Fiber sheet

Abstract

To provide a technique that suppresses variation of a color and glossiness due to friction, in a fiber sheet with a metal layer arranged on a fibrous substrate.SOLUTION: A fiber sheet having a fiber substrate and a metal layer arranged on the fiber substrate, in which the fiber sheet has a concavo-convex structure X different from a concavo-convex structure due to a constituent fiber of the fiber substrate, a difference Δh of heights of a convex region a and a concave region b in the concavo-convex structure X is 3 to 15 μm, and in an optional 3 cm × 3 cm region, two of the area a and the area b are possessed.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a fiber sheet and the like.

Background Art

[0002] Fiber base materials are used in various fields where design is required. For example, carbon fiber base materials are used to form composite materials (such as carbon fiber reinforced plastics) together with resins, and are widely used from relatively large ones such as aircraft bodies to relatively small and familiar ones such as sports goods, interior and exterior materials of cars, and clothes. Therefore, fiber base materials may be colored to enhance their design. Also, in that case, glossiness may be imparted due to their unique design.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the course of research, the present inventor has found that by disposing a metal layer on a fiber base material, it is possible to impart color and metallic luster while leaving the texture of the fiber base material, and it has been found that the design can be further enhanced. However, in the course of further research, it has been found that in a fiber sheet employing this technique, changes in color and luster occur due to friction on the surface of the metal layer.

[0005] An object of the present invention is to provide a technique for suppressing changes in color and luster due to friction in a fiber sheet having a metal layer disposed on a fiber base material.

Means for Solving the Problems

[0006] As a result of intensive research in view of the above problems, the inventor has found that a fiber sheet having a fiber base material and a metal layer disposed on the fiber base material, wherein the fiber sheet has an uneven structure X different from the uneven structure formed by the constituent fibers of the fiber base material, the height difference Δh between the convex region a and the concave region b in the uneven structure X is 3 to 15 μm, and there are two or more of the region a or the region b in any 3 cm × 3 cm region can solve the above problems. Based on this finding, the inventor has further conducted research and completed the present invention.

[0007] That is, the present invention includes the following aspects.

[0008] Item 1. A fiber sheet having a fiber base material and a metal layer disposed on the fiber base material, wherein the fiber sheet has an uneven structure X different from the uneven structure formed by the constituent fibers of the fiber base material, the height difference Δh between the convex region a and the concave region b in the uneven structure X is 3 to 15 μm, and there are two or more of the region a or the region b in any 3 cm × 3 cm region.

[0009] Item 2. The fiber sheet according to Item 1, wherein the ratio of the area of the region b to the area of any 3 cm × 3 cm region is 20 to 70%.

[0010] Item 3. The fiber sheet according to Item 1 or 2, wherein in any 3 cm × 3 cm region, the region a and the region b form an island-in-sea structure P, or the region a and the region b form a structure Q in which a plurality of each are laid.

[0011] Item 4. The fiber sheet according to Item 3, wherein the any 3 cm × 3 cm region is the island-in-sea structure P having the region b as an island portion or the structure Q, and the area of one region b is 3.1 cm 2 or less. fiber sheet.

[0012] Item 5. The area of one region b is 0.05 cm2 The fiber sheet according to any one of items 1 to 4 above as described above.

[0013] Item 6. The arbitrary 3 cm × 3 cm area is the sea-island structure P having the area a as an island portion and the area of one area a is 0.05 to 3.1 cm 2 The fiber sheet according to item 3 above sheet.

[0014] Item 7. The fiber sheet according to any one of items 1 to 6 above, wherein the fiber constituting the fiber base material is 10 to 70 denier as described above.

[0015] Item 8. The fiber sheet according to any one of items 1 to 7 above, further having a color tone adjustment layer

Advantages of the Invention

[0016] According to the present invention, it is possible to provide a fiber sheet having a color and metallic luster imparted by a metal layer and having resistance to discoloration due to friction as described above.

Brief Description of the Drawings

[0017] [Figure 1] The part of Δh in the schematic cross-sectional view of the fiber sheet is shown.

Embodiments for Carrying Out the Invention

[0018] In this specification, the expressions "containing" and "including" include the concepts of "containing", "including", "substantially consisting of", and "consisting only of".

[0019] 1. Fiber sheet In one aspect, the present invention relates to a fiber sheet having a fiber base material and a metal layer disposed on the fiber base material, wherein the fiber sheet has an uneven structure X different from the uneven structure formed by the constituent fibers of the fiber base material, and the height difference Δh between the convex region a and the concave region b in the uneven structure X is 3 to 15 μm, and there are two or more of the region a or the region b in any 3 cm × 3 cm region. (In this specification, it may also be referred to as "the fiber sheet of the present invention"). The following will explain this.

[0020] <1-1. Fiber base material> The fiber base material is a base material containing fibers or fiber bundles as raw materials. As long as it has an uneven structure X different from the uneven structure formed by the constituent fibers, the height difference Δh between the convex region a and the concave region b in the uneven structure X is 3 to 15 μm, and it has two or more of the region a or the region b in any 3 cm × 3 cm region, it is not particularly limited. By using such a fiber base material, the uneven structure X can be reflected in the fiber sheet of the present invention, the peeling of the metal layer due to friction can be reduced in the concave region b, and thereby the discoloration due to friction in the entire fiber sheet can be suppressed.

[0021] The fiber base material is a base material containing fibers or fiber bundles as raw materials.

[0022] The fibers constituting the fiber substrate are not particularly limited, and examples thereof include synthetic fibers (such as nylon fibers, polyester fibers, acrylic fibers, vinylon fibers, polyolefin fibers, polyethylene fibers, polypropylene fibers, polyurethane fibers, polyamide fibers, polyacrylonitrile fibers, etc.), regenerated fibers (such as rayon, polynosic, cupra, lyocell, acetate, etc.), plant fibers (such as cotton fibers, hemp fibers, linen fibers, rayon fibers, polynosic fibers, cupra fibers, lyocell fibers, acetate fibers, etc.), animal fibers (such as wool, silk, tussah silk, mohair, cashmere, camel, llama, alpaca, vicuña, angora, spider silk, etc.) and other organic fibers; carbon fibers (such as PAN-based carbon fibers, pitch-based carbon fibers, carbon nanotubes, etc.), glass fibers (such as glass wool, glass fiber, etc.), mineral fibers (such as chrysotile asbestos, white asbestos, crocidolite asbestos, amosite asbestos, anthophyllite asbestos, tremolite asbestos, actinolite asbestos, etc.), man-made mineral fibers (such as rock wool, ceramic fiber, etc.), metal fibers (such as stainless steel fibers, aluminum fibers, iron fibers, nickel fibers, copper fibers, etc.) and other inorganic fibers, which can be widely used.

[0023] The form of the fiber may be any of continuous long fibers, short fibers obtained by cutting continuous long fibers, milled yarns pulverized into powder form, etc.

[0024] The thickness of the fiber is not particularly limited. From the viewpoint of resistance to fading due to friction, the fiber is preferably 5 to 200 denier, more preferably 5 to 100 denier, and still more preferably 10 to 70 denier.

[0025] The fiber may be a single type or a combination of two or more types.

[0026] The fiber bundle is not particularly limited as long as it is composed of a plurality of fibers. The number of fibers constituting the fiber bundle is, for example, 5 or more, 10 or more, 20 or more, 50 or more, while on the other hand, it is, for example, 50000 or less, 20000 or less, 15000 or less, 2000 or less. These upper and lower limit values can be arbitrarily combined.

[0027] The fibrous substrate 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 substrate is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and usually less than 100% by mass.

[0028] Examples of the fibrous substrate include woven fabrics (e.g., plain weave, twill weave (diagonal weave), crepe weave, etc.), knitted fabrics, non-woven fabrics, paper, and the like. Among these, from the viewpoint of enhancing the design property of the fiber sheet of the present invention, woven fabrics, knitted fabrics, etc. are preferably mentioned, and woven fabrics are more preferably mentioned.

[0029] The fibrous substrate has an uneven structure X different from the uneven structure formed by the constituent fibers.

[0030] The uneven structure formed by the constituent fibers is a fine uneven structure caused by the thickness, shape, etc. of the constituent fibers. For example, when the fibrous substrate is a woven fabric, the step between the warp or a bundle thereof and the weft or a bundle thereof disposed thereon (or thereunder) (the thickness of the warp or a bundle thereof or the weft or a bundle thereof in the woven fabric) and the groove formed between adjacent yarns in the bundle of warp or weft constitute the uneven structure formed by the constituent fibers.

[0031] The uneven structure X is different from the uneven structure formed by the constituent fibers and is not particularly limited as long as it is different. The fibrous substrate having the uneven structure X can be obtained by various methods. The fibrous substrate having the uneven structure X can be obtained, for example, by laminating a fibrous substrate on a partial region of a fibrous substrate having only the uneven structure formed by the constituent fibers to form a convex region, or by pressing a partial region of a fibrous substrate having only the uneven structure formed by the constituent fibers to form a concave region.

[0032] The height difference Δh between the convex region a and the concave region b in the uneven structure X in the fiber substrate is 3 to 15 μm. Δh is preferably 5 to 13 μm, more preferably 6 to 12 μm, and still more preferably 6.5 to 11.5 μm from the viewpoint of the fade resistance to friction. When Δh is 3 μm or more, the frictional force on the fiber substrate can be appropriately dispersed by the uneven structure X, and the fade resistance is improved. When it is 15 μm or less, the excessive concentration of the frictional force on the convex region a is suppressed, and the fade resistance of the entire fiber substrate is improved. For example, when forming the uneven structure X by an embossing process, Δh can be adjusted by the shape of the embossing roll, the height of the die pressing portion, the heating temperature of the embossing roll and the heat roll, the pressing conditions, and the like.

[0033] Δh can be obtained using a digital microscope observation and image analysis software. More specifically, for the regions a and b within an arbitrarily cut 3 cm × 3 cm sample, observe with a digital microscope (Digital Microscope DVM6 manufactured by Leica Microsystems or its equivalent), and obtain the height difference between the convex region a and the concave region b using image analysis software (LAX X manufactured by Leica Microsystems or its equivalent). Observe at a magnification that includes the regions a and b and includes the uneven structure formed by the constituent fibers at three or more locations in each region, and obtain the height difference between the adjacent regions a and b from the cross-sectional profile analysis. Here, the heights of the regions a and b are obtained from the same cross-sectional profile. For the uneven structure formed by the constituent fibers in each region, as shown in FIG. 1, the average of the heights of three points of the peaks and three points of the valleys of the uneven structure, a total of six points, is taken as the height of each region, and the difference is taken as Δh. The boundary between the regions a and b is determined from the difference in appearance due to the shape, contrast, etc. of the uneven structure X.

[0034] The number of Region a or Region b in any 3 cm × 3 cm area of the fiber substrate is two or more. From the perspective of resistance to color fading against friction, the number is preferably 2 to 250, more preferably 3 to 100, still more preferably 3 to 50, and even more preferably 3 to 20. For example, when forming the concavo-convex structure X by embossing treatment, the number of Region a or Region b can be adjusted according to the shape of the embossing roll and the like.

[0035] The number of Region a or Region b in any 3 cm × 3 cm area can be counted visually. When the convex region or the concave region straddles the boundary line of any 3 cm × 3 cm area, the area formed by the boundary line of the convex region or the concave region and the boundary line of the 3 cm × 3 cm area is treated as one Region a or Region b.

[0036] From the perspective of resistance to color fading against friction, the ratio of the area of Region b to the area of any 3 cm × 3 cm area of the fiber substrate is preferably 10 to 90%, more preferably 10 to 80%, still more preferably 20 to 70%, even more preferably 45 to 65%, and particularly preferably 50 to 60%. For example, when forming the concavo-convex structure X by embossing treatment, the ratio of the area of Region b can be adjusted according to the shape of the embossing roll and the like.

[0037] The area of Region b and its ratio to the area of any 3 cm × 3 cm area can be obtained by using digital microscope observation and image analysis software. More specifically, for all Region b in an arbitrarily cut 3 cm × 3 cm sample, observe with a digital microscope (Leica Microsystems digital microscope DVM6 or its equivalent), and use image analysis software (Leica Microsystems LAX X or its equivalent) to obtain the area of Region b one by one. The area ratio of Region b is obtained from the percentage of the total area value of all Region b in the sample with respect to the area (9 cm 2 ) of an arbitrarily cut 3 cm × 3 cm sample.

[0038] The ratio of the area of region a to the area of any 3 cm × 3 cm region of the fiber substrate is preferably 10 to 90%, more preferably 20 to 80%, still more preferably 30 to 80%, even more preferably 35 to 55%, and particularly preferably 40 to 50% from the viewpoint of resistance to color fading against friction. For example, when forming the concavo-convex structure X by embossing treatment, the ratio of the area of region a can be adjusted according to the shape of the embossing roll and the like.

[0039] The ratio of the area of region a to the area of any 3 cm × 3 cm region is measured in the same manner as the ratio of the area of region b.

[0040] The area of one region b is preferably 0.01 cm 2 or more, more preferably 0.05 cm 2 or more, still more preferably 0.3 cm 2 or more, even more preferably 0.6 cm 2 or more from the viewpoint of resistance to color fading against friction. Also, the area of one region b is preferably 4 cm 2 or less, more preferably 3.5 cm 2 or less, still more preferably 3.1 cm 2 or less, even more preferably 2 cm 2 or less from the viewpoint of resistance to color fading against friction. The area of one region b is preferably 0.01 to 4 cm 2 , more preferably 0.05 to 3.1 cm 2 , still more preferably 0.3 to 3.1 cm 2 , even more preferably 0.6 to 2 cm 2 from the viewpoint of resistance to color fading against friction. For example, when forming the concavo-convex structure X by embossing treatment, the area of one region b can be adjusted according to the shape of the embossing roll and the like.

[0041] The area of one region a is preferably 0.01 cm 2 or more, more preferably 0.05 cm 2 or more, still more preferably 0.3 cm 2 or more, even more preferably 0.6 cm 2The above is the case. Also, the area of one region a is preferably 4 cm from the viewpoint of resistance to fading due to friction. 2 or less, more preferably 3.5 cm 2 or less, even more preferably 3.1 cm 2 or less, still more preferably 2 cm 2 or less. The area of one region a is preferably 0.01 - 4 cm from the viewpoint of resistance to fading due to friction. 2 , more preferably 0.05 - 3.1 cm 2 , even more preferably 0.3 - 3.1 cm 2 , still more preferably 0.6 - 2 cm 2 is the case. For example, when forming the concavo-convex structure X by embossing treatment, the area of one region a can be adjusted according to the shape of the embossing roll or the like.

[0042] The area per one of region b and region a is measured as follows. The area per one of region b and region a is obtained using digital microscope observation and image analysis software. Specifically, for region b and region a in an arbitrarily cut 3 cm × 3 cm sample, observation is carried out with a digital microscope (Digital Microscope DVM6 manufactured by Leica Microsystems or its equivalent), and the area is obtained with image analysis software (LAX X manufactured by Leica Microsystems or its equivalent). The areas of all region b and region a existing in the 3 cm × 3 cm sample are obtained.

[0043] In the fiber base material, a three-dimensional pattern is formed by region a and region b. The three-dimensional pattern is not particularly limited, and examples include a three-dimensional pattern formed by region a and region b constituting the sea-island structure P, and a three-dimensional pattern formed by region a and region b being laid in a plurality respectively to constitute structure Q (for example, a lattice pattern, a checkered pattern, etc.). In the sea-island structure P, either region a or region b may be the island part.

[0044] In a preferred embodiment of the present invention, in any 3 cm × 3 cm area, area a and area b form a sea-island structure P, or area a and area b are each laid in a plurality to form a structure Q. In this embodiment, from the viewpoint of resistance to fading due to friction, any 3 cm × 3 cm area is a sea-island structure P or structure Q having area b as the island part, and the area of one of the areas b is 3.1 cm 2 or less, or any 3 cm × 3 cm area is a sea-island structure P having area a as the island part, and the area of one of the areas a is 0.05 to 3.1 cm 2 is preferable.

[0045] By adopting a fiber base material with higher smoothness as the fiber base material, the metallic feeling of the fiber sheet of the present invention can be enhanced more. Further, by increasing the flatness of area b of the fiber base material, the design property of the decorative fiber sheet of the present invention becomes higher.

[0046] The layer structure of the fiber base material is not particularly limited. The fiber base material may be composed of a single type of fiber base material, or may be a combination of two or more types of fiber base materials.

[0047] The thickness of the fiber base material can vary depending on the type of fiber and is not particularly limited. The thickness of the fiber base material is, for example, 3 to 500 μm, preferably 10 to 50 μm.

[0048] The above-mentioned fiber base material may have a known finishing agent such as a flame retardant, a water absorbent, a water repellent, a softening agent, a heat storage agent, an ultraviolet ray shielding agent, an antistatic agent, an antibacterial agent, a deodorant, an insect repellent, a mosquito repellent, a phosphorescent agent, a retroreflective agent, etc. attached thereto.

[0049] The fiber base material having the above-mentioned concavo-convex structure X can be manufactured by various methods as described above. As an example, when using a thermoplastic resin fiber as the fiber, it can be manufactured by performing embossing on the fiber base material containing the thermoplastic resin fiber with an embossing device composed of an embossing roll and a heat roll. Hereinafter, this manufacturing method will be described in detail.

[0050] As the thermoplastic resin fiber, synthetic fibers such as polyester, polyamide, and polyacrylonitrile can be preferably used. Also, as the fabric, any of woven fabric, knitted fabric, non-woven fabric, tuft (embroidery) fabric, electrodeposited fabric, etc. may be used. Further, it may or may not have a pile.

[0051] The embossing roll and the heat roll are preferably made of metal with a surface coated such as plating, and both are of a type that is heated from inside the roll. The diameter is preferably 150 mm to 600 mm. The heating temperature is preferably 100 to 250°C. To emboss the fabric, the fabric is first heated by the heat roll, and when it has advanced 1 / 2 to 3 / 4 of a rotation, it is pressed between the heated embossing roll and embossed. When both are made of metal, it is easy to fix the pattern and a sharp die-pressed pattern can be imparted. From the viewpoint of the texture of the fiber sheet, etc., the heating temperature of the embossing roll and the heat roll is preferably 100 to 250°C.

[0052] Also, the distance between the embossing roll and the heat roll is appropriately adjusted according to the thickness and density of the fabric, but from the viewpoint of suppressing unevenness in the pattern, it is preferable that the embossing roll and the heat roll are kept parallel at an interval of 0.05 mm to 2 mm.

[0053] Also, by passing the fabric through between the embossing roll and the heat roll arranged at an appropriate interval in a state where it is pressed at a processing speed of 0.3 m / min to 20 m / min, the fabric is sufficiently heated and a pattern with excellent durability is imparted.

[0054] The embossing portions on the surface of the embossing roll are preferably arranged in a dispersed state. The height of the embossing portions depends on the thickness of the fabric, but is preferably 0.1 mm to 10 mm. The embossing portions correspond to the pressing portions of the fabric, and although it also depends on the design of the pattern, the total area of the embossing portions is preferably 10 to 90%, more preferably 10 to 80%, even more preferably 20 to 70%, still more preferably 45 to 65%, and particularly preferably 50 to 60% of the surface area of the embossing roll. The embossing portions are preferably arranged in a dispersed manner.

[0055] <1-2. Metal layer> The metal layer is disposed on the fiber substrate. Another layer may be provided between the metal layer and the fiber substrate. Preferably, the metal layer is disposed on the fiber substrate without an intervening other layer.

[0056] The metal layer is not particularly limited as long as it is a layer containing a metal as a material. The metal layer may contain components other than the metal. In that case, the amount of metal in the metal layer is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, and usually less than 100% by mass.

[0057] The metal constituting the metal layer is not particularly limited, and examples thereof include gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, niobium, indium, chromium, nickel, tungsten, tantalum, stainless steel, nickel-chromium alloy, nickel-copper alloy, etc. Among these, from the viewpoints of glossiness, color saturation and lightness, and durability such as colorfastness, gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, niobium, indium, etc. are preferably used. Also, in clothing applications, etc., titanium is preferably used from the viewpoints of reducing metal allergic reactions and preventing false detection by a needle detector.

[0058] When the fiber sheet of the present invention includes a color tone adjustment layer described below and the color tone adjustment layer contains a metal element, from the viewpoints of metallic luster, increasing the lightness and chroma of colors, etc., it is preferable that the metal element most contained in the color tone adjustment layer is different from the metal element most contained in the metal layer.

[0059] The metal element most contained in the metal layer is preferably gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, niobium, or indium.

[0060] The metal may be a single species or a combination of two or more species.

[0061] The thickness of the metal layer is not particularly limited, and is, for example, 1 to 200 nm. From the viewpoints of increasing the lightness and chroma of colors, etc., the thickness is preferably 5 to 100 nm, more preferably 10 to 80 nm.

[0062] The layer structure of the metal layer is not particularly limited. The metal layer may be a single layer composed of one layer, or may be a plurality of layers having the same or different compositions. Also, on one or both of the two main surfaces of the metal layer, the surface may be composed of a film such as an oxide film.

[0063] <1-3. Color Tone Adjustment Layer> The color tone adjustment layer is a layer disposed on the fiber substrate. The color tone adjustment layer can be disposed on the fiber substrate via another layer (for example, the aforementioned metal layer).

[0064] The color tone adjustment layer is preferably a layer containing a metal element or a metalloid element as a material. The color tone adjustment layer may contain components other than the metal element and the metalloid element. In that case, the content of the metal element and the metalloid element in the color tone adjustment layer is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, very preferably 99% by mass or more, and usually less than 100% by mass.

[0065] The metal or metalloid constituting the color tone adjustment layer is not particularly limited. Examples of the metal include gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, niobium, or indium, etc., and examples of the metalloid include silicon, germanium, antimony, boron, phosphorus, bismuth, etc. Among these, from the viewpoints of the breadth of the selection range of impartable colors, the durability of the fiber sheet, etc., silicon, germanium, etc. are preferably mentioned, and silicon, etc. are more preferably mentioned.

[0066] The metal element and the metalloid element may be single or a combination of two or more.

[0067] The color tone adjustment layer may be composed of a metal, metalloid or alloy composed of a metal element or a metalloid element, may be composed of a compound containing a metal element or a metalloid element, or may be composed of a mixture thereof. Examples of the compound containing a metal element or a metalloid element include oxides, nitrides, carbides, and oxynitrides, etc.

[0068] Examples of the above-mentioned oxide include 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 metalloid element.] The compound represented thereby is mentioned.

[0069] Examples of the above-mentioned nitride include 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 metalloid element.] The compound represented thereby is mentioned.

[0070] Examples of the above-mentioned carbide include 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 metalloid element.] The compound represented thereby is mentioned.

[0071] Examples of the above-mentioned oxynitride include 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 semimetal), and M is a semimetal element.]. Examples of the compound represented thereby include those described below.

[0072] Regarding the oxidation number X of the above oxide or oxynitride, for example, in the case of MO x or MO x N y The cross-section of the layer containing [it] is subjected to elemental analysis by 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 MO x or MO x N y Thereby, the valence of the oxygen atom can be calculated.

[0073] Regarding the nitrogenation number Y of the above nitride or oxynitride, for example, in the case of MN y or MO x N y The cross-section of the layer containing [it] is subjected to elemental analysis by 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 the nitrogen atom can be calculated.

[0074] Regarding the carbonation number Z of the above carbide, for example, the cross-section of the layer containing MCz is subjected to elemental analysis by 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 the carbon atom can be calculated.

[0075] The color tone adjustment layer preferably has a layer containing MOx (where M represents an n-valent semi-metal and x represents a number of 0 or more and less than n / 2), MNy (where M represents an n-valent semi-metal and y represents a number of 0 or more and less than or equal to n / 3), or MCz (where M represents an n-valent metal or semi-metal and z represents a number of 0 or more and less than or equal to n / 4). In this case, M is preferably silicon, germanium, gallium, zinc, silver, gold, titanium, aluminum, molybdenum, niobium, or indium, respectively. Among these, from the viewpoint of increasing the chroma of the color, etc., preferably silicon, germanium, titanium, etc. are mentioned, and more preferably silicon, germanium, etc. are mentioned.

[0076] From the viewpoint of further increasing the chroma of the color, etc., in MO x when M in it is silicon, X preferably represents a number less than 1, and more preferably represents a number less than 0.5. In MN y when M in it is silicon, Y preferably represents a number less than or equal to 4 / 3. In MC z when M in it is silicon, Z preferably represents a number less than or equal to 1.

[0077] The color tone adjustment layer preferably contains a semi-metal element, and it is more preferably a layer in which the semi-metal is the main component (for example, 80 mass% or more, preferably 90 mass% or more, more preferably 95 mass% or more, still more preferably 99 mass% or more). The semi-metal element most contained in the color tone adjustment layer is preferably silicon or germanium.

[0078] The thickness of the color tone adjustment layer is not particularly limited, but is, for example, 1 to 200 nm. From the viewpoint of the metallic luster feeling, the viewpoint of increasing the lightness and chroma of the color, etc., it is preferably 3 to 140 nm, and more preferably 4 to 140 nm.

[0079] The layer structure of the color tone adjustment layer is not particularly limited. The color tone adjustment layer may be a single layer consisting of one layer, or may be a plurality of layers having the same or different compositions. The color tone adjustment layer may have a surface composed of a film such as an oxide film on one or both of its two main surfaces.

[0080] <1-4. Oxide layer> It is preferable that the fiber sheet of the present invention has an oxide layer on the surface on the opposite side of the fiber base material from the metal layer or the color tone adjustment layer. The oxide layer can further improve durability such as discoloration resistance.

[0081] The oxide layer is not particularly limited as long as it contains an oxide of a metal or a metalloid as a material. The oxide layer may 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, still more preferably 99% by mass or more, and usually less than 100% by mass.

[0082] The metalloid oxide constituting the oxide layer is not particularly limited, and examples thereof include oxides of metalloids such as silicon, germanium, antimony, bismuth, etc. (preferably silicon). More specifically, as the metalloid oxide, AO X [wherein, X is a number satisfying the formula: n / 2.5 ≦ X ≦ n / 2 (n is the valence of the metalloid), and A is a metalloid selected from the group consisting of silicon, germanium, antimony, bismuth, and.]. Compounds represented by the above formula are exemplified. When A in the above formula is a metalloid element, A is preferably silicon from the viewpoint of being able to favorably adjust the color tone of the fiber sheet, and it is more preferable that the metalloid oxide is SiO2. The metalloid oxide may be a single species or a combination of two or more species.

[0083] The metal oxide constituting the oxide layer is not particularly limited, and examples thereof include oxides of metals such as titanium, zinc, aluminum, niobium, cobalt, nickel, etc. (preferably titanium, zinc, and aluminum). More specifically, as the metal oxide, AO X[In the formula, 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.]. Examples of the compound represented by the above formula include those in which, when A in the above formula is a metal element, from the viewpoint of being able to favorably adjust the color tone of the fiber sheet, A is preferably titanium and aluminum, and the metal oxides are more preferably TiO2, ZnO, and Al2O5. The metal oxides may be used alone or in combination of two or more.

[0084] From the viewpoints of durability such as discoloration resistance, transparency, and ease of adjusting the color, 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, still 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.

[0085] The thickness of the oxide layer is not particularly limited and is, for example, 1 to 50 nm. From the viewpoints of simultaneously achieving improvement in durability such as discoloration resistance and transparency, and easy adjustment of the color, the thickness is preferably 2 to 20 nm, and more preferably 3 to 10 nm.

[0086] The layer structure of the oxide layer is not particularly limited. The oxide layer may be a single layer consisting of one layer or may be a plurality of layers having the same or different compositions.

[0087] <1-5. Fiber Sheet> In the fiber sheet of the present invention, on the outermost surface on the metal layer side, there is an uneven structure X in which the uneven structure X of the above-described fiber base material is reflected. That is, the fiber sheet of the present invention, like the fiber base material, has an uneven structure X different from the uneven structure formed by the constituent fibers of the fiber base material, and the height difference Δh between the convex region a and the concave region b in the uneven structure X is 3 to 15 μm, and there are two or more of the region a or the region b in any 3 cm × 3 cm region. The uneven structure X in the fiber sheet of the present invention and the convex region (region a) and the concave region (region b) in the structure are the same as the uneven structure X and the regions a and b in the above-described fiber base material.

[0088] <1-6. Manufacturing method> The manufacturing method of the fiber sheet of the present invention is not particularly limited. As an example, it can be obtained by a method including a step of forming a semi-metal element-containing layer as a color tone adjustment layer on the surface of a fiber substrate. When a metal layer is included, for example, after forming a metal layer on the surface of the fiber substrate, the decorative fiber sheet of the present invention can be manufactured by forming a color tone adjustment layer on the metal layer.

[0089] Although not particularly limited, the deposition can be performed, for example, by a sputtering method, a vacuum evaporation method, an ion plating method, a chemical vapor deposition method, a pulsed laser deposition method, or the like. Among these, from the viewpoint of film thickness controllability, the sputtering method is preferable.

[0090] The sputtering method is not particularly limited, and examples thereof include direct current magnetron sputtering, high frequency magnetron sputtering, and ion beam sputtering. Also, the sputtering apparatus may be of a batch type or a roll-to-roll type.

[0091] 2. Use Since the fiber sheet of the present invention has a metallic feeling, it can be used in various fields as a fiber material having a unique design.

[0092] Specifically, the fiber sheet of the present invention can be used, for example, in clothing such as coats, jackets, trousers, skirts, sportswear, shirts, knitted shirts, blouses, sweaters, cardigans, nightwear, underwear, supporters, socks, tights, hats, scarves, mufflers, collars, gloves, linings of clothes, cores of clothes, waddings of clothes, work clothes, uniforms, school uniforms for schoolchildren, etc., and fiber products such as curtains, futon covers, futon waddings, pillowcases, sheets, mats, carpets, towels, handkerchiefs, masks, filters, decorative fabrics / textiles, wall fabrics, wallpapers, and floor coverings.

[0093] Also, as another specific example, it is also possible to use the fiber sheet of the present invention and a composite material containing a resin (which may be referred to as "the composite material of the present invention" in this specification).

[0094] The composite material of the present invention is not particularly limited as long as it contains the fiber sheet of the present invention and a resin. 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 a base material.

[0095] The resin is not particularly limited, and various resins can be adopted. Examples of the resin include polyamide-based resins (e.g., nylon), polyphenylene ether, polyoxymethylene, polybutylene terephthalate, polycarbonate, polymethyl methacrylate (PMMA), polystyrene, polypropylene, polyetherimide, polyethersulfone, polyvinyl chloride, and the like.

[0096] The composite material of the present invention can be manufactured according to a conventional method and can be utilized in various applications such as structural materials for manufacturing automobiles (especially interior and exterior parts of automobiles), aircraft, sports-related products (golf shafts, tennis rackets, badminton rackets, fishing rods, ski boards, snowboards, bats, archery, bicycles, boats, canoes, yachts, windsurfing, etc.), medical instruments, building members, and electrical equipment (cases of personal computers, etc., speaker cones).

Examples

[0097] Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited by these examples.

[0098] (1) Preparation of fiber substrate (Fiber base material 1) As the fiber base material, a plain-woven nylon fiber base material ("TM3001" manufactured by Masuda Co., Ltd., 30 denier) was used. (Fiber base material 2) As the fiber substrate, a plain-woven nylon fiber substrate ("RIP-15" manufactured by Masuda Co., 15 denier) was used. (Fiber substrate 3) As the fiber substrate, a plain-woven nylon fiber substrate ("NBR20" manufactured by Masuda Co., 20 denier) was used. (Fiber substrate 4) As the fiber substrate, a plain-woven nylon fiber substrate ("MX-11W" manufactured by Masuda Co., 50 denier) was used. (Fiber substrate 5) As the fiber substrate, a plain-woven nylon fiber substrate ("TM-22M" manufactured by Masuda Co., 70 denier) was used.

[0099] (2) Measurement of uneven structure of fiber substrate (2-1) Measurement of Δh The height difference Δh between the convex region a and the concave region b in the uneven structure X different from the uneven structure formed by the constituent fibers was measured. Specifically, the measurement was carried out as follows. For the regions a and b within an arbitrarily cut 3 cm × 3 cm sample, observation was made with a digital microscope (Digital Microscope DVM6 manufactured by Leica Microsystems GmbH or its equivalent), and the height difference between the convex region a and the concave region b was obtained using image analysis software (LAX X manufactured by Leica Microsystems GmbH or its equivalent). Observation was made at a magnification that included the regions a and b and at least three uneven structures formed by the constituent fibers in each region, and the adjacent height difference between the regions a and b was obtained from cross-sectional profile analysis. Here, the heights of the regions a and b were obtained from the same cross-sectional profile. For the uneven structure formed by the constituent fibers in each region, the average of the heights of three peaks and three valleys of the uneven structure, a total of six points as shown in FIG. 1, was taken as the height of each region, and the difference was defined as Δh.

[0100] (2-2) Measurement of concave area ratio and convex area ratio The ratio of the area of each of Region b and Region a to the area of an arbitrary 3 cm × 3 cm region was measured. Specifically, the measurement was performed as follows. For all Region a and Region b within an arbitrarily cut 3 cm × 3 cm sample, observation was carried out using a digital microscope (Digital Microscope DVM6 manufactured by Leica Microsystems or its equivalent), and the areas of Region a and Region b were determined using image analysis software (LAX X manufactured by Leica Microsystems or its equivalent). The area ratio of Region a and Region b was determined as the percentage of the total area of all Region a and the total area of Region b within the sample with respect to the area of the arbitrarily cut 3 cm × 3 cm sample.

[0101] (2-3) Measurement of concave area and convex area The area of each of Region b and Region a was measured. Specifically, the measurement was performed as follows. For Region b and Region a within an arbitrarily cut 3 cm × 3 cm sample, observation was carried out using a digital microscope (Digital Microscope DVM6 manufactured by Leica Microsystems or its equivalent), and the area was calculated using image analysis software (LAX X manufactured by Leica Microsystems or its equivalent). The area was determined for all Region b and Region a existing within the 3 cm × 3 cm sample.

[0102] (2-4) Measurement of number of concaves and number of convexes The number of each of Region a and Region b in an arbitrary 3 cm × 3 cm region was visually measured.

[0103] (3) Manufacture of fiber sheet (Example 1) The fiber substrate 1 was embossed. A concavo-convex roller with convex portions arranged in a checkered pattern was heated to 140°C, and the fiber substrate was embossed at a pressure of 40 kg / cm 2 and a processing speed of 10 m / min. The surface of the fiber substrate had a structure Q (checkered pattern) in which a plurality of Region a and Region b were laid out respectively.

[0104] Next, the embossed fiber substrate was installed in a sputtering apparatus, and 5.0 × 10-4 It was evacuated to a pressure of less than 1 Pa. Subsequently, argon gas was introduced, and a Ti layer (average thickness: 35 nm) was formed as a metal layer on the surface of the fibrous substrate by high-frequency sputtering to obtain a fibrous sheet formed by laminating the fibrous substrate and the metal layer in this order.

[0105] (Examples 2 to 4 and 21 to 32, and Comparative Examples 1 to 3 and Comparative Examples 8 to 10) Except for using fibrous substrates with embossing conditions and fibrous substrate types changed so as to have Δh, region a, and region b as shown in the following table, fibrous sheets formed by laminating the fibrous substrate and the metal layer in this order were obtained in the same manner as in Example 1.

[0106] Note that the fibrous substrate having a sea-island structure was embossed using an uneven roller such that the island portions were squares having the areas described in the following table. That is, it has a sea-island structure P in which squares of the same area (the areas described in the following table) are regularly dispersed.

[0107] (Examples 5 to 19, and Comparative Examples 4 to 7) A fibrous substrate having Δh, region a, and region b shown in the following table was placed in a sputtering apparatus and evacuated to a pressure of 5.0×10 -4 Pa or less. Subsequently, argon gas was introduced, and a Ti layer (average thickness: 35 nm) was formed as a metal layer on the surface of the fibrous substrate by high-frequency sputtering to obtain a fibrous sheet formed by laminating the fibrous substrate and the metal layer in this order. Further, the laminate of the fibrous substrate and the metal layer was placed in a vacuum apparatus and evacuated to a pressure of 5.0×10 -4 Pa or less. Subsequently, argon gas was introduced, and an Si layer (average thickness: 20 nm) was formed as a color tone adjustment layer on the surface of the metal layer opposite to the fibrous substrate by high-frequency sputtering to obtain a fibrous sheet.

[0108] (Example 20) A fibrous sheet was obtained in the same manner as in Example 5 et al. except that an SiO x layer (average thickness: 20 nm) was formed as a color tone adjustment layer.

[0109] (4) Evaluation of friction resistance The friction resistance of the fiber sheet was evaluated as follows. For the evaluation of friction resistance, a Gakushin type friction tester (Friction Tester II type) (manufactured by Yasuda Seiki Seisakusho, product number No. 428) was used. A dry friction test was conducted on the surface side of the metal layer of the fiber sheet in accordance with JIS L0849: Dyeing fastness test for rubbing (Friction Tester II type (Gakushin type) method). Regarding the color change on the metal surface side of the sample before and after the friction test, 10 evaluators were asked to evaluate and judge according to the following criteria.

[0110] <Friction resistance> When 9 or more out of 10 people evaluated that the change before and after was small, it was rated as ◎ When 7 - 8 out of 10 people evaluated that the change before and after was small, it was rated as ○, When 5 - 6 out of 10 people evaluated that the change before and after was small, it was rated as △, When 4 or fewer out of 10 people evaluated that the change before and after was small, it was rated as ×.

[0111] (5) Results The results are shown in Tables 1 - 5.

[0112]

Table 1

[0113]

Table 2

[0114]

Table 3

[0115]

Table 4

[0116]

Table 5

Claims

1. A fiber sheet having a fiber substrate (excluding a paper substrate) and a metal layer disposed on the fiber substrate, wherein the fiber sheet has an uneven structure X different from the uneven structure formed by the constituent fibers of the fiber substrate, the height difference Δh between the convex region a and the concave region b in the uneven structure X is 3 to 15 μm, and the fiber sheet having two or more of the region a or the region b in any 3 cm × 3 cm region.

2. The fiber sheet according to claim 1, wherein the ratio of the area of the region b to the area of any 3 cm × 3 cm region is 20 to 70%.

3. The fiber sheet according to claim 1 or 2, wherein in any 3 cm × 3 cm region, the region a and the region b constitute an island-in-sea structure P, or the region a and the region b constitute a structure Q formed by being stacked in plurality, respectively.

4. Any of the 3 cm × 3 cm regions is the sea-island structure P or the structure Q having the region b as an island portion, and the area of one of the regions b is 3.1 cm ２ The fiber sheet according to claim 3, wherein the following conditions are satisfied.

5. The area of one of the regions b is 0.05 cm ２ or more. The fiber sheet according to any one of claims 1 to 4.

6. Any of the 3 cm × 3 cm regions is the sea-island structure P having the region a as an island portion, and the area of one region a is 0.05 to 3.1 cm ２ The fiber sheet according to claim 3, which is as described above.

7. The fiber sheet according to any one of claims 1 to 6, wherein the fibers constituting the fiber substrate are 10 to 70 denier.

8. The fiber sheet according to any one of claims 1 to 7, further having a color tone adjustment layer, wherein the color tone adjustment layer is a layer containing a metal element or a metalloid element as a material.

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