Matting article

Abstract

The present application provides a matte article having excellent visibility and texture of a matte effect, and excellent rough tactile sensation. The matte article has a surface shape having an Spc (arithmetic mean curvature of a protrusion top) of more than 4000 mm ‑1 , and an Rsm (average length of a curved element) of 30 μm or more as defined in JIS B0601:2013.

Description

Technical Field

[0001] This invention relates to matte articles. Background Technology

[0002] Traditionally, decorative materials or decorative sheets have been used to decorate and protect the surfaces of various building components, such as interior components (walls, ceilings, floors), exterior components (eaves, roofs, fences, etc.), window frames, doors, door frames, handrails, crossbeams, perimeter edges, trim strips, etc., as well as general furniture (wardrobes, shelves, tables, etc.), kitchen furniture (dining tables, sinks, etc.), and the housings of home appliances and office equipment. They are also used for interior or exterior components of vehicles. Furthermore, decorative materials, for example, those with a surface layer possessing the desired function, are often used.

[0003] For decorative materials used in these applications, the method of enhancing texture by utilizing a matte effect is common in order to improve their design. For example, Patent Document 1 discloses a decorative sheet that utilizes a matte effect, having a pattern layer and a masking layer on one side of a substrate sheet, and a gloss adjustment layer (matte layer, gloss layer) on the other side. In the decorative sheet of Patent Document 1, the difference in gloss between the matte layer and the gloss layer of the gloss adjustment layer achieves a design effect that highlights the pattern layer and the masking layer. In its embodiment, a matte ink containing 50 parts by weight of a matting agent (10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate per 100 parts by weight of resin component) is used in the matte layer applied to the entire surface.

[0004] In addition, Patent Document 2 proposes a decorative material having a printed layer and a transparent resin layer in sequence on a substrate, with an embossed pattern applied to the outermost surface of the transparent resin layer.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2000-062081

[0008] Patent Document 2: Japanese Patent Application Publication No. 2011-073207 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] As a method to improve texture through a matte effect, the main examples include the use of a matting agent (also called a "matting agent") as described in Patent Document 1 above, which achieves a matte effect through its own light diffusion effect, and the method of forming an uneven shape on the outermost surface by performing an embossing process as described in Patent Document 2 above.

[0011] However, when using matting agents as described in Patent Document 1, increasing the amount used is necessary to achieve a better matting effect. However, with increased usage, surface properties tend to decrease due to several reasons: the matting agent may detach from the coating, damaging it and reducing scratch resistance; damage may become more noticeable due to gloss changes caused by the absence of matting agent; and contaminants may penetrate the tiny gaps at the interface between the matting agent and the resin, adsorbing onto the matting agent itself and reducing stain resistance. On the other hand, reducing the amount used to suppress the decrease in surface properties tends to reduce the matting effect; surface properties and matting effect are inversely related. Therefore, the matte effect achieved using matting agents is limited.

[0012] Furthermore, in cases where embossing is used, as in Patent Document 2, the production of the embossing printing plate is laborious and difficult, and a separate plate needs to be made for each desired pattern. Therefore, it cannot be said to be a method that easily and adequately addresses the diversity of customer needs.

[0013] However, customer demands are diverse and multifaceted, requiring not only the visual matte finish described above but also a superior tactile feel. For example, when using a matting agent like that in Patent Document 1, increasing the amount used exposes the outline of the matting agent on the surface of the decorative sheet, sometimes resulting in a slightly rough surface feel, or a "rough" tactile sensation. Furthermore, when using embossing as in Patent Document 2, the tactile feel is sometimes affected by the uneven shape of the surface formed by the embossing plate. However, in both cases, the tactile feel is not adequately addressed, resulting in a situation where the tactile experience cannot be considered sufficiently good. In other words, conventional decorative sheets and materials cannot simultaneously achieve excellent matte finish and a superior tactile feel. In this invention, a "rough" tactile feel is specifically emphasized.

[0014] The objective of this invention is to provide matte articles with excellent visibility and texture, as well as a superior rough tactile feel.

[0015] Methods for solving problems

[0016] To address the aforementioned issues, the present invention provides the following matte articles.

[0017] [1] A matte article having at least a portion of its surface having a Spc (arithmetic mean curvature of the apex of the protrusion) greater than 4000 mm. -1 Surface shapes for which Rsm (average length of curve feature) is 30 μm or more as specified in JIS B0601:2013.

[0018] [2] According to the matte article described in [1], the peak and height parameters of the profile curve specified in JIS B0601:2013 for the surface shape described above, namely Rz (maximum height), are 8.00 μm or more and 30.00 μm or less.

[0019] [3] According to the matte article described in [1] or [2], the parameter Ra (arithmetic mean roughness) of the height direction of the profile curve specified in JIS B0601:2013 of the above-mentioned surface shape is 1.00 μm or more and 5.50 μm or less.

[0020] [4] The matte article according to any one of [1] to [3] has a matte layer, and the surface shape is formed by the surface of the matte layer.

[0021] [5] The matte article according to any one of [1] to [4], wherein the surface of the matte layer forming the above-mentioned surface shape has an uneven shape composed of irregular folds.

[0022] [6] According to the matte article described in [5], the irregular wrinkles are composed of a concave portion and a plurality of convex portions, the convex portions being formed by a plurality of line protrusions, and the concave portions being formed by being surrounded by the plurality of line protrusions.

[0023] [7] A matte article according to any one of [4] to [6], wherein the matte layer is formed from a cured resin composition comprising a resin and a wrinkle-forming stabilizer, wherein the wrinkle-forming stabilizer has an average particle size with an upper limit of less than 100% of the thickness of the matte layer and less than 30 μm, and the matte layer comprises more than 0.5 parts by mass of the wrinkle-forming stabilizer relative to 100 parts by mass of the resin.

[0024] [8] The matte article described in any one of [1] to [7] has a substrate.

[0025] [9] According to the matte article described in [8], the substrate is in sheet form.

[0026]

[10] According to the matte article described in [8] or [9], wherein the matte layer is disposed on the entire surface of one side of the substrate.

[0027]

[11] The matte article described in any one of [1] to

[10] , wherein the 60° gloss value of the surface shape is 10.0 or less.

[0028] Invention Effects

[0029] According to the present invention, matte articles with excellent visibility and texture and excellent rough tactile feel can be provided. Attached Figure Description

[0030] Figure 1 This is a schematic diagram illustrating the surface shape of the matte article of the present invention.

[0031] Figure 2 This is a schematic diagram illustrating the surface shape of the matte article of the present invention.

[0032] Figure 3 This is a top view schematic diagram showing one embodiment of the matte article of the present invention.

[0033] Figure 4 This is a cross-sectional view showing one embodiment of the matte article of the present invention.

[0034] Figure 5 This is a cross-sectional view showing one embodiment of the matte article of the present invention.

[0035] Figure 6 This is a cross-sectional view showing one embodiment of the matte article of the present invention.

[0036] Figure 7 This is an optical microscope image of the surface of the matte article obtained in Example 1.

[0037] Figure 8 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 1.

[0038] Figure 9 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 2.

[0039] Figure 10 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 3.

[0040] Figure 11 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 4.

[0041] Figure 12 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 5.

[0042] Figure 13 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 6. Detailed Implementation

[0043] [Matte items]

[0044] Hereinafter, embodiments of the present invention (hereinafter sometimes referred to as "this embodiment") will be described. It should be noted that in this specification, the values ​​related to "above", "below" and "~" in relation to the description of numerical ranges are numerical values ​​that can be arbitrarily combined, and the numerical values ​​in the embodiments are numerical values ​​that can be used as the upper and lower limits of the numerical range.

[0045] The matte article of this embodiment is characterized in that at least a portion of its surface has a Spc (arithmetic mean curvature of the apex of the protrusion) greater than 4000 mm. -1 Surface shapes for which Rsm (average length of curve feature) is 30 μm or more as specified in JIS B0601:2013.

[0046] [Regarding surface shape]

[0047] The description will focus on the surface shape (hereinafter also simply referred to as "surface shape") of at least a portion of the surface of the matte article of this embodiment.

[0048] The surface shape requires an Spc (arithmetic mean curvature of the protrusion apex) greater than 4000 mm. -1 The Rsm (average length of the curve element) specified in JIS B0601:2013 is 30 μm or more. By having such a surface shape, the matte article of this embodiment exhibits excellent visibility and texture of the matte effect (hereinafter, they are sometimes collectively referred to as "matte effect"), and as a tactile sensation, it exhibits a particularly "rough" feel. The "rough" feel is a sensory perception, and in this specification, "rough" encompasses all tactile sensations that are generally perceived as "rough." Specifically, it refers to the tactile sensation felt when touching a rough surface with the fingertip; it can also be described as a rough and non-smooth feel, like a rough, burr-like sensation. Examples of materials with a "rough" feel include, for example, coarse cotton fabrics such as Oxford cloth using coarse yarn of around 10 to 50 count (coarse to medium count), or linen fabrics using coarse yarn of around 10 to 50 count.

[0049] (Spc (arithmetic mean curvature of the apex of the protrusion))

[0050] Spc (arithmetic mean curvature of the apex of the protrusion) is one of the three-dimensional surface property parameters. It is the average curvature (average sharpness) of the tip of the peak, calculated by the arithmetic mean of the radii of curvature of the peaks (protrusion apexes) of the parts classified as peaks (protrusions) in the shape image contained in the reference region. Therefore, Spc is the reciprocal of the radius (mm). -1 ).

[0051] The larger the Spc, the larger the front end of the peak (convex part) ( Figure 1 The greater the curvature of (1a) in the equation (the smaller its reciprocal radius of curvature, the sharper the shape of the front end), the more pronounced the curvature of the protrusion (the smaller the radius of curvature). Conversely, the smaller the value of Spc, the sharper the shape of the protrusion's apex (…). Figure 1 The smaller the curvature of 1b) (the larger its reciprocal radius of curvature, the blunter the shape of the front end). That is, the smaller the Spc, the more rounded the protrusion, the closer it is to a plane, and therefore the greater the gloss. Therefore, in order to suppress gloss by focusing only on the value of Spc, if we set it to a surface shape with a large Spc (a surface shape with a sharp apex of the protrusion), that is, greater than 4000 mm... -1 If the surface has a planar shape, the scattering of light at the surface will be stronger, and the gloss will be reduced.

[0052] A small Spc value results in a soft feel due to the rounded corners at the apex of the protrusions, but a large value, greater than 4000mm, will result in a softer surface texture. -1 (With a radius of curvature less than 0.25 mm), a sharp tip shape can be felt at a moderate contact frequency when touched with the fingertip. This is believed to be related to the tactile sensation felt when touching a rough surface with the fingertip—not a soft feel, but a rough, burr-like sensation, i.e., a "rough" feel. However, if the average spacing between the apexes of these sharp protrusions is too close, the presence of each sharp tip shape falls below the resolution threshold of the fingertip's tactile sensation, and the sharp tactile sensation of each protrusion disappears, transforming into a smooth and soft feel. Therefore, the surface shape of matte objects, except for those with a Spc > 4000 mm, is considered suitable. -1 In addition to the necessary condition, as described later, it is also necessary to satisfy the condition that Rsm (average length of curve element) corresponding to the average protrusion interval is ≥30μm.

[0053] In relation to Rsm (average length of the curve element) discussed later, from the viewpoint of improving matting effect and "rough" tactile feel, Spc is preferably 4200mm. -1 The above is preferred, with 4250mm being even better. -1 The above, preferably 4300mm -1 The above, as an upper limit, is preferably 7000mm. -1 The preferred value is 6000mm. -1 Below, 5000mm is preferred. -1 The following is a further preferred size: 4500mm -1 The following is a cutoff value of 0.8 mm for the Spc measurement in this specification.

[0054] The Spc value is obtained by measuring a rectangular area (1024 μm × 768 μm) of any part of the surface shape of the matte article using a shape analysis laser microscope. The measurement conditions can be adjusted appropriately, for example, the measurement can be performed under the conditions described in the examples. In addition, Rsm (average length of the curve element), Rz (maximum height), and Ra (arithmetic mean roughness), which will be described later, can also be measured in the same way.

[0055] (Rsm (average length of curve feature))

[0056] Rsm (average length of curve elements) is a lateral parameter of the profile curve in the three-dimensional surface property parameters specified in JIS B0601:2013, and is the average length of the profile curve elements in the reference length. The larger Rsm is, the more convexity ( Figure 2 The fewer (2a and 2b) there are. Therefore, the surface shape with a large Rsm has sparsely distributed convex apexes. By dispersing the convex parts in this way, i.e. by setting them to 30 μm or more, a sharp tip shape can be felt at a moderate contact frequency when touched with the fingertip. This is thought to be related to the tactile sensation felt when touching a rough surface with the fingertip, not a soft feel but a rough, burr-like feel, i.e., a "rough" feel.

[0057] Furthermore, decreasing Rsm increases the number of protrusions within the reference length. This results in a large number of protrusions on the surface, requiring precise manufacturing processes. Therefore, setting Rsm to 30 μm or higher simplifies the manufacturing process.

[0058] In this embodiment, increasing the Spc (arithmetic mean curvature of the protrusion vertices) improves the matting effect and provides a "rough" tactile feel. However, even with increased Spc, if the Rsm (radius density) is small, the protrusion vertices are densely packed, resulting in a larger contact area with the finger when touching the surface, thus exhibiting a softer feel. Therefore, it is considered that increasing the Spc (arithmetic mean curvature of the protrusion vertices) to greater than 4000 mm is beneficial. -1 It also ensures that the Rsm (average length of curve elements) is above 30μm, which can achieve a high level of balance between matte finish and "rough" tactile feel.

