Decorative fiber sheet

Abstract

To provide a decorative fiber sheet with a higher washing resistance even though a metal layer containing aluminum is provided on a fiber base material.SOLUTION: There is provided a decorative fiber sheet including a fiber base material and a metal layer. The metal layer includes a mixed layer containing aluminum and a metal other than aluminum.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to decorative 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. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-006409 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In the course of their research, the inventors discovered that by placing a metal layer on a fiber substrate, it is possible to impart color and metallic luster while preserving the texture of the fiber substrate, thereby further enhancing its design appeal (Patent Document 1). In this technology, using aluminum in the metal layer allows for high design appeal. However, further research revealed that fiber sheets using aluminum in the metal layer are prone to delamination of the metal layer and exhibit a relatively large degree of color change due to washing.

[0005] The present invention aims to provide a decorative fiber sheet that has a metal layer containing aluminum arranged on a fiber base material, yet exhibits high wash resistance. [Means for solving the problem]

[0006] In view of the above problems, the inventors diligently conducted research and found that the above problems can be solved if the decorative fiber sheet includes a fiber base material and a metal layer, wherein the metal layer includes a mixed layer containing aluminum and other metals. Based on this finding, the inventors furthered their research and completed the present invention. That is, the present invention encompasses the following embodiments.

[0007] Item 1. A decorative fiber sheet comprising a fiber base material and a metal layer, wherein the metal layer includes a mixed layer containing aluminum and other metals.

[0008] Item 2. The decorative fiber sheet according to Item 1, wherein the metal layer includes a reflective layer.

[0009] Item 3. The decorative fiber sheet according to Item 2, wherein the reflective layer contains titanium.

[0010] Item 4. The decorative fiber sheet according to Item 1, wherein the metal other than aluminum contained in the mixed layer is at least one metal selected from the group consisting of titanium and silver.

[0011] Item 5. The decorative fiber sheet according to any one of items 1 to 4, wherein the aluminum content in the mixed layer is 5% by mass or more and 80% by mass or less.

[0012] Item 6. The decorative fiber sheet according to any one of items 1 to 4, wherein the aluminum content in the mixed layer is 60% by mass or more and 80% by mass or less.

[0013] Item 7. The decorative fiber sheet according to any one of items 1 to 4, wherein the mixed layer has a concentration gradient in which the aluminum is more abundant, in the thickness direction of the decorative fiber sheet, from the surface of the mixed layer opposite to the fiber substrate toward the surface of the mixed layer toward the fiber substrate.

[0014] Item 8. The design fiber sheet according to any one of Items 1 to 4, wherein the metal layer includes a reflective layer, and the fiber base material, the reflective layer, and the mixed layer are laminated in this order.

[0015] Item 9. The design fiber sheet according to any one of Items 1 to 4, wherein the thickness of the mixed layer is 3 nm or more.

[0016] Item 10. The design fiber sheet according to any one of Items 1 to 4, wherein the fiber base material includes fibers of 5 denier or more and 70 denier or less.

[0017] Item 11. The design fiber sheet according to any one of Items 1 to 4, wherein a color-developing layer is included on the surface of the mixed layer opposite to the fiber base material.

[0018] Item 12. The design fiber sheet according to Item 11, wherein the color-developing layer includes a semi-metal or an oxide.

[0019] Item 13. It includes a fiber base material and a metal layer. The metal layer includes a reflective layer containing titanium, and a mixed layer containing aluminum and at least one metal selected from the group consisting of titanium and silver. The content of aluminum in the mixed layer is 5% by mass or more and 80% by mass or less. The mixed layer has a concentration gradient in which aluminum is more contained from the surface of the mixed layer opposite to the fiber base material toward the surface of the mixed layer on the fiber base material side in the thickness direction of the design fiber sheet, and The fiber base material, the reflective layer, and the mixed layer are laminated in this order. A design fiber sheet.

Advantages of the Invention

[0020] According to the present invention, it is possible to provide a design fiber sheet having higher washing resistance while having a metal layer containing aluminum disposed on a fiber base material.

