and having a visible light transmittance of 30 It is possible to obtain a fiber sheet of more than% and having an infrared radiation transmittance or an ultraviolet radiation transmittance of 70% or less, and further provide the property of the fiber sheet exhibiting the color and pattern of its surface without metallic color.

Example 3

In the closed chamber, two sets of vapor deposition apparatuses are arranged in rows, and sputtering is continuously performed on both front and rear surfaces to form the above physically vapor deposited film. For example, the first water-cooled cylinder and the second water-cooled cylinder are provided horizontally in the center of the left-right side of the sealed chamber, the first water-cooled cylinder on the left rotates counterclockwise, and the second water-cooled cylinder on the right is clockwise. Relative to the direction of rotation. Sputtering is carried out by winding the fiber sheet from the left side so that its back side is in contact with the lower half of the first water-cooled cylinder. Next, the sheet is connected to the upper right side of the second water-cooled cylinder, and the sputtering is carried out by wrapping the fiber sheet from the right side. The front face is in contact with the lower half of the second water-cooled cylinder.

As the fiber sheet (F) of Example 1, a 190-count taffeta using polyester multifilament yarns as weft and warp yarns was used, and physical vapor deposition of titanium oxide on one side by sputtering was carried out. Form a transparent film. As the oxygen supply control, "Dual Magnetron Cathode Plasma Emission Monitor" ("von Alden", Germany) is used. Monochromatic light (wavelength 453 nm) of metallic titanium alone determines its intensity through a collimator, which is expressed in intensity, the intensity at zero oxygen supply is 100, the intensity at excess oxygen supply Is 10 and Test Sample A is obtained when the strength is 50. Test Sample B is also obtained when the strength is 30.

The components of the physical vapor deposited film for Test Sample A and Test Sample B were analyzed by X-ray photoelectron spectrophotometry. As the analyzer, SSX-100 model X-ray photoelectron spectrophotometer (SSI) is used. When analyzed using monochromatic AlKa (100W) as the X-ray source, in test sample A of strength 50, about 5% of the trivalent oxide Ti ₂ 0 ₃ is also present in the tetravalent normal oxide. Also in Test Sample B of strength 30, the vapor deposited film is almost completely formed with tetravalent normal oxide TiO ₂ . The ratio of titanium to oxygen in the vapor deposited film is 1 / 2.15 in Test Sample A and 1 / 2.39 in Test Sample B. In addition, the apparent state with respect to said test sample A and B is compared, and the result is shown in following Table 1 with said analysis result.

Table 1

Trial Sample A Trial Sample B burglar 50 30 Thickness of Vapor Deposition Film (μm) 50 50 An apparent condition transparent transparent Titanium / Oxygen (atomic ratio) 1 / 2.15 1 / 2.39 Amount of oxide with low valence 5% 0%

The said vapor deposition film of titanium oxide has a thickness of 50 micrometers, and is formed on the transparent film containing polyethylene terephthalate, and measures the electrical conductivity and the light transmittance of the said vapor deposition film. At this time, the test samples 1-6 are prepared by changing the strength in six steps, 70, 60, 50, 40, 30, 20. The electrical conductivity and light transmittance are then measured for test samples 1-6 at wavelengths of 400-1000 nm, respectively. The electrical conductivity is shown in Table 2, the light transmittance is shown in FIG. 2, and the light reflectance is shown in FIG.

TABLE 2

Test Sample No. One 2 3 4 5 6 burglar 70 60 50 40 30 20 Electrical conductivity (Ω / cm) 8 × 10 ³ 1 × 10 ⁴ 7 × 10 ⁴ 4 × 10 ⁷ - -

As shown in Table 2 above, when the electrical conductivity is compared with the resistance value, Test Sample 1 of strength 70 including the oxide having the lowest valence has the lowest resistance value. At the lowest valence oxides, the resistance decreases in the order of test sample 2 with strength 60, test sample 3 with strength 50, and test sample 4 with strength 40, and the test sample 5 with strength 30 and strength 20 For test sample 6, no resistance was measured, and the electrical conductivity was essentially zero.

 Furthermore, as shown in FIG. 2, at light transmittance, low intensity test samples 4-6 exhibited high transmittance and increased transparency, on the contrary, high intensity test samples 1-3 decreased in transmittance, and apparent state There was a tendency for the metallic color to appear. In addition, in test sample 6 of intensity 20, the transmittance was 60% or more in the whole range including infrared radiation in ultraviolet radiation at a wavelength of 400 nm to 1000 nm. In test sample 5 of intensity 30, the ultraviolet radiation transmittance at a wavelength of 400 nm was less than 50%, but for the remaining visible and infrared radiation, the transmittance was 50-70%. In test sample 4 of strength 40, although somewhat similar to test sample 3, the infrared radiation transmittance was less than 70%.