[0059] Regarding the relationship with Spc mentioned above, from the viewpoint of improving the matting effect and the "rough" tactile feel, Rsm is preferably 32.0 μm or more, more preferably 35.0 μm or more, and even more preferably 37.5 μm or more as a lower limit, and 60.0 μm or less as an upper limit, more preferably 50.0 μm or less, and even more preferably 40.0 μm or less as an upper limit. By setting the upper limit to the above range, the planar shape exhibits a "rough" tactile feel, and manufacturing does not become excessively difficult, which is preferable. It should be noted that the cutoff value for Rsm measurement in this specification is 0.8 mm.

[0060] (wrinkles)

[0061] The surface shape of the matte article in this embodiment preferably has the characteristics described later. Figure 3 The diagram shows minute wrinkles (creases) visible from a top view. These wrinkles are preferably irregular, uneven in shape. Regarding the surface shape of the matte article of this embodiment, the Spc (arithmetic mean curvature of the protrusion apex) and Rsm (average length of the curve element), and preferably the Rz (maximum height) and Ra (arithmetic mean roughness), which will be described later, are easily formed within a specific range due to the presence of these minute wrinkles (creases). On the other hand, these minute wrinkles (creases) are easily formed by having Spc (arithmetic mean curvature of the protrusion apex) and Rsm (average length of the curve element) within a specific range, and preferably Rz (maximum height) and Ra (arithmetic mean roughness) within a specific range. Thus, it can be said that Spc (arithmetic mean curvature of the protrusion apex) and Rsm (average length of the curve element), etc., are integral to the minute wrinkles (creases). Furthermore, by having such a surface shape, the matte effect is improved along with the "rough" tactile feel.

[0062] In the surface shape of a matte article, in order to set Spc (arithmetic mean curvature of the protrusion apex) and Rsm (average length of the curve element) within the specific numerical range mentioned above, and preferably set them as Rz (maximum height) and Ra (arithmetic mean roughness) as described later, as above, it is preferable that:

[0063] (1) A micro-wrinkled structure is formed on the surface of the matte layer. Preferably:

[0064] (2) Optimize the composition of the resin composition used to form the matte layer, especially the types, number of functional groups, molecular weight, presence or absence of wrinkle-forming stabilizers, and particle size and content of wrinkle-forming stabilizers when used.

[0065] (3) Optimize the irradiation conditions of the resin composition for matting formation, especially the wavelength, cumulative light intensity, and ultraviolet power density of light with a wavelength of 100 nm or more and 380 nm or less that can cause partial curing and shrinkage of the surface of the matting layer.

[0066] (4) In addition to the above, optimize the type and thickness of the substrate, the thickness of the matte layer, etc. By optimizing them, it is easy to make Spc (arithmetic mean curvature of the protrusion apex) and Rsm (average length of the curve element) within the specific numerical range mentioned above for the surface shape of the matte article of this embodiment, and preferably easy to make Rz (maximum height) and Ra (arithmetic mean roughness) described later within the specified numerical range.

[0067] (Rz (maximum height))

[0068] In this embodiment, as the surface shape, the lateral parameter Rz (maximum height) of the profile curve specified in JIS B0601:2013 is preferably 8.00 μm or more and 30.00 μm or less.

[0069] Rz (maximum height) is one of the peak and height parameters of the profile curve. It is the sum of the height of the highest peak and the depth of the deepest valley in the profile curve of the reference length. The larger the value of Rz (maximum height), the more prominent (higher) the convex parts appear when viewed from the valley (concave part), becoming an indicator of the tendency for such convex parts to exist in large quantities. Therefore, in a surface shape that satisfies the above-mentioned Spc (arithmetic mean curvature of the apex of the protrusion) and Rsm (average length of the curve element), if Rz (maximum height) is 8.00 μm or more and 30.00 μm or less, the characteristic that the front end shape of the convex parts, based on the above-mentioned Spc (arithmetic mean curvature of the apex of the protrusion) and Rsm (average length of the curve element), is a sharp shape is emphasized, and the rough tactile feel is improved. In addition, the matting effect is also improved.

[0070] From the viewpoint of improving the matte finish and the rough tactile feel, Rz (maximum height) is preferably 8.50 μm or more, more preferably 9.00 μm or more, even more preferably 9.50 μm or more, and as an upper limit, preferably 26.00 μm or less, more preferably 24.00 μm or less, even more preferably 22.00 μm or less. It should be noted that the cutoff value for measuring Rz (maximum height) in this specification is 0.8 mm.

[0071] (Ra (arithmetic mean roughness))

[0072] In this embodiment, as the surface shape, the lateral parameter Ra (arithmetic mean roughness) of the profile curve specified in JIS B0601:2013 is preferably 1.00 μm or more and 5.50 μm or less.

[0073] Ra (arithmetic mean roughness) is one of the parameters in the height direction of a profile curve. In a profile curve of a reference length, it is the average value of the height difference from the average surface. The smaller the value of Ra (arithmetic mean roughness), the smaller the height difference between the convex parts and the corresponding concave parts in the surface shape. Ra (arithmetic mean roughness) is an indicator of the tendency to become a smoother and more uniform shape. Therefore, in a surface shape that satisfies the above-mentioned Spc (arithmetic mean curvature of the apex of the protrusion) and Rsm (average length of the curve element), if Ra (arithmetic mean roughness) is 1.00 μm or more and 5.50 μm or less, there is a greater presence of a more uniform and smoother shape in the convex parts of the surface shape, thus suppressing abnormal tactile sensations, especially improving the rough tactile sensation. In addition, the matting effect is also improved.

[0074] From the viewpoint of improving the matting effect and the rough tactile feel, the Ra (arithmetic mean roughness) is preferably 5.25 μm or less, more preferably 5.00 μm or less, and even more preferably 4.50 μm or less. As a lower limit, it is preferably 1.00 μm or more, more preferably 1.50 μm or more, and even more preferably 1.75 μm or more. It should be noted that the cutoff value for the Ra (arithmetic mean roughness) measurement in this specification is 0.8 mm.

[0075] [Regarding layer composition]

[0076] The matte article of this embodiment does not have any particular limitation on the layer structure as long as it has the shape specified by the above parameters as the surface shape, and any layer structure can be adopted.

[0077] For example, the simplest layer structure of the matte article of this embodiment can be exemplified by: Figure 4 The structure is a single layer as shown. As... Figure 4 The articles shown may include, for example, articles in which the surface shape described above is on one side of a cured resin composition layer, preferably a cured resin composition containing a curable resin such as an ionizing ray curable resin described later, or articles in which the surface shape is shaped by embossing or other processing on the surface of a resin molded article, and other articles consisting of a single layer.

[0078] Furthermore, from the perspective of more flexibly addressing various performance requirements corresponding to different needs, such as the mechanical strength, post-processing adaptability, and design appearance of items, as well as from the perspectives of manufacturing adaptability and usage handling adaptability, one can also cite... Figure 5 and6 A laminated body as shown, consisting of multiple layers, such as an article composed of a laminated body having a substrate and having a cured layer of a resin composition having the aforementioned surface shape in at least a portion thereon as a matte layer.

[0079] Hereinafter, regarding the layers constituting the matte article of this embodiment, for an article constituting a laminate as one of the preferred embodiments, we will describe the layers constituting a laminate having a substrate and a cured layer (matte layer) having the above-described surface shape in at least a portion thereof.

[0080] [Substrate]

[0081] The shape (or form) of the substrate forming the matte article of this embodiment is not particularly limited, and various shapes such as film, sheet or plate, polyhedron, polygonal prism, cylinder, sphere, and ellipsoid of revolution are preferred. Here, film, sheet, and plate are referred to as film, sheet, and plate starting from the thinnest, but in this specification, there is no particularly strict distinction between these three terms, and the interpretation of the claims of this invention will not differ due to the different types of film, sheet, and plate. Therefore, in this specification, film, sheet, and plate are sometimes collectively referred to as "sheet," "sheet-like," etc.

[0082] In the case where the matte article of this embodiment is composed of a laminate, the shape of the substrate is preferably sheet-like. If the substrate is sheet-like, it is particularly easy to form the matte layer described later, thus improving manufacturing adaptability. In addition, it is easy to integrate with resin molded articles by means of bonding, thus improving post-processing adaptability.

[0083] There are no particular limitations on the constituent materials of the substrate; various materials such as resins, metals, non-metallic inorganic materials, fibrous materials, and wood-based materials can be appropriately selected according to the application. The substrate composed of these various materials can be used as a single layer, or as a multilayer consisting of two or more layers. In the case of a multilayer design, stacking two or more layers of different materials to form a single unit allows for the complementary use of the functions of each layer.

[0084] When using a multilayer substrate, for example, when describing the laminate consisting of layers of material A and material B as "A / B", the following approach is preferred:

[0085] (1) Resin / wood-based materials

[0086] (2) Resin / metal

[0087] (3) Resin / fibrous materials,

[0088] (4) Resin / non-metallic inorganic materials

[0089] (5) Resin 1 / Resin 2 (for example, the case where there are multiple layers composed of different resins such as "olefin resin / acrylic resin")

[0090] (6) Metal / wood-based materials

[0091] (7) Metallic / non-metallic inorganic materials

[0092] (8) Metal / fibrous materials

[0093] (9) Metal 1 / Metal 2 (e.g., the case of having multiple layers made of different metals such as "copper / chromium")

[0094] (10) Non-metallic inorganic materials / fibrous materials, etc.

[0095] In addition, when the substrate is multilayered, between the layers of the multilayered substrate, as a layer used to improve the adhesion of adjacent layers, there may be an adhesive layer, a bonding agent layer, and a primer layer (also known as an anchoring layer or an easy-to-adhere layer).

[0096] Various synthetic resins and natural resins can be cited as resins that can be used as substrates. Among synthetic resins, thermoplastic resins and curable resins can be cited. However, thermoplastic resins are preferred when considering their suitability for manufacturing, processing, and post-processing of matte articles.

[0097] Preferred thermoplastic resins include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, and polyester-based thermoplastic elastomers; and poly(methyl methacrylate), poly(ethyl methacrylate), and poly(methyl methacrylate). Acrylic resins such as butyl acrylate and methyl methacrylate-butyl acrylate copolymer; polyamide resins represented by nylon 6 and nylon 66; cellulose resins such as cellulose triacetate, celluloid, and celluloid; styrene resins such as polystyrene, acrylonitrile-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer (ABS resin); polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate resin, and polyimide resin.

[0098] Natural resins such as natural rubber, rosin, and amber are preferred examples.

[0099] In addition, as the curable resin, thermosetting resins, radiation-curable resins, etc., which are exemplified as the constituent materials of the light-shielding layer described later, can be preferably selected.

[0100] As the metal that can be used for the substrate, for example, aluminum alloys such as aluminum or duralumin can be preferably selected; iron alloys such as iron, carbon steel, or stainless steel; copper alloys such as copper or brass; gold, silver, chromium, nickel, cobalt, tin, titanium, etc. In addition, as the substrate made of metal, substrates with these metals applied to the surface by plating or the like can also be preferably selected.

[0101] As the non-metallic inorganic materials that can be used for the substrate, for example, non-ceramic industry materials such as cement, ALC (lightweight aerated concrete), gypsum, calcium silicate, and wood chip cement can be preferably selected; ceramic industry materials such as ceramics, pottery, glass, and enamel; natural stones such as limestone (including marble), granite, and andesite, etc.

[0102] As the fibrous materials that can be used for the substrate, for example, papers such as tissue paper (Japanese: 薄枼紙), kraft paper, high-quality paper, Japanese paper, titanium white paper, cotton linter paper, sulfuric acid paper, paraffin paper, parchment paper, cellophane, lining paper for wallpaper, cardboard, base paper for gypsum board, etc. can be preferably selected; woven fabrics or non-woven fabrics formed of fibers such as polyester resin fibers, acrylic resin fibers, silk, cotton, linen, and other protein or cellulose-based natural fibers, glass fibers, carbon fibers, etc. Among these materials, in order to improve the inter-fiber strength of the paper substrate made of paper or the interlayer strength with other substrates used in combination with the paper substrate, and in order to prevent fluffing, various resins such as acrylic resins, styrene-butadiene rubbers, melamine resins, and urethane resins can be further added (these resins are impregnated after papermaking or filled during papermaking). As the paper added with resin, for example, paper-interlayer reinforced paper, resin-impregnated paper, etc. can be preferably selected.

[0103] It should be noted that in the case of a substrate made of fibrous materials such as paper, when the liquid resin composition for forming the light-shielding layer is coated, the liquid composition penetrates into the substrate, and thus the influence of the uneven shape of the fibers on the substrate surface appears on the surface of the light-shielding layer, and sometimes the desired values of Spc and Rsm cannot be obtained. In such a case, it is preferable to form a known penetration-preventing resin layer on the surface of the light-shielding layer side of the fibrous material substrate by coating or other methods. As the resin for forming the penetration-preventing resin layer, for example, two-component curable urethane resin can be cited.

[0104] In addition, as the laminate formed by laminating a layer made of fibrous materials and a layer made of resin, wallpaper raw materials obtained by laminating a layer made of various resins such as a vinyl chloride resin layer, an olefin resin layer, and an acrylic resin layer on the surface of the lining paper for wallpaper commonly used in the building materials field can be preferably selected.

[0105] Wood-based materials that can be used as substrates include, for example, veneers, plywood, engineered wood, particleboard, and medium-density fiberboard (MDF) made of various woods such as cedar, cypress, pine, beech, oak, oak, walnut, lauan, teak, and rubber tree.

[0106] As the substrate, any substrate made of the aforementioned materials can be used without restriction; furthermore, it can be appropriately selected according to the desired properties. From the viewpoint of improving the matte effect and the rough tactile feel, a substrate made of resin or a substrate made of fibrous material is preferred. Among the resins, olefin resins, vinyl chloride resins, polyester resins, and acrylic resins are preferred, and olefin resins, vinyl chloride resins, and polyester resins are more preferred. As an olefin resin, polyethylene and polypropylene are preferred; as a vinyl chloride resin, polyvinyl chloride is preferred; and as a polyester resin, polyethylene terephthalate is preferred. In addition, among the fibrous materials, paper is preferred. By using a substrate made of these materials, the aforementioned surface shape is particularly easy to obtain, and the rough tactile feel is easily improved.

