Fiber sheet

Abstract

To provide a fiber sheet provided with discoloration resistance while exhibiting deodorant.SOLUTION: A fiber sheet comprising: a fiber base material; and a copper element-containing alloy layer arranged on the fiber base material, wherein a content of a metal element having a higher ionization tendency than copper in the copper element-containing alloy layer is 20 at% or more relative to 100 at% of a metal element in the copper element-containing alloy layer, and a content of a copper element present as copper oxide (II) in the copper element-containing alloy layer is 15 at% or more relative to 100 at% of the metal element in the copper element-containing alloy layer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to fiber sheets and the like. [Background technology]

[0002] Fiber substrates are used in various fields where aesthetic appeal is required. For example, carbon fiber substrates, together with resins, constitute composite materials (such as carbon fiber reinforced plastics) and are widely used in a range of applications, from relatively large items such as aircraft bodies to relatively small, everyday items such as sporting goods, car interior and exterior materials, and clothing. For this reason, fiber substrates are sometimes colored to enhance their aesthetic appeal. Furthermore, due to their unique aesthetic properties, gloss may be added during this process.

[0003] It is desirable to impart deodorizing properties to the inside or outside of a fibrous substrate. Patent Document 1 discloses a deodorizing fibrous sheet in which a metal vapor-deposited film made of copper or silver is laminated on the surface of a fabric. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2006-014965 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, deodorizing fiber sheets using copper or silver lack sufficient durability and may discolor due to aging or thermal degradation. On the other hand, using alloys with excellent discoloration resistance may result in insufficient deodorizing properties.

[0006] The present invention aims to provide a fiber sheet that exhibits deodorizing properties while also possessing resistance to discoloration. [Means for solving the problem]

[0007] As a result of intensive research in view of the above problems, the present inventors have found that a fiber sheet including a fiber substrate and a copper element-containing alloy layer disposed on the fiber substrate can solve the above problems, wherein the content of a metal element having a greater ionization tendency than copper in the copper element-containing alloy layer is 20 at% or more with respect to 100 at% of the metal elements in the copper element-containing alloy layer, and the content of the copper element present as copper(II) oxide in the copper element-containing alloy layer is 15 at% or more with respect to 100 at% of the metal elements in the copper element-containing alloy layer. Based on this finding, the present inventors have further conducted research and completed the present invention. That is, the present invention includes the following aspects.

[0008] Item 1. A fiber sheet including a fiber substrate and a copper element-containing alloy layer disposed on the fiber substrate, where the content of a metal element having a greater ionization tendency than copper in the copper element-containing alloy layer is 20 at% or more with respect to 100 at% of the metal elements in the copper element-containing alloy layer, and the content of the copper element present as copper(II) oxide in the copper element-containing alloy layer is 15 at% or more with respect to 100 at% of the metal elements in the copper element-containing alloy layer.

[0009] Item 2. The fiber sheet according to Item 1, wherein the content of the copper element in the copper element-containing alloy layer is 50 at% or more with respect to 100 at% of the metal elements in the copper element-containing alloy layer.

[0010] Item 3. The fiber sheet according to Item 2, wherein the content of the copper element present as copper(II) oxide in the copper element-containing alloy layer is 25 at% or more with respect to 100 at% of the copper elements in the copper element-containing alloy layer.

[0011] Item 4. The fiber sheet according to any one of Items 1 to 3, wherein the metal element having a greater ionization tendency than copper is at least one metal element selected from the group consisting of nickel, zinc, and aluminum.

[0012] Item 5. The amount of copper element adhered to the fiber substrate is 20 μg / cm 2The above is a fiber sheet as described in any of items 1 to 4.

[0013] Item 6. The density of the fibrous base material is 0.015 g / cm³. 3 ~0.3g / cm 3 A fiber sheet as described in any of items 1 to 5.

[0014] Item 7. Textile products containing a fiber sheet as described in any of Items 1 to 6.

[0015] Item 8. Textile products as described in Item 7, which are decorative items. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a fiber sheet that exhibits deodorizing properties while also having resistance to discoloration. [Modes for carrying out the invention]

[0017] In this specification, the terms “contains” and “includes” include the concepts of “contains,” “includes,” “substantially consist of,” and “consist solely of.”