Brief Description of the Drawings

[0021] [Figure 1]An example of a method for forming a mixed layer is shown. [Figure 2] A schematic cross-sectional view is shown illustrating an example of the decorative fiber sheet of the present invention. [Figure 3] A schematic cross-sectional view is shown illustrating an example of the decorative fiber sheet of the present invention. [Figure 4] A schematic cross-sectional view is shown illustrating an example of the decorative fiber sheet of the present invention. [Modes for carrying out the invention]

[0022] In this specification, the terms “contains” and “includes” include the concepts of “contains,” “includes,” “substantially consist of,” and “consist solely of.”

[0023] 1. Decorative fiber sheet In one embodiment, the present invention relates to a decorative fiber sheet (sometimes referred to as "the fiber sheet of the present invention" in this specification) comprising a fiber base material and a metal layer, wherein the metal layer comprises a mixed layer containing aluminum and other metals. This will be described below.

[0024] <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, paper, etc. Among these, woven fabrics and knitted fabrics are preferred, and woven fabrics are preferred, from the viewpoint that the fiber surface is flat and the light reflectivity is relatively high, which further enhances the design of the fibrous sheet of the present invention. The fibrous base material may be subjected to various treatments such as cire treatment, embossing treatment, and calendering treatment. By using a fibrous base material with higher smoothness, the metallic feel of the fibrous sheet of the present invention can be further enhanced.

[0025] 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.

[0026] 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.).

[0027] 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.

[0028] The fineness of the fibers is not particularly limited, but from the viewpoint of reducing weight, it is preferably 5 denier or more and 70 denier or less, more preferably 10 denier or more and 50 denier or less, and even more preferably 15 denier or more and 30 denier or less.

[0029] The fibers may be a single type or a combination of two or more types.

[0030] 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.

[0031] 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 500 μm, preferably 10 to 50 μm.

[0032] The above-mentioned fiber base material may have known finishing agents attached to it, such as flame retardants, water absorbents, water repellents, softeners, heat storage agents, ultraviolet shielding agents, antistatic agents, antibacterial agents, deodorizers, insect repellents, mosquito repellents, phosphorescent agents, and retroreflective agents.

[0033] <1-2. Metal layer> The metal layer is placed on the fibrous substrate. Other layers may be provided between the metal layer and the fibrous substrate. Preferably, the metal layer is placed on the fibrous substrate without any other layers in between.

[0034] <1-2-1. Mixed layer> The metal layer includes a mixed layer containing aluminum and other metals.

[0035] The mixed layer is a layer containing aluminum and metals other than aluminum as materials. The mixed layer may also contain components other than the said materials. In that case, the total content of aluminum and metals other than aluminum in the mixed 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.

[0036] Other metals are not particularly limited as long as they have higher alkali resistance than aluminum. Examples of such metals include titanium, silver, gold, molybdenum, niobium, indium, chromium, nickel, tungsten, tantalum, stainless steel, nickel-chromium alloys, nickel-copper alloys, etc. Among these, titanium, silver, gold, copper, iron, molybdenum, niobium, indium, etc. are preferred from the viewpoints of luster, color saturation and brightness, and durability such as resistance to discoloration, and titanium and silver, etc. are more preferred, and titanium is particularly preferred. Furthermore, in clothing applications, titanium is preferably used from the viewpoint of reducing metal allergy reactions and preventing false detections by metal detectors.

[0037] The metals other than aluminum may be a single type or a combination of two or more types.

[0038] If the fiber sheet of the present invention includes a color-developing layer described later, and the color-developing layer contains a metal element, it is preferable that the metal element most abundant in the color-developing layer and the metal element most abundant in the mixed layer are different, from the viewpoint of metallic luster, brightness, and saturation of the colors.

[0039] The aluminum content in the mixed layer (preferably, the aluminum content relative to 100% by mass of the total of aluminum and other metals in the mixed layer) is not particularly limited, but from the viewpoint of wash resistance, it is preferably 80% by mass or less, and more preferably 75% by mass or less. The lower limit of the aluminum content in the mixed layer is not particularly limited, and is, for example, 5%, 10%, 20%, 30%, 40%, 50%, 60%, or 65% by mass. From the viewpoint of design, the lower limit of the aluminum content in the mixed layer is preferably 55% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more. From the viewpoint of wash resistance, the aluminum content in the mixed layer can preferably be 5% by mass or more and 80% by mass or less, and from the viewpoint of wash resistance and design, it can preferably be 60% by mass or more and 80% by mass or less.