Furthermore, in Test Sample 3 of intensity 50, the visible light transmittance at 550 nm wavelength was 50%, about 45% for ultraviolet radiation at 400 nm wavelength and about 43% for infrared radiation at 1000 nm wavelength. Moreover, in test sample 2 of intensity 60, 40-45% was observed with almost uniform transmission in the range from infrared radiation of 400 nm wavelength to visible light of 700 nm wavelength. The transmittance gradually decreased beyond 700 nm and was nearly 35% in infrared radiation at a wavelength of 1000 nm. In addition, in test sample 1 of intensity 70, the transmittance gradually decreases from 37% to 30% from 400 nm wavelength ultraviolet radiation to 1000 nm wavelength infrared radiation, and moreover, the light transmittance of the film itself is about 85 at 400 nm wavelength. %, About 88% at 550 nm wavelength, about 89% at 1000 nm wavelength, the right side tended to rise slightly.

On the other hand, as shown in Figure 3, the light reflectance tends to be slightly lower toward the right side in the low intensity test sample 4-6, and slightly higher toward the right side in the high intensity test sample 1-3. However, test sample 6 of intensity 20 exhibits a high reflectance of about 28% at a wavelength of 500-600 nm in the visible region, a sudden decrease in the ultraviolet radiation region, and a gradual decrease in the infrared radiation region, resulting in a mountain shape. It was. In addition, in the test sample 5 of the intensity 30 and the test sample 4 of the intensity 40, the shape lowering toward the right is somewhat similar, the reflectivity is about 33% at the wavelength of 400 nm, and the reflectance is 17-19 at the wavelength of 1000 nm. Was%.

Moreover, Test Sample 3 with a strength of 50 exhibited a low reflectance of about 19% at the wavelength of 500-600 nm in the visible range, gradually increasing toward 400 nm and 1000 nm, increasing approximately 22-23%. It became. In addition, Test Sample 2 of intensity 60 exhibited a nearly constant reflectance of 16-17% at a wavelength of 550 nm, and gradually increased to a reflectance of 26% at a wavelength of 1000 nm. In Test Sample 1 of intensity 70, the reflectance increased substantially linearly with the wavelength to about 18% at the wavelength of 400 nm and about 37% at the wavelength of 1000 nm. Moreover, the reflectance of the film itself exhibited a constant value of about 11% over the entire wavelength range of 400-1000 nm.

As described above, in the functional fiber sheet according to the present invention, the metal oxide constituting the physically vapor deposited film includes not only normal oxide but also a small amount of low valence oxide, and the amount of oxide having low valence in the amount of the mixture. It is possible to maintain the transparency of the vapor deposition film, thereby exhibiting the color and pattern of the fiber sheet, and to maintain the characteristics and properties of the fiber sheet, and at the same time, through the vapor deposition film, electrical conductivity, heat shielding, infrared radiation Provides functionality such as protection, UV radiation protection, pollution prevention, antibacterial and corrosion resistance. Moreover, productivity is satisfactory, and it is excellent in washing | cleaning resistance, peeling prevention, etc. Thus, the functional fiber sheet is an industrial material such as mesh screens and filters, which can be satisfied with aesthetic effects and various functions, and has excellent corrosion resistance and wash resistance, and insect screens, household packaging materials, outdoor tents, umbrellas, interior decorative walls. It is well suited for use in applications such as patterned materials, ceiling materials, interior materials and the like.

As described in the three embodiments of the present invention, many changes and applications are possible without departing from the scope and meaning of the present invention as defined in the appended claims.

Claims (6)

In one or both surfaces coated with a physical vapor-deposited film, the vapor-deposited film is a functional fiber sheet composed of synthetic fibers comprising a metal oxide, And the metal oxide comprises a mixture of a normal oxide as a main component and a small amount of oxide having a lower valency than the normal oxide as a secondary component. The method of claim 1, The amount of the low valence oxide relative to the total amount of the metal oxide is 0.1 to 20% by weight, the thickness of the physical vapor-deposited film is 5 to 500 nm functional fiber sheet. The method according to claim 1 or 2, The metal oxide is titanium oxide, the normal oxide of the titanium oxide is a tetravalent oxide, the oxide having a low valence is a functional fiber sheet is a divalent or trivalent oxide. Forming a film on which the metal oxide is physically vapor deposited on the fiber sheet through a process of physical vapor deposition; By increasing the amount of oxygen supplied in the process of the physical vapor deposition method, the main component of the metal oxide of the physical vapor deposition film is formed of a normal oxide, Reducing the amount of oxygen supplied in the course of the physical vapor deposition, thereby forming the secondary component of the metal oxide into a small amount of oxide having a lower valency than the normal oxide. The method of claim 1, The said synthetic fiber is a functional fiber sheet which is a synthetic fiber used for the use of normal fabric and knitted fabric. The method of claim 1, The synthetic fibers are polyester fibers, nylon fibers, acrylic fibers or polyimide fibers.