[0018] 1. Fiber sheet In one embodiment, the present invention relates to a fiber sheet (sometimes referred to as "the fiber sheet of the present invention" in this specification) comprising a fiber substrate and a copper-containing alloy layer disposed on the fiber substrate, wherein the content of a metal element having a greater ionization tendency than copper in the copper-containing alloy layer is 20 at% or more relative to 100 at% of the metal elements in the copper-containing alloy layer, and the content of copper element existing as copper(II) oxide in the copper-containing alloy layer is 15 at% or more relative to 100 at% of the metal elements in the copper-containing alloy layer. This will be described below.

[0019] <1-1. Textile base materials> The fibrous base material is a base material containing fibers or fiber bundles as a material, and is not particularly limited as long as it is in the form of a sheet. The fibrous base material may contain components other than fibers and fiber bundles, as long as the effects of the present invention are not significantly impaired. In that case, the total amount of fibers and fiber bundles in the fibrous base material is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more, and is usually less than 100% by mass. Examples of fibrous base materials include woven fabrics (e.g., plain weave, twill weave, satin weave, etc.), knitted fabrics, nonwoven fabrics, mesh, paper, etc. Among these, nonwoven fabrics are preferred from the viewpoint of deodorizing properties. Furthermore, from the viewpoint of having a flat fiber surface and relatively high light reflectivity, which further enhances the design of the fibrous sheet of the present invention, woven fabrics, knitted fabrics, etc. are preferred, and woven fabrics are preferred. The fibrous base material may be subjected to various treatments such as silé treatment, embossing treatment, calendering treatment, etc. By using a fibrous base material with higher smoothness, the metallic feel of the fibrous sheet of the present invention can be further enhanced.

[0020] The layer structure of the fiber base material is not particularly limited. The fiber base material may consist of a single fiber base material, or it may be a combination of two or more fiber base materials.

[0021] The fibers constituting the fibrous base material are not particularly limited and include, for example, synthetic fibers (e.g., nylon fibers, polyester fibers, acrylic fibers, vinylon fibers, polyolefin fibers, polyethylene fibers, polypropylene fibers, polyurethane fibers, etc.), regenerated fibers (e.g., rayon, polynosic, cupro, lyocell, acetate, etc.), plant fibers (e.g., cotton fibers, hemp fibers, flax fibers, rayon fibers, polynosic fibers, cupro fibers, lyocell fibers, acetate fibers, etc.), and organic fibers such as animal fibers (e.g., wool, silk, wild silk, mohair, cashmere, camel, llama, alpaca, vicuña, angora, spider silk, etc.); A wide range of inorganic fibers can be used, such as carbon fibers (e.g., PAN-based carbon fibers, pitch-based carbon fibers, carbon nanotubes, etc.), glass fibers (e.g., glass wool, glass fiber, etc.), mineral fibers (e.g., hot asbestos, white asbestos, blue asbestos, brown asbestos, orthophthalmic asbestos, tremolite asbestos, sunflower asbestos, etc.), artificial mineral fibers (e.g., rock wool, ceramic fibers, etc.), and metal fibers (e.g., stainless steel fibers, aluminum fibers, iron fibers, nickel fibers, copper fibers, etc.).

[0022] The fiber form can be any of the following: continuous long fibers, short fibers obtained by cutting continuous long fibers, or milled yarn obtained by grinding into a powder.

[0023] The fibers may be a single type or a combination of two or more types.

[0024] The fiber bundle is not particularly limited as long as it consists of multiple fibers. The number of fibers constituting the fiber bundle can be, for example, 5 or more, 10 or more, 20 or more, or 50 or more, while on the other hand, it can be, for example, 50,000 or less, 20,000 or less, 15,000 or less, or 2,000 or less. These upper and lower limits can be combined arbitrarily.

[0025] The thickness of the fibrous substrate may vary depending on the type of fiber and is not particularly limited. The thickness of the fibrous substrate is, for example, 3 to 7000 μm. The thickness is preferably 5 to 2000 μm, more preferably 10 to 1000 μm, even more preferably 20 to 700 μm, and even more preferably 50 to 500 μm.

[0026] The density of the fiber substrate is not particularly limited, for example, it is 0.005 to 0.4 g / cm 3 There is. From the viewpoint of deodorizing property and the like, the density is preferably 0.35 g / cm 3 or less, more preferably 0.3 g / cm 3 or less. From the viewpoint of discoloration durability, the density is preferably 0.01 g / cm 3 or more, more preferably 0.015 g / cm 3 or more, still more preferably 0.025 g / cm 3 or more, even more preferably 0.05 g / cm 3 or more, particularly preferably 0.065 g / cm 3 or more.