[0040] The aluminum content in the mixed layer is measured as follows: The aluminum content in the mixed layer can be determined by X-ray fluorescence analysis. Specifically, a scanning X-ray fluorescence analyzer (for example, Rigaku ZSX PrimusIII+ or equivalent) is used 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 metal component to be measured is measured, and the intensity at the background position is also measured in addition to the peak position so that the net intensity can be calculated. The amount of each metal attached can be converted from the measured intensity values ​​using a calibration curve prepared in advance. The same sample is analyzed five times, and the average value is taken as the average content. The amount of the mixed layer is calculated by subtracting the amount of the reflective layer and the amount of the fiber substrate from the amount of the fiber sheet, and then calculating the aluminum content.

[0041] In the mixed layers, aluminum and other metals are present together (i.e., they are mixed). Therefore, the mixed layers do not contain any layers consisting solely of aluminum as the metal.

[0042] From the viewpoint of wash resistance, it is preferable that the mixed layer has a concentration gradient in which aluminum is more abundant in the thickness direction of the decorative fiber sheet, from the surface of the mixed layer opposite to the fiber base material toward the surface of the mixed layer toward the fiber base material side.

[0043] The concentration gradient is measured as follows: The concentration gradient of the mixed layer can be determined by X-ray photoelectron spectroscopy (XPS). Depth profile measurement is performed using ion sputtering to measure the concentration distribution in the depth direction. The elemental analysis conditions in the thickness direction are set to a sputtering rate of 3.63 nm / min (2 kV) in SiO2 equivalent, and C1s is set to 284.8 eV as normalization. The atomic concentration is quantified from the X-ray intensity of the target metal. A graph is obtained with the thickness direction on the horizontal axis and the elemental concentration on the vertical axis. The composition ratio is determined from the atomic densities of the two target metals on the vertical axis. The presence or absence of a concentration gradient in the mixed layer is determined from the movement of the composition ratio values ​​in each thickness direction. In the XPS graph showing the change in content (vertical axis) in the thickness direction (horizontal axis), the presence or absence and direction of the concentration gradient are determined after ignoring minute fluctuation peaks (e.g., peaks of content change of 5% or less).

[0044] The thickness of the mixed layer is not particularly limited, and is, for example, 1 to 200 nm. From the viewpoint of design, the thickness is preferably 3 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more. Furthermore, if there is no reflective layer as described later, the mixed layer is preferably relatively thick, specifically, for example, 15 nm or more, preferably 20 nm or more, and even more preferably 30 nm or more. The total thickness of the mixed layer and the reflective layer described later (the thickness of the mixed layer alone if there is no reflective layer) is preferably 20 nm or more, more preferably 30 nm or more, and even more preferably 40 nm or more. The upper limit of the thickness of the mixed layer is not particularly limited, and is, for example, 100 nm, 80 nm, or 60 nm.

[0045] The thickness of the mixed layer and the thickness of each layer described below can be determined by X-ray fluorescence analysis. Specifically, the analysis is performed using a scanning X-ray fluorescence analyzer (for example, a 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 rays of the metal component to be measured is measured, and the intensity at the background position is also measured in addition to the peak position so that the net intensity can be calculated. The measured intensity values ​​can be converted to deposition amounts from a calibration curve prepared in advance. Furthermore, the thickness can be calculated from the converted deposition amount and the density of the target material. The same sample is analyzed five times, and the average value is taken as the average thickness.

[0046] The layer structure of the mixed layer is not particularly limited. The mixed layer is preferably a single layer (preferably a single layer having an aluminum concentration gradient). In addition, one or both of the two main surfaces of the mixed layer may be composed of a film such as an oxide film.

[0047] <1-2-2. Reflective layer> The metal layer may further include a reflective layer. This can improve wash resistance. When the metal layer includes a reflective layer, from the viewpoint of wash resistance, it is preferable that the layers are laminated in the order of fiber base material, reflective layer, and mixed layer. When the metal layer includes a reflective layer, in one embodiment of the present invention, there is no other layer between the mixed layer and the metal layer, and in another embodiment, there is a other layer between the mixed layer and the metal layer.

