JP7443681B2 - makeup sheet - Google Patents

Description

The present invention relates to a decorative sheet.

In recent years, for example, as shown in Patent Documents 1 to 5, many decorative sheets using olefin resins have been proposed as decorative sheets to replace decorative sheets made of polyvinyl chloride.
However, some of these decorative sheets do not have sufficient long-term weather resistance.
Therefore, there is currently a need to develop decorative sheets with excellent long-term weather resistance.

Japanese Unexamined Patent Publication No. 2-128843 Japanese Patent Application Publication No. 4-083664 Japanese Patent Application Publication No. 6-001881 Japanese Unexamined Patent Publication No. 6-198831 Japanese Patent Application Publication No. 9-328562

The present invention aims to solve the above-mentioned problems and provide a decorative sheet with excellent long-term weather resistance.

In order to achieve the above object, a decorative sheet according to one aspect of the present invention is a decorative sheet in which a raw fabric layer, a barrier layer, a transparent resin layer, and a top coat layer are laminated in this order, and the barrier layer is an inorganic compound, and the measurement conditions were 40°C, 90%R. H. The water vapor permeability is 0.8 g/m ² ·day or less, and the measurement conditions are 40°C and 90% R. H. It is characterized by an oxygen permeability of 0.5 cc/m ² ·day · atm or less.

According to the present invention, a decorative sheet with excellent long-term weather resistance is provided. Here, "long-term weather resistance" refers to exhibiting excellent weather resistance for a long period of time (10 years or more) even under harsh environments such as outdoor placement.

FIG. 1 is a cross-sectional view showing the configuration of a decorative sheet according to an embodiment of the present invention.

Hereinafter, embodiments according to the present invention will be described with reference to the drawings. In the description of the drawings below, the same or similar parts are designated by the same or similar symbols. However, it should be noted that the drawings are schematic and the relationship between thickness and planar dimensions, the ratio of the thickness of each layer, etc. are different from reality. Therefore, the specific thickness and dimensions should be determined with reference to the following explanation. Furthermore, it goes without saying that the drawings include portions with different dimensional relationships and ratios.
In addition, the embodiments shown below exemplify devices and methods for embodying the technical idea of the present invention. etc. are not specified as those listed below. The technical idea of the present invention can be modified in various ways within the technical scope defined by the claims.

[Composition of decorative sheet]
As shown in FIG. 1, a decorative sheet 10 according to an embodiment of the present invention (hereinafter referred to as the present embodiment) includes a primer layer 5, a raw fabric layer 7, a pattern layer 2, an adhesive layer 6, and a barrier layer. 8, the transparent resin layer 1, and the top coat layer 4 are laminated in this order. The details of these layers will be explained below.

[Original fabric layer]
The raw fabric layer 7 may be made of paper such as tissue paper, titanium paper, resin-impregnated paper, polyethylene, polypropylene, polystyrene, polybutylene, etc. in the case of a decorative sheet with special design properties, scratch resistance, and processing suitability. , polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, synthetic resins such as acrylic, or foams of these synthetic resins, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene. Butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, rubber such as polyurethane, organic or inorganic nonwoven fabric, synthetic paper, metal such as aluminum, iron, gold, silver, etc. It can be appropriately selected from foil and the like. Further, the raw fabric layer 7 may be a sheet made of the same resin composition as the transparent resin layer 1.

In addition, when a base material with an inert surface such as an olefin-based raw material layer is used as the raw material layer 7, the front and back surfaces of the raw material layer 7 may be subjected to corona treatment, plasma treatment, ozone treatment, electron beam treatment, etc. , ultraviolet ray treatment, dichromic acid treatment, etc. are desirable. Furthermore, a primer layer (not shown) may be provided between the original fabric layer 7 and the pattern layer 2 to ensure close contact.
Furthermore, if it is desired to impart concealing properties to the decorative sheet 10, a colored sheet with concealing properties may be used as the raw fabric layer 7, or a concealing layer (not shown) may be provided separately.

When imparting nonflammability to the decorative sheet 10, it is preferable to add an inorganic filler to the raw fabric layer 7. When the main component of the raw fabric layer 7 is a polyolefin resin, the inorganic filler is preferably contained in a proportion of 50 parts by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the polyolefin resin, and 100 parts by mass It is more preferable that the content is from 1 part to 400 parts by mass.
In addition, in this embodiment, the content of the inorganic filler in the raw fabric layer 7 after formation is specified by the mixing ratio when preparing the resin composition that constitutes the raw fabric layer 7. This is due to the following reasons.

When the finished decorative sheet 10 is subjected to post-processing such as bending, the raw fabric layer 7 formed from the resin composition obtained by adding the above-mentioned amount becomes inorganic due to the deformation of the processing. A phenomenon in which the filler moves occurs. The movement of the inorganic filler does not occur uniformly over the entire fabric layer 7; for example, near the surface, the resin deforms greatly, and the amount of movement of the inorganic filler increases accordingly. As a result, there is a difference between the density of the inorganic filler inside the raw fabric layer 7 and the density of the inorganic filler near the surface. It is practically difficult to determine the content. In addition, when specifying the content of inorganic filler in the raw fabric layer 7 after being formed, the resin composition constituting the raw fabric layer 7 is separated into an inorganic material and an organic material, and the content of the inorganic filler in the inorganic material is It is necessary to analyze the content of inorganic filler in the product, and performing this analysis requires multiple pretreatment steps. For this reason, determining the content of inorganic filler in the raw fabric layer 7 after it is formed requires a huge amount of time and is not practical.

Examples of the inorganic filler include calcium carbonate, talc, and titanium oxide. Among these, calcium carbonate is suitable for reducing the cost of decorative sheets because it is easy to control the particle size through manufacturing methods and the compatibility with polyolefin resin through surface treatment, and the material cost is low. It is.

Examples of polyolefin resins include polypropylene, polyethylene, polybutene, and other α-olefins (e.g., propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1 -decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3 -Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 - Ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) or copolymerization of two or more types, ethylene and acetic acid. Vinyl copolymer, ethylene/vinyl alcohol copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/butyl methacrylate copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer Examples include copolymerization of ethylene or α-olefin with other monomers, such as polymers and ethylene/butyl acrylate copolymers. Among these, high-density polyethylene is particularly preferred from the viewpoint of compatibility with inorganic fillers.

