Matting article

Abstract

The present application provides a matte article having excellent visibility and texture of a matte effect, and excellent soft touch. The matte article has, at least a part of a surface, a surface shape in which Spc (arithmetic mean curvature of a top of a protrusion) prescribed in JIS B0601:2013 is greater than 4000 mm ‑1 , and Rsm (average length of a curved element) prescribed in JIS B0601:2013 is less than 30 μm.

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 methods to improve texture through 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 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" feel. 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 feel cannot be considered sufficiently expressed. In other words, conventional decorative sheets and materials cannot be said to simultaneously achieve excellent matte finish and tactile feel. In this invention, a "soft touch" (soft feel) is particularly emphasized in terms of tactile feel.

[0014] The objective of this invention is to provide matte articles with excellent visibility and texture, as well as excellent soft touch (soft 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 as specified in JIS B0601:2013. -1 Surface shapes with an Rsm (average length of curve elements) of less than 30 μm 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 12.5 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 surface shape is 2.0 μm or less.

[0020] [4] The matte article described in 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] According to the matte article described in [4], 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 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 soft touch (soft 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 Example 2.

[0038] Figure 9 This is an optical microscope image of the surface of the matte article obtained in Example 3.

[0039] Figure 10 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 1.

[0040] Figure 11 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 2.

[0041] Figure 12 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 3.

[0042] Figure 13 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 4.

[0043] Figure 14 This is an optical microscope image of the surface of the matte article obtained in Comparative Example 5. Detailed Implementation

[0044] Matte finish items

[0045] 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.

[0046] 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, as specified in JIS B0601:2013. -1 Surface shapes with an Rsm (average length of curve elements) of less than 30 μm as specified in JIS B0601:2013.

[0047] [Regarding surface shape]

[0048] 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.

[0049] The surface shape requirement, as specified in JIS B0601:2013, is that the Spc (arithmetic mean curvature of the apex of the protrusion) is greater than 4000 mm. -1The Rsm (average length of the curve element) specified in JIS B0601:2013 is less than 30 μm. By having such a surface shape, due to the light diffusion caused by this surface shape, the matte article of this embodiment exhibits excellent visibility and texture of the matting effect (hereinafter, they are sometimes collectively referred to as "matting effect"), and as a tactile sensation, it exhibits a particularly "soft touch" (soft feel). "Soft touch" is a sensory perception, and in this specification, "soft touch" encompasses all tactile sensations that are generally perceived as "soft." Specifically, it refers to the tactile sensation felt when touching a smooth, dry surface with the fingertip, unlike the cold, rough tactile sensation commonly found in conventional resin decorative sheets. Examples of materials with a "soft touch" include high-grade paper (not coated paper with a surface coating), Oxford cloth made with fine yarns of around 60 to 120 count (fine to very fine yarn count), cloth made from natural fibers such as baby skin, silk, and Tencel, cloth made from synthetic fibers such as Prometheus, rayon, and cupro, cloth made from chemical fibers such as regenerated fibers, or cloth made from these chemical fiber cloths that have undergone a peach skin treatment (a thin napping process that gives it a texture similar to the skin of a peach).

[0050] (Spc (arithmetic mean curvature of the apex of the protrusion))

[0051] Spc (arithmetic mean curvature of the apex of the protrusion) is one of the three-dimensional surface characteristic parameters specified in JIS B0601:2013. 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 apex) 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 ).

[0052] The larger the value of Spc, the higher 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 protrusions are, the closer they are to a plane, and therefore the greater the gloss. Therefore, in order to suppress gloss by focusing only on the value of Spc, if a surface shape with a large Spc (a surface shape with sharp apexes of the protrusions) is set, the scattering of light at the surface becomes stronger, and the gloss is reduced.

[0053] A small Spc (spec) results in a soft feel due to the rounded corners of the protrusions. Conversely, increasing the Spc value results in a loss of roundness in the protrusions, compromising the softness, but improving the matte finish. For example, if the Spc is small, i.e., 4000mm... -1 Below this range (radius of curvature greater than 0.25mm), the desired matting effect cannot be obtained. However, if the Spc is increased to greater than 4000mm... -1 (If the radius of curvature is less than 0.25mm, the softness is reduced; therefore, the matte finish and the softness are essentially opposites. In this invention, in addition to Spc, Rsm (described later) is set to a specific range, thereby achieving a balance between the matte finish and the softness.

[0054] In relation to Rsm (average length of the curve element) discussed later, from the viewpoint of improving matting effect and soft touch, Spc is preferably 4200mm. -1 The above, preferably 4300mm -1 The above is preferred, with 4400mm being the more desirable. -1 The above, as an upper limit, is preferably 7000mm. -1 The preferred value is 6500mm. -1 Below, 6000mm is preferred. -1 The following is a further preferred size: 5700mm -1 The cutoff value for Spc in this specification is 0.8 mm.

