JP7458087B2 - metallic style sheet - Google Patents

Description

The present invention is applicable to membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, and sunshade tents, as well as metallic sheets (tarpaulins) used for architectural curing and soundproofing sheets. ) and, in particular, metallic sheets (canvas) used for truck hoods, truck bed covers, house tents, seat houses, etc. More specifically, the glitter coating resin layer provided on the metallic tarpaulin and canvas has durability against bending and scratches caused by physical loads during sewing and construction, and the glitter coating resin layer It can be easily handled during sewing and construction without easily causing optical scars due to disordered arrangement of glitter pigments, and the resin layer of the glitter coating does not easily wear off or fall off during use. This invention relates to an invention of a metallic-like sheet.

Filament fabrics made from polyester long fibers are used as a base material for membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, and stadium sunshade tents, as well as architectural curing and soundproofing sheets. Tarpaulins made by thermally laminating soft vinyl chloride resin films on both sides have become widely used, and spun fabrics made from spun polyester staple fibers are now being used for truck hoods, truck bed covers, house tents, seat houses, etc. Waterproof canvas is widely used, which is made by coating a soft vinyl chloride resin paste on both sides of a polyvinyl chloride resin paste and heating it to gel. In particular, the exterior colors of large tents (pavilions), tent warehouses, membrane roofs (ceilings) of architectural spaces, stadium sunshade tents, house tents, seat houses, etc., such as white and ivory, have low heat storage properties and light transmission and daylighting. While bright light colors are becoming more popular, dark colors such as dark green and olive drab are also becoming more popular for the exterior colors of truck hoods and truck bed covers, which have high light-shielding properties and make dirt less noticeable. In particular, for amusement applications such as pavilions and circus tents, there is a need for a metallic appearance with a strong presence such as silver or gold.On the other hand, for truck hoods, there is a need for silver canvas for wing hoods with aluminum bodies. ing. Furthermore, there is a need for silver-colored tarpaulin leather as a material for emergency bags (disaster prevention supplies).

The production of such metallic sheets can be broadly divided into two types: 1) a decorative method in which a metallic film made of a composition compound containing a metallic pigment is laminated onto a soft polyvinyl chloride resin to impregnate the entire tarpaulin with the metallic pigment, or a decorative method in which a paste composition containing a metallic pigment is applied to a soft polyvinyl chloride resin, which is then heated and gelled to form a metallic resin coating, thereby impregnating the entire canvas with the metallic pigment, and 2) a decorative method in which, for example, a tarpaulin or canvas colored white (any hue) is produced, and the surface of the tarpaulin or canvas is solid-printed with a paint containing a metallic pigment to impregnate only the surface of the tarpaulin or canvas. In order to obtain a particularly metallic appearance, it is necessary to increase the concentration of the metallic pigment in either method, but in this case, the latter manufacturing method is more reasonable and by far cheaper to produce. Aluminum flake powder and aluminum flakes are preferred as versatile metallic pigments, and by using paint containing leafing-treated aluminum flake powder in particular, the leafing effect, in which the scaly aluminum is oriented and arranged horizontally in the coating liquid like fallen leaves floating on the water surface, gives a mirror-like glossy chrome-plated appearance. On the other hand, if aluminum flakes with large scale particles that have not been leafing-treated are used, the arrangement in the coating liquid becomes random, resulting in a sparkling, dynamic silver appearance. Gold decoration can be easily obtained by using these aluminum pigments with yellow to orange accent colors, and color metallic decoration can be freely achieved by using any accent color.

The metallic-look tarpaulin, canvas and other raw fabrics obtained in this way are generally 1-2m wide. To manufacture large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings), sunshade tents, truck hoods and other membrane structures, these raw fabrics and parts must be sewn together and connected to expand them. However, the bulk and weight of the intermediate sewn products increases due to the large number of connections, making it extremely difficult to handle the intermediate products by hand. This sewn work is carried out by several people in a large space such as a gymnasium, but the repeated handling of turning the product over and folding parts that get in the way of the work causes scratches on the metallic decorative surface and scratches (chalk marks) caused by rubbing the metallic decorative surface against the floor. These scratches and scratches are mainly due to physical damage such as cracks and scraping of the metallic layer, as well as optical scratches (diffuse reflection of light) caused by displacement of the orientation and arrangement of the metallic pigment particles in the metallic layer. In addition, when the folded welded sewn fabric is unfolded at the construction site and installed on frame structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings), sunshade tents, and truck hoods, problems such as creases on the metallic decorative surface or scratches on the frame or ground (chalk marks) have occurred. In particular, mirror surfaces with scaly aluminum in an orderly horizontal orientation and arrangement are prone to disturbance in the horizontal orientation and arrangement, and even minor scratches have the disadvantage of causing optical scars that appear due to diffuse reflection of light. Such optical scars due to diffuse reflection that appear due to physical load on the metallic decorative surface can occur not only with aluminum pigments, but also with scaly synthetic mica (pearl pigments), metal-deposited glass flakes, etc.

The applicant has proposed that the antifouling layer provided on the tarpaulin and canvas has resistance to bending and abrasion loads, does not easily cause deterioration such as cracks in the antifouling layer, and can be easily removed. As an invention for an industrial sheet material that does not wear out or fall off and has long-term stain resistance, a coating layer made of a thermoplastic resin composition is provided on the front and back sides of the fabric, and an anti-fouling layer is further added to the surface coating layer. In the industrial sheet material formed by forming the antifouling layer, the main component of the antifouling layer is an organic polymer or an organic/inorganic condensate, and cellulose nanofiber, modified cellulose nanofiber, cellulose nanocrystal, and modified cellulose nano However, the antifouling layer according to this proposal does not contain metallic pigments such as aluminum pigments, and does not contain metallic pigments such as aluminum pigments. Even if it contains, it does not suggest the problem of optical scratches that become folds or scratch marks (chalk marks) on the metallic antifouling layer, nor does it suggest any improvement measures for this problem. There is also a process of coating a base paint on the object to be coated to form a base coating film, a process of coating a glittering pigment dispersion on the base coating film to form a glittering coating film, and a process of coating a glittering pigment dispersion on the base coating film to form a glittering coating film. A method for forming a multi-layer coating film, which includes a step of forming a clear coating film on a substrate, and a step of simultaneously curing a base coating film, a glittering coating film, and a clear coating film by heating, in which a glittering pigment dispersion is used. , an invention (Patent Document 2) relating to a method for forming a multilayer coating film characterized by containing water, a scaly glitter pigment, a resin emulsion, and cellulose nanofibers is disclosed. According to the description in paragraph [0289], the role of cellulose nanofibers in this invention is to serve as a viscosity modifier for obtaining a multilayer coating film with excellent metallic gloss, that is, to precipitate the glitter pigment in the glitter pigment dispersion. The aim is to obtain a multilayer coating film with excellent metallic luster by controlling this. Therefore, Patent Document 2 discloses that in the resulting multilayer coating film with a metallic gloss, the presence of cellulose nanofibers and a silane coupling agent reactant causes creases and abrasion marks (chalk marks) in the metallic coating film. There is no mention or suggestion of the optical scarring problem and that improvements to this problem can be made. Therefore, in the current situation, there is a strong demand for metallic decorative sheets (tarpaulin, canvas) to have a property that does not easily cause optical scars due to the disordered arrangement of bright pigments due to the physical stress of bending or abrasion of the metallic coating film. An effective solution had not yet been found.

JP2021-66122A Japanese Patent No. 6834068

The present invention is characterized in that the glitter coating layer provided on the metallic tarpaulin and canvas has durability against bending and scratches caused by physical loads during sewing and construction, and the glitter coating layer has shine. A metallic-like sheet that does not easily generate optical scars due to disordered arrangement of pigments, can be handled freely during sewing and construction, and has a glitter coating layer that does not easily wear off or fall off during use. The challenge is to provide the following. By solving this problem, the appearance quality of the metallic sheet is preserved and maintained, so the metallic tarpaulin can be used for large tents (pavilions), tent warehouses, membrane roofs (ceilings) of architectural spaces, stadium sunshade tents, and house shapes. It is suitable for tents, seat houses, etc., and the metallic canvas is suitable for wing hoods of aluminum-bodied trucks. These materials are also suitable as materials for emergency bags (disaster prevention supplies).

As a result of repeated studies taking these points into consideration, the present invention has been developed by providing a coating layer made of a thermoplastic resin composition on the front and back surfaces of the fabric, and further forming a glitter coating layer on one or more surfaces of this coating layer. A metallic-like sheet comprising at least a glittering pigment, a silane coupling agent reactant, and cellulose nanofibers in the glittering coating layer , and the glittering pigment contains aluminum (colored) scale powder, flakes, etc. selected from shaped (colored) aluminum, scale-like interference colored mica, scale-like (colored) mica, interference colored glass flakes, metal-deposited glass flakes, metal-deposited (colored) film crushed bodies, and hologram film crushed bodies. one or more types of cellulose nanofibers, and the cellulose nanofibers include unmodified cellulose, carboxymethylated cellulose, oxidized cellulose, boric esterified cellulose, phosphoric esterified cellulose, silicate esterified cellulose, isocyanated cellulose, and aminosilane-modified cellulose. One or more types of nano selected from cellulose, vinylsilane-modified cellulose, epoxysilane-modified cellulose, methacrylsilane-modified cellulose, acrylicsilane-modified cellulose, chlorosilane-modified cellulose, mercaptosilane-modified cellulose, isocyanurate-silane-modified cellulose, and isocyanate-silane-modified cellulose. The fiber is a fiber, and the silane coupling agent reactant contains at least a condensate resulting from a reaction between silane coupling agents, and further includes a decomposed product of the silane coupling agent bonded to the glitter pigment and a decomposition product of the silane coupling agent bonded to the cellulose nanofiber. contains a decomposed product of a silane coupling agent, and the silane coupling agent is one or more selected from aminosilane, vinylsilane, epoxysilane, methacrylsilane, acrylicsilane, chlorosilane, mercaptosilane, isocyanuratesilane, and isocyanatesilane. The glitter coating layer of the metallic-like sheet obtained by the method has durability against bending and scratches caused by physical loads during sewing and construction, and the glitter coating layer is coated with glitter pigments. The present invention was developed based on the discovery that optical scars due to disordered arrangement do not easily occur, and the glitter coating layer does not easily wear off or fall off during use, and can be handled freely during sewing and construction. was completed.

The metallic sheet of the present invention is characterized in that the bright pigment includes aluminum (colored) scale powder, flaky (colored) aluminum, scaly interference colored mica, scaly (colored) mica, interference colored glass flakes, and metal vapor deposition. Preferably, the material is one or more selected from glass flakes, metal-deposited (colored) film crushed bodies, and hologram film crushed bodies. Particularly preferred are aluminum (colored) scale powder and/or flaky (colored) aluminum, and these are preferably leafing-type scale powder or flakes that have been surface-treated with a long-chain saturated fatty acid such as stearic acid. The horizontal arrangement of leafing flakes gives a dense glossy chrome-plated appearance, and the horizontal arrangement of leafing flakes gives a bright chrome-plated appearance.At the same time, the horizontal arrangement of leafing flakes provides a gas barrier effect and prevents corrosion of the substrate. You can get sex. On the other hand, non-leafing scale powder or flakes treated with unsaturated fatty acids such as oleic acid or fatty acids with relatively short carbon chains are preferred. Alternatively, coated scale powder or coated flakes treated with a transparent resin such as acrylic resin or epoxy resin are preferable. The random arrangement of the coating flakes gives a shimmery twinkle effect appearance, and the random arrangement of the coating flakes gives a shimmery glitter effect appearance.