Moreover, it is preferable that the original fabric layer 7 consists of a uniaxially stretched sheet or a biaxially stretched sheet. By using a uniaxially stretched sheet or a biaxially stretched sheet that has been subjected to a uniaxial stretching process or a biaxial stretching process, it is possible to obtain an original fabric layer that has even more excellent mechanical strength as a film. In addition, if the inorganic filler is highly loaded, the resulting film surface may become uneven and have poor smoothness, but by forming a uniaxially or biaxially stretched sheet, the smoothness of the film surface can be The raw fabric layer 7 can be made to have excellent printability and good ink receptivity when pattern printing is performed.

According to the technical standards for noncombustible materials stipulated in the Building Standards Act Construction Order, the following requirements must be met in a heat generation test using a cone calorimeter tester compliant with ISO 5660-1 (Building Standards Act Construction Order Article 108-2 Items 1 and 2). In order for the decorative sheet 10 of this embodiment to be certified as a noncombustible material, it must meet the following conditions 1 to 3 when heated with 50kW/ ^m2 radiant heat for 20 minutes while bonded to a noncombustible base material. All required items must be met.
1. Total calorific value is 8MJ/ ^m2 or less 2. Maximum heat generation rate does not exceed 200kW/ ^m2 for 10 seconds or more 3. Cracks and holes penetrating to the back surface that are detrimental to flame resistance do not occur.The noncombustible base material can be selected from gypsum board, fiber-mixed calcium silicate board, or galvanized steel board.

The decorative sheet 10 of this embodiment, which includes the original fabric layer 7 to which the above-mentioned inorganic filler is added, was tested using a cone calorimeter tester in accordance with ISO5660-1 in a state where it was bonded to the non-combustible base material. In the heat generation test, a noncombustible material was realized that met both the requirements set forth in Article 108-2, Items 1 and 2 of the Construction Order.
By making the decorative sheet 10 including the original fabric layer 7 to which an inorganic filler is added, the decorative sheet can be used as a "noncombustible material" that satisfies the technical standards for noncombustible materials as stated in the Building Standards Act Construction Order. 10. As a result of adding the inorganic filler, the proportion of the resin component in the decorative sheet 10 can be reduced, and the amount of carbon dioxide emitted during incineration after disposal can be extremely reduced.
Furthermore, by forming the raw fabric layer 7 as a uniaxially stretched sheet or a biaxially stretched sheet, the raw fabric layer can have smoothness and high mechanical strength.

[Picture layer]
The pattern layer 2 is a layer that imparts a pattern to the decorative sheet 10, and is formed on the raw fabric layer 7.
There are no particular restrictions on the type of pattern formed by the pattern layer 2, and for example, wood grain patterns, stone grain patterns, cloth grain patterns, abstract patterns, geometric figures, characters, symbols, etc. may be used singly or in combination with two or more types. It may be formed by combining.
The pattern layer 2 may be a layer formed by applying an ink containing an acrylic resin as a binder (hereinafter also referred to as a pattern layer forming ink) to one surface of the raw fabric layer 7. Examples of acrylic resins included as binders in the ink for forming a pattern layer include ethylene-methyl acrylate copolymer resin (EMA), ethylene-ethyl acrylate copolymer resin (EEA), and ethylene-methacrylate copolymer resin. Those containing an acrylate copolymer resin as a main component, such as a polymeric resin (EMAA), an ethylene-acrylic acid copolymer resin (EAA), an ionomer resin, or a mixture thereof, can be used. Here, the term "main component" refers to the component having the highest content among the components constituting the pattern layer 2.

Note that the pattern layer 2 may be a layer formed by applying ink containing a urethane resin as a binder to one surface of the original fabric layer 7. As the urethane resin, a urethane resin obtained by reacting an acrylic polyol and an isocyanate may be used. Examples of isocyanates include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), and methylhexane diisocyanate (HTDI). ), methylcyclohexanone diisocyanate (HXDI), trimethylhexamethylene diisocyanate (TMDI), etc.; however, in consideration of weather resistance, it is preferable to use hexamethylene diisocyanate (HMDI), which has a linear molecular structure. preferable.

The pattern layer forming ink may contain, together with the acrylic resin, a crosslinking agent that crosslinks the acrylic resin. Since this crosslinking agent has the function of crosslinking the acrylic resin and imparting mechanical strength to the entire pattern layer 2, it is also generally referred to as a "curing agent." Examples of the crosslinking agent (curing agent) that can be added to the ink for forming a pattern layer include a urethane curing agent. More specifically, examples of the urethane curing agent that can be added to the ink for forming a pattern layer include IPDA (isofluorone diamine) and HDI (hexamethylene diisocyanate). In this embodiment, these can be used alone or in combination.
When the ink for forming a pattern layer contains a crosslinking agent, the content of the crosslinking agent is within the range of more than 0 parts by weight and not more than 10 parts by weight, when the content of the acrylic resin in the pattern layer 2 is 100 parts by weight. It is preferable that there be. If the content of the crosslinking agent is within the above numerical range, the coatability of the ink for forming a pattern layer will be improved. Preferably, the content of the crosslinking agent is 3 parts by mass when the content of the acrylic resin in the pattern layer 2 is 100 parts by mass.

In addition to the above-mentioned binder, the ink for forming the pattern layer may contain, for example, organic or inorganic dyes or pigments, extender pigments, fillers, tackifiers, dispersants, antifoaming agents, stabilizers, and other additives as necessary. may be added as appropriate. Further, the ink for forming the pattern layer is adjusted to a desired viscosity using a suitable diluting solvent.
There are no particular restrictions on the method of forming the pattern layer 2, and any printing method such as gravure printing, offset printing, screen printing, flexographic printing, letterpress printing, inkjet printing, etc. can be used. It is.
In addition, when a solid ink layer (not shown) is provided between the original fabric layer 7 and the pattern layer 2 for the purpose of base coloring, the solid ink layer can be formed by using, for example, the various printing methods described above. Any coating method can be used, such as roll coating, gravure coating, rod coating, knife coating, air knife coating, spray coating, lip coating, and die coating.

