Decorative member and method for manufacturing same

Abstract

The present disclosure provides a decorative member having a metal base material and a design layer in the stated order in the thickness direction, wherein the design layer contains an organic colorant, and the decorative member has, on a first surface positioned on the design-layer side with reference to the metal base material, a region X having a flop index of 4.5 or higher.

Description

Decorative member and manufacturing method thereof

[0001] The present disclosure relates to decorative members and methods for producing the same.

[0002] For example, decorative materials in which a metal substrate and a design layer are laminated in the thickness direction are known as interior or exterior components for buildings. For example, Patent Document 1 discloses a decorative material having a texture region on a metal substrate where a plurality of independent protrusions are aggregated, and the protrusions contain a resin binder and glittering flake particles.

[0003] International Publication No. 2022 / 209543

[0004] In decorative components using a metal substrate, unique designs can be created by taking advantage of the glossiness of the metal substrate, and by utilizing these unique designs, the range of design expression can be expanded. On the other hand, if the design layer excessively conceals the glossiness of the metal substrate, it may be difficult to fully utilize the glossiness of the metal substrate. Conversely, if emphasis is placed on utilizing the glossiness of the metal substrate, it may be necessary to limit the concealment of the glossiness by the design layer, which may narrow the range of design expression.

[0005] The present disclosure has been made in consideration of the above-mentioned circumstances, and has as its main object to provide a decorative member that can express a wide range of designs while making use of the glossiness of a metal substrate.

[0006] The present disclosure provides a decorative element having a metal substrate and a design layer, in that order in the thickness direction, wherein the design layer contains an organic colorant, and the decorative element has a region X on a first surface located on the design layer side relative to the metal substrate, where the flop index is 4.5 or greater.

[0007] The present disclosure also provides a method for manufacturing a decorative member, which manufactures the above-mentioned decorative member, and which includes a metal substrate preparation step for preparing the metal substrate, and a design layer formation step for forming the design layer by applying a composition containing the organic colorant to one side of the metal substrate and heating and curing the composition.

[0008] The present disclosure has the effect of providing a decorative member that can express a wide range of designs while taking advantage of the glossiness of a metal substrate.

[0009] FIG. 1 is a schematic cross-sectional view illustrating a decorative member according to the present disclosure. FIG. 2 is a schematic cross-sectional view illustrating a decorative member according to the present disclosure. FIG. 3 is a schematic cross-sectional view illustrating a method for manufacturing a decorative member according to the present disclosure. FIG. 4 is a graph showing the results of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4. FIG. 5 is a graph showing the results of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-4. FIG. 6 is a graph showing the results of Examples 3-1 to 3-4. FIG. 7 is a graph showing the results of Examples 4-1 to 4-4.

[0010] Below, embodiments will be described with reference to the drawings etc. However, the present disclosure can be implemented in many different forms and should not be limited to the description of the embodiments exemplified below. Furthermore, to make the explanation clearer, the drawings may show the width, thickness, and shape of each part schematically compared to the actual form, but this is merely an example and should not be interpreted as limiting.

[0011] In this specification, when describing a mode in which another component is disposed on a certain component, the term "above" or "below" refers to both a case in which another component is disposed directly above or below the certain component so as to be in contact with the component, and a case in which another component is disposed above or below the certain component with another component interposed therebetween, unless otherwise specified. Also, in this specification, when describing a mode in which another component is disposed on the surface of a certain component, the term "on the surface" refers to both a case in which another component is disposed directly above or below the certain component so as to be in contact with the component, and a case in which another component is disposed above or below the certain component with another component interposed therebetween, unless otherwise specified.

[0012] The decorative member and the method for manufacturing the decorative member according to the present disclosure will be described in detail below.

[0013] 1 and 2 are schematic cross-sectional views illustrating examples of decorative members in the present disclosure. The decorative member 10 shown in FIG. 1 is a metal substrate 1 and a decorative layer 2 arranged in a thickness direction D. ＴThe decorative member 10 has, in this order, a first surface S located on the decorative layer 2 side with respect to the metal substrate 1. １ 2, the decorative member 10 has a region X where the flop index is 4.5 or more. As shown in FIG. 2, the decorative member 10 has a metal substrate 1, a primer layer 3, a base layer 4, a design layer 2, and a surface protective layer 5 arranged in a thickness direction D. Ｔ In this order,

[0014] According to the present disclosure, the decorative layer contains an organic colorant, and the flop index on the first surface is 4.5 or higher, resulting in a decorative component that can express a wide range of designs while taking advantage of the glossiness of the metal substrate. As described above, decorative components using metal substrates can create unique designs by taking advantage of the glossiness of the metal substrate, and by utilizing these unique designs, the range of design expressions can be expanded. In other words, design expressions that take advantage of the natural characteristics of the metal substrate, more specifically, metallic design expressions that vary greatly in lightness, saturation, and hue depending on the viewing angle, are possible.

[0015] On the other hand, if the design layer excessively conceals the glossiness of the metal substrate, it may be difficult to fully utilize the glossiness of the metal substrate. Conversely, if emphasis is placed on utilizing the glossiness of the metal substrate, it may be necessary to limit the concealment of the glossiness by the design layer, which may narrow the range of design expression. For example, when an inorganic colorant is used, increasing the proportion of the inorganic colorant (increasing the color) increases the concealing ability of the design layer, making it difficult to fully utilize the glossiness of the metal substrate. On the other hand, if emphasis is placed on utilizing the glossiness of the metal substrate, it becomes difficult to increase the proportion of the inorganic colorant (increasing the color), narrowing the range of design expression.

