JP7526006B2 - Decorative fiber sheet - Google Patents

Description

The present invention relates to decorative fiber sheets, etc.

Fiber substrates are used in various fields where design is required. For example, carbon fiber substrates, together with resins, form composite materials (such as carbon fiber reinforced plastics) and are used in a wide range of applications, from relatively large items such as aircraft bodies to relatively small, everyday items such as sporting goods, interior and exterior materials for cars, and clothing. For this reason, fiber substrates are sometimes colored to enhance their design. In addition, due to their unique design, they may be given a glossy finish when colored.

Conventionally, the coloring of these substrates has generally been achieved by applying paint containing dyes, pigments, etc. (Patent Document 1).

JP 2010-229587 A

In the course of their research, the inventors discovered that by placing a semi-gold layer on a fiber substrate, it is possible to impart color and metallic luster while retaining the texture of the fiber substrate, thereby further enhancing the design.

In order to further improve the design, the inventors focused on patterns that are expressed by differences in gloss and considered applying this. However, in the course of their investigation, they found that the clarity of the patterns that were applied was insufficient.

Therefore, the objective of the present invention is to provide a technology that can impart color and metallic luster, as well as create clear patterns.

In the course of research into the above-mentioned problems, the inventors focused on creating a pattern by creating linear depressions in the fiber substrate before laminating the semi-metal layer. Further research led them to discover that the clarity of the pattern can be adjusted by adjusting the width of the depressions.

The inventors conducted extensive research based on these findings and discovered that the above problems could be solved by a decorative fiber sheet having a fiber substrate with linear depressions measuring 30 to 200 μm in width and a color tone adjusting layer disposed on the fiber substrate. The inventors conducted further research based on these findings and completed the present invention.

That is, the present invention includes the following aspects:

Item 1. A decorative fiber sheet having a fiber substrate with linear depressions of 30 to 200 μm in width and a color tone adjustment layer disposed on the fiber substrate.

Item 2. The decorative fiber sheet according to item 1, in which the fiber substrate has two or more linear depressions arranged in parallel, with an average period of 200 to 600 μm.

Item 3. The decorative fiber sheet according to item 1 or 2, in which there are two or more sets of linear depressions arranged in parallel in any 3 cm x 3 cm area of the fiber substrate, and one or more sets have a different direction from the others.

Item 4. The decorative fiber sheet according to any one of Items 1 to 3, wherein the color tone adjusting layer has a layer containing MO _x (M represents an n-valent metal or metalloid, and x represents a number of 0 or more and less than n/2), MN _y (M represents an n-valent metal or metalloid, and y represents a number of 0 or more and n/3 or less), or MC _z (M represents an n-valent metal or metalloid, and z represents a number of 0 or more and n/4 or less).

Item 5. The decorated fiber sheet according to Item 4, wherein M in the MO _x , M in the MN _y , and M in the MC _z are silicon, germanium, gallium, zinc, silver, gold, titanium, aluminum, molybdenum, niobium, or indium.

Item 6. A decorative fiber sheet according to any one of items 1 to 5, having at least a fiber substrate, a metal layer, and a semi-metal layer, which are laminated in this order.

Item 7. The decorative fiber sheet according to item 6, wherein the metal element most abundant in the semimetal layer is silicon or germanium, and the metal element most abundant in the metal layer is gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, niobium, or indium.

The present invention makes it possible to provide a decorative fiber sheet that has color, metallic luster, and a clear pattern.

In this specification, the expressions "contain" and "include" include the concepts of "contain," "include," "consist essentially of," and "consist only of."

1. Decorative fiber sheet In one aspect, the present invention relates to a decorative fiber sheet (also referred to as the "decorative fiber sheet of the present invention" in this specification) having a fiber substrate having linear depressions with a width of 30 to 200 μm and a color tone adjusting layer disposed on the fiber substrate. This will be described below.

<1-1. Fiber base material>
The fiber substrate is not particularly limited as long as it is a substrate containing fibers or fiber bundles as a material and is in the form of a sheet having linear depressions with a width of 30 to 200 μm. By forming linear depressions with a width in this range, a clear pattern can be expressed.

The width of the linear depression is preferably 40 to 180 μm, and more preferably 50 to 150 μm, from the standpoint of the clarity and visibility of the pattern.

