Decorative sheets and metal decorative components

Abstract

To provide a decorative sheet which is excellent in base material adhesion and moist heat resistance, and a metallic decorative member using the decorative sheet.SOLUTION: A decorative sheet 10 includes a sheet base material 1, a pattern layer 2, a heat adhesive resin layer 3, a weather resistant resin layer 4, and a stain resistant resin layer 5 containing a fluorine resin or an ethylene vinyl alcohol copolymer resin, which are sequentially layered on the sheet base material 1, wherein the pattern layer 2 contains a urethane resin containing polycaprolactone polyol, polyalkylene glycol and polyisocyanate as components, as a binder resin.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a decorative sheet and a metal decorative member.

Background Art

[0002] In applications such as building exteriors and bathrooms, decorative sheets may be required to have durability against high temperatures and high humidity (moisture and heat resistance). The pattern layer for imparting a design to this decorative sheet is generally formed by printing an ink containing a binder resin and a pigment on a base material such as polyolefin or polyester. Conventionally, as the binder resin for the pattern layer, nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc. have been used (Patent Document 1). However, it may be difficult to achieve both good adhesion to the above base material and moisture and heat resistance with these binder resins. For example, polyester and polyester-based polyurethanes show good adhesion to the above base material, but are liable to undergo hydrolysis and may have insufficient moisture and heat resistance. In addition, embrittlement of the binder resin due to hydrolysis may cause peeling of the pattern layer or peeling in the transparent resin layer provided on the pattern layer.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a decorative sheet excellent in both substrate adhesion and moisture and heat resistance, and a metal decorative member using the decorative sheet.

Means for Solving the Problems

[0005] To solve the above problems, a decorative sheet according to one aspect of the present invention comprises a sheet substrate, a pattern layer, a heat-adhesive resin layer, a weather-resistant resin layer, and a stain-resistant resin layer containing a fluororesin or ethylene vinyl alcohol copolymer resin, which are sequentially laminated on the sheet substrate, wherein the weather-resistant resin layer contains at least one ultraviolet absorber selected from a mixture of acrylic resin and acrylic resin-based rubber, and benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers, and the amount of ultraviolet absorber added is such that the acrylic resin and acrylic The acrylic resin-based rubber mixture is characterized by being composed of 0.2% to 0.8% by mass relative to the total mass, having a mass ratio of acrylic resin to acrylic resin-based rubber in the range of 40:60 to 70:30, having a total thickness of 200 μm or less, and having a combined thickness of 20 μm to 80 μm of the weather-resistant resin layer and the stain-resistant resin layer, and the pattern layer containing a urethane resin as a binder resin, which includes polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as constituent elements.

[0006] To solve the above problems, another aspect of the present invention provides a metal decorative member characterized in that the decorative sheet is bonded to a metal substrate. [Effects of the Invention]

[0007] According to aspects of this disclosure, it is possible to provide a decorative sheet with excellent adhesion to a substrate and excellent resistance to moisture and heat, and a metal decorative member using the decorative sheet. [Brief explanation of the drawing]

[0008] [Figure 1] This is a cross-sectional view showing one example of the configuration of a decorative sheet according to the first embodiment of this disclosure. [Figure 2] This is a cross-sectional view showing an example of the configuration of a decorative sheet according to the second embodiment of this disclosure. [Figure 3] This is a cross-sectional view showing an example of the configuration of a metal decorative member according to the third embodiment of this disclosure. [Figure 4]This is a cross-sectional view showing an example of the configuration of a metal decorative member according to a modified example of the third embodiment of the present disclosure. [Modes for carrying out the invention]

[0009] As a result of diligent research, the inventors have discovered that by using a urethane resin containing specific components as the binder resin for the pattern layer, it is possible to impart excellent substrate adhesion and moisture and heat resistance to the decorative sheet. The present disclosure will be described below through embodiments, but these embodiments are not intended to limit the invention as defined in the claims. Furthermore, not all combinations of features described in the embodiments are necessarily essential to the solution of the invention. In addition, the drawings schematically illustrate the invention as defined in the claims, and the relationship between thickness and planar dimensions, the ratio of the thickness of each layer, etc., may differ from reality. Furthermore, the embodiments shown below are illustrative of configurations for realizing the technical idea of ​​the present disclosure, and the technical idea of ​​the present disclosure is not limited to the materials, shapes, structures, etc. of the components described below. The technical idea of ​​the present invention can be modified in various ways within the technical scope defined by the claims described in the claims.

[0010] 1. First Embodiment Figure 1 is a schematic cross-sectional view illustrating an example of the configuration of a decorative sheet 10 according to the first embodiment of this disclosure (hereinafter referred to as "this embodiment"). As shown in Figure 1, the decorative sheet 10 according to the embodiment of this disclosure comprises at least a sheet substrate 1, and a pattern layer 2, a heat-adhesive resin layer 3, a weather-resistant resin layer 4, and a stain-resistant resin layer 5 laminated in order on the sheet substrate 1. The total thickness of the decorative sheet 10 is 200 μm or less. As shown in Figure 1, the decorative sheet 10 may also have a primer layer 6 on the side of the sheet substrate 1 opposite to the pattern layer 2. In other words, the decorative sheet 10 may have a configuration in which the primer layer 6, sheet substrate 1, pattern layer 2, heat-adhesive resin layer 3, weather-resistant resin layer 4, and stain-resistant resin layer 5 are laminated in this order. The primer layer 6 is a layer that is provided as needed to improve the adhesion between the decorative sheet 10 and the substrate to which the decorative sheet 10 is attached (for example, a metal substrate 9 described later, or a predetermined wall surface, building material, etc.).