[0016] In contrast, in the present disclosure, the design layer contains an organic colorant, enabling design expression with high brightness and saturation (diverse color expression) without excessively concealing the glossiness of the metal substrate. Specifically, it is possible to reproduce design expressions such as brass, copper, corrosion patterns, and polished patterns at a higher level than before. Furthermore, in the present disclosure, the flop index on the first surface is 4.5 or higher, allowing the glossiness of the metal substrate to be fully utilized. Conventional color difference evaluation is significantly affected by the glossiness of the surface of the decorative member, making it difficult to quantitatively evaluate the glossiness of the metal substrate. In contrast, in the present disclosure, by focusing on the flop index, it is possible to quantitatively evaluate the glossiness of the metal substrate without being significantly affected by the glossiness of the surface of the decorative member.

[0017] 1. Flop Index As shown in FIG. 1, the decorative member of the present disclosure has a first surface S located on the side of the design layer 2 with respect to the metal substrate 1 as a reference. １ , there is a region X where the flop index is 4.5 or more.

[0018] The glossiness of a metal substrate changes significantly in lightness, saturation, and hue depending on the position and angle of light reception and observation. The characteristic of this change is called flop, and the flop index is an index that quantitatively evaluates the flop. The flop index is calculated by the L at effective angles of 15°, 45°, and 110°. ＊ (L ＊ １５ , L ＊ ４５ , L ＊ １１０ ) and calculated using the following formula: Flop index = 2.69 × (L ＊ １５ -L ＊ １１０ ) １．１１ / (L ＊ ４５ ) ０．８５ The method for measuring the flop index will be described in detail in the examples below.

[0019] The flop index in region X may be 5 or more, 6 or more, 7 or more, or 8 or more. When viewed in the thickness direction, region X is usually a region containing an organic colorant.

[0020] When the decorative material is viewed from the design layer side, the area of ​​the design layer is S Ａ Let the area of ​​the region X be S Ｂ Let's say. Ａ S against Ｂ The ratio (S Ｂ / S Ａ ) is, for example, 1% or more, may be 3% or more, or may be 5% or more. Ｂ / S Ａ Although it depends on the design of the design layer, it may be 100% or less. In the latter case, the design will have an area (area X) that makes the most of the glossiness of the metal substrate and an area (area Y that does not correspond to area X) that does not make the most of the glossiness of the metal substrate. Ｂ / S Ａ may be 80% or less, or may be 60% or less.

[0021] The design layer in the present disclosure is a layer that imparts design to the decorative member and contains an organic colorant. The design layer may be a design layer having a design (pattern), a solid layer (a layer coated with ink), or a combination of a design layer and a solid layer.

[0022] Examples of patterns in the design layer include wood grain patterns, marble patterns, stone patterns, sand patterns, tile patterns, brickwork patterns, fabric patterns, leather-striped patterns, geometric shapes, letters, symbols, abstract patterns, floral patterns, wave patterns, striped patterns, metallic patterns, and rust-like patterns.

[0023] The design layer contains an organic colorant (organic pigment or organic dye), such as a perylene-based colorant, a cyanine-based colorant, a nickel-azo complex-based colorant, an azomethine-based colorant, a quinacridone-based colorant, or an isoindolinone-based colorant.

[0024] The average particle size of the organic colorant is, for example, 100 μm to 350 μm, or may be 200 μm to 300 μm. In this specification, the average particle size refers to the 50% particle size (d50: median diameter) when the particle size distribution measured by a dynamic light scattering method is expressed as a volume cumulative distribution. Furthermore, the content of the organic colorant in the layer containing the organic colorant is, for example, 1 part by mass to 40 parts by mass per 100 parts by mass of the resin component.

[0025] On the other hand, the design layer may contain an inorganic colorant (inorganic pigment or inorganic dye). Examples of inorganic colorants include carbon black, iron black, titanium white, antimony white, titanium yellow, yellow iron oxide, red iron oxide, cadmium red, ultramarine blue, and cobalt blue. The design layer may also contain metallic colorants such as aluminum and brass; or pearl colorants such as titanium dioxide-coated mica and basic lead carbonate.

[0026] The design layer contains a resin. The resin contained in the design layer is preferably a cured product (crosslinked structure) of a curable resin, and more preferably a cured product of a thermosetting resin. Examples of resins contained in the design layer include fluorine-based resins, epoxy-based resins, phenol-based resins, urea-based resins, polyester-based resins, melamine-based resins, alkyd-based resins, amide-based resins, polyimide-based resins, silicone-based resins, acrylic-based resins, urethane-based resins, urethane-acrylic resins, styrene-based resins, and cellulose-based resins. Among these, fluorine-based resins are preferred as the curable resin because they have good weather resistance. Examples of fluorine-based resins include fluoroethylene-vinyl ether copolymers, fluoroethylene-vinyl ester copolymers, and fluoroethylene-acrylic copolymers.

[0027] The resin contained in the design layer may be a cured product of a resin composition containing a curable resin and a curing agent. Examples of the curing agent include isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID), and xylylene diisocyanate (XDI). The ratio of the curing agent to 100 parts by mass of the curable resin is not particularly limited, but may be, for example, 30 parts by mass or more and 70 parts by mass or less, or 35 parts by mass or more and 65 parts by mass or less. The design layer may also contain additives such as weathering agents. Details of the weathering agents will be described later.

[0028] The design layer may have a single layer structure or a laminated structure of two or more layers. The design layer preferably has a pattern layer containing an organic colorant. The pattern layer containing an organic colorant may be one layer or two or more layers. The design layer may also have a solid layer containing an organic colorant. The solid layer containing an organic colorant may be one layer or two or more layers. The design layer has at least a layer containing an organic colorant, but may also have a layer containing an inorganic colorant. The layer containing an inorganic colorant may be a pattern layer containing an inorganic colorant, a solid layer containing an inorganic colorant, or both. The pattern layer containing an inorganic colorant and the solid layer containing an inorganic colorant may each be one layer or two or more layers.