In the metallic sheet of the present invention, the silane coupling agent reactant contains at least a condensate produced by the reaction between silane coupling agents, and further contains a decomposition product of the silane coupling agent bonded to the glittering pigment and a decomposition product of the silane coupling agent bonded to the cellulose nanofiber, and the silane coupling agent is preferably one or more selected from aminosilane, vinylsilane, epoxysilane, methacrylsilane, acrylicsilane, chlorosilane, mercaptosilane, isocyanurate silane, and isocyanate silane. The glittering coating layer contains cellulose nanofibers, and the cellulose nanofibers are present between the glittering pigment (particularly scale-like or flake-like) and the glittering pigment (particularly scale-like or flake-like), so that when the glittering coating layer is subjected to a physical load such as bending or rubbing, the arrangement (horizontal arrangement or random arrangement) of the glittering pigment (particularly scale-like or flake-like) is disturbed, i.e., the displacement that causes diffuse reflection is resisted, and a spring-like cushioning effect that restores the displacement is expressed. At this time, it is preferable that the cellulose nanofiber support has a silane coupling agent reactant between the glitter pigment (especially the scaly or flake-like surface) and the cellulose nanofiber, and is chemically bonded.The support of such a silane coupling agent reactant further strengthens the spring-like cushioning effect that restores the above-mentioned displacement.In particular, the presence of the condensate resulting from the reaction between the silane coupling agents contained in the glitter coating layer improves the durability and abrasion resistance of the glitter coating layer, making it possible to maintain the metallic appearance of the glitter coating layer for a long period of time.

In the metallic sheet of the present invention, the cellulose nanofibers include unmodified cellulose, carboxymethylated cellulose, oxidized cellulose, borate-esterified cellulose, phosphoric-esterified cellulose, silicate-esterified cellulose, isocyanated cellulose, and aminosilane-modified cellulose. One or more types of nano selected from cellulose, vinylsilane-modified cellulose, epoxysilane-modified cellulose, methacrylsilane-modified cellulose, acrylicsilane-modified cellulose, chlorosilane-modified cellulose, mercaptosilane-modified cellulose, isocyanurate-silane-modified cellulose, and isocyanate-silane-modified cellulose. Preferably it is a fiber. Cellulose nanofibers are contained in the glitter coating layer, and the cellulose nanofibers are interposed between the glitter pigment (especially scale-like or flake-like) and the glitter pigment (especially scale-like or flake-like). When a physical load such as bending or scratching is applied to the glitter coating layer, the arrangement (horizontal arrangement or random arrangement) of the glitter pigments (especially scale-like or flake-like) is disturbed, that is, diffused reflection occurs. A spring-like buffering effect is developed that resists the displacement that causes it and restores it. At this time, it is preferable that a silane coupling agent reactant be present between the bright pigment (particularly scale-like or flake-like) and cellulose nanofibers to chemically bond them. The presence of such cellulose nanofibers further strengthens the spring-like buffering effect that restores displacement. In particular, the presence of a condensate resulting from the reaction between silane coupling agents contained in the glitter coating layer improves the durability and scratch resistance of the glitter coating layer. This prevents optical scars caused by disordered alignment, making it possible to maintain a metallic appearance for a long period of time.

In the metallic sheet of the present invention, the glittering coating layer is made of acrylic resin, urethane resin, acrylic/silicon copolymer resin, fluorine copolymer resin, acrylic resin and fluorine copolymer resin. It is preferable to use one or more selected from blends of , urethane/silicon-based graft copolymer resins, and urethane/fluorine-based graft copolymer resins. By using these resins as the main components of the glitter coating layer, they contribute to durability against bending and abrasion loads, and at the same time, exhibit long-term sustainable stain resistance.

In the metallic sheet of the present invention, an antifouling coating layer is further formed on the glittering coating layer, and within this antifouling coating layer, photocatalytic titanium oxide, photocatalytic titanium peroxide, photocatalytic titanium oxide, It is preferable to contain one or more photocatalytic metal oxides selected from zinc, photocatalytic tin oxide, photocatalytic strontium titanate, photocatalytic tungsten oxide, photocatalytic bismuth oxide, and photocatalytic iron oxide. . The photocatalytic activity of these photocatalytic metal oxides promotes the decomposition of organic substances (soot, tar, bird droppings, mold, algae, etc.), and a self-cleaning effect due to rainfall is expressed. In particular, by supporting such a photocatalytic metal oxide in the sol-gel condensate, damage to the glitter coating layer due to photocatalytic activity can be reduced.

In the metallic sheet of the present invention, it is preferable that the antifouling coating layer is mainly composed of an organosilicate compound or a sol-gel condensate of a silanol group-containing organosilane compound. By using such a sol-gel condensate as the main component of the antifouling coating layer, it improves the antifouling properties of the antifouling coating layer, exhibits durability against abrasion loads and chemicals, and at the same time improves the gas barrier effect. be high. In addition, the sol-gel condensate acts as an armor that protects the antifouling coating layer itself from radical attack due to photocatalytic activity, and also serves as a barrier to protect the glitter coating layer from radical attack due to photocatalytic activity.

According to the present invention, the glitter coating resin layer provided on metallic tarpaulin and canvas has durability against bending and scratches caused by physical loads during sewing and construction, and the glitter coating resin layer A metallic finish that does not easily create optical scars due to disordered arrangement of glitter pigments, can be handled freely during sewing and construction, and does not easily wear away or fall off the glitter coating layer during use. The objective is to provide an invention for a sheet. By solving this problem, the appearance quality of the metallic sheet is preserved and maintained, so the metallic tarpaulin can be used for large tents (pavilions), tent warehouses, membrane roofs (ceilings) of architectural spaces, stadium sunshade tents, and house shapes. It is suitable for tents, seat houses, etc., and the metallic canvas is suitable for wing hoods of aluminum-bodied trucks. These materials are also suitable as materials for emergency bags (disaster prevention supplies).

The metallic sheet of the present invention has a coating layer made of a thermoplastic resin composition on the front and back surfaces of the fabric, and a glitter coating layer is further formed on one or more surfaces of the coating layer. The film layer contains at least a bright pigment such as aluminum (colored) scale powder, flaky (colored) aluminum, a silane coupling agent reactant, and cellulose nanofiber, and further contains a photocatalytic metal oxide. This is an embodiment in which an antifouling coating layer is formed on a glittering coating layer.

The woven fabrics used for the metallic sheet of the present invention are plain woven fabrics (warp/weft 2-axis woven fabrics, warp/weft/upper left/upper right bias 3-axis woven fabrics, warp/weft/upper left/upper right bias 4-axis woven fabrics), oblique woven fabrics (2× 2, 3 x 3, 4 x 4, etc., regular basket weave, 3 x 2, 4 x 2, 4 x 3, 5 x 3, 2 x 3, 2 x 4, 3 x 4, 3 x 5, etc. regular diagonal weave), twill weave (having a minimum constituent unit of at least three warps and wefts: 3-ply diagonal, 4-ply diagonal, 5-ply diagonal, 6-ply diagonal, etc.), satin weave ( Both warp and weft have a minimum structural unit of at least five yarns: regular satin (2-skip, 3-skip, 4-skip, 5-skip, etc.), modified plain woven fabrics, modified twill woven fabrics, modified satin woven fabrics, etc., as well as honeycomb woven fabrics. Fabrics such as pear cloth fabric, torn oblique fabric, day and night satin fabric, twisted fabric (gain fabric, gauze fabric), sewn fabric, and double fabric can be used. In particular, either 1) a woven fabric with warp and weft, or 2) a triaxial woven fabric with warp and upper left/upper right bias yarn, or 3) a four-axis woven fabric with warp, weft, and upper left/upper right bias yarn. It is preferable that there be. In particular, if triaxial fabrics or quadriaxial fabrics are used, the intersection of the threads becomes complex, and the network that spreads in multiple directions increases the diffusibility of stress, and by distributing stress over a wide area, it is even more likely to cause tearing. The resistance to external forces is dramatically improved. The suitable weight of the fabric used for the metallic sheet is 100 to 500 g/m ² . The porosity of the woven fabric is preferably 0 to 25%, if the industrial sheet material is tarpaulin, the porosity is 5 to 25%, and if the industrial sheet material is tarpaulin, the porosity is 0 to 5%. These textiles may be subjected to known dyeing and finishing treatments such as scouring, bleaching, dyeing, softening, water repellency, mildewproofing, flameproofing, calendering, etc.

The threads constituting the fabric can be of any type, including synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers, and mixed fibers consisting of two or more of these fibers, but generally speaking, polypropylene fibers, polyethylene fibers, etc. Synthetic fibers such as fibers, polyvinyl alcohol fibers, polyester (polyethylene terephthalate: PET, polybutylene terephthalate: PBT, polynaphthalene terephthalate: PNT, etc.) fibers, nylon fibers, and mixed fibers (mixed twists and combined twists) of these fibers, and is any one selected from 1) multifilament yarn, 2) short fiber spun yarn, 3) and covering yarn, which are made of chemically recycled fibers. In particular, in the yarn arrangement of the woven structure of the fabric described in paragraph [0017], for example, the type of warp yarn and the type of weft yarn may be different, or the warp yarn and/or weft yarn may be of different types. It is also possible to use multiple types of threads in combination, such as alternately or randomly arranging different threads. Multifilament yarn is a long fiber spun bundle (50 to 500 filament bundles) that is made by extruding thermoplastic resin such as nylon or polyester from a spinneret and spinning the long fiber spun yarn, which is stretched 3 to 5 times. Untwisted yarn or yarn twisted 1 to 200 times/m with a fineness of 125 to 2000 denier (139 to 2222 dtex) can be used. These multifilament yarns include bulky yarns such as Taslan yarn and Woolly yarn. The short fiber spun yarn is a staple made by cutting a long fiber spun bundle (which may be stretched) into a length of about 3.8 to 5.8 mm by extruding a thermoplastic resin such as nylon or polyester from a spinneret and spinning it. The sliver that has been opened and kneaded is stretched to form a roving (roving), which is then drafted and twisted to a predetermined count thickness and spun tow. Twisted yarn is made by pulling a single yarn or two single yarns together and twisting them S (right) or Z (left), or by pulling two twisted yarns that are made by pulling a single yarn or two single yarns and first twisting them. Double yarns made by ply twisting are examples. The number of twists of these twisted yarns is about 200 to 2000 times/m. Further, the covering yarn includes a covering yarn in which the short fibers are wound around the outer periphery of the multifilament yarn bundle, and in the present application, a core-sheath composite yarn is also included in the covering yarn.