[0107] There are no particular restrictions on the shape and size of the substrate, which is composed of a single layer or a laminate. It can be appropriately selected as long as the application, the desired performance, and the adaptability to post-processing are taken into account.

[0108] When using films, sheets, or plates, thickness is a representative dimension in the design of matte articles. There are no particular limitations on this thickness; considering manufacturing adaptability, handling adaptability, post-processing adaptability, mechanical strength, and economy, a thickness of 10 μm or more and 10 cm or less is preferred. When using films or sheets, a thickness of 20 μm or more and 300 μm or less is preferred. When using plates, a thickness of 1 mm or more and 2 cm or less is preferred.

[0109] From the viewpoint of improving the adhesion to other layers such as the matte layer that constitute the matte article, and the adhesion to bonded materials such as resin molded articles of laminated matte articles, at least one side of the substrate can be subjected to physical surface treatments such as oxidation and embossing, as well as chemical surface treatments to improve the ease of adhesion.

[0110] Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone-ultraviolet treatment. Examples of surface treatments include sandblasting and solvent treatment. These surface treatments can be selected appropriately according to the type of substrate. Considering the improved adhesion and workability brought about by the surface treatment, corona discharge treatment is preferred.

[0111] The substrate can be colored or not (it can be transparent). If it is colored, there are no particular restrictions on the way it is colored; it can be transparent or opaque (masking color), and they can be chosen arbitrarily.

[0112] When the substrate is colored, colorants include, for example, white pigments such as titanium dioxide, inorganic pigments such as iron black, chrome yellow, titanium yellow, iron red, cadmium red, ultramarine, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, nickel-azo complexes, azomethyl alkali azo black pigments, and perylene black pigments; metallic pigments formed from flake-like foils of aluminum, brass, etc.; and pearlescent (pearlescent) pigments formed from flake-like foils of titanium dioxide coated with mica, alkaline lead carbonate, etc. For example, when the surface tone of the bonded material, such as resin molded articles of laminated matte articles, is uneven, and it is desired to mask the surface tone and improve the tone stability of the decorative layer to be applied as required, inorganic pigments such as white pigments can be used.

[0113] When coloring a resin-based substrate, any method can be used, such as adding a colorant to the resin (mixing, internal addition) or forming a film by coating a paint containing the resin and colorant. When coloring a substrate made of fibrous materials such as paper, woven fabric, or nonwoven fabric, it can be done by any method, such as mixing with pulp or fibrous materials, or forming a film, or a combination thereof.

[0114] When coloring a substrate made of wood-based materials, it can be done by dyeing with dyes, coating formation, or a combination thereof. When coloring a substrate made of metal, in addition to coating formation, electrolytic coloring methods, such as forming a metal oxide film on the surface using anodizing, can also be used. Furthermore, when coloring a substrate made of non-metallic inorganic materials, it can be done by coating formation, adding to the substrate, or a combination thereof.

[0115] Additives can be incorporated into the substrate as needed. Examples of additives, when the main component is resin, include inorganic substances such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, UV absorbers, and light stabilizers. The amount of additives is not particularly limited as long as it does not impair surface properties, processing characteristics, etc., and can be appropriately set according to required properties.

[0116] From the viewpoint of improving the weather resistance of the matte article of this embodiment, weather-resistant agents such as ultraviolet absorbers and light stabilizers are preferably used among the above-mentioned additives.

[0117] Examples of substances that can be included in the matting layer described later, such as ultraviolet absorbers and light stabilizers, can be cited as ultraviolet absorbers and light stabilizers.

[0118] These UV absorbers, light stabilizers, and other weather-resistant agents, as well as various other additives, can be used alone or in combination.

[0119] In this embodiment, the aforementioned substrate can be used alone or in combination. It can be a substrate composed of multiple paper substrates, or a substrate composed of paper substrates combined with fiber substrates, paper substrates combined with resin substrates, fiber substrates combined with resin substrates, or paper substrates combined with fiber substrates and resin substrates. Furthermore, the resin substrate can be a single layer of the aforementioned resin substrate, or a multilayer composed of the same or different types of resin.

[0120] As described above, when the substrate is a film or sheet of the aforementioned resin, the thickness is preferably 20 μm or more, and preferably 300 μm or less as an upper limit. Considering manufacturing adaptability, use processing adaptability, post-processing adaptability, mechanical strength, economy, etc., it is more preferably 40 μm or more, and preferably 200 μm or less as an upper limit. Furthermore, it is even more preferably 100 μm or less.

[0121] From the same perspective, when the substrate is paper, the weight per unit area is typically preferably 20–150 g / m². 2 More preferably 30–100 g / m 2 .

[0122] [Matte Layer]

[0123] In this embodiment, the matte layer in the matte article is preferably a single layer or is stacked on at least a portion of the substrate and has the aforementioned surface shape, i.e., Spc (arithmetic mean curvature of the protrusion apex) is greater than 4000 mm. -1 A matte layer with a surface shape having an Rsm (average length of the curve element) of 30 μm or more is provided on the entire surface of one side of the aforementioned substrate. In the case of a matte article having a substrate, such as... Figure 5 As shown, the layer is provided such that the surface having this surface shape is the side opposite to the substrate side. Therefore, the matte article of this embodiment preferably has a matte layer and has the above-mentioned surface shape formed by the surface of the matte layer. In addition, from the viewpoints of mechanical strength and manufacturing adaptability, the matte layer is preferably a layer composed of a cured resin composition, preferably a cured resin composition containing a cured resin.

[0124] From the viewpoint of obtaining a matte article with excellent matte effect and a superior rough feel, a resin composition comprising a resin and a wrinkle-forming stabilizer (hereinafter, sometimes referred to as "resin composition for forming a matte layer") is preferred as the resin composition for forming the matte layer. That is, in this embodiment, the matte layer is preferably a layer comprising a resin and a wrinkle-forming stabilizer.

[0125] (Wrinkle formation stabilizer)

[0126] The wrinkle-forming stabilizer functions as follows: by stabilizing the formation of wrinkles on at least one surface of the matte layer, it uniformly displays the visibility of the matte effect across the entire surface of the matte layer, which has the surface shape of at least a portion of the surface of the matte article, reducing local gloss unevenness, and imparting stable visibility of the matte effect (hereinafter, sometimes only expressions such as "stable visibility of the matte effect" or expressions based thereon are used), as well as the uniformity of the surface state (also known as "texture") resulting from the stable formation of wrinkles across the entire surface of the matte layer. Furthermore, the wrinkles formed in the matte layer also greatly contribute to the expression of a rough tactile feel.

[0127] In this specification, "wrinkle formation stabilization" means that the in-plane distribution (dispersion σ) of the wrinkle shape and its geometric properties (length, width, and ratio of each protrusion) and its statistical indices (Spc, Rsm, Rz, and Ra in this specification, and Sm, Ssk, Sku, etc. as needed) converges with the addition of a wrinkle formation stabilizer compared to the absence of one. Consequently, the in-plane distribution (dispersion σ) of the 60° gloss value of the surface shape, described later, also converges.

[0128] Therefore, even if the so-called "matte agent" in the prior art and the "wrinkle-forming stabilizer" in this embodiment are the same in terms of their constituent substances and average particle size, their matting mechanisms (effects), the structures used to express matting, and the relationship between the amount used and the degree of surface gloss (gloss value) are different. In addition, they also differ from "matte agents" in that they exhibit a rough tactile feel by forming wrinkles.

[0129] In the prior art, such as Patent Document 1, the matting agent used for matting effect exhibits a visible matting effect through light diffusion caused by its physical shape. Specifically, the substance commonly referred to as a matting agent typically has a difference in refractive index between the matting agent particles and the surrounding resin and air. The matting effect is visible through light diffusion produced by the interface of reflection and refraction of light corresponding to the contour shape of the particles. On the other hand, in the matting article of this embodiment, the wrinkle-forming stabilizer does not exhibit a visible matting effect through light diffusion caused by the reflection and refraction of light from the particles themselves. Instead, the wrinkle-forming stabilizer stabilizes the formation of wrinkles on the surface of the matting layer, thereby stably imparting a visible matting effect and texture to the matting article through the light diffusion effect at the interface of the refractive index difference between the surface and air. Therefore, the wrinkle-forming stabilizer used in this embodiment and the matting agent that exhibits a visible matting effect (even assuming that the constituent materials and average particle size of the two are the same) have different matting mechanisms (functions) and structures used to exhibit matting.

[0130] Furthermore, the relationship between the content of "wrinkle formation stabilizers" and "matte agents" and the surface gloss (gloss value) differs. Using the same substance A as a wrinkle formation initiator AW (W: wrinkle) and containing it in a specific amount C, the 60° gloss value G of the surface when wrinkles are formed is... 60° AW (C) is significantly lower than the 60° gloss value G of a surface when substance A is used as a simple matting agent AM and it is contained in this specific amount C but does not form wrinkles on the surface. 60° AM (C). That is, the following relation holds.

[0131] G 60° AW (C) < G 60° AM (C)

[0132] The matte layer in the matte article of this embodiment may contain reagents conventionally used as matting agents. However, considering the characteristics of the effect of this invention—namely, consistently achieving an extremely superior matte effect that cannot be obtained even with the use of matting agents and obtaining a rough, textured feel—it is preferable that it does not contain matting agents. Thus, it can be said that the matte article of this embodiment possesses extremely superior matte effect visibility and texture even though it substantially does not contain matting agents conventionally used to achieve the visibility of the matte effect. Here, "without matting agents" means that, apart from being completely free of matting agents, even if it contains matting agents, it does not possess the visibility of a matte effect based on the effect of the matting agents themselves. Specifically, the content of matting agents is less than 15.0 parts by weight relative to 100 parts by weight of resin, preferably 10.0 parts by weight or less, and more preferably 3.0 parts by weight or less.

[0133] It should be noted that, in this application specification, "matte agent" refers to particles having an average particle size that is less than 100% of the thickness of the matte layer, i.e., the layer containing the matte agent, and more than 30 μm, based on the viewpoint of forming a protrusion by utilizing the exposure effect as described above.

[0134] In this embodiment, as a wrinkle-forming stabilizer, it can be used without particular restrictions as long as it is not a matting agent and the average particle size is limited to the smaller of 100% or less of the thickness of the matting layer and 30 μm or less.

[0135] From the viewpoint of improving the matting effect and the rough tactile feel, for wrinkle-forming stabilizers with an upper limit of the smaller of 100% or less of the thickness of the matting layer and 30 μm or less, it is preferable to use at least one of two wrinkle-forming stabilizers distinguished by their average particle size. Specifically, the two wrinkle-forming stabilizers are wrinkle-forming stabilizer 1 with an average particle size of 1 μm or more and an upper limit of the smaller of 100% or less of the thickness of the matting layer and 30 μm or less, and wrinkle-forming stabilizer 2 with an average particle size of less than 1 μm. In this embodiment, if at least one of the two wrinkle-forming stabilizers is used, the formation of wrinkles is stable, and an excellent matting effect can be consistently obtained, as well as a rough tactile feel.

[0136] In this embodiment, wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 can be used alone or in combination. From the viewpoint of improving the matte effect and the rough feel, it is more preferable to use wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 in combination.

[0137] As a wrinkle-forming stabilizer, organic particles or inorganic particles can be used, for example.

[0138] Examples of organic compounds that constitute organic particles include polymethyl methacrylate, acrylic-styrene copolymer resins, melamine resins, polycarbonate, polystyrene, polyvinyl chloride resins, benzoguanamine-melamine-formaldehyde condensates, silicones, fluorinated resins, and polyester resins.

[0139] Inorganic substances that constitute inorganic particles include silicon dioxide, aluminum oxide, calcium carbonate, aluminum silicate, and barium sulfate, among which silicon dioxide, which has excellent transparency, is preferred.

[0140] There are no particular limitations on the shape of the wrinkle-forming stabilizer; for example, spherical, polyhedral, scaly, and amorphous shapes are possible.

[0141] The average particle size of the wrinkle-forming stabilizer 1 is 1 μm or more, and is limited to the smaller of 100% or less of the thickness of the matte layer and 30 μm or less. From the viewpoint of stably improving the matte effect and enhancing the rough tactile feel, the average particle size of the wrinkle-forming stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, and even more preferably 1.8 μm or more. As an upper limit, it is preferably 90% or less of the thickness of the matte layer, more preferably 80% or less of the thickness of the matte layer, and even more preferably 70% or less of the thickness of the matte layer. Regarding the absolute value, it is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and even more preferably 7 μm or less. It can be set to any smaller of any combination of the upper limit relative to the thickness of the matte layer and the upper limit of the absolute value. For example, the smaller of 90% or less of the thickness of the matte layer and 20 μm or less can be used as the upper limit, or the smaller of 90% or less of the thickness of the matte layer and 10 μm or less can be used as the upper limit. It should be noted that the thickness of the matte layer will be explained later.

[0142] Furthermore, the average particle size of the wrinkle-forming stabilizer 2 is less than 1 μm. From the viewpoint of stabilizing wrinkle formation, steadily improving matte effect, and enhancing rough tactile feel, the average particle size of the wrinkle-forming stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more, even more preferably 5 nm or more, and as an upper limit, preferably 900 nm or less, more preferably 700 nm or less, and even more preferably 500 nm or less.

[0143] In this specification, the average particle size of the wrinkle-forming stabilizer is determined as the mass average value d50 in particle size distribution determination based on laser diffraction.