[0048] The reflective layer is not particularly limited as long as it is a layer containing metal as a material. The reflective layer may also contain components other than metal. In that case, the amount of metal in the reflective 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.

[0049] The metal constituting the reflective layer is not particularly limited, and examples include titanium, silver, gold, molybdenum, niobium, indium, chromium, nickel, tungsten, tantalum, stainless steel, nickel-chromium alloy, nickel-copper alloy, etc. Among these, titanium, silver, gold, copper, iron, molybdenum, niobium, indium, etc. are preferred from the viewpoint of gloss, color saturation and brightness, and durability such as resistance to discoloration, and titanium, silver, etc. are more preferred, and titanium is particularly preferred. Furthermore, in clothing applications, titanium is preferably used from the viewpoint of reducing metal allergy reactions and preventing false detections by metal detectors.

[0050] If the fiber sheet of the present invention includes a color-developing layer described later, and the color-developing layer contains a metal element, it is preferable that the metal element most abundant in the color-developing layer and the metal element most abundant in the reflective layer are different, from the viewpoint of metallic luster, brightness, and saturation of the colors.

[0051] The most abundant metallic element in the reflective layer is preferably titanium, silver, gold, copper, iron, molybdenum, niobium, or indium.

[0052] The metal may be a single type or a combination of two or more types.

[0053] The thickness of the reflective layer is not particularly limited, and is, for example, 1 to 200 nm. From the viewpoint of increasing the brightness and saturation of the colors, the thickness is preferably 5 to 100 nm, and more preferably 10 to 80 nm.

[0054] The layer structure of the reflective layer is not particularly limited. The reflective layer may be a single layer or a plurality of layers having the same or different compositions. Furthermore, the reflective layer may have a coating, such as an oxide film, on one or both of its two main surfaces. From the viewpoint of wash resistance, it is preferable that the reflective layer does not contain a layer made solely of aluminum as the metal.

[0055] <1-3. Color-developing layer> The fiber sheet of the present invention preferably includes a color-developing layer. In one embodiment of the present invention, the color-developing layer is located on the surface of the mixed layer opposite to the fiber substrate. Other layers may be provided between the color-developing layer and the mixed layer, but it is preferable that no other layers are present. The color-developing layer can primarily adjust the saturation and hue of the color.

[0056] The mechanism by which the fiber sheet of the present invention is imparted a metallic luster, color, and angle-dependent color is thought to involve (1) the influence of light absorption by the color-generating layer, (2) the influence of optical interference caused by the color-generating layer, the mixed layer, and / or the reflective layer, and (3) the influence of light absorption and reflection by the mixed layer and / or the reflective layer.

[0057] The color-developing layer is preferably a layer containing a metallic element or a metalloid element. The color-developing layer may also contain components other than metallic elements and metalloid elements. In that case, the content of metallic elements and metalloid elements in the color-developing layer is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 75% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, very preferably 99% by mass or more, and is usually less than 100% by mass.

[0058] The metallic and / or metalloid elements constituting the colored layer are not particularly limited. Examples of metals include gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, niobium, or indium. Examples of metalloids include silicon, germanium, antimony, boron, phosphorus, and bismuth. Among these, silicon, germanium, and titanium are preferred from the viewpoint of metallicity, angle dependence of color, and increasing the brightness and saturation of the color, with silicon being more preferred.

[0059] Preferably, the most abundant metallic or metalloid element in the colored layer is titanium, silicon, or germanium.

[0060] The metallic element and the metalloid element may be single or in combination of two or more kinds.

[0061] The color - emitting layer may be composed of a metal, a metalloid or an alloy composed of the above - mentioned metallic element or metalloid element, may be composed of a compound containing the above - mentioned metallic element or metalloid element, or may be composed of a mixture thereof. Examples of the compound containing a metallic element or a metalloid element include oxides, nitrides, carbides, oxynitrides, etc.

[0062] Examples of the above - mentioned oxide include, for example, MO X [wherein, X is a number satisfying the formula: n / 100 ≤ X ≤ n / 2 (n is the valence of the metalloid), and M is a metallic element or a metalloid element.] The compound represented thereby is mentioned.

[0063] Examples of the above - mentioned nitride include, for example, MN y [wherein, Y is a number satisfying the formula: n / 100 ≤ Y ≤ n / 3 (n is the valence of the metalloid), and M is a metallic element or a metalloid element.] The compound represented thereby is mentioned.