In particular, in order to improve the tensile breaking strength, tear strength, explosion proof pressure resistance, heat resistance, fire resistance, etc. of the metallic sheet of the present invention, fluororesin fibers, wholly aromatic polyester fibers, fully aromatic polyamide fibers are used. It is suitable to design textiles mainly using multifilament yarns such as, or to use in combination with yarns made from the general-purpose synthetic fibers mentioned above (insertion of ripstop structure). In addition, for use as noncombustible materials certified by the Minister of Land, Infrastructure, Transport and Tourism (noncombustible membrane materials for tent structures), glass fibers, silica fibers, alumina fibers, silica-alumina fibers, carbon fibers, and fibers mixed with these fibers (mixed twisted and combined twisted fibers) are used. ) etc., which are mainly composed of inorganic multifilament yarns, are suitable. In particular, in order to dramatically improve tensile strength, tear strength, explosion proof pressure resistance, heat resistance, fire resistance, etc., fabrics are made of polybenzimidazole (PBI), polybenzoxazole (PBO), etc. , polybenzothiazole (PBT) systems, and copolymer polymers thereof (benzimidazole-benzoxazole copolymerization system, benzimidazole-benzothiazole copolymerization system, benzoxazole-benzothiazole copolymerization system, benzimidazole-benzoxazole- Yarns (multifilament yarns, short fiber spun yarns) made of one or more aromatic heterocyclic polymer fibers selected from the group of benzothiazole copolymerization system, the above-mentioned copolymerization system containing an aromatic polyamide component) , covering yarns), or the combination of yarns made of the above-mentioned general-purpose fibers (insertion of ripstop structure) are suitable. The ripstop structure is, for example, a plain weave fabric in which polyester fiber yarns are used as warp and weft yarns, and yarns made of aromatic heterocyclic polymer fibers are regularly placed at arbitrary positions in the warp and weft yarns, or Fabrics that are randomly arranged and form a lattice pattern (or irregular lattice pattern) in appearance, triaxial fabrics, and quadriaxial fabrics are suitable. Specifically, in the yarn arrangement 1, 2, 3, 4, 5...n (n is an integer) of the warp group and weft group, the aroma is added to each thread in multiples of 10 (10, 20, 30... This is an embodiment in which group heterocyclic polymer fiber threads are inserted to form a lattice pattern. In addition, in a four-axis fabric, any or all of the warp, weft, upper left bias yarn, upper right bias yarn can be made of aromatic heterocyclic polymer fiber yarn, and specifically, the warp and weft can be aromatic heterocyclic polymer fiber yarns. A configuration in which the ring polymer fiber yarn, the upper left bias yarn and the upper right bias yarn are used as other fiber yarns, or the upper left bias yarn and the upper right bias yarn are used as other aromatic heterocyclic polymer fiber yarns, and the warp and weft are used as other fiber yarns. The structure is made up of fiber threads.

Furthermore, when a tent membrane structure in which the metallic sheet of the present invention is sewn as a part is used, in order to obtain the effect of inhibiting rainwater from permeating through the joint cross section of the membrane structure (water absorption prevention property), the entire fabric is made with a permeable material. It is preferable that the fluoroalkyl group-containing copolymer resin is attached to the surface and further attached by impregnation. The adhering solid content of the perfluoroalkyl group-containing copolymer resin is 0.1 to 10 g/m ² , particularly 0.3 to 3 g/m ² per 1 m ² of fabric having a basis weight of 150 to 250 g/m ² . The perfluoroalkyl group-containing copolymer resin is an ethylenic resin having a perfluoroalkyl group having 8 or less carbon atoms, preferably 6 or less carbon atoms, or a perfluoroalkenyl group having 8 or less carbon atoms, preferably 6 or less carbon atoms. A water-repellent copolymer made of unsaturated monomers. These specifically include acrylates and/or methacrylates having perfluoroalkyl groups and other monomers copolymerizable therewith (e.g., acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamide, methacrylamide, Examples include water-repellent copolymers obtained by polymerizing with maleic acid alkyl esters, phthalic acid alkyl esters, vinyl chloride, vinylidene chloride, ethylene, styrene, etc.). It is preferable that these water-repellent copolymers be in the form of an emulsion and dilutable with water, since these are easy to handle when treating textiles. In these water-repellent copolymers, the copolymerized components adhere strongly to textiles in particular, and the perfluoroalkyl groups are aligned by heat curing at 120 to 180°C, lowering the surface energy and increasing water repellency. It becomes what it is. If necessary, 1 to 25% by mass of the perfluoroalkyl group-containing copolymer resin may be added to a silicone water repellent such as methylchlorosilane, methylpolysiloxane resin, dimethylpolysiloxane, or methylhydrodienepolysiloxane, or a carbon number It can also be used in place of a paraffin-based water repellent such as n-paraffin wax having a temperature of 20 to 48°C and a melting point of 50 to 70°C.

In the metallic-look sheet of the present invention, the coating layer of the thermoplastic resin composition formed on the front and back of the woven fabric is formed from a composition mainly composed of a known thermoplastic resin, elastomer, etc., and these are, for example, soft polyvinyl chloride resin (blended with plasticizer), vinyl chloride copolymer resin, chlorinated polyvinyl chloride resin, olefin resin (PE, PP), olefin copolymer resin, ethylene-vinyl acetate copolymer resin (EVA), ethylene-(meth)acrylic acid (ester) copolymer resin, urethane resin, vinyl acetate copolymer resin, styrene copolymer resin, polyester copolymer resin, fluorine-containing copolymer resin, etc., thermoplastic resins or elastomers with a Shore A hardness of about 45 to 85, including urethane rubber, acrylic rubber, butadiene rubber, chlorosulfonated polyethylene, SBR, EPDM, EPM, etc., and may be ones with enhanced rubber elasticity. An elastomer is a block copolymer resin made of two or more monomers, and each block component is a resin that constitutes a hard segment and a soft segment. Of these thermoplastic resins and elastomers, it is preferable to contain 50% by mass or more of soft vinyl chloride resins, vinyl chloride copolymer resins, chlorinated vinyl chloride resins, ethylene-vinyl acetate copolymer resins (EVA), ethylene-(meth)acrylic acid (ester) copolymer resins, urethane resins, and fluorine-containing copolymer resins, which have high-frequency weldability, as components that impart high-frequency weldability to the coating layer. The coating layer of the metallic-toned sheet of the present invention can contain any combination of known additives, such as stabilizers, fillers, colorants, pigments, metallic pigments, phosphorescent pigments, flame retardants, flame retardants, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, antistatic agents, and crosslinking agents.

In the metallic sheet of the present invention, the front and back coating layers constituting the tarpaulin in particular are made by hot kneading a thermoplastic resin composition (especially preferably vinyl chloride resin/plasticizer, etc.) and melting it by a calender method or a T-die extrusion method. A film (sheet) having a rolled thickness of 80 to 800 μm, particularly 150 to 300 μm is used. In addition, the lamination of the front and back coating layers on the fabric uses a laminator that has one or two continuous pressing units of hot rolls/rubber rolls, a cooling roll unit, and a winding unit, and a process of passing through the laminator once or twice. An example of this is a method of hot melt compression bonding. The tarpaulin (metallic-like sheet) of the present invention is suitably produced by thermocompression bonding a film obtained by calender molding to both sides of an open fabric using a laminator, and has a thickness of 0.4 to 1.0 mm and a mass of 150 to 1000 g/ M fabric is suitable for membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, and sunshade tents, as well as tarpaulins for emergency bags (disaster prevention supplies). ing.

The front and back coating layers constituting the metallic-finished sheet (canvas) of the present invention are canvas formed by applying a solution-type thermoplastic resin composition (particularly preferably a paste of vinyl chloride resin/plasticizer, etc.) to the front and back of a woven fabric by a coating method such as knife coating, clearance coating, or gravure coating, and then thermally drying or heat-gelling the resulting product to a thickness of 50 to 300 μm, and particularly 80 to 200 μm; or canvas formed by dipping a woven fabric into a liquid bath filled with a solution-type thermoplastic resin composition (particularly preferably a vinyl chloride resin paste), pulling it out and simultaneously squeezing it between a pair of rubber rolls, and immediately thermally drying or heat-gelling the resulting product to a thickness of 50 to 300 μm, and particularly 80 to 200 μm. The canvas (industrial sheet material) of the present invention is suitable for dipping using a paste made of polyvinyl chloride resin/plasticizer, etc., and a thickness of 0.3 to 0.8 mm and a mass of 400 to 1000 g/m are suitable for applications such as truck hoods (for wing hoods with aluminum bodies), truck bed sheets, rooftop tents, and sheet houses.

A glitter coating layer containing at least a glitter pigment, a silane coupling agent reactant, and cellulose nanofibers is formed on the coating layer on the surface side of the metallic sheet (tarpaulin, canvas) of the present invention. The binder resin that mainly constitutes the glitter coating layer is preferably an acrylic resin, a urethane resin, an acrylic/silicon copolymer resin, a fluorine copolymer resin, or an acrylic resin and a fluorine copolymer. It is preferably one or more selected from blends of resins, urethane/silicon-based graft copolymer resins, and urethane/fluorine-based graft copolymer resins. The acrylic resin is a polymer of one or more monomers selected from acrylic acid alkyl esters having an alkyl group of 1 to 18 carbon atoms and methacrylic acid alkyl esters having an alkyl group of 1 to 18 carbon atoms; and a copolymer resin. In addition, as acrylic resins, ethylenically unsaturated carboxylic acids, amide compounds, epoxy group-containing (meth)acrylic acids, α-olefins, vinyl ethers, alkenyls, vinyl esters, aromatic vinyl compounds, etc. It is also possible to use resins copolymerized with monomers, and acrylic/silicon copolymer resins copolymerized with organosiloxanes are particularly preferred. The above urethane resins include aromatic polyurethanes (ester-based, ether-based, polycarbonate-based), aliphatic polyurethanes (ester-based, ether-based, polycarbonate-based), alicyclic polyurethanes (ester-based, ether-based, polycarbonate-based), etc. In terms of light fastness, aliphatic polyurethanes and alicyclic polyurethanes are preferred, and in terms of weather fastness (hydrolysis resistance), ether-based and polycarbonate-based urethane resins are particularly preferred. Urethane copolymer resins include urethane/silicone graft copolymer resins in which organosiloxanes are grafted onto the urethane resin as the main chain, and urethane/fluorine resins in which fluoroolefins are grafted to the urethane resin as the main chain. Examples include graft copolymer resins. The above fluorine-based copolymer resin is a copolymer of two or more fluorine atom-containing monomers such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene. A copolymer obtained by copolymerizing the above fluorine atom-containing monomer with a vinyl monomer (β-methyl-β-alkyl substituted-α-olefins, alkyl vinyl ethers, alkyl allyl ethers, vinyl group-containing esters, etc.) The obtained fluoroolefin copolymers and the like can be used alone or in combination of multiple types. These are preferably copolymers containing hydroxyl groups or carboxy groups in the molecular structure that generate crosslinking sites when used in combination with reactive compounds such as isocyanate compounds, aziridine compounds, oxazoline compounds, and carbodiimide compounds. In particular, the isocyanate compound is preferably an aliphatic compound or an alicyclic compound, such as hexamethylene diisocyanate, isophorone diisocyanate, trimers thereof (isocyanurate type, trimethylpropane type, biuret type), and block isocyanate forms thereof. can be used. Further, as the oxazoline compound, a polymer type crosslinking agent (emulsion type) having an oxazoline group in the side chain of an acrylic resin (acrylic copolymer resin, acrylic/styrene copolymer resin) can also be used. As other binders, a blend of the above-mentioned acrylic resin and the above-mentioned fluorine-based copolymer resin can also be used.