[0055] 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.

[0056] (Rsm (average length of curve feature))

[0057] Rsm (average length of curve features) is the 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 features in the reference length. The smaller Rsm is, the more convexity ( Figure 2The more of 2a and 2b in the model, the better. Therefore, a surface shape with a small Rsm has a dense distribution of protrusions at the apex, so when touching the surface with a finger, the area in contact with the finger increases, resulting in a better soft feel. In this way, if Rsm is large, i.e., above 30 μm, the desired soft feel cannot be obtained, but if Rsm is reduced, i.e., below 30 μm, a good soft feel can be obtained.

[0058] In the matte article of this embodiment, the density of the raised portion is increased by reducing Rsm. The matte effect is improved by increasing Spc, and the soft feel is further improved by reducing Rsm. The relationship between Spc and Rsm is more specifically as follows.

[0059] As described above, increasing the surface area (Spc) achieves a matte finish, but results in a rougher feel, preventing the attainment of a soft touch. In this invention, by increasing the Spc and further decreasing the surface area (Rsm), a high degree of balance between matte finish and a soft touch is achieved. Increasing the Spc results in a surface shape with sharp protrusions, but decreasing the Rsm causes these protrusions to become more tightly packed together. Therefore, unevenness disappears at the point of contact with the fingertip, thus improving the soft touch. It is believed that this achieves both an excellent matte finish and improved softness, resulting in a high degree of balance between these two aspects.

[0060] In relation to the aforementioned Spc, from the viewpoint of improving the matte finish and soft touch, Rsm is preferably 29.5 μm or less, more preferably 29.0 μm or less, and even more preferably 28.5 μm or less. As a lower limit, it is preferably 10.0 μm or more, more preferably 12.0 μm or more, and even more preferably 13.5 μm or more. By setting the lower limit value within the above range, the planar shape exhibits a matte finish, and manufacturing does not become excessively difficult, therefore it is preferred. It should be noted that when measuring Rsm in this specification, the cutoff value is 0.8 mm.

[0061] (wrinkles)

[0062] The surface shape of the matte article in this embodiment preferably has the characteristics described later. Figure 3The top-view observation shows minute wrinkles (creases). 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 Rz (maximum height) and Ra (arithmetic mean roughness), which will be described later, are easily within a specific range of values ​​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 of values, and preferably Rz (maximum height) and Ra (arithmetic mean roughness) within a specific range of values. Thus, it can be said that Spc (arithmetic mean curvature of the protrusion apex) and Rsm (average length of the curve element) are integral to the minute wrinkles (creases). Furthermore, by having such a surface shape, the matte effect is improved along with the soft touch (soft feel).

[0063] 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:

[0064] (1) A micro-wrinkled structure is formed on the surface of the matte layer. Preferably:

[0065] (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.

[0066] (3) Optimize the irradiation conditions of the resin composition for matting, 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.

[0067] (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.

[0068] (Rz(maximum height))

[0069] In this embodiment, as the surface shape, the lateral parameter Rz (maximum height) of the profile curve specified in JIS B0601:2013 is preferably 12.50 μm or less.

[0070] Rz (maximum height) is one of the peak and height parameters of a profile curve. It is the sum of the height of the highest peak and the depth of the deepest valley in a profile curve of a reference length. The larger the value of Rz (maximum height), the more prominent (higher) the convex parts appear when viewed from the valleys (concave areas), making it an indicator of a tendency for such convex parts to be abundant. 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 below 12.50 μm, the deviation in the height of the convex parts is also smaller, and the softness of the touch is improved.

[0071] From the viewpoint of improving matte finish and soft touch, Rz (maximum height) is preferably 12.0 μm or less, more preferably 11.5 μm or less, even more preferably 11.0 μm or less, and the lower limit is preferably 3.25 μm or more, more preferably 3.50 μm or more, and even more preferably 4.00 μm or more. It should be noted that the cutoff value for measuring Rz (maximum height) in this specification is 0.8 mm.

[0072] (Ra (arithmetic mean roughness))

[0073] 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 2.00 μm or less.

[0074] 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 less than 2.00 μm, there is a greater presence of a more uniform and gentle shape of the convex parts of the surface shape, thus suppressing abnormal tactile sensations, especially improving the softness of the touch. In addition, the matting effect is also improved.

[0075] From the viewpoint of improving matting effect and soft touch, the Ra (arithmetic mean roughness) is preferably 1.90 μm or less, more preferably 1.80 μm or less, and even more preferably 1.75 μm or less. As a lower limit, it is preferably 0.10 μm or more, more preferably 0.40 μm or more, and even more preferably 0.60 μm or more. It should be noted that when measuring the Ra (arithmetic mean roughness) in this specification, the cutoff value is 0.8 mm.