[0064] Examples of the above - mentioned carbide include, for example, MC z [wherein, Z is a number satisfying the formula: n / 100 ≤ Z ≤ n / 4 (n is the valence of the metalloid), and M is a metallic element or a metalloid element.] The compound represented thereby is mentioned.

[0065] Examples of the above - mentioned oxynitride include, for example, MO X N y [wherein, X and Y satisfy n / 100 ≤ X, n / 100 ≤ Y, and X + Y < n / 2 (n is the valence of the metal or metalloid), and M is a metallic element or a metalloid element.] The compound represented thereby is mentioned.

[0066] Regarding the oxidation number X of the above - mentioned oxide or oxynitride, for example, MO x or MO x N yThe cross-section of the layer containing [it] is subjected to elemental analysis using a field emission type transmission electron microscope FE-TEM-EDX (for example, "JEM-ARM200F" manufactured by JEOL Ltd.), and X is calculated from the elemental ratio of M and O per unit area of the cross-section of the layer containing MOx or MOxNy, whereby the valence of oxygen atoms can be calculated.

[0067] Regarding the degree of nitridation Y of the above nitride or oxynitride, for example, MN y or MO x N y The cross-section of the layer containing [it] is subjected to elemental analysis using a field emission type transmission electron microscope FE-TEM-EDX (for example, "JEM-ARM200F" manufactured by JEOL Ltd.), and Y is calculated from the elemental ratio of M and N per unit area of the cross-section of the layer containing MN y or MO x N y Thereby, the valence of nitrogen atoms can be calculated.

[0068] Regarding the degree of carbonization Z of the above carbide, for example, MC Z The cross-section of the layer containing [it] is subjected to elemental analysis using a field emission type transmission electron microscope FE-TEM-EDX (for example, "JEM-ARM200F" manufactured by JEOL Ltd.), and Z is calculated from the elemental ratio of M and C per unit area of the cross-section of the layer containing MC Z Thereby, the valence of carbon atoms can be calculated.

[0069] The color-forming layer is MO x or MN y In the case of a layer containing [it] (in the case of MO x y M represents an n-valent metal or semi-metal, and X represents a number of 0 or more and n / 2 or less. MNIn this case, M represents an n-valent metal or metalloid, and Y represents a number between 0 and n / 3. It is preferable to have ). In this case, M is preferably titanium, silicon, or germanium. Among these, silicon, germanium, and titanium are preferred from the viewpoint of increasing color saturation, and silicon, germanium, and the like are more preferred. From the viewpoint of further increasing color saturation, the value of x in MOx is preferably n / 4 or less, more preferably n / 8 or less, and even more preferably n / 16 or less. MO x When M is silicon, X preferably represents a number less than 1, more preferably 0.5 or less, and even more preferably less than 0.5. MN y If M is silicon, Y preferably represents a number less than or equal to 4 / 3. z If M is silicon, Z preferably represents a number less than or equal to 1.

[0070] The coloring layer preferably contains a metalloid element.

[0071] The coloring layer preferably contains a metalloid or oxide (metal oxide or metalloid oxide). In this case, it is preferable that the metalloid or oxide contains at least one selected from the group consisting of silicon, germanium, antimony, boron, phosphorus, bismuth, silicon oxide, and titanium oxide.

[0072] The thickness of the color-developing layer is not particularly limited, but is, for example, 1 to 500 nm. From the viewpoint of metallicity, angle dependence of color, and increasing the brightness and saturation of the color, the thickness is preferably 5 to 300 nm, more preferably 10 to 150 nm, even more preferably 100 nm or less, and even more preferably 80 nm or less. These upper and lower limits can be combined arbitrarily.

[0073] The layer structure of the color-developing layer is not particularly limited. The color-developing layer may be a single layer or a plurality of layers having the same or different compositions. The color-developing layer may have one or both of its two main surfaces composed of a film such as an oxide film.

[0074] <1-4. Oxide layer> The fiber sheet of the present invention preferably has an oxide layer on the outermost surface opposite to the fiber base material. The oxide layer can further improve durability, such as resistance to discoloration.

[0075] 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.