[0029] The design layer may have, in the thickness direction from the metal substrate side, a layer containing an inorganic colorant and a layer containing an organic colorant, in this order. The layer containing an inorganic colorant and the layer containing an organic colorant may each independently be a solid layer or a pattern layer. For example, by providing a solid layer containing an inorganic colorant, the color of the metal substrate can be adjusted. Alternatively, by overlapping a pattern layer containing an inorganic colorant with a pattern layer containing an organic colorant, the layer containing the organic colorant can be used to maintain the glossiness of the metal substrate, while the layer containing the inorganic colorant can be used to provide a partial concealing area, allowing for complex design expression.

[0030] Similarly, the design layer may have, in the thickness direction from the metal substrate side, a layer containing an organic colorant and a layer containing an inorganic colorant, in that order. In this case, the layer containing the organic colorant and the layer containing the inorganic colorant may each independently be a solid layer or a pattern layer. Furthermore, the design layer may have a layer containing both an organic colorant and an inorganic colorant. Note that the design layer does not necessarily have a layer containing an inorganic colorant.

[0031] The design layer is preferably a baked layer. The baked layer is a layer formed by heat-curing (baking coating) the applied composition, and is a layer different from the design layer attached via an adhesive layer, for example. The thickness of the design layer is not particularly limited, but may be, for example, 1 μm to 10 μm, or 3 μm to 7 μm. When the design layer has multiple layers, it is preferable that the total thickness of the multiple layers is within the above range.

[0032] 3. Metal Substrate The metal substrate in the present disclosure is a substrate containing a metal element. Examples of the metal element contained in the metal substrate include aluminum, iron, copper, and titanium. The metal substrate preferably contains the above metal element as a main component.

[0033] The metal substrate may be a simple metal containing one type of metal element, or an alloy containing two types of metal elements. The metal substrate may also contain a carbon component. Specific examples of the metal substrate include aluminum substrates, aluminum alloy substrates (e.g., duralumin substrates), steel substrates (steel substrates), stainless steel substrates, copper substrates, copper alloy substrates (e.g., brass substrates, bronze substrates), titanium substrates, and titanium alloy substrates. The surface of the metal substrate may be plated.

[0034] The shape of the metal substrate is not particularly limited, but may be, for example, a plate. The plate-shaped metal substrate may be bent. The thickness of the metal substrate is not particularly limited, but may be, for example, 0.02 mm to 5 mm, and may be, for example, 0.4 mm to 3 mm.

[0035] 4. Primer Layer The decorative member according to the present disclosure may have a primer layer between the metal substrate and the decorative layer. By providing the primer layer, the adhesion between the two layers adjacent to the primer layer is improved.

[0036] The primer layer contains a resin. The resin contained in the primer layer is preferably a cured product (crosslinked structure) of a curable resin, and more preferably a thermosetting resin. Examples of resins contained in the primer layer include urethane-based resins, acrylic polyol-based resins, acrylic resins, ester-based resins, amide-based resins, butyral-based resins, styrene-based resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers (urethane-acrylic copolymers derived from polymers (polycarbonate polyols) having carbonate bonds in the polymer main chain and two or more hydroxyl groups at the terminals and side chains), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene-based resins, nitrocellulose-based resins (nitrocellulose), cellulose acetate-based resins, and fluorine-based resins.

[0037] The resin contained in the primer layer may be a cured product of a resin composition containing a curable resin and a curing agent. Examples of the curing agent include isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID), and xylylene diisocyanate (XDI). The primer layer may also contain additives such as weathering agents. Details of the weathering agents will be described later.

[0038] The primer layer is preferably a baked layer. The thickness of the primer layer is not particularly limited, but may be, for example, from 1 μm to 10 μm, or from 2 μm to 5 μm.

[0039] 5. Underlayer The decorative member of the present disclosure may have an underlayer between the metal substrate and the design layer. For example, by providing an underlayer, the glossiness of the metal substrate can be adjusted. To maximize the glossiness of the metal substrate, the underlayer is usually a transparent layer (colored transparent or colorless transparent).

[0040] The underlayer contains a resin. The resin contained in the underlayer is preferably a cured product (crosslinked structure) of a curable resin, and more preferably a cured product of a thermosetting resin. The curable resin is preferably a fluorine-based resin, as this has good weather resistance. The underlayer may or may not contain a colorant. The underlayer may also contain an inorganic colorant. The curable resin and colorant are the same as the curable resin used in the design layer described above, and therefore a description thereof will be omitted here. The underlayer may also contain an additive such as a weather resistant agent. Details of the weather resistant agent will be described later.

[0041] The underlayer is preferably a baked layer. The thickness of the underlayer is not particularly limited, but may be, for example, 5 μm to 40 μm, or 10 μm to 30 μm.

[0042] 6. Surface Protective Layer The decorative member according to the present disclosure may have a surface protective layer on the opposite side of the decorative layer from the metal substrate. By providing the surface protective layer, for example, the scratch resistance of the decorative member can be improved.

[0043] The surface protective layer contains a resin. The resin contained in the surface protective layer is preferably a cured product (crosslinked structure) of a curable resin, and more preferably a cured product of a thermosetting resin. The curable resin is preferably a fluorine-based resin, as this has good weather resistance. The surface protective layer may also contain a colorant. The curable resin and colorant are the same as the curable resin used in the design layer described above, and therefore will not be described here.

[0044] The surface protective layer may contain one or more fillers. An example of the filler is an organic filler. Examples of the organic filler include resin fillers such as acrylic resins, urethane resins, nylon resins, olefin resins, and urea resins. Among these, acrylic resin fillers (acrylic beads) are preferred. This is because acrylic resin fillers have good heat resistance and are less restricted in terms of production. Meanwhile, other examples of fillers include inorganic fillers. Examples of inorganic fillers include silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, and synthetic silicates.

[0045] The average particle size of the filler is, for example, 5 μm or more and 60 μm or less, or may be 10 μm or more and 50 μm or less, or may be 20 μm or more and 40 μm or less.