[0011] (Sheet base material) The sheet substrate 1 is a sheet-like layer formed from a thermoplastic resin. The thermoplastic resin constituting the sheet substrate 1 may include, for example, polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene; polyolefin copolymers such as ethylene-vinyl acetate copolymer or its saponified product, and ethylene-(meth)acrylic acid (ester) copolymer; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, and copolymerized polyester (typically 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin, commonly known as PET-G). Examples of suitable resins include ester resins, acrylic resins such as polymethyl methacrylate, polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, and 12-nylon, styrene resins such as polystyrene, AS resin, and ABS resin, cellulose acetate and nitrocellulose derivatives, chlorine resins such as polyvinyl chloride and polyvinylidene chloride, fluorine resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymers, or copolymers, mixtures, or composites of two or more of these selected from the above. The sheet substrate 1 may be composed of a laminate made of such thermoplastic resins. Flame retardants and ultraviolet absorbers can also be mixed into the sheet substrate 1 to maintain flame retardancy or fade resistance. In particular, considering productivity in melt extrusion equipment, environmental compatibility, mechanical strength as a flooring material, durability, and cost, it is more preferable to construct the sheet base material 1 from a polyolefin resin (e.g., polypropylene). Furthermore, if the sheet base material 1 is made of a polyolefin resin, good processing suitability and hydrolysis resistance can be achieved.

[0012] It is preferable that the sheet substrate 1 is colored. By coloring the sheet substrate 1, the substrate (metal substrate 9, described later) to which the decorative sheet 10 is bonded can be concealed, and a suitable hue can be selected as the base color for the pattern layer 2. For example, the sheet substrate 1 can be colored by mixing or kneading a coloring agent such as a pigment into the thermoplastic resin material that constitutes the sheet substrate 1. Alternatively, a colored layer (not shown) can be provided beneath the pattern layer 2 as a solid ink layer before the pattern layer 2 is applied, using a coating or printing method.

[0013] Organic and inorganic pigments (including titanium dioxide) can be used as colorants. Furthermore, while benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, formamidine-based, oxanilide-based, and hindered amine-based UV absorbers can be used, benzotriazole-based, oxanilide-based, hindered amine-based, and mixtures thereof are particularly preferred because they exhibit excellent UV absorption and also have excellent compatibility with olefin resins and the like. As flame retardants, inorganic types (aluminum hydroxide, magnesium hydroxide, antimony trioxide, etc.), phosphorus-based types (organic: phosphate esters, ammonium phosphate, etc., inorganic: red phosphorus), and reactive types (vinyl compounds that undergo vinyl addition polymerization, having functional groups such as carboxylic acid groups, hydroxyl groups, and epoxy groups, and used as some raw materials (copolymer monomers) for polymers) can be used. However, aluminum hydroxide and magnesium hydroxide are preferred because they are superior in terms of compatibility with resins, flame retardant effect, and environmental safety.

[0014] (Picture layer) The pattern layer 2 imparts design characteristics as a decorative material to the decorative sheet 10. As patterns as designs, in addition to wood grain patterns, for example, cork patterns, stone patterns, tile patterns, porcelain patterns, abstract patterns, etc., desired printed patterns suitable for the location where they are used can be selected. In this embodiment, the pattern layer 2 is formed by printing pattern ink using, as a binder resin, a urethane resin containing at least specific components, namely polycaprolactone polyol, polyalkylene glycol, and polyisocyanate, on the sheet base material 1. That is, the pattern layer 2 contains, as a binder resin, a urethane resin containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as components. The urethane resin in this embodiment can be synthesized by a known technique, namely an addition polymerization reaction of a polyol and a polyisocyanate. The terminal of the urethane resin is usually an isocyanate group blocked with a hydroxyl group or an amine. When the terminal of the urethane resin is a hydroxyl group, the pattern layer 2 can be reacted (cured) to form a coating film by blending a curing agent such as isocyanate into the pattern ink.

[0015] The polycaprolactone polyol constituting the urethane resin of this embodiment is a material obtained by ring-opening polymerization of ε-caprolactone and has an ester bond inside. Therefore, the adhesion to the sheet base material 1, that is, the substrate adhesion, is improved. The above polycaprolactone polyol generally has excellent hydrolysis resistance compared to general-purpose polyester polyols obtained by polycondensation of dicarboxylic acids such as adipic acid and diols. As the polycaprolactone polyol, for example, polycaprolactone diol, polycaprolactone triol, polycaprolactone tetraol, or a copolymer thereof can be used.

[0016] The polyalkylene glycol constituting the urethane resin in this embodiment has a polyether structure and exhibits superior hydrolysis resistance compared to the aforementioned polycaprolactone polyol, but tends to have inferior heat resistance and substrate adhesion. In this embodiment, by using polyalkylene glycol in combination with polycaprolactone polyol, both substrate adhesion and moisture and heat resistance are achieved. In other words, by including a urethane resin containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as binder resin in the pattern layer 2, a decorative sheet 10 with excellent substrate adhesion and moisture and heat resistance can be obtained. Furthermore, because the pattern layer 2 contains the above-mentioned urethane resin, the decorative sheet 10 can maintain substrate adhesion and moisture and heat resistance over a long period of time, and its weather resistance can also be improved. Polyalkylene glycols can include, for example, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, with polytetramethylene glycol being preferred from the viewpoint of improving heat and humidity resistance due to its high hydrophobicity.

[0017] The urethane resin of this embodiment preferably further contains neopentyl glycol as a component. The inclusion of neopentyl glycol improves its resistance to moisture and heat. The polycaprolactone polyol and polyalkylene glycol in this embodiment can be appropriately selected from various commercially available materials based on their molecular weight, number of functionalities (number of hydroxyl groups per molecule), and other factors. Furthermore, the polyisocyanate (isocyanate curing agent) used for curing the urethane resin in this embodiment is not particularly limited. For example, it can be appropriately selected from commercially available curing agents containing diisocyanates and their hydrogenated derivatives, such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), and tolylene diisocyanate (TDI), or diphenylmethane diisocyanate and its hydrogenated derivatives. However, isophorone diisocyanate is preferred in terms of its resistance to moisture and heat.

[0018] In the urethane resin of the present embodiment, the total of the content (A) of polycaprolactone polyol and the content (B) of polyalkylene glycol (total content) is more than the content (C) of polyisocyanate (A + B > C). Thereby, the pattern ink using the urethane resin as a binder resin can be satisfactorily reacted (cured) to surely form a coating film.