[0076] [Regarding layer composition]

[0077] 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.

[0078] 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.

[0079] 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 and 6 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.

[0080] 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.

[0081] [Substrate]

[0082] 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 preferably adopted. 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.

[0083] 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.

[0084] 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.

[0085] 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:

[0086] (1) Resin / wood-based materials

[0087] (2) Resin / metal

[0088] (3) Resin / fibrous materials,

[0089] (4) Resin / Non-metallic inorganic materials

[0090] (5) Resin 1 / Resin 2 (for example, the case where there are multiple layers composed of different resins such as "olefin resin / acrylic resin")

[0091] (6) Metal / wood-based materials

[0092] (7) Metallic / non-metallic inorganic materials

[0093] (8) Metal / fibrous materials,

[0094] (9) Metal 1 / Metal 2 (e.g., the case of having multiple layers composed of different metals such as "copper / chromium")

[0095] (10) Non-metallic inorganic materials / fibrous materials, etc.

[0096] 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).

[0097] 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.

[0098] 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.

[0099] Natural resins such as natural rubber, rosin, and amber are preferred examples.

[0100] In addition, thermosetting resins and ionizing ray curing resins, which are used as constituent materials of the matte layer described later, are preferred examples of curable resins.

[0101] Examples of metals suitable for use as substrates include aluminum alloys such as aluminum or duralumin; iron alloys such as iron, carbon steel, and stainless steel; copper alloys such as copper, brass, and bronze; and metals such as gold, silver, chromium, nickel, cobalt, tin, and titanium. Furthermore, substrates with these metals applied to their surfaces through plating or other methods are also preferred examples of substrates made of metal.

[0102] As non-metallic inorganic materials that can be used for a substrate, for example, non-ceramic industry materials such as cement, ALC (lightweight aerated concrete), gypsum, calcium silicate, wood chip cement, etc. can be preferably selected; ceramic industry materials such as ceramics, pottery, glass, enamel, etc.; natural stones such as limestone (including marble), granite, andesite, etc.

[0103] As fibrous materials that can be used for a substrate, for example, thin paper (Japanese: 薄枼 )), kraft paper, high-quality paper, Japanese paper, titanium white paper, cotton linter paper, sulfuric acid paper, paraffin paper, parchment paper, cellophane, backing 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, hemp and other natural fibers of protein or cellulose series, glass fibers, carbon fibers, etc. Among these materials, in order to improve the inter-fiber strength of the paper substrate composed of paper or the inter-layer strength with other substrates used in combination with the paper substrate, and in order to prevent fluffing, various resins such as acrylic resin, styrene-butadiene rubber, melamine resin, urethane resin, etc. can be further added (these resins are impregnated after papermaking or filled internally during papermaking). As papers added with resins, for example, paper inter-strengthening paper, resin-impregnated paper, etc. can be preferably selected.

[0104] It should be noted that in the case of a substrate of fibrous materials such as paper, when a liquid resin composition for forming a matte 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 matte layer surface, and sometimes the desired values of Spc and Rsm cannot be obtained. In such a case, it is preferable to form a known resin layer for preventing penetration on the surface of the substrate of the fibrous material on the side where the matte layer is formed by coating or other methods. As the resin for forming the resin layer for preventing penetration, for example, a two-component curable urethane resin can be cited.

[0105] In addition, as a laminate formed by laminating a layer composed of a fibrous material and a layer composed of a resin, for example, a wallpaper raw material obtained by laminating a layer composed of various resins such as a vinyl chloride resin layer, an olefin resin layer, and an acrylic resin layer on the surface of a backing paper for wallpaper commonly used in the building materials field can be preferably selected.

[0106] As wood-based materials that can be used for a substrate, for example, veneers, plywood, laminated wood, particle boards, medium density fiberboards (MDF), etc. composed of various woods such as cedar, cypress, pine, beech, oak, oak, walnut, lauan, teak, rubber tree, etc. can be preferably selected.

[0107] As a substrate, any substrate made of the aforementioned materials can be used without restriction; furthermore, it can be appropriately selected according to the desired properties, etc. From the viewpoint of improving the matte effect and soft touch, a substrate made of resin, a substrate made of fibrous material, and a substrate made of resin are preferred, with a substrate made of resin being more preferred.