The glittering pigment contained in the glittering coating layer of the metallic sheet (tarpaulin, canvas) of the present invention is preferably one or more selected from aluminum (colored) scale powder, flake-like (colored) aluminum, scale-like interference coloring mica, scale-like (colored) mica, interference coloring glass flakes, metal-deposited glass flakes, metal-deposited (colored) film fragments, and hologram film fragments. Of these, aluminum (colored) scale powder and flake-like (colored) aluminum are distinguished by particle size. In the present invention, aluminum (colored) scale powder is classified as having an average particle size (major axis) of 3 μm to 30 μm, and flake-like (colored) aluminum is classified as having an average particle size (major axis) of 31 μm to 100 μm. The average particle size of the scales or flakes refers to the 50% particle size (D ₅₀ ) of the volume-based particle size distribution, and can be determined from the particle size distribution using a laser diffraction/scattering particle size distribution measuring device. The aspect ratio of the scales or flakes is determined by the ratio (D _{50 /T) of the average particle diameter (D 50 )} and the average thickness (T) of the scale-like pigment, and is preferably 50 to 100, which makes the average thickness (T) 1 μm or less. Either leafing or non-leafing type may be used for the aluminum (colored) scale powder and flake-like (colored) aluminum, and aluminum pastes that are moistened with mineral spirits (petroleum-based solvent) to prevent dust scattering are preferred. In particular, by using a paint containing leafing-type aluminum scale powder, the scale-like aluminum particles are horizontally oriented and arranged in the coating liquid like fallen leaves (leaves) on the water surface, resulting in a leafing effect, and not only can a mirror-like glossy chrome-plated appearance be obtained, but also a gas barrier effect and anti-corrosion properties of the base are exhibited. The leafing type aluminum flake powder has an average particle size (long diameter) of 3 μm to 20 μm and a water surface diffusion area of 10,000 to 70,000 cm ² /g, and is preferably contained in an amount of 0.5 to 10 mass % relative to the glittering coating layer. On the other hand, if aluminum flakes with large scale particles that have not been leafing-treated are used, the arrangement in the coating liquid becomes random, resulting in a sparkling, dynamic silver appearance. The non-leafing type aluminum flake powder has an average particle size of 10 μm to 30 μm and a water surface diffusion area of 5,000 to 20,000 cm ² /g, and is preferably contained in an amount of 0.5 to 10 mass % relative to the glittering coating layer. The aluminum flake powder and flake-like aluminum can be colored freely with any accent color to achieve color metallic decoration. For example, gold decoration can be easily obtained by using these aluminum pigments and accent colors of yellow to orange. The leafing type is surface-treated with long-chain saturated fatty acids such as myristic acid, palmitic acid, stearic acid, and behenic acid, and has a large surface tension and a weak affinity with solvents and paints, so it floats on the surface side (upper side) of the coating film and is oriented almost uniformly, thereby showing a chrome-plated appearance with excellent base material hiding power. On the other hand, the non-leafing type is treated with unsaturated fatty acids such as linoleic acid, linoleic acid, ricinoleic acid, and oleic acid, or fatty acids with relatively short carbon chains, and has a small surface tension and a strong affinity with solvents and paints, so it sinks to the back side (lower side) of the coating film and is oriented unevenly, thereby showing a sparkling twinkle effect. In addition, by mixing the leafing type and the non-leafing type in any ratio, a sparkling twinkle effect can be added to the chrome-plated appearance. In addition, it may be a coating scale powder or coating flake that has been treated with a transparent resin such as an acrylic resin or an epoxy resin, or a colored transparent resin. The random arrangement of the (colored) coating flakes not only gives a highly glittering, twinkle-effect appearance, but also provides excellent affinity and adhesion with the binder resin of the coating film, increases durability against scratches, and also prevents sparks when high-frequency welding is performed on metallic-look sheets.

In addition, the scale-like interference coloring type mica used for glitter pigments is made by coating mica scales (natural mica or synthetic mica) with an average particle size of 5 to 100 μm with a thin film of titanium dioxide at a coverage rate of 43 to 80%. Examples include glitter pigments, and the content thereof is preferably 0.5 to 10% by mass based on the glitter coating layer. This pearlescent pigment can control the reflected color and transmitted color in stages depending on the titanium dioxide coverage.For example, if the titanium dioxide coverage is 43%, the reflected color is gold and the transmitted color is violet. When the coverage is 47%, the reflected color is orange and the transmitted color is green, and when the coverage is 52%, the reflected color is blue and the transmitted color is yellow. Further, when the coverage is 57%, a scale-like interference colored mica having a green reflection color and a red transmission color can be obtained. Two or more types of these scale-like interference coloring synthetic mica may be used as a blend. In addition, the flaky (colored) mica used in glitter pigments is a silvery-white color obtained by coating the surface of mica scales (natural mica or synthetic mica) with an average particle size of 5 to 100 μm with a thin film of titanium dioxide at a coverage rate of 12 to 42%. Mica, a gold-colored pearlescent pigment that is made by coating this silvery white mica with a thin film of iron (II) oxide at a coverage of 2 to 30%, and a coating of iron (II) oxide at a coverage of 20 to 60%, preferably 31 Examples include bronze-colored pearlescent pigments coated with a thin film at a concentration of 60% to 60%, and the content is preferably 0.5 to 10% by mass based on the glitter coating layer. The aspect ratio of these scale-like interference colored mica and scale-like (color-forming) mica is 20 to 20 depending on the ratio (D ₅₀ /T) of the average particle diameter (D ₅₀ ) to the average thickness (T) of the scale-like mica. 100 (25 to 50 for natural mica) is preferable. As the synthetic mica used for the above-mentioned scale-like interference colored mica and scale-like (color-forming) mica, fluorine tetrasilicon mica in which the hydroxyl group of natural mica (Na tetrasilicon mica) is replaced with a fluorine atom is used.

In addition, interference coloring type glass flakes used for glitter pigments include glitter pigments in which the surface of glass flakes with an average particle size of 50 to 300 μm is coated with a thin film of titanium dioxide to a thickness of 50 to 200 nm, and the glitter coating layer is The content is preferably 0.5 to 10% by mass. This glittering pigment can control the iris color step by step depending on the coating thickness of titanium oxide. For example, if the coating thickness of titanium dioxide is 50 to 70 nm, it will change from silver to platinum, and if the coating thickness of titanium dioxide is 70 to 120 nm, it will change from gold to reddish. Gold, red to purple metallic at 120 to 140 nm, blue metallic at 150 to 165 nm, and green metallic at 165 to 185 nm. In addition, as types that control the iris color in stages by controlling the thickness of the iron oxide coating, bronze coloring, copper coloring, russet coloring, and gold with a two-layer coating of titanium oxide and iron oxide can be used. Metal-deposited glass flakes are produced by forming a mirror-like metal-plated thin film on the surface of glass flakes with an average particle size of 50 to 300 μm using a known vacuum deposition method of metals such as aluminum, chromium, zinc, silver, copper, and nickel. This is what I did. In addition, a metal-deposited (colored) film crushed body is a product in which a metal-plated thin film is formed on the surface of a PET (polyethylene terephthalate) film by using a known vacuum deposition method to coat metals such as aluminum, chromium, zinc, silver, copper, and nickel. is crushed into 1-2 mm size, or a PET film with a (colored) PET film laminated on the vapor-deposited film is crushed into 1-2 mm size. Further, the hologram film crushed body is a laminate in which a known hologram foil is adhered to a PET film, or a hologram processed film crushed into a size of 1 to 2 mm.

The silane coupling agent reactant contained in the glitter coating layer contains at least a condensate resulting from a reaction between silane coupling agents, and further contains a decomposed product of the silane coupling agent bonded to the surface of the glitter pigment described above, and a decomposition product of the silane coupling agent as described below. It contains a decomposed product of a silane coupling agent bonded to cellulose nanofibers. Cellulose nanofibers are contained in the glitter coating layer, and the cellulose nanofibers are present between the glitter pigment (especially scale-like or flake-like) and the glitter pigment (especially scale-like or flake-like). When a physical load such as bending or scratching is applied to the glitter coating layer, the arrangement (horizontal arrangement or random arrangement) of the glitter pigments (especially scale-like or flake-like) is disturbed, that is, diffused reflection occurs. A spring-like buffering effect is developed that resists the displacement that causes it and restores it. At this time, a silane coupling agent reactant is present between the support of the cellulose nanofibers and the glittering pigment (particularly on the scale-like or flaky surface) and the cellulose nanofibers, and they are chemically bonded. is preferred. The support of such a silane coupling agent reactant further strengthens the spring-like buffering effect that restores the above-mentioned displacement. In particular, the presence of a condensate resulting from the reaction between silane coupling agents contained in the glitter coating layer improves the durability and scratch resistance of the glitter coating layer, resulting in a metallic appearance of the glitter coating layer. can be maintained for a long period of time. Examples of the silane coupling agent serving as a source of silane coupling agent reactant include one or more selected from aminosilane, vinylsilane, epoxysilane, methacrylsilane, acrylicsilane, chlorosilane, mercaptosilane, isocyanuratesilane, and isocyanatesilane. can. The silane coupling agent is an alkoxysilane compound having two or more different reactive groups in the molecule represented by the general formula: XR-Si(Y) ₃ , for example, X = amino group, vinyl group, epoxy group, Methacryl group, acrylic group, chloro group, mercapto group, isocyanurate group, isocyanate group, etc. (R=alkyl chain), Y=methoxy group, ethoxy group, etc. In the glitter coating layer of the present invention, the silane coupling agent is hydrolyzed in _an aqueous solution to produce the general formula: However, for such a condensate, a silane coupling agent in which X=amino group, epoxy group, mercapto group, isocyanate group, etc. is particularly suitable. On the other hand, the decomposition product of the silane coupling agent bonded to the glitter pigment is dissolved in an aqueous solution containing the glitter pigment and the silane coupling agent. It contains an aspect of "hydrolyzate/glitter pigment". In addition, the decomposition product of the silane coupling agent bonded to the cellulose nanofibers is dissolved in an aqueous solution containing the cellulose nanofibers and the above-mentioned silane coupling agent, which will be described later. etc., and contains an embodiment of "cellulose nanofiber/hydrolyzate". On the other hand, the decomposed product of the silane coupling agent bonded to the glitter pigment and the cellulose nanofibers is dissolved in an aqueous solution containing the glitter pigment, the cellulose nanofibers described below, and the silane coupling agent. Contains an embodiment of "cellulose nanofiber/hydrolyzate/glitter pigment" in which the hydrolyzate increases the bonding strength to the surface of the glitter pigment and to the hydroxyl group, carboxy group, etc. of cellulose nanofibers.