[0019] The composition of the urethane resin of the present embodiment is not particularly limited. However, considering the printing suitability of the pattern layer 2 formed by ordinary printing and various performances of the decorative sheet 10, when the amounts of substances of respective parts of the urethane resin (caprolactone unit (CL), alkylene glycol unit (AG), diisocyanate unit (I), neopentyl glycol (NPG)) shown by the following structural formula are respectively X, Y, Z, and N, it is preferable to satisfy the following relational expressions (1) to (3).

[0020]

Chem.

[0021] 3 < (X + Y + N) / Z < 50 (Formula 1) 0.1 < X / Y < 10 (Formula 2) N / (X + Y + X + N) < 0.2 (Formula 3) Within the above numerical range, the printing suitability can be easily improved.

[0022] The molecular weight of the urethane resin of the present embodiment is not particularly limited. For example, considering the printing suitability of the pattern layer 12 formed by ordinary printing and various performances of the decorative sheet 10, the mass average molecular weight (MW) is preferably in the range of 5,000 or more and 100,000 or less. Within the above numerical range, the printing suitability can be easily improved. If the mass average molecular weight is 5,000 or less, the toughness as a resin may be reduced. If the mass average molecular weight is 100,000 or more, the coating property may be deteriorated and the processing propriety may not be good.

[0023] The pattern layer 2 is usually formed by printing a pattern ink using the urethane resin of this embodiment as the binder resin onto the sheet substrate 1, but other resin components may be added as needed. In addition to the binder resin, the components of the pattern ink can include various additives such as colorants (pigments, dyes, etc.), extenders, solvents, and light stabilizers. Examples of pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolon, cobalt, phthalocyanine, carbon, titanium dioxide, iron oxide, mica, and other pearl pigments. The method for creating the second image layer is not particularly limited, and conventional printing methods such as gravure printing, offset printing, screen printing, flexographic printing, and inkjet printing can be used. In addition, if the entire surface is to be colored, coating techniques and equipment may be used in addition to printing methods.

[0024] (thermal adhesive resin layer) The heat-adhesive resin layer 3 is provided between the pattern layer 2 and the weather-resistant resin layer 4, enabling adhesion of the pattern layer 2 and the weather-resistant resin layer 4 by heat lamination, and is provided for the purpose of achieving adhesive strength between the two layers. The heat-adhesive resin layer 3 is formed from a heat-adhesive resin containing an acrylic-polyester-vinyl chloride resin. In this embodiment, in particular, a heat-adhesive resin layer 3 formed using an acrylic-polyester-vinyl chloride resin (specifically, an acrylic-polyester-vinyl chloride / vinyl acetate copolymer resin) is used as the heat-adhesive resin. This heat-adhesive resin takes advantage of the benefits of acrylic resins and vinyl chloride resins, which easily melt and exhibit adhesive properties when heated, while also incorporating the characteristics of polyester resins, which show little reduction in cohesive force even under heating. Furthermore, this heat-adhesive resin exhibits sufficient adhesive properties and can be heat-laminated even under relatively low temperature conditions, without adversely affecting the sheet substrate 1 or the weather-resistant resin layer 4, such as rupture, elongation, deformation, or deterioration. Furthermore, this heat-adhesive resin maintains sufficient peel resistance and does not lose adhesive strength even under high-temperature usage conditions in semi-exterior applications.

[0025] In acrylic-polyester-vinyl chloride resins, the blending ratio of acrylic resin, polyester resin, and vinyl chloride resin is preferably in the range of 10% to 60% by mass for acrylic resin, 10% to 60% by mass for polyester resin, and 10% to 60% by mass for vinyl chloride resin, and more preferably in the range of 20% to 50% by mass for acrylic resin, 20% to 50% by mass for polyester resin, and 20% to 50% by mass for vinyl chloride resin.

[0026] (Weather-resistant resin layer) The weather-resistant resin layer 4 is composed of a mixture of acrylic resin (polymethyl methacrylate resin) and acrylic resin-based rubber (polymethyl methacrylate resin-based rubber). The mass ratio of acrylic resin to acrylic resin-based rubber is in the range of 40:60 to 70:30. That is, the amount of acrylic resin mixed in the weather-resistant resin layer 4 is 40% to 70% by mass, and the amount of acrylic resin-based rubber mixed is 30% to 60% by mass.

[0027] Furthermore, the weather-resistant resin layer 4 contains at least one ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers. The amount of ultraviolet absorber added is preferably 0.2% by mass or more and 0.8% by mass or less, relative to the total mass of the acrylic resin and acrylic resin-based rubber. If the amount of ultraviolet absorber added is less than 0.2% by mass, the effect of adding the ultraviolet absorber may be reduced. If the amount of ultraviolet absorber added exceeds 0.8%, it may become difficult to add the ultraviolet absorber uniformly. It is undesirable to add an amount of ultraviolet absorber to the resin that causes the resin to become colored.

[0028] The added UV absorber is either a benzotriazole-based UV absorber or a triazine-based UV absorber, either alone or in a mixture of both. By adding a UV absorber to the resin material (acrylic resin and acrylic resin-based rubber) that constitutes the weather-resistant resin layer 4, the light resistance and weather resistance of the weather-resistant resin layer 4 can be improved. Furthermore, the thickness of the weather-resistant resin layer 4 is preferably 10 μm or more and less than 80 μm. Furthermore, the weather-resistant resin layer 4 may have an embossed or other uneven surface. Providing an uneven surface on the weather-resistant resin layer 4 can improve its aesthetic appeal. Specifically, the weather-resistant resin layer 4 may have an uneven pattern applied to it, for example, from the upper side (the side with the stain-resistant resin layer 5) by heat shaping or the like. By providing a pattern layer 2 and a weather-resistant resin layer 4 with an uneven pattern, an excellent decorative sheet 10 can be obtained that combines aesthetic appeal with a richly expressive pattern.

[0029] (Stain-resistant resin layer) The stain-resistant resin layer 5 is a resin layer containing fluororesin or ethylene vinyl alcohol resin (ethylene vinyl alcohol copolymer resin (EVOH)). The stain-resistant resin layer 5 may also contain acrylic resin. Fluororesin and ethylene vinyl alcohol resin (EVOH) are materials with excellent solvent resistance, oil resistance, stain resistance, and transparency. It is more preferable that the stain-resistant resin layer 5 be formed of fluororesin.