[0144] From the viewpoint of stabilizing the wrinkles formed by the wrinkle-forming stabilizer, steadily improving the matte effect, and enhancing the rough feel, the content of the wrinkle-forming stabilizer (the total content of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 when used in combination) relative to 100 parts by weight of the resin forming the matte layer is preferably 0.5 parts by weight or more, more preferably 0.75 parts by weight or more, even more preferably 1.0 parts by weight or more, and even more preferably 1.2 parts by weight or more. As an upper limit, there are no particular limitations from the viewpoint of steadily improving the matte effect and enhancing the rough feel. For example, from the viewpoint of improving the productivity of decorative materials based on the coatability of the resin composition for forming the matte layer, and effectively improving the visibility and texture of the matte effect, it is preferably 25.0 parts by weight or less, more preferably 15.0 parts by weight or less, even more preferably 10.0 parts by weight or less, even more preferably 7.5 parts by weight or less, and particularly preferably 6.0 parts by weight or less.

[0145] When wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 are used in combination, there are no particular restrictions on the content of each wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 as long as the total content is within the above-mentioned range. The content of wrinkle-forming stabilizer 2 relative to 100 parts by weight of resin is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, even more preferably 1.0 parts by weight or more, and as an upper limit, preferably 10.0 parts by weight or less, more preferably 7.5 parts by weight or less, even more preferably 5.0 parts by weight or less, and even more preferably 3.5 parts by weight or less. Furthermore, regarding the mixing ratio of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2, based on the amount of wrinkle-forming stabilizer 1 when their total amount is set to 100 parts by weight, it is preferably 0.05 parts by weight or more and 0.95 parts by weight or less, more preferably 0.10 parts by weight or more and 0.90 parts by weight or less, even more preferably 0.20 parts by weight or more and 0.80 parts by weight or less, and even more preferably 0.30 parts by weight or more and 0.70 parts by weight or less.

[0146] As described above, organic and inorganic particles can be used as wrinkle-forming stabilizers, but these particles themselves can include substances that have been used as matting agents in the past, such as the matte layer of the decorative sheet described in Patent Document 1, which uses matting agents such as spherical alumina and calcium carbonate. For matting agents such as spherical alumina and calcium carbonate, in order to achieve visible matting effects through light diffusion caused by their physical shape, as described in Patent Document 1, they need to be used at a total of about 50 parts by weight relative to 100 parts by weight of the resin component, which is 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate. However, in this embodiment, as described above, even if the content is set to a small amount—that is, even if it is set to a content less than that required to achieve visible matting effects through light diffusion caused by their physical shape—an extremely superior matting effect can be obtained compared to the effect obtained by using a matting agent, and a rougher tactile feel is also achieved. Therefore, it can be said that although the matte article of this embodiment does not actually contain matting agent, it achieves a more stable and superior matting effect in terms of visibility compared to the case where a matting agent is used, by stably forming wrinkles on the surface, while also obtaining texture and a rougher tactile feel.

[0147] (Surface shape of the matte layer)

[0148] The matte layer in the matte article of this embodiment is a layer having the surface shape described above, and is preferably a layer composed of a cured resin composition for forming a matte layer containing the specific wrinkle-forming stabilizer described above in a specific amount. As described above, by stably forming wrinkles on the surface of the matte layer, it becomes a layer that stably exhibits a matte effect through the light diffusion effect caused by the shape of the wrinkles, and also exhibits a rough tactile feel. Figure 3 This is a top view schematic diagram showing one embodiment of the matte article of this embodiment, illustrating the surface of the matte article obtained in the embodiment. Figure 3 The image shows that the matte article of this embodiment has wrinkles formed on its surface, i.e., on the surface of the matte layer. Here, "top view" refers to... Figures 4-6 In the XYZ coordinate system shown, the surface of the matte object is viewed from the positive Z-axis direction.

[0149] There are no particular restrictions on the surface shape of the wrinkles on at least one surface of the matte layer, as long as they have the surface shape described above, i.e., having Spc and Rsm within the specific numerical range described above, preferably other Rz and Ra within the specific numerical range described above. The surface shape is achieved by the wrinkles, and thus the formation is stabilized by the wrinkle-forming stabilizer, stably exhibiting a matte effect, and also exhibiting a rough touch.

[0150] Regarding the wrinkles, from the viewpoint of exhibiting the aforementioned surface shape, improving the matte effect, and enhancing the rough tactile feel, at least one surface of the matte layer preferably has a concave-convex shape composed of irregular wrinkles. The irregular wrinkles preferably consist of recesses and multiple protrusions, wherein the multiple protrusions are formed by multiple raised portions, and the recesses are formed by being surrounded by multiple raised portions. The raised portions preferably have linear protrusions. In this specification, a "linear protrusion" (hereinafter also referred to as a "linear protrusion") refers to a protrusion whose length-to-width ratio (length / width) is 3 or more, preferably 5 or more, and more preferably 10 or more. The method for determining this length and width is described below.

[0151] In this embodiment, more preferably, the irregular folds are composed of concave portions and multiple convex portions, wherein the multiple convex portions are formed by multiple line protrusions, and the concave portions are formed by being surrounded by the multiple line protrusions.

[0152] As a way related to these folds, for example, can be cited as Figure 3 As shown. In Figure 3 The image also shows irregular wrinkles on the surface of a matte article, i.e., the surface of the matte layer, when viewed from above. These irregular wrinkles are formed by multiple protrusions 2 formed by multiple curved line protrusions and recesses 3 formed by being surrounded by these protrusions. Furthermore, at least a portion of each of the curved protrusions 2 is formed by a meandering line protrusion, and a meandering recess 3 is formed such that it is surrounded by this meandering line protrusion. The matte article of this embodiment is... Figure 3 The stable formation of the folds results in a consistent matte finish and a rough, textured feel.

[0153] Here, "curve" refers to a portion in which the extension direction of a continuous line's protrusion 2, when viewed from above, reverses from one side to the other at one or more points. Examples of portions where the extension direction reverses from one side to the other include those with inflection points when approximating a continuous curve, neglecting the width of the line's protrusion 2 in its top view (assuming the width is 0). Furthermore, when approximating a straight line while neglecting the width of the line's protrusion 2 in its top view, examples include V-shaped broken lines or portions approximating a triangle with two sides containing one vertex.

[0154] Furthermore, "winding" refers to a portion where the extension direction of a protrusion 2, which has at least two continuous lines when viewed from above, reverses from one side to the other (hereinafter also referred to as "reversed portion"). And when the protrusion 2 of the line moves along its extension direction, adjacent portions alternately have sections where the extension direction of the protrusion 2 reverses in the opposite direction. For example, if the width of the top-view shape of the protrusion 2 of the line is ignored and approximated as a continuous curve, a shape approximating the Roman letter "S" can be given. Similarly, if the width of the top-view shape of the protrusion 2 of the line is ignored and approximated as a straight line, a shape approximating the Roman letter "W" can be given.

[0155] In this specification, "irregular" refers to a shape that cannot be described as having a fixed regularity or being arranged in a fixed pattern. Typical examples of non-irregular shapes (regular shapes) include, for instance, a so-called "lenticular lens," which is formed by arranging multiple cylindrical unit lenses adjacent to each other in a direction orthogonal to their length direction, or a shape arranged in a certain periodicity in a specific direction. Therefore, the irregular wrinkles in this embodiment include the following cases: the shape of a protrusion itself is not formed according to a fixed regularity such as periodicity but is irregular; furthermore, the shapes of multiple protrusions formed by multiple protrusions are not formed and arranged according to a fixed regularity but are irregular; and furthermore, the shape of the concave portion surrounded by such multiple protrusions is also irregular.

[0156] In the matte article of this embodiment, if any of the following is irregular: the shape of a protrusion (a raised portion), the shape and arrangement of the multiple protrusions (multiple raised portions), or the shape of the recess surrounded by the multiple protrusions, a matte effect and a rough tactile feel resulting from irregular wrinkles can be obtained; however, it is preferable that all of these are irregular. The matte article of this embodiment, by having irregular wrinkles, improves the visibility and texture of its matte effect, consistently exhibits an extremely excellent matte effect, and also exhibits a rough tactile feel.

[0157] As described above, the matte layer has wrinkles, i.e., an uneven shape, on at least one surface. Regarding the convex and concave parts in the uneven shape, for example, by using the brightness difference of the surface image of the decorative material of this embodiment, the darkest part of the density distribution image is set to grayscale 255, and the lightest part of the density distribution image is set to grayscale 0. For grayscale 0 to 255, grayscale 0 to 127 is set as concave parts, and grayscale 128 to 255 is set as convex parts, and binarization processing is performed to distinguish them.

[0158] The surface of the matte article in this embodiment preferably has irregular wrinkles formed in at least a portion of it, and more preferably, irregular wrinkles are formed on the entire surface. There are no particular limitations on the location of the wrinkles, as long as they are on the surface of the matte article; for example, they are not limited to the area corresponding to the pattern described later (on the pattern). As long as the wrinkles are on at least a portion of the surface, they exhibit a matte effect and a rough tactile feel due to their formation. For example, in the case of a decorative layer described later, where irregular wrinkles are formed in a portion, if the wrinkles are formed in the area corresponding to the pattern of the decorative layer (e.g., on the pattern), the pattern is visually perceived as a more matte area compared to its surroundings, thus enabling an improvement in design.

[0159] In addition, as Figure 3 As shown, it is preferable to have multiple protrusions formed by multiple irregular protrusions with a certain degree of homogeneity and concave portions surrounded by these protrusions. Therefore, in a single protrusion (protrusion), the shape with extreme variations in width is difficult to achieve the aforementioned surface shape, and it cannot be considered a preferred method in terms of both the visibility and texture of the matte effect, nor can it be considered a preferred method in terms of achieving a rough tactile feel. Regarding the shape of the protrusions (protrusions) and concave portions that form irregular wrinkles, the following will explain specific ways in which it can be advantageous in terms of consistently improving the matte effect and improving the rough tactile feel. By having the following shape for the wrinkles, the aforementioned surface shape is easily achieved, and the matte effect and rough tactile feel are improved.

[0160] Regarding the shape of the wrinkles formed on at least one surface of the matte layer, the height of the protrusion (the height of the raised portion) is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, with an upper limit of approximately 10 μm or less. Furthermore, the width of the protrusion is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.5 μm or more, with an upper limit of approximately 10 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. If the height and width of the protrusion are within the above ranges, the aforementioned surface shape is easily achieved, and due to the relationship with the concave portion, the matte effect is stably improved, and the rough tactile feel is enhanced.

[0161] Here, the aforementioned dimensions of the protrusions are the average of any 10 protrusions (raised portions) from any 10 locations (100μm square areas × 10 locations) in the matte article of this embodiment, i.e., a total of 100 protrusions. Additionally, as... Figure 3 As shown, within a single protrusion (protrusion), the width varies, resulting in different widths. Therefore, the width of a single protrusion (protrusion) is set as the average of the widths at any five points within that protrusion (protrusion). The same applies to the height of the protrusion (protrusion).

[0162] The depth of the recess is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, with an upper limit of approximately 10 μm or less. Furthermore, the width of the recess is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more, with an upper limit of approximately 10 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. If the depth and width of the recess are within the above ranges, the aforementioned surface shape is easily achieved. Due to its relationship with the convex portion, the matte finish is consistently improved, and the rough tactile feel is enhanced.

[0163] Here, the dimensions of the concave portion are determined in the same way as the dimensions of the convex portion described above.

[0164] The distance from the top of the convex portion to the bottom of the concave portion (the height difference between the convex and concave portions) is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more. As an upper limit, it is preferably 20 μm or less, more preferably 8 μm or less, and even more preferably 7 μm or less. If this distance is within the above range, the above-mentioned surface shape is easily achieved, the matting effect is stably improved, and the rough tactile feel is improved.

[0165] Here, the dimensions of the concave portion are determined in the same way as the dimensions of the convex portion described above.

[0166] The proportion of the protrusion is preferably 15% or more, more preferably 20% or more, even more preferably 30% or more, and preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less, as an upper limit. If the proportion of the protrusion is within the above range, the above-mentioned surface shape is easily achieved. Due to the relationship with the proportion of the concave portion surrounded by the protrusion, the matte effect is stably improved, and the rough tactile feel is improved.

[0167] Here, the occupancy ratio of the protrusion is the average of the occupancy ratio of the protrusion in any 10 locations (100μm square areas × 10 locations) of the matte article of this embodiment.

[0168] The convex and concave portions can have approximately the same direction and approximately the same width, but from the viewpoint of improving the matte finish and the rougher tactile feel, a shorter length is preferred. Specifically, the continuous length of the convex and concave portions with approximately the same direction and approximately the same width is preferably 95 μm or less, more preferably 80 μm or less, even more preferably 70 μm or less, and as a lower limit, preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more. If this length is within the above range, the wrinkles become more irregular, thus the matte finish is consistently improved, and the rougher tactile feel is enhanced.

[0169] Here, regarding any 10 locations (10 square areas of 100 μm × 10 locations) of the matte article of this embodiment, it is preferable that at least 80% of the 10 protrusions and recesses (i.e., a total of 100 protrusions and recesses) satisfy the above conditions, more preferably at least 85%, further preferably at least 90%, and even more preferably at least 95%. Furthermore, in this specification, "approximately the same" means roughly the same, without any branching; in the case of direction, it means a difference within ±3°, and in the case of width, it means a difference within ±5%.

[0170] Furthermore, the number of protrusions (raised portions) in a 100μm square area is preferably 10 or more, more preferably 20 or more, even more preferably 30 or more, and as an upper limit, preferably 200 or less, more preferably 100 or less, and even more preferably 70 or less. If the number of protrusions is within the above range, the matting effect is stably improved, and the rough tactile feel is improved.

[0171] The number of protrusions is the average number of protrusions in 10 locations (100μm square areas × 10 locations) of the matte article of this embodiment.

[0172] Figure 4 This is a cross-sectional view showing one embodiment of the matte article of this embodiment. It is a cross-sectional view obtained by cutting the matte article 10 with a plane parallel to its thickness direction (Z direction in this figure).