[0027] The above fiber substrate may have known finishing agents such as flame retardants, water absorbents, water repellents, softeners, heat storage agents, ultraviolet ray blockers, antistatic agents, antibacterial agents, deodorants, insect repellents, mosquito repellents, phosphorescent agents, retroreflective agents, etc. attached thereto.

[0028] <1-2. Copper element-containing alloy layer> The fiber sheet of the present invention includes a copper element-containing alloy layer. The copper element-containing alloy layer is disposed on the fiber substrate. Another layer may be provided between the copper element-containing alloy layer and the fiber substrate. Preferably, the copper element-containing alloy layer is disposed on the fiber substrate without passing through another layer.

[0029] The copper element-containing alloy layer is a layer containing an alloy containing a copper element as a raw material. The copper element-containing alloy layer may contain components other than the alloy containing a copper element. In that case, the content of the alloy containing a copper element in the copper element-containing alloy layer is, for example, 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, even more preferably 99% by mass or more, and usually less than 100% by mass with respect to 100% by mass of the copper element-containing alloy layer.

[0030] In the fiber sheet of the present invention, the copper-containing alloy layer contains a metal element with a greater ionization tendency than copper. Examples of metal elements with a greater ionization tendency than copper include nickel, zinc, aluminum, iron, gallium, titanium, tin, molybdenum, niobium, indium, chromium, tungsten, tantalum, cobalt, lead, antimony, beryllium, manganese, magnesium, and zirconium. Among these, nickel, zinc, aluminum, and iron are preferred from the viewpoint of more effectively suppressing copper oxidation and further improving durability, more preferably nickel, zinc, and aluminum, and particularly preferably nickel and zinc. The metal element with a greater ionization tendency than copper may be a single element or a combination of two or more elements.

[0031] In the fiber sheet of the present invention, the content of metal elements having a greater ionization tendency than copper in the copper element-containing alloy layer is 20 at% or more relative to 100 at% of the metal elements in the copper element-containing alloy layer (Feature 1). By setting the content within this range, good discoloration resistance can be achieved. The content is preferably 30 at% or more, more preferably 40 at% or more. The upper limit of the content is not particularly limited, but from the viewpoint of ensuring a certain level of copper content and being able to exhibit the decorative properties of copper metal and the deodorizing properties of copper to a certain level or more, it is preferably 70 at%, more preferably 60 at%, even more preferably 50 at%, and even more preferably 45 at%.

[0032] In the fiber sheet of the present invention, the copper element-containing alloy layer contains copper(II) oxide (CuO).

[0033] In the fiber sheet of the present invention, the content of copper elements present as copper(II) oxide in the copper element-containing alloy layer is 15 at% or more relative to 100 at% of the metal elements in the copper element-containing alloy layer (Feature 2). By setting the content within this range, good deodorizing properties can be achieved. The content is preferably 16 at% or more, more preferably 17 at% or more, and even more preferably 18 at% or more. The upper limit of the content is not particularly limited, but from the viewpoint of ensuring a certain level of copper metal content and being able to exhibit a certain level of decorative properties of copper metal, it is preferably 80 at%, more preferably 70 at%, even more preferably 60 at%, and even more preferably 50 at%.

[0034] The fiber sheet of the present invention, by possessing features 1 and 2, can exhibit both good deodorizing properties and discoloration resistance. While we do not wish for a restrictive interpretation, the mechanism is thought to be as follows: Copper(II) oxide exhibits good deodorizing properties without changing color, while metal elements with a higher ionization tendency than copper oxidize before copper. Therefore, by adjusting the content of these elements as defined in features 1 and 2, both good deodorizing properties and discoloration resistance can be achieved.

[0035] In the fiber sheet of the present invention, the copper content in the copper element-containing alloy layer is preferably 50 at% or more relative to 100 at% of the metal elements in the copper element-containing alloy layer. By setting the content within this range, the decorative properties of copper metal and the deodorizing properties of copper can be exhibited more effectively. The content is preferably 55 at% or more. The upper limit of the content is not particularly limited, but from the viewpoint of ensuring a certain level of content of metal elements with a higher ionization tendency than copper, and exhibiting better discoloration resistance, it is preferably 80 at%, more preferably 70 at%, and even more preferably 60 at%.