[0030] If the stain-resistant resin layer 5 is made of fluororesin, the stain-resistant resin layer 5 may be formed by coating with fluororesin, or by laminating a fluororesin film to the weather-resistant resin layer 4. As fluororesins, polyvinyl fluoride resin (PVF), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), etc. can be used, and ethylene-tetrafluoroethylene copolymer (ETFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) are particularly preferred in terms of melt moldability and stain resistance.

[0031] Furthermore, if the stain-resistant resin layer 5 is composed of EVOH, the stain-resistant resin layer 5 may be formed by coating with EVOH, or by laminating an EVOH film to the weather-resistant resin layer 4. Two types of EVOH are known: one with an ethylene content of 82 mol% to 90 mol%, and another with an ethylene content of 25 mol% to 50 mol%. Among these, the type with an ethylene content of 25 mol% to 50 mol%, which is particularly excellent in terms of solvent resistance, oil resistance, stain resistance, and transparency, is preferred for use.

[0032] Furthermore, the stain-resistant resin layer 5 can be made more light-resistant and weather-resistant by using an ultraviolet absorber in combination. However, it is undesirable to add so much ultraviolet absorber that it becomes colored in the fluororesin or ethylene vinyl alcohol resin mentioned above. When forming a stain-resistant resin layer 5 using a fluororesin film, if the surface of the stain-resistant resin layer 5 is to be textured with an embossed or other uneven pattern, it is desirable to perform the textured processing after laminating the fluororesin film onto the weather-resistant resin layer 4.

[0033] Furthermore, when forming the stain-resistant resin layer 5 using EVOH, if an embossed or other textured pattern is to be applied to the surface of the stain-resistant resin layer 5, the textured processing may be performed after laminating the EVOH film onto the weather-resistant resin layer 4, or the textured processing may be performed when the EVOH is heat-melt extruded. For example, the textured processing may be performed when the weather-resistant resin layer 4 and the EVOH resin are co-extruded and laminated. Here, the combined thickness of the weather-resistant resin layer 4 and the stain-resistant resin layer 5 is between 20 μm and 80 μm. If the combined thickness of the weather-resistant resin layer 4 and the stain-resistant resin layer 5 is less than 20 μm, the weather resistance of the decorative sheet 10 will decrease. Also, if the combined thickness of the weather-resistant resin layer 4 and the stain-resistant resin layer 5 exceeds 80 μm, the non-flammability of the decorative sheet 10 will decrease.

[0034] As described above, the total thickness of the decorative sheet is 200 μm or less, and the combined thickness of the weather-resistant resin layer 4 and the stain-resistant resin layer 5 is between 20 μm and 80 μm. According to this, the decorative sheet 10, when bonded to a metal plate (metal substrate 9 described later) selected from aluminum, stainless steel, copper, and steel plate, undergoes a heat generation test using a cone calorimeter testing machine in accordance with the fire resistance test method and performance evaluation standards based on Article 2, Item 9 of the Building Standards Act and Article 108-2 of the Enforcement Order of the Building Standards Act, and (1) the total heat generation amount for 20 minutes after the start of heating is 8 MJ / m³. 2 The following conditions apply: (2) For 20 minutes after the start of heating, the maximum heating rate remains at 200 KW / m² for at least 10 seconds. 2 (3) It does not exceed the limit and is non-flammable to the extent that it is free from fire-hazardous cracks and holes for 20 minutes after the start of heating.

[0035] (Primer layer) As described above, the primer layer 6 is provided on the side of the sheet substrate 1 opposite to the pattern layer 2. For the primer layer 6, for example, polyester resins, polyurethane resins, or mixtures thereof can be used. Furthermore, by using a two-component type consisting of a polyol and an isocyanate, the adhesion between the sheet substrate 1 and the primer layer 6 and the cohesive force of the primer layer 6 itself are improved. Examples of polyols include acrylic polyols and polyester polyols. Examples of isocyanates include aromatic polyols such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, and aliphatic polyols such as hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate. It is preferable to use an aromatic polyol for the primer layer 6 in terms of rapid reactivity and heat resistance.

[0036] The thickness of the primer layer 6 is preferably 1 μm or more. By making the thickness of the primer layer 6 1 μm or more, it is possible to prevent the adhesive from dissolving due to the solvent, which would cause the primer layer 6 to disappear and reduce adhesion. Furthermore, if the surface to which the decorative sheet 10 is to be applied has significant irregularities, it is advisable to fill the gaps with putty beforehand and apply a primer as needed. Also, as mentioned above, the primer layer 6 is provided as needed, and the primer layer 6 may be omitted in the decorative sheet 10. For example, if the substrate to which the decorative sheet 10 is to be attached has a function as a primer layer, the primer layer 6 can be omitted.

[0037] (Effects of the first embodiment) The decorative sheet 10 of this embodiment can achieve the following effects. (1) The sheet substrate 1 comprises a pattern layer 2, a heat-adhesive resin layer 3, a weather-resistant resin layer 4, and a stain-resistant resin layer 5 containing a fluororesin or ethylene vinyl alcohol copolymer resin, which are laminated in order on the sheet substrate 1. The weather-resistant resin layer 4 contains a mixture of acrylic resin and acrylic resin-based rubber, and at least one ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers, the amount of the ultraviolet absorber added is 0.2% by mass or more and 0.8% by mass or less with respect to the total mass amount of the mixture of acrylic resin and acrylic resin-based rubber, the mass ratio of the acrylic resin to the acrylic resin-based rubber is in the range of 40:60 to 70:30, the total thickness is 200 μm or less, and the combined thickness of the weather-resistant resin layer 4 and the stain-resistant resin layer 5 is 20 μm or more and 80 μm or less. The pattern layer 2 contains a urethane resin containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as components as a binder resin. This makes it possible to provide a decorative sheet with excellent adhesion to the substrate as well as excellent resistance to moisture and heat by incorporating a urethane resin containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as components in the pattern layer 2.