[0046] The surface protective layer preferably contains a weather-resistant agent. Since the organic colorant contained in the design layer generally has low weather resistance, while inorganic colorants generally have low weather resistance, it is preferable that the surface protective layer has sufficient weather resistance. Examples of the weather-resistant agent include an ultraviolet absorber and a light stabilizer.

[0047] Examples of the ultraviolet absorber include organic ultraviolet absorbers such as triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, oxybenzophenone-based ultraviolet absorbers, salicylic acid ester-based ultraviolet absorbers, and cyano(meth)acrylate-based ultraviolet absorbers, and inorganic ultraviolet absorbers such as titanium dioxide, cerium oxide, and zinc oxide. Among these, triazine-based ultraviolet absorbers are preferred.

[0048] Examples of triazine-based ultraviolet absorbers include hydroxyphenyltriazine-based ultraviolet absorbers, such as 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine. azine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5[2-(2-ethylhexanoyloxy)ethoxy]phenol.

[0049] The content of the ultraviolet absorber in the surface protective layer is, for example, 0.5 parts by mass to 10 parts by mass, or alternatively, 0.8 parts by mass to 8 parts by mass, or alternatively, 1 part by mass to 5 parts by mass, relative to 100 parts by mass of the resin component. If the content of the ultraviolet absorber is too high, bleeding out of the ultraviolet absorber may occur, whereas if the content of the ultraviolet absorber is too low, sufficient ultraviolet absorption performance may not be obtained.

[0050] On the other hand, examples of the light stabilizer include hindered amine light stabilizers, such as 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine).

[0051] The content of the light stabilizer in the surface protective layer is, for example, 1 part by mass to 10 parts by mass, or alternatively 1.5 parts by mass to 8 parts by mass, or alternatively 2 parts by mass to 5 parts by mass, relative to 100 parts by mass of the resin component. If the content of the light stabilizer is too high, bleed-out of the light stabilizer may occur, whereas if the content of the light stabilizer is too low, sufficient light stability may not be obtained.

[0052] The surface protection layer is preferably a baked layer. The thickness of the surface protection layer is not particularly limited, but may be, for example, from 5 μm to 40 μm, or from 10 μm to 30 μm.

[0053] 7. Decorative Member The decorative member of the present disclosure has a metal substrate and a decorative layer, in this order in the thickness direction. The decorative member may further have at least one of the above-mentioned primer layer, undercoat layer, and surface protection layer. The layer structure of the decorative member of the present disclosure is not particularly limited, but examples include the following layer structures. The symbol " / " indicates the boundary between each layer. Furthermore, the two members separated by the symbol " / " may be arranged in direct contact with each other, or may be arranged with another member interposed therebetween.

[0054] (1) Metal substrate / design layer (2) Metal substrate / primer layer / design layer (3) Metal substrate / base layer / design layer (4) Metal substrate / primer layer / base layer / design layer (5) Metal substrate / design layer / surface protective layer (6) Metal substrate / primer layer / design layer / surface protective layer (7) Metal substrate / base layer / design layer / surface protective layer (8) Metal substrate / primer layer / base layer / design layer / surface protective layer

[0055] The decorative member of the present disclosure may have multiple protrusions (raised portions) on a first surface located on the design layer side of the metal substrate. The protrusions preferably contain at least one of a filler and a colorant, and a binder resin that aggregates the filler and the colorant. The type of colorant is not particularly limited, but examples include pearlescent colorants. The average height of the protrusions is, for example, 10 μm to 60 μm, or 15 μm to 45 μm, or 25 μm to 35 μm. The average height of the protrusions is calculated, for example, as the arithmetic average of the heights of 100 or more protrusions.

[0056] The use of the decorative member in the present disclosure is not particularly limited. It may be used as an interior member (an indoor member) or an exterior member (an outdoor member). Examples of uses of the decorative member include architectural members such as walls, floors, ceilings, roofs, balcony screens, and eaves; fittings such as partitions, doors, window frames, handrails, trim, entrance doors, and moldings; components of vehicles such as automobiles and trains; bathroom products such as modular baths; furniture; home appliances; and kitchen products.

[0057] B. Manufacturing Method of Decorative Member FIG. 3 is a schematic cross-sectional view illustrating a manufacturing method of a decorative member according to the present disclosure. First, as shown in FIG. 3(a), a metal substrate 1 is prepared (metal substrate preparation step). Next, as shown in FIG. 3(b), a primer layer 3 is formed on one side of the metal substrate 1 (primer layer formation step). Next, as shown in FIG. 3(c), a base layer 4 is formed on the side of the primer layer 3 opposite the metal substrate 1 (base layer formation step). Next, as shown in FIG. 3(d), a composition containing an organic colorant is applied to the side of the base layer 4 opposite the primer layer 3, and the applied composition is heat-cured to form a design layer 2 (design layer formation step). Next, as shown in FIG. 3(e), a surface protection layer 5 is formed on the side of the design layer 2 opposite the base layer 4 (surface protection layer formation step). This results in a decorative member 10. The decorative member 10 has a first surface S located on the side of the design layer 2 relative to the metal substrate 1. １ The flop index is 4.5 or greater.

[0058] According to the present disclosure, a decorative layer is formed using a composition containing an organic colorant, and the flop index on the first surface is 4.5 or more, thereby making it possible to obtain a decorative component that can express a wide range of designs while taking advantage of the glossiness of the metal substrate.

[0059] 1. Metallic Substrate Preparation Step The method for producing a decorative member according to the present disclosure includes a metallic substrate preparation step of preparing a metallic substrate. The metallic substrate is the same as that described above in "A. Decorative member."

[0060] 2. Primer Layer Forming Step The method for producing a decorative member according to the present disclosure may include a primer layer forming step of forming a primer layer on one surface of the metal substrate. In the primer layer forming step, the primer layer may be formed directly on one surface of the metal substrate, or may be formed via another layer.