[Adhesive layer]
The adhesive layer 6 is a layer for increasing the adhesion between the pattern layer 2 and the barrier layer 8, and as shown in FIG. is formed.
The adhesive layer 6 is a layer formed by applying an ink containing a urethane resin (hereinafter also referred to as adhesive layer forming ink) to the surface of the pattern layer 2 opposite to the surface on the raw fabric layer 7 side. It is.
The coating amount (formation amount) of the adhesive layer 6 is preferably in the range of 5.0 g/m ² or more and 6.0 g/m ^{2 or} less. Further, the thickness of the adhesive layer 6 is preferably within the range of 5 μm or more and 6 μm or less. If the coating amount (layer thickness) of the adhesive layer 6 is within the above numerical range, the adhesion between the pattern layer 2 and the barrier layer 8 can be increased to a level that poses no problem in use, and the occurrence of appearance defects can be further reduced. becomes possible.

Furthermore, the ink for forming an adhesive layer contains, together with the urethane resin, a curing agent (crosslinking agent) that crosslinks the urethane resin. Examples of the curing agent that can be added to the adhesive layer forming ink include urethane curing agents. More specifically, examples of the urethane curing agent that can be added to the adhesive layer forming ink include IPDI (isophorone diisocyanate) and HDI (hexamethylene diisocyanate). In this embodiment, these can be used alone or in combination.
When the adhesive layer forming ink contains a curing agent, the content of the curing agent is in the range of more than 0 parts by mass and 20 parts by mass or less, when the content of the urethane resin in the adhesive layer 6 is 100 parts by mass. It is preferable that it be within. If the content of the curing agent is within the above numerical range, the coatability of the ink for forming an adhesive layer will be improved.

Further, the adhesive layer 6 may be formed using an inorganic adhesive. As the inorganic adhesive, it is preferable to use, for example, a silica adhesive containing silica as a main component, a ceramic adhesive containing ceramic as a main component, and a cement adhesive containing cement as a main component. Note that as the above-mentioned inorganic adhesive, for example, sodium silicate, modified silicone adhesive, alumina adhesive, or magnesia adhesive may be used. The amount of the inorganic adhesive added is preferably in the range of 50% by mass or more and 100% by mass or less, and is in the range of 70% by mass or more and 100% by mass or less, based on the total mass of the adhesive layer 6. It is more preferable that the amount is in the range of 90% by mass or more and 100% by mass or less. If the amount of the inorganic adhesive added is within the above numerical range, the nonflammability can be reliably improved, and the adhesion between the pattern layer 2 and the barrier layer 8 can also be improved.
By forming the adhesive layer 6 using an inorganic adhesive, it is possible to improve fire resistance compared to the adhesive layer 6 formed using an organic adhesive. Moreover, it becomes possible to improve nonflammability.

[Barrier layer]
The barrier layer 8 is a layer composed of an inorganic compound to be described later, and is measured under measurement conditions of 40° C. and 90% R. H. The water vapor permeability is 0.8 g/m ² ·day or less, and the measurement conditions are 40°C and 90% R. H. This layer has an oxygen permeability of 0.5 cc/m ² ·day · atm or less. If the water vapor permeability exceeds 0.8 g/m ² ·day, hydrolysis etc. will occur in each resin layer composing the decorative sheet 10, making it difficult to impart long-term weather resistance to the decorative sheet 10. . In addition, if the oxygen permeability exceeds 0.5 cc/m ² ·day · atm, oxidative deterioration etc. will occur in each resin layer constituting the decorative sheet 10, and long-term weather resistance will not be imparted to the decorative sheet 10. becomes difficult. That is, the barrier layer 8 was measured under the measurement conditions of 40° C. and 90% R. H. The water vapor permeability is 0.8 g/m ² ·day or less, and the measurement conditions are 40°C and 90% R. H. If the layer has an oxygen permeability of 0.5 cc/m ² ·day · atm or less, hydrolysis and oxidative deterioration of each resin layer constituting the decorative sheet 10 can be sufficiently reduced. 10 can be imparted with long-term weather resistance.

The barrier layer 8 is a thin film made of a metal such as Si, Al, Ti, Zn, Sn, Fe, Mn, or an inorganic compound containing one or more of these metals. Examples of the inorganic compounds include oxides, nitrides, carbides, and fluorides. Among these, at least one selected from metals and metal oxides is preferred. Specific examples include silicon oxides (SiOx) such as silicon monoxide and silicon dioxide, aluminum oxide, titanium oxide, magnesium oxide, and tin oxide.

Optimum conditions for the thickness of the barrier layer 8 vary depending on the type, composition, and formation method of the inorganic compound used, but in general, the thickness of the barrier layer 8 formed by vapor deposition is in the range of 10 nm or more and 500 nm or less. It is preferable that the value is within the range of 0 and 1, and the value is selected as appropriate. If the thickness of the barrier layer 8 formed by vapor deposition is less than 10 nm, a uniform film may not be obtained or the film thickness may not be sufficient, and the function as a decorative sheet 10 with long-term weather resistance may not be sufficient. may not be able to fulfill their duties. Furthermore, if the thickness of the barrier layer 8 formed by vapor deposition exceeds 500 nm, flexibility cannot be maintained due to residual stress in the thin film, and there is a risk that cracks may occur in the thin film due to external factors after the film is formed. So there is a problem. A more preferable thickness of the barrier layer 8 is within the range of 30 nm or more and 150 nm or less.

In this embodiment, the barrier layer 8 may be directly laminated on the transparent resin layer 1.
Examples of the method for laminating the barrier layer 8 on the transparent resin layer 1 include a vacuum evaporation method, a sputtering method, an ion plating method, and a plasma vapor deposition method (CVD). Incidentally, in consideration of productivity, the vacuum evaporation method is the most excellent. As a heating means for vacuum evaporation, it is preferable to use one of the following: electron beam heating, resistance heating, or induction heating; however, considering the wide range of selectivity of evaporation materials, electron beam heating or resistance heating is It is more preferable to use the method. Further, in order to improve the adhesion between the barrier layer 8 and the transparent resin layer 1 and the density of the barrier layer 8, it is also possible to perform vapor deposition using a plasma assist method or an ion beam assist method. Furthermore, in order to improve the transparency of the deposited film, it is perfectly acceptable to use reactive deposition in which various gases such as oxygen are blown into the film during deposition.