[0076] 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, as metalloid oxides, AO X Compounds represented by the formula [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 ] are examples. When A in the above formula is a metalloid element, silicon is preferred for A, and SiO2 is more preferred for the metalloid oxide, from the viewpoint of being able to adjust the color tone of the fiber sheet well. The metalloid oxide may be a single type or a combination of two or more types.

[0077] The metal oxide constituting the oxide layer is 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, as metal oxides, AOX Examples of compounds represented by the formula [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] are given. When A in the above formula is a metallic 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] <1-5. Washing resistance> The fiber sheet of the present invention has higher washing resistance despite having a metal layer containing aluminum arranged on a fiber base material. For example, the color change (ΔE00) measured according to "(2-2) Evaluation of Washing Resistance" in the examples described below can be, for example, less than 10, preferably less than 8, more preferably less than 6, even more preferably less than 5, even more preferably less than 4, particularly preferably less than 3, and especially preferably less than 2.5.

[0082] <1-6. 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 a step of forming a mixed layer on the surface of a fiber substrate. If a reflective layer is included, for example, the fiber sheet of the present invention can be manufactured by forming a reflective layer on the surface of a fiber substrate and then forming a metal layer on the reflective layer.

[0083] While not particularly limited, the formation can be carried out by methods such as sputtering, vacuum deposition, ion plating, chemical deposition, and pulsed laser deposition. Among these, sputtering is preferred from the viewpoint of film thickness control.

[0084] 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.

[0085] A mixed layer can be obtained, for example, in the case of sputtering, by using a dual cathode and pulsed power supply to form a film while transporting the substrate in one direction, as illustrated in Figure 1. In this example, a metal with a relatively high aluminum content is deposited on the substrate first (in (1) in Figure 1), followed by a metal with roughly equal aluminum and titanium content (in (2) in Figure 1), and finally a metal with a relatively high titanium content (in (3) in Figure 1). In this way, a single-layer mixed layer with an aluminum concentration gradient can be formed. Even when forming a mixed layer by a method other than sputtering, the mixed layer can be formed by a method similar to the one described above.

[0086] 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.

[0087] The fiber sheet 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, collars, 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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]

[0092] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0093] (1) Manufacturing of decorative fiber sheets (Example 1) A fibrous substrate (Toyota Tsusho Corporation's "FY1499" (nylon fiber (20 denier), plain weave)) is placed inside a roll-to-roll sputtering device, and 5.0 × 10 -4 The vacuum was evacuated until the pressure was below Pa. Subsequently, argon gas was introduced, and with a gas pressure of 0.5 Pa, a Ti layer (reflective layer, average thickness 35 nm) was formed on one surface of the fiber substrate by DC magnetron sputtering to obtain sheet 1.

[0094] Next, sheet 1 is placed inside a roll-to-roll sputtering machine, and 5.0 × 10 -4 The vacuum was evacuated until the pressure was below Pa. Subsequently, argon gas was introduced, and the gas pressure was set to 0.5 Pa. Using a dual cathode with an Al target on one side (upstream) and a Ti target on the other side (downstream), a mixed layer (average thickness 10 nm) consisting of Ti and Al, and containing both Ti and Al, was formed on the Ti layer of sheet 1 by DC bipolar pulse sputtering. A decorative fiber sheet was obtained by laminating the fiber substrate, reflective layer, and mixed layer in that order.

[0095] The Al ratio in the mixed layer was measured as follows. The aluminum content in the mixed layer was determined by X-ray fluorescence analysis. Specifically, a scanning X-ray fluorescence analyzer (e.g., Rigaku ZSX Primus III+) was used with an acceleration voltage of 50 kV, an acceleration current of 50 mA, and an integration time of 60 seconds. The X-ray intensity of the Kα line of the metal component to be measured was measured, and the intensity at the background position was also measured in addition to the peak position so that the net intensity could be calculated. The measured intensity values ​​were converted to the amount of each metal attached using a calibration curve prepared in advance. Five analyses were performed on the same sample, and the average value was taken as the average content. The average content of the mixed layer was calculated by subtracting the average content of the reflective layer and the fiber substrate from the average content of the fiber sheet, and the aluminum content was calculated. As a result, the Al ratio in the mixed layer of the decorative fiber sheet obtained in Example 1 was 70 mass%.