[0173] As the shape of the concave portion, for example, it can be like Figure 4 It can be acute-angled like 3a, or semi-circular or semi-elliptical like 3b, or a combination of both. Alternatively, it can be a convex part with a concave part, such as... Figure 4 It has a shape like the 3C.

[0174] On the other hand, the shape of the convex part presents as... Figure 4 It has a width of semicircle or semiellipse, like 2c and 2d.

[0175] The thickness of the matte layer is only required to form the aforementioned wrinkles in a way that stably exhibits a matte effect and a rough, tactile feel. There are no particular limitations. However, if ease of fabrication is also considered, it is typically 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and even more preferably 5 μm or more. As an upper limit, it is preferably 300 μm or less, more preferably 200 μm or less, even more preferably 150 μm or less, and even more preferably 100 μm or less.

[0176] In this specification, regarding the thickness of the matte layer, a scanning electron microscope (SEM) was used to photograph the cross-section of the matte article. The thickness was measured at 20 points from the captured images, and the average value of these 20 points was taken as the thickness of the matte layer. It should be noted that the SEM accelerating voltage was set to 3kV, and the magnification was set according to the thickness. The same procedure applies to the thickness of other layers.

[0177] The matte layer is a layer that presents the aforementioned surface shape on its entire surface. Since the matte article of this embodiment has a surface shape on at least a portion of its surface, it can be provided on at least a portion of the surface of the matte article, or it can be provided on its entire surface. In the case where the matte article of this embodiment has the aforementioned substrate and matte layer, it can be provided on at least a portion of the surface of the substrate, or it can be provided on its entire surface.

[0178] If the matte layer is placed in a position within the matte article that is visually recognized and touched by the consumer, that is, if the aforementioned surface shape is placed in a position within the matte article that is visually recognized and touched by the consumer, then the invention's effects, such as a matte finish and a rough, tactile feel, can be achieved.

[0179] Furthermore, when the substrate is in the form of a film, sheet, or plate, the matte layer only needs to be applied to the parts of the matte article that the user visually identifies and touches. It only needs to be applied to at least a portion of one surface, or it can be applied to the entire surface. From the viewpoint of improving the matte effect and the rough tactile feel, such as... Figures 4-6 As shown, it is preferred to set it on the entire surface of one face.

[0180] (Resin)

[0181] As the resin for forming the matte layer, any resin that is formed by curing a matte layer-forming resin composition containing the aforementioned wrinkle-forming stabilizer in a specified amount can be used to form a cured product constituting the matte layer. Examples of such resins include ionizing radiation-curable resins. For instance... Figures 4-6 As shown, the matte layer is a layer that can be provided on the outermost surface of the matte article in this embodiment. Therefore, from the viewpoint of improving the usability of the matte article, in addition to resins that easily form wrinkles through wrinkle-forming stabilizers, resins that easily exhibit surface properties such as processing characteristics, stain resistance, scratch resistance, and weather resistance are preferred. From these viewpoints, ionizing ray curable resins are preferred. Since the matte article of this embodiment contains very little wrinkle-forming stabilizer in the matte layer, the performance of the resin forming the matte layer is more directly reflected in its surface properties.

[0182] Ionizing radiation-curable resins are resins containing ionizing radiation-curable functional groups. These functional groups are groups that are cross-linked and cured by irradiation with ionizing radiation. Examples of preferred functional groups include (meth)acryloyl, vinyl, and allyl groups, which possess olefinic double bonds. It should be noted that in this specification, (meth)acryloyl means acryloyl or methacryloyl. Additionally, in this specification, (meth)acrylate means acrylate or methacrylate.

[0183] In addition, ionizing rays refer to electromagnetic waves or charged particle beams that contain energy quanta capable of polymerizing and / or cross-linking molecules. They are usually ultraviolet (UV) or electron beams (EB). In addition, they also include electromagnetic waves such as X-rays and gamma rays, charged particle beams such as alpha rays and ion beams.

[0184] Examples of ionizing ray curable resins include electron beam curable resins and ultraviolet curable resins. From the viewpoints of stabilizing wrinkle formation through wrinkle-forming stabilizers, steadily improving matting effect, and enhancing roughness, ultraviolet curable resins are preferred.

[0185] Specifically, ionizing ray curable resins can be appropriately selected from polymeric monomers and polymeric oligomers that have been conventionally used as ionizing ray curable resins.

[0186] As polymerizable monomers, (meth)acrylate monomers having free radical polymerizable unsaturated groups in the molecule are preferred, and polyfunctional (meth)acrylate monomers are preferred. Here, "(meth)acrylate" means "acrylate or methacrylate".

[0187] Examples of multifunctional (meth)acrylate monomers include those having two or more ionization-curable functional groups in their molecules, and having at least one (meth)acryloyl group as such a functional group.

[0188] From the viewpoints of stabilizing wrinkle formation to steadily improve matte finish, enhancing roughness, and improving surface properties such as post-processing characteristics, scratch resistance, and weather resistance, the number of functional groups in the multifunctional (meth)acrylate monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, further preferably 2 or more and 4 or less, and even more preferably 2 or more and 3 or less. Furthermore, with the aforementioned number of functional groups, the aforementioned surface shape is particularly easy to obtain, and the roughness is easily improved.

[0189] These multifunctional (meth)acrylates can be used alone or in combination.

[0190] Examples of polymerizable oligomers include (meth)acrylate oligomers that have two or more ionizing radiation-curable functional groups in their molecules, and at least one (meth)acryloyl group as such a functional group. Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.

[0191] In addition, as polymerizable oligomers, there are also highly hydrophobic polybutadiene (meth)acrylate oligomers with (meth)acrylate groups on the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers with polysiloxane bonds in the main chain, amino plastic resin (meth)acrylate oligomers modified from amino plastic resins with a large number of reactive groups in small molecules, and oligomers with cationic polymerizable functional groups in the molecules, such as linear phenolic epoxy resins, bisphenol epoxy resins, aliphatic vinyl ethers, and aromatic vinyl ethers.

[0192] These polymeric oligomers can be used alone or in combination.

[0193] From the perspectives of stabilizing the formation of wrinkles and steadily improving the matte effect, enhancing the rough tactile feel, and improving surface properties such as post-processing characteristics, scratch resistance, and weather resistance, urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers are preferred, urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are more preferred, and urethane (meth)acrylate oligomers are even more preferred.

[0194] From the viewpoints of stabilizing the formation of wrinkles and steadily improving the matte effect, improving the rough tactile feel, and improving surface properties such as processing characteristics, scratch resistance, and weather resistance, the number of functional groups in these polymeric oligomers is preferably 2 or more and 8 or less, with an upper limit, more preferably 6 or less, and even more preferably 4 or less.

[0195] Furthermore, from the same perspective, the weight-average molecular weight of these polymeric oligomers is preferably 2,500 or more and 7,500 or less, more preferably 3,000 or more and 7,000 or less, and even more preferably 3,500 or more and 6,000 or less. Here, the weight-average molecular weight is the average molecular weight determined by GPC analysis and converted to standard polystyrene.

[0196] In this embodiment, the resin used to form the matte layer is preferably a combination of the aforementioned polymeric oligomer and polymeric monomer. In this case, the polymeric oligomer is preferably a multifunctional urethane (meth)acrylate oligomer, more preferably a multifunctional urethane acrylate oligomer. Furthermore, the polymeric monomer is preferably a multifunctional polymeric monomer, more preferably a multifunctional (meth)acrylate monomer, and even more preferably a multifunctional acrylate monomer. This stabilizes the formation of wrinkles, steadily improves the matte effect, enhances the rough tactile feel, and also improves surface properties such as processing characteristics, scratch resistance, and weather resistance.

[0197] When used in combination, from the same viewpoint, the content of the polymeric oligomer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, further preferably 55 parts by mass or more, and even more preferably 60 parts by mass or more, with an upper limit of preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less. Alternatively, polymeric oligomers may be used in combination, preferably two polymeric oligomers with different numbers of functional groups. In this case, the content of the polymeric oligomer with a larger number of functional groups relative to 100 parts by mass of the total polymeric oligomers is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, further preferably 60 parts by mass or more, and even more preferably 65 parts by mass or more.

[0198] (Resin composition)

[0199] The matte layer is preferably composed of a cured resin composition containing the aforementioned wrinkle-forming stabilizer in a predetermined amount, wherein the resin composition preferably contains the aforementioned resin and the aforementioned wrinkle-forming stabilizer in a predetermined amount. In addition to the aforementioned wrinkle-forming stabilizer and resin, the resin composition used in this embodiment may also contain other components depending on desired properties, etc.

[0200] The resin composition used to form the matte layer may contain monofunctional (meth)acrylates, for example, for the purpose of reducing its viscosity. These monofunctional (meth)acrylates may be used alone or in combination.

[0201] Furthermore, when the aforementioned resin is an ultraviolet-curable resin that is cured by ultraviolet light, it is preferable to include additives such as photopolymerization initiators and photopolymerization accelerators. By including these additives, the resin can be cured even when using ultraviolet light (even without using ionizing rays), and surface properties that are beneficial for practical use can be obtained.

[0202] As photopolymerization initiators, one or more can be selected from acetophenone, benzophenone, α-hydroxyalkyl benzophenone, michaelone, benzoin, benzoyl dimethyl ketal, benzoylbenzoate, α-acyl oxime ester, thioxanone, etc.

[0203] In addition, photopolymerization accelerators can reduce polymerization hindrance caused by air during curing and accelerate the curing speed. Examples include one or more selected from p-dimethylaminobenzoate isoamyl ester, p-dimethylaminobenzoate ethyl ester, etc.

[0204] Since the matte layer is the outermost layer that can be applied to the matte article of this embodiment, it is preferably a weather-resistant layer, such as one that contains various weather-resistant agents such as ultraviolet absorbers and light stabilizers.

[0205] As ultraviolet absorbers, commonly used ultraviolet absorbers found in decorative materials and panels can be used without particular restrictions. Examples include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and hydroxyphenyltriazine-based ultraviolet absorbers. As light stabilizers, commonly used light stabilizers found in decorative materials and panels can also be used without particular restrictions. Examples include hindered amine light stabilizers such as piperidine sebacate light stabilizers. Furthermore, these ultraviolet absorbers and light stabilizers can have reactive functional groups with olefinic double bonds, such as (meth)acryloyl, vinyl, or allyl groups, in their molecules.

[0206] These UV absorbers, light stabilizers, and other weather-resistant agents can be used alone or in combination.

[0207] [60° gloss value]

[0208] The matte article of this embodiment is an article with excellent visibility and texture due to its matte effect. In this specification, "matte" means that the gloss is not easily visible. It varies depending on the color tone, pattern, etc. of the article, so it cannot be generalized. However, for example, if the 60° gloss value is 20.0 or less, preferably about 10.0 or less, it is generally considered to be "matte".

[0209] To date, for example, in matte articles exhibiting black and other dark colors ("dark colors" refers to low brightness, such as an L* value (hereinafter sometimes simply referred to as "L* value") in the CIE (International Commission on Illumination) L*a*b* color system measured according to JIS Z8781-4:2013, typically around 40 or less, preferably 30 or less), the use of matting agents can achieve excellent visibility of the matting effect with a 60° gloss value of 20.0 or less, preferably 10.0 or less. However, due to the large amount of matting agent used, streaks and unevenness are generated during layer formation, making it difficult to manufacture easily, and surface properties are reduced. Furthermore, for example, regarding matte articles exhibiting hues other than black and other dark colors, even with the use of matting agents, there is a lower limit to the 60° gloss value. Similar to matte articles exhibiting black, it is not easy to obtain matte articles with excellent surface properties and excellent visibility and texture of the matting effect in either case. This trend is more pronounced the smaller the 60° gloss value.

[0210] In the matte article of this embodiment, by using two wrinkle-forming stabilizers having a specified average particle size in combination and keeping their content as small as described above, not only is a stable and extremely excellent matte effect in terms of visibility and texture obtained, but also a rough tactile feel is achieved. Furthermore, by suppressing the amount of wrinkle-forming stabilizer used to a very small amount, a significant increase in the viscosity of the resin composition can be prevented, thus facilitating the formation of this layer and naturally resulting in excellent surface properties such as stain resistance, scratch resistance, and weather resistance, corresponding to the characteristics of the resin used in the matte layer.

[0211] The matte article of this embodiment varies depending on the hue as described above, so it cannot be generalized. For example, in the case of black and other dark colors, the visibility of the matte effect can be extremely excellent with a 60° gloss value of 10.0 or less, and further 7.5 or less, 5.0 or less, 4.0 or less, 3.6 or less, and 2.0 or less as the gloss value of the matte layer side.

[0212] Furthermore, matte articles exhibiting hues other than black and other dark colors can also possess the aforementioned 60° gloss value. In this embodiment, the 60° gloss value on the matte layer side of the matte article is substantially the same as the 60° gloss value of the surface of the layer forming the outermost surface of the matte article; it is the 60° gloss value of the surface of the matte layer unless further layers are present. When further layers are present and these other layers are disposed on the surface side of the matte layer, the 60° gloss value refers to the 60° gloss value of those other layers; however, the specific 60° gloss value of the matte article in this embodiment substantially depends on the composition of the matte layer.

[0213] In this specification, the 60° gloss value on the matte layer side is the 60° specular gloss measured according to JIS K 5600-4-7:1999, which is the average value of the values ​​measured from the matte layer side at any 10 locations using a gloss meter or the like.

[0214] [Other layers]

[0215] In addition to the matte layer and substrate described above, the matte article of this embodiment may also have other layers as needed, such as a base coating layer, a transparent resin layer, a decorative layer, and an adhesive layer. A cross-sectional view showing one embodiment of the matte article of this embodiment having these layers is shown in the figure. Figure 5 and Figure 6 . Figure 5 and Figure 6 This is a cross-sectional view showing one embodiment of the matte article of this embodiment. It is a cross-sectional view obtained by cutting the matte article 10 with a plane parallel to its thickness direction (Z direction in this figure).