[0036] In the fiber sheet of the present invention, the content of copper elements present as copper(II) oxide in the copper element-containing alloy layer is preferably 25 at% or more relative to 100 at% of copper elements in the copper element-containing alloy layer. By setting the content within this range, the deodorizing properties can be exhibited more effectively. The content is preferably 30 at% or more. The upper limit of the content is not particularly limited, but from the viewpoint of ensuring a certain level of copper metal content and exhibiting a certain level of decorative properties of copper metal, it is preferably 70 at%, more preferably 60 at%, even more preferably 50 at%, and even more preferably 40 at%.

[0037] In the fiber sheet of the present invention, the content of copper elements present as copper compounds other than copper(II) oxide in the copper element-containing alloy layer is 40 at% or less, 30 at% or less, 20 at% or less, 15 at% or less, 10 at% or less, 5 at% or less, or 1 at% or less, relative to 100 at% of copper elements in the copper element-containing alloy layer.

[0038] The metallic elements in the copper-containing alloy layer may consist only of copper and metallic elements with a higher ionization tendency than copper, or they may also contain other metallic elements. Examples of other metallic elements include alloys of silver, gold, palladium, rhodium, iridium, tellurium, platinum, and stainless steel.

[0039] In the fiber sheet of the present invention, the content of the above-mentioned other metal elements in the copper element-containing alloy layer is, for example, 20 at% or less, 10 at% or less, 5 at% or less, 2 at% or less, 1 at% or less, 0.5 at% or less, 0.2 at% or less, or 0.1 at% or less, relative to 100 at% of the metal elements in the copper element-containing alloy layer.

[0040] The content of metal elements in the above copper-containing alloy layer can be measured and calculated by the following method. First, the amount of metal elements deposited in the copper-containing alloy layer is measured and calculated as follows: Using a scanning X-ray fluorescence analyzer (Rigaku ZSX PrimusIII+ or equivalent), the acceleration voltage is set to 50kV, the acceleration current to 50mA, and the integration time to 60 seconds. The X-ray intensity of the Kα line of the component to be measured is measured, and the intensity at the background position is also measured in addition to the peak position to calculate the net intensity. From a calibration curve prepared in advance, the measured intensity values ​​are converted to the amount of deposit, and the same sample is measured five times. The average value is taken as the average amount of deposit for each metal element. Next, the composition (at%) of each metal element is calculated from the value of the amount of deposit of metal elements in the copper-containing alloy layer and the atomic weight of each metal element.

[0041] The copper(II) oxide content in the above copper-containing alloy layer is measured and calculated by the following method. It is possible.

[0042] The copper content (at%) relative to 100 at% of copper in the copper-containing alloy layer) is measured as follows: Using an X-ray photoelectron spectroscopy (XPS) instrument (ULVAC-FI PHI5000 VersaProbeII, or equivalent), measurements are taken under the following conditions to calculate the copper content (at%) relative to 100 at% of copper in the copper-containing alloy layer. (XPS measurement conditions) • X-ray source: Monochromatic AlKα (1486.6 eV) • Spectrometer: Electrostatic concentric hemispherical analyzer ·Photoelectron extraction angle: 45 degrees • Neutralization of static charge: Yes • X-ray beam diameter: 200 μm (50W 15kV) • Passage energy: 117 eV (survey), 58.7 eV (narrow).

[0043] The content of copper element present as copper(II) oxide in the copper element-containing alloy layer (content (at%) relative to 100 at% of metal elements in the copper element-containing alloy layer) is calculated as follows: From the content (at%) of copper element present as copper(II) oxide within the copper element in the copper element-containing alloy layer and the composition (at%) of copper element in the copper element-containing alloy layer, the content of copper element present as copper(II) oxide in the copper element-containing alloy layer (content (at%) relative to 100 at% of metal elements in the copper element-containing alloy layer) is calculated.

[0044] The amount of copper element adhering to the fibrous substrate is 10 μg / cm³. 2 It is preferable that the amount of adhesion is within this range. By setting the amount of adhesion within this range, the decorative properties of copper metal and the deodorizing properties of copper can be better exhibited. The amount of adhesion is preferably 15 μg / cm³. 2 More preferably 20 μg / cm³ 2 More preferably 30 μg / cm³ 2 That concludes the explanation. There is no particular upper limit on the amount of adhesion; for example, 150 μg / cm³. 2 , 120 μg / cm³ 2 , 100 μg / cm³ 2 , 80 μg / cm³ 2 70 μg / cm³ 2 60 μg / cm³ 2 , or 50 μg / cm³ 2 That is the case.