The width of the recessed line can be measured by the following method:
The width of the recessed line is determined by observation with a digital microscope. Specifically, observation and measurement are performed with a digital microscope (Leica Microsystems Digital Microscope DVM6 or an equivalent product). The magnification is 300 times, and the distance from one end to the other end of the recessed line in the width direction is measured at any five points, and the average value is taken as the width of the recessed line.

The depth of the recessed lines is not particularly limited, but is, for example, 1 to 200 μm. From the viewpoints of durability of the fiber substrate and clarity of the pattern, the depth is preferably 5 to 150 μm, and more preferably 10 to 100 μm.

The depth of the dent line can be measured by the following method:
The depth of the recessed line is determined by observation with a laser microscope. Specifically, observation and measurement are performed with a laser microscope (Keyence Corporation laser microscope (VK-8710 or equivalent). The objective lens is set to 20x, and the difference in height between the center position of the recessed line in the width direction and the end portion in the width direction (the outer edge of the recessed line) is measured. Measurements are performed at any five points, and the average value is taken as the depth of the recessed line.

The length of the recessed line is not particularly limited, but is, for example, 1 to 1,000,000 μm. From the standpoint of design and pattern clarity, the length is preferably 5 to 100,000 μm, and more preferably 10 to 30,000 μm.

The shape of the recessed line is not particularly limited, but usually includes a linear region. Note that "linear" does not mean only a completely straight line. A linear line means, for example, that a straight line connecting any points at each of the two longitudinal ends of the recessed line falls within the width of the recessed line, but is not limited to this. The proportion of the linear region to 100% of the length of the recessed line is, for example, 30% or more, preferably 50% or more, more preferably 70% or more, even more preferably 90% or more, and even more preferably 95% or more.

In a preferred embodiment of the present invention, two or more linear depressions in the fiber substrate are arranged in parallel. Here, "parallel" does not mean completely parallel. Parallel means, for example, that the acute angle between any one depression line and another depression line is less than 2 degrees.

In this preferred embodiment, the average period is more preferably 200 to 600 μm. In other words, the interval between the recessed lines is preferably 200 to 600 μm. This allows the pattern to be more clearly distinguished. The range is more preferably 250 to 550 μm, and even more preferably 300 to 500 μm.

The average period of the indentation lines can be measured by the following method:
The average period of the recessed lines is determined by digital microscope observation. Specifically, observation and measurement are performed using a digital microscope (Leica Microsystems Digital Microscope DVM6 or an equivalent product). The magnification is 300 times, and the distance between two or more adjacent recessed lines is measured. More specifically, the reference recessed line is set as the reference line, and an arbitrary measurement start point on the outer edge of one of the recessed lines is set as the reference point. The distance between the reference point and the intersection point between a straight line extended from the reference point in the width direction of the reference line and the adjacent recessed line is measured. Note that the intersection point is an intersection point on the same side as the reference point of the outer edge of the adjacent recessed line.
Five reference points are arbitrarily selected, the distance between each of the reference points and the intersection point is measured, and the average value is taken as the average period of the recessed lines.

In this preferred embodiment, within any 3 cm x 3 cm area of the decorative fiber sheet, there are preferably 2 or more parallel linear depressions, more preferably 40 or more, and even more preferably 50 or more. There is no particular upper limit to the number, but from the viewpoint of visibility of the pattern, it is, for example, 1000 or less, preferably 300 or less, more preferably 200 or less, and even more preferably 130 or less.

In a preferred embodiment of the present invention, in any 3 cm x 3 cm area of the fiber substrate, there are two or more sets of linear indentations arranged in parallel, and one or more sets have a different directionality from the others. This creates two areas with different degrees of emphasis depending on the viewing angle, further enhancing the design. Here, "different directions" is not particularly limited, but means, for example, that the acute angle formed by any set of indentation lines and another set of indentation lines is 2 degrees or more. From the viewpoint of design, the angle is preferably 10 degrees or more, more preferably 30 degrees or more. There is no particular limit to the upper limit of the angle, but it is usually 90 degrees or less.

It is preferable that the linear depressions in each region have different line widths and/or average periods. By making the line widths and/or average periods different, it is possible to obtain designs with different glossiness. Furthermore, by making the directionality of each region different, it is possible to obtain designs in which different regions are emphasized depending on the viewing direction, and in which different glossiness is obtained in each region.