[0216] Figure 5 The matte decorative material 10 shown has a substrate 12 and a matte layer 11 in sequence. Figure 6 The matte article 10 shown has, in sequence, a substrate 12, a decorative layer 13, an adhesive layer 14, a transparent resin layer 15, a base coating layer 16, and a matte layer 11.

[0217] (Undercoat)

[0218] In the case where the matte article of this embodiment is composed of multiple layers, a base layer may be provided in order to improve the interlayer adhesion of the multiple layers.

[0219] In the case where the matte article of this embodiment has a layer other than the matte layer, for example, in the case where it has a matte layer and a substrate, in order to improve the interlayer adhesion, a base coating layer can be provided between the matte layer and the substrate.

[0220] The base coating is mainly composed of adhesive resin and may contain additives such as UV absorbers and light stabilizers as needed.

[0221] Preferred adhesive resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate-urethane-acrylic copolymers (urethane-acrylic copolymers derived from polymers (polycarbonate polyols) having carbonate bonds in the polymer backbone and two or more hydroxyl groups at the ends and side chains), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chloropropylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins. These resins can be used alone or in combination.

[0222] Alternatively, the adhesive resin can also be a resin obtained by adding isocyanate-based curing agents, epoxy-based curing agents, or other curing agents to these resins and then cross-linking and curing them. Among these, a resin obtained by cross-linking and curing polyol resins such as acrylic polyol resins with isocyanate-based curing agents is preferred, and a resin obtained by cross-linking and curing acrylic polyol resins with isocyanate-based curing agents is more preferred.

[0223] The thickness of the base coating is preferably 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 8 μm or less, and even more preferably 2 μm or more and 6 μm or less.

[0224] The matte article of this embodiment aims to improve adhesion to bonded materials such as resin molded articles on which the article is laminated. A base coating (also called a "back base coating") may be provided on the opposite side of at least one wrinkled surface of the matte layer. In addition, when a substrate is provided, a base coating may also be provided on the opposite side of the side of the substrate on which the matte layer is provided.

[0225] (Transparent resin layer)

[0226] In order to improve the strength of the matte article of this embodiment, and in the case of having a decorative layer described later, a transparent resin layer may be provided from the viewpoint of protecting the decorative layer. When a substrate is provided, the transparent resin layer can be disposed between the substrate and the matte layer; when a decorative layer is provided, the transparent resin layer can be disposed between the decorative layer and the matte layer to protect the decorative layer.

[0227] Examples of resins constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, and vinyl chloride resins. Among these, polyolefin resins and vinyl chloride resins are preferred from the viewpoint of post-processing adaptability. In addition, two or more of these various resins may be layered or mixed.

[0228] The transparent resin layer only needs to be transparent enough to visually identify the substrate side compared to the transparent resin layer. Furthermore, in the case of a decorative layer, the transparency only needs to be transparent enough to visually identify the decorative layer; besides colorless transparency, it can also be colored transparency or semi-transparent. That is, in this embodiment, "transparency" refers to colorless transparency, colored transparency, and semi-transparency.

[0229] The transparent resin layer may contain weather-resistant agents such as ultraviolet absorbers and light stabilizers, as well as additives such as colorants.

[0230] From the viewpoint of protecting the decorative layer and taking into account post-processing adaptability, the thickness of the transparent resin layer is preferably 20 μm or more and 150 μm or less, more preferably 40 μm or more and 120 μm or less, and even more preferably 60 μm or more and 100 μm or less.

[0231] (Decorative layer)

[0232] From the viewpoint of improving design, the matte article of this embodiment can have a decorative layer. The decorative layer can be provided on the side opposite to the matte layer that has at least one wrinkled side. If a substrate is provided, it can be provided between the substrate and the matte layer. Alternatively, if a transparent resin layer is provided, it can be provided in the order of decorative layer, transparent resin layer and matte layer.

[0233] The decorative layer can be, for example, a colored layer that covers the entire surface (a so-called solid colored layer). Figure 6 The “13a” in the text can also be a pattern layer formed by printing various patterns using ink and a printing press. Figure 6 (13b in the text). Additionally, as... Figure 6 As shown, solid color layers and patterned layers can also be combined.

[0234] There are no particular restrictions on the patterns (patterns) used as pattern layers. Any pattern that corresponds to the desired pattern can be used. Examples include wood grain patterns such as annual rings and duct grooves on the surface of wood panels, stone patterns on the surface of marble and granite, fabric patterns on the surface of cloth, leather patterns on the surface of leather, geometric patterns, text, graphics, and patterns formed by combining them.

[0235] The ink used in the decorative layer is an ink in which pigments, dyes and other colorants, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, ultraviolet absorbers, light stabilizers and so on are appropriately mixed into the binder resin.

[0236] There are no particular limitations on the adhesive resin used as the decorative layer. Examples include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, allyl chloride resins, nitrocellulose resins, and cellulose acetate resins. Furthermore, various types of resins can be used, such as one-component curing resins and two-component curing resins containing isocyanate compounds or other curing agents.

[0237] As a colorant, pigments with excellent hiding power and weather resistance are preferred. The same pigments exemplified as those that can be used as a base material can be used.

[0238] The content of colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and even more preferably 30 parts by mass or more and 70 parts by mass or less, relative to 100 parts by mass of the resin constituting the decorative layer.

[0239] The decorative layer may contain UV absorbers, light stabilizers and other weather-resistant agents, colorants and other additives.

[0240] The thickness of the decorative layer can be appropriately selected according to the desired pattern. From the viewpoint of masking the background color of the bonded material and improving the design, it is preferably 0.5μm or more and 20μm or less, more preferably 1μm or more and 10μm or less, and even more preferably 2μm or more and 5μm or less.

[0241] (Adhesive)

[0242] In the case where the matte article of this embodiment has a substrate and a transparent resin layer, an adhesive layer may be provided between the substrate and the transparent resin layer in order to improve the adhesion between the two layers.

[0243] When a decorative layer is further provided between the substrate and the transparent resin layer, the positional relationship between the adhesive layer and the decorative layer is not particularly limited. Specifically, the decorative layer, adhesive layer and transparent resin layer may be provided sequentially from the side closest to the substrate, or the adhesive layer, decorative layer and transparent resin layer may be provided sequentially from the side closest to the substrate.

[0244] The adhesive layer can be composed of adhesives such as urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, and rubber-based adhesives. Among these adhesives, urethane-based adhesives are preferred from the perspective of adhesive strength.

[0245] Examples of urethane-based adhesives include two-component curing urethane resins that utilize curing agents such as polyol compounds including polyether polyols, polyester polyols, acrylic polyols, and isocyanate compounds.

[0246] From the viewpoint of efficiently obtaining the desired adhesive strength, the thickness of the adhesive layer is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less.

[0247] The matte article of this embodiment sometimes has a substrate made of an opaque material or has a decorative layer. Therefore, the total light transmittance of the matte article of this embodiment can be low. Specifically, the total light transmittance of the matte article of this embodiment, as measured according to JIS K7361-1:1997, is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less.

[0248] In this specification, the total transmittance of the matte article is the total transmittance measured according to JIS K7361-1:1997, which is the average value of measurements taken at any 10 locations.

[0249] [Manufacturing method for matte finish items]

[0250] The first manufacturing method of the matte article of this embodiment is characterized by having a matte layer forming step, in which a layer of a resin composition for matte layer forming, comprising the above-mentioned resin and a wrinkle forming stabilizer, is irradiated with light of a wavelength of at least 100 nm and less than 380 nm to form a matte layer.

[0251] The first manufacturing method enables the manufacture of, for example... Figure 5 and 6 The matte article shown is a laminate consisting of multiple layers, such as a substrate and a cured layer of a resin composition having the aforementioned surface shape in at least a portion thereof as a matte layer. For example, if the resin composition for forming the matte layer is coated onto a substrate, a layer of the resin composition is formed on the substrate, and a matte layer is formed by the aforementioned irradiation, a matte article having a substrate and a matte layer can be manufactured. The preferred manufacturing method is to give the matte article the aforementioned surface shape (giving the surface on the matte layer side the aforementioned surface shape) by passing the matte layer over the matte article, thereby producing a matte article with a matte effect of a 60° gloss value of 20.0 or less, 10.0 or less, and a rough tactile feel on the matte layer side.

[0252] The matte article of this embodiment can be easily obtained by the manufacturing method of the matte article described above. Specifically, when forming the matte layer, by irradiating a short-wavelength ultraviolet light of at least 100 nm and less than 380 nm onto a resin composition for forming the matte layer containing a wrinkle-forming stabilizer, wrinkles can be formed on at least one surface of the matte layer, thereby imparting a matte effect and a rough tactile feel to the matte article (matte layer).

[0253] The details of the mechanism by which wrinkles are formed on at least one surface of the matte layer by irradiating the resin composition used to form the matte layer with such short-wavelength ultraviolet light, thereby exhibiting a matte effect and a rough tactile feel, are not yet clear, but it is speculated to be based on the following mechanism.

[0254] If a coating layer formed by a resin composition for forming a matte layer, applied to a specified thickness, is irradiated with short-wavelength ultraviolet light, the energy of the ultraviolet light only penetrates to the surface portion and does not reach the lower layers. Therefore, only the surface portion of the resin composition begins to cure, and it is considered that only the surface undergoes curing shrinkage, forming wrinkles. Thus, it is believed that wrinkles form when curing occurs only along a certain thickness direction from the surface of the resin composition for forming the matte layer, due to irradiation with short-wavelength ultraviolet light.

[0255] Furthermore, based on the comparison of the embodiments and comparative examples described later, without a wrinkle-forming stabilizer, wrinkle formation becomes unstable, and the visibility and texture of the matte effect are not consistently and fully expressed across the entire surface of the matte layer. Additionally, the rough texture is not sufficiently exhibited. Therefore, the stable expression of this matte effect and rough texture cannot be explained solely by curing only the surface portion using short-wavelength ultraviolet light. In other words, in order for the matte article of this embodiment to stably possess wrinkles and exhibit both a matte effect and a rough texture, the inclusion of a wrinkle-forming stabilizer is essential. If it is considered that a stable matte finish and rough texture resulting from wrinkle formation cannot be obtained without a wrinkle-forming stabilizer, then the wrinkle-forming stabilizer functions as a core that triggers wrinkle formation. Centered on this core, the resin on the surface portion of the resin composition aggregates to form the convex portion (protrusion) of the wrinkle, and at the same time as forming the convex portion (protrusion), the concave portion is formed. As a result, the wrinkle formation is considered stable, and a stable matte finish and rough texture are exhibited.

[0256] The wrinkle-forming stabilizer and the resin composition for forming a matte layer containing the wrinkle-forming stabilizer used in the manufacturing method of this embodiment are the same as those described above as wrinkle-forming stabilizers and resin compositions for forming matte layers that can be used in the matte decorative material of this embodiment.

[0257] In the manufacturing method of this embodiment, a resin composition for forming a matte layer is irradiated with light of a wavelength of at least 100 nm and less than 380 nm. Through this irradiation, as described above, the energy of the ultraviolet light only penetrates to the surface portion and does not reach the lower layers. Therefore, only the surface portion of the resin composition begins to cure, and only surface curing shrinkage occurs, thereby stabilizing the formation of wrinkles. The surface layer of the resin composition becomes a cured product, constituting a matte layer. Then, curing proceeds from the portion near the surface where curing is slower to the deeper portion in the depth direction, and the layer of the resin composition becomes a cured product, thus curing over the entire thickness of the resin composition. A light diffusion effect is exhibited on the surface, forming a wrinkled matte layer with a rough, tactile feel. From the viewpoint of promoting curing to the deeper portion, as described later, it is preferable to perform further irradiation treatment after irradiation with light of a wavelength of 100 nm and less than 380 nm.

[0258] "Excimer light" refers to light with a wavelength of at least 100 nm and less than 380 nm, preferably light from an excimer, i.e., an excimer, formed by the discharge of rare gases such as Ar, Kr, Xe, Ne, halides of rare gases based on halogens such as F, Cl, I, Br, or mixtures thereof, that contains the ultraviolet wavelength region. For example, light with wavelengths of 126 nm (hereinafter referred to as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), 193 nm (ArF), 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), and 351 nm (XeF) radiated from an excimer of Ar2 is preferred. As excimer light, either spontaneous emission light or highly coherent (interferometric) lasers based on stimulated emission can be used, but spontaneous emission light is usually sufficient. It should be noted that discharge lamps emitting this light (ultraviolet light) are also called "excimer lamps".

[0259] The excimer light has a single wavelength peak, and as a characteristic, its half-width at half-maximum (WWHM) is narrower than that of ordinary ultraviolet light (such as ultraviolet light emitted from metal halide lamps, mercury lamps, etc.). By using such excimer light, wrinkle formation is stabilized, the matting effect is consistently improved, and the rougher tactile feel is also enhanced.

[0260] From the viewpoint of stabilizing the formation of wrinkles, consistently improving the matting effect, and enhancing the rough tactile feel, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, even more preferably 150 nm or more, and even more preferably 155 nm or more. As an upper limit, it is preferably 320 nm or less, more preferably 300 nm or less, even more preferably 250 nm or less, even more preferably 200 nm or less, and most preferably 172 nm (Xe2). Thus, in this embodiment, from the viewpoint of consistently improving the matting effect and enhancing the rough tactile feel, it is also preferable to use shorter wavelength light, more preferably medium-wavelength ultraviolet light (wavelength: 280–320 nm) and short-wavelength ultraviolet light (wavelength: 280 nm or less), and even more preferably short-wavelength ultraviolet light.