Cellulose nanofiber is obtained by mechanically defibrating (coarsely defibrating/finely defibrating) cellulose raw materials (chemically treated pulp, mechanically crushed pulp, waste paper pulp, etc.) to make the fiber diameter nano-sized. Short fibers with a ratio (average fiber length/average fiber diameter) of 10 or more and 50 or less, an average fiber diameter of 3 nm to 100 nm, and an average fiber length of 100 μm or less, especially 300 nm to 500 nm, consisting of a crystalline part, a quasi-crystalline part, and an amorphous part. Nanofibers can be used alone, or can be longitudinally torn, entangled, or aggregated in a network structure, and can be dried, slurried, water, or dispersed in an organic solvent. Mechanical defibration of cellulose fibers can be performed using modified pulp direct kneading method (fiber diameter 3-100 nm), high-pressure homogenizer method (fiber diameter 10 nm-several μm), opposed jet impingement method (fiber diameter 10 nm-several tens of nanometers), and grinder method (fiber diameter 10 nm-several tens of nanometers). Fiber diameter 10 nm - several 10 nm), ball mill grinding method (fiber diameter 100 nm - several μm), bead mill grinding method (fiber diameter 10 nm - several tens nm), freeze grinding method (fiber diameter 10 nm - several tens nm), biaxial kneading method (fiber diameter 10 nm - several tens nm), For example, a method in which the diameter is 10 to 100 nm) is used. Chemical defibration is also possible, including the TEMPO oxidation method, C2,C3-dicarboxylation (selectively cleaving the C2-C3 positions of cellulose molecules in pulp with sodium hypochlorite, and C2,C3-dicarboxylation). phosphoric acid esterification method (forming the hydroxyl groups of cellulose molecules in the pulp with ammonium phosphate or ammonium phosphite/urea), carboxymethylation method (forming isopropyl Using alcohol/concentrated NaOH/Na monochloroacetate to obtain carboxymethyl cellulose with a degree of substitution of about 0.4 to 1.2), xanthate method (pulp is mixed with concentrated NaOH and carbon disulfide to replace the hydroxyl groups of cellulose with Na xanthate ester groups), converting into salt to obtain viscose rayon and cellophane), sulfonation method (converting the hydroxyl groups of cellulose molecules in pulp to sulfate esters with sulfamic acid/urea), enzymatic hydrolysis method, acid hydrolysis method, bacterial synthesis method Examples include. The fiber diameter from the TEMPO oxidation method to the sulfonation method described above is about 3-5 nm. In the present invention, both unmodified cellulose nanofibers obtained by mechanical defibration and modified cellulose nanofibers obtained by chemical defibration can be used. Modified cellulose nanofibers can also be used.

Modification types of modified cellulose nanofibers include carboxymethylation, oxidative modification, esterification (one or more selected from boric acid esterification, phosphoric acid esterification, silicate esterification), isocyanation, and silane coupling agent. Treatment (one or more selected from aminosilane modification, vinylsilane modification, epoxysilane modification, methacrylsilane modification, acrylicsilane modification, chlorosilane modification, mercaptosilane modification, isocyanurate silane modification, isocyanate silane modification), It is cellulose nanofiber that has undergone more than one type of modification. In particular, carboxymethylation is performed by arbitrarily carboxymethylating the primary and secondary hydroxyl groups (2, 3, and 6 positions) of cellulose and mechanically fibrillated, and oxidative modification is performed using TEMPO (2, 2, 6, 6 positions). -tetramethylpiperidine-1-oxy radical) catalyst, NaBr, and an oxidation catalyst solution containing Na hypochlorite, selectively converts only the primary hydroxyl group (C6-OH group) in the cellulose molecules of the pulp to C6-carboxylic acid. It is converted into a basic Na salt to have a COOH group content of 0.8 to 1.7 mmol/g, and then fibrillated. In addition, silane coupling agent treatment (one or more selected from aminosilane modification, vinylsilane modification, epoxysilane modification, methacrylsilane modification, acrylic silane modification, chlorosilane modification, mercaptosilane modification, isocyanurate silane modification, isocyanate silane modification) For modification, cellulose nanofibers are treated with an aqueous solution containing one or more silane coupling agents, and a hydrolyzate of the silane coupling agent: XR-Si(OH) ₃ (X, Y are as described in paragraph [0028]) The same) is one or more reactants bonded to the hydroxyl group, carboxy group, etc. of cellulose nanofibers, even if it is vinyl silane/methacrylic silane modification, amino silane/mercapto silane modification, etc. by using two types of silane coupling agents together. Alternatively, modification may be performed by using three or more types of silane coupling agents in combination. As the silane coupling agent, those described in paragraph [0028] can be used. Silane coupling agent-treated cellulose nanofibers are cellulose nanofibers that have been treated with a silane coupling agent in advance. It is distinguished from a silane coupling agent reactant contained in a coating solution containing fibers. That is, the embodiment of the glitter coating layer includes "silane coupling agent-modified cellulose nanofiber/silane coupling agent hydrolyzate/glitter pigment". In the present invention, by using unmodified cellulose nanofibers, particularly modified cellulose nanofibers, and more particularly, silane coupling agent-treated modified products, the bonding strength of the silane coupling agent-treated modified products to the glitter pigment surface is increased, Forms the form of "modified cellulose nanofiber/hydrolyzate/glitter pigment" and enables the glitter pigment to exhibit position stability against external physical loads within the glitter coating layer. Not only that, but gas barrier properties can also be imparted at the same time.

Among the modifications by esterification, boric acid esterification is a modification in which cellulose nanofibers are treated with boric acid such as orthoboric acid (H ₃ BO ₃ ) or metaboric acid (HBO ₂ ), or with an aqueous solution of a borate such as sodium tetraborate hydrate (Na ₂ B ₄ O _{7.10H 2} O) or sodium pentaborate (NaB ₅ O ₈ ), and the boric acid component is reacted with the hydroxyl groups and carboxyl groups of the cellulose nanofibers. Phosphate esterification is a modification in which nanocellulose is treated with orthophosphoric acid (H ₃ PO ₄ ), pyrophosphoric acid, polyphosphoric acid (HPO ₃ )n, phosphorous acid, phosphinous acid, or other phosphoric acid, or metal salts or ammonium salts derived from these phosphoric acids, and the phosphoric acid component is reacted with the hydroxyl and carboxyl groups of the cellulose nanofibers, and silicate esterification is a modification in which the cellulose nanofibers are treated with silicic acid and an aqueous solution of a silicate such as sodium silicate (water glass), lithium silicate, or potassium silicate, and the silicic acid component is reacted with the hydroxyl and carboxyl groups of the cellulose nanofibers. These ester modifications may be boric acid/phosphoric acid esterification by combined treatment with an aqueous solution of a borate salt and an aqueous solution of a phosphate salt, boric acid/silicic acid esterification by combined treatment with an aqueous solution of a borate salt and an aqueous solution of a silicate salt, phosphoric acid/silicic acid esterification by combined treatment with an aqueous solution of a phosphate salt and an aqueous solution of a silicate salt, or the like. By using such an esterified modified product, when a physical load such as bending or rubbing is applied to the glittering coating layer, the arrangement (horizontal arrangement or random arrangement) of the glittering pigment (especially scale-like or flake-like) is disturbed, i.e., a stable position is maintained against the displacement that causes diffuse reflection, and a spring-like cushioning effect that restores the displacement is exerted, while at the same time preventing damage such as cracks in the glittering coating layer and preventing wear and falling off of the glittering coating layer. Furthermore, these modifications can impart not only antiseptic properties and flame retardancy to the cellulose nanofibers, but also gas barrier properties.

The composition (mass content) of the glittering coating layer is: 1 to 50% by mass of glittering pigment, 1 to 10% by mass of silane coupling agent reactant, 1 to 10% by mass of cellulose nanofiber, and 30% by mass of binder resin. The range is from 1 to 97% by mass, preferably 5 to 20% by mass of the glitter pigment, 1 to 5% by mass of the silane coupling agent reactant, 1 to 5% by mass of cellulose nanofiber, and 70 to 70% by mass of the binder resin. 93% by mass, more preferably 5 to 10% by mass of the bright pigment, 1 to 3% by mass of the silane coupling agent reactant, 1 to 3% by mass of cellulose nanofibers, and 84 to 93% by mass of the binder resin. be. The glitter coating layer may optionally contain 0.1 to 5% by mass of known additives such as ultraviolet absorbers, antioxidants, hindered amine light stabilizers, antistatic agents, antifungal agents, and antibacterial agents. Can be done. In particular, by containing a benzotriazole compound, a benzophenone compound, a triazine compound, etc. as an ultraviolet absorber, the light resistance of the glitter coating layer is improved and a beautiful metallic appearance can be maintained for a long time. The glitter coating layer is formed by applying a paint (solvent-based or water-based) composition containing the above composition to a method such as gravure roll coating, offset coating, flexo coating, screen coating, spray coating, wire bar coating, etc. It is preferably formed to a thickness of about 10 to 100 μm using a known coating method. This glittering coating layer may be a multi-layered layer consisting of two to three coatings; for example, the lower layer contains 6% by mass of leafing-type aluminum scale powder (average particle size D ₅₀ : 10 μm). This embodiment is a metallic coating film in which the upper layer contains 1% by mass of leafing-type aluminum scale powder (average particle diameter D ₅₀ : 30 μm). For example, the lower layer is a metallic coating film containing 8% by mass of scaly blue interference colored mica (average particle size D ₅₀ : 10 to 60 μm), and the upper layer is a leafing-type aluminum scale powder (average particle size D ₅₀ : 30 μm). This is an embodiment of a metallic coating film containing 0.5% by mass of.