The fiber substrate may contain components other than fibers and fiber bundles, so long as the effect of the present invention is not significantly impaired. In that case, the total amount of fibers and fiber bundles in the fiber substrate 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 the fiber substrate include woven fabrics (e.g., plain weave, twill weave (twill weave), satin weave, etc.), knitted fabrics, nonwoven fabrics, paper, etc. Among these, from the viewpoint that the recessed lines formed on the fiber surface are flat and have a relatively high light reflectance, and the design of the decorative fiber sheet of the present invention is enhanced, preferred are woven fabrics and knitted fabrics, more preferred are woven fabrics. The fiber substrate may be embossed or calendared, so long as the effect of the present invention is not significantly impaired. By adopting a fiber substrate with higher smoothness, the metallic feel of the decorative fiber sheet of the present invention can be further enhanced. In addition, by increasing the flatness of the recessed lines of the fiber substrate, the design of the decorative fiber sheet of the present invention can be further enhanced.

The layer structure of the fiber substrate is not particularly limited. The fiber substrate may be composed of a single type of fiber substrate, or may be composed of a combination of two or more types of fiber substrates.

The fibers constituting the fiber substrate are not particularly limited, and examples of the fibers include organic fibers such as synthetic fibers (e.g., nylon fibers, polyester fibers, acrylic fibers, vinylon fibers, polyolefin fibers, polyethylene fibers, polypropylene fibers, polyurethane fibers, polyamide fibers, polyacrylonitrile fibers, etc.), regenerated fibers (e.g., rayon, polynosic, cupra, lyocell, acetate, etc.), plant fibers (e.g., cotton fibers, hemp fibers, flax fibers, rayon fibers, polynosic fibers, cupra fibers, lyocell fibers, acetate fibers, etc.), and animal fibers (e.g., wool, silk, wild silk, mohair, cashmere, camel, llama, alpaca, vicuna, angora, spider silk, etc.); A wide range of inorganic fibers can be used, including 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., chrysotile asbestos, white asbestos, blue asbestos, brown asbestos, ectoparasite asbestos, exothermic asbestos, etc.), artificial mineral fibers (e.g., rock wool, ceramic fiber, etc.), and metal fibers (e.g., stainless steel fibers, aluminum fibers, iron fibers, nickel fibers, copper fibers, etc.).

The fiber may be in any form, such as continuous long fibers, short fibers cut from continuous long fibers, or milled yarns pulverized into a powder.

The fibers may be of one type alone or a combination of two or more types.

There are no particular limitations on the fiber bundle, so long as it is made up of multiple fibers. The number of fibers constituting the fiber bundle is, for example, 5 or more, 10 or more, 20 or more, or 50 or more, while it is, for example, 50,000 or less, 20,000 or less, 15,000 or less, or 2,000 or less. These upper and lower limit values can be combined in any manner.

The thickness of the fiber substrate may vary depending on the type of fiber, and is not particularly limited. The thickness of the fiber substrate is, for example, 3 to 500 μm, and preferably 10 to 50 μm.

The above-mentioned fiber substrate may be coated with known finishing agents such as flame retardants, water absorbents, water repellents, softeners, heat storage agents, UV protection agents, antistatic agents, antibacterial agents, deodorants, insect repellents, mosquito repellents, phosphorescent agents, and retroreflective agents.

The fiber substrate having the above-mentioned recessed lines can be manufactured by various methods. As an example, when using thermoplastic resin fibers as the fibers, it can be manufactured by embossing a fiber fabric made of thermoplastic resin fibers with an embossing device consisting of an embossing roll and a heat roll. This manufacturing method is described in detail below.

As the thermoplastic resin fiber in the present invention, synthetic fibers such as polyester, polyamide, polyacrylonitrile, etc. can be suitably used. In addition, the fabric may be any of knitted fabric, woven fabric, nonwoven fabric, tufted (embroidered) fabric, electroplated fabric, etc. In addition, it may have pile or may not have pile.