[0261] In this embodiment, from the viewpoint of stabilizing the formation of wrinkles, consistently improving the matting effect, and enhancing the rough tactile feel, the cumulative light intensity of the aforementioned wavelength is preferably 1 mJ / cm. 2 The above, more preferably 10 mJ / cm 2 The above is further optimized to 30 mJ / cm. 2 The above is further optimized to 50 mJ / cm. 2 That's all. Furthermore, as an upper limit, there is no particular restriction, but from the viewpoint of reducing the number of lamps required for wavelength light irradiation and improving production efficiency, a limit of 1000 mJ / cm² is preferred. 2 Below, 500 mJ / cm is more preferred. 2 The following is a further preferred value: 300 mJ / cm 2 Based on the same viewpoint, the ultraviolet power density is preferably 0.001 W / cm or more, more preferably 0.01 W / cm or more, even more preferably 0.03 W / cm or more, and as an upper limit, preferably 10 W / cm or less, more preferably 5 W / cm or less, and even more preferably 3 W / cm or less.

[0262] In addition, the oxygen concentration when irradiated with the above wavelength of light is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and even more preferably 300 ppm or less.

[0263] In the matte layer formation process of the method for manufacturing matte articles according to this embodiment, in addition to the irradiation with light of a wavelength of at least 100 nm and less than 380 nm as described above, other treatments that help cure the resin composition for matte layer formation may also be performed.

[0264] For example, from the viewpoint of stabilizing the formation of wrinkles caused by the difference in the degree of curing between the surface portion and the deeper portion in the depth direction, and promoting the curing process towards the deeper portion, the resin composition for forming the matte layer can be pre-cured by irradiating with light of a wavelength exceeding 380 nm, preferably between approximately 385 nm and 400 nm, and then irradiated with light of a wavelength between 100 nm and 380 nm. Alternatively, after irradiation with light of a wavelength between 100 nm and 380 nm, post-curing can be performed to further cure the resin composition. Regarding pre-curing and post-curing, it is appropriate to determine whether they are necessary based on the desired properties of the matte layer (e.g., processing characteristics, surface properties such as stain resistance). Furthermore, the aforementioned wavelengths are ultraviolet light, but not limited to ultraviolet light; other ionizing rays, such as electron beams, can also be used. For example, in post-curing, from the viewpoint of improving the surface properties of the matte layer, an electron beam is preferred.

[0265] In the manufacturing method of this embodiment, the matte layer can be formed by irradiating the coating layer (uncured resin layer) with light of a wavelength of at least 100 nm and less than 380 nm. The coating layer (uncured resin layer) is obtained by coating the resin composition for forming the matte layer using known methods such as gravure printing, bar coating, roller coating, reverse roller coating, and comma coating.

[0266] Furthermore, the matte article obtained in the manufacturing method of this embodiment may have a substrate, which is described as a layer that can be used in the matte article of this embodiment, and other layers such as a transparent resin layer.

[0267] For example, the decorative layer, adhesive layer, and primer layer can be formed by applying a coating liquid containing the composition forming each layer in the manner known above, and then drying and curing as needed. Alternatively, in the case of forming a transparent resin layer, the resin film forming the transparent resin layer can be formed by dry lamination or the like.

[0268] In the matte articles of this embodiment, such as Figure 4 The article shown, which is composed of a single layer, such as a cured resin composition and has the aforementioned surface shape on one side of its surface, can be manufactured by the following second manufacturing method.

[0269] The second manufacturing method is characterized by comprising: a step of coating a matte article forming resin composition comprising resin and wrinkle forming stabilizer onto the release layer of a support sheet having a release layer to form a coating layer; a step of irradiating the coating layer with light of a wavelength of at least 100 nm and less than 380 nm; and a step of peeling off the support sheet.

[0270] As the support sheet, it is appropriate to select from the sheets exemplified as support sheets that can be used as the aforementioned substrate, such as substrates made of fibrous materials, preferably paper such as high-quality paper. After the resin composition is made into a matte article, it is easy to peel off from the matte article, making processing easy and economical.

[0271] A release layer is a layer provided to facilitate the peeling of the support sheet from a matte article after the resin composition has been made. Examples of release layers with excellent peelability include release layers made from acrylic resins, vinyl chloride-vinyl acetate, olefin resins, silicone resins, fluoropolymers, and various silicone or fluorine-modified resins, and waxes can be mixed as needed.

[0272] Examples of waxes include microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylenes, wood wax, beeswax, whale wax, white wax, wool wax, shellac wax, candelilla wax, petrolatum, some modified waxes, fatty acid esters, fatty acid amides, and other waxes.

[0273] The resin composition for forming matte articles, which includes resin and wrinkle-forming stabilizer, can be from resins and wrinkle-forming stabilizers that are examples of substances that can be used in resin compositions for forming matte layers. Furthermore, the content of the wrinkle-forming stabilizer, etc., is the same as that of the resin composition for forming matte layers.

[0274] The coating of the resin composition for forming matte articles can be performed in the same way as the coating of the resin composition for forming matte layers described above. In addition, the method of irradiating the coated layer with light of a wavelength of at least 100 nm and less than 380 nm is the same as the method of irradiating the layer of the resin composition for forming matte layers.

[0275] Furthermore, the thickness of the coating layer is the same as the thickness of the directly obtained matte article. The thickness of the coating layer can be determined according to the desired thickness and is not particularly limited. It can be selected from the widest range of the aforementioned substrate thicknesses, from 1 μm to 10 cm. Considering manufacturing adaptability, processing adaptability, etc., the thickness of the coating layer is preferably 3 μm or more, more preferably 5 μm or more, and as an upper limit, preferably 300 μm or less, more preferably 200 μm or less.

[0276] Furthermore, to enhance design flexibility, a decorative layer can be applied before forming the coating layer of the resin composition used for forming matte articles. Therefore, in the process of... Figure 4 In the case of a single-layer structure as shown, a matte article may further have a decorative layer. The decorative layer may be configured to have the same structure as the decorative layer described above, which is a layer that a matte article having the aforementioned substrate and matte layer can have.

[0277] By irradiating the coating layer of the resin composition used to form a matte article with light of the aforementioned wavelength, similar to the aforementioned matte layer, only the surface undergoes curing shrinkage, thereby stabilizing the formation of wrinkles. The surface layer of the resin composition becomes a cured product with the aforementioned surface shape. Curing proceeds from the surface layer, which cures more slowly, to the deeper portion that is further away in the depth direction. The entire resin composition is cured, thereby becoming a matte article with the aforementioned surface shape on at least a portion of its surface.

[0278] In addition, regarding irradiation, post-curing can be performed to promote curing to deeper parts, or pre-curing can be performed.

[0279] After the coating layer of the resin composition for forming a matte article is cured by irradiating it with light of the specified wavelength, the support sheet is peeled off, thereby obtaining a matte article having the surface shape described above in at least a portion of its surface.

[0280] Furthermore, in the matte articles of this embodiment, such as Figure 4 The matte article shown, which consists of a single layer, such as a resin article having the above-described surface shape on at least a portion of the surface of a resin article or other resin article, can be manufactured by the following third manufacturing method.

[0281] The third manufacturing method is characterized by having a step of embossing at least a portion of the surface of a resin molded article using an embossing plate, a shaping sheet, or the like, thereby imparting the aforementioned surface shape.

[0282] Embossing plates and shaped sheets can be used without particular restrictions as long as they can impart the aforementioned surface shapes. The surface shape of the embossing plate or shaped sheet is the opposite of the surface shape it shapes. Specifically, the shape of the concave portion of the shaped sheet, which forms a convex portion in the shaped surface shape, is such that the absolute value of the surface shape's Spc is greater than 4000 mm. -1 Therefore, the Rsm of the shaping sheet only needs to be above 30μm. It should be noted that the values ​​related to the surface shape of the shaping sheet and the matte finish are only theoretical values ​​and will naturally have some errors.

[0283] In addition, examples of matte articles in this embodiment include high-pressure melamine resin decorative panels, low-pressure melamine resin decorative panels, diallyl phthalate (DAP) resin decorative panels, polyester decorative panels, guanidine resin decorative panels, and phenolic resin decorative panels, etc., which are thermosetting resin decorative panels. Thermosetting resin decorative panels are obtained as follows: A material, such as paper, woven fabric, or non-woven fabric, which can be used as the substrate for the aforementioned matte article, is impregnated with an uncured liquid form of thermosetting resin. This material is then subjected to pressure molding or heat-press molding under conditions such as a heating temperature of 100–200°C, a pressure of 0.1–9.8 MPa, and a molding time of 10 seconds to 120 minutes. During pressure molding or heat-press molding, the decorative panel is obtained by stacking the substrate with the aforementioned embossing plate and molding sheet, resulting in a matte article having the aforementioned surface shape.

[0284] In this case, the thermosetting resin that impregnates the substrate can preferably include, for example, melamine resin, urea resin, melamine-urea resin, guanidine resin, diallyl phthalate resin, polyester resin, phenolic resin, epoxy resin, amino alkyd resin, silicone resin, polysiloxane resin, etc., and thermosetting resins such as melamine resin, urea resin, melamine-urea resin, guanidine resin, and sulfonamide resin can preferably be included. Among these, melamine resin, melamine-urea resin, and phenolic resin are preferred, and melamine resin is particularly preferred.

[0285] (use)

[0286] As will be described later, the matte article of this embodiment can be used as a decorative component.

[0287] Furthermore, the matte article of this embodiment can also be used as a shaped sheet. When used as a shaped sheet, it can be used as an embossing plate or shaped sheet in the embossing process of the second and third manufacturing methods described above, thereby obtaining an article or thermosetting resin decorative panel composed of the above-described single layer.

[0288] The surface shape of the object being shaped (an article consisting of a single layer, a thermosetting resin decorative panel, etc.) is as described above, and becomes a shape that is opposite to the surface shape of the shaped sheet (the matte article of this embodiment).

[0289] [Decorative components]

[0290] The matte article of this embodiment can be used directly as a decorative component. Alternatively, it can be layered, composited, or combined with the adhesive material to be used as a decorative component. The choice of which method to use depends on the specific needs. When using the matte article of this embodiment as a decorative component, it is preferable that the matte article has a decorative layer.

[0291] When an adhesive material is present, the decorative component comprises the adhesive material and the matte article of this embodiment described above. Specifically, it is formed by stacking the surface of the adhesive material to be decorated and the surface of the matte article opposite to the side that forms wrinkles with the matte layer to exhibit a matte effect and a rough texture, facing each other. Furthermore, when an adhesive material is present, considering ease of lamination, the matte article of this embodiment preferably has a film or sheet form.

[0292] On the other hand, the matte article of this embodiment is Figure 4 The single-layer article shown is suitable for direct use as a decorative component, and matte articles having the aforementioned surface shape on at least a portion of the surface of resin articles such as resin molded articles are particularly suitable. When the matte article of this embodiment is used directly as a decorative component, it is suitable, for example, for use as a decorative component constituting the surface of buildings, various furniture, vehicles, home appliances, etc.

[0293] in addition, Figure 4 The matte article shown, which is composed of a single layer, can be directly used as a decorative component. It is made of a cured resin composition for forming matte articles, which is obtained by the second manufacturing method described above. In addition, depending on the thickness, it can also be used in combination with the material to be bonded.

[0294] (Materials to be bonded)

[0295] Examples of materials that can be bonded include flat or curved panels, cylindrical or polygonal prisms, and sheets (or films) made from various raw materials. For instance, examples include wooden components made from various types of wood such as fir, cypress, pine, and willow, used as wood veneers, plywood, engineered wood, particleboard, MDF (medium-density fiberboard), and other wood fiberboards, as well as three-dimensional objects; metal components made from metals such as iron, aluminum, copper, and alloys containing one or more of these metals, used as panels, three-dimensional objects, or sheets; kiln components made from ceramic materials such as glass and ceramics, gypsum, cement, ALC (lightweight aerated concrete), and calcium silicate-based materials, used as panels and three-dimensional objects; and resin components made from resins such as acrylic resins, polyester resins, polystyrene resins, polyolefin resins such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resins, vinyl chloride resins, cellulose resins, and rubber, used as panels, three-dimensional objects, and sheets. In addition, these components can be used individually or in combination.

[0296] The materials to be bonded can be appropriately selected from the above according to the purpose. When the materials are used for interior components of buildings such as walls, ceilings, and floors, or exterior components such as exterior walls, roofs, eaves, ceilings, fences, and doors, as well as window frames, doors, handrails, crossbeams, perimeter edges, and trim strips, it is preferable to form them from at least one of wood components, metal components, and resin components. When the materials are used for exterior components such as entrance doors, window frames, and door and window equipment, it is preferable to form them from at least one of metal components and resin components.

[0297] The thickness of the material to be bonded can be appropriately selected according to the application and the material, preferably 0.1 mm or more and 100 mm or less, more preferably 0.3 mm or more and 5 mm, and even more preferably 0.5 mm or more and 3 mm or less.

[0298] (Adhesive layer)

[0299] To achieve excellent adhesion, the materials to be bonded and the matte articles are preferably bonded together via an adhesive layer.

[0300] There are no particular limitations on the adhesive used as the adhesive layer; any known adhesive can be used, selected appropriately according to the application. For example, moisture-curing adhesives, anaerobic-curing adhesives, dry-curing adhesives, UV-curing adhesives, heat-sensitive adhesives (e.g., hot-melt adhesives), pressure-sensitive adhesives, and other adhesives are preferred.

[0301] Examples of resins used in these adhesives include acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, polyester resins, amide resins, cyanoacrylate resins, and epoxy resins. These can be used alone or in combination. Additionally, two-component curing urethane adhesives and ester adhesives using isocyanate compounds as curing agents can also be used.

[0302] Alternatively, adhesives can also be used in the adhesive layer. Various adhesives, such as acrylic, urethane, silicone, and rubber adhesives, can be appropriately selected as adhesives.

[0303] There is no particular limitation on the thickness of the adhesive layer. From the viewpoint of obtaining excellent adhesion, it is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less, and even more preferably 10 μm or more and 30 μm or less.

[0304] (Manufacturing method of decorative components)

[0305] Decorative components can be manufactured by a process of laminating the matte material of this embodiment with the adhesive material.