[0038] (2) In the decorative sheet 10, the pattern layer 2 further contains neopentyl glycol as a component of the urethane resin. This makes it possible to provide a decorative sheet with superior adhesion to the substrate and better resistance to moisture and heat.

[0039] (3) In the urethane resin contained in the pattern layer 2, the polyalkylene glycol is polytetramethylene glycol. This makes it possible to provide a decorative sheet with excellent adhesion to the substrate and even better resistance to moisture and heat.

[0040] (4) In the urethane resin contained in the pattern layer 2, the polyisocyanate is isophorone diisocyanate. This makes it possible to provide a decorative sheet with excellent adhesion to the substrate and even better resistance to moisture and heat.

[0041] (5) In the decorative sheet 10, the weather-resistant resin layer 4 has an uneven surface. This improves the aesthetic appeal of the weather-resistant resin layer 4.

[0042] (6) In the decorative sheet 10, the heat-adhesive resin layer 3 is made of an acrylic-polyester-vinyl chloride / vinyl acetate copolymer resin. This ensures that the adhesive strength is not lost even under high-temperature usage conditions in semi-exterior applications, and that sufficient peel resistance is maintained. (7) In the heat-adhesive resin layer 3 of the decorative sheet 10, the blending ratio of acrylic resin, polyester resin, and vinyl chloride resin in the acrylic-polyester-vinyl chloride / vinyl acetate copolymer resin is 20% by mass or more and 50% by mass or less for acrylic resin, 20% by mass or more and 50% by mass or less for polyester resin, and 20% by mass or more and 50% by mass or less for vinyl chloride resin. This allows for further improvement in peel resistance.

[0043] (8) In the decorative sheet 10, the ethylene vinyl alcohol copolymer resin contained in the stain-resistant resin layer 5 has an ethylene content within the range of 25 mol% to 50 mol%. This allows for improved physical properties such as solvent resistance, oil resistance, stain resistance, and transparency. (9) In the decorative sheet 10, the sheet base material 1 contains a resin component, and the resin component of the sheet base material 1 is a polyolefin resin. This improves the processing suitability and hydrolysis resistance of the decorative sheet 10.

[0044] 3. Second Embodiment The decorative sheet according to the second embodiment of this disclosure will be described below with reference to Figure 2. Figure 2 is a schematic cross-sectional view illustrating one example of the configuration of a decorative sheet 20 according to the second embodiment of this disclosure (hereinafter referred to as "this embodiment").

[0045] As shown in Figure 2, the decorative sheet 20 according to this embodiment comprises a sheet substrate 1 and a pattern layer 2, a heat-adhesive resin layer 3, a weather-resistant resin layer 4, and a stain-resistant resin layer 5, which are laminated in that order on the sheet substrate 1. The decorative sheet 20 also has a primer layer 26 on the side of the sheet substrate 1 opposite to the pattern layer 2. In other words, the decorative sheet 20 has a structure in which the primer layer 26, sheet substrate 1, pattern layer 2, heat-adhesive resin layer 3, weather-resistant resin layer 4, and stain-resistant resin layer 5 are laminated in this order. In other words, the decorative sheet 20 differs from the decorative sheet 10 according to the first embodiment in that it includes a primer layer 26 instead of the primer layer 6. As will be described in detail later, the decorative sheet 20 according to this embodiment has a structure in which a urethane resin containing the above-mentioned specific components is used as a binder resin in both the pattern layer and the primer layer. The decorative sheet 20 has a total thickness of 200 μm or less, similar to the decorative sheet 10 according to the first embodiment.

[0046] The primer layer 26 will be described below. Note that the other layers (sheet substrate 1, pattern layer 2, heat-adhesive resin layer 3, weather-resistant resin layer 4, and stain-resistant resin layer 5) have the same configuration as the other layers of the decorative sheet 10, and therefore are denoted by the same reference numerals and their descriptions will be omitted.

[0047] (Primer layer) In this embodiment, the primer layer 26 is formed by coating the sheet substrate 1 with a binder resin made of a urethane resin containing at least specific components, namely polycaprolactone polyol, polyalkylene glycol, and polyisocyanate. That is, the primer layer 26 contains a urethane resin containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as components as the binder resin. In other words, by containing a urethane resin containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as components as the binder resin in both the pattern layer 2 and the primer layer 26, a decorative sheet 20 with even better adhesion to the substrate and superior moisture and heat resistance can be obtained. The composition of the urethane resin contained in the primer layer 26 as a binder resin is equivalent to that of the urethane resin contained in the pattern layer 2, and since it has the same effects, a detailed explanation is omitted. Furthermore, the aforementioned urethane resin containing specific components can easily improve the coating suitability of the primer layer 6 to the sheet substrate 1 by satisfying the above relational equations (1) to (3).

[0048] Furthermore, inorganic particles may be added to the primer layer 26 as a component other than the binder resin. Specifically, inorganic particles such as silica particles, alumina (α-alumina, etc.), and barium sulfate may be added to the urethane resin used as the binder resin in the primer layer 26, either individually or in a mixture of multiple types. Adding inorganic particles to the primer layer 26 is effective in preventing blocking during winding and storage of decorative sheets, and in improving adhesive strength through an anchoring effect. Here, it is preferable to use precipitated barium sulfate obtained by double decomposition of barium sulfide and sodium sulfate as the barium sulfate. In addition, calcium carbonate, kaolinite, aluminosilicate, etc. may be used as the inorganic particles.

[0049] The decorative sheet 20 of this embodiment can achieve the following effects. The decorative sheet 20 further comprises a primer layer 26 provided on the side of the sheet substrate 1 opposite to the pattern layer 2, and the primer layer 26 contains the same urethane resin as the pattern layer 2 as a binder resin. This makes it possible to provide a decorative sheet with excellent adhesion to the substrate and even better resistance to moisture and heat.

[0050] 3. Third Embodiment A metal decorative member according to the third embodiment of this disclosure will be described with reference to Figure 3. Figure 3 is a cross-sectional view illustrating one example of the configuration of the metal decorative member 100 according to the third embodiment of this disclosure.