An antifouling coating layer is further formed on the glittering coating layer of the metallic sheet (tarpaulin, canvas) of the present invention, and within this antifouling coating layer, photocatalytic titanium oxide, photocatalytic titanium peroxide, By containing one or more photocatalytic metal oxides selected from photocatalytic zinc oxide, photocatalytic tin oxide, photocatalytic strontium titanate, photocatalytic tungsten oxide, photocatalytic bismuth oxide, and photocatalytic iron oxide. It exhibits photocatalytic activity to promote the decomposition of organic matter (soot, tar, hand grime, mold, algae, etc.) and achieves a self-cleaning effect due to rainfall. In particular, by using a photocatalytic metal oxide supported on inorganic porous particles such as zeolite, damage to the glitter coating layer due to photocatalytic activity can be reduced. In addition, by making the antifouling coating layer mainly composed of an organosilicate compound or a sol-gel condensate of an organic silane compound containing a silanol group, it increases the durability of the antifouling coating layer against abrasion loads and chemicals, and at the same time provides a gas barrier. Increase effectiveness. In addition, the sol-gel condensate is an armor that protects the antifouling coating layer itself from radical attacks caused by photocatalytic activity, and a barrier that protects the glitter coating layer from radical attacks caused by photocatalytic activity. The organosilicate compound forming the sol-gel condensate is a tetrafunctional hydrolyzable silane compound represented by the chemical formula: Si _n O _n-1 (OR) _{2 (n+1)} , where R is a carbon atom number of 1 to 10 alkyl groups (especially lower alkyl groups having 1 to 3 carbon atoms) or aryl groups (especially phenyl groups), n is the degree of polymerization (so-called n-mer) representing the number of condensed molecules of the tetrafunctional hydrolyzable silane compound Examples of compounds where n is an integer of 1 or more and n is 1 include tetramethoxysilane (Si(OCH ₃ ) ₄ : also known as tetramethylsilicate), tetraethoxysilane (Si(OC ₂ H ₅ ) 4 : also known as tetraethylsilicate), tetramethoxysilane (Si(OCH 3 ) ₄ : also known as tetraethylsilicate), Propoxysilane (Si(OC ₃ H ₇ ) ₄ : Also known as tetrapropyl silicate), Tetrabutoxysilane (Si(OC ₄ H ₉ ) ₄ : Also known as tetrabutyl silicate), Tetraphenoxysilane (Si(OC ₆ H ₆ ) ₄ : Compounds where n is 2 or more, such as dimethoxydiethoxysilane (Si(OCH ₃ ) ₂ (OC ₂ H ₅ ) ₂ : also known as dimethylhyethylsilicate), are tetrafunctional hydrolyzable silane compounds. It is a multimer produced by the condensation of two or more molecules through a reaction between silanol groups produced by decomposition, and the degree of multimerization represented by n means the number of Si atoms contained in one molecule of the multimer. In the present invention, it is preferable to use tetramethoxysilane having a polymerization degree of 2 to 10, preferably 4 to 6, or a silanol group-containing silane compound obtained by hydrolyzing tetraethoxysilane, since the structure of the sol-gel condensate can be made finer. preferable. The concentration of the organosilicate hydrolysis product contained in the coating solution (water/alcohol) that forms the antifouling coating layer is preferably in the range of 0.01 to 30% by mass, particularly 0.1 to 5% by mass. . In addition, in this coating liquid, inorganic colloids (silica sol, antimony sol, alumina sol, zirconia sol, etc.) are added to the hydrolysis products of organosilicate to further enhance the abrasion resistance and durability of the antifouling coating layer. It can be contained in an amount of 0.1 to 25% by mass based on the concentration. Furthermore, by adding a hydrolyzate of a silane coupling agent (alkoxysilane compound) to a part of the structure of the sol-gel condensate formed by the hydrolysis product of an organosilicate or a silanol group-containing organosilane compound, a sol-gel is formed. By imparting flexibility to the condensate, a coating film that is more resistant to bending can be obtained. The silane coupling agent (alkoxysilane compound) described in paragraph [0028] can be used at a maximum of 25% by mass of the sol-gel condensate.

This antifouling coating layer contains photocatalytic titanium oxide, photocatalytic titanium peroxide, photocatalytic zinc oxide, photocatalytic tin oxide, photocatalytic strontium titanate, photocatalytic tungsten oxide, photocatalytic bismuth oxide, and photocatalytic oxide. It is preferable to contain 10 to 50% by mass of one or more photocatalytic metal oxides selected from iron, based on the sol-gel condensate, and further, Pt, Rh, RuO ₂ , Nb, Cu, Sn, NiO Metals and metal oxides such as can be added as photocatalytic activity synergizers. To support photocatalytic metal oxide particles on the sol-gel condensate, a photocatalytic metal oxide sol with an average particle size of 50 nm or less, especially 20 nm or less is mixed with an organosilicate hydrolysis product or a silanol group-containing organic silane compound. After dispersing and coating this on a glitter coating layer (eg, gravure roll method), sol-gel condensation is performed to obtain a thin film with a thickness of 0.5 to 15 μm. The photocatalytic activity of these photocatalytic metal oxides promotes the decomposition of organic substances (soot, tar, bird droppings, mold, algae, etc.), and a self-cleaning effect due to rainfall is expressed. In particular, by supporting such a photocatalytic metal oxide in a sol-gel condensate having a network structure, damage to the glitter coating layer due to photocatalytic activity is reduced. Self-cleaning effect is the effect of restoring the appearance of the product before dirt was attached by washing away organic matter residues such as dirt (soot, tar, bird droppings), mold, and algae that have been decomposed by photocatalytic activity with rain. This is a cleaning system that requires no assistance. By applying such a glittering coating layer to membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, etc., it is possible to create metallic-like exteriors of membrane structures. It can last beautifully.

The metallic sheet of the present invention will be specifically explained by giving Examples and Comparative Examples.
Durability of metallic appearance (1): JIS L1096 8.19.2 B method) Scott method
2.5cm (vertical) x 12cm (horizontal) and 2.5cm (horizontal) x 12cm (vertical) specimens taken from the metallic sheet were mounted on a Scott type tester (stroke 4cm), and a 1kgf load was applied. After 100 times of bending and rubbing (rubbing the surfaces of the glitter coating layers), the metallic appearance of the rubbed surfaces was observed with a magnifying glass, and optical bends and scratches due to disordered arrangement of the glitter pigments were observed. The presence/absence and degree of bleaching marks were determined.
1: Neither creases nor whitening marks are observed on the glitter coating layer.
2: Creases are observed in the glitter coating layer, but no whitening marks are observed.
3: Creases and whitening marks are observed on the glitter coating layer.
Durability of glitter coating layer (1): JIS L1096 8.19.2 B method) Scott type method
2.5cm (vertical) x 12cm (horizontal) and 2.5cm (horizontal) x 12cm (vertical) specimens taken from the metallic sheet were mounted on a Scott type tester (stroke 4cm), and a 1kgf load was applied. After 3000 times of bending and rubbing (rubbing the surfaces of the glitter coating layers), the glitter coating layer on the rubbed surface was observed with a magnifying glass to determine the presence or absence and degree of shedding.
1: No shedding of the glitter coating layer
2: Abrasion observed in the glitter coating layer
3: Significant peeling off of the glitter coating layer is observed.
Durability of metallic appearance (2): JIS L1096 8.19.3 C method) Taber type method
A disk with a diameter of 13 cm taken from a metallic sheet was used as a test piece, and was attached to a Taber type abrasion tester (wear wheel CS-10), and an abrasion load of 100 rotations was applied to the surface of the bright coating layer at a load of 2.45N. Thereafter, the metallic appearance was observed with a magnifying glass to determine the presence and extent of optical scratch marks and optical whitening marks due to disordered arrangement of the glitter pigments.
1: Neither scratches nor whitening marks are observed on the glitter coating layer.
2: Scratches are observed on the glitter coating layer, but no whitening marks are observed.
3: Scratches and whitening marks are observed on the glitter coating layer.
Durability of glitter coating layer (2): JIS L1096 8.19.3 C method) Taber type method
A disk with a diameter of 13 cm taken from a metallic sheet was used as a test piece, and was attached to a Taber type abrasion tester (wear wheel CS-10), and an abrasion load of 2000 rotations was applied to the surface of the bright coating layer at a load of 2.45N. Thereafter, the metallic appearance was observed with a magnifying glass to determine the presence and extent of optical scratch marks and optical whitening marks due to disordered arrangement of the glitter pigments.
1: No shedding of the glitter coating layer
2: Abrasion observed in the glitter coating layer
3: Significant peeling off of the glitter coating layer is observed.

[Example 1]
<fabric>
PET multifilament yarn made of 1000 denier (1111 dtex) polyethylene teretalate (PET) fibers (192 filaments) and subjected to S twist of 50 T/m is used for the warp and weft groups, and the warp groups are separated by 1 inch. A plain woven fabric having a weave structure with 16 weft threads and 16 weft threads per inch was used. The mass of this fabric (1) was 150 g/m ² , and the porosity (total number of holes) was 14%.
<Tarpaulin base material>
Using this woven fabric as a base material, melt lamination was performed by thermocompression bonding with a laminator using a 0.2 mm thick calender molded film made of the following [formulation 1] as a covering layer on both sides of the fabric. A white tarpaulin base material having a thickness of 0.7 mm and a mass of 830 g/m ² was obtained.
[Formulation 1]: Soft vinyl chloride resin composition (compound)
Vinyl chloride resin (degree of polymerization 1300) 100 parts by mass Diisononyl phthalate (plasticizer) 55 parts by mass Tricresyl phosphate (flame retardant plasticizer) 10 parts by mass Epoxidized soybean oil (stabilizer and plasticizer) 5 parts by mass Barium/zinc Composite stabilizer 2 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Rutile titanium oxide (white pigment) 5 parts by mass Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass
<Metallic sheet (1): Tarpaulin>
On one surface of the white tarpaulin base material, the following metallic paint [Formulation 2] was gravure coated on one side (surface) of the tarpaulin base material using a 100 mesh gravure roll, and dried by heating in a hot air oven at 120°C for 2 minutes. , a glitter coating layer (1) was formed using the metallic paint of [Formulation 2], and the thickness of the cross-sectional structure of "Glitter coating layer [Formulation 2]/covering layer/fabric/covering layer" was 0.71 mm, A glossy chrome plated sheet (1) having a mass of 835 g/m ² was obtained.
[Formulation 2] Paint for forming glitter coating layer
Hydroxyl group-containing fluoroolefin vinyl ether copolymer 100 parts by mass *Fluororesin emulsion (solid content 50% by mass)
Acrylic/styrene polymer curing agent having oxazoline group 10 parts by mass *Emulsion (solid content 40 mass%): Oxazoline group amount 1.8 mmol/g (solid content)
Epoxy-based silane coupling agent 2 parts by mass *3-glycidoxypropyltrimethoxysilane Unmodified cellulose nanofiber (2% by mass aqueous solution) 100 parts by mass *Fiber width 3-10 nm: fiber length 30-100 μm
Leafing type aluminum scale powder 3 parts by mass *Average particle diameter (D ₅₀ ) 10 μm: Water surface diffusion area 13,000 cm ² /g

[Example 2]
The same procedure as in Example 1 was carried out except that the glitter coating layer (1) of [Formulation 2] in Example 1 was changed to the glitter coating layer (2) of [Formulation 3]. [Formulation 3] / Covering layer / Textile / Covering layer” A chrome-plated sheet (2) with a glittering appearance and a cross-sectional structure with a thickness of 0.71 mm and a mass of 835 g/m ² was obtained.
[Formulation 3] Paint for forming glitter coating layer
Hydroxyl group-containing fluoroolefin vinyl ether copolymer 100 parts by mass *Fluororesin emulsion (solid content 50% by mass)
Acrylic/styrene polymer curing agent having oxazoline group 10 parts by mass *Emulsion (solid content 40 mass%): Oxazoline group amount 1.8 mmol/g (solid content)
Amino-based silane coupling agent 2 parts by mass *N-2-(aminoethyl)-3-aminopropyltrimethoxysilane Unmodified cellulose nanofiber (2% by mass aqueous solution) 100 parts by mass *Fiber width 3-10 nm: fiber length 30 ～100μm
Non-leafing aluminum scale powder 3 parts by mass *Average particle diameter (D ₅₀ ) 30 μm: Water surface diffusion area 9,500 cm ² /g