[0108] Among the resins, olefin resins, vinyl chloride resins, polyester resins, and acrylic resins are preferred, with olefin resins, vinyl chloride resins, and polyester resins being more preferred. As olefin resins, polyethylene and polypropylene are preferred; as vinyl chloride resins, polyvinyl chloride is preferred; and as polyester resins, polyethylene terephthalate is preferred. Furthermore, among fibrous materials, paper is preferred. By using a substrate made of these materials, the aforementioned surface shape is particularly easy to obtain, and a soft touch is easily improved.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] The substrate can be colored or uncolored (it can be transparent). If it is colored, there are no particular restrictions on the coloring method. It can be transparent coloring or opaque coloring (masking coloring). They can be chosen arbitrarily.

[0114] 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 installed as required, inorganic pigments such as white pigments can be used.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] These UV absorbers, light stabilizers, and other weather-resistant agents, as well as various other additives, can be used alone or in combination.

[0121] 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.

[0122] 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.

[0123] 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 .

[0124] [Matte Layer]

[0125] In this embodiment, the matte layer in the matte article is either a single layer or 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 Layers with surface shapes having an Rsm (average length of the curve element) of less than 30 μm, in the case of matte articles 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.

[0126] From the viewpoint of obtaining a matte article with excellent matte effect and excellent soft touch, 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 above-mentioned 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.

[0127] (Wrinkle formation stabilizer)

[0128] 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 matte effect visibility (hereinafter, sometimes only expressions such as "stable matte effect visibility" 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 soft tactile feel.

[0129] In this specification, "wrinkle formation stabilization" means that the in-plane distribution (dispersion σ) of the shape of the wrinkles and their geometric properties (length, width, and ratio of each protrusion) and their 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.

[0130] 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 soft touch by forming wrinkles.

[0131] 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.

[0132] 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 of C but does not form wrinkles on the surface. 60° AM (C). That is, the following relation holds.

[0133] G 60° AW (C) < G 60° AM (C)

[0134] 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 the present invention—namely, consistently obtaining an extremely superior matte effect that cannot be achieved even with the use of matting agents and obtaining a soft touch—it is preferable that it does not contain matting agents. Thus, it can be said that the matte article of this embodiment has extremely superior matte effect visibility and texture even if it does not substantially contain matting agents conventionally used to obtain 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 have the visibility of the 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.

[0135] 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.

[0136] 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.

[0137] From the viewpoint of improving matting effect and soft touch, 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 of the average particle size, 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 of the average particle size, 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, wrinkle formation is stable, excellent matting effect can be consistently obtained, and a soft touch can also be obtained.

[0138] In this embodiment, wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 can be used alone or in combination. From the viewpoint of improving matte effect and soft touch, it is more preferable to use wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 in combination.

[0139] As a wrinkle-forming stabilizer, organic particles or inorganic particles can be used, for example.

[0140] 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.

[0141] Examples of 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.

[0142] There are no particular limitations on the shape of the wrinkle-forming stabilizer; for example, spherical, polyhedral, scaly, and amorphous shapes are possible.

[0143] 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 soft touch, 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.

[0144] 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 softness, 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.

[0145] 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.

[0146] From the viewpoint of stabilizing the wrinkles formed by the wrinkle-forming stabilizer, steadily improving the matte effect, and enhancing the soft touch, 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 soft touch. 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.

[0147] 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 0.0 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.

[0148] 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 soft touch 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 soft touch.

[0149] (Surface shape of the matte layer)

[0150] The matte layer in the matte article of this embodiment is a layer having the above-described surface shape, preferably a layer composed of a cured resin composition for forming a matte layer containing the above-described specific wrinkle-forming stabilizer 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 soft touch. 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.

[0151] 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 soft touch.

[0152] Regarding the wrinkles, from the viewpoint of exhibiting the aforementioned surface shape, improving the matte effect, and enhancing the soft touch, 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.

[0153] 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.

[0154] As a way related to these folds, for example, can be cited as Figure 3 As shown. In Figure 3The diagram 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 curved linear 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 meandering linear protrusions, and meandering recesses 3 are formed such that they are surrounded by these meandering linear protrusions. The matte article of this embodiment is... Figure 3 The stable formation of the folds creates a matte finish and a soft feel.

[0155] 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.

[0156] 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"). When the protrusion 2 of the line extends along its extension direction, adjacent portions alternately have sections where the extension direction of the protrusion 2 reverses. 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.

[0157] In this specification, "irregular" refers to a shape that cannot be described as having a fixed regularity or a pattern that is not arranged in a fixed regularity. 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 that is 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.

[0158] 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 soft 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 soft feel.

[0159] 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.

[0160] 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, the matte effect and soft feel resulting from the formation of the wrinkles are achieved. 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 design improvements.