[0051] (Metal decorative components) As shown in Figure 3, the metal decorative member 100 according to this embodiment comprises a metal substrate (metal substrate 9) and a decorative sheet 10 according to the first embodiment, with the decorative sheet 10 being bonded to the metal substrate 9. This makes it possible to obtain a metal decorative member 100 with excellent adhesion to the substrate as well as excellent resistance to moisture and heat. In this case, the metal plate and the decorative sheet 10 are bonded together such that the metal substrate 9 and the sheet base material 1 of the decorative sheet 10 face each other. Examples of metals that make up the metal substrate 9 include aluminum, stainless steel, copper, and steel plate.

[0052] As shown in Figure 3, the metal substrate 9 is bonded to the decorative sheet 10 via an adhesive layer 8. The adhesive layer 8 is provided as needed to improve the adhesion between the decorative sheet 10 and the metal substrate 9. The adhesive layer 8 is composed of, for example, a urethane resin-based adhesive.

[0053] In this embodiment, the metal decorative member 100 has a pattern layer 2, a heat-adhesive resin layer 3, a weather-resistant resin layer 4, and a stain-resistant resin layer 5 laminated in this order on at least one side of the sheet substrate 1, and a metal substrate 9 is provided on the other side of the sheet substrate 1. In order to improve the adhesion between the decorative sheet 10 and the metal substrate 9, a primer layer 6 may be provided on the side of the decorative sheet 10 opposite to the pattern layer 2 of the sheet substrate 1 (the side that is attached to the metal substrate), and an adhesive layer 8 may be provided on the metal substrate 9, if necessary.

[0054] The metal decorative member 100 of this embodiment can achieve the following effects. The metal decorative member 100 is constructed by laminating a decorative sheet 10 onto a metal substrate. This makes it possible to provide a metal decorative member with excellent substrate adhesion and resistance to moisture and heat.

[0055] As mentioned above, the total thickness of the decorative sheet 10 is 200 μm or less, and the combined thickness of the weather-resistant resin layer 4 and the stain-resistant resin layer 5 is between 20 μm and 80 μm. According to this, a metal decorative member 100, which is composed of a decorative sheet 10 laminated onto a metal substrate 9 selected from aluminum, stainless steel, copper, and steel plate, exhibits the following characteristics in a heat generation test using a cone calorimeter tester in accordance with the fire resistance test method and performance evaluation standards based on Article 2, Item 9 of the Building Standards Act and Article 108-2 of the Enforcement Order of the Building Standards Act: (1) The total heat generation during the 20 minutes after the start of heating is 8 MJ / m³. 2 The following conditions apply: (2) For 20 minutes after the start of heating, the maximum heating rate remains at 200 KW / m² for at least 10 seconds. 2 (3) It does not exceed the limit and is non-flammable to the extent that it is free from fire-hazardous cracks and holes for 20 minutes after the start of heating. This makes it possible to provide a metal decorative component that has excellent adhesion to the substrate, resistance to moisture and heat, and is also non-flammable.

[0056] (modified version) A modified example of the metal decorative member according to this embodiment will be described with reference to Figure 4. Figure 4 is a schematic cross-sectional view illustrating one example of the configuration of the metal decorative member 101 according to a modified example of this embodiment. As shown in Figure 4, the decorative sheet 20 according to the second embodiment may be bonded to the metal substrate 9. In other words, the metal decorative member according to this embodiment may be a metal decorative member 101 comprising a metal substrate (metal substrate 9) and the above-mentioned decorative sheet 20, wherein the decorative sheet 20 is bonded to the metal substrate 9. This makes it possible to obtain a metal decorative member with even better adhesion to the substrate and better resistance to moisture and heat.

[0057] <Examples> The decorative sheet relating to this disclosure will be described below with reference to examples. This disclosure is not limited to the embodiments described below.

[0058] <Example 1> (Decorative sheet) As the sheet substrate 1, a resin sheet made of opaque colored polypropylene resin (PP) with a thickness of 70 μm was prepared. After corona discharge treatment was applied to the front and back surfaces of this sheet substrate 1, a wood grain pattern was formed on the sheet substrate 1 by gravure printing using a urethane-based printing ink (pattern ink), thereby forming a pattern layer 2 (thickness: 3 μm). As the pattern ink, a urethane resin containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as components was used as the binder resin. Specifically, the urethane resin components used were polycaprolactone diol as the polycaprolactone polyol, polytetramethylene glycol (PTMG) as the polyalkylene glycol, and isophorone diisocyanate (IPDI) as the polyisocyanate. Furthermore, neopentyl glycol (NPG) was also used as a component of the urethane resin. Using these components, a known addition polymerization method can be used to obtain a number-average molecular weight of 2 × 10⁻¹⁶. 4A urethane resin with hydroxyl-terminated groups was synthesized. A copper phthalocyanine pigment was dispersed in this urethane resin in a mass ratio of pigment / urethane resin = 20 / 80 to prepare a pattern ink. Furthermore, in the urethane resin that serves as the binder resin for the pattern layer 2, the total content of polycaprolactone polyol and polyalkylene glycol was greater than the content of polyisocyanate.

[0059] (Coating liquid for the primer layer on the back surface) On the other hand, a backside primer layer (thickness: 1 μm) was formed on the back surface of the sheet substrate 1 by gravure printing using a coating liquid for a backside primer layer with the composition described below. The composition of the coating liquid for the primer layer on the back surface, as described above, is as follows: Two-component curable polyester urethane (mixture of polyester polyol and polyisocyanate in a 100:5 (mass ratio)): 100 parts by mass Diluting solvent (mixed solvent of ethyl acetate and methyl isobutyl ketone in a 1:1 (mass ratio): 20 parts by mass)

[0060] Next, a weather-resistant resin layer forming mixture and polyvinylidene fluoride resin (fluororesin) were melted and extruded using a T-die to form a laminate consisting of a weather-resistant resin layer 4 and a stain-resistant resin layer 5 made of fluororesin (thickness of stain-resistant resin layer 5: 5 μm, thickness of weather-resistant resin layer 4: 15 μm, total thickness: 20 μm).