[Example 3]
On the glitter coating layer (1) of the glossy chrome plated sheet (1) of Example 1, a glitter coating layer according to [Formulation 4] was added to form a two-layer glitter coating layer (3). Other than that, the same as in Example 1, the thickness of the cross-sectional structure of "Glitter coating layer [Formulation 4]/Glitter coating layer [Formulation 2]/Coating layer/Textile/Coating layer" was 0.72 mm, and the mass was 840 g. A metallic-like sheet (3) with an appearance that had ^both glossy chrome plating and a glittery appearance was obtained.
[Formulation 4] Paint for forming glitter coating layer
Hydroxyl group-containing fluoroolefin vinyl ether copolymer 100 parts by mass *Fluororesin emulsion (solid content 50% by mass)
Acrylic/styrene polymer curing agent having oxazoline group 10 parts by mass *Emulsion (solid content 40 mass%): Oxazoline group amount 1.8 mmol/g (solid content)
Isocyanate-based silane coupling agent 2 parts by mass *3-Isocyanatepropyltriethoxysilane Unmodified cellulose nanofiber (2% by mass aqueous solution) 100 parts by mass *Fiber width 3-10 nm: fiber length 30-100 μm
Non-leafing aluminum scale powder 0.5 parts by mass *Average particle diameter (D ₅₀ ) 30 μm: Water surface diffusion area 9,500 cm ² /g

[Example 4]
The same procedure as in Example 1 was carried out except that the glitter coating layer (1) according to [Formulation 2] in Example 1 was changed to the glitter coating layer (4) according to [Formulation 5]. [Formulation 5]/Coating layer/fabric/coating layer” A glossy gold-plated sheet (4) having a cross-sectional structure with a thickness of 0.71 mm and a mass of 835 g/m ² was obtained.
[Formulation 5] Paint for forming glitter coating layer
Hydroxyl group-containing fluoroolefin vinyl ether copolymer 100 parts by mass *Fluororesin emulsion (solid content 50% by mass)
Acrylic/styrene polymer curing agent having oxazoline group 10 parts by mass *Emulsion (solid content 40 mass%): Oxazoline group amount 1.8 mmol/g (solid content)
Epoxy-based silane coupling agent 2 parts by mass *3-glycidoxypropyltrimethoxysilane Boric acid ester modified cellulose nanofiber (2 mass% aqueous solution) 100 parts by mass *3 mass% boric acid + 78 mass% ethyl cellosolve aqueous solution Modified product made by reacting carboxymethyl groups of carboxymethylated cellulose nanofibers (carboxymethylation of primary and secondary hydroxyl groups (2, 3, 6 positions) of cellulose): Fiber width 3-10 nm: Fiber length 30 ～
100μm
Leafing type aluminum scale powder 3 parts by mass *Average particle diameter (D ₅₀ ) 10 μm: Water surface diffusion area 13,000 cm ² /g
Disazo yellow (yellow pigment) 0.3 parts by mass

[Example 5]
The same procedure as in Example 1 was carried out except that the glitter coating layer (1) according to [Formulation 2] in Example 1 was changed to the glitter coating layer (5) according to [Formulation 6]. [Formulation 6]/Coating layer/fabric/coating layer" A glossy chrome-plated sheet (5) having a cross-sectional structure with a thickness of 0.71 mm and a mass of 835 g/ ^m2 was obtained.
[Formulation 6] Paint for forming glitter coating layer
Hydroxyl group-containing fluoroolefin vinyl ether copolymer 100 parts by mass *Fluororesin emulsion (solid content 50% by mass)
Acrylic/styrene polymer curing agent having oxazoline group 10 parts by mass *Emulsion (solid content 40 mass%): Oxazoline group amount 1.8 mmol/g (solid content)
Epoxy-based silane coupling agent 2 parts by mass *3-glycidoxypropyltrimethoxysilane Phosphate esterified modified cellulose nanofiber (2 mass% aqueous solution) 100 parts by mass *3 mass% phosphoric acid + 78 mass% ethyl cellosolve aqueous solution Carboxymethylated cellulose nanofiber (carboxymethylated primary and secondary hydroxyl groups (2, 3, 6 positions) of cellulose)
Modified product reacted with carboxymethyl group: Fiber width 3-10 nm: Fiber length 30-100
μm
Leafing type aluminum scale powder 3 parts by mass *Average particle diameter (D ₅₀ ) 10 μm: Water surface diffusion area 13,000 cm ² /g

[Example 6]
The same procedure as in Example 1 was carried out except that the glitter coating layer (1) of [Formulation 2] in Example 1 was changed to the glitter coating layer (6) of [Formulation 7]. [Formulation 7]/Coating layer/fabric/coating layer” A glossy gold-plated sheet (6) having a cross-sectional structure with a thickness of 0.71 mm and a mass of 835 g/m ² was obtained.
[Formulation 7] Paint for forming glitter coating layer
Hydroxyl group-containing fluoroolefin vinyl ether copolymer 100 parts by mass *Fluororesin emulsion (solid content 50% by mass)
Acrylic/styrene polymer curing agent having oxazoline group 10 parts by mass *Emulsion (solid content 40 mass%): Oxazoline group amount 1.8 mmol/g (solid content)
Epoxy-based silane coupling agent 2 parts by mass *3-glycidoxypropyltrimethoxysilane Aminosilane-modified cellulose nanofiber (2% by mass aqueous solution) 100 parts by mass *N-2-(aminoethyl)-3-aminopropyltrimethoxysilane Silane coupling treated modified product obtained by reacting the hydrolyzate of (amino-based silane coupling agent) with the hydroxyl groups of cellulose nanofibers: Fiber width 3-10 nm: Fiber length 30-100 μm
Leafing type aluminum scale powder 3 parts by mass *Average particle diameter (D ₅₀ ) 10 μm: Water surface diffusion area 13,000 cm ² /g
Disazo yellow (yellow pigment) 0.3 parts by mass

[Example 7]
The same procedure as in Example 1 was carried out except that the glitter coating layer (1) of [Formulation 2] in Example 1 was changed to the glitter coating layer (7) of [Formulation 8]. [Formulation 8]/Coating layer/fabric/coating layer” A blue pearlescent metallic sheet (7) with a cross-sectional structure having a thickness of 0.71 mm and a mass of 835 g/m ² was obtained.
[Formulation 8] Paint for forming glitter coating layer
Hydroxyl group-containing fluoroolefin vinyl ether copolymer 100 parts by mass *Fluororesin emulsion (solid content 50% by mass)
Acrylic/styrene polymer curing agent having oxazoline group 10 parts by mass *Emulsion (solid content 40 mass%): Oxazoline group amount 1.8 mmol/g (solid content)
Epoxy-based silane coupling agent 2 parts by mass *3-glycidoxypropyltrimethoxysilane Unmodified cellulose nanofiber (2% by mass aqueous solution) 100 parts by mass *Fiber width 3-10 nm: fiber length 30-100 μm
Scaly blue interference colored mica (average particle diameter _D50 : 10-60 μm) 4 parts by mass

[Example 8]
On top of the glitter coating layer (7) of the blue pearlescent metallic sheet (7) of Example 7, a glitter coating layer according to [Formulation 4] was added to form two glitter coating layers. The thickness of the cross-sectional structure of "Glitter coating layer [Formulation 4]/Glitter coating layer [Formulation 8]/Coating layer/Textile/Coating layer" was 0 as in Example 7 except for (8). A metallic-like sheet (8) having a size of .72 mm and a mass of 840 g/m ² and having a blue pearlescent luster and a glittering appearance was obtained.

[Examples 9 to 16]
An antifouling coating layer having the following [Formulation 9] was formed on the surface of the glittering coating layer of the metallic-toned sheets (1) to (8) of Resin Examples 1 to 8, to obtain metallic-toned sheets (9) to (16), respectively. The obtained antifouling coating layer contains photocatalytic titanium oxide particles in the structure of a sol-gel condensate of an organosilicate compound.
[Formulation 9] Paint for forming antifouling coating film layer
Ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ )
*Tetraethoxysilane pentamer of [ _{Si5O4 ( OC2H5} ) ₁₂ ] 100 parts by weight _Hydrolysis catalyst: 2% hydrochloric acid 5 parts by weight Photocatalytic titanium oxide sol 50 parts by weight Nitric acid acid: Particle diameter 10 nm: 30% solids in ethanol solution Vinyl-based silane coupling agent (*vinyltrimethoxysilane) 5 parts by weight Silica sol (particle diameter 12 nm: 30% solids in ethanol solution) 50 parts by weight

In the examples of the present invention, the glitter coating layer of the metallic sheets (1) to (8) contains a glitter pigment, a silane coupling agent reactant, and cellulose nanofiber. The presence of cellulose nanofibers between the glitter pigment (particularly scale-like or flake-like) and the glitter pigment (particularly scale-like or flake-like) allows the glitter paint layer to bend (bending and rubbing resistance test) and scratch ( It is like a spring that resists and restores the displacement that causes irregularities in the arrangement (horizontal arrangement or random arrangement) of glitter pigments, that is, diffuse reflection, when subjected to physical loads such as abrasion resistance tests). At this time, a silane coupling agent reactant is interposed between the glitter pigment and the cellulose nanofibers, and as a result of the chemical bonding, a buffering effect is created that restores the displacement of the glitter pigment. The effect was even stronger. The presence of a condensate resulting from the reaction between the silane coupling agents contained in this glitter coating layer improves the durability and scratch resistance of the glitter coating layer, and improves the durability of the metallic appearance (1) and The durability of the metallic appearance (2) effectively suppresses the occurrence of optical scars due to disordered arrangement of glitter pigments, and the durability of the glitter coating layer (1) and glitter properties are also achieved. Due to the durability (2) of the coating layer, it was confirmed that the glittering coating layer would not easily wear off or fall off, so the metallic sheet of the present invention could be used in large tents (pavilions), tent warehouses, Used as raw material for membrane roofs (ceilings) of architectural spaces, stadium sunshade tents, house tents, seat houses, wing canopies of aluminum-bodied trucks, and emergency bags (disaster prevention supplies) due to handling during sewing work. It can be expected to have the effect of making it difficult to cause bends and abrasions, and it can also be expected to have the advantage of increasing the degree of freedom in handling during construction. In addition, in the examples of the present invention, metallic sheets (9) to (16) in which an antifouling coating layer was formed on the glittering coating layer of metallic sheets (1) to (8), In addition to the performance of the coating layer, by supporting photocatalytic titanium oxide fine particles in the structure of a sol-gel condensate of an organosilicate compound or a silanol group-containing organic silane compound, the decomposition effect of organic matter due to the photoactivity of photocatalytic titanium oxide can be improved. The antifouling effect was demonstrated. This antifouling effect was confirmed in a 120-hour accelerated weather resistance test (JIS K5600-7-7) using a xenon weather meter on a sheet piece with the letters "HIRAOKA" written on it with a commercially available oil-based pen (red). This is clear from the contrast in that the red ink letters on the metallic sheets (1) to (8) remained clear and pale red, whereas the pigment had decomposed and disappeared. Therefore, the metallic sheets of Examples 9 to 16 are suitable for permanent outdoor applications such as membrane structures such as large tents (pavilions), circus tents, tent warehouses, and membrane roofs (ceilings) of architectural spaces.