[0045] The amount of metal elements with a higher ionization tendency than copper adhering to the fibrous substrate is 5 μg / cm³. 2 It is preferable that the amount of adhesion is greater than or equal to this. By keeping the amount of adhesion within this range, better discoloration resistance can be achieved. The amount of adhesion is preferably 10 μg / cm³. 2 More preferably, 15 μg / cm³ 2 More preferably 20 μg / cm³ 2 That concludes the explanation. There is no particular upper limit on the amount of adhesion; for example, 100 μg / cm³. 2 , 80 μg / cm³ 2 70 μg / cm³ 2 60 μg / cm³ 2 50 μg / cm³ 2, 40 μg / cm³ 2 , or 30 μg / cm³ 2 That is the case.

[0046] The amount of metal elements deposited in the copper-containing alloy layer described above can be measured by the following method: Using a scanning X-ray fluorescence analyzer (Rigaku ZSX PrimusIII+ or equivalent), with an acceleration voltage of 50kV, an acceleration current of 50mA, and an integration time of 60 seconds, the X-ray intensity of the Kα line of the component to be measured is measured, and the intensity at the background position is also measured in addition to the peak position to calculate the net intensity. The measured intensity values ​​are converted to the amount of deposit using a calibration curve prepared in advance, and the same sample is measured five times, with the average value being taken as the amount of deposit for each metal element.

[0047] The thickness of the copper-containing alloy layer is not particularly limited, and is, for example, 1 to 200 nm. From the viewpoint of deodorizing properties and texture, the thickness is preferably 5 to 100 nm, and more preferably 10 to 80 nm.

[0048] The layer structure of the copper-containing alloy layer is not particularly limited. The copper-containing alloy layer may be a single layer or a plurality of layers having the same or different compositions. The copper-containing alloy layer is preferably a single layer. Furthermore, the copper-containing alloy layer may have a coating, such as an oxide film, on one or both of its two main surfaces.

[0049] <1-3. Oxide layer> The fiber sheet of the present invention may have an oxide layer on the side of the copper-containing alloy layer opposite to the fiber substrate side. The oxide layer can improve durability, such as resistance to discoloration.

[0050] The oxide layer is not particularly limited as long as it is a layer containing an oxide of a metal or metalloid as a material. The oxide layer may also contain components other than the oxide, as long as the effects of the present invention are not significantly impaired. In that case, the amount of the oxide in the oxide layer is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more, and is usually less than 100% by mass.

[0051] The metalloid oxide constituting the oxide layer is not particularly limited, and examples include oxides of metalloids (preferably silicon) such as silicon, germanium, antimony, and bismuth. More specifically, examples of metalloid oxides include compounds represented by AOX [wherein X is a number satisfying the formula: n / 2.5 ≤ X ≤ n / 2 (where n is the valence of the metalloid), and A is a metalloid selected from the group consisting of silicon, germanium, antimony, bismuth, and ]. When A in the above formula is a metalloid element, from the viewpoint of being able to adjust the color tone of the fiber sheet well, A is preferably silicon, and more preferably the metalloid oxide is SiO2. The metalloid oxide may be a single type or a combination of two or more types.

[0052] The metal oxides constituting the oxide layer are not particularly limited, and examples include oxides of metals such as titanium, zinc, aluminum, niobium, cobalt, and nickel (preferably titanium, zinc, and aluminum). More specifically, examples of metal oxides include compounds represented by AOX [wherein X is a number satisfying the formula: n / 2.5 ≤ X ≤ n / 2 (where n is the valence of the metal), and A is a metal selected from the group consisting of titanium, aluminum, niobium, cobalt, and nickel]. When A in the above formula is a metal element, from the viewpoint of being able to adjust the color tone of the fiber sheet well, A is preferably titanium and aluminum, and the metal oxide is more preferably TiO2, ZnO, and Al2O5. The metal oxide may be a single type or a combination of two or more types.

[0053] From the viewpoint of durability such as resistance to discoloration, transparency, and ease of color adjustment, X in the above formula is preferably n / 2.4 or more and n / 2 or less, more preferably n / 2.3 or more and n / 2 or less, even more preferably n / 2.2 or more and n / 2 or less, and particularly preferably n / 2.1 or more and n / 2 or less.

[0054] The thickness of the oxide layer is not particularly limited, and is, for example, 1 to 50 nm. From the viewpoint of simultaneously achieving improved durability such as resistance to discoloration and transparency, as well as easy adjustment of color, the thickness is preferably 2 to 20 nm, more preferably 3 to 10 nm.