The barrier layer 8 may not only be a film formed by the above-mentioned method, but also a film formed by applying a coating liquid containing the above-mentioned inorganic compound to the transparent resin layer 1 and drying it. The thickness of the barrier layer 8 formed by coating is preferably in the range of 100 nm or more and 10 μm or less, and the value is selected as appropriate. If the thickness of the barrier layer 8 formed by coating is less than 100 nm, the film thickness may not be sufficient, and it may not be able to sufficiently function as a decorative sheet 10 with long-term weather resistance. . Furthermore, if the thickness of the barrier layer 8 formed by coating exceeds 10 μm, flexibility cannot be maintained due to residual stress in the thin film, and there is a risk that cracks may occur in the thin film due to external factors after the film is formed. There is a problem because there is. A more preferable film thickness is within the range of 200 nm or more and 5 μm or less.

[Transparent resin layer]
The transparent resin layer 1 is a sheet-like layer formed using a transparent resin so that the pattern of the pattern layer 3 can be seen through, and is laminated on the top surface of the pattern layer 3.
As a method for laminating the transparent resin layer 1, for example, a method is used in which the transparent resin layer 1 is laminated by lamination on a laminate including the raw fabric layer 7, the pattern layer 2, the adhesive layer 6, and the barrier layer 8. Is possible. Another method for laminating the transparent resin layer 1 is, for example, by laminating a laminate including the raw fabric layer 7, the pattern layer 2, and the adhesive layer 6, so that the transparent resin layer 8 on which the barrier layer 8 is formed is laminated. It is also possible to use a method of laminating layer 1.
The transparent resin forming the transparent resin layer 1 is not particularly limited, and any known transparent resin can be used.

Therefore, examples of the transparent resin forming the transparent resin layer 1 include polyolefin resins, ethylene-vinyl acetate copolymers, saponified products thereof, polyolefin copolymers, polyester resins, polymethyl methacrylates, etc. Acrylic resin, polyamide resin, styrene resin, cellulose derivative, chlorine resin, fluorine resin, etc. alone, or a mixture, copolymer, composite, or laminate of two or more selected from these materials. It is possible to use the body etc. as appropriate.
In particular, in manufacturing using melt extrusion equipment, it is recommended to use polyolefin resin as the transparent resin forming the transparent resin layer 1, considering productivity, environmental compatibility, mechanical strength, durability, price, etc. is more preferable.

As the polyolefin resin, for example, polyethylene, polypropylene, polybutene, polymethylpentene, etc. can be used, and polypropylene is most preferred. Further, as the polyolefin copolymer, for example, ethylene-(meth)acrylic acid (ester) copolymer or the like can be used.
Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, and copolymerized polyester (typically, 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin commonly known as PET-). G) etc. can be used.
As the polyamide resin, for example, 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon, etc. can be used.
As the styrene resin, for example, polystyrene, AS resin, ABS resin, etc. can be used.

As the cellulose derivative, for example, cellulose acetate, nitrocellulose, etc. can be used.
As the chlorine-based resin, for example, polyvinyl chloride, polyvinylidene chloride, etc. can be used.
As the fluororesin, for example, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, etc. can be used.

The thickness of the transparent resin layer 1 is preferably within the range of 20 μm or more and 150 μm or less, and preferably within the range of 45 μm or more and 90 μm or less, in order to improve both the strength and transparency of the transparent resin layer 1. is more preferable.
The transparent resin layer 1 may contain existing heat stabilizers, flame retardants, ultraviolet absorbers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss adjusters as necessary. It is possible to add various additives such as. In order to improve the surface strength, it is preferable to use a highly crystalline polypropylene resin. In addition, as a thermal stabilizer, for example, a phenol type, a sulfur type, a phosphorus type, a hydrazine type, etc. can be used. As the flame retardant, for example, aluminum hydroxide, magnesium hydroxide, etc. can be used. As the ultraviolet absorber, for example, benzotriazole type, benzoate type, benzophenone type, triazine type, etc. can be used. As the light stabilizer, for example, a hindered amine type or the like can be used. Furthermore, an embossed pattern 1a having a predetermined uneven pattern as shown in FIG. 1 may be formed on the surface of the transparent resin layer 1, if necessary.

(embossed pattern)
The embossed pattern 1a is, for example, a pattern consisting of concave portions and convex portions that are synchronized with the pattern of the pattern layer 2. The concave portions and convex portions of the embossed pattern 1a can provide a three-dimensional effect through tactile sensation. It is preferable that the deviation between the embossed pattern 1a and the pattern of the pattern layer 2 be within the range of, for example, 10 mm or less in the longitudinal direction and 3 mm or less in the lateral direction (width direction) with respect to the shape of the pattern. For example, if the picture pattern is wood grain, the direction in which the wood grain conduit extends is the "longitudinal direction with respect to the shape of the picture pattern", and the direction perpendicular to the longitudinal direction is the "short direction with respect to the shape of the picture pattern". Become. In particular, when the wood grain conduits extend along the longitudinal direction of the decorative sheet 10, the longitudinal direction of the decorative sheet 10 becomes the "longitudinal direction with respect to the shape of the pattern", and the lateral direction (width direction) of the decorative sheet 10 ) is the "short direction with respect to the shape of the picture pattern". Since the transparent resin layer 1 and top coat layer 4 are transparent, the embossed pattern 1a is only strongly visible when reflected from oblique light, but if the deviation between the embossed pattern 1a and the pattern of the pattern layer 2 is within the above range. , it is difficult to visually recognize the transmitted light of the pattern layer 2 at the same time as the reflected light, so there is no sense of discomfort. By suppressing the deviation between the embossed pattern 1a and the pattern of the pattern layer 2 within a certain range, it is possible to obtain a decorative sheet 10 in which the shape and distribution of the pattern are uniform and precisely matched over the entire surface of the sheet. Further, the height difference between the concave portion and the convex portion of the embossed pattern 1a is, for example, within a range of 3 μm or more and 200 μm or less. For the height difference, a value suitable for the intended design of the decorative sheet 10 can be selected. For example, it is also possible to take a continuous multi-step shape within the maximum height difference (200 μm). In particular, in order to obtain the shape of a macroscopic three-dimensional object, the height difference is more preferably in the range of 10 μm or more and 150 μm or less.