[0061] The primer layer can be formed, for example, by applying a primer layer composition and then heat-curing the applied composition. Examples of the composition application method include roll coating, reverse coating, air spray coating, electrostatic coating, and powder coating. When viewed in the thickness direction, the primer layer is formed, for example, over the entire surface of the metal substrate. The heating temperature (substrate temperature) is, for example, 100°C or higher and 300°C or lower.

[0062] The method for producing a decorative member according to the present disclosure may include a step of forming a base layer on one surface of the metal substrate. In the step of forming a base layer, the base layer may be formed directly on one surface of the metal substrate, or may be formed via another layer such as the primer layer described above.

[0063] Examples of methods for forming the underlayer include coating a composition for the underlayer and then heat-curing the coating. Examples of methods for applying the composition include flow coating, roll coating, reverse coating, air spray coating, electrostatic coating, and powder coating. When viewed in the thickness direction, the underlayer is formed, for example, so as to cover the entire surface of the metal substrate. The heating temperature (substrate temperature) is, for example, 150°C or higher and 300°C or lower, and may be 200°C or higher and 250°C or lower.

[0064] The method for manufacturing a decorative member according to the present disclosure includes a design layer forming step in which a composition containing an organic colorant is applied to one side of a metal substrate and then heat-cured to form a design layer. In the design layer forming step, the design layer may be formed directly on one side of the metal substrate, or may be formed via another layer such as the primer layer or undercoat layer described above.

[0065] Examples of methods for forming the design layer include coating a composition for the design layer and heat-curing it. Examples of methods for applying the composition include gravure printing, offset printing, gravure-offset printing, flexographic printing, letterpress printing, screen printing, inkjet printing, and transfer printing. When viewed in the thickness direction, the design layer may be formed so as to cover the entire surface of the metal substrate, or may be formed so as to cover a portion of the metal substrate. The heating temperature (substrate temperature reached) may be, for example, 150°C or higher and 300°C or higher, or 200°C or higher and 250°C or lower. Furthermore, when a process for forming other layers, such as a surface protection layer described below, is performed as a later process, heat-curing to form the design layer may be performed before the later process, or may be performed simultaneously with heat-curing to form other layers in the later process.

[0066] 5. Surface Protective Layer Forming Step The method for producing a decorative member according to the present disclosure may include a surface protective layer forming step of forming a surface protective layer on the side of the decorative layer opposite the metal substrate. In the surface protective layer forming step, the surface protective layer may be formed directly on the side of the decorative layer opposite the metal substrate, or may be formed via another layer.

[0067] Examples of methods for forming the surface protective layer include a method of applying a composition for the surface protective layer and then heat-curing the applied composition. Examples of methods for applying the composition include flow coating, roll coating, reverse coating, air spray coating, electrostatic coating, and powder coating. When viewed in the thickness direction, the surface protective layer is formed so as to cover the entire surface of the metal substrate. The heating temperature (substrate temperature) may be, for example, 150°C or higher and 300°C or lower, or 200°C or higher and 250°C or lower.

[0068] 6. Decorative Member The decorative member obtained by the above-described steps is the same as that described above in "A. Decorative Member."

[0069] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included within the technical scope of the present disclosure.

[0070] [Example 1-1] An aluminum plate (A3004PH32, dimensions: 300 mm × 600 mm, thickness: 1.0 mm, chromate-treated) was prepared as a metal substrate. Next, as a pretreatment, the prepared aluminum plate was washed with hot water and then dried at 150°C (the temperature reached by the substrate).

[0071] Next, the following composition for the underlayer was applied to the entire surface of the aluminum plate using a curtain flow coater so that the film thickness after drying would be 18 μm. Then, the underlayer was formed by baking at 216°C (substrate temperature). (Composition for the underlayer) Thermosetting fluororesin (fluoroethylene-vinyl ether copolymer) Curing agent (isocyanate) Gray colorant (titanium oxide, chromium oxide; 5% by mass relative to the thermosetting fluororesin) Solvent (xylene:toluene = 1:1, mass ratio) Solid content: 17% by mass

[0072] Next, the entire surface of the underlayer was coated with the following composition for the design layer by gravure offset printing so that the film thickness after drying would be 0.5 μm or more and 1.5 μm or less. (Composition for the design layer) Thermosetting fluororesin (fluoroethylene-vinyl ether copolymer) Curing agent (isocyanate) Organic colorant (a three-color blend of perylene pigment (red), cyanine pigment (blue), and nickel azo complex pigment (yellow); 15% by mass relative to the thermosetting fluororesin) Solvent (xylene:cyclohexane = 1:1, mass ratio) Solids concentration: 19% by mass

[0073] Next, the following composition A for the surface protective layer was applied to the entire surface of the design layer using a bar coater so that the film thickness after drying would be 19 μm. The coating was then baked at 224°C (the temperature reached by the substrate material) to form a surface protective layer, and a decorative member was obtained. The resulting surface protective layer is referred to as surface protective layer A. (Composition A for the surface protective layer) Thermosetting fluororesin (fluoroethylene-vinyl ether copolymer) Curing agent (isocyanate) Solvent (xylene:toluene = 1:1, mass ratio) Solid content: 30 mass%

[0074] [Example 1-2] A decorative member was obtained in the same manner as in Example 1-1, except that the following composition B for the surface protective layer was used instead of composition A for the surface protective layer. The obtained surface protective layer is referred to as surface protective layer B. (Composition B for the surface protective layer) Thermosetting fluororesin (fluoroethylene-vinyl ether copolymer) Curing agent (isocyanate) Filler (silica, average particle size 1 μm; 10% by mass relative to the thermosetting fluororesin) Solvent (xylene:toluene = 1:1, mass ratio) Solid content: 30% by mass