[0161] 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 soft touch. Regarding the shape of the protrusions (protrusions) and concave portions that form irregular folds, the following describes specific ways in which it can be advantageous in terms of consistently improving the matte effect and enhancing the soft touch. By having the following shape for the folds, the aforementioned surface shape is easily achieved, and the matte effect and soft touch are improved.

[0162] 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 soft touch is enhanced.

[0163] 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) of 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).

[0164] 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 matting effect is consistently improved, and the soft tactile feel is enhanced.

[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 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 soft touch is enhanced.

[0167] Here, the dimensions of the concave portion are determined in the same way as the dimensions of the convex portion described above.

[0168] 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 matting effect is stably improved, and the soft touch is enhanced.

[0169] Here, the occupancy ratio of the protrusions is the average occupancy ratio of the protrusions in any 10 locations (100μm square areas × 10 locations) of the matte article of this embodiment.

[0170] 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 enhancing the softness of the touch, a shorter length is preferable. 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 softness of the touch is enhanced.

[0171] Here, regarding any 10 protrusions and recesses (i.e., a total of 100 protrusions and recesses) in any 10 locations (10 square areas of 100 μm) of the matte article of this embodiment, it is preferable that at least 80% of them satisfy the above conditions, more preferably at least 85%, further preferably at least 90%, and even more preferably at least 95%. Furthermore, the term "approximately the same" in this specification means roughly the same, without any branching; in the case of direction, it refers to a difference within ±3°, and in the case of width, it refers to a difference within ±5%.

[0172] 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 soft touch is enhanced.

[0173] 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.

[0174] 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).

[0175] 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.

[0176] 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.

[0177] The thickness of the matte layer is not particularly limited as long as it can stably exhibit a matte effect and a soft touch to form the aforementioned wrinkles. However, considering ease of fabrication, it is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, further 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, further preferably 150 μm or less, and even more preferably 100 μm or less.

[0178] 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.

[0179] 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.

[0180] 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 soft touch, can be achieved.

[0181] 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 soft touch, such as... Figures 4-6 As shown, it is preferred to set it on the entire surface of one face.

[0182] (resin)

[0183] As the resin for forming the matte layer, any resin that forms a matte layer by forming a resin composition for matte layer formation containing a predetermined amount of the aforementioned wrinkle-forming stabilizer and then curing it to become a cured product and constitute the matte layer can be used. 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.

[0184] 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. Furthermore, in this specification, (meth)acrylate means acrylate or methacrylate.

[0185] 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 (EB) beams. In addition, they also include electromagnetic waves such as X-rays and gamma rays, charged particle beams such as alpha rays and ion beams.

[0186] 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 soft touch, ultraviolet curable resins are preferred.

[0187] 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.

[0188] 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".

[0189] 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.

[0190] From the viewpoints of stabilizing wrinkle formation and thus steadily improving matte finish, enhancing softness, 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. Furthermore, with the aforementioned number of functional groups, the aforementioned surface shape is particularly easy to obtain, and the softness is easily improved.

[0191] These multifunctional (meth)acrylates can be used alone or in combination.

[0192] 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.

[0193] 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.

[0194] These polymeric oligomers can be used alone or in combination.

[0195] From the viewpoints of stabilizing the formation of wrinkles and steadily improving the matte effect, enhancing the soft touch, 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.

[0196] From the viewpoints of stabilizing the formation of wrinkles and steadily improving the matte effect, enhancing the soft touch, 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 of 6 or less, and even more preferably 4 or less.

[0197] 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.

[0198] 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 soft touch, and also improves surface properties such as processing characteristics, scratch resistance, and weather resistance.

[0199] 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.

[0200] (Resin Composition)

[0201] The matte layer is preferably composed of a cured product of a resin composition containing the aforementioned wrinkle-forming stabilizer in a specified amount, wherein the resin composition preferably contains the aforementioned resin and the aforementioned wrinkle-forming stabilizer in a specified 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] These UV absorbers, light stabilizers, and other weather-resistant agents can be used alone or in combination.

[0209] [60° gloss value]

[0210] 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".

[0211] 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.

[0212] 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 consistently excellent matte effect in terms of visibility and texture obtained, but also a soft touch 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.

[0213] 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.

[0214] 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.

[0215] 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.

[0216] [Other layers]

[0217] 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 The soft touch is a cross-sectional view of one embodiment of the matte article of this embodiment, which 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).

[0218] 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.

[0219] (Base coat)

[0220] 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.

[0221] 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.

[0222] When the release layer forms a base coating, it is preferable to perform surface treatment on the release layer, and corona irradiation is preferred as a surface treatment.

[0223] The base coating is mainly composed of adhesive resin and may contain additives such as UV absorbers and light stabilizers as needed.

[0224] 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.

[0225] 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.

[0226] 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 1.5 μm or more and 6 μm or less.