Note that the decorative sheet 10 of this embodiment may include an adhesive resin layer (not shown) between the pattern layer 2 and the top coat layer 4 or the transparent resin layer 1. By providing the adhesive resin layer, the adhesion between the pattern layer 2 and the top coat layer 4 or the transparent resin layer 1 can be improved. The material of the adhesive resin layer is not particularly limited, but can be appropriately selected from, for example, acrylic, polyester, polyurethane, epoxy, and the like. Specifically, the adhesive resin layer may be made of acid-modified resin such as polypropylene, polyethylene, or acrylic resin, and the thickness is preferably 2 μm or more for the purpose of improving adhesive strength. Note that if it is too thick, it will be affected by the softness of the adhesive resin layer itself, even though the surface hardness has been improved by the highly crystalline transparent resin layer 1, so it is preferably 20 μm or less.
The method for forming the adhesive resin layer can be selected as appropriate depending on the composition (viscosity) of the resin constituting the adhesive resin layer, but generally, gravure coating is used to coat the pattern layer 2. After being applied by gravure coating, it is laminated with the top coat layer 4 or the transparent resin layer 1.

[Top coat layer]
A top coat layer 4 is provided on the outermost surface of the decorative sheet 10, which serves to protect the surface and adjust gloss. The thickness of the top coat layer 4 is preferably 2 μm or more and 10 μm or less. If the thickness of the top coat layer 4 is within the above range, flexibility can be maintained while obtaining sufficient mechanical properties such as abrasion resistance and surface hardness. If the thickness of the top coat layer 4 is less than 2 μm, sufficient mechanical properties such as abrasion resistance and surface hardness may not be obtained. Moreover, when the thickness of the top coat layer 4 exceeds 10 μm, the flexibility may decrease.
The resin material that is the main component of the top coat layer 4 may be selected from polyurethane-based, acrylic silicone-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, aminoalkyd-based, urea-based resin materials, etc. It can be used selectively. The form of the resin material is not particularly limited, and may be water-based, emulsion, solvent-based, or the like. The curing method can be appropriately selected from one-liquid type, two-liquid type, ultraviolet curing method, etc.

As the resin material that is the main component of the top coat layer 4, a urethane-based resin material using isocyanate is preferable from the viewpoints of workability, price, cohesive force of the resin itself, and the like. Isocyanates include, for example, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), and bis(methyl isocyanate). The curing agent can be appropriately selected from adducts, burettes, isocyanurates, etc., which are derivatives of cyclohexane (HXDI), trimethylhexamethylene diisocyanate (TMDI), etc., but in consideration of weather resistance, linear Curing agents based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) having the molecular structure are suitable. In addition, in order to improve the surface hardness, it is preferable to use a resin that is cured by active energy rays such as ultraviolet rays and electron beams. Note that these resins can be used in combination with each other; for example, a hybrid type of thermosetting type and photocuring type can be used to improve surface hardness, suppress curing shrinkage, and improve adhesion. can be achieved.

Further, in order to improve the weather resistance of the decorative sheet 10, an ultraviolet absorber and a light stabilizer may be added as appropriate. Furthermore, functional additives such as antibacterial agents and antifungal agents can be optionally added to impart various functions. Furthermore, alumina, silica, silicon nitride, silicon carbide, glass beads, etc. can be optionally added to adjust the surface design and gloss, or to further impart wear resistance.

[Primer layer]
The primer layer 5 is a layer for increasing the adhesion between the raw fabric layer 7 and a base material (not shown) to be described later, and is formed on the surface of the raw fabric layer 7 opposite to the surface on the pattern layer 2 side. This is the layer where
The material for the primer layer 5 may be appropriately selected from, for example, nitrified cotton as a binder, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc., singly or modified. Can be used. These may be of any particular form, such as water-based, solvent-based, or emulsion type. Furthermore, the curing method can be appropriately selected from among a one-component type that is cured alone, a two-component type that uses a curing agent together with the main ingredient, and a type that is cured by irradiation with ultraviolet rays, electron beams, etc. The general curing method is a two-component type in which a urethane-based base resin is combined with an isocyanate-based curing agent. It is suitable from this point of view. In addition to the binder described above, coloring agents such as pigments and dyes, extender pigments, solvents, various additives, etc. are added. In particular, since the primer layer 5 is located at the backmost side of the decorative sheet 10, considering that the decorative sheet 10 is wound up as a continuous plastic film (web-like), the films adhere to each other and are difficult to slip. Inorganic fillers such as silica, alumina, magnesia, titanium oxide, barium sulfate, etc. may be added in order to avoid blocking such as peeling or failure to peel, and to enhance adhesion with the adhesive. . The layer thickness is preferably within the range of 0.1 μm or more and 3.0 μm or less since the purpose is to ensure adhesion with a substrate (not shown) to be described later.

[substrate]
A decorative board is constructed by bonding the decorative sheet 10 according to this embodiment to a substrate (not shown).
The substrate of this embodiment is a plate-shaped member formed using, for example, a metal material, a wood material, or an inorganic material.
As the metal material, for example, aluminum, steel, stainless steel, composite panel, etc. can be used.
As a composite panel, for example, one including a resin layer serving as a core material and metal plates (aluminum, galvalume, stainless steel, etc.) attached to both surfaces of the resin layer can be used.
As the wood-based material, for example, MDF (Medium Density Fiberboard), plywood, particle board, etc. can be used.
As the inorganic material, for example, gypsum board, fiber-mixed calcium silicate board, etc. can be used.

[Method for manufacturing decorative sheet]
An example of a method for manufacturing the decorative sheet 10 will be briefly described.
(Formation of transparent resin layer)
First, a resin material is prepared by adding a hindered phenol antioxidant, a benzotriazole ultraviolet absorber, and a hindered amine light stabilizer to a homopolypropylene resin. Here, as the homopolypropylene resin, a material with a mesopentad fraction of 97.8%, an MFR (melt flow rate) of 15 g/10 min (230°C), and a molecular weight distribution MWD (Mw/Mn) of 2.3 is used. do.
Furthermore, 500 PPM of a hindered phenolic antioxidant is added to the homopolypropylene resin. Further, 2000 PPM of a benzotriazole-based ultraviolet absorber is added to the homopolypropylene resin. Further, 2000 PPM of a hindered amine light stabilizer is added to the homopolypropylene resin.