[0075] Example 1-3 A decorative member was obtained in the same manner as in Example 1-1, except that the following composition C for the surface protective layer was used instead of composition A for the surface protective layer. The obtained surface protective layer is referred to as surface protective layer C. (Composition C for the surface protective layer) Thermosetting fluororesin (fluoroethylene-vinyl ether copolymer) Curing agent (isocyanate) Filler (silica, average particle size 1 μm; 10% by mass relative to the thermosetting fluororesin) Filler (acrylic beads, average particle size 10 μm; 4% by mass relative to the thermosetting fluororesin) Filler (acrylic beads, average particle size 30 μm; 2% by mass relative to the thermosetting fluororesin) Solvent (xylene:toluene=1:1, mass ratio) Solids concentration: 30% by mass

[0076] [Example 1-4] A decorative member was obtained in the same manner as in Example 1-1, except that the following composition D for the surface protective layer was used instead of composition A for the surface protective layer. The obtained surface protective layer is referred to as surface protective layer D. (Composition D for Surface Protective Layer) Thermosetting fluororesin (fluoroethylene-vinyl ether copolymer) Curing agent (isocyanate) Filler (silica, average particle size 1 μm; 10% by mass relative to the thermosetting fluororesin) Filler (acrylic beads, average particle size 30 μm; 4% by mass relative to the thermosetting fluororesin) Filler (acrylic beads, average particle size 50 μm; 2% by mass relative to the thermosetting fluororesin) Solvent (xylene:toluene = 1:1, mass ratio) Solid content concentration... 30% by mass

[0077] [Examples 2-1 to 2-4] Decorative members were obtained in the same manner as in Examples 1-1 to 1-4, except that only a perylene pigment (red) was used as the organic colorant contained in the composition for the design layer.

[0078] Examples 3-1 to 3-4 Decorative members were obtained in the same manner as in Examples 1-1 to 1-4, except that only a cyanine pigment (blue) was used as the organic colorant contained in the composition for the design layer.

[0079] [Examples 4-1 to 4-4] Decorative members were obtained in the same manner as in Examples 1-1 to 1-4, except that only a nickel azo complex pigment (yellow) was used as the organic colorant contained in the composition for the design layer.

[0080] [Comparative Examples 1-1 to 1-4] Decorative members were obtained in the same manner as in Examples 1-1 to 1-4, except that an inorganic colorant (a three-color blend of iron oxide pigment (red), cobalt pigment (blue), and iron oxide pigment (yellow)) was used instead of the organic colorant contained in the composition for the design layer.

[0081] [Comparative Examples 2-1 to 2-4] Decorative members were obtained in the same manner as in Examples 1-1 to 1-4, except that an iron oxide pigment (red) was used instead of the organic colorant contained in the composition for the design layer.

[0082] [Evaluation] The decorative members obtained in each Example and Comparative Example were used to measure the flop index. Specifically, the decorative members were placed horizontally with the surface protective layer facing up, and the lightness index L was measured using a three-dimensional goniospectrophotometric colorimeter (manufactured by Murakami Color Research Laboratory, model number GCMS-4). ＊ The measurement conditions were an incident angle of 45°, a tilt angle of 0°, an in-plane rotation angle of 0°, a light source of D65, and L at light receiving angles of 30°, 0°, and -65°. ＊ The flop index was then calculated using the following formula. The results are shown in Tables 1 and 2. Flop index = 2.69 × (L ＊ １５ -L ＊ １１０ ) １．１１ / (L ＊ ４５ ) ０．８５ (L＊ １５ is L at an acceptance angle of 30° ＊ This corresponds to L ＊ ４５ is L at an acceptance angle of 0° ＊ This corresponds to L ＊ １１０ is L at an acceptance angle of -65° ＊ (corresponding to

[0083]

[0084]

[0085] As shown in Table 1, in each example, the flop index was high, and it was confirmed that the glossiness of the metal substrate was well expressed. Furthermore, because an organic colorant was used, it was possible to suppress concealment of the glossiness by the design layer while still achieving a vivid design. In contrast, as shown in Table 2, in each comparative example, the flop index was low, and it was confirmed that the glossiness of the metal substrate was not well expressed. This is presumably because the use of an inorganic colorant resulted in significant concealment of the glossiness by the design layer.

[0086] FIG. 4 is a graph showing the results of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4. The triangles in FIG. 4 represent the flop indexes of samples prepared in the same manner as Examples 1-1 to 1-4 except that no design layer was formed. The same applies to the triangles in FIGS. 5 to 7 described below. As shown in FIG. 4, Examples 1-1 to 1-4 had higher flop indexes than Comparative Examples 1-1 to 1-4, confirming that the glossiness of the metal substrate was well expressed. Furthermore, when comparing Examples 1-1 to 1-4, it was confirmed that the flop index was less affected by the glossiness of the first surface (the surface of the surface protective layer) and that the glossiness of the metal substrate could be accurately evaluated.

[0087] FIG. 5 is a graph showing the results of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-4. As shown in FIG. 5, Examples 2-1 to 2-4 had a higher flop index than Comparative Examples 2-1 to 2-4, confirming that the glossiness of the metal substrate was well expressed. FIG. 6 is a graph showing the results of Examples 3-1 to 3-4, and FIG. 7 is a graph showing the results of Examples 4-1 to 4-4. As shown in FIGS. 6 and 7, Examples 3-1 to 3-4 and Examples 4-1 to 4-4 had a high flop index, confirming that the glossiness of the metal substrate was well expressed.