[0055] The layer structure of the oxide layer is not particularly limited. The oxide layer may be a single layer or a plurality of layers having the same or different compositions.

[0056] <1-4. Manufacturing method> The method for manufacturing the fiber sheet of the present invention is not particularly limited. For example, it can be obtained by a method that includes the step of forming a copper element-containing alloy layer on the surface of a fiber substrate.

[0057] The above process can be carried out by, for example, sputtering, vacuum deposition, ion plating, chemical deposition, pulsed laser deposition, etc. Among these, sputtering is preferred from the viewpoint of film thickness controllability.

[0058] The sputtering method is not particularly limited, but examples include DC magnetron sputtering, high-frequency magnetron sputtering, and ion beam sputtering. The sputtering apparatus may be a batch type or a roll-to-roll type.

[0059] 2.Applications Since the fiber sheet of the present invention has a metallic appearance, it can be used in various fields as a fiber material with a unique design.

[0060] The fiber sheets of the present invention can be used specifically in textile products such as coats, jackets, trousers, skirts, sportswear, dress shirts, knit shirts, blouses, sweaters, cardigans, nightwear, underwear, supporters, socks, tights, hats, scarves, mufflers, neckwear, gloves, clothing linings, clothing interlinings, clothing padding, work clothes, uniforms, school uniforms, etc., as well as curtains, bedding fabrics, bedding cotton, pillowcases, sheets, mats, carpets, towels, handkerchiefs, masks, filters, decorative fabrics, wall coverings, wallpaper, and floor coverings. Among these textile products, decorative items (e.g., clothing made from decorative fabrics, interior items (e.g., curtains, wallpaper, wall coverings, etc.)) are particularly preferred.

[0061] Furthermore, as another specific example, the present invention can also be used as a composite material (which may be referred to as "composite material of the present invention" in this specification) containing the fiber sheet and resin.

[0062] The composite material of the present invention is not particularly limited as long as it contains the fiber sheet and resin of the present invention. Preferably, the composite material of the present invention is a fiber-reinforced plastic in which the fiber material of the present invention is contained in a resin that is the base material.

[0063] There are no particular restrictions on the resin used, and a wide variety of resins can be employed. Examples of resins include polyamide resins (e.g., nylon), polyphenylene ether, polyoxymethylene, polybutylene terephthalate, polycarbonate, polymethyl methacrylate (PMMA), polystyrene, polypropylene, polyetherimide, polyethersulfone, and polyvinyl chloride.

[0064] The composite material of the present invention can be manufactured by conventional methods and can be used in a variety of applications, such as structural materials for manufacturing automobiles (especially the interior and exterior of automobiles), aircraft, sports-related products (golf shafts, tennis rackets, badminton rackets, fishing rods, skis, snowboards, bats, archery equipment, bicycles, boats, canoes, yachts, windsurfing equipment, etc.), medical devices, building materials, electrical equipment (casings for personal computers, speaker cones, etc.), and more. [Examples]

[0065] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0066] (1) Manufacturing of fiber sheets (Example 1) Nonwoven fabric as a fiber base material (basis weight: 30g / m²) 2 Thickness: 0.29 mm, Density: 0.1034 g / cm³ 3 A fiber substrate (composition: glass fiber / acrylic resin) was used. The fiber substrate was placed in a roll-to-roll sputtering apparatus and evacuated to a vacuum of 5.0 × 10⁻⁴ Pa or less. Subsequently, argon gas and oxygen gas were introduced, and the gas pressure was set to 0.5 Pa. Using the DC magnetron sputtering method, a copper-nickel alloy (copper content: 57.5 at%, nickel content: 42.5 at%) was formed on one side of the fiber substrate as a copper-containing alloy layer. A fiber sheet was obtained in which the fiber substrate and the copper-containing alloy layer were laminated in that order.

[0067] (Example 2) As a fiber base material, nonwoven fabric (basis weight: 41g / m²) 2 , Thickness: 0.3mm, Density: 0.1367g / cm 3 A fiber sheet was obtained in the same manner as in Example 1, except that a polyester fiber sheet was used.

[0068] (Example 3) As a fiber base material, mesh fabric (basis weight: 23.6g / m²) 2 Thickness: 0.115 mm, Density: 0.2052 g / cm³3 A fiber sheet was obtained in the same manner as in Example 1, except that a polyester fiber sheet was used.