Such a resin material is extruded using a melt extruder to form a transparent resin sheet made of polypropylene having a thickness of 80 μm, that is, a sheet-shaped transparent resin layer 1.
In addition, by controlling the cooling conditions during extrusion film formation, the haze value of the crystalline polypropylene resin of the transparent resin layer 1 formed into a film can be set to 10% or less.
Subsequently, both surfaces of the obtained sheet-like transparent resin layer 1 are subjected to corona treatment, and the wetting tension of the surface of the transparent resin layer 1 is set to 40 dyn/cm or more.

(Barrier layer formation process)
Next, an aluminum oxide film is formed on one side of the thus obtained transparent resin layer 1 using a vacuum evaporator to form a barrier layer 8.

(Formation process of raw fabric layer)
100 parts by mass of an inorganic filler such as calcium carbonate is added to 100 parts by mass of high-density polyethylene. Next, after melt-kneading using an intermeshing twin-screw extruder, pelletization is performed by a strand cutting method to obtain pellets of the thermoplastic resin composition. A sheet-like original fabric layer 7 having a thickness of 70 μm and having a hiding property is formed by a calender molding method using pellets of this thermoplastic resin composition.
A pattern is printed on the sheet-like raw fabric layer 7 thus obtained using a two-component curable urethane ink to form a pattern layer 2. Further, a primer layer 5 is provided by applying a primer coat to the back surface of the original fabric layer 7.
After that, the barrier layer 8 deposited on the transparent resin layer 1 made of highly crystalline polypropylene is applied to the two sides of the pattern layer of the original fabric layer 7 through a dry lamination method via an adhesive layer 6 containing an adhesive for dry lamination. Paste together. In this way, a laminate including the raw fabric layer 7, the pattern layer 2, the adhesive layer 6, the barrier layer 8, and the transparent resin layer 1 is obtained.

(Top coat layer formation process)
Next, an embossed pattern 1a is applied to the transparent resin layer 1 of the laminated body formed by bonding together by pressing using an embossing die roll. Thereafter, a two-component curable urethane top coat is applied on the surface of the embossed pattern 1a at a coating amount of 3 g/m ² to obtain a decorative sheet 10 having a total thickness of 154 μm as shown in FIG. 1.

[Example]
Below, specific examples of the decorative sheet of the present invention will be discussed.
<Example 1>
(Formation process of resin sheet for transparent resin layer)
First, a resin material is prepared by adding a hindered phenol antioxidant, a benzotriazole ultraviolet absorber, and a hindered amine light stabilizer to a homopolypropylene resin. Here, as the homopolypropylene resin, a material with a mesopentad fraction of 97.8%, an MFR (melt flow rate) of 15 g/10 min (230°C), and a molecular weight distribution MWD (Mw/Mn) of 2.3 is used. did. Further, 500 PPM of a hindered phenol antioxidant (Irganox 1010: manufactured by BASF) was added to the homopolypropylene resin. Further, 2000 PPM of a benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by BASF) was added to the homopolypropylene resin. Furthermore, 2000 PPM of a hindered amine light stabilizer (Kimasorb 944: manufactured by BASF) was added to the homopolypropylene resin. Such a resin material was extruded using a melt extruder to form a transparent resin sheet made of polypropylene with a thickness of 80 μm to be used as the transparent resin layer 1.
By controlling the cooling conditions during extrusion film formation, the haze value of the crystalline polypropylene resin of the formed transparent resin sheet was 6.8%.
Subsequently, both surfaces of the obtained transparent resin sheet were subjected to corona treatment, and the wet tension on the surface of the transparent resin sheet was set to 40 dyn/cm or more.

(Barrier layer formation process)
An aluminum oxide film, which is a vapor-deposited film, was formed on one side of the obtained transparent resin sheet using a vacuum vapor deposition method to form a barrier layer 8. Further, the film thickness of the barrier layer 8 was set to 5 nm. The barrier layer 8 of Example 1 thus formed was measured under the following conditions: 40° C., 90% R. H. The water vapor permeability was 0.8 g/m ² ·day. Furthermore, the measurement conditions of the barrier layer 8 of Example 1 were 40° C. and 90% R. H. The oxygen permeability was 0.5 cc/m ² ·day · atm.
In each of the Examples and Comparative Examples described below, water vapor permeability and oxygen permeability were measured using a water vapor permeability measuring device (MOCON Aquatran, manufactured by MOCON) and an oxygen permeability measuring device (MOCON OX-TRAN, manufactured by MOCON). , in an atmosphere of 40° C./90% RH.

(Formation process of raw fabric layer)
High-density polyethylene resin (manufactured by Prime Polymer: Hi-ZEX 5305E MFR = 0.8 g/10 min (190°C)) is melt-kneaded using an intermeshing twin-screw extruder, and then pelletized using a strand cutting method to make it thermoplastic. Pellets of the resin composition were obtained. Next, a raw sheet as the raw fabric layer 7 having a thickness of 70 μm and having a hiding property was formed by a calendar molding method using pellets of this thermoplastic resin composition.
A pattern was printed on the obtained raw sheet using a two-component curing urethane ink (V180: manufactured by Toyo Ink Manufacturing Co., Ltd.) to provide a pattern layer 2. Further, a primer layer 5 was provided by applying a primer coat to the back side of the original sheet. Thereafter, a barrier layer 8 deposited on a transparent resin sheet made of highly crystalline polypropylene is applied to the surface of the original sheet on which the pattern layer 2 is formed using a dry laminating adhesive (Takelac A540, manufactured by Takeda Pharmaceutical Co., Ltd.; coating amount: 2 g). / ^m2 ) by a dry lamination method via an adhesive layer 6.

(Top coat layer formation process)
Next, the bonded transparent resin sheets are pressed using an embossing mold roll to form an embossed pattern 1a, and then a two-component curable urethane top coat (W184 : manufactured by Dainippon Ink Co., Ltd.) was applied at a coating amount of 3 g/m ² . In this way, the decorative sheet 10 of Example 1 was obtained.

<Example 2>
A decorative sheet 10 of Example 2 was obtained in the same manner as Example 1 except that the thickness of the barrier layer 8 was 10 nm.
<Example 3>
By forming the barrier layer 8 using a plasma assist method, the measurement conditions are 40° C. and 90% R. H. The water vapor permeability at 0.5 g/m ² ·day was measured under the following conditions: 40°C, 90% R. H. The decorative sheet 10 of Example 3 was obtained in the same manner as Example 2, except that the oxygen permeability was set to 0.3 cc/m ² ·day · atm.