[0088] Example 5-1 First, a base layer was formed on the entire surface of an aluminum plate in the same manner as in Example 1-1. Next, the entire surface of the base layer was coated by gravure offset printing with the following first composition for the design layer so that the film thickness after drying would be 0.5 μm or more and 1.5 μm or less, to form an inorganic colorant layer. (First composition for the design layer) Thermosetting fluororesin (fluoroethylene-vinyl ether copolymer) Curing agent (isocyanate) Inorganic colorant (carbon black; 4% by mass relative to the thermosetting fluororesin) Solvent (xylene:cyclohexane = 1:1, mass ratio) Solids concentration: 15% by mass

[0089] Next, the entire surface of the inorganic colorant layer was coated by gravure offset printing with the second composition for the design layer described below so that the film thickness after drying would be 0.5 μm or more and 1.5 μm or less, to form an organic colorant layer. This resulted in a design layer having an inorganic colorant layer and an organic colorant layer. (Second composition for the design layer) Thermosetting fluororesin (fluoroethylene-vinyl ether copolymer) Curing agent (isocyanate) Organic colorant (a three-color blend of perylene pigment (red), cyanine pigment (blue), and nickel azo complex pigment (yellow); 15% by mass relative to the thermosetting fluororesin) Solvent (xylene:cyclohexane = 1:1, mass ratio) Solids concentration: 19% by mass

[0090] Next, a surface protective layer A was formed on the entire surface of the design layer in the same manner as in Example 1-1, to obtain a decorative member.

[0091] [Examples 5-2 to 5-4] Decorative members were obtained in the same manner as in Example 5-1, except that only perylene pigment (red), only cyanine pigment (blue), or only nickel azo complex pigment (yellow) was used as the organic colorant contained in the second composition for the design layer.

[0092] Comparative Example 3-1 A decorative member was obtained in the same manner as in Example 5-1, except that the organic colorant layer was not formed.

[0093] [Comparative Example 3-2] A decorative member was obtained in the same manner as in Example 5-1, except that an organic colorant layer was not formed and the above-described composition B for the surface protective layer was used instead of the composition A for the surface protective layer.

[0094] [Comparative Example 3-3] A decorative member was obtained in the same manner as in Example 5-1, except that an organic colorant layer was not formed and the above-described composition C for the surface protective layer was used instead of the composition A for the surface protective layer.

[0095] [Comparative Example 3-4] A decorative member was obtained in the same manner as in Example 5-1, except that no organic colorant layer was formed and the above-described composition D for the surface protective layer was used instead of composition A for the surface protective layer.

[0096] [Evaluation] The decorative members obtained in Examples 5-1 to 5-4 and Comparative Examples 3-1 to 3-4 were used to measure the flop index. The measurement method was the same as above. The results are shown in Tables 3 and 4.

[0097]

[0098]

[0099] As shown in Tables 3 and 4, it was confirmed that Examples 5-1 to 5-4, which had an organic colorant layer, had a high flop index similar to that of Comparative Examples 3-1 to 3-4, which did not have an organic colorant layer. In other words, it was confirmed that the concealment of glossiness by the organic colorant layer was limited, and that the organic colorant layer enabled vivid design expression.

[0100] [Examples 6-1 to 6-3] Decorative members were obtained in the same manner as in Examples 2-1, 3-1, and 4-1, respectively, except that the following composition X for the base layer was used as the composition for the base layer, and the following composition A2 for the surface protective layer was used instead of the composition A for the surface protective layer. (Composition X for the base layer) Thermosetting fluororesin (fluoroethylene-vinyl ether copolymer) Curing agent (isocyanate) Gray colorant (titanium oxide, chromium oxide; 5% by mass relative to the thermosetting fluororesin) Ultraviolet absorber Hindered amine light stabilizer Solids concentration: 17% by mass

[0101] (Surface protection layer composition A2) Thermosetting fluororesin (fluoroethylene-vinyl ether copolymer) Curing agent (isocyanate) UV absorber Hindered amine light stabilizer Solvent (xylene:toluene=1:1, mass ratio) Solid content: 30 mass%

[0102] [Evaluation] The weather resistance of the decorative members obtained in Examples 6-1 to 6-3 was evaluated. The decorative members obtained were subjected to an accelerated weathering test using a Sunshine Weather Meter (SWOM). Specifically, under the following irradiation conditions, the test was carried out by repeating a cycle of 102 minutes of irradiation, followed by 18 minutes of irradiation and spraying, for a total of 120 minutes, until the total ultraviolet irradiation time was 10,000 hours.

[0103] <Conditions for accelerated weathering test> (Test equipment) Suga Test Instruments, product name "S80" (Irradiation conditions) Illuminance: 255 W / m ２ , Black panel temperature: 65°C, chamber humidity: 50% RH, time: 102 minutes of irradiation, followed by 18 minutes of irradiation and spraying

[0104] The weather resistance of the decorative member was evaluated by color difference and gloss retention. Regarding color difference, the color difference (ΔE) before and after an accelerated weathering test was measured using a spectrophotometer (Konica Minolta CM-5 spectrophotometer). Regarding gloss retention, the 60° gloss value of the surface protective layer was measured using a gloss meter in accordance with JIS K 5600. The 60° gloss value was calculated as the average of the values ​​measured at 10 locations. The results are shown in Table 5.

[0105]

[0106] As shown in Table 5, Examples 6-1 to 6-3 were confirmed to have small color difference (ΔE), high gloss retention, and good weather resistance. Organic colorants are known to have lower weather resistance than inorganic colorants, but Examples 6-1 to 6-3 were able to obtain decorative components that can also be used for exterior components, even while using organic colorants.

[0107] [Example 7] An aluminum plate (A3004PH32, dimensions: 300 mm × 600 mm, thickness: 1.0 mm, chromate-treated) was prepared as a metal substrate. Next, as a pretreatment, the prepared aluminum plate was washed with hot water, coated with a polyester-based primer, and then dried at 200°C (the temperature reached by the substrate).