The embossing roll and heat roll suitable for the present invention are made of metal with a surface coating such as plating, both of which are heated from the inside of the roll and preferably have a diameter of 150 mm to 600 mm. The heating temperature is preferably 100 to 250°C, and to emboss the fabric, the fabric is first heated by the heat roll and then, after 1/2 to 3/4 of a turn, is pressed between the heated embossing roll and embossed. As both are made of metal, the pattern is easily fixed and a sharp embossed pattern can be imparted. From the viewpoints of the clarity of the pattern and the texture of the decorative fiber sheet, the heating temperature of the embossing roll and heat roll is preferably 100 to 250°C.

The distance between the embossing roll and the heat roll is adjusted as appropriate depending on the thickness and density of the fabric, but from the perspective of suppressing unevenness in the pattern, it is preferable that the embossing roll and the heat roll are kept parallel with a distance of 0.05 mm to 2 mm.

In addition, by passing the fabric under pressure between an embossing roll and a heat roll, which are placed at an appropriate distance apart, at a processing speed of 0.3 m/min to 10 m/min, the fabric is heated sufficiently to impart a durable pattern.

In the present invention, the embossed portions on the surface of the embossing roll are preferably arranged in a dispersed state, and the height of the embossed portions depends on the thickness of the fabric, but is preferably 0.1 mm to 10 mm. The embossed portions correspond to the pressed portions of the fabric, and although it depends on the design of the pattern, the total area of the embossed portions is preferably 20 to 60% of the surface area of the embossing roll, and they are preferably arranged in a dispersed state.

<1-2. Color tone adjustment layer>
The color tone adjusting layer is a layer disposed on the fiber substrate. The color tone adjusting layer is disposed on the fiber substrate directly or via another layer (for example, a metal layer described later).

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 metal elements and metalloid elements. In that case, the content of metal elements and metalloid elements 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, 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.

The metal or metalloid constituting the color tone adjusting layer is not particularly limited, and examples of metals include gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, niobium, and indium, and examples of metalloids include silicon, germanium, antimony, boron, phosphorus, and bismuth. Among these, silicon and germanium are preferred, and silicon is more preferred, from the viewpoint of the wide range of colors that can be imparted and the durability of the decorative fiber sheet.

The metal elements and metalloid elements may be of one type alone or of two or more types in combination.

The color tone adjusting layer may be made of a metal, semi-metal, or alloy made of a metallic element or a semi-metallic element, or may be made of a compound containing a metallic element or a semi-metallic element, or may be made of a mixture of these. Examples of compounds containing a metallic element or a semi-metallic element include oxides, nitrides, carbides, and nitride oxides.

The oxide may be, for example, a compound represented by _MOx , where X is a number that satisfies the formula: n/100)≦X<n/2 (n is the valence of the metalloid), and M is a metalloid element.

The nitride may be, for example, a compound represented by MN _y , where Y is a number satisfying the formula: n/100≦Y≦n/3 (n is the valence of the semimetal), and M is a semimetal element.

The carbide may be, for example, a compound represented by MC _z , where 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.

An example of the _nitride oxide is a compound represented by _MOxNy , where X and Y satisfy n/100≦X, n/100≦Y, and X+Y<n/2 (n is the valence of the metalloid), and M is a metalloid element.

Regarding the oxidation number X of the oxide or nitride oxide, for example _, a cross section of a layer containing _MOx or _MOxNy is subjected to elemental analysis by FE-TEM-EDX (for example, "JEM-ARM200F" manufactured by JEOL Ltd.), and X is calculated from the element ratio of M and O per area of the cross section of the layer containing _{MOx or MOxNy} , whereby the valence of the oxygen atom can be calculated.

Regarding the nitrogen number Y of the nitride or nitride oxide, for example, a cross section of _{a layer containing MNy or MOxNy is subjected} to elemental analysis by FE-TEM-EDX (for example, "JEM-ARM200F" manufactured by JEOL Ltd.), and Y is calculated from the element ratio of M to N per area of the cross section of the layer containing _{MNy or MOxNy} , whereby the valence of the nitrogen atom can be calculated.

Regarding the carbon number Z of the carbide, for example, a cross section of a 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 element ratio of M and C per area of the cross section of the layer containing _MCz , whereby the valence of the carbon atom can be calculated.

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

From the viewpoint of increasing the saturation of the color, when M in MO _x is silicon, X preferably represents a number less than 1, and more preferably represents a number less than 0.5. When M in MN _y is silicon, Y preferably represents a number of 4/3 or less. When M in MC _z is silicon, Z preferably represents a number of 1 or less.