<Example 4>
A decorative sheet 10 of Example 4 was obtained in the same manner as Example 1 except that the thickness of the barrier layer 8 was 500 nm.
<Example 5>
A decorative sheet 10 of Example 5 was obtained in the same manner as Example 1 except that the thickness of the barrier layer 8 was 520 nm.

<Example 6>
A coating liquid was prepared by adding and dispersing plate-shaped aluminum oxide fine particles having an average particle size of 15 nm and MEK in an epoxy resin. In the above liquid, the solid content weight ratio of aluminum oxide fine particles and epoxy resin was adjusted to be 70:30.
Next, the above liquid was applied to one side of a transparent resin sheet using a gravure coating method, and then exposed to hot air at 60°C to evaporate the solvent. Thereby, the decorative sheet 10 of Example 6 was obtained in the same manner as in Example 1 except that the barrier layer 8 was formed and the thickness of the barrier layer 8 was set to 80 nm.

<Example 7>
A decorative sheet 10 of Example 7 was obtained in the same manner as Example 6 except that the thickness of the barrier layer 8 was 100 nm.
<Example 8>
A decorative sheet 10 of Example 8 was obtained in the same manner as Example 6 except that the thickness of the barrier layer 8 was 10 μm.
<Example 9>
A decorative sheet 10 of Example 9 was obtained in the same manner as Example 6 except that the thickness of the barrier layer 8 was 12 μm.

<Example 10>
Example 2 except that the raw fabric layer 7 contained a polyolefin resin and an inorganic filler (calcium carbonate with an average particle size of 3 μm), and the content of the inorganic filler was 50 parts by mass with respect to 100 parts by mass of the polyolefin resin. In the same manner as above, a decorative sheet 10 of Example 10 was obtained. Note that the above average particle diameter was obtained by a laser diffraction/scattering method based on ISO 13320.
The formation of the original fabric layer 7 in Example 10 will be described below.
50 parts by mass of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.: Softon 2000) as an inorganic filler was added to 100 parts by mass of high-density polyethylene (manufactured by Prime Polymer: Hizex 5305E MFR=0.8 g/10 min (190° C.)). Next, this resin containing calcium carbonate and high-density polyethylene was melt-kneaded using an intermeshing twin-screw extruder, and then pelletized by a strand cutting method to obtain pellets of a thermoplastic resin composition. Next, a raw sheet as the raw fabric layer 7 having a thickness of 70 μm and having a hiding property was formed by a calendar molding method using pellets of this thermoplastic resin composition.

<Example 11>
The decorative sheet 10 of Example 11 was obtained in the same manner as in Example 2, except that the content of the inorganic filler (calcium carbonate with an average particle size of 3 μm) in the raw fabric layer 7 was 900 parts by mass.
<Example 12>
The decorative sheet 10 of Example 12 was obtained in the same manner as Example 7, except that the content of the inorganic filler (calcium carbonate with an average particle diameter of 3 μm) in the raw fabric layer 7 was 50 parts by mass.

<Example 13>
The decorative sheet 10 of Example 13 was obtained in the same manner as in Example 7, except that the content of the inorganic filler (calcium carbonate with an average particle diameter of 3 μm) in the raw fabric layer 7 was 900 parts by mass.
<Example 14>
The decorative sheet 10 of Example 14 was obtained in the same manner as Example 3, except that the content of the inorganic filler (calcium carbonate with an average particle size of 3 μm) in the raw fabric layer 7 was 50 parts by mass.
<Example 15>
A decorative sheet 10 of Example 15 was obtained in the same manner as Example 14 except that the thickness of the barrier layer 8 (coating film) was 100 nm.

<Comparative example 1>
By forming the barrier layer 8 using a sputtering method, the measurement conditions are 40° C. and 90% R. H. The water vapor permeability was 0.9 g/m ² ·day, and the measurement conditions were 40°C and 90% R. H. A decorative sheet 10 of Comparative Example 1 was obtained in the same manner as in Example 2, except that the oxygen permeability was set to 0.6 cc/m ² ·day · atm.
<Comparative example 2>
By forming the barrier layer 8 using a sputtering method, the measurement conditions are 40° C. and 90% R. H. The water vapor permeability was 0.9 g/m ² ·day, and the measurement conditions were 40°C and 90% R. H. A decorative sheet 10 of Comparative Example 2 was obtained in the same manner as in Example 7, except that the oxygen permeability was set to 0.6 cc/m ² ·day · atm.

Table 1 shows the long-term weather resistance, bending suitability test, and nonflammability evaluation results of each decorative sheet.

<Long-term weather resistance test>
A high-temperature, high-humidity test was conducted to evaluate long-term weather resistance, and the water vapor permeability and oxygen permeability were measured after the high-temperature, high-humidity test.
The high temperature and high humidity test was conducted in accordance with JIS C 8990 10.13 in an environment of 85° C. and 85% temperature for 1000 hours. The evaluation criteria for long-term weather resistance are as follows.

◎: Even after the high-temperature, high-humidity test, the water vapor permeability and oxygen permeability values did not change at all (the gas barrier performance did not deteriorate) compared to before the high-temperature, high-humidity test, and the long-term weather resistance was I was able to maintain it.
○: After the high temperature and high humidity test, both the water vapor permeability and oxygen permeability values increased (gas barrier performance decreased) compared to before the high temperature and high humidity test, but the rate of increase was higher than that before the high temperature and high humidity test. Compared to the water vapor permeability and oxygen permeability values, they were each less than 0.1%. As a result, although long-term weather resistance decreased, there were no problems in use.
×: After the high-temperature, high-humidity test, the water vapor permeability and oxygen permeability values both increased (gas barrier performance decreased) compared to before the high-temperature, high-humidity test, and the rate of increase was higher than that before the high-temperature, high-humidity test. Compared to each numerical value of permeability and oxygen permeability, each was 0.1% or more. As a result, long-term weather resistance deteriorated, causing problems in use.
In addition, in this example, "○" and "◎" were regarded as passes.