[0096] The concentration gradient of Al and Ti in the thickness direction of the mixed layer can be measured as follows. The concentration gradient of the mixed layer can be determined by X-ray photoelectron spectroscopy (XPS). Depth profile measurement is performed using ion sputtering to measure the concentration distribution in the depth direction. The elemental analysis conditions in the thickness direction are set to a sputtering rate of 3.63 nm / min (2 kV) in SiO2 equivalent, and C1s is set to 284.8 eV as normalization. The atomic concentration is quantified from the X-ray intensity of the target metal. A graph is obtained with the thickness direction on the horizontal axis and the elemental concentration on the vertical axis. The composition ratio is determined from the atomic densities of the two target metals on the vertical axis. The concentration gradient of the mixed layer is calculated from the movement of the composition ratio values ​​in each thickness direction. From its manufacturing method, the mixed layer has a concentration gradient in the thickness direction of the decorative fiber sheet, with a higher Al content from the surface of the mixed layer opposite the fiber substrate toward the surface of the mixed layer toward the fiber substrate.

[0097] (Example 2) The decorative fiber sheet obtained in Example 1 was placed in a roll-to-roll sputtering apparatus, and 5.0 × 10 -4The vacuum was evacuated until the pressure was below Pa. Subsequently, argon gas was introduced, and with a gas pressure of 0.5 Pa, a Si layer (coloring layer, average thickness 20 nm) was formed on the mixed layer by MF magnetron sputtering. A decorative fiber sheet was obtained in which the fiber substrate, reflective layer, mixed layer, and coloring layer were laminated in that order.

[0098] (Example 3) A decorative fiber sheet was obtained in the same manner as in Example 2, except that the thickness of the coloring layer was changed.

[0099] (Example 4) A decorative fiber sheet was obtained in the same manner as in Examples 1 and 2, except that the thickness of the mixed layer was changed and the Al ratio in the mixed layer was increased. Specifically, the Al ratio in the mixed layer was increased by changing the output ratio of the Ti target and the Al target in DC bipolar pulse sputtering. Specifically, the Al ratio in the mixed layer was increased by using a DC bipolar pulse sputtering unit (e.g., Advanced Energy's Asent(R)30K / DC Ascent(R)DMS or equivalent) and pulse control software (e.g., Advanced Energy's PowerView(R)VFP or equivalent) to increase the duty cycle.

[0100] (Example 5) A decorative fiber sheet was obtained in the same manner as in Example 1 and Example 2, except for changing the thickness of the mixed layer.

[0101] (Example 6) A decorative fiber sheet was obtained in the same manner as in Examples 1 and 2, except that the Al ratio in the mixed layer was reduced. Specifically, the Al ratio in the mixed layer was reduced by decreasing the duty cycle, in the same manner as in Example 4.

[0102] (Example 7) A decorative fiber sheet was obtained in the same manner as in Example 1 and Example 2, except that the Al ratio in the mixed layer was increased.

[0103] (Example 8) A decorative fiber sheet was obtained in the same manner as in Example 1 and Example 2, except that a reflective layer was not formed and the thickness of the mixed layer was changed.

[0104] (Example 9) A decorative fiber sheet was obtained in the same manner as in Examples 1 and 2, except that the concentration gradients of Al and Ti in the mixed layer were changed in opposite directions. Specifically, the concentration gradient was changed in the opposite direction by changing the arrangement of the Ti target and Al target in DC bipolar pulse sputtering. For example, the Ti target was set on one side (upstream direction) and the Al target on the other side (downstream direction), and the process was carried out in the same manner as in Examples 1 and 2.

[0105] From its manufacturing method, the mixed layer has a concentration gradient in the thickness direction of the decorative fiber sheet, with a higher Al content from the surface of the mixed layer on the fiber substrate side toward the surface of the mixed layer opposite the fiber substrate.

[0106] (Comparative Example 1) A decorative fiber sheet was obtained in the same manner as in Example 1 and Example 2, except that no mixed layer was formed and the reflective layer was an Al layer.

[0107] (Comparative Example 2) A decorative fiber sheet was obtained in the same manner as in Example 1 and Example 2, except that a mixed layer was not formed and the reflective layer was a multilayer (3-layer) structure consisting of a Ti layer (average thickness 10 nm), an Al layer (average thickness 10 nm), and a Ti layer (average thickness 25 nm) from the fiber substrate side.