The color tone adjusting layer preferably contains a metalloid element, and more preferably is a layer in which a metalloid is the main component (e.g., 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). The metalloid element contained in the largest amount in the color tone adjusting layer is preferably silicon or germanium.

The thickness of the color tone adjusting layer is not particularly limited, but is, for example, 1 to 200 nm. From the viewpoint of metallic luster and increasing the brightness and saturation of the color, the thickness is preferably 3 to 140 nm, and more preferably 4 to 140 nm.

The layer structure of the color tone adjustment layer is not particularly limited. The color tone adjustment layer may be a single layer or may be multiple layers having the same or different compositions. The color tone adjustment layer may have a surface formed of a coating such as an oxide coating on one or both of its two main surfaces.

<1-3. Metal layer>
The decorative fiber sheet of the present invention preferably has a metal layer. The metal layer is disposed on the fiber substrate. When the decorative fiber sheet of the present invention has a metal layer, in a preferred embodiment, the decorative fiber sheet of the present invention has at least a fiber substrate, a metal layer, and a color tone adjustment layer (preferably a semi-metal layer), which are laminated in this order. The metal layer can further improve the gloss, color fastness, color vividness, etc. The metal layer can adjust the brightness of the color mainly by optical interference or light reflection. Another layer may be provided between the metal layer and the fiber substrate.

The metal layer is not particularly limited as long as it is a layer that contains a metal as a material. The metal layer may contain components other than 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, and even more preferably 99% by mass or more, and is usually less than 100% by mass.

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 alloys, nickel-copper alloys, etc. Among these, from the viewpoints of gloss, color saturation and brightness, and durability such as resistance to discoloration, etc., preferred are gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, niobium, indium, etc. Furthermore, in clothing applications, etc., titanium is preferably used from the viewpoints of reducing metal allergy reactions and preventing erroneous detection by needle detectors.

When the decorative fiber sheet of the present invention contains a metal element in the color tone adjustment layer, it is preferable that the metal element contained in the largest amount in the color tone adjustment layer is different from the metal element contained in the largest amount in the metal layer, from the viewpoint of metallic luster, increasing color brightness and saturation, etc.

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

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

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

The layer structure of the metal layer is not particularly limited. The metal layer may be a single layer or may be multiple layers having the same or different compositions. In addition, the metal layer may have a surface formed of a coating such as an oxide coating on one or both of its two main surfaces.

<1-4. Oxide layer>
The decorative fiber sheet of the present invention preferably has an oxide layer on the surface of the metal layer or color tone adjusting layer opposite to the fiber substrate. The oxide layer improves durability such as discoloration resistance. can be further improved.

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

The semi-metal oxide constituting the oxide layer is not particularly limited, and examples thereof include oxides of semi-metals (preferably silicon) such as silicon, germanium, antimony, and bismuth. More specifically, examples of the semi-metal oxide include compounds represented by _AOx [wherein X is a number satisfying the formula: n/2.5≦X≦n/2 (n is the valence of the semi-metal), and A is a semi-metal selected from the group consisting of silicon, germanium, antimony, bismuth, and. ]. When A in the above formula is a semi-metal element, A is preferably silicon, and the semi-metal oxide is more preferably _SiO2 , from the viewpoint of being able to well adjust the color tone of the fiber sheet. The semi-metal oxide may be one type alone or two or more types in combination.

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, and nickel (preferably titanium, zinc, and aluminum). More specifically, examples of metal oxides include compounds represented by _AOx [wherein X is a number satisfying the formula: n/2.5≦X≦n/2 (n is the valence of the metal), and A is a metal selected from the group consisting of titanium, aluminum, niobium, cobalt, and nickel. ]. When A in the above formula is a metal element, A is preferably titanium and aluminum, and the metal oxide is more preferably _TiO2 , ZnO, and _Al2O5 , from the viewpoint of being able to well adjust the color tone of the fiber sheet. The metal oxide may be one type alone or two or more _types in combination.

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.

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 color adjustment, the thickness is preferably 2 to 20 nm, and more preferably 3 to 10 nm.