[0069] (Example 4) As a fiber base material, knitted fabric (weight: 84g / m 2 Thickness: 0.29mm, Density: 0.2897g / cm³ 3 A fiber sheet was obtained in the same manner as in Example 1, except that a polyester fiber sheet was used.

[0070] (Example 5) A fiber sheet was obtained in the same manner as in Example 4, except that a copper-nickel alloy (copper content: 67.9 at%, nickel content: 32.1 at%) was used as the copper element-containing alloy layer.

[0071] (Example 6) As a fiber base material, mesh fabric (basis weight: 47.9g / m²) 2 Thickness: 0.675 mm, Density: 0.071 g / cm³ 3 A fiber sheet was obtained in the same manner as in Example 1, except that a polyester fiber sheet was used.

[0072] (Example 7) As a fiber base material, nonwoven fabric (basis weight: 90.8 g / m²) 2 Thickness: 5.3mm, Density: 0.0171g / cm³ 3 A fiber sheet was obtained in the same manner as in Example 1, except that a polyester fiber sheet was used.

[0073] (Example 8) As a fiber base material, nonwoven fabric (basis weight: 64.4 g / m²) 2 Thickness: 0.215mm, Density: 0.2995g / cm³ 3 A fiber sheet was obtained in the same manner as in Example 1, except that a polyester fiber sheet was used.

[0074] (Example 9) As a fiber base material, woven fabric (basis weight: 213.2 g / m²) 2 Thickness: 0.6mm, Density: 0.3553g / cm³ 3A fiber sheet was obtained in the same manner as in Example 1, except that a polyester fiber sheet was used.

[0075] (Example 10) A fiber sheet was obtained in the same manner as in Example 2, except that a copper-zinc alloy (copper content: 76 at%, zinc content: 24 at%) was used as the copper element-containing alloy layer.

[0076] (Comparative Example 1) A fiber sheet was obtained in the same manner as in Example 4, except that the copper(II) oxide content in the copper element-containing alloy layer was changed.

[0077] (Comparative Example 2) A fiber sheet was obtained in the same manner as in Example 4, except that copper (copper content: 100 at%) was used as the copper element-containing alloy layer.

[0078] (Comparative Example 3) A fiber sheet was obtained in the same manner as in Example 4, except that a copper-nickel alloy (copper content: 31 at%, nickel content: 69 at%) was used as the copper element-containing alloy layer.

[0079] (2) Measurement (2-1) Measurement of the amount of metal elements deposited in the copper-containing alloy layer The amount of metal elements adhering to a fibrous substrate from a copper-containing alloy layer was measured as follows: Using a scanning X-ray fluorescence analyzer (Rigaku ZSX PrimusIII+), the acceleration voltage was set to 50kV, the acceleration current to 50mA, and the integration time to 60 seconds. The X-ray intensity of the Kα line of the target component was measured, and the intensity at both the peak and background positions was measured to calculate the net intensity. The measured intensity values ​​were converted to the amount of adhering elements using a pre-prepared calibration curve. Five measurements were performed on the same sample, and the average value was taken as the amount of adhering elements for each metal element.

[0080] (2-2) Measurement of the composition of metallic elements in copper-containing alloy layers The composition of metal elements in the copper-containing alloy layer was calculated as follows: The composition (at%) of each metal element was calculated from the amount of metal elements deposited in the copper-containing alloy layer measured in (2-1) above and the atomic weight of each metal element.

[0081] (2-3) Measurement of the proportion of copper elements present as copper(II) oxide in copper element-containing alloy layers The content of copper element present as copper(II) oxide in the copper element-containing alloy layer (content (at%) relative to 100 at% of copper element in the copper element-containing alloy layer) was measured as follows.

[0082] Using an X-ray photoelectron spectroscopy (XPS) instrument (ULVAC-PHI, PHI5000 VersaProbeII), measurements were performed under the following conditions to calculate the content of copper element present as copper(II) oxide in the copper element-containing alloy layer (content (at%) relative to 100 at% of copper element in the copper element-containing alloy layer). (XPS measurement conditions) • X-ray source: Monochromatic AlKα (1486.6 eV) • Spectrometer: Electrostatic concentric hemispherical analyzer ·Photoelectron extraction angle: 45 degrees • Neutralization of static charge: Yes • X-ray beam diameter: 200 μm (50W 15kV) • Passage energy: 117 eV (survey), 58.7 eV (narrow).