[0108] (Comparative Example 3) A decorative fiber sheet was obtained in the same manner as in Example 1 and Example 2, except that no mixed layer was formed.

[0109] (2) Measurement and evaluation (2-1) Evaluation of design quality The saturation of the surface of the decorative fiber sheet opposite the fiber substrate was measured, and the aesthetic appeal was evaluated based on this saturation. Specifically, the following procedure was followed: As a method for evaluating aesthetic appeal, chromaticity measurement was performed using a colorimeter. A KONICA MINOLTA CM2500d colorimeter was used to measure the samples. The saturation C was calculated from the a* and b* values ​​obtained by analyzing the measurement results using the color management software CM-S100W SpectraMagic(R)NX. The calculation results were compared with Comparative Example 3, and evaluated as × if the saturation C was the same, △ if it was slightly higher, and ○ if it was significantly higher.

[0110] (2-2) Evaluation of washing tolerance The wash resistance of decorative fiber sheets was evaluated. Specifically, the following procedure was followed: Washing was performed in accordance with the C4M method of JIS L1930, and after washing, hanging drying (Method A) was used. This was performed 20 times, with each cycle considered one. After that, the L*, a*, and b* of the samples were measured. The samples were measured using a KONICA MINOLTA CM2500d colorimeter. The measurement results were analyzed using the color management software CM-S100W SpectraMagic(R)NX to calculate L*, a*, and b*. Samples were measured similarly before washing, and the color change before and after washing was calculated as ΔE00 based on CIEDE2000. A result of ΔE00 < 5 was judged as ○, 5 ≤ ΔE00 < 10 as △, and 10 ≤ ΔE00 as ×.

[0111] (3) Results The results are shown in Table 1.

[0112] [Table 1] [Explanation of Symbols]

[0113] 1. Fiber base material 2. Mixed layer 3 reflective layer 4. Color-developing layer

Claims

1. A decorative fiber sheet comprising a fiber base material and a metal layer, The aforementioned metal layer includes a mixed layer containing aluminum and titanium, The aluminum content in the mixed layer is 5% by mass or more and 85% by mass or less relative to the total mass of aluminum and titanium in 100% by mass. The total content of aluminum and titanium in the aforementioned mixed layer is 80% by mass or more, The mixed layer has a concentration gradient in the thickness direction of the decorative fiber sheet, from the surface of the mixed layer opposite to the fiber substrate toward the surface of the mixed layer toward the fiber substrate side, with a higher concentration of aluminum. Decorative fiber sheet.

2. The decorative fiber sheet according to claim 1, wherein the metal layer includes a reflective layer.

3. The decorative fiber sheet according to claim 2, wherein the reflective layer contains titanium.

4. The decorative fiber sheet according to claim 1, wherein the total content of aluminum and titanium in the mixed layer is 90% by mass or more.

5. The decorative fiber sheet according to any one of claims 1 to 4, wherein the aluminum content in the mixed layer is 5% by mass or more and 80% by mass or less.

6. The decorative fiber sheet according to any one of claims 1 to 4, wherein the aluminum content in the mixed layer is 60% by mass or more and 80% by mass or less.

7. The decorative fiber sheet according to any one of claims 1 to 4, wherein the aluminum content in the mixed layer is 20% by mass or more and 80% by mass or less relative to 100% by mass of the total of aluminum and titanium.

8. The decorative fiber sheet according to any one of claims 1 to 4, wherein the metal layer includes a reflective layer, and the fiber substrate, the reflective layer, and the mixed layer are laminated in that order.

9. The decorative fiber sheet according to any one of claims 1 to 4, wherein the thickness of the mixed layer is 3 nm or more.

10. The decorative fiber sheet according to any one of claims 1 to 4, wherein the fiber base material contains fibers of 5 denier or more and 70 denier or less.

11. The decorative fiber sheet according to any one of claims 1 to 4, further comprising a color-developing layer on the surface of the mixed layer opposite to the fiber substrate.

12. The decorative fiber sheet according to claim 11, wherein the color-developing layer contains a metalloid or an oxide.

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