[0306] This process involves laminating the bonding material with the matte article of this embodiment. The bonding material is laminated with the side to be decorated facing the side opposite to the side of the matte article of this embodiment that has wrinkles forming with the matte layer, resulting in a matte effect and a rough texture. Alternatively, when the matte article of this embodiment has a substrate, the bonding material is laminated with the side to be decorated facing the substrate side. Examples of methods for laminating the bonding material and the matte article include lamination methods where the matte article is pressed onto a sheet-like bonding material using a pressure roller via an adhesive layer.

[0307] When using a hot melt adhesive ("thermosensitive adhesive"), the heating temperature is preferably 160°C or higher and 200°C or lower, depending on the type of resin constituting the adhesive. For reactive hot melt adhesives, the temperature is preferably 100°C or higher and 130°C or lower. Furthermore, in the case of vacuum forming, the process is typically performed while heating is in progress, preferably at 80°C or higher and 130°C or lower, and more preferably at 90°C or higher and 120°C or lower.

[0308] The decorative components obtained above can be cut arbitrarily, and milling machines, cutting machines, and other cutting machines can be used to perform grooving, chamfering, and other decorative processes on the surface and cross-sections. Furthermore, they are suitable for various applications, such as interior components for buildings (walls, ceilings, floors, etc.), exterior components for exterior walls, eaves, roofs, fences, etc., window frames, doors, door frames, handrails, crossbeams, perimeter edges, inlays, etc., as well as surface decorative panels for wardrobes, shelves, tables, dining tables, sinks, etc., kitchen furniture, or the housings of home appliances, OA equipment, etc., and interior and exterior components for vehicles.

[0309] In addition to decorative components used in buildings and the like, the matte articles of the present invention can be used directly as individual units, or in a form where the matte articles are layered, compounded, or combined with other raw materials (adhesive materials) for packaging materials, anti-glare films for displays, whiteboards or blackboards, various cards such as credit cards, cash cards, phone cards, and various certificates, keyboards for various keyboards, transparent panels (window glass, etc.) for windows, doors, partitions, artificial leather, etc. In these applications, it is generally preferred to present the matte articles of the present invention, which exhibit a matte effect and a rough tactile feel, on the outermost surface; however, other forms of use are also possible depending on the application and purpose.

[0310] Example

[0311] The invention will now be described in further detail through examples, but the invention is not limited by these examples.

[0312] (Measurement of surface shape)

[0313] Spc (arithmetic mean curvature of the protrusion apex), Rsm (mean length of the curve element), Rz (maximum height), and Ra (arithmetic mean roughness) of the articles obtained in the examples and comparative examples were measured for a rectangle (1024 μm × 768 μm) of any part of the surface shape of the article using a shape analysis laser microscope (“VK-X150 (control unit) / VK-X160 (measuring unit)”, manufactured by KEYENCE Co., Ltd.), with objective lens: 50x, laser wavelength: 658 nm, measurement mode: surface shape mode, measurement interval: 0.13 μm, and measurement quality: high speed mode.

[0314] In addition, the cutoff values ​​for Rsm (average length of curve feature), Rz (maximum height), and Ra (arithmetic mean roughness) are set to 0.8 mm.

[0315] (Evaluation method: 60° gloss value)

[0316] For the articles obtained in the examples and comparative examples, the specular gloss at 60° was measured using a gloss meter (“Microgloss (model name)”, manufactured by BYK Gardner) in accordance with K 5600-4-7:1999.

[0317] (Evaluation of texture (uniformity of surface condition))

[0318] For the articles obtained in the examples and comparative examples, any 20 adults evaluated the texture (uniformity of surface condition) of the surface according to the following criteria.

[0319] A: More than 18 people rated it as having a uniform surface condition and high visibility of the matte effect.

[0320] B: Evaluations by 15 to 17 people indicate that the surface is uniform and the matte effect is highly visible.

[0321] C: Less than 14 people rated it as having a uniform surface condition and high visibility of the matte effect.

[0322] (Evaluation of the rough texture)

[0323] As a benchmark for the rough texture, Oxford cloth made with 40-count cotton yarn was used. For the articles obtained in the examples and comparative examples, any 20 adults evaluated the surface texture according to the following benchmark.

[0324] A: The feel is close to the benchmark, according to more than 18 people, and is rough.

[0325] B: The feel is close to the benchmark, with 15 to 17 people giving the evaluation. It is a rough and rough feel.

[0326] C: The feel is close to the benchmark if rated by 14 or fewer people, and is rough.

[0327] [Example 1]

[0328] (Preparation of resin composition for matte layer formation)

[0329] 60 parts by mass of a multifunctional urethane acrylate oligomer (functional group number: 4), 30 parts by mass of a multifunctional acrylate monomer (2 functional groups), and 10 parts by mass of a monofunctional acrylate monomer were mixed, and 3 parts by mass of a wrinkle-forming stabilizer (silica particles, average particle size: 5 nm) and 0.8 parts by mass of a photopolymerization initiator (benzophenone-based) were added to obtain resin composition A for matte layer formation.

[0330] (Manufacturing of matte finish items)

[0331] Using colored paper base paper (thickness: 30 μm) for building materials as the substrate, a colored layer (thickness: 3 μm (dry)) is coated on one side of the substrate by gravure printing. Then, resin composition A for forming the matte layer (coating amount: 5 μm (dry)) is coated onto the colored layer. Next, ultraviolet light (wavelength: 395 nm, UV dose: 0.6 W / cm²) is irradiated using a UV irradiation device composed of LEDs. 2 Then, ultraviolet light (wavelength: 172nm (Xe2), ultraviolet power density: 1W / cm, cumulative light intensity: 10~100mJ / cm) was irradiated using an excimer light irradiation device. 2 The substrate was irradiated with a nitrogen atmosphere (oxygen concentration below 200 ppm) and then further irradiated with a high-pressure mercury lamp (ultraviolet power density: 200 W / cm²) to form a matte layer, resulting in a matte article with a substrate and a matte layer. For the obtained matte article, the Spc (arithmetic mean curvature of the protrusion apex), Rsm (mean length of the curve element), and 60° gloss value were measured. Texture (uniformity of surface condition) and roughness were also evaluated. These results are shown in Table 1.

[0332] [Comparative Example 1]

[0333] Using a PET sheet (COSMOSHINE (registered trademark) A4160 (50μm) manufactured by Toyobo Co., Ltd.) as a substrate, the resin composition A for forming the matte layer obtained in Example 1 was coated onto the easily bondable surface of the substrate by gravure printing (coating amount: 18μm (when dry)). Then, in the same manner as in Example 1, the substrate was irradiated with ultraviolet light using a UV irradiation device composed of LEDs, irradiated with ultraviolet light using an excimer light irradiation device, and irradiated with a high-pressure mercury lamp to obtain a matte article.

[0334] [Comparative Example 2]

[0335] Based on Comparative Example 1, the coating amount of the resin composition A used to form the matte layer was set to 5 μm (when drying), and a matte article was obtained in the same manner.

[0336] [Comparative Example 3]

[0337] A polypropylene sheet (PP, thickness: 100 μm) that has undergone corona discharge treatment was used as a substrate. A resin composition (urethane resin, coating amount: 2 μm (when dry)) for forming a base layer was coated on one side of the substrate. The resin composition A for forming a matte layer (coating amount: 5 μm (when dry)) was then coated on the base layer. Then, in the same manner as in Example 1, ultraviolet light was irradiated using a UV irradiation device composed of LEDs, ultraviolet light was irradiated using an excimer light irradiation device, and ultraviolet light was irradiated using a high-pressure mercury lamp to obtain a matte article.

[0338] [Comparative Example 4]

[0339] Based on Comparative Example 2, without irradiation with ultraviolet light using a UV irradiation device made of LEDs, a matte article was obtained in the same manner.

[0340] [Comparative Example 5]

[0341] Based on Comparative Example 1, instead of the resin composition A for forming a matte layer obtained in Example 1 above, a resin composition B for forming a matte layer was obtained by mixing 60 parts by mass of a polyfunctional urethane acrylate oligomer (functional group number: 7), 30 parts by mass of a polyfunctional acrylate monomer (2 functional groups), and 10 parts by mass of a monofunctional acrylate monomer, and adding 15 parts by mass of a wrinkle-forming stabilizer (silica particles, average particle size: 5 nm) and 0.8 parts by mass of a photopolymerization initiator (benzophenone-based). A matte article was also obtained in the same way.

[0342] [Comparative Example 6]

[0343] Based on Comparative Example 5, the coating amount of the resin composition B used to form the matte layer was set to 5 μm (drying), and a matte article was obtained in the same manner.

[0344] For the matte articles obtained in Comparative Examples 1 to 6, Spc (arithmetic mean curvature of the protrusion apex), Rsm (mean length of the curve element), and 60° gloss value were measured, and the texture (uniformity of surface condition) and roughness were evaluated. These results are shown in Table 1.

[0345] [Table 1]

[0346]

[0347] Based on the results in Table 1, it was confirmed that the matte article of this embodiment has a 60° gloss value of 1.3 on the matte layer side, making it an article with extremely excellent visibility of the matte effect, and also with excellent texture. In addition, it was also confirmed that the rough texture is also excellent.

[0348] On the other hand, it can be seen that the matte items of Comparative Examples 1-3, with an Rsm less than 30μm, have poor texture and do not achieve a rough or abrasive feel. It can be seen that although the Rsm is above 30μm, the Spc is 4000mm. -1 The matte articles of Comparative Examples 4-6 below have a 60° gloss value of 2.9-5.4, and their texture is worse than that of the matte articles of Comparative Examples 1-3. Furthermore, it is also found that the matte articles of Comparative Examples 4-6 have a rougher, less tactile feel than those of Example 1.

[0349] Figures 7-13These are microscope images of the matte articles obtained in Example 1 and Comparative Examples 1 to 6.

[0350] Industrial availability

[0351] The matte finish article of this embodiment has excellent visibility and texture of matte effect, and a superior rough tactile feel, making it suitable for various applications. It is suitable for use as interior components for walls, ceilings, floors, etc.; exterior components for walls, eaves, roofs, fences, etc.; window frames, doors, door frames, handrails, crossbeams, perimeter edges, trim strips, etc.; surface decorative panels for wardrobes, shelves, tables, etc.; kitchen furniture such as dining tables and sinks; or housings for home appliances, OA equipment, etc.; and interior trim for vehicles. Decorative components for various components such as exterior components; in addition to the decorative components used in the aforementioned buildings, the matte articles of this embodiment can be used directly as individual units or in the form of layers, composites, or combinations of the matte articles with other raw materials (adhesive materials) as packaging materials, anti-glare films for displays, whiteboards or blackboards, various cards such as credit cards, cash cards, phone cards, various certificates, keyboards for various keyboards, transparent panels (window glass, etc.) for windows, doors, partitions, etc., artificial leather, etc.

[0352] Explanation of reference numerals in the attached figures

[0353] 1a: Vertex of the protrusion (Spc large)

[0354] 1b: Vertex of the protrusion (Spc small)

[0355] 2: convex part

[0356] 2a: Convex portion (small Rsm)

[0357] 2b: Convex part (Rsm is large)

[0358] 3: concave part

[0359] 10: Matte items

[0360] 11: Matte finish

[0361] 12: Substrate

[0362] 13: Decorative layer

[0363] 13a: Shading layer

[0364] 13b: Pattern layer

[0365] 14: Adhesive layer

[0366] 15: Transparent resin layer

[0367] 16: Primer coating

Claims

1. A matte article having at least a portion of its surface having an arithmetic mean curvature of Spc (specified portion apex) greater than 4000 mm. -1 JIS B0601:2013 defines Rsm (mean smoothness) as the average length of a curved feature of a surface shape with a length of 30 μm or more. The arithmetic mean curvature of the apex of the protrusion is the average curvature of the leading edge of the peak, calculated as the arithmetic mean of the radii of curvature of the peaks classified as peaks in the shape image contained in the reference region. Here, a peak is a convex part, the peak apex is the vertex of the protrusion, and the average curvature is the average sharpness. The matte article has a matte layer, and the surface shape is formed by the surface of the matte layer. The surface of the matte layer forming the surface shape has an uneven shape composed of irregular wrinkles, which are composed of concave portions and multiple convex portions. The multiple convex portions are formed by multiple linear protrusions, and the concave portions are formed by being surrounded by the multiple linear protrusions. The matte layer is formed from a cured resin composition comprising a resin and a wrinkle-forming stabilizer. The resin composition contains a polyfunctional urethane (meth)acrylate oligomer as a polymerizable oligomer and a polyfunctional (meth)acrylate as a polymerizable monomer. The content of the polymerizable oligomer is 60 parts by weight or more, relative to a total of 100 parts by weight of the polymerizable oligomer and the polymerizable monomer. The matte layer is formed by irradiating at least one layer of the resin composition comprising the resin and the wrinkle-forming stabilizer with excimer light. The matte article has a substrate, and paper is used as the substrate.

2. The matte article according to claim 1, wherein, The peak and height parameters Rz of the profile curve specified in JIS B0601:2013 for the surface shape are above 8.00 μm and below 30.00 μm.

3. The matte article according to claim 1 or 2, wherein, The parameter Ra in the height direction of the profile curve specified in JIS B0601:2013 for the surface shape, i.e., the arithmetic mean roughness, is 1.00 μm or more and 5.50 μm or less.

4. The matte article according to claim 1, wherein, The wrinkle-forming stabilizer has an average particle size with an upper limit of less than 100% of the thickness of the matte layer and less than 30 μm, and the matte layer contains more than 0.5 parts by mass of the wrinkle-forming stabilizer relative to 100 parts by mass of the resin.

5. The matte article according to claim 1, wherein, The substrate is in sheet form.

6. The matte article according to claim 5, wherein, The matte layer is disposed on the entire surface of one side of the substrate.

7. The matte article according to claim 1, wherein, The surface shape has a 60° gloss value of 10.0 or less.

Images