[0083] (2-4) Measurement of the proportion of copper element present as copper(II) oxide in the metallic elements of a copper-containing alloy layer The content of copper element present as copper(II) oxide in the copper element-containing alloy layer (content (at%) relative to 100 at% of metal elements in the copper element-containing alloy layer) was measured as follows.

[0084] From the copper content (at%) of copper elements present as copper(II) oxide in the copper element-containing alloy layer measured in (2-3) above, and the copper element composition (at%) in the copper element-containing alloy layer measured in (2-2) above, the content of copper elements present as copper(II) oxide in the copper element-containing alloy layer (content (at%) relative to 100 at% of metal elements in the copper element-containing alloy layer) was calculated.

[0085] (3) Evaluation (3-1) Deodorizing Test The deodorizing properties of the fiber sheets in the examples and comparative examples were evaluated as follows. The tests were conducted in accordance with the deodorizing properties test method using the detector tube method of the SEK Mark Textile Product Certification Standards established by the Japan Textile Evaluation Technology Council.

[0086] After placing the sample (100 cm², 1.0 g, or 200 cm²) into a 5 L bag, 3 L of hydrogen sulfide gas was injected into the bag to achieve a concentration of 4 ppm. After 2 hours, the remaining hydrogen sulfide gas concentration was measured. A blank sample was prepared in the same manner except that no sample was added. The remaining hydrogen sulfide gas concentration of this blank sample was measured, and the total amount of hydrogen sulfide gas removed was calculated from the measurements of both companies. The reduction rate of hydrogen sulfide gas was then calculated. <Evaluation Criteria> ◎: Decrease rate of 99% or more. ○: The decrease rate is between 50% and 99%. △: Decrease rate is between 25% and 50%. ×: The decrease rate is less than 25%.

[0087] (3-2) Color change test The color changes of the fiber sheets in the examples and comparative examples were evaluated as follows: Using a spectrophotometer (SD7000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), the L*, a*, and b* values ​​in the L*, a*, b* color system were measured on the surface of the fiber sheet to which the copper-containing alloy layer was attached, in accordance with JIS Z 8781-4 (2013).

[0088] The color difference was calculated using the ΔE00 formula specified in CIE DE2000 from the L*, a*, and b* values ​​obtained after exposing the fiber sheet to a 120°C atmosphere for 120 hours, and from the L*, a*, and b* values ​​obtained before the color change test. <Evaluation Criteria> ◎: ΔE00 is less than 5.0. ○: ΔE00 is 5.0 or greater and less than 15. ×: ΔE00 is 15 or greater.

[0089] (3-3) Overall evaluation Based on the deodorizing properties and color change evaluations, a comprehensive evaluation was conducted according to the following evaluation criteria. <Evaluation Criteria> ○: The deodorizing performance evaluation is ○ or ◎, and the color change evaluation is ○ or ◎. ×: The deodorizing performance evaluation is ×, and / or the color change evaluation is ×.

[0090] (4) Evaluation The results are shown in Tables 1 and 2.

[0091] [Table 1]

[0092] [Table 2]

Claims

1. The material comprises a fibrous substrate and a copper-containing alloy layer disposed on the fibrous substrate. A fiber sheet wherein the content of a metal element having a greater ionization tendency than copper in the copper element-containing alloy layer is 20 at% or more relative to 100 at% of the metal elements in the copper element-containing alloy layer, and the content of copper element existing as copper(II) oxide in the copper element-containing alloy layer is 15 at% or more relative to 100 at% of the metal elements in the copper element-containing alloy layer.

2. The fiber sheet according to claim 1, wherein the copper content in the copper element-containing alloy layer is 50 at% or more relative to 100 at% of the metal elements in the copper element-containing alloy layer.

3. The fiber sheet according to claim 2, wherein the content of copper elements present as copper(II) oxide in the copper element-containing alloy layer is 25 at% or more relative to 100 at% of copper elements in the copper element-containing alloy layer.

4. The fiber sheet according to any one of claims 1 to 3, wherein the metal element having a greater ionization tendency than copper is at least one metal element selected from the group consisting of nickel, zinc, and aluminum.

5. The amount of copper element adhering to the aforementioned fibrous substrate is 20 μg / cm³. ２ The fiber sheet according to any one of claims 1 to 3.

6. The density of the aforementioned fibrous base material is 0.015 g / cm³. ３ ~0.3 g / cm ３ The fiber sheet according to any one of claims 1 to 3.

7. A textile product comprising a fiber sheet according to any one of claims 1 to 3.

8. A textile product according to claim 7, which is a decorative item.

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