[0227] 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.

[0228] (Transparent resin layer)

[0229] 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.

[0230] 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.

[0231] 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.

[0232] The transparent resin layer may contain weather-resistant agents such as ultraviolet absorbers and light stabilizers, as well as additives such as colorants.

[0233] 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.

[0234] (Decorative layer)

[0235] 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.

[0236] The decorative layer can be, for example, a colored layer that covers the entire surface (a so-called solid colored layer). Figure 6 "13a" in the text can also refer to a pattern layer formed by printing various patterns using ink and a printing press. Figure 6 (13b in the text). Additionally, such as... Figure 6 As shown, solid color layers and patterned layers can also be combined.

[0237] 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 conduit 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.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] 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.

[0242] The decorative layer may contain UV absorbers, light stabilizers and other weather-resistant agents, colorants and other additives.

[0243] 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.

[0244] (Adhesive)

[0245] 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.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] 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.

[0250] 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.

[0251] In this specification, the total transmittance of matte articles is the total transmittance measured according to JIS K7361-1:1997, which is the average value of measurements taken at any 10 locations.

[0252] [Manufacturing Method for Matte Finish Items]

[0253] 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.

[0254] 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 aforementioned 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 below on the matte layer side, and a soft touch.

[0255] 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 soft feel to the matte article (matte layer).

[0256] 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 soft touch, are not yet clear, but it is speculated to be based on the following mechanism.

[0257] 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.

[0258] 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 adequately expressed across the entire surface of the matte layer. Additionally, a soft touch is not sufficiently achieved. Therefore, the stable performance of this matte effect and soft touch 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 a matte effect and soft touch, the inclusion of a wrinkle-forming stabilizer is essential. Considering that a stable matte effect and soft touch resulting from wrinkle formation cannot be obtained without a wrinkle-forming stabilizer, the wrinkle-forming stabilizer functions as a core that triggers wrinkle formation. Around this core, resin on the surface portion of the resin composition aggregates to form the protrusions (raised portions) of the wrinkles, and concave portions are formed simultaneously with the formation of the protrusions (raised portions). As a result, wrinkle formation is considered stable, and a stable matte effect and soft touch are consistently expressed.

[0259] 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.

[0260] 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 matte layer with wrinkles exhibiting a soft touch. 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.

[0261] "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 is in an excited state and includes 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".

[0262] The excimer light has a single wavelength peak, and as a characteristic, its half-width at half-maximum (WWHM) is narrower than that of typical ultraviolet light (e.g., 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 soft touch is enhanced.

[0263] From the viewpoint of stabilizing the formation of wrinkles, consistently improving the matting effect, and enhancing the soft touch, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, further 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, further 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 soft touch, 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.

[0264] In this embodiment, from the viewpoint of stabilizing the formation of wrinkles, consistently improving the matting effect, and enhancing the soft touch, 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 1,000 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, 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.

[0265] 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.

[0266] 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.

[0267] 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 curing 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.

[0268] 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 a resin composition for forming the matte layer using known methods such as gravure printing, bar coating, roller coating, reverse roller coating, and comma coating.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] 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.

[0274] 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.

[0275] 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.

[0276] 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.

[0277] 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.

[0278] 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.

[0279] 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 3 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.

[0280] 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.

[0281] In addition, regarding irradiation, post-curing can be performed to promote curing to deeper parts, or pre-curing can be performed.

[0282] 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.

[0283] 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.

[0284] 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.

[0285] 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 less than 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.

[0286] 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 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 substrate, embossed plate, and shaped sheet are stacked and formed to obtain a matte article having the aforementioned surface shape.

[0287] 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.

[0288] (use)

[0289] As will be described later, the matte article of this embodiment can be used as a decorative component.

[0290] 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.

[0291] 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).

[0292] [Decorative components]

[0293] 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.

[0294] 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 soft touch, 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.

[0295] 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.

[0296] 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.

[0297] (Materials to be bonded)

[0298] 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, used as panels or 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 or 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.

[0299] 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.

[0300] 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.

[0301] (Adhesive layer)

[0302] To achieve excellent adhesion, the materials to be bonded and the matte articles are preferably bonded together via an adhesive layer.

[0303] 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 the like are preferred.

[0304] 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.

[0305] 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.

[0306] 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.

[0307] (Manufacturing method of decorative components)

[0308] Decorative components can be manufactured by a process of laminating the matte material of this embodiment with the adhesive material.

[0309] 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 to exhibit a matte effect and a soft feel. 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.

[0310] 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.

[0311] 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.

[0312] 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 the form of layers, composites, or combinations of the matte articles with other raw materials (adhesive materials), in 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 soft touch, on the outermost surface, but other forms of use are also possible depending on the application and purpose.