[0061] (Mixture for forming weather-resistant resin layer) The composition of the above-mentioned mixture for forming a weather-resistant resin layer is as follows: Acrylic resin (PMMA resin, constituent unit: methyl methacrylate): 40 parts by mass Acrylic rubber (PMMA-based resin rubber, "SA-FW001 (product name)", manufactured by Kuraray Co., Ltd., methacrylic resin, constituent unit: methyl methacrylate, particulate, average particle size: 100 nm): 60 parts by mass UV absorber (benzotriazole-based UV absorber, tinuvin 326): 0.5 parts by mass

[0062] Next, an acrylic-polyester-vinyl chloride-based heat-adhesive resin (acrylic / polyester / vinyl chloride = 1 / 1 / 1 (mass ratio)) was applied to the pattern layer 2 formed on the surface of the sheet substrate 1 using a gravure coating method to form a heat-adhesive resin layer 3. The coating amount of the heat-adhesive resin layer 3 after drying was 2 g / m². 2 The amount of acrylic-polyester-vinyl chloride-based heat-adhesive resin applied was adjusted to form the desired shape. Finally, a laminate consisting of a weather-resistant resin layer 4 and a stain-resistant resin layer 5 was laminated onto the surface of the heat-adhesive resin layer 3 so that the heat-adhesive resin layer 3 and the weather-resistant resin layer 4 faced each other, and the laminate was bonded by a heat lamination method to obtain a decorative sheet 10.

[0063] (Metal decorative components) A two-component urethane adhesive (coating amount in dry state: 25g / m²) is applied to a 1mm thick aluminum plate (metal substrate). 2 A metal decorative member was created by bonding a decorative sheet 10 to the metal plate via a ). The metal plate and the decorative sheet 10 were bonded together so that the aluminum plate and the sheet base material 1 of the decorative sheet 10 faced each other.

[0064] <Example 2> In the synthesis of the urethane resin that forms the binder resin for the pattern layer 2, neopentyl glycol was not used. Otherwise, the metal decorative member of Example 2 was obtained in the same manner as in Example 1. <Example 3> In the synthesis of the urethane resin that forms the binder resin for the pattern layer 2, neopentyl glycol was not used, and instead polypropylene glycol (PPG) was used as the polyalkylene glycol. Otherwise, the metal decorative member of Example 3 was obtained in the same manner as in Example 1. <Example 4> In the synthesis of the urethane resin that forms the binder resin for the pattern layer 2, xylylene diisocyanate (XDI) was used as the polyisocyanate. Otherwise, the metal decorative member of Example 4 was obtained in the same manner as in Example 1. <Example 5> In the synthesis of the urethane resin that forms the binder resin for the pattern layer 2, neopentyl glycol was not used, and xylylene diisocyanate was used as the polyisocyanate. Otherwise, the metal decorative member of Example 5 was obtained in the same manner as in Example 1. <Example 6> In the synthesis of the urethane resin that forms the binder resin for the pattern layer 2, polypropylene glycol was used as the polyalkylene glycol. Otherwise, the metal decorative member of Example 6 was obtained in the same manner as in Example 5. <Example 7> In the synthesis of the urethane resin that forms the binder resin for the pattern layer 2, neopentyl glycol was not used. Furthermore, a urethane resin with the same composition as the pattern layer 2 was used as a coating liquid to form the back surface primer layer. Otherwise, the metal decorative member of Example 7 was obtained in the same manner as in Example 1.

[0065] <Comparative Example 1> In the synthesis of the urethane resin that forms the binder resin for the pattern layer, polyalkylene glycol was not used. Otherwise, the metal decorative member of Comparative Example 1 was obtained in the same manner as in Example 1. <Comparative Example 2> In the synthesis of the urethane resin that forms the binder resin for the pattern layer, polycaprolactone polyol was not used. Otherwise, the metal decorative member of Comparative Example 2 was obtained in the same manner as in Example 1. <Comparative Example 3> In the synthesis of the urethane resin that forms the binder resin for the pattern layer, polycaprolactone polyol was not used, polypropylene glycol was used as the polyalkylene glycol, and neopentyl glycol was not used. Otherwise, the metal decorative member of Comparative Example 3 was obtained in the same manner as in Example 1.

[0066] [Evaluation Method] The metal decorative members using the decorative sheets obtained in the above examples and comparative examples were evaluated for substrate adhesion, moisture and heat resistance, and weather resistance using the following method. The composition of the decorative sheets and the evaluation results for the above examples and comparative examples are shown in Table 1. (a) Evaluation of adhesion to the substrate The T-shaped peel strength between the heat-adhesive resin layer and the sheet substrate was measured for samples of the metal decorative members of Examples 1-7 and Comparative Examples 1-3 that were stored at room temperature for 24 hours after fabrication (sample width: 25 mm, tensile speed: 5 mm / s). <Evaluation Criteria> ◎: The sheet substrate breaks without forming a peel interface. ○: Creates a peel surface while causing deformation in the sheet substrate. △: A peel surface is generated without deformation of the sheet substrate. ×: Peeling occurred during sample handling, making measurement impossible. In this example, a rating of "○" or higher was considered a passing grade.

[0067] (b) Evaluation of resistance to moisture and heat After fabricating the metal decorative members of Examples 1-7 and Comparative Examples 1-3, samples were stored at room temperature for 24 hours. A pressure cooker test was then performed using a HAST chamber (105°C, 100% RH, 192 hours), and the T-shaped peel strength between the heat-adhesive resin layer and the sheet substrate was measured (sample width: 25 mm, tensile speed: 5 mm / s). <Evaluation Criteria> ◎: The sheet substrate breaks without forming a peel interface. ○: Creates a peel surface while causing deformation in the sheet substrate. △: A peel surface is generated without deformation of the sheet substrate. ×: Peeling occurred during sample handling, making measurement impossible. In this example, a rating of "△" or higher was considered a passing grade.