[0108] Next, the following composition for the undercoat layer was applied to the entire surface of the aluminum plate using a curtain flow coater so that the film thickness after drying would be 18 μm. Then, the undercoat layer was formed by baking at 216°C (substrate temperature). (Composition for the undercoat layer) Thermosetting polyester resin Solvent (xylene:cyclohexanone = 1:1) Solid content concentration... 40 mass%

[0109] Next, the entire surface of the underlayer was coated with the following composition for the design layer by gravure offset printing so that the film thickness after drying was 0.5 μm to 1.5 μm. (Composition for the design layer) Thermosetting polyester resin Organic colorant (a three-color blend of perylene pigment (red), cyanine pigment (blue), and nickel azo complex pigment (yellow); 7.5% by mass relative to the thermosetting fluororesin) Solvent (xylene:cyclohexane = 1:1, mass ratio) Solid content: 19% by mass

[0110] Next, the following composition for the surface protection layer was applied to the entire surface of the design layer using a bar coater so that the film thickness after drying would be 22 μm. Then, the coating was baked at 224°C (the temperature reached by the substrate material) to form a surface protection layer, and a decorative member was obtained. (Composition for the surface protection layer) Thermosetting polyester resin, UV absorber, hindered amine light stabilizer, filler (silica, average particle size 2 μm; 3% by mass relative to the thermosetting polyester resin), solvent (xylene:cyclohexanone = 1:1), solid content concentration... 42% by mass

[0111] The weather resistance of the resulting decorative member was evaluated in the same manner as above. As a result, the color difference (ΔE) and gloss retention were maintained to a certain extent up to 500 hours of UV irradiation time, but when the UV irradiation time reached 1000 hours, the color difference (ΔE) became 4.3 and the gloss retention became 10%. Comparing Example 7 with Examples 6-1 to 6-3, it was confirmed that the use of a fluororesin as the thermosetting resin significantly improved weather resistance.

[0112] Thus, the present disclosure provides, for example, the following inventions.

[0113] [1] A decorative element having a metal substrate and a design layer in this order in the thickness direction, wherein the design layer contains an organic colorant, and the decorative element has a region X on a first surface located on the design layer side relative to the metal substrate, where the flop index is 4.5 or more.

[0114] [2] When viewed from the thickness direction, the area of ​​the design layer is S Ａ Let the area of ​​the region X be S Ｂ In this case, the above S Ａ The above S Ｂ The ratio (S Ｂ / S Ａ The decorative material according to [1], wherein the content of the porosity is 1% or more.

[0115] [3] The decorative member according to [1] or [2], wherein the design layer has a pattern layer containing the organic colorant.

[0116] [4] The decorative member according to any one of [1] to [3], wherein the design layer is a baked layer.

[0117] [5] The decorative member according to any one of [1] to [4], wherein the metal substrate is an aluminum substrate, an aluminum alloy substrate, a steel substrate, or a stainless steel substrate.

[0118] [6] The decorative member according to any one of [1] to [5], wherein the design layer contains a cured product of a thermosetting resin.

[0119] [7] The decorative member according to any one of [1] to [6], wherein the decorative member has a base layer between the metal substrate and the design layer.

[0120] [8] The decorative member according to [7], wherein the underlayer contains a cured product of a thermosetting resin.

[0121] [9] The decorative member according to any one of [1] to [8], wherein the decorative member has a surface protective layer on the side opposite to the metal substrate with respect to the design layer.

[0122]

[10] The decorative member according to [9], wherein the surface protective layer contains a cured product of a thermosetting resin.

[0123]

[11] The decorative member according to any one of [1] to

[10] , wherein the decorative member has a surface protective layer on the opposite side of the design layer from the metal substrate, and the surface protective layer contains a cured product of a fluorine-based resin that is a thermosetting resin.

[0124]

[12] The decorative member according to any one of [1] to

[11] , wherein the decorative member is an exterior member.

[0125]

[13] The decorative member according to any one of [1] to

[11] , wherein the decorative member is an interior material.

[0126]

[14] A method for manufacturing a decorative member according to any one of [1] to

[13] , comprising: a metal substrate preparation step of preparing the metal substrate; and a design layer formation step of applying a composition containing the organic colorant to one side of the metal substrate and heat-curing the composition to form the design layer.

[0127] DESCRIPTION OF SYMBOLS 1... Metal substrate 2... Design layer 3... Primer layer 4... Undercoat layer 5... Surface protective layer 10... Decorative member

Claims

1. A decorative component having a metal base material and a design layer in that order in the thickness direction, wherein the design layer contains an organic colorant, and the decorative component has a region X on a first surface located on the design layer side relative to the metal base material, the region X having a flop index of 4.5 or more.

2. When viewed from the thickness direction, the area of ​​the design layer is S Ａ Let the area of ​​the region X be S Ｂ In this case, the S Ａ The above S Ｂ The ratio of (S Ｂ / S Ａ 2. The decorative member according to claim 1, wherein the ratio of the surface area to the surface area is 1% or more.

3. The decorative member according to claim 1, wherein the design layer has a pattern layer containing the organic colorant.

4. The decorative member according to claim 1, wherein the design layer is a baked layer.

5. The decorative member of claim 1, wherein the metal substrate is an aluminum substrate, an aluminum alloy substrate, a steel substrate, or a stainless steel substrate.

6. The decorative member according to claim 1, wherein the decorative layer contains a cured product of a thermosetting resin.

7. The decorative member according to claim 1, wherein the decorative member has a base layer between the metal substrate and the design layer.

8. The decorative member according to claim 7, wherein the undercoat layer contains a cured product of a thermosetting resin.

9. The decorative member according to claim 1, further comprising a surface protective layer on the opposite side of the decorative layer to the metal substrate.

10. The decorative member according to claim 9, wherein the surface protective layer contains a cured product of a thermosetting resin.

11. The decorative component according to claim 1, wherein the decorative component has a surface protective layer on the opposite side of the design layer to the metal substrate, and the surface protective layer contains a cured product of a fluorine-based resin which is a thermosetting resin.

12. The decorative member of claim 11, wherein the decorative member is an exterior member.

13. The decorative member according to claim 11, wherein the decorative member is an interior member.

14. A method for producing a decorative part according to any one of claims 1 to 13, comprising: a metal substrate preparation step of preparing the metal substrate; and a design layer formation step of applying a composition containing the organic colorant to one side of the metal substrate and heating and curing the composition to form the design layer.

Images