[0313] Example

[0314] The invention will now be described in further detail through examples, but the invention is not limited by these examples.

[0315] (Measurement of surface shape)

[0316] 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.

[0317] 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.

[0318] (Evaluation method: 60° gloss value)

[0319] For the articles obtained in the examples and comparative examples, the specular gloss at 60° was measured using a gloss meter (“Microgloss”, manufactured by BYK Gardner, Inc.) in accordance with K 5600-4-7:1999.

[0320] (Evaluation of texture (uniformity of surface condition))

[0321] 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.

[0322] A: More than 18 people rated it as having a uniform surface condition and high visibility of the matte effect.

[0323] B: Evaluations by 15 to 17 people indicate that the surface is uniform and the matte effect is highly visible.

[0324] C: Less than 14 people rated it as having a uniform surface condition and high visibility of the matte effect.

[0325] Set A and B as qualified.

[0326] (Evaluation of the soft touch)

[0327] As a benchmark for the soft touch, Oxford cloth made with 80-count cotton yarn was used. For the articles obtained in the examples and comparative examples, any 20 adults evaluated the surface touch according to the following benchmark.

[0328] A: The feel is close to the benchmark, according to more than 18 people, and is soft to the touch.

[0329] B: The feel is close to the benchmark and is soft when rated by 15 to 17 people.

[0330] C: The feel is close to the benchmark for 14 or fewer people, and is a soft feel.

[0331] Set A and B as qualified.

[0332] [Example 1]

[0333] (Preparation of resin composition for matte layer formation)

[0334] 60 parts by weight of a polyfunctional urethane acrylate oligomer (functional group number: 4), 30 parts by weight of a polyfunctional acrylate monomer (2 functional groups), and 10 parts by weight of a monofunctional acrylate monomer were mixed, and 3 parts by weight of a wrinkle-forming stabilizer (silica particles, average particle size: 5 nm) and 0.8 parts by weight of a photopolymerization initiator (benzophenone-based) were added to obtain a resin composition (resin A) for forming a matte layer.

[0335] (Manufacturing of matte finish items)

[0336] Using a PET sheet (COSMOSHINE (registered trademark) A4160 (50μm) manufactured by Toyobo Co., Ltd.) as the substrate, the resin composition (resin A) for forming the matte layer was coated onto the easily bondable surface of the substrate by gravure printing (coating amount: 18μm (when dry)). Then, the substrate was irradiated with ultraviolet light (wavelength: 395nm, UV dose: 0.6W / cm²) using a UV irradiation device composed of LEDs. 2 Then, ultraviolet light (wavelength: 172nm (Xe2), ultraviolet power density: 1W / cm², cumulative light intensity: 10–100mJ / cm²) was applied using an excimer laser 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 (UV 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 softness were also evaluated. These results are shown in Table 1.

[0337] [Examples 2 and 3]

[0338] Except that the coating amount of the resin composition (resin A) for forming the matte layer and the substrate were set to the coating amount and substrate shown in Table 1, the same procedure as in Example 1 was followed to obtain the matte article of Example 2.

[0339] The coating amount of the resin composition for forming the matte layer was set to the coating amount shown in Table 1. A polypropylene sheet (PP, thickness: 100 μm) that had undergone corona discharge treatment on the substrate was used as the substrate. A resin composition for forming the base layer (urethane resin, coating amount: 2 μm (when dry)) was coated on one side of the substrate. The above-mentioned resin composition for forming the matte layer was then coated on the base layer. Otherwise, the operation was the same as in Example 1, and the matte article of Example 3 was obtained.

[0340] [Example 4]

[0341] Based on Example 1, a PET sheet (COSMOSHINE (registered trademark) A4160 (50μm) manufactured by Toyobo Co., Ltd.) was used as a substrate. After coating the easily bondable surface of the substrate with a coloring layer (thickness: 3μm (when dry)), the above-mentioned resin composition (resin A) for forming the matte layer was coated on the coloring layer. Otherwise, a matte article was obtained in the same way.

[0342] For the matte articles obtained in Examples 2-4, 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 softness were evaluated. These results are shown in Table 1.

[0343] [Comparative Example 1]

[0344] Using colored paper base paper for building materials (thickness: 30 μm) as the substrate, a colored layer (thickness: 3 μm (when dry)) was coated on one side of the substrate, and then the above-mentioned resin composition (resin A) for forming the matte layer (coating amount: 5 μm (when dry)) was coated on the colored layer. Otherwise, the same procedure as in Example 1 was followed to obtain the matte article of Comparative Example 1.

[0345] [Comparative Example 2]

[0346] Based on Example 2, without using a UV irradiation device made of LEDs to irradiate ultraviolet light, the matte article of Comparative Example 2 was obtained in the same way.