[0068] (c) Weather resistance evaluation Using metal weathering materials, the following weather resistance tests were conducted. For the metal decorative members of Examples 1 to 7 and Comparative Examples 1 to 3, a test was conducted in which ultraviolet light was irradiated for 20 hours in the irradiation mode under the following conditions, followed by 4 hours of condensation in the condensation mode under the following conditions. This constituted one cycle (24 hours), and the test was repeated for 25 cycles (600 hours). • Illumination mode: Illuminance 65mW / cm 2(Measured with Ushio Unimeter UIT-101), black panel temperature 63°C, relative humidity 50%, 20 hours of irradiation. • Condensation mode: Ambient temperature 30°C, relative humidity 98%, 4 hours (10 seconds of shower spray before and after condensation mode) <Evaluation Criteria> After 600 hours, visual observation revealed: ○: No significant discoloration or peeling has occurred. △: Significant discoloration or peeling has occurred. ×: Significant discoloration and peeling have occurred. In this example, a rating of "○" or higher was considered a passing grade.

[0069] [Table 1]

[0070] As can be seen from Table 1, in the decorative sheets of Examples 1 to 7, the urethane resin, which is the binder resin that forms the pattern layer, is composed of three components: polycaprolactone polyol, polyalkylene glycol, and polyisocyanate. As a result, the metal decorative members to which the decorative sheets of Examples 1-7 were applied showed good adhesion to the substrate, good resistance to humidity and heat (passed), and also good weather resistance (passed). Furthermore, compared to Example 2, the metal decorative member to which the decorative sheet of Example 1 was applied exhibited better humidity and heat resistance. This is because the urethane resin forming the pattern layer contains neopentyl glycol in addition to the three components mentioned above, resulting in improved humidity and heat resistance. Furthermore, in the metal decorative member to which the decorative sheet of Example 7 was applied, good substrate adhesion and moisture and heat resistance were observed, similar to Example 1, even without containing neopentyl glycol. This is because the primer layer contains a urethane resin with the same composition as the pattern layer, which improved substrate adhesion and moisture and heat resistance.

[0071] On the other hand, as in Comparative Examples 1 to 3, when the urethane resin, which is the binder resin forming the pattern layer, does not contain all three components: polycaprolactone polyol, polyalkylene glycol, and polyisocyanate, at least one of the substrate adhesion and moisture and heat resistance is reduced compared to the metal decorative members of each example, and weather resistance is also reduced.

[0072] Specifically, as in Comparative Example 1, when polyalkylene glycol was not used in the synthesis of the urethane resin that forms the binder resin for the pattern layer, the evaluation of humidity and heat resistance and weather resistance was reduced compared to the metal decorative members of each example. Furthermore, as in Comparative Examples 2 and 3, when polycaprolactone polyol was not used in the synthesis of the urethane resin that forms the binder resin for the pattern layer, the evaluation of substrate adhesion and weather resistance was reduced compared to the metal decorative members of each example. In Comparative Example 3, since neither polycaprolactone polyol nor neopentyl glycol was used in the synthesis of the urethane resin, the evaluation of moisture and heat resistance was also reduced compared to the metal decorative members of each example. [Industrial applicability]

[0073] This disclosure is a technology suitable for building exteriors and semi-exterior building materials, namely entrance doors, their frames, window frames and bay window counters, as well as surface decorative materials for building interiors, partitions, storage furniture, etc., and decorative sheets and metal decorative components that require durability against high temperatures and humidity, such as in bathrooms. [Explanation of symbols]

[0074] 1 sheet substrate 2 Image Layers 3 Heat adhesive resin layer 4 Weather-resistant resin layer 5. Stain-resistant resin layer 6.26 Primer layer 8 Adhesive layer 9 Metal substrate 10, 20 decorative sheets 100, 101 Metal decorative components

Claims

1. The material comprises a sheet substrate, and a pattern layer, a heat-adhesive resin layer, a weather-resistant resin layer, and a stain-resistant resin layer containing a fluororesin or ethylene vinyl alcohol copolymer resin, which are sequentially laminated on the sheet substrate. The weather-resistant resin layer contains a mixture of acrylic resin and acrylic resin-based rubber, and at least one ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers, wherein the amount of ultraviolet absorber added is 0.2% by mass or more and 0.8% by mass or less, relative to the total mass amount of the mixture of acrylic resin and acrylic resin-based rubber. The mass ratio of the acrylic resin to the acrylic resin-based rubber is in the range of 40:60 to 70:

30. The total thickness is 200 μm or less, and the combined thickness of the weather-resistant resin layer and the stain-resistant resin layer is 20 μm or more and 80 μm or less. The aforementioned pattern layer contains a urethane resin as a binder resin, which includes polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as constituent elements. In the urethane resin, the sum of the content of the polycaprolactone polyol and the content of the polyalkylene glycol is greater than the content of the polyisocyanate. A decorative sheet characterized by the following features.

2. The aforementioned urethane resin further comprises neopentyl glycol. The decorative sheet according to feature 1.

3. The polyalkylene glycol is polytetramethylene glycol. A decorative sheet according to claim 1 or 2.

4. The polyisocyanate is isophorone diisocyanate. A decorative sheet according to any one of claims 1 to 3.

5. The sheet substrate further comprises a primer layer provided on the side opposite to the pattern layer, The primer layer contains the urethane resin as a binder resin. A decorative sheet according to any one of claims 1 to 4.

6. The primer layer contains the urethane resin having the same configuration as the pattern layer. The decorative sheet according to feature 5.

7. The aforementioned heat-adhesive resin layer is formed of an acrylic-polyester-vinyl chloride / vinyl acetate copolymer resin. A decorative sheet according to any one of claims 1 to 6.

8. The blending ratio of acrylic resin, polyester resin, and vinyl chloride resin in the aforementioned acrylic-polyester-vinyl chloride / vinyl acetate copolymer resin is 20% to 50% by mass for acrylic resin, 20% to 50% by mass for polyester resin, and 20% to 50% by mass for vinyl chloride resin. The decorative sheet according to feature 7.

9. A metal decorative member characterized in that a decorative sheet described in any one of claims 1 to 8 is bonded to a metal substrate.

Images