[Comparative example 1]
Example 1 except that 100 parts by mass of modified cellulose nanofibers (2% by mass aqueous solution) was omitted from the glitter coating layer [Formulation 2] of Example 1 and replaced with 100 parts by mass of water [Formulation 9]. Similarly, a metallic sheet (17) having a thickness of 0.7 mm and a mass of 830 g/m ² was obtained. By omitting cellulose nanofibers, when a physical load such as bending or abrasion is applied to the glitter coating layer, it resists the disturbance of the horizontal alignment of the aluminum scale powder, that is, the displacement that causes diffuse reflection. , the spring-like buffering effect that restores displacement lapses, and the durability of the metallic appearance (1) is affected by noticeable optical damage due to disordered arrangement of aluminum scale powder in the glitter coating layer (fluorine-based resin). Creases and optical whitening marks occurred. (In Example 1, no optical creases or optical whitening marks were observed.) In addition, abrasion damage was observed in the durability of the metallic appearance (2), and aluminum scale powder was observed on the bright coating layer. The occurrence of optical scratch marks and optical whitening marks due to disordered alignment was remarkable. (In Example 1, no optical scratch marks or optical whitening marks were observed.) Furthermore, due to the durability (1) of the glitter coating layer and the durability (2) of the glitter coating layer, this glitter The metallic sheet of Comparative Example 1 is suitable for use on membrane roofs of large tents (pavilions), tent warehouses, and architectural spaces. (ceilings), stadium awning tents, house tents, seat houses, etc., it is prone to bends and abrasions due to handling during sewing work, and increasing bends and abrasions during handling during construction. It is foreseeable that the appearance of the property will be significantly damaged.

[Comparative example 2]
Same as Example 1 except that 2 parts by mass of the epoxy silane coupling agent (3-glycidoxypropyltrimethoxysilane) was omitted from the glitter coating layer [Formulation 2] of Example 1 and it was changed to [Formulation 10]. Similarly, a metallic sheet (18) having a thickness of 0.7 mm and a mass of 830 g/m ² was obtained. Due to the omission of the silane coupling agent, there is no presence to support the action of cellulose nanofibers, and when a physical load such as bending or abrasion is applied to the glitter coating layer, aluminum scale powder The effect of cellulose nanofibers, which has a spring-like buffering effect that resists displacement that causes disturbance of horizontal alignment, that is, diffused reflection, and restores the displacement, is not fully demonstrated, and the durability of the metallic appearance (1) In this case, optical creases occurred in the glitter coating layer (fluororesin) due to disordered arrangement of aluminum scale powder. (In Example 1, no optical creases were observed.) In addition, abrasion damage was observed in the durability of the metallic appearance (2), and optical damage was observed due to the disordered arrangement of aluminum scale powder in the glitter coating layer. Scratch marks were visible. (No optical scratch marks were observed in Example 1.) Furthermore, due to the durability of the glitter coating layer (1) and the durability of the glitter coating layer (2), this glitter coating layer was It was confirmed that the metallic sheet of Comparative Example 1 was more likely to wear out and fall off than the glittering coating layer of Example 1, so it could be used for large tents (pavilions), tent warehouses, membrane roofs (ceilings) of architectural spaces, stadium sunshades, etc. When used as raw material for tents, house tents, seat houses, etc., folds and abrasions occur due to handling during sewing work, and folds and abrasions increase during handling during construction, damaging the appearance of the constructed object. can be predicted.

[Comparative Example 3]
A metallic-look sheet (19) having a thickness of 0.7 mm and a mass of 830 g/m2 was obtained in the same manner as in Example 7, except that 100 parts by mass of modified cellulose nanofiber ( ² % by mass aqueous solution) was omitted from the glittering coating layer [Blend 8] of Example 7 and replaced with 100 parts by mass of water [Blend 11]. By omitting the cellulose nanofiber, when the glittering coating layer was subjected to physical load such as bending or rubbing, the spring-like cushioning effect that resists the disorder of the arrangement of the scaly mica, i.e., the displacement that causes diffuse reflection, and restores the displacement was lost, and in the durability of the metallic appearance (1), the glittering coating layer (fluororesin) had noticeable optical creases and optical whitening marks due to the disorder of the arrangement of the scaly mica. (In Example 1, no optical creases or optical whitening marks were observed.) In addition, wear damage was observed in the durability of metallic appearance (2), and the occurrence of optical scratches and optical whitening marks due to the disorder of the arrangement of scaly mica in the glittering coating layer was significant. (In Example 1, no optical scratches or optical whitening marks were observed.) Furthermore, the durability of the glittering coating layer (1) and the durability of the glittering coating layer (2) confirmed that this glittering coating layer is more likely to wear out and fall off than the glittering coating layer of Example 1. Therefore, the metallic sheet of Comparative Example 1 is likely to be broken or scratched due to handling during sewing work as a raw material for large tents (pavilions), tent warehouses, membrane roofs (ceilings) of architectural spaces, stadium sunshade tents, house tents, seat houses, etc., and it can be predicted that the appearance of the construction object will be significantly impaired by increasing the number of breaks and scratches during handling during construction.

[Comparative example 4]
Same as Example 1 except that 2 parts by mass of the epoxy silane coupling agent (3-glycidoxypropyltrimethoxysilane) was omitted from the glitter coating layer [Formulation 8] of Example 7 to form [Formulation 12]. Similarly, a metallic sheet (20) having a thickness of 0.7 mm and a mass of 830 g/m ² was obtained. Due to the omission of the silane coupling agent, there is no presence to support the action of cellulose nanofibers, and when a physical load such as bending or abrasion is applied to the glitter coating layer, scaly mica The effect of cellulose nanofibers, which has a spring-like buffering effect that resists displacement that causes disordered alignment, that is, diffused reflection, and restores the displacement, is not fully demonstrated, and the durability of the metallic appearance (1) is insufficient. , optical creases occurred in the glitter coating layer (fluororesin) due to disordered arrangement of scale-like mica. (No optical breakage was observed in Example 1.) In addition, abrasion damage was observed in the durability of the metallic appearance (2), and optical damage due to disordered arrangement of scale-like mica in the glitter coating layer was observed. Scratch marks were visible. (No optical scratch marks were observed in Example 1.) Furthermore, due to the durability of the glitter coating layer (1) and the durability of the glitter coating layer (2), this glitter coating layer was It was confirmed that the metallic sheet of Comparative Example 1 was more likely to wear out and fall off than the glittering coating layer of Example 1, so it could be used for large tents (pavilions), tent warehouses, membrane roofs (ceilings) of architectural spaces, stadium sunshades, etc. When used as raw material for tents, house tents, seat houses, etc., folds and abrasions occur due to handling during sewing work, and folds and abrasions increase during handling during construction, damaging the appearance of the constructed object. can be predicted.

According to the present invention, the glitter coating resin layer provided on metallic tarpaulin and canvas has durability against bending and scratches caused by physical loads during sewing and construction, and the glitter coating resin layer A metallic finish that does not easily create optical scars due to disordered arrangement of glitter pigments, can be handled freely during sewing and construction, and does not easily wear away or fall off the glitter coating layer during use. The objective is to provide an invention for a sheet. By solving this problem, the appearance quality of the metallic sheet is preserved and maintained, so the metallic tarpaulin can be used for large tents (pavilions), tent warehouses, membrane roofs (ceilings) of architectural spaces, stadium sunshade tents, and house shapes. It is suitable for tents, seat houses, etc., and the metallic canvas is suitable for wing hoods of aluminum-bodied trucks. These materials are also suitable as materials for emergency bags (disaster prevention supplies).

Claims (4)

A metallic-toned sheet comprising a coating layer made of a thermoplastic resin composition on the front and back surfaces of a woven fabric, and a glittering coating layer formed on at least one surface of the coating layer, the glittering coating layer containing at least a glittering pigment, a silane coupling agent reactant, and cellulose nanofibers , the glittering pigment being at least one selected from aluminum (colored) scale powder, flake-like (colored) aluminum, scaly interference coloring mica, scaly (colored) mica, interference coloring glass flakes, metal-deposited glass flakes, metal-deposited (colored) film fragments, and hologram film fragments, and the cellulose nanofibers being at least one selected from unmodified cellulose, carboxymethylated cellulose, oxidized cellulose, borate esterified cellulose, phosphate esterified cellulose, silicate esterified cellulose, isocyanated cellulose, aminosilane-modified cellulose, vinylsilane-modified cellulose, cellulose ester ... the silane coupling agent reactant comprises at least a condensate produced by a reaction between silane coupling agents, and further comprises a decomposition product of a silane coupling agent bonded to the luster pigment, and a decomposition product of a silane coupling agent bonded to the cellulose nanofibers, and the silane coupling agent is at least one selected from the group consisting of aminosilane, vinylsilane, epoxysilane, methacrylsilane, acrylicsilane, chlorosilane, mercaptosilane, isocyanurate silane, and isocyanate silane; the silane coupling agent reactant comprises at least a condensate produced by a reaction between silane coupling agents, and further comprises a decomposition product of a silane coupling agent bonded to the cellulose nanofibers, and the silane coupling agent is at least one selected from the group consisting of aminosilane, vinylsilane, epoxysilane, methacrylsilane, acrylicsilane, chlorosilane, mercaptosilane, isocyanurate silane, and isocyanate silane . 2. The metallic-look sheet according to claim 1, wherein the glittering coating layer is one or more selected from the group consisting of acrylic resins, urethane resins, acrylic/silicone copolymer resins, fluorine-based copolymer resins, blends of acrylic resins and fluorine-based copolymer resins, urethane/silicone graft copolymer resins, and urethane /fluorine graft copolymer resins. An antifouling coating layer is further formed on the glittering coating layer, and in this antifouling coating layer, photocatalytic titanium oxide, photocatalytic titanium peroxide, photocatalytic zinc oxide, photocatalytic tin oxide, and photocatalyst are formed. The metallic sheet according to claim 1 or 2, containing one or more photocatalytic metal oxides selected from photocatalytic strontium titanate, photocatalytic tungsten oxide, photocatalytic bismuth oxide, and photocatalytic iron oxide. . The metallic sheet according to claim 3 , wherein the antifouling coating layer is mainly composed of an organosilicate compound or a sol-gel condensate of a silanol group-containing organosilane compound.