[0347] [Comparative Example 3]

[0348] Based on Example 1, instead of the resin composition (resin A) for forming the matte layer, a resin composition (resin B) for forming the 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), 10 parts by mass of a monofunctional 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). Otherwise, the matte article of Comparative Example 3 was also obtained.

[0349] [Comparative Example 4]

[0350] Based on Example 2, the resin composition (resin B) for forming the matte layer obtained in Comparative Example 3 was used instead of the resin composition (resin A) for forming the matte layer, and otherwise, the matte article of Comparative Example 4 was obtained in the same manner.

[0351] [Comparative Example 5]

[0352] Based on Example 2, instead of the resin composition (resin A) for forming the matte layer, a resin composition (resin C) for forming the matte layer was obtained by mixing 60 parts by mass of a polyfunctional urethane acrylate oligomer (functional group number: 4), 30 parts by mass of a polyfunctional acrylate monomer (2 functional groups), and 10 parts by mass of a monofunctional acrylate monomer, and adding 40 parts by mass of a matting agent (silica particles, average particle size: 7 μm), 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). Otherwise, the matte article of Comparative Example 5 was also obtained.

[0353] For the matte articles of Comparative Examples 1 to 5, 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 softness were evaluated. These results are shown in Table 1.

[0354] Figures 7-14 These are microscope images of the matte articles obtained in Examples 1-3 and Comparative Examples 1-5.

[0355] [Table 1]

[0356] Table 1

[0357]

[0358] The resin in Table 1 refers to the resin composition used to form the matte layer.

[0359] Based on the results in Table 1, it was confirmed that the 60° gloss value of the matte layer side of the matte article of this embodiment is 1.6 to 1.9, which is an article with extremely excellent visibility of the matte effect and excellent texture. In addition, it was also confirmed that the soft touch is also excellent.

[0360] On the other hand, while the matte item in Comparative Example 1, with an Rsm of 30μm or higher, exhibited excellent 60° gloss and texture, it lacked a soft touch. It is known that an Rsm of 30μm or higher, and an Spc of 4000mm... -1 The matte articles of Comparative Examples 2 to 4 below have a 60° gloss value of 2.9 to 5.4, and their texture is worse than that of the matte article of Comparative Example 1. They also cannot achieve a soft touch. It can be seen that the matte article of Comparative Example 5, which uses a resin composition for forming a matte layer containing a matting agent, also has a poor 60° gloss value, texture, and soft touch, just like Comparative Examples 2 to 4.

[0361] Industrial availability

[0362] The matte article of this embodiment has excellent visibility and texture with a matte effect, and a superior soft touch. Therefore, it is suitable for various applications, including interior components for buildings such as walls, ceilings, and floors; exterior components for exterior walls, eaves, roofs, fences, etc.; window frames, doors, door frames, handrails, crossbeams, perimeter edges, inlays, etc.; surface decorative panels for general furniture such as wardrobes, shelves, and tables; kitchen furniture such as dining tables and sinks; and housings for home appliances, OA equipment, etc.; interior and exterior components for vehicles, etc. In addition to the decorative components used in the above-mentioned buildings, the matte article of this embodiment can be used directly as a single unit, or in a form of layering, compounding, or combining the matte article 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, and various certificates, keyboards for various keyboards, transparent panels (window glass, etc.) for windows, doors, partitions, etc., and artificial leather, etc.

[0363] Explanation of reference numerals in the attached figures

[0364] 1a: Vertex of the protrusion (Spc large)

[0365] 1b: Vertex of the protrusion (Spc small)

[0366] 2: convex part

[0367] 2a: Convex portion (small Rsm)

[0368] 2b: Convex part (Rsm is large)

[0369] 3: concave part

[0370] 10: Matte items

[0371] 11: Matte finish

[0372] 12: Substrate

[0373] 13: Decorative layer

[0374] 13a: Shading layer

[0375] 13b: Pattern layer

[0376] 14: Adhesive layer

[0377] 15: Transparent resin layer

[0378] 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 as the surface shape with an average length of less than 30 μm for curve features. Spc refers to the average curvature of the leading edge of a 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 a 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. The irregular wrinkles are composed of concave portions and multiple convex portions. The multiple convex portions are formed by multiple linear protrusions, and the concave portions are 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 comprises 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 mass or more, relative to a total of 100 parts by mass of the polymerizable oligomer and the polymerizable monomer. The matte layer is formed by irradiating the layer containing the resin composition 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 parameter Rz of the profile curve specified in JIS B0601:2013 for the surface shape, i.e., the maximum height, is less than 12.5 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 less than 2.0 μm.

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 1, 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