<Bending suitability test>
Each decorative sheet was bonded to a steel plate using a two-component urethane adhesive, and then cured at 25° C. for 3 days. Thereafter, a bending suitability test was performed. The bending test was conducted under low temperature and high speed bending conditions so as not to be affected by the processing machine or the environment during processing. Specifically, the surface state tensionless bending test was performed 1000 times at 30 times/min.
Thereafter, each decorative sheet was peeled off from the steel plate, and its water vapor permeability and oxygen permeability were measured. The evaluation criteria for the bending suitability test are as follows.

◎: Even after the bending test, the water vapor permeability and oxygen permeability values did not change at all (the gas barrier performance did not deteriorate) compared to before the bending test, and long-term weather resistance was maintained.
○: After the bending test, the water vapor permeability and oxygen permeability values both increased compared to before the bending test (gas barrier performance decreased), but the rate of increase was greater than the water vapor permeability and oxygen permeability before the bending test. It was less than 0.1% compared to each numerical value of degree. As a result, although long-term weather resistance decreased, there were no problems in use.
×: After the bending test, the water vapor permeability and oxygen permeability values both increased (gas barrier performance decreased) compared to before the bending test, and the rate of increase was the same as that of the water vapor permeability and oxygen permeability before the bending test. These values were 0.1% or more, respectively. As a result, long-term weather resistance deteriorated, causing problems in use.
In addition, in this example, "○" and "◎" were regarded as passes.

<Nonflammability test>
According to the technical standards for non-combustible materials stipulated in the Building Standards Act Construction Order, the following requirements must be met in a heat generation test using a cone calorimeter tester compliant with ISO 5660-1 (Building Standards Act Construction Order). Article 108-2 items 1 and 2). In order for a decorative sheet to be certified as a noncombustible material, it must meet all of the requirements 1 to 3 below when heated with 50kW/ ^m2 radiant heat for 20 minutes when attached to a noncombustible base material. There is a need.
1. Total calorific value is 8MJ/ ^m2 or less 2. Maximum heat generation rate does not exceed 200kW/ ^m2 for 10 seconds or more 3. No cracks or holes penetrating the back surface, which would be detrimental to flame protection, were created. As the noncombustible base material, gypsum board was used.

○: All requirements 1 to 3 above are met when the decorative sheet is attached to a nonflammable base material and heated for 20 minutes using 50 kW/m ² of radiant heat.
×: Even if one of the requirements 1 to 3 above is not met when the decorative sheet is attached to a nonflammable base material and heated for 20 minutes using 50kW/ ^m2 radiant heat. be.
In addition, in this example, "○" was defined as a pass.

As is clear from Table 1, the decorative sheets of Examples 1 to 16 were decorative sheets with excellent long-term weather resistance.

Note that the decorative sheet of the present invention is not limited to the above-described embodiments and examples, and various changes can be made without impairing the characteristics of the invention.

1 Transparent resin layer 1a Embossed pattern 2 Pattern layer 4 Top coat layer 5 Primer layer 6 Adhesive layer 7 Original fabric layer 8 Barrier layer 10 Decorative sheet

Claims (11)

A decorative sheet in which a raw fabric layer, a barrier layer, a transparent resin layer and a top coat layer are laminated in this order,
The barrier layer is composed of an inorganic compound,
The laminate including the barrier layer and the transparent resin layer was measured under measurement conditions of 40° C. and 90% R. H. The water vapor permeability is 0.8 g/m ² ·day or less, and the measurement conditions are 40°C and 90% R. H. The oxygen permeability is 0.5 cc/m ² ·day · atm or less,
The barrier layer is a vapor deposited film containing Al , and the thickness thereof is in the range of 5 nm or more and 10 nm or less,
A decorative sheet , wherein the transparent resin layer is a layer containing a polyolefin resin . A decorative sheet in which a raw fabric layer, a barrier layer, a transparent resin layer and a top coat layer are laminated in this order,
The barrier layer is composed of an inorganic compound,
The laminate including the barrier layer and the transparent resin layer was measured under measurement conditions of 40° C. and 90% R. H. The water vapor permeability is 0.8 g/m ² ·day or less, and the measurement conditions are 40°C and 90% R. H. The oxygen permeability is 0.5 cc/m ² ·day · atm or less,
The barrier layer is a coating film containing Al , and the thickness thereof is in the range of 10 μm or more and 12 μm or less,
A decorative sheet , wherein the transparent resin layer is a layer containing a polyolefin resin . The decorative sheet according to claim 1 or 2, wherein the barrier layer further contains at least one of Si , Ti , Zn, Sn, Fe, and Mn. 3. The decorative sheet according to claim 1, wherein the barrier layer further contains at least one of Ti, Zn, Sn, Fe, and Mn. 3. The decorative sheet according to claim 2, wherein the barrier layer contains the aluminum oxide fine particles containing Al and an epoxy resin. The decorative sheet according to any one of claims 1 to 5, wherein the original fabric layer contains a polyolefin resin. The decorative sheet according to claim 1, wherein the vapor deposited film is an aluminum oxide film containing the Al. 8. The decorative sheet according to claim 6, wherein the transparent resin layer is a layer formed of homopolypropylene resin. The raw fabric layer contains a polyolefin resin and an inorganic filler, and contains the inorganic filler in a range of 50 parts by mass or more and 900 parts by mass or less based on 100 parts by mass of the polyolefin resin,
A cone that complies with ISO5660-1 when bonded to a noncombustible base material, and complies with the fire resistance test method and performance evaluation standard based on Article 2, Item 9 of the Building Standards Act and Article 108-2 of the Building Standards Act Enforcement Order. In the exothermic test using a calorimeter tester, (1) the total calorific value (MJ/m ² ) for 20 minutes after the start of heating is 8 MJ/m ² or less, and (2) the maximum exothermic rate for 20 minutes after the start of heating is 10 According to any one of claims ¹ to 8, the non-combustible material satisfies the following conditions: (3) the base material has no cracks or holes; cosmetic sheet. The barrier layer and a pattern layer provided between the barrier layer and the raw fabric layer are laminated via an adhesive layer,
The decorative sheet according to any one of claims 1 to 9, wherein the coating amount of the adhesive layer is within a range of 5.0 g/m ² or more and 6.0 g/m ² or less. . The decorative sheet according to claim 10, wherein the thickness of the adhesive layer is within a range of 5 μm or more and 6 μm or less.

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