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

<1-5. Manufacturing method>
The method for producing the decorative fiber sheet of the present invention is not particularly limited. As an example, the sheet can be obtained by a method including a step of forming a semi-metallic element-containing layer as a color tone adjusting layer on the surface of a fiber substrate. In the case where it is contained, for example, a metal layer is formed on the surface of the fiber substrate, and then a color tone adjusting layer is formed on the metal layer, thereby producing the decorated fiber sheet of the present invention.

Although not particularly limited, the deposition can be performed by, for example, a sputtering method, a vacuum deposition method, an ion plating method, a chemical vapor deposition method, a pulsed laser deposition method, etc. Among these, the sputtering method is preferred from the viewpoint of film thickness controllability.

The sputtering method is not particularly limited, but examples include DC magnetron sputtering, radio frequency magnetron sputtering, and ion beam sputtering. The sputtering device may be of either a batch type or a roll-to-roll type.

2. Applications The decorative fiber sheet of the present invention has a metallic feel and can be used in various fields as a fiber material with unique design properties.

Specific examples of the decorative fiber sheet of the present invention include 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, and other clothing, as well as textile products such as curtains, bedding materials, bedding batting, pillowcases, sheets, mats, carpets, towels, handkerchiefs, masks, filters, decorative cloth/fabric, wall cloth, wallpaper, and floor coverings.

As another specific example, the decorative fiber sheet of the present invention can be used as a composite material (sometimes referred to as the "composite material of the present invention" in this specification) that contains both the decorative fiber sheet of the present invention and a resin.

The composite material of the present invention is not particularly limited as long as it contains the decorative 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 matrix material.

There are no particular limitations on the resin, and various resins can be used. Examples of resins include polyamide resins (e.g., nylon), polyphenylene ether, polyoxymethylene, polybutylene terephthalate, polycarbonate, polymethyl methacrylate (PMMA), polystyrene, polypropylene, polyetherimide, polyethersulfone, polyvinyl chloride, etc.

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

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

(1) Production of fiber sheet (Example 1)
As the fiber base material, "Silfine Nylon Taffeta TM3001" (nylon fiber (30 denier), plain weave) manufactured by Masuda Co., Ltd. was used.

The uneven roller with the protrusions arranged in stripes was heated to 180°C, and the fiber substrate was embossed at a line pressure of 150 kg/cm and a processing speed of 5 m/min. The surface of the fiber substrate had recessed lines with a line width of 35 μm and an average period of 400 nm.

The embossed fiber substrate was placed in a sputtering device and evacuated to 5.0×10 ⁻⁴ Pa or less. Then, argon gas was introduced, and a Ti layer (average thickness 36 nm) was formed as a metal layer on the surface of the fiber substrate by high-frequency sputtering, and a laminate was obtained in which the fiber substrate and the metal layer were laminated in this order. Further, the laminate of the fiber substrate and the metal layer was placed in a vacuum device and evacuated to 5.0×10 ⁻⁴ Pa or less. Then, argon gas was introduced, and a Si layer (average thickness 26 nm) was formed as a color tone adjustment layer on the surface of the metal layer opposite to the fiber substrate by high-frequency sputtering, to obtain a decorated fiber sheet.

(Comparative Example 1)
A decorated fiber sheet was obtained in the same manner as in Example 1, except that a fiber base material that had not been embossed was used.

(Examples 2 to 4, 14 to 15 and Comparative Examples 2 to 3)
A decorated fiber sheet was obtained in the same manner as in Example 1, except that the shape of the convex portions of the uneven roller was changed and the width of the concave lines of the fiber substrate was changed.

(Examples 5 to 7)
A decorated fiber sheet was obtained in the same manner as in Example 1, except that the line width of the recessed lines in the fiber substrate was set to 80 μm and the average period was changed.

(Example 8)
A decorated fiber sheet was obtained in the same manner as in Example 3, except that no metal layer was formed.

(Examples 9 to 10)
A decorated fiber sheet was obtained in the same manner as in Example 5, except that the interval between the convex portions of the uneven roller was changed to change the average period of the concave lines of the fiber substrate.

(Example 11)
A striped fiber substrate was used in which a 2 cm-wide region A on the surface of the fiber substrate had fine recessed lines with a line width of 50 μm and an average period of 400 nm, and a region B adjacent to the region A had 2 cm-wide recessed lines with the same line width and average period, but the directions of the recessed lines were 90° different. Otherwise, a decorative fiber sheet was obtained in the same manner as in Example 2.

Example 12
A decorated fiber sheet was obtained in the same manner as in Example 11, except that the line width and average period of region B were changed.

(Example 13)
A decorated fiber sheet was obtained in the same manner as in Example 11, except that the angle between areas A and B was changed.

(Example 16)
A decorated fiber sheet was obtained in the same manner as in Example 1, except that the uneven roller had only one convex portion and the fiber base material had only one concave line.

(Comparative Example 4)
The same procedure was followed as in Example 3, except that the metal layer and the semi-metal layer were not formed.

(2) Measurement and evaluation
(2-1) Line width The width of the recessed line was determined by digital microscope observation. Specifically, the width was observed and measured using a digital microscope (Leica Microsystems Digital Microscope DVM6). The magnification was 300 times, and the distance between two ends of the recessed line in the width direction was measured at five arbitrary points, and the average value was taken as the width of the recessed line.

(2-2) Average Period The average period of the recessed lines was determined by digital microscope observation. Specifically, observation and measurement were performed using a digital microscope (Leica Microsystems Digital Microscope DVM6). The magnification was 300 times, and the distance between two or more adjacent recessed lines was measured. More specifically, the reference recessed line was used as the reference line, and an arbitrary measurement start point at one end of the reference line was used as the reference point. On a straight line extending from the reference point in the width direction of the reference line, the distance to one end of the adjacent recessed line on the same side as the reference point was measured. The reference points were measured at five arbitrary positions, and the average value was used as the average period of the recessed lines.

(2-3) Pattern clarity The pattern clarity was evaluated by illuminating the sample with a white light and visually evaluating it from a direction of 45° to the sample surface. In addition, in Examples 11 and 12, the sample was rotated in the surface direction and the degree of change in the pattern was also evaluated. Ten evaluators evaluated the following criteria.

<Pattern clarity evaluation criteria>
⊚: 10 out of 10 judged the pattern to be clear.
A: 7 to 9 out of 10 judged the pattern to be clear.
Δ: 5 to 6 out of 10 judged the pattern to be clear.
×: 0 to 4 out of 10 judged the pattern to be clear.

<Criteria for determining the degree of pattern change>
⊚: The highlighted area differs depending on the viewing direction, and the glossiness also differs.
○: Different areas are highlighted depending on the viewing direction.

The results are shown in Tables 1 to 3. In Example 16, a linear pattern was visible.

Claims (7)

A fiber substrate having a linear depression having a width of 30 to 200 μm and a color tone adjusting layer disposed on the fiber substrate ,
The color tone adjusting layer is a layer composed of a metal, a metalloid, or an alloy composed of a metal element or a metalloid element, a compound containing a metal element or a metalloid element, or a mixture thereof; and
A decorative fiber sheet having a fiber substrate having linear depressions of 30 to 200 μm in width in any 3 cm x 3 cm area, and a color tone adjusting layer made of a semi-metallic layer disposed on the fiber substrate . The decorative fiber sheet according to claim 1, in which the fiber substrate has two or more linear depressions arranged in parallel, with an average period of 200 to 600 μm. The decorative fiber sheet according to claim 1 or 2, wherein in any 3 cm x 3 cm area of the fiber substrate, there are two or more sets of linear depressions arranged in parallel, and one or more sets have a different direction from the others. The decorative fiber sheet according to any one of claims 1 to 3, wherein the color tone adjusting layer comprises a layer containing MO _x (M represents an n-valent metal or metalloid, and x represents a number of 0 or more and less than n/2), MN _y (M represents an n-valent metal or metalloid, and y represents a number of 0 or more and n/3 or less), or MC _z (M represents an n-valent metal or metalloid, and z represents a number of 0 or more and n/4 or less). The decorated fiber sheet according to claim 4, wherein M in the MO _x , M in the MN _y , and M in the MC _z are silicon, germanium, gallium, zinc, silver, gold, titanium, aluminum, molybdenum, niobium, or indium. A decorative fiber sheet according to any one of claims 1 to 5, comprising at least a fiber base material, a metal layer, and a semi-metal layer, which are laminated in this order. The decorative fiber sheet according to claim 6, wherein the metal element most abundant in the semi-metal layer is silicon or germanium, and the metal element most abundant in the metal layer is gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